NL8802360A - LOW-VISCOUS STABLE NON-AQUEOUS SUSPENSION CONTAINING ORGANOFILE CLAY AND LOW DENSITY FILLER. - Google Patents

Description

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No. 1283 -

Low-viscous stable non-aqueous suspension containing organophilic clays low density filler.

(1) Field of the invention

This invention relates to stabilized non-aqueous liquid suspensions, in particular a non-aqueous liquid tissue-treating composition. More particularly, this invention relates to non-aqueous liquid detergent compositions that are stable to phase separation even at relatively low viscosity, and even more particularly which remain stable under both static and dynamic conditions and are easily pourable, to the process for the preparation of these compositions and for the use of these compositions for cleaning dirty tissue.

φ (2) State of the art

High performance liquid non-aqueous detergent compositions are well known in the art. Compositions of that type include, e.g. a liquid nonionic detergent in which builder particles are dispersed, such as e.g. described in U.S. Patent Nos. 4,316,812; 3,630,929; 4,254,466 and 4,661,280.

It is found that liquid detergents are often easier to use than dry powdered or finely divided products, so they have therefore found considerable consumer demand. They are easily measured, dissolve quickly in the wash water, are easily applied in concentrated solutions or dispersions on contaminated parts of the laundry and garments and are non-dust forming, while usually taking up less storage space. In addition, the liquid detergents may include blending materials which are not resistant to the drying treatment steps without deterioration, which are often desirable for use in the manufacture of finely divided detergent products.

Although the liquid detergents have many advantages over one-piece or finely divided solid products. 8802360. 2.

4 + - 2 - they also have certain inherent disadvantages, which must be overcome to produce acceptable commercial detergent products.

Thus, some products curdle on storage while others curdle on cooling and are not so readily dispersed.

In some cases, the product viscosity changes and the products become either too thick to pour or so thin that they resemble water. Some clear products will become cloudy while others will gel on standing up.

The rheological behavior of non-ionic liquid detergent systems in which particulate matter is suspended has been thoroughly investigated. Non-aqueous liquid detergent compositions with builders are of particular interest and thus also the problems of phase separation and sagging of the suspended builder and other detergent additives. These considerations have e.g. influence on product pourability, dispersibility and. stability.

It is known that one of the major problems of liquid detergents with builders is their physical stability. This problem arises because the density of the solid suspended particles 20 is greater than the density of the liquid matrix. Therefore, the particles tend to form layers according to Stoke's law.

In fact, the non-aqueous liquid suspensions of the builder particles, such as polyphosphate builders, in particular sodium tripolyphosphate (TPP) in a nonionic detergent rheologically appear almost entirely according to the Casson equation: cr 1/2 = <r01 / 2 * r ^ t / 2 ^ / 2 where ^ dg is AFSCf, ul. ΰ is the shear stress; 6 is the yield stress (or yield value) and is 30 ^ "plastic viscosity" (apparent viscosity at an infinite shear rate), to be supported. The yield stress is the minimum stress necessary to cause plastic deformation (yield) of the slurry. once the yield stress is overcome, the suspended particle network breaks at some intersections and the sample begins to flow, but with a very high apparent viscosity. If the shear stress is much higher than the yield stress, the particles are partially flocculated by shear and the apparent viscosity drops.

Finally, if the shear stress is much higher than the yield stress value, the particles are flocculated completely and the apparent viscosity is very low, as if no particle interaction is present.

Therefore, the higher the yield stress of the slurry, the higher the apparent low shear viscosity and the better the physical stability of the product.

There are two basic solutions for solving the sedimentation problem: Increasing the liquid matrix viscosity and decreasing the solid particle size.

Grinding as an option to reduce particle size and increase product stability provides the following advantages: 1. The specific surface area of the particles increases due to the proportion of particle wetting by the non-aqueous carrier (liquid non-ionic detergent) in proportion is being improved.

2. The average distance between the pigment particles is reduced with a proportional increase in the particle-to-particle interaction. Each of these effects contributes to increasing residual gel strength and slurry yield stress while at the same time grinding significantly reduces plastic viscosity.

The above-mentioned U.S. Patent No. 4,616,812 describes the advantages of grinding solid particles, e.g. builder and bleach to an average particle diameter of less than 10 micro-25 meters. However, it has been found that grinding to such a small particle size alone does not in itself provide sufficient long-term stability to phase dispersion.

It is e.g. Known / such anti-settling suspensions can be stabilized by inorganic or organic thickeners or dispersants, such as e.g. inorganic materials with very high specific surface, e.g. add finely divided silica, clays, etc., organic thickeners, such as cellulose ethers, acrylic and acrylamide polymers, polyelectrolytes, etc. However, such an increase in the slurry viscosity is naturally limited by the condition that the liquid slurry, even at low temperature, is easily pourable and. 1180 2360 - 4 - * - 4 - i must remain liquid. These additives do not further contribute to the cleaning effect of the mixture. U.S. Patent 4,661 * 280 discloses the use of aluminum stearate to increase the stability of suspensions of builder salts in liquid nonionic detergents.

By adding small amounts of aluminum stearate, the yield stress is increased without the plastic viscosity being increased.

According to US patent 3,985,668, an apparent thick liquid aqueous abrasive composition is prepared from an aqueous liquid and a suitable colloid-forming material, such as clay or other inorganic or organic thickening or suspending agent, in particular smectite clay products, and a relatively light, water-insoluble particulate filler material, which, like the abrasive material, is suspended by the apparent thick liquid fluid phase. The lightweight filler has a particle diameter in the range of 1-250 microns and a specific gravity less than that of the apparent thick liquid fluid phase. According to this specification, it is suggested that incorporation of the relatively light, insoluble filler into the apparently thick liquid fluid phase minimizes phase separation, ie minimizes the formation of a clear liquid layer above the thick liquid abrasive composition, firstly due to buoyancy. that exerts an upward force on the structure of the colloid-forming agent in the viscous phase, which counteracts the tendency of the heavy abrasive to compress the viscous structure and express liquid. Second, the filler material acts as a volume increasing agent, replacing some of the water normally used in the absence of the filler material, resulting in less aqueous liquid being available to cause clear layering and separation.

British Patent Application 2,168,377A, published June 18, 1986, discloses aqueous liquid dishwashing detergents containing a colloidal clay thickener and a low density particulate filler in the range of from about 1 to about 250 microns and densities in the range of about. 86 0 2.36 0 - 5 -% * - 5 - 0 »Q1 to about 0.5 g / cubic cm, used at a level of about 0.07% to about 1% by weight of the composition, as abrasive additives. It is suggested that the filler material improves stability by reducing the specific gravity of clay so that it will float in the liquid phase of the composition. The type and amount of the filler is selected such that the specific gravity of the final composition is adjusted to match that of the clear liquid (i.e., the composition without clay or abrasive materials).

10 The finely divided low-density fillers as described on page 4, r. 33-35 of the British patent application are also useful as the low-density filler in the compositions of the present invention. According to this application, the filler material improves stability by reducing the specific gravity of the clay mass to float in the aqueous liquid phase. The type and amount of the filler material are selected such that the density of the final composition is adjusted to match that of the clear liquid (without clay and abrasive).

It is also known an inorganic insoluble thickener or dispersant with a very high specific surface area, such as finely divided silica with exceptionally fine particle size (eg 5-100 millimicronclimeter as purchased under the trade name Aerosil) or the other highly bulky inorganic carrier materials as described in U.S. Patent 3,630,929.

It has long been known that aqueous swelling colloidal clays, such as bentonite and montmorillonite clays, can be modified by exchanging the metallic cation groups with organic groups to convert the hydrophilic clays into organophilic clays. The use of such organophilic clay products as gel-forming clay products is described in U.S. Patent 2,531,427.

Improvements and modifications of the organophilic gel-forming clays are e.g. described in the following United States patents: 2,966,506; 4,105,578; 4,208,218; 4,287,086; 4,434,075; 4,434,076. According to these patents, said * 88 © Z3 $ 0 - * - * 4 - 6 - organophilic clay gelling agents are useful in greases, oil based drilling fluids, oil base packing fluids, paints, varnishes, varnish removers, adhesives, sealants, inks, polyester gel coatings and the like. However, use as a stabilizer in a non-aqueous liquid detergent composition for fabric washing has not been proposed.

In contrast, the use of clays in combination with quaternary ammonium compounds (often referred to as "QA" compounds) to impart tissue softening benefits to the composition to be washed has already been described. Reference may be made to British Patent Application 2,141,152 A of December 12, 1984 and many patents cited therein regarding fabric softening compositions based on organophilic QA clays.

According to the aforementioned United States Patent Specification 4,264,466 15, the physical stability of a dispersion of finely divided materials, such as detergent builders, in a non-aqueous liquid phase is improved by using an insensitive chain structure type clay, including sepiolite, attapulgite and polygorskite, as the primary suspension agent. to use clay products. In this patent specification 20, e.g. with the comparative examples shown that other types of clay products, such as Montmorillonite clay, e.g. Bentolite L, hectorite clay (e.g. Veegum T) and kaolinite clay (e.g. Hydrite PX), even when used together with an auxiliary suspending agent, including cationic surfactants including QA compounds, are only poor suspending agents.

In said patent specification, reference is further made to the use of other clay products as suspension aids and, for example, U.S. Pat. Nos. 4,049,034; 4,005,027 (both aqueous systems); 4,166,038; 3,259,574; 3,557,037; 3,549,542; and 30, British Patent Specification 2,017,072.

Pending Patent Application Serial No. 063,199, filed June 12, 1987, of Applicant describes the incorporation in up to about 1% by weight of an organophilic water-swellable smectite clay modified with a cationic nitrogen-containing compound in / non-aqueous liquid tissue-treating composition. contains at least one long hydrocarbon of about 8 to about 22 carbon atoms to form an elastic network or .880236 C "7" - 7% "elastic structure by the suspension to increase the yield stress and the stability of the suspension increase.

Although the addition of the organophilic clay improves the stability of the slurry, further improvements are still desired, particularly for finely divided slurries with relatively low flow values to optimize pour and dispersion in use.

In the pending U.S. application, serial no. 073,653, filed June 15, 1987, entitled "Stable non-aqueous cleaning composition containing a low-density filler and use thereof", the use of a low-density filler material for stabilizing liquid suspensions of particulate solids against phase separation material in a liquid phase by equalizing the densities of the dispersed particle phase and the liquid phase. These modified liquid suspensions exhibit excellent phase stabilization when left for extended periods of up to 6 months or longer or even when subjected to moderate shaking. There was. however, it has recently been observed that when the low-density filler-modified suspension is subjected to strong vibrations, such as are found during transport by railways, trucks, etc., the homogeneity of the dispersion deteriorates as part of the low-density filler migrates to the top surface of the liquid suspension.

Therefore, further improvements in the stability of non-aqueous liquid tissue-treating compositions were still desired. This desire has been met by adding a small amount, up to about 1% by weight, of an organophilic clay to a liquid suspension of finely divided functionally active suspended particles, which have a small amount of low, based on the discovery of the present inventors. density filler, wherein the filler and the other functional suspended particles co-operate in such a manner that essentially a suspension of composite particles having a density of substantially the same value as the density of the continuous liquid phase is provided, a stronger network structure is provided , effectively reducing the tendency of the suspended functional particles, e.g.

. 8 & 0236O '8 i - 8 - detergent builder, bleach, anti-static agent, etc., is prevented from settling and vice versa, the rise of the low-density filler or the formation of a clear liquid phase, when the composition is subjected to strong decomposition power. countered. Thus, in the pending application, serial no.

073,551 filed July 15, 1987, Applicant discloses a liquid cleaning composition consisting of a suspension of functionally active particles in a liquid nonionic detergent, the composition comprising an amount of low density filler 10 to enhance the stability of the suspension at rest and upon shaking, as well as an amount of organophilic clay to improve the stability of the composition when subjected to strong vibrational forces.

Although the stability of the non-aqueous suspension has been significantly improved by the low-density filler / organophilic clay stabilization system, certain drawbacks have nevertheless become apparent. First, it has been observed that over time, the viscoelastic structure imparted by the organophilic clay weakens, which is reflected by a steady decrease in flowability. Thus, within the expected life of the product, there may come a time when the flow value will drop below a level required to maintain the stability of the low-density filler, especially under strong vibrational forces.

A second disadvantageous consequence of the known stabilization system is that the incorporation of the low-density filler, such as microspheres, increases the plastic viscosity of the product and consequently decreases its fluidity.

In accordance with the present invention, it has now been discovered that the problem of increased viscosity of the low-density filler-stabilized non-aqueous suspension and the problem of change in yield value over time for the organophilic clay-stabilized non-aqueous suspension are substantially completely overcome by incorporating a small but effective amount of certain phosphate esters into the organophilic clay and / or the low-density filler-stabilized liquid cleaning composition. The addition of the phosphate ester compounds reduces the plastic viscosity of the compositions containing the low-density filler and stabilizes the aging yield of the compositions containing the organophilic clay.

Thus, it is an object of the invention to provide liquid tissue treating compositions which are suspensions of insoluble tissue treating particles in a non-aqueous liquid and which are time-stable, easily pourable and dispersible in cold, warm or being hot water.

It is also an object of this invention to provide a viscoelastic, non-aqueous suspension of insoluble tissue-treating particles that can maintain their rheological properties over time, even when subjected to strong vibrational forces.

Another object of the present invention is to formulate a strong builders non-aqueous liquid non-ionic detergent composition that is resistant to sagging of the suspended solids or separation of the liquid phase and is easily liquid .

It is a specific object of this invention to provide a stable high performance non-aqueous liquid non-ionic detergent composition with builders comprising a non-aqueous liquid composed of a non-ionic detergent agent, tissue-treating solid particles suspended in the non-aqueous liquid, at least one of a low-density filler in an amount of * up to about 10% by weight to substantially equalize the density of the continuous liquid phase and the density of the suspended fine particle phase - including of the low-density fillers and other suspended particles, such as builder particles, and an organophilic modified clay in an amount of up to about 1% by weight, to prevent loss of product homogeneity even when the composition is subjected to strong vibrational forces, as well as an amount lecithin or glycol phosphate, polyglycol phosphate or glycerophosphate ester for the effective reducing the plastic viscosity and stabilizing the flowability of the composition.

A more specific object of the invention is to provide a method for improving the stability and the performance. 10.

Decrease the viscosity of a non-aqueous suspension of functionally active solids stabilized with low-density filler and organophilic clay. In another aspect, the invention provides a method of cleaning contaminated fabrics by contacting the contaminated fabrics with the liquid nonionic detergent composition as described above.

According to yet another aspect of the invention, there is provided a method of stabilizing a suspension of a first finely divided functionally active solid substance in a continuous liquid carrier phase, wherein the suspended solid particles have a density greater than the density of the liquid phase which method comprises adding to the suspension of solid particles an amount of a finely divided filler having a density less than the density of the liquid phase, such that the density of the dispersed solid particles together with the filler becomes equal to the density of the liquid phase, which filler also increases the plastic viscosity of the slurry, a small amount of an organophilic clay to enhance the structure cohesion of the slurry and overcome the tendency of the filler to the surface of the composition to rise when the composition to strong vibration cr eights, as subjected during transportation, and a small amount of lecithin, glycol phosphate ester, polyglycol phosphate ester or glycerophosphate ester to effectively lower the plastic viscosity of the suspension and maintain its structural adhesion.

The viscosity-reducing flow-stabilizing phosphate ester compound used in the invention is preferably lecithin. Pure lecithin is a fatty acid substituted phosphatidyl choline of the general structural formula la of the formula sheet.

In practice, however, lecithin is rarely available in pure form, and generally speaking, lecithin refers to a complex, naturally occurring mixture of phosphatides, triglycerides, carbohydrates, sterols and other minor ingredients.

Lecithin is generally obtained from vegetable oil, with soybean oil being the main source. Other lecithin sources include egg yolk, milk, and animal brains. The phosphatides present in lecithin are similar except that their amounts vary. Likewise, the other minor components of lecithin vary according to their particular source.

Typical fatty acid profiles of commercially available lecithin 5 are shown in the following table:

Comparative fatty acid profiles (wt%)

Number of carbon atoms Soybean Commercial oil-free commercial and double bonds _ lecithin cial lecithin saturated C16: Q 9 15 19 C18: Q 55 5, yg Total 14 20 24

Unsaturated C18: 1 26 17 10 C18: 2 53 55 59 20 r ü18: 3 78 7

Total 86 80 76

A typical composition of soy lecithin, the most common 2g commercial product is as follows:%

Phosphatidylcholine (I) 20

Phosphatidylethanolamide (II) 15

Phosphatidylinositide (III) 20 2q Phosphatinic acids and other phosphatides 5

Carbohydrates, sterols 5

Triglycerides 35 wherein I, II and III are represented by formulas 1-3 35 of the formula sheet. In these formulas, R ^, R2 = C ^ g.g, C ^ .q, C18: 1 * C18: 2, C18: 3 *

Any of these naturally occurring lecithin forms can be used in the present invention. Furthermore, the lecithin need not be pure and any of the commercially available quality etflecitins, which are generally mixtures of phosphatidylcholine, phosphatidylethanolamine, phosphatidylinositol (phosphatides) and triglycerides, regardless of their source, e.g. egg yolk, soybeans, etc., are used as the viscosity-lowering stabilizer.

However, it is generally preferred to use a double bleached form of lecithin to minimize any base odors that may be present in their natural products.

Other useful phosphate ester compounds include phosphate esters of glycols, polyglycols and glycerols. As glycols one can mention e.g. ethylene glycol, propylene glycol, butylene glycol and glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether etc. The polyglycols may contain up to about 20 repeating oxyethylene or oxypropylene units, preferably up to about 10 oxyethylene units. As glycerol compounds, mention can be made of not only glycerol but also alkyl or alkenyl substituted glycerols, e.g. glycerols having up to about 20 carbon atoms, preferably up to about 10 carbon atoms, such as 1,2,3-butanetriol, 1,2,3-pentanetriol, 1,2,3-decane triol, 1,2, 3-hex -2-a triol and the like. The nonphosphated hydroxyl groups of the glycol compound and at least one of the nonphosphated hydroxyl groups of the glycerol compounds are esterified with a long chain fatty acid.

Suitable phosphate ester compounds, including the preferred active phosphatidylcholine of lecithin may be represented by the following general formulas 4 or 5 of the formula sheet, wherein R is a straight or branched chain alkyl or alkenyl group having 1 to 8 carbon atoms and which may be substituted with an aminc group of the formula -NR ^ Rg, wherein R ^ and Rg are independently hydrogen or alkyl of 1-4 carbon atoms, or by a quaternized nitrogen of the formula -NR ^ RgRg, wherein R ^ and Rg are as above are defined and Rg is hydrogen or alkyl of 1-4 carbon atoms;

Rq is hydrogen or lower alkyl or lower alkenyl; R, j is an acyl residue of a long chain fatty acid; R 1 is hydrogen or an acyl radical of a long chain fatty acid; . 6802360 - is - - 13 - is hydrogen or an acyl residue of a long chain fatty acid; provided that R2 and R3 cannot both be hydrogen at the same time; and n is a number from 1-10.

As used herein, the term "lower alkyl" or "lower alkenyl" refers to alkyl or alkenyl of 1-5, preferably 1-4 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 having about 8 to about 22 carbon atoms, preferably 10-18 carbon atoms, especially 12-18 carbon atoms, including mixtures of such fatty acids. 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 alkyl amine * alkenyl amine *, alkyl ammonium or alkenylammonium phosphate ester of a glycol, polyglycol or glycerol with at least one long chain fatty carboxylic ester group present in the molecule is.

The viscosity-lowering stabilizing additive is used in an amount effective to reduce the plastic viscosity of the composition to less than 800 mPa.s (800 centipoise), preferably less than about mPa.s, such as about 400 mPa.s to lower. Generally, amounts of about 0.1 to 3 wt. 2, based on the total composition, provide viscosities within the desired range.

In the preferred embodiment of special interest herein, the liquid phase of the composition of this invention consists essentially or completely of a liquid nonionic synthetic organic detergent. However, part of the liquid phase may be composed of organic solvents which enter the composition as solvent carriers or thinners for one or more of the solid particulate ingredients, such as in enzyme suspensions, perfumes and the like. As will be described in detail below, organic solvents such as alcohols and ethers can be used as viscosity controlling and anti-gelling agents.

The nonionic synthetic organic detergents: 8802360 - η - - 14 - used in the practice of the invention may consist of any series of such compounds which are well known and e.g. are described in detail in the text Surface Active Agents, band II, by Schwartz, Perry and Berch, published in 1958 by 5 Interscience Publishers and in McCutcheon's Detergents and Emulsifiers yearbook 1969, the relevant descriptions of which are incorporated herein by reference. Usually, the nonionic detergents are poly-lower alkoxylated lipophiles, the desired hydrophilic-lipophilic balance being obtained by adding a hydrophilic poly-lower alkoxy group to an lipophilic moiety. A preferred class of nonionic detergent agent employed is a poly-lower alkoxylated higher alkanol, wherein the alkanol contains 10-22 carbon atoms and the number of moles of lower alkylene oxide (2 or 3 carbon atoms) ranges from 3 to 20. Of such materials, it is preferred to use those in which the higher alkanol contains a higher fatty alcohol with 3 to 11 or 12 to 15 carbon atoms and which contains 5-18, preferably 6-14 lower alkoxy groups per mole. The lower alkoxy is usually etoxy, but in some cases it may be desirable to mix it with propoxy, the latter if present often being in a minor (less than 50%) amount. Examples of such compounds are those in which the alkanol contains 12-15 carbon atoms and the latter containing about 7 ethylene oxide groups per mole, e.g. Neodol 25-7 and Neodol 23-6.5, which products are made by. Shell Chemical 25 Company Inc. The first is a condensation product of a mixture of higher fatty alcohols with an average of 12 to 15 carbon atoms, with about 7 moles of ethylene oxide, the latter being a corresponding mixture in which the carbon atom content of the higher fatty alcohol is 12-13 and the number of ethylene oxide groups present is on average about 30. spring is 6.5. The higher alcohols are primary alkanols.

Other examples of such detergents include Tergi-tol 15-S-7 and Tergitol 15-S-9, both of which are straight secondary alcohol ethoxylates made by Union Carbide Corp. to be. The first is one.

a mixed etoxylation product of 11-15 carbon atoms and / linear secondary alkanol with 7 moles of ethylene oxide, the latter being a similar product but converting 9 moles of ethylene oxide.

.4802360 - 15 - -15-.

Also useful in the present compositions as a component of the nonionic detergent agent are higher molecular weight nonionics such as Neodol 45-11 which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being 14 to 15 carbon atoms and the number of ethylene oxide groups per mole is about 11. Such products are also made by Shell Chemical Company. Another preferred class of useful nonionics is represented by the commercially known class of nonionics which are the reaction product of a higher straight alcohol and a mixture of ethylene and propylene oxides, which is a mixed chain of ethylene oxide and propylene oxide contains terminated by a hydroxyl group. Examples include the nonionics sold under the trademark Plurafac of BASF such as Plurafac RA30, Plurafac RA40 (a C12 -Cg fat alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide), Plurafac D25 (C ^ 3-C ^ fatty alcohol condensed with 5 mill propylene oxide and 10 mill ethylene oxide), Plurafac B26 and Plurafac R50 (a mixture of equal parts Plurafac D25 and Plurafac RA40).

Generally, the mixed ethylene oxide-propylene oxide may represent fatty alcohol condensation products represented by the general formula R0 (C3H60) p (c2H4 °) qH, where R is a straight or branched primary or secondary aliphatic hydrocarbon, preferably alkyl or alkenyl, especially alkyl with 6-20, preferably 10-18 and in particular 12-18 carbon atoms, 25 is p a number from 2-8, preferably 3-6 and q is a number from 2-12 preferably 4-10. applied when lower foaming properties are desired. In addition, these detergents have the advantage of low gelation temperatures.

Another group of liquid nonionics are available from Shell Chemical Company Inc. under the trademark Dobanol: Dobanol & 91-5 is an ethoxylated Cg-C15 fatty alcohol with an average of 5 moles of ethylene oxide, Dobanol 25-7 is an ethoxylated C12 "C15 fatty alcohol with an average of 7 moles of ethylene oxide, etc.

In the preferred poly-lower alkoxylated higher alkanols, in order to achieve the best balance of hydrophilic and lipophilic units, the number of lower alkoxy groups will usually be 40-100% of the number of carbon atoms in the higher alcohol, such as 40-60%. 8802360 'm' - 16 - thereof, while the nonionic detergent will often contain at least 50¾ of such a preferred poly-lower alkoxy higher-alkanol.

High-nolecular alkanols and various normally solid non-ionic detergents and surfactants can contribute to the gelation of the liquid detergent and, therefore, they are preferably omitted from or limited in amount in the present composition, although minor amounts thereof are useful for their cleansing properties. properties etc.

As to both preferred and less preferred nonionic detergent agents, the alkyl groups contained therein are generally straight, although branching may be tolerated, such as with a carbon adjacent to or two carbon atoms removed Of the straight chain terminal carbon atom and descending from the alkoxy chain, if such a branched alkyl has no more than 3 carbon atoms in length. Normally, the percentage of carbon atoms in such a branched configuration will be minor and rarely more than 20% of the total carbon atom content of the alkyl. Although straight alkyls joined to the alkylene oxide chains are highly preferred and will result in the best combination of scrubbing power, biodegradability and non-gelling properties, medial or secondary combinations of the alkylene oxide in the chain may also occur. This is usually only a minor amount of such alkyls, generally less than 20%, but as is the case with the listed Tergitols, it may be greater. Also, when propylene oxide is present in the lower alkylene oxide chain, it is usually less than 20% thereof and preferably less than 10% thereof.

When using larger amounts of non-terminal alkoxylated alkanols, propylene oxide-containing poly-lower alkoxylated alkanols, and less hydrophilic Tipophilically Balanced Nonionic Detergents than above, and when using other nonionic detergents in place of those mentioned herein If preferred nonionic detergents are used, the resulting product may not have such good washing power, stability, viscosity and non-gelling properties as the preferred compositions but using viscosity and gel. instetient compounds can also improve the properties of the detergents based on such non-ionic detergents. In some cases, such as when a higher-molecular poly-lower gealkoxy-5-tar higher already canoe! is used, usually because of its washing power, the amount thereof will be adjusted or limited according to the results of routine tests, to achieve the desired washing power with the product still being non-gelling and having the desired viscosity. It has also been found that it is only rarely necessary to use high molecular weight nonionic detergent compositions because of their washing power properties, as the preferred nonionogamic detergent compositions described herein allow the desired viscosity in the liquid detergent to be achieved without gelation at low temperatures. Mixtures of two or more of these liquid nonionics can also be used, and in some cases advantages can be achieved by using such mixtures.

Because of their low gelation temperatures and low pour points, another preferred class of nonionic detergent agents 20 includes the secondary fatty alcohols having relatively narrow ethylene oxide contents in the range of about 7 to 9 moles, especially about 8 moles of ethylene oxide per molecule and the C 3 -C 4, especially C 3 fatty alcohols, ethoxylated with about 6 moles of ethylene oxide.

Furthermore, it may be advantageous in the composition of this invention to include an organic solvent or diluent which can function as a viscosity adjusting and gel inhibiting agent for the liquid nonionic surfactants. Lower (C 1 -C 8 -jaliphatic alcohols and glycols such as ethanol, isopropanol, ethylene glycol, hexylene glycol and the like have been used for this purpose. Polyethylene glycols such as PEG 400 are also useful diluents. Alkylene glycol ethers such as the compounds sold under the trademarks Carbopol and Carbitol which are relatively short hydrocarbon chains (kj-Cg) and a low content of ethylene oxide (about 2-6 35 EO units per molecule) have its particularly useful viscosity adjusting and anti-gelling solvents in the formulation. -

of this invention. This use of the alkylene glycol ethers is described in the pending application serial no. 687,815 filed December 31, 1984 to applicant, the disclosure of which is incorporated herein by reference. Suitable glycol ethers can be identified by the following general formula R0 (CH2CH2O) nH

wherein R is a C 2 -C 8, preferably C 2 -C 8 alkyl group, and n is a number of about t-6, preferably 1 - 4 on average. Specific examples of suitable solvents include ethylene glycol monoethyl ether (C 2 H 5 -O-CH 2 CH 2 OH), diethylene glycol monobutyl ether (C 2 Hg-O- (CH 2 CH 2 O) 2H), tetraethylene glycol mono octyl ether (Cg H 2 -CHCHgCH 2 O ^ H) etc. Particularly preferred diethylene glycol monobutyl ether.

Another useful anti-gelling agent which can be included as a minor component of the liquid phase is an aliphatic straight or aliphatic monocyclic dicarboxylic acid, such as the C8 -C18 alkyl and alkenyl derivatives of succinic or maleic acid, and the corresponding anhydrides or their aliphatic monocyclic dicarboxylic acid compound. The use of these compounds as an anti-gelling agent in non-aqueous liquid high performance detergent formulation with builders gives rise to a clear anti-gelling effect.

The aliphatic dicarboxylic acid can be saturated or unsaturated, but is preferably unsaturated, the aliphatic straight portion being straight or branched. The aliphatic monocyclic molecules can be saturated and comprise a single ring double bond. Furthermore, the aliphatic hydrocarbon ring may contain 5- or 6-30 carbon atoms in the ring, such as cyclopentyl, cyclopentenyl, cyclohexyl or cyclohexenyl, where a carboxyl group is bonded directly to a carbon atom in the ring and the other carboxyl group via a straight alkyl or alkenyl group is attached to the ring.

The aliphatic and straight dicarboxylic acids have at least about 35 carbon atoms in the aliphatic chain and may be alkyl or alkenyl of up to about 14 carbon atoms, with a preferred range of 8-13 carbon steams, especially 9-12 carbon 8802360 ' 19 '-19 - dust atoms. One of the carboxylic acid groups (-C00H) is preferably bonded to the terminal (alpha) carbon of the aliphatic chain while the other carboxyl group is preferably bonded to the next adjacent (beta) carbon or it may be 2 or 3 carbon atoms from the alpha position, ie to the gamma or delta carbon atoms. The preferred aliphatic dicarboxylic acids are the alpha, beta dicarboxylic acids and the corresponding anhydrides, with derivatives of succinic or maleic acid in particular being preferred which have the general formulas 6 or 7 of the formula sheet, wherein R is an alkyl or alkenyl group having about 6-12 carbon atoms, preferably 7-11 carbon atoms, especially 8-10 carbon atoms. The alkyl or alkenyl groups can be straight or branched. The straight alkenyl group are particularly preferred. It is not necessary that R represent a single alkyl or alkenyl group, and also mixtures of different carbon lengths may be present depending on the starting materials for the preparation of the dicarboxylic acid.

The aliphatic monocyclic dicarboxylic acids can be either 5- or 6-carbon rings with one or two straight aliphatic groups bonded to the ring carbon atoms. The straight aliphatic groups have at least about 6, preferably at least about 8, especially preferably at least about 10 carbon atoms in total, and up to about 22, preferably up to about 18, especially up to about 15 carbon atoms. When two aliphatic carbon atoms attached to the aliphatic ring are present, they are preferably placed para to each other. Thus, the preferred aliphatic cyclic dicarboxylic acid compounds can be represented by the structural formula of the formula sheet wherein -T- represents -CH> -, -CH = »" or -CH = CH-; R2 is an alkyl or alkenyl group with 3-12. represents carbon atoms; and 3 R represents a hydrogen atom or an alkyl or alkenyl group having 1-12 carbon atoms, 2

provided that the total number of carbon atoms in R.

3 35 and R is about 6 to about 22.

Preferably -T-C 1 represents -CHg- or -CH = CH-, particularly preferably -CH = CH-.

2 3 R and R are each preferably alkyl groups having about 3 to 8802360 - 2a: - 20 - about 10 carbon atoms, especially about 4 to about 29 carbon atoms, the total number of carbon atoms in R and 3 R being about 8 to is about 15. The alkyl or alkenyl groups can be straight or branched but are preferably straight chains.

The amount of the nonionic detergent agent is generally in the range of about 20 to about 70%, such as about 22 to 60%, for example, 25%, 30%, 35%, or 40% by weight of the composition. The amount of solvent or diluent, when present, is usually up to 20%, preferably up to 15%, e.g. 0.5 to 15%, in particular 5.0 to 12%. the weight ratio of nonionic detergent to alkylene glycol ether as the viscosity adjusting and anti-flea agent, when the latter is present, as in the preferred embodiment of the invention is in the range of about 100: 1 to 1: 1, preferably about 5 5: 1 to about 2: 1, such as 10: 1, 8: 1, 6: 1, 4: 1 or 3: 1.

The amount of the dicarboxylic acid gel inhibitor compound, when used, depends on factors such as the nature of the liquid nonionic detergent, e.g. its gelation temperature, the nature of the dicarboxylic acid, other ingredients in the composition that could affect the yeast temperature and the intended use (eg, with hot or cold water, geographic climate, etc.). It is generally possible to lower the gelling temperature to no more than about 3 ° C, preferably no more than about 0 ° C, with amounts of dicarboxylic acid anti-gelling agent in the range of 1 to about 30%, preferably about 1.5 to about 15% by weight based on the weight of the liquid nonionic detergent, although in any particular case the optimum amount can be easily determined by routine testing.

In the preferred embodiment, the detergent compositions according to the invention also comprise, as an essential ingredient, water-soluble and / or water-dispersible detergent builder salts. Typical suitable builders include those described in the aforementioned U.S. Pat. Nos. 4,316,812, 4,262,466, 3,630,929 and many others. Water-soluble inorganic alkaline builder salts that can be used only with the detergent compound or mixed with other builders * 880236O - 21 - - 21 are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. (One can also use ammonium or substituted ammonium salts). Specific examples of such salts are sodium 5-tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono- and di-orthophosphate and potassium phosphate. Sodium tropolyphosphate (TPP) is particularly preferred when phosphate-containing ingredients are not i.v.m.

10 environmental problems are banned. The Al Potassium Silicates are useful builder salts which also function to make the composition anti-corrosion against washing machine parts. Sodium silates with Na 2 O / SiO 2 ratios of 1.6 / 1 to 1 / 3.2, especially about 1/2 to t / 2.8, are preferred.

Potassium silicates with the same proportions can also be used.

Another class of builders is formed by the water-insoluble alumino silicates, both of the crystalline and amorphous type. Several crystalline zeolites (i.e., aluminosilates) are described in British Patent 1,504,168, U.S. Patent 4,409,136 and Canadian Patents 1,072,835 and 1,087,477, all of which are incorporated herein by reference for such descriptions.

An example of useful amorphous zeolites can be found in Belgian patent 835,351 and this patent is also incorporated herein by reference.

The zeolites generally have the formula (Μ20) χ (Α1203). (SiO2) z.WH20 where x is 1, y is 0.8-1.2 and preferably is 1, z is 1.5-3.5 or higher and preferably 2-3 is and w is 0-9, preferably 2.5-6 and N is preferably sodium. A typical zeolite is type A or a similar structure, with 4A being particularly preferred. The preferred alumino silicates have calcium ion exchange capacities of about 200 milliequivalents per gram or more, e.g. 400 meq / g.

Examples of organic alkaline sequestrant builder-35 salts useful only with the detergent or mixed with other organic and inorganic builders are alkali metal "86D2 36 0.22.

22 - ammonium or substituted ammonium, aminopolycarboxylates, e.g. sodium and potassium ethylenediaminotetraacetate (EDTA), sodium and potassium nitrillotriacetates (NTA) and triethanolammonium N- (2-hydroxyethylnitrilodiacetates) Mixed salts of these polycar-5 boxylates are also suitable.

Other suitable organic type builders include carboxymethyl succinates, tartronates and glycols and the polyacetal carboxylates. The polyacetal carboxylates and their use in detergent compositions are described in 4,144 * 226; 4,315,092 and 4,146,495. Other patents concerning similar builders include 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. Also relevant are European patent applications Nos. 0015024, 0021491 and 0063399.

The amount of the suspended detergent builder based on the total composition is usually in the range of about 10 to 60% by weight, such as about 20 to 50% by weight, e.g. about 25-40% by weight of the composition.

According to an embodiment of the invention, the physical stability of the suspension of the detergent builder compound or compounds or any other finely divided suspended solid additive such as bleach, pigment etc. in the liquid carrier is greatly improved by the presence of a low density filler such that the density of the continuous liquid phase is approximately equal to the density of the finely divided solid particulate dispersed phase including the low density filler.

The low-density filler can be any inorganic or organic particulate material which 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 must have sufficient mechanical strength to withstand the shear stresses that will be experienced during product composition, packaging, transportation, etc.

Within the aforementioned general criteria, suitable particulate filler materials have effective densities in the range / .8802360-23.

From about 0.01 to 0.50 g / cc, preferably from 0.02 to 0.50 g / cc, in particular up to about 0.20 g / cc, especially from 0.02 to 0.20 g / cc cc, measured at room temperature, e.g. 23 ° C and particle size diameters in the range from about 1 to 300 µm, preferably 5 or 5 to 200 µm, with the average particle size diameters in the range from about 20 to 100 µm preferably from about 30 to 80 µm.

The types of inorganic and organic fillers that have such low bulk densities generally consist of hollow micro-beads or microbeads or at least highly porous solid particulate material.

For example, either inorganic or organic microspheres or glass spheres are preferred. Specific non-limiting examples of organic polymer material microspheres include poly-vinylidene chloride, polystyrene, polyethylene, polypropylene, polyethylene terephthalate, polyurethanes, polycarbonates, polyamides anz.

More generally, any of the low-density particulate filler materials described in the aforementioned British Patent 2,168,377A on page 4, lines 43-55, including those cited in the patents of Moorehoude et al and Wolinski , et al. in the non-aqueous composition of this invention. In addition to the hollow microspheres, other low-density inorganic filler materials can also be used, such as aluminosilicate zeolites, spray dried clays, etc.

However, according to a particularly preferred embodiment of the invention, the lightweight filler is formed from a water-soluble material. This has the advantage that the water-soluble particles when used for washing contaminated fabrics will dissolve in an aqueous wash bath and therefore will not settle on the fabric to be washed. In contrast, the water-insoluble filler particles can more easily adhere to or be adsorbed on or to the fibers or surface of the washed fabric. For a specific example of such a lightweight filler which is insoluble in the non-aqueous liquid phase of the composition of the invention but which is water-soluble, reference may be made to sodium borosilicate glass, such as the hollow microspheres available under the trade name Q-cell, in in particular Q-cell 400, • 880,236 o - 24 - * - 24 - Q-cell 200, Q-cell 500 etc. These materials have the further advantage that they provide silica ions in the washing bath which act as anti-corrosion agents to be.

As examples of water-soluble organic materials suitable for the production of hollow microspheres from low-density particles, one can e.g. refer to starch, hydroxyethyl cellulose, polyvinyl alcohol and polyvinylpyrrolidone, the latter also providing functional properties such as dirty suspension agent when dissolved in the aqueous wash bath. The amount of low-density filler added to the non-aqueous liquid suspension is such that the average statistically weighted density of the suspended particles of the low-density filler is equal to or not much different from the density of the liquid phase (including non-ionic detergent and other solvents, liquids and dissolved ingredients). What this means in practical terms is that the density of the entire composition, upon addition of the low-density filler, is approximately the same, i.e. the same as the density of the liquid phase alone and also the density of the dispersed phase alone, Therefore, the amount of low density to be added will be. filler depend on the density of the filler, the density of the liquid phase alone and the density of the total composition excluding the low-density filler. For any given liquid starting dispersion, the amount of low-density fillers required will increase as the density of the filler increases, and conversely, a small amount of the low-density filler is required to achieve a certain reduction in the density of the egg composition. when the density of the filler decreases.

The amount of low-density filler needed to equalize the densities of the liquid phase (known) and the dispersed phase can be theoretically calculated using the following equation, which is based on the assumption of ideal mixing of the low- density filler and the non-aqueous dispersion:

Mms = ^ ms ^ ó- ^ liq 35 Mf d d.

lie o-ms where Mms is the mass fraction of the low-density filler (e.g.

WT

- 25 - - 25 - microspheres) added to the slurry to make the final composition density equal to the liquid density; ^ ms = liquid displacement density of the low-density filler; ^ density of the liquid suspension phase; j o = density of the starting composition (i.e. suspension for addition of filler);

Mf = mass of final composition (i.e. after addition of the filler); and

Mns = mass of the filler to be added.

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

Although it is preferred to equalize the liquid phase density and dispersed phase density, i.e., ^ liq / dsf = 1.0, to achieve the highest degree of stability, 20 small differences in the densities, e.g. d ^ .q / ds ^ = 0.90 to 1.10, in particular 0.95 to 1.05, (where d ^ is the final density of the dispersed phase after addition of the filler) is still acceptable in many cases give stabilities, which is generally manifested by the absence of phase separation, ie

No appearance of a clear liquid phase, for at least 3-6 months or more.

As just described, the addition to the non-aqueous liquid suspension of finely divided tissue-treating solid particles, of an amount of low-density filler, is sufficient to provide a statistical average density of the solid particles and filler particles equal to the density of the continuous liquid phase has the function of stabilizing the suspension against phase separation. The mere fact that one has a statistically averaged density of the dispersed phase equal to the density of the liquid phase does not in itself explain how and why the low-density filler exerts its stabilizing effect, since the final composition still has the relatively • eeoueo 26 · 4 - 26 - dense dispersed tissue-treating solid particles, e.g. phosphates that would normally settle and the low-density filler that would normally rise in the liquid phase.

Although one does not wish to commit to any particular theory, 5 it is believed, and experimental data and microscopic observations seem to confirm this, that the dispersed detergent active particles, such as builders, bleach, etc., are in fact attracted to and attached to and shaped a mono- or poly-layer of dispersed particles surrounding the particles of low-density filler, forming "mixed" particles which actually function as single unitary particles. It can then be assumed that these mixed particles have a density that approximates a volume weighted average of the densities of all the individual particles forming the mixed particles;

5 d dH + VL dL

cp V

1 * VL

¥ 20 where d = density of mixed particles; dj ^ = density of dispersed phase (heavy particles); d ^ = density of filler (light particles :) :; V ^ | = total volume of dispersed phase particles in the mixing particles; 25 = total volume of fill dust particle in mixed particles.

However, to make the density of the mixed particles equal to that of the liquid phase, it is necessary that a large number of dispersed particles interact with each of the filler particles, eg, depending on the relative densities, 30 different hundreds to several thousand of the dispersed (heavy) particles associate with each low-density filler particle.

Thus, in order to achieve the full benefits of this invention, the average particle size diameter of the low-density filler must be greater than the average particle size diameter of the dispersed phase particles, such as detergent builder, etc., in order to obtain v 68 023 6 0. 27 - - 27 - include the large number of dispersed particles on the surface of the filler particle. In this regard, it has been found that the ratio of the average particle size diameter of the low-density filler particles to the average particle size diameter of the dispersed particles should be at least 6: 1, such as 6: 1 to 30: 1, especially 8: 1 to 20: 1, with best results achieved at a ratio of about 10: 1.

At diameter ratios less than 6: 1, some improvement in stabilization is possible depending on the relative densities of the dispersed particles and the liquid particles and the density of the liquid phase, but satisfactory results will generally not be achieved.

Thus, for the preferred range of mean particle size diameter for the low density filler particles of 20-100 microns, especially 30-80 microns, the dispersed phase particles serve mean particle sizes of about 1 to 18 microns, especially 2-10 microns to own. These particle sizes can be obtained by a suitable mold treatment as described below.

In addition to adding that the low-density filler greatly reduces any tendency of the suspended or dispersed phase to settle or rise or form a clear liquid layer at the top of the composition, the low-density filler also has the function of "plastic viscosity" (to increase the slurry.) Although such an increase in viscosity is not necessarily disadvantageous, in many instances the consumer still prefers the product to be more fluid, that is, to increase the plastic viscosity. lowered.

However, such a decrease in plastic viscosity should not be achieved at the expense of a reduced flow value of the non-aqueous slurry, otherwise physical stability would be adversely affected. According to the present invention, the reduction of the plastic viscosity without substantially a decrease in the flow value is achieved by the inclusion of lecithin 35 or another phosphate ester additive as described above. In the absence of the viscosity-reducing additive, the non-aqueous suspensions containing low-density filler e.g. plastic -68 0236 0 "28" - 28 - viscosities in the range of about 500 to 5000 mPa.s (1 mPa.s = 1 centipoise). By adding lecithin or another phosphate ester, the viscosity can be reduced by even 50¾ or more, e.g. from about 200 to 3000 mPa.s, preferably from 250 to 1000 mPa.s, especially especially from 300 to 600 mPa.s. The correct amount of the additive required to reduce the plastic viscosity to a certain value cannot be accurately determined, but depends on such factors as the initial plastic viscosity, the certain additive and the specific ingredients of the non-aqueous suspension . Generally, amounts of viscosity-reducing additive of about 0.1 to 3 wt%, preferably about 0.3 to 2 wt%, especially 0.5 to 1.5 wt%, based on the total composition will deliver desired results.

Incorporation into the non-aqueous suspension of finely divided tissue treatment particles suspended in nonionic liquid organophilic clay detergent detergent as described in pending U.S. Pat. patent application serial no. 063,199 provides a viscoelastic network which also improves the physical stability of the non-aqueous suspension. The inclusion of lecithin or another phosphate ester compound as defined above in the amounts described further enhances the physical stability of the non-aqueous suspension.

In the preferred embodiment of the invention, the non-aqueous suspension of tissue treatment additive includes both the. low-density filler like organophilic clay. In this preferred embodiment, incorporation of lecithin or other phosphate ester compound additive within the amounts described above reduces the plastic viscosity and promotes maintenance of the viscoelastic network structure imparted by the organophilic clay.

In this preferred embodiment, it has been discovered that under transport conditions, the low-density filler-containing compositions exhibit strong and repetitive vibration forces that normally occur with e.g. transport by rail or truck are exposed to the low-density filler tends to the top. 8802360. 29.

To rise from the composition accompanied by a corresponding degree of settling of the functional active solid suspended particles to the bottom of the vessel in which the composition is stored.

5 Although the reason for the detrimental effect of the strong vibratory forces has not yet been fully elucidated, it can be assumed that the vibrational forces are sufficiently strong to counteract the weak attraction between the low-density filler and the functionally active suspended particles in the mixed particles. previously described to overcome. Another theory is that it is possible that the strong Vibration forces lead to localized disturbances where the yield stress is greater than the yield value of the slurry causing destabilization. Whatever the mechanism by which the low-density filler migrates to the top surface of the liquid suspension, the homogeneity of the liquid suspension can be maintained, even under strong vibration forces, by entering the composition before, during or after the introduction of the low-density filler contains a small amount, generally up to about 1 weight percent of the composition of an organophilic modified clay.

The suitable organophilic modified clay products form a viscoelastic network structure in the composition and it is believed, although one does not wish to be bound by any particular theory of action, that this elastic network structure is able to absorb the strong vibrational forces and thereby even the suspensions under these unfavorable conditions, more particularly, it is believed that organophilic clay additive increases the pour point of the slurry so that the yield stress due to vibration does not exceed the pour point.

Each of the high gel yield swellable organophilic modified clay products as disclosed in pending U.S. Pat. Serial Nos. 063,199, filed June 17, 1987, and serial no.

0.73,551 filed July 15, 1987 can be used in the present composition.

The organophilic modified clay can be based on any swellable clay modified to exhibit a high gelling efficiency in the organic liquid carrier. Examples of such swellable clay materials that are useful (after suitable modification as described herein) are the smectite clay products, in particular the bentonite, e.g. sodium and lithium bentonites; Montmorillonites, e.g. sodium and calcium montmorillonites; sapo staples e.g. sodium saponites and hectorites e.g. sodium hepatites. Other representative clay products include beidellite and stevensite. Hectorites that have excellent swelling capacity are particularly preferred.

The aforementioned smectite-type clay products are three-layer clay products characterized in that the layered structure is able to increase its volume several times by swelling or expanding in the presence of water to form a thixotropic gelatinous substance. There are two main classes of smectite-type clay products: in the first class, aluminum oxide is present in the silicate crystal lattice; in the second class, magnesium oxide is present in the silicate crystal lattice. Atomic substitution by iron, magnesium, sodium, potassium, calcium and the like can occur within the crystal lattice of the smectite clays.

20 It is customary to distinguish between clay products on the basis of their predominant cations. A sodium clay is e.g. a clay in which the cation is predominantly sodium. Aluminum silicates in which sodium is the predominant cation are preferred such as e.g. bentonite clay products. Among the bentonite clays, those from Wyoming (commonly referred to as western or Wyoming bentonite) are particularly preferred.

Preferred swellable bentonite clay products are sold under the trademark Mineral Colloid as industrial bentonite, by Benton Clay Company, a subsidiary of Georgia Kaolin 30 Co. These materials, which are the same as those previously sold under the trademark THIXQ-JEL, are selectively mined and enriched bentonite, and those considered to be the most useful are available as Mineral Colloid Nos. 101, etc. corresponding to THIXO-JELs Nos. 1, 2, 3 and 4. Such materials 35 have pH values (6% concentration in water) in the range of 8-9.4, maximum free moisture contents of about 8% and specific gravities of about 2.6 , while of the pulverized quality .8802360 - 31 - - 31 - at least about 85¾ (and preferably 100%) by a 200 US mesh sieve passes (less than 0.074 mm). Most preferably, the bentonite consists of particles that are substantially (i.e., at least 90% thereof, preferably more than 85%) less than 0.044 mm, preferably 5 all particles are less than 0.044 mm (pass through No. 325 U.S. sieve). The swelling capacity of the bentonite in water is common in the range of 2-15 ml / gram and its viscosity at a 6% concentration in water is usually from 8 to 30 centipoise.

Instead of using THIXO-JEL or Mineral Colloid 10 bentonite, one can also use products such as those sold by American Colloid Company; industrial department, as general purpose bentonite powder, 0.044 mm (325 mesh), of which at least 95% of it is less than 0.044 mm in diameter (wet particle size) and at least 36% smaller than 0.074 mm in diameter (dry particle size). Such an aqueous aluminum silicate mainly consists of Montmorillonite (90% minimal), with smaller amounts of field fir, biotite and selenite. A typical analysis on a "water-free" basis is 63.0% silica, 21.5% alumina, 3.3% ferrous iron (as FegOg), 0.4% ferrous iron (as FeO), 2, 7% magnesium (as Mg), 2.6% sodium and potassium (as NagO), 0.7% calcium (as CaO), 5.6% crystal water (as H20) and 0.7% trace elements.

Although western bentonites are preferred, it has also become possible to use other bentonites, such as those made by treating relatively small amounts of exchangeable monovalent metals (sodium and potassium) containing Italian or similar bentonites with alkaline materials, such as sodium carboxylic materials. to increase the cation exchange capacity of such products. It is believed that the content of the bentonite should be at least about 0.5%, preferably at least 1%, and most preferably at least 2% so that the clay will exhibit satisfactory swelling . Preferred swollen bentonites of the types described above are sold under the trade names Laviosa and Winkelmann, e.g. Laviosa AGB and Winkelmann G-13. Other Examples include Veegum F and Laponite SP, both sodium hepatites, Gelwhite, a calcium montmorillonite, Gelwhite GP, a sodium montmorillonite,

Barasym LIH 200, a lithium hctorite.

.8802360. 32.

- 32 -

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

Therefore, the organophobic nature of the smectite clay materials is converted to an organophilic nature. This can be achieved by the metal-rost cation, e.g. Na, K, Li, Ca, etc. of the clay exchange an organic cation, at least on the surface of the clay particles, e.g. by mixing the clay, organic cation and water together, preferably at a temperature within the range of 20-100 ° C, for a sufficient period of time to allow the organic cation to slip between the clay particles at least on the surface, followed by filtering , washing, drying and grinding. For further details, reference may be made to any of the aforementioned US Patents 2,531,427, 2,966,506, 4,105,578, 4,208,218, 4,287,086, 4,424,075 and 4,434,076, the disclosure of which is incorporated herein by reference in its entirety.

The organic cationic material is preferably a quaternary ammonium compound, preferably with surfactant properties, which indicate at least one long hydrocarbon group (eg, with about 8 to about 22 carbon atoms), although surfactant properties or other fabric favorable properties. are not necessary, nor is it essential that the cationic modifying agent itself be useful as a suspending agent. However, any of the cationic surfactant compounds listed as useful auxiliary suspending agents in the aforementioned U.S. Patent 4,264,466 in columns 23-29, the disclosure of which is incorporated herein in its entirety, can be used to modify the Smectite clay material to last. organo-30 file. The organic cationic nitrogen compounds described in the aforementioned U.S. Patent 2,531,427 or those disclosed in any of the U.S. Patents 2,966,506; 4,105,578 etc., the disclosure of which is incorporated herein by reference, may also be used with advantage.

The preferred modifiers are the quaternary ammonium compounds of the formula. 8802360. 33.

> - 33 -

DiW 1 * x 'wherein R 4, R 5, R 3 and R 3 are each independently hydrogen or a hydrophobic organic alkyl, aryl, aralkyl, alkaryl, or alkenyl group of 1-300 carbon atoms, preferably T-22 carbon atoms 5, wherein at least two R groups, preferably 1-6 carbon atoms and at least one R group, preferably at most two R groups have 8-22 carbon atoms; X is an anion, which may be inorganic, such as halide, e.g. chloride or bromide, sulfate, phosphate, hydroxide or nitrate, or organic such as methyl sulfate, ethyl-10 sulfate or fatty acid, e.g. acetate, propionate, laurate, mirystate, palmitate, oleate or stearate.

Examples of preferred organophilic modifiers include the mono- and di-long (e.g., C 1 -C 20 g, especially C 1 -C 18 Cl) alkyl quaternary compounds. Representative examples of the mono-15 long-chain quaternary ammonium surface active agents include stearyl trimethyl ammonium chloride, tallow trimethyl ammonium chloride, benzylstearyldimethylammoniumchloride, benzyl hydrogenated talkdi-methyl ammonium chloride, benzylcetyldimethylammoniumchloride and the corresponding bromides, iodides, sulfates, methosulfates, 20 acetates and other previously mentioned anions. Typical representative examples of the di-long chain quaternary ammonium compounds include dimethyl distearyl ammonium chloride, dimethyl dicetylammonium chloride, dimethyl stearyl cetyl ammonium chloride, dimethyl ditl ammonium chloride, dimethyl myristyl cetyl ammonium chloride, and the corresponding bromides, iodides, sulfates, acetosulfates, methosulfates previously mentioned. Other representative compounds include octadecylammonium chloride, hexadecylammonium acetate, etc. Most preferred of the QA compounds are dimethylalkylarylanmonium salts because of their high polarity.

In addition to the quaternary ammonium (QA) compounds, other quaternizable nitrogenous organic cations can also be used to form organophilic clay particles. For example, one can report imidazolinium compounds such as e.g. 1- (2-hydroxyethyl) -2-dodecyl-1-benzyl-2-imidazolinium chloride, and heterocyclic nitrogen ring-containing compounds such as long hydrocarbon substituted pyrrolidones, pyridenes, morpholines and the like, such as N, N-octadecylmorpholinium chloride.

* 8802360 '34 "- 34 -

The amount of the organic cation substitution need only be that amount which imparts the required organophilic properties to the clay to provide the desired enhanced stabilization characteristic. Generally, depending on the nature of the organic substituent, this amount can range from about 10 to 100% and is preferably 20-100%, such as 30%, 40%, 50% or 60% of the available basic exchange capacity of the clay material. Usually and preferably, at least enough of the organic compound is used to coat or cover the surface of the clay particles.

Suitable organophilic clay products useful in this invention are commercially available, e.g. the products sold under the Benton trademark of NL Industries, New York, New York, such as Benton 27, which consists of a hectorite clay (magnesium-15 montmorillonite) modified with benzyldimethyl hydrogenated tallow ammonium chloride and Benton 38, which is a hectorite clay modified with dimethyldioctadecyl ammonium chloride is. Other suppliers of organophilic clay products are e.g. Sud Chemie, Munich Germany; Laviosa, Livorno, Italy, Laporte, France and Perchem, U.K.

The organophilic clay products are used in only minor amounts, generally less than 1.0% by weight, preferably less than 0.7% by weight, based on the total composition.

Usually, the amounts of at least about 0.1 wt%, preferably 0.2 wt%, such as 0.25%, 0.3%, 0.35%, and 0.4% are sufficient to make stable, mildly thixotropic non-aqueous liquid suspensions of finely divided detergent builder or other water-soluble or dispersible fabric treating agent.

The organophilic modified clay may be in the non-aqueous liquid dispersion of the suspended particulate ingredients either directly as a powder or after first being dispersed in part of the liquid carrier of the suspension, e.g. the liquid nonionic detergent is included, the latter method being preferred. Furthermore, the organophilic clay, either added to a slurry directly as a powder or pre-gelled in a portion of the liquid carrier, may be added to the slurry before or after the slurry to an average particle size. sizes of not more than 15 micrometers, preferably not more than 10, especially 1-10 micrometers, most preferably 4-8 micrometers, are added.

In a preferred embodiment, the organophilic clay 5 is first predispersed either in a portion of the liquid non-ionic detergent that forms the main liquid carrier or in another non-ionic detergent or solvent or diluent as previously described, or in any suitable mixture of surfactants and / or solvents and / or diluents pre-dispersed. The pre-dispersed clay slurry can be milled in a high shear if necessary to form an organophilic clay gel. Separately, the residual solid particulate material can be suspended in the liquid non-ionic detergent and optionally diluent / solvent and then subjected to grinding. The clay pre-gel and the finely divided material slurry can be ground to the desired average end-particle size before they are mixed together, or the pre-gel and the suspension can be mixed and then subjected to further grinding. In the latter case, the suspended finely divided material can further contribute to the trituration of the organophilic clay particles.

It is an additional advantage of this preferred embodiment of the invention, in which the organophilic clay is subjected to a grinding step, that the incorporation of the lecithin or other phosphate ester increases the viscosity of the predispersed clay suspension, with or without other solid particulate material, does decrease. The grinding step is thus greatly simplified and the use of process aids or a heating step is not necessary.

In any of the aforementioned embodiments where the organophilic clay is subjected to grinding, such as to form an organophilic clay gel, the clay is added separately from the low-density filler since the latter must not be subjected to high shear or grinding forces . In addition, it is preferred that low-density filler is added as the final component of the formulation under conditions where the shear forces applied to the low-density filler are minimal, while still distributing the filler uniformly throughout the filler. entire composition is delivered. In order to achieve this result. 8802360 - 36 - - 36 - it has been found to be easy to mix all ingredients including the organophilic clay when used as previously described except for the 1-density filler and form a thickened suspension and then subject the suspension to low shear mixing with a propeller-type blade mixer, which rotates at between 2,000 and 500 rpm, to form a cavity (vortex) in the center of the mixing vessel, after which the low density filler is added near the top of the vertebra so that the filler is dispersed uniformly throughout the composition.

In addition to its main advantages as a viscosity-reducing agent and rheological stabilizer, the use of lecithin in particular confers several other advantages. Lecitin can e.g. by its amphoteric nature, interact with the nonionic detergent that forms the liquid phase and enhance the wash power of this agent. Lecithin, which has two fatty acid groups and a quaternary ammonium group, can also provide better softening to tissues treated therewith. Lecithin can also act as a heavy metal sequestrant and thus can function in the role of bleach stabilizer. Because of these additional advantages, lecithin and the other phosphate ester compound become useful additives in non-aqueous suspensions of functionally active solids with laundry additives, even when neither the low-density filler nor the organophilic clay additives are present.

Since the compositions of this invention are generally highly concentrated and can therefore be used at relatively low dosages, it is often desirable to add to a phosphate builder (such as sodium tripolyphosphate) an adjuvant builder such as a polymeric carboxylic acid with high calcium binding capacity to otherwise attack by hindering the formation of an insoluble calcium phosphate. Such auxiliary tumblers are also known in the art. For example, one can mention e.g. Sokol an CP5, which is a copolymer of approximately equal amounts of moles of methacrylic acid and maleic anhydride, is completely neutralized to form its sodium salt.

The amount of the auxiliary builder is generally up to about 6 wt.%, 8802560 - 37 - - 37 - preferably J up to 4%, such as 1%, 2% or 3%, based on the total weight of the composition. Of course, where required by environmental constraints, the present compositions can be achieved without a phosphate builder.

In addition to the detergent builders, various other detergent additives or adjuvants may be present in the detergent product to impart additional desirable properties, either of a functional or aesthetic nature. Thus, minor amounts of soil-suspending or anti-graying agents, e.g. polyvinyl alcohol, fatty acid amides, sodium carboxymethyl cellulose, hydroxypropylmethyl cellulose, usually in amounts up to 10% by weight, e.g. 0.1 to 10%, preferably 1-5%; optical brighteners, e.g. cotton, polyamide and polyester brighteners, e.g. stilbene, triazole and benzidine sulfone compositions ,. in particular, include sulfonated, substituted triazinyl stilbene, sulfonated naphtho-triazole stilbene, benzidine sulfone, etc., most preferably stilbene and triazole combinations. Typically, an amount of up to about 2 wt%, preferably up to 1 wt%, such as 0.1 to 0.8 wt% optical whitener can be used. Bluing agents such as ultra-marin blue, enzymes, preferably proteolytic enzymes such as subtilisin, bromelin, papain, trypain and pepsin, as well as amylase type enzymes, lipase type enzymes and mixtures thereof; bactericides e.g. tetrachlorosalisyl anilide, hexachlorophene; fungicides; dyes; pigments (water dispersible); preservatives; ultra-25 violet and absorbents; anti-comparatives, such as sodium carboxymethyl cellulose, a complex of C 2 -C 22 alkyl alcohol with Gl 2 C 18 alkyl sulfate; pH modifiers and pH buffers; colorfast bleaches, perfume and anti-foaming agents or suds suppressants, e.g. silicone compounds are also useful.

For the sake of convenience, the bleaches are classified as chlorine bleaches and oxygen bleaches. Chlorine bleaches are typified by sodium hypochlorite (NaOCl), potassium dichloroisocyanuate (59% available chlorine) and trichloroisocyanuric acid (95% available chlorine). Oxygen bleaching agents 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 monoper- * 8802360 '38'

a

- 38 - sulfate. The perborates, in particular sodium perborate monohydrate, are particularly preferred. The peracid compound is preferably mixed with an activator. Suitable activators which can lower the effective working temperature of the peroxide bleach are e.g. described in U.S. Patent 4,264,466 or in column 1 of U.S. Patent 4,430,244, the relevant disclosures of which are incorporated herein by reference. Polyacylated compounds are preferred activators; of these, the compounds such as tetraacetyl-10 ethylenediamine (TAED) and pentaacetylglycose are particularly preferred.

Other suitable activators include e.g. acetylsalicylic acid derivatives, ethylidene benzoate acetal and its salts, ethylidene carboxylate acetate and its salts, alkyl and alkenyl succinic anhydride, tetraacetylglycouril (TAGU) and their derivatives.

Other suitable classes of activators are e.g. described in U.S. Patents 4,111,826, 4,422,950, and 3,661,789.

The bleach activator usually interacts with the peroxygen compound to form a peroxyacid bleach in the wash water. It is preferable to include a high complexing ability sequestrant to counteract any undesired reaction between such peroxyacid and hydrogen peroxide in the wash solution in the presence of metal ions. Preferred sequestrants are capable of complexing with Cu2 + ions, such that the stability constant (pK) of the complex ng is equal to 25 or greater than 6 at 25 ° C in water, with an ionic strength of 0.1 mol / liter, the pK usually being defined by the formula: pK = -log K, where K represents the equilibrium constant. Thus, e.g. the pK values for complexion of copper ions with NTA and EDTA under the stated conditions are 12.7 and 18.8, respectively. Suitable sequestrants include e.g. in addition to those mentioned above, the compounds traded under the trademark JDequest as e.g. diethylene triamine pentaacetic acid (DETPA), diethylene triamine pentamethylene phosphonic acid (DTPMP); and ethylenediamine tetramethylene phosphonic acid (EDITEMPA).

In order to avoid loss of peroxide bleach, e.g. sodium perborate, which results from enzyme-induced decomposition, such as by. To prevent catalase, the compositions may also contain an enzyme inhibitor compound, such as a compound capable of inhibiting the enzyme-induced decomposition of the peroxide bleach. Suitable inhibitor compounds are described in U.S. Patent 3r606,990, the relevant disclosure of which is incorporated herein by reference.

Of particular interest as an inhibitor compound, mention can be made of hydroxylamine sulfate and other water-soluble hydrophilic amine salts. In the preferred non-aqueous compositions of this invention, suitable amounts of the hydroxylamine salt inhibitors may be no more than about 0.01 to 0.4 µ. In general, suitable amounts of enzyme inhibitors are possible up to about 15%, e.g. 0.1 to 10% by weight of the composition.

Although it is not necessary to achieve acceptable product stability, it is within the scope of this invention to include other suspension stabilizers, rheological additives and anti-gelling agents. For example, the aluminum salts of higher fatty acids, especially aluminum stearate, as described in U.S. Patent 4,661,280, the disclosure of which is incorporated herein by reference, may be added to the composition, e.g. in amounts of 0 to 3 wt%, preferably 0 to 1 wt%.

Another potentially useful stabilizer for use in connection with the low-density filler is an acidic organic phosphorus compound with an acidic POH group as described in pending U.S. Pat. patent application serial no. 781,189, filed September 25, 1985, to applicant, the disclosure of which is incorporated herein by reference. The acidic organic phosphorus compound can e.g. a partial ester of phosphoric acid and an alcohol, such as an alkanol of lipophilic character, which are e.g. more than 5 carbon atoms, e.g. Contains 8-20 carbon atoms. A specific example is a partial ester of phosphoric acid and a C 1 -C-C 1 alkanol. Marchon Empiphos 5632 is composed of approximately 35% monoester and 65% diester. In use, the amounts of the phosphoric acid compounds up to about 3%, preferably up to 1%, are sufficient.

As described in the pending U.S. patent application serial no.

. No. 880236 0-440-4262651 filed November 3, 1986, the disclosure of which is incorporated herein by reference, a nonionic surfactant modified to convert a free hydroxyl group in a unit with the free carboxyl group. such as a partial ester of a nonionic surfactant and a polycarboxylic acid are included in the composition to further improve rheological properties.

Amounts of the acid-terminated nonionic surfactant of up to one per part of the nonionic active agent, such as 0.1 to 0.8 part, are e.g. Enough. Suitable ranges of these optional detergent additives are: enzymes - 0-2%, especially 0.1-1.3%; corrosion inhibitors - about 0-40% and preferably 5-30%; anti-foaming agents and suds suppressors - 0-15%, preferably 0-5%, e.g. 0.1-3% ;. thickener and dispersant - 0-15%, e.g. 0.1-10%, preferably 1-5%; dirt suspending or anti-graying agents and anti-yellowing agents - 0-10%, preferably 0.5-5%; dyes perfumes, whiteners and bluing agents. total weight 0-about 2% and preferably 0-about 1%; pH modifiers and pH buffer 0-5%, preferably 0-2%, bleach-0-40% and preferably 0-about 25%, e.g. 2-20%; bleach stabilizers and bleach activators 0-about 15%, preferably 0-10%, e.g. 0.1-8%; enzyme inhibitors 0-15%, e.g. 0 ^ 01-15%, preferably 0.1-10%; high complexing ability sequestrant, in the range of up to about 5%, preferably--3%, such as about -2 -2%. When selecting the adjuvants, they should be selected to be compatible with the main ingredients of the detergent composition.

In a preferred form of the invention as described above, the mixture of liquid nonionic surfactant and solid ingredients (other than the low density filler) is subjected to grinding e.g. in a sand mill or ball mill. Particularly suitable are the friction mill types, such as those sold by e.g. Wiener-Amsterdam or Netzsch-Germany, wherein the particle dimensions of the solid ingredients are reduced to less than about 18 microns, e.g. to an average particle size of from 2 to 10 microns or even less (e.g., a micron).

.880236 0 - 41 - - 41 -

Preferably less than about 10%, especially less than about 5%, of all suspended particles have particle sizes greater than 15 microns, preferably the size is 10 microns.

In view of the increased cost of energy consumption when decreasing the particle size, it is often preferred that the average particle size be at least 3 microns, especially about 4 microns. Compositions whose dispersed particles are of such small size have improved stability against shearing or settling on storage. Other types of grinding mills, such as a tooth mill, stud mill and the like, are also useful.

In the milling treatment it is preferred that the amount of solid ingredients is high enough (eg at least about 40%, even about 50%), that the solid particles are in contact with each other and are not almost completely shielded from each other by the non- ionic surfactant liquid. Mills in which grinding balls (ball mills) or similar movable grinding elements are used give very good results. Thus, a laboratory scale ball mill with steatite grinding balls of 8 mm diameter can be used.

20 For larger-scale work, a continuously operating mill can be used, in which balls with a diameter of 1 mm or 1.5 mm exert their action in a very small clearance between a stator and a rotor that are in operation at relatively high speed ( eg a CoBall mill); when using such a mill, it is desirable to first pass the mixture of nonionic detergent and the solid particles through a mill that does not perform such fine grinding (eg, a colloid mill) to reduce the particle size to less than 100 micrometers ( (eg, about 40 microns) prior to the milling step to an average 30 particle diameter below about 18 or 15 microns in the continuous ball mill.

Optionally, the powdery solid particles can be finely ground to the desired size before being mixed with the liquid matrix, e.g. in a jet mill. The final compositions of this invention are non-aqueous liquid suspensions, which generally exhibit non-Newton flow properties.

~ 88 023 6 0 - 42 -

The compositions are often slightly thixotropic after addition of the low-density filler, since they exhibit a reduced viscosity under an applied stress or shear, and therefore behave almost entirely rheologically according to the Casson-5 equation. The final compositions are characterized by a flow value between about 2.5 and 45 pascals, usually between 10 and 35 pascals, such as 15, 20 or 25 pascals. Furthermore, after addition of lecithin or phosphate ester compound, the compositions have a viscosity, measured at room temperature with an LVT-D viscometer, with No. 4 spindle, 10 at 50 rpm, in the range of 200 to 3000 centipoise, usually about 250 to 1000 centipoise, and they are readily liquid, generally not requiring tension or shaking to be applied. Thus, the compositions of this invention may suitably be packaged in normal vessels, such as of glass or plastic, in rigid or bendable containers, bottles or other containers, and dispensed therein directly into the aqueous wash bath, such as in an automatic washing machine, in usual amounts such as 1/4 to 1 1/2 cup, eg 1/2 cup, per laundry load (approximate e.g.

1.3 to 6 1/2 kg) for each laundry load in usually 30 to 180 20 liters of water. The preferred compositions remain stable (usually no, but no more than 1 or 2 mm, liquid phase separation) when left for a period of 3-6 months or more, even when shaken.

It is clear that the aforementioned detailed description is given by way of illustration only and that variations can be made herein without departing from the scope of the invention.

It is also clear that as used in the description and in the claims, the term "non-aqueous" means the absence of water, however, small amounts of water such as up to about 5%, preferably up to about 2%, may be tolerated in the composition and therefore "non-aqueous" compositions may include such small amounts of water, either added directly or as a carrier or solvent for any of the other ingredients of the composition. The liquid tissue treating composition of this invention can be packaged in conventional glass or plastic containers. 8802360 - 43 - - 43 - also in single-use packages such as dispensers and disposable sachet dispensers packaged in the pending U.S. Pat. patent application serial no. 063,199, filed June 17, 1987, by applicant, have been described, the disclosure of which is incorporated herein by reference.

The invention will now be further illustrated by the following non-limiting example in which all amounts and percentages are by weight unless otherwise indicated. Atmospheric pressure is also applied unless otherwise indicated.

10

Example I

A non-aqueous builder liquid detergent composition according to the invention is prepared by mixing and finely grinding the following ingredients to about 4 micrometers, excluding t5 of the Q cell filler, in the following approximate amounts and then stirring the resulting dispersion with stirring. Q cell filler is added. To add the lightweight filler, the low-shear ground dispersion is mixed with a propeller-type blade mixer rotating at 3500 rpm to form a cavity 2Q (vortex) in the center of the mixing vessel, mixing the Q- cell filler particles near the top of the vertebra are added, whereby the filler particles are uniformly dispersed throughout the composition while minimizing the shear forces that would allow the hollow microspheres to break.

Composition I is thereby obtained. A control composition II is obtained by the same procedure as described above with the exception that the lecithin is omitted. A second control composition II-I is prepared in the same manner as control composition Ting II with the exception that the Benton 27 is added afterwards to the remaining ingredients in the same mixing vessel as the Q cell filler particles. The control composition II is prepared in the same manner as composition I with the exception that Q cell 400 and lecithin are omitted.

.8802360 - «- - 44 -

Amount in wt% I_H (control)

Non-ionic detergent 1) 36.45 36.3

Diethylene glycol monobutyl ether 8.8 9.8 5 Sodium polyphosphate (hydrated) 28.70 29.1

Sokol an HC 9786 2) 2.0 1.9

Sodium perborate monohydrate 10.5 10.6

Tetraacetylethylenediamine 4.5 4.3

Carboxymethyl cellulose 1.0 1.0 10 DEQUEST 2066 4) 1.0 1.0 '

Enzyme (mixed proteolytic and amylase) 0.55 0.5 Q-Cell 400 5) 4.0 4.0

Perfume 0.5 0.5 ÜO2 (Rutile) 0.4 0.4 15 Optical whitener 0.3 0.3

Lecitin, soy 1.0 -

Benton 3) 0.3 0.3 100.00 100.00

Viscosity centipoise 400 800 20 1) Purchased from BASF, mixed propylene oxide (4 mol) -ethylene oxide (7 mol) condensate of a fatty alcohol with 13-15 carbon atoms.

2) Copolymer of metiacrylic acid and maleic anhydride.

3) Hectorite clay, modified with dimethylbenzyl hydrogenated nc talc ammonium chloride 35¾ cation exchanged, from NL Industries.

4) Diethylene triamine pentamethylene phosphonic acid 5) Sodium borosilicate hollow glass microspheres - particle size range 10-200 microns, average particle size 75 microns, effective density 0.16-0.18 g / cc.

30

Compositions I, II and II-I are stored overnight in a clear plastic container. At the end of the first day and after aging for 7 days, 15 days, 30 days and 60 days, the flow value and plastic viscosity of each composition are measured. The results are shown in Tables A and B, respectively.

»8802360 - 45 - *

- 45 - Table A

LIQUID VALUE (PASCAL) WITH AGING Composition Aging time (days) t 7 15 30 60 5 I 11.3 12.2 12.2 12.7 - II 8.9 7.8 7.0 5.4 4.2 II-I 10, 8 9.4 7.6 6.2 -

Table B

10 PLASTIC VISCOSITY (mPa.s) THE AGING

Composition Aging period (days) 1 7 15 30 60 I 390 400 400 420 II 750 800 800 830 870 15 II-I 600 600 650 700 III 200 230 250 270 270 by

From the above results, it can be seen that / the incorporation of 1¾ lecithin into the low-density filler / organophilic clay stabilized non-aqueous suspension greatly stabilizes the aged composition while maintaining its flow value and even slightly increasing the plastic viscosity is reduced by about 50%. Although one does not wish to bind to any particular theory of action, it is believed that the lecithin is effective to strongly stabilize the flowability of the composition by enhancing the hydrogen bonding between Benton (the organophilic clay) platelets under the phosphate group. Moreover, apparently the quaternary ammonium group (-N + (CH3) 3) of the phosphatidylcholine component is substituted on or fixed to the Benton platelets.

It is thus seen that the addition of small amounts of lecithin or structurally similar phosphate ester compounds, especially those in which the phosphate ester comprises a terminal quaternary ammonium nitrogen atom bonded through one or more, preferably from 2 to 6 carbon atoms to the phosphate group, at a non-aqueous suspension containing at least a low-density filler and / or an organophilic clay significantly improves the physical stability of the non-aqueous suspensions, even under severe vibration forces, while reducing the plastic viscosity that the suspension is easily liquid.

If the above example is repeated, with the exception that instead of 4% Q-Cell 400, 1% Expancel (polyvinylidene chloride microspheres) with a particle size range of 10-100 µm, average particle size of 40 µm; density 0.03 g / cc is used, similar results are obtained. Similar results are also obtained by replacing the nonionic detergent with Plurafac RA20, Plurafac 10 D25, Plurafac RA50 or Bobanol 25-7 or Neodol 23-6.5. If the above example is repeated with the exception that instead of

Benton 27 If a Benton 38 (hectorite clay modified with diemethyl-dioctadecylammonium chloride) is used, the same results are obtained.

If in composition I the amount of lecithin is reduced to 0.3% by weight, the plastic viscosity increases to 500 cps, which still means easy pourability.

. 8802360 - 47 -

Claims (21)

1. A non-aqueous liquid fabric treating composition comprising (a) a non-aqueous liquid comprising a non-ionic surfactant, (b) functionally active laundry additive solids suspended in said non-aqueous liquid , at least one of (c) and (d): (c) a low-density filler in an amount sufficient to measure the density of the continuous liquid phase and the density of the suspended particulate phase including the low-density filler and the suspended functionally active solid particles, nearly equalizable, preventing sagging of the suspended particles while the composition is at rest, and (d) an amount of an organophilic clay to prevent phase separation when the composition is subjected to strong vibrational forces subjected to (e) lecithin or a phosphate ester of glycol, polycol or glycerol, to reduce the viscosity and further stabilize the rheological egg properties of the composition. Composition according to claim 1, characterized in that component (e) is lecithin. Composition according to claim 1, characterized in that component (e) is a phosphate ester compound of the formula 4 or 5 of the formula sheet, wherein R represents a straight or branched chain alkyl or alkenyl group having 1 to 8 carbon atoms, which is amine group of formula -NR ^ Rg, wherein R ^ and Rg are independently hydrogen or alkyl of 1-4 carbon atoms, or by a quaternized nitrogen of formula -NR ^ RgRg, wherein R ^ and Rg have the aforementioned meanings and Rg is hydrogen or alkyl is with 1-4 carbon atoms, may be substituted; Rq is hydrogen or lower alkyl or lower alkenyl; Rj is an acyl residue of a long fatty acid; R 2 is hydrogen or an acyl radical of a long fatty acid; R3 is hydrogen or an acyl radical of a long fatty acid; provided that R 2 and R 2 are not both hydrogen at the same time; and n is a number from 1-10. - 48 - .8802360 * - 48 - Composition according to claim 3, characterized in that the component (c) is present. Composition according to claim 3, characterized in that the component (d) is present. Composition according to claim 3, characterized in that the components (c) and (d) are both present. A composition according to claim 1, characterized in that the amount of component (e) is sufficient to decrease the plastic viscosity of the composition within the range from about 200 to about 1000 mPa.s. 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 within the range of about 300 to 600 mPa.s. Tissue-treating composition according to claim 6, characterized in that the low-density filler consists of hollow plastic or glass microspheres with a density in the range of about 0.05 to 0.5 g / cc. 10. A composition according to claim 9, characterized in that the low-density filler comprises water-soluble borosilicate glass microspheres. 11. A composition according to claim 6, characterized in that the organophilic clay comprises a swellable smectite clay modified by a nitrogen-containing compound containing at least one long hydrocarbon with about 8 to about 22 carbon atoms. Composition according to claim 7, characterized in that said nitrogen-containing compound is a quaternary ammonium compound. 13. A compound according to claim 12, characterized in that the quaternary ammonium compound is a compound of the formula (rr ^ rn +] x "wherein ^, R2» R3 and R ^ each independently hydrogen or an alkyl-, alkenyl-, aryl, aralkyl or alkaryl group having from 1 to 22 carbon atoms contain at least two of R 1 R 1 to about 6 carbon-35 atoms and at most two of R 1 -R 3 contain about 8 to about 22 carbon atoms ; X is an inorganic or organic anion. * 8802360 '49' - 49 - 14. A composition according to claim 1, characterized in that the non-aqueous liquid comprises about 30 to about 70% by weight of the composition and the suspended solid particles comprise about 70 to about 30% by weight of the composition. Composition according to claim 14, characterized in that the non-aqueous liquid comprises about 40-65% by weight of the composition and the suspended solid particles comprise about 60 to 35% by weight of the composition. The composition of claim 1, comprising about 30 to about 50% alkoxylated fatty alcohol nonionic detergent agent; about 0 to about 20% alkylene glycol ether viscosity controlling and anti-gelling agent; J5 about 15 to about 50% of detergent builder particles; About 0 to about 50% in total of optionally one or more detergent additives selected from the following; enzymes, enzyme inhibitors, corrosion inhibitors, anti-foaming agents, suds suppressors, soil suspending agents, anti-yellowing agents, dyes, perfumes, optical brighteners, bluing agents, pH modifiers, pH buffers, bleaches, bleach stabilizers and sequestrants; about 0.01 to about 10% low density hollow microbeads filler, based on the weight of the filler addition composition; about 0.2 to about 0.7% organophilically modified clay and about 0.1 to 3% lecithin or an alkylamine, alkenylamine, alkenylammonium or alkenylaamonium phosphate ester of glycol, polyglycol or glycerol with at least one long fatty carboxylic ester group 30 in the molecule. A powerful liquid thickened non-aqueous detergent composition with builders comprising about 30 to about 40% of a liquid nonionic surfactant which is a mixed ethylene oxide-propylene oxide condensate of a fatty alcohol of about 12 to about 18 carbon atoms; about 25 to about 40% al potassium metal phosphate detergent builder salt; about 5 to about 12% of an alkylene glycol ether. 8802360 - 50 - 50 - solvent as viscosity regulating and anti-gelling agent; about 2 to about 20% of the peroxide bleach; about 0.1 to about 8% of a bleach activator; up to about 2% enzymes; 5 to about 10% of soil suspending, anti-graying, and anti-forgetting agents; up to about 5% high complexing sequestrant; up to about 2% each of one or more dyes, perfumes and optical brighteners; Wherein the solid components of said composition have an average particle size in the range of about 2-10 microns, and no more than about 10% of the particles have a particle size greater than 1 microns; about 0.05 to about 6% inorganic or organic filler particles with a density of about 0.0T to 0.50 g / cc and an average size particle diameter of about 20 to 80 microns; about 0.2 to about 0.7% of an organophilically modified smectite clay in which about 10 to 100% of the available base exchange capacity of the smectite clay has been replaced by an organic cationic nitrogen compound with at least one long hydrocarbon of about 8 to about 22 carbon atoms; which composition, after addition of said filler particles, has a viscosity in the range of about 500 to 5000 centipoise; and about 0.1 to 3 wt% lecithin, such that the viscosity of the composition is reduced to within the range of about 200 to 1000 centipoise. Detergent composition according to claim 17, characterized in that the filler particles consist of sodium borosilicate hollow glass microspheres. A method of cleaning soiled fabrics comprising contacting the soiled fabrics with the detergent composition of claim 1 in an aqueous wash bath. Method according to claim 18, characterized in that the contact takes place in an automatic washing machine. 21. Method for stabilizing against dispersion of the dispersed particulate phase of a suspension of said solid particles in a non-aqueous liquid phase, which solids have densities greater than the density of the liquid phase, which method comprises adding to the suspension 5 of said solid particles an amount of finely divided filler having a density lower than the density of the liquid phase such that the density of the dispersed solid particles together with that of the filler becomes equal to the density of the liquid phase, an amount of organophilically modified clay to provide a viscoelastic network structure to the composition and thereby phase separation of the suspended solids or filler particles, even when the composition is subjected to severe vibration is prevented, and lecithin or an alkylamine, alkenylamine, alkyl ammonium or alkenylammonium-15 phosphate ester of a glycol, polyglycol or glycerol with at least one long fatty carboxylic acid ester in the molecule to reduce the plastic viscosity of the composition and to stabilize the viscoelastic network structure of the composition. .8802360