LU86557A1 - LIQUID DETERGENT COMPOSITIONS CONTAINING SUSPENSION STABILIZING AGENTS AND A UREA-LIKE ADDITIVE AND METHODS FOR CLEANING TISSUES USING THE SAME - Google Patents

Description

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The present invention relates to non-aqueous liquid compositions for the treatment of tissue. More particularly, the present invention relates to non-aqueous liquid bleaching detergent compositions which are stable against phase separation and gelation and are readily suitable for pouring, and the use thereof of these compositions for cleaning soiled fabrics.

Non-aqueous detergent compositions which are suitable for heavy laundry work are well known in the art. For example, compositions of this type may include a nonionic liquid surfactant in which particles of a detergency builder are dispersed, as described, for example, in U.S. Patents. No. 4,316,812, No. 3,630,929 and No. 4,264,466 and in British patents No. 1,205,711, No. 1,270,040 and r 1,600,981.

Liquid detergents are often considered to be more convenient to use than particulate or dry powder products and, therefore, have found great success with consumers. They can be easily dosed, they dissolve quickly in washing water, they can be easily applied in concentrated solutions or dispersions on soiled parts of garments to be cleaned and do not generate dust, and they generally occupy little storage space. In addition, liquid detergents may contain, in their formulation, materials which do not

could not withstand drying operations without deteriorating, which materials are often used advantageously in the manufacture of detergents and particulate products. Although they have many advantages over unitary or particulate solid products, liquid detergents often have certain inherent disadvantages which must be overcome to obtain commercially acceptable detergent products. Thus, some of these products separate on storage and others separate on cooling and cannot easily be redispersed. In some cases, the viscosity of the product changes and the product becomes either too thick to pour, or liquid to the point of looking like water. Some clear products become cloudy and others gel on standing.

The Applicant has studied the behavior of nonionic liquid surfactant systems containing a particulate matter in suspension. Reinforced non-aqueous liquid laundry detergent compositions and the problem of sedimentation of the suspended detergency builder and other laundry additives as well as the gelation problem associated with non-ionic surfactants of particular interest. These considerations have an impact for example on stability, the aptitude to be poured and the dispersal. . r sabilite of the product.

It is known that one of the major problems encountered with liquid bleach-enhanced detergents is their physical stability. This problem stems from the fact that the density of the solid particles dispersed in the nonionic liquid surfactant is greater than the density of the liquid surfactant.

Consequently, the dispersed particles have r 2 3 t

J

tendency to separate by sedimentation. Two basic solutions exist for solving the problem of sedimentation: increasing the viscosity of the liquid nonionic surfactant and reducing the particle size of the dispersed solids.

It is known that suspensions can be stabilized against sedimentation by the addition of organic or inorganic thickeners or dispersants, for example very large surface mineral materials, such as finely divided silica, clays, etc., organic thickeners such as cellulose ethers, acrylic and acrylamide polymers, polyelectrolytes, etc. However, these increases in viscosity of the suspensions are naturally limited by the need that the liquid suspension can be easily poured and can flow, even at low temperatures. In addition, these additives do not contribute to the cleaning power of the formulation.

Grinding to reduce the particle size provides the following advantages: 1. The specific contact surface of the dispersed particles is increased and, therefore, the wetting of the particles by the nonaqueous vehicle (liquid nonionic surfactant) is improved by proportion.

2. The average distance between the dispersed particles is reduced with a corresponding increase in the interaction between particles. Each of these effects contributes to increasing the gelling resistance at rest and the flow limit of the suspension; grinding at the same time significantly reducing the plastic viscosity.

The flow limit is defined as the minimum stress necessary to cause plastic r deformation (flow) of the suspension. Thus, by representing the suspension as a loose network of dispersed particles, if the applied stress is less than the flow limit, the suspension behaves like an elastic gel and no plastic flow occurs. As soon as the flow limit is exceeded, the network breaks at certain points and the sample begins to flow, but with a very high apparent viscosity. If the shear stress is much higher than the flow limit, the pigments are partially deflocculated by shearing and the apparent viscosity decreases. Finally, if the shear stress is much higher than the flow limit, the dispersed particles are completely deforested by shearing and the apparent viscosity is very low, as if there were no interaction between particles.

Consequently, the higher the flow limit of the suspension, the higher the apparent viscosity at a low shear rate and the better the physical stability against sedimentation of the product.

In addition to the problem of sedimentation or phase separation, nonaqueous liquid laundry detergents based on nonionic liquid surfactants have the disadvantage that nonionic surfactants tend to gel when added to water. 'Cold water. This is a particularly acute problem during common use of automatic European household washing machines in which the user places the laundry detergent composition in a dispensing device (eg a dispensing drawer) of the machine. During the operation of the machine, the detergent contained in the dispenser 5 i> »Λ is subjected to a current of cold water which transfers it into the main mass of the washing solution. Particularly during the winter months, when the detergent composition and the water introduced into the dispenser are particularly cold, the viscosity of the detergent increases sharply and a gel is formed. As a result, part of the composition is not completely swept out of the dispenser during operation of the machine, and a deposit of composition accumulates during repeated washing cycles, ultimately forcing the user to sweep the dispenser with hot water.

The phenomenon of gelation can also be a problem when it is desired to carry out washing in cold water, as may be recommended for certain synthetic and delicate fabrics or fabrics which can shrink in lukewarm or hot water.

The tendency of concentrated detergent compositions to gel during storage is compounded by storage of the compositions in unheated storage areas or by transporting the compositions during the winter months in non-transport vehicles heated.

Partial solutions to the gelation problem have been proposed, for example by diluting the nonionic liquid surfactant with certain viscosity-acting solvents and certain gelation inhibiting agents, such as lower alkanols, for example ethyl alcohol ( see USA patent

No. 3,953,380), alkali metal formates and adipates (see US Pat. No. 4,368,147), hexylene glycol, polyethylene glycol, etc., and by modification and optimization of the structure of nonionic surfactants. As an example of modification of nonionic surfactants, a result 6 was obtained - particularly advantageous by acidifying the hydroxyl-terminated portion of the nonionic molecule.

The advantages of introducing a carboxylic acid at the end of the nonionic surfactant include inhibition of gelation upon dilution; a decrease in the drop point of nonionic surfactants; and forming an anionic surfactant by neutralization in the wash liquor. Optimization of the nonionic structure related to the chain length of the hydrophobic-lipophilic moiety and the number and constitution of the alkylene oxide units (eg, ethylene oxide) of the hydrophilic moiety. For example, it has been found that a fatty alcohol ethoxylated with 8 moles of ethylene oxide has only a limited tendency to gel.

Nevertheless> it is desired to improve both the stability and the inhibition of the gelling of non-aqueous liquid compositions, for the treatment of tissues.

According to the present invention, a non-aqueous, stable, highly concentrated laundry detergent composition is prepared by adding to the composition small effective amounts of an anti-sedimentation stabilizing additive of the urea type or urea derivative or small effective amounts of an anti-sedimentation stabilizing additive of the surfactant quaternary ammonium compound type.

The compositions of the present invention contain, as an essential ingredient, an anti-sedimentation stabilizing additive of the urea or urea derivative type or an anti-sedimentation stabilizing additive of the quaternary ammonium surfactant compound type.

The anti-sedimentation stabilizing additive of the urea type or urea derivative is supposed to act in the detergent composition T1 as a surfactant to make the detergency builder phosphate more compatible with the nonionic surfactant detergent.

- Urea or its derivative is supposed to interact with anionic detergency builder salts of the phosphate type to make the detergency builder salts more compatible with the nonionic surfactant and improve the contact between the detergency builder salts and the nonionic surfactant. Improving the contact between the phosphate and the nonionic surfactant increases the stability of the phosphate suspension in the nonionic surfactant.

Urea or its derivative, even when added to the composition in small amounts, improves the dispersibility of the detergency builder salt suspension by inhibiting gelation of the detergency builder salt suspension.

Urea or its derivative improves dispersibility by inhibiting gelation of the suspension of particles of detergency builder salt when water is added to the composition, for example in the dispensing drawer of a dishwasher and / or when the composition is added to water.

The urea which is used in the y compositions of the present invention has the formula f ^ NCONt ^.

Urea forms a tautomer which has the formula i ^ NCNHOH and is called carbamide.

The anti-sedimentation stabilizing additives of the quaternary ammonium type are cationic surfactants. The cationic surfactants of the quaternary ammonium type which are useful in the present invention are the surfactant compounds which contain a hydrophobic long-chain hydrocarbon group in their molecular structure and a hydrophilic group, i.e. an anionic group. water-soluble salt trainer. The cationic surfactant anti-sedimentation stabilizers of the quaternary ammonium type of the present invention are well known and are commercially available. The quaternary ammonium compounds have been used as fabric softeners and as surface active detergents.

The preferred quaternary ammonium compounds used according to the present invention are the mono- and upper dialkyl-lower alkyl-quaternary ammonium salts and the mono- and di-higher alkyl-diethoxylated quaternary ammonium salts.

The quaternary ammonium salts are believed to interact with the anionic phosphate-type detergency builder salts so as to coat the anionic phosphate with a lipophilic film. The lipophilic coating makes the anionic phosphates adjuvant detergents more compatible with the nonionic surfactant and improves the contact between the phosphate and the nonionic surfactant. Improving the contact between phosphate and the nonionic surfactant improves the stability of the phosphate suspension in the nonionic surfactant.

The preferred cationic surfactant anti-sedimentation stabilizers of the quaternary ammonium type of the present invention are chosen from: I - Salts of mono (higher alkyl) -tri (lower alkyl) quaternary ammonium.

II - Salts of di (higher alkyl) -di (lower alkyl) quaternary ammonium.

III - Salts of upper monoialkyl) rmono-30 (lower alkyl) diethoxylated quaternary ammonium; IV - Salts of di (higher alkyl) diethoxylated quaternary ammonium.

The cationic quaternary ammonium compounds used as anti-sedimentation stabilizing agents of i (iw 9 the present invention are quickly described below: ~ The compounds of formula I are mono- (higher alkyl) -tri (lower alkyl) salts ) quaternary ammonium: represented by the formula;: 5 R2 1 + 1 I, _

—1 * X I

The * J

10 'in which R ^ is a long chain aliphatic radical of 10 to 22 carbon atoms, the radicals R are independently lower alkyl or hydroxyalkyl radicals having 1 to 4 carbon atoms, and X is united.

15 water-soluble salt-forming anion.

The compounds of formula II are di- (higher alkyl) -di (lower alkyl) quaternary ammonium salts represented by the formula: 20 Wire R1 + R * —N —R2 X "(II) 12 ΈΓ 25 in which the radicals R1 are independently long chain aliphatic radicals of 10 to 22 carbon atoms, R radicals are independently of lower alkyl or hydroxyalkyl radicals of 1 to 4 carbon atoms, and X is a water-soluble salt-forming anion.

The compounds of formula III are mono (higher alkyl) -mono (lower alkyl) diethoxylated quaternary ammonium salts represented by the formula: »10 R * * R1 - A _ (CHaCHa0) xH X '(III)

7 _ (CHjCHjO) yH

5 in which R ^ is a long chain aliphatic radical of 10 to 22 carbon atoms, R is a lower alkyl or hydroxyalkyl radical of 1 to 4 carbon atoms, x and y are each at least a positive number /.

f 10 equal to 1 and the sum x + y is from 2 to 15, and X is a water-soluble salt-forming anion.

The compounds of formula IV are di (higher alkyl) diethoxylated quaternary ammonium salts represented by the formula: R1 Ί + 1 "R1 — N - (CHjCH20) xH X (IV) (CH2CH20) yH 1 in which the radicals R ^ are independently of the long chain aliphatic radicals of 10 to 22 carbon atoms, x and y are each a positive number at least equal to 1 and the sum x + y is from 2 to 15, and X is _ an anion water-soluble salt trainer.

In order to improve the viscosity characteristics of the composition, an acid-terminated nonionic surfactant can be added. To further improve the viscosity characteristics of the composition and the storage properties of the composition, viscosity improvers and antifreeze agents such as alkylene glycols, polyalkylene glycols and monoalkyl ethers of alkylene glycol, and anti-sedimentation agents

»J

11 additional such as phosphoric acid esters and / or aluminum stearate. In one embodiment of the invention, the detergent composition contains an acid-terminated nonionic surfactxf, an alkylene glycol monoalkyl ether and a urea or urea derivative anti-sedimentation stabilizer or an ammonium anti-sedimentation stabilizer quaternary.

Sanitizers or bleaches and their activators can be added to improve the bleaching and cleaning characteristics of the composition.

In one embodiment of the invention, the detergency builder components of the composition are ground to a particle size of less than 100 microns and preferably less than 10 microns in order to further improve the stability of the suspension of the builder components. detergency in liquid nonionic over-factive detergent.

In addition, other ingredients can be added to the composition, such as anti-scaling agents, anti-foaming agents, optical brightening agents, enzymes, anti-deposition agents, perfumes and colorants.

Washing machines currently manufactured for home use normally operate at washing temperatures up to 95 ° C. Up to 20 liters of water are used during the wash and rinse cycles.

Normally about 200-250 grams of powdered detergent is used per wash.

According to the present invention, when using the highly concentrated liquid detergent, normally only about 100 grams (78 cm) of liquid detergent composition is required to wash a full load of dirty laundry.

Therefore, in one aspect, the present invention provides a liquid composition for heavy duty laundry, composed of a suspension of an adjuvant detergency salt or an anionic salt adjuvant detergency, for example a phosphate, in a nonionic liquid surfactant, the composition comprising an effective amount of urea or a urea derivative to increase the stability of the suspension against sedimentation and the dispersibility of the suspension in water,. or a quaternary ammonium type surfactant to increase the stability of the suspension against sedimentation.

In another aspect, the invention provides a concentrated liquid detergent composition for heavy laundering, which is stable, does not settle out during storage and does not gel during storage and in use. The liquid compositions of the present invention can easily be poured, they are easily dosed and are easy to introduce into the washing machine.

In another aspect, the invention provides a method for dispensing a non-ionic liquid laundry detergent composition in and / or with cold water without causing gelation. In particular, there is provided a method for filling a container 25 with a non-aqueous liquid laundry detergent composition in which the detergent consists, at least predominantly, of a liquid non-ionic surfactant and for dispensing the composition from the container in an aqueous washing bath, the distribution being effected by directing a stream of unheated water on the composition of matter so that the composition is entrained by the stream of water in the washing bath. urea and its derivatives specified below will be called globally hereafter "urea compounds" for short.

Addition of the urea compound to the detergent compositions reduces the problem of sedimentation of the dispersed particles and phase separation and improves the dispersibility in water of the detergent particles in suspension. The addition of quaternary ammonium type surfactants to the detergent compositions reduces the problem of sedimentation of the dispersed particles and phase separation.

The concentrated nonaqueous liquid detergent laundry compositions with nonionic surfactant of the present invention combine the advantages of being stable, of not being sedimented during storage and of not gelling during storage. The liquid compositions are easy to pour, easy to dose and easy to introduce into washing machines.

An object of the present invention is to provide a stable liquid non-aqueous nonionic detergent composition for heavy laundry work, containing at least one urea compound as an anti-sedimentation stabilizing agent and optionally an anionic phosphate type detergency builder salt in suspension. in a nonionic surfactant.

Another object of the present invention is to provide a stable, non-aqueous nonionic detergent composition, liquid, for heavy laundry work, containing at least one detergency builder of the anionic phosphate type, suspended in a nonionic surfactant.

Another object of the invention is to provide liquid tissue treatment compositions which are suspensions in a non-aqueous liquid of insoluble mineral particles and which are stable on storage, m 4 14 and easy to pour and pour disperse in cold, lukewarm or hot water.

Another object of the present invention is to formulate highly reinforced non-aqueous liquid detergent compositions with non-ionic surfactant, for heavy laundering work, which can be poured at all temperatures and which can be repeatedly dispersed from the device. for dispensing automatic washing machines 10 in the European style without clogging or obstructing the dispenser even during the winter months.

A particular object of the present invention is to provide stable, non-gelling suspensions of reinforced nonionic non-aqueous liquid detergent composition for heavy laundry work, which contain an effective amount of a urea compound or agent. surfactant of the quaternary ammonium type, in an amount sufficient to increase the flow limit of the composition to thereby increase its stability, that is to say prevent sedimentation of the detergency builder particles, etc., while preferably reducing, or at least not increasing, the plastic viscosity (viscosity under shear conditions) of the composition.

These and other objects of the invention which will become apparent from the following detailed description of preferred embodiments are generally achieved by preparing a detergent composition by adding to the non-aqueous liquid nonionic surfactant an effective amount of a anti-sedimentation stabilizing agent of the urea compound type or a surfactant anti-sedimentation stabilizing agent of the quaternary ammonium type, in an amount sufficient to inhibit the sedimentation of the particles in suspension, said composition containing organic tissue treatment additives or minerals, for example viscosity improving agents and one or more anti-gelling agents, anti-encrustation agents, pH-acting agents, bleaching agents, activators of bleaching agents, anti-foaming agents, optical brightening agents, enzymes, anti-deposition agents, perfumes and dyes.

According to the present invention, the physical stability of the suspension of the anionic phosphate-type detergency builder or anionic detergency builder (s) or any other additive in suspension, for example bleach, etc. in the liquid nonionic surfactant vehicle is substantially improved by the addition of an anti-sedimentation stabilizer which is a urea compound or a surfactant of the quaternary ammonium type.

The addition of very small amounts of urea compound as an anti-sedimentation stabilizing agent or of quaternary ammonium compound as a surface active anti-sedimentation stabilizing agent is sufficient to substantially improve the physical stability of the detergent compositions. The anti-sedimentation agent of the urea compound type also significantly improves the dispersibility of the compositions in water.

In one embodiment of the present invention, the compositions contain, as an essential ingredient, an anti-sedimentation stabilizing additive of the urea compound type. The anti-sediment stabilizing additive may include one or more urea compounds.

The urea compounds which are used in the compositions of the present invention are represented by the formula: ♦ Λ * i 16 R-.R-NCNR-.R.

1 2 h 3 4

X

wherein at least one of R ^ to R ^ is hydrogen, and the others are alkyl, preferably C 1 to C 4 alkyl (aryl, preferably phenyl, hydroxyl or chloro, and X is 0 or NH. Urea forms a tautomer of formula F ^ NCNHOH which is called carbamide. Urea and carbamide and their derivatives such as methyl-urea, dimethyl-urea, ethyl-urea, propyl-urea, butyl urea, hydroxyl urea and phenyl urea, and their salts, are suitable for use in the present invention.

In addition to their action as a physical stabilizer, urea compounds have the advantages, compared to other physical stabilizers, of being compatible with the nonionic surfactant component and of appreciably improving the suitability of the detergent composition. to be poured into cold water.

Although the Applicant does not wish to be bound by any particular theory as to how urea or carbamide compounds act to prevent sedimentation of suspended particles of anionic phosphate-type detergency builder, assumes that urea or carbamide compounds interact with adjuvant anionic phosphate-type salts to make phosphate more compatible with non-ionic surfactant, improve contact between phosphate and non-ionic surfactant and increasing the wettability by the nonionic surfactant of the surfaces of the dispersed solid phosphate particles. The improvement of the contact between the phosphate and the nonionic surfactant and the better wettability of the phosphate particles dispersed by the nonionic surfactant increases the stability of the phosphate suspension * ·· ï i "17 in the non-surface active agent ionic and allows the suspended phosphate to remain more easily in suspension.

The greater physical stability is manifested by an increase in the flow limit of the composition, compared to the same composition without stabilizer. As described above, the higher the flow limit, the higher the viscosity related to a low shear rate and the better the physical stability.

The urea compound, even when added to the composition in small amounts, improves the dispersibility of the detergent builder salt suspension by acting so as to inhibit gel formation of the suspension. detergency builder on contact with water.

The urea compound improves dispersibility by inhibiting gelation of the suspension of detergency builder salt particles when water is added to the composition, for example in the dispenser drawer of a dishwashing machine and / or when the composition is added to the wash water.

Only very small amounts of the urea compound are required to significantly improve the physical stability of the detergent composition and the; dispersibility of the composition in cold water. For example, based on the total weight of the nonionic liquid surfactant composition, suitable amounts of the urea compound range from about 0.1% to about 0.5%, preferably about 0.2 % to about 2.0%, and more preferably about 0.5 to 1.5%.

In another embodiment of the present invention, the compositions contain, as an essential ingredient, a stabilizing additive anti-sedimentation: surfactant quaternary ammonium type. The anti-sedimentation stabilizing additive may comprise one or more surface-active agents of the quaternary ammonium type.

The anionic surfactants which are useful in the present invention are the ten cationic surfactants which contain a hydrophobic long-chain hydro-carbon group in their molecular structure and a hydrophilic group, i.e. an anionic group forming a water-soluble salt. 1

The preferred cationic surfactant anti-sedimentation stabilizers of the quaternary ammonium type of the present invention are chosen from: I - The salts of mono- (higher alkyl) tri- (lower alkyl) quaternary ammonium.

II - The salts of di (higher alkyl) di- (lower alkyl) quaternary ammonium.

III - The salts of mono- (higher alkyl) -mono- (lower alkyl) -diethoxylated quaternary ammonium; and IV - The di- (higher alkyl) diethoxylated quaternary ammonium salts.

The cationic anti-sedimentation stabilizers of formula I used in the present invention are mono (higher alkyl) -tri (lower alkyl) quaternary ammonium salts represented by the following formula: R2 + il 2

Rl_N— HT X CI) 30. R2 in which R1 is a long aliphatic radical

nâ 1 Λ â 0 0 s f aidao a λ aa4— 1 aa 4 a * miD

2 19 are independently alkyl or hydroxy-lower alkyl and X is a water-soluble salt-forming anion such as a halide, for example chloride, bromide, io-hard; a sulfate, nitrate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate or a similar mineral or organic solubilization radical. The carbon chain R of the aliphatic radical containing 10 to 22 carbon atoms, in particular 12 to 20, preferably 12 to 18, and in particular 16 to 18 carbon atoms, can be straight or branched, and saturated or unsaturated . The lower alkyl radicals R have 1 to 4 carbon atoms, for example methyl, ethyl, propyl and butyl, preferably 1 or 2 carbon atoms, preferably methyl, and can contain a hydroxyl radical.

The preferred ammonium salt is a mono (higher alkyl) trimethylammonium chloride in which the alkyl group is derived from tallow, hydrogenated tallow or stearic acid. Particular examples of anti-sedimentation stabilizers of the quaternary ammonium type of formula I, suitable for use in the composition of the present invention, include the following: tallow chloride -trimethylammonium chloride (hydrogenated tallow) trimethyl-ammonium 25 stearyl-trimethyl-ammonium chloride stearyl-triethyl-ammonium chloride cetyl-trimethyl-ammonium chloride soy chloride-trimethyl-ammonium stearyl-dimethylethyl-ammonium chloride 30 tallow chloride-diisopropylmethyl-ammonium

It is also possible to use the corresponding sulfates, metho-sulfates, ethosulfates, bromides and hydroxides.

The cationic anti-sedimentation stabilizers of formula II used in the present invention are higher diialkyl) di (lower alkyl) quaternary ammonium salts represented by the following formula; 5 _ _ R1 + 1 1 2 - R— N— R * X (II) I 2 R * 10 in which the radicals R * are independently of the long-chain aliphatic radicals of 10 to 22 carbon atoms, and X is a water-soluble salt-forming anion, for example a halide, i.e. chloride, bromide, iodide; a sulfate, nitrate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate or a similar inorganic or organic solubilization radical. The carbon chains R 1 of the aliphatic radicals containing 10 to 22 carbon atoms, in particular 12 to 20, preferably 12 to 18, and better still 16 to 18 carbon atoms, can be straight or branched, and saturated or unsaturated. The lower alkyl radicals R have 1 to 4 carbon atoms, for example methyl, ethyl, propyl and butyl, preferably 1 or 2 carbon atoms, better still methyl, and can contain a hydroxyl radical.

- Representative examples of cationic compounds of formula II include the following: distearyl dimethyl ammonium chloride di-tallow-dimethyl ammonium chloride dihexadecyl dimethyl ammonium chloride distearyl dimethyl ammonium bromide hydrogenated dilsuif bromide ) -dimethyl-ammonium di-tallow-isopropyl-methyl-ammonium chloride distearyl-di- (isopropyl) ammonium chloride 21 distearyl dimethyl ammonium methosulfate.

A preferred class of cationic compounds is represented by formula II in which two of the * · 1 2 R groups are C 1 -C 4 g, Bn radical R is methyl, or ethyl and the other radical R2 is methyl, ethyl, isopropyl, n-propyl, hydroxyethyl or hydroxypropyl group.

The cationic anti-sedimentation stabilizers of formula III used herein

. I

10 invention are salts of higher monotalkyle) mono- (lower alkyl) diethoxylated quaternary ammonium, represented by the following formula: H2 +

15 i I

R1 — N - (CH2CH20) xH X (III)

(CH2CH20) yH

wherein R ^ is a long chain aliphatic radical having 10 to 22 carbon atoms, and R is a lower alkyl or hydroxyalkyl radical, x and y are each a positive number at least 1 and the sum x + y goes from 2 to 15, and X is a water-soluble salt-forming anion such as a halide, i.e. chloride, bromide, iodide; a sulfate, nitrate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate or a similar inorganic or organic solubilization radical.

The carbon chain R * of the aliphatic radical containing 10 to 22 carbon atoms, in particular 12 30 to 20, preferably 12 to 18, and better still 16 to 18 carbon atoms, can be straight or branched, and 2 saturated or unsaturated . The lower alkyl radicals R have 1 to 4 carbon atoms, for example methyl, ethyl, propyl and butyl, preferably 1 or 2 carbon atoms, in particular methyl, and may contain a hydroxyl radical.

Representative examples of the cationic anti-sedimentation stabilizers of the quaternary ammonium type of formula III, suitable for use in the composition of the present invention include the following: copra-methyl-ammonium chloride diethoxylate (x + y = 2) chloride diethoxylated copra-methyl-ammonium (x + y = 15) 10 diethoxylated oleyl-methyl-ammonium chloride (x + y * 2) diethoxylated oleyl-methyl-ammonium chloride (x + - * 15) stearyl chloride diethoxylated methyl-ammonium (x + y = 2) diethoxylated stearyl-methyl-ammonium chloride (x + y = * 15) diethoxylated tallow chloride-methyl-ammonium (x + y = 10) 15 Anti-sedimentation stabilizers cationic compounds of formula IV used in the present invention are di (higher alkyl) diethoxylated quaternary ammonium salts represented by the general formula: 2 ° _ - - R * + 1 * R - N— (CH2CH20) xH X (IV)

(CH2CH20) yH

25 wherein the symbols are independently a long chain aliphatic radical of 10 to 22 carbon atoms, x and y are each a positive number at least 1 and the sum x + y is from 2 to 15, and X is 30 a water-soluble salt-forming anion, for example a halide, that is to say chloride, bromide, iodide; a sulfate, nitrate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate, or a similar mineral or organic solubilization radical. The carbon chains 23 R1 of the aliphatic radicals containing 10 to 22 carbon atoms, in particular 12 to 20, preferably 12 to 18, and better still 16 to 18 carbon atoms, can be straight or branched, saturated or unsaturated .

5 A particular example of a cationic anti-sedimentation stabilizer of the quaternary ammonium type of formula IV suitable for use in the composition of the present invention is di-tallow-ammo-nium diethoxylated chloride (x + y = 4) (Ethoquat 2T / 14).

! The diethoxylated mono- and di (higher alkyl) compounds are stable in both acidic and alkaline solutions, and have higher water solubility and compatibility than other related compounds.

In the compounds of formulas I to IV, the long carbon chains are obtained from long chain fatty acids, such as those derived from tallow and soybean oil. The terms "soy" and "tallow," etc., as used herein, refer to the source from which the long chain fatty alkyl chains originate.

Mixtures of anti-sedimentation stabilizers of the quaternary ammonium compound type can be used.

The quaternary ammonium (linear higher alkyl) salts are readily biodegradable and are preferred.

Although the Applicant does not wish to be bound by any theory as to how quaternary ammonium surfactants act to prevent sedimentation of anionic phosphate particles 30 detergency builder, it is believed that ammonium salts quaternary interact with adjuvant detergency salts of the anionic phosphate type so as to coat the anionic phosphate with a cationic lipophilic film by making phosphate 24 more compatible with the nonionic surfactant, improve B the contact between the phosphate and the surfactant non-ionic and increase the wettability of the surfaces of the dispersed solid particles of phosphate by the non-ionic surfactant. The improved contact between the phosphate and the nonionic surfactant and the greater wettability of the phosphate particles dispersed by the nonionic surfactant improve the stability of the phosphate suspension and allow the suspended phosphate to remain more easily in suspension.

The improved physical stability is manifested by an increase in the flow limit of the composition, for example from 6.5 Pa to 26.0 Pa and by an increase in the apparent viscosity from 2350 to 3250 (LVT, pin No. 4.60 rpm), compared to the same composition without the stabilizing agent of the quaternary ammonium salt type. As described above, the higher the flow limit, the higher the apparent viscosity at a low shear rate and the better the physical stability.

In addition to their action as a physical stabilizer, quaternary ammonium (higher alkyl) salts have other advantages, compared to other physical stabilizers, of being cationic in nature and of being compatible with the nonionic surfactant component.

Only very small amounts of quaternary ammonium salt are needed as a stabilizer to achieve a significant improvement in physical stability. For example, based on the total weight of the nonionic liquid surfactant composition, suitable amounts of the quaternary ammonium salt are in the range of about 0.1 to about 5%, preferably about 0.3 to about 2.0%, and more preferably about 0.5 to 1.5%.

Although urea compounds and quaternary ammonium salts are effective in their physical stabilizing action, other known physical stabilizers can be added to the formulation, such as, for example, an acidic organic phosphorus compound having a group 5 -POH acid, such as a partial ester of phosphorous acid and an alkanol and / or an aluminum salt of a fatty acid.

Nonionic Surfactant Detergent The nonionic synthetic organic detergents used in the practice of the invention can be any of a wide variety of such compounds, which are well known.

As is known, non-ionic synthetic organic detergents are characterized by the presence of a hydrophobic organic group and a hydrophilic organic group and they are generally produced by the condensation of a hydrophobic aliphatic or alkyl-aromatic organic compound with ethylene oxide (hydrophilic in nature). Almost any hydrophobic compound comprising a carboxy, hydroxy, amido or amino group having a free hydrogen atom linked to nitrogen can be condensed with ethylene oxide or with its polyhydration product, polyethylene glycol, to form a nonionic detergent. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to achieve the desired ratio between the hydrophobic and hydrophilic groups. Representative examples of suitable nonionic surfactants are those described in the U.S. Patents. N ° 4 316 812 and N ° 3 630 929.

In general, nonionic detergents are lipophilic compounds alkoxylated by a poly (lower alkoxy) group in which the desired hydrophilic / lipophilic ratio is obtained by the addition of a hydrophilic poly (lower alkoxy) group to a lipophilic moiety. A preferred class of nonionic detergents used is the higher alkanols alkoxylated by poly (lower alkoxy) groups in which the alkanol has 9 to 18 carbon atoms and in which the number of moles of oxide d the lower alkylene (of 2 or 3 carbon atoms) is from 3 to 12. Among these materials, it is preferred to use those in which the higher alkanol is a higher fatty alcohol of 9 to 11 or 12 to 15 carbon atoms, and which contain 5 to 8 or 5 to 9 lower alkoxy groups per mole. Preferably, the lower alkoxy group is the ethoxy group, but in certain cases it can be advantageously mixed with the propoxy group, the possible presence of which often only represents a minor proportion (less than 50%).

Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole, for example Neodol 25-7 and Neodol 23-6.5, which are products manufactured by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols having on average about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide, and the second is a corresponding mixture in which the carbon atom content of the higher fatty alcohol is 12 or 13, and the number of ethylene oxide groups present represents an average of about 6.5. Higher alcohols are primary alkanols.

Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15-S-9, which are both linear secondary alcohol ethoxylates manufactured by Union Carbide Corporation. The first is a mixed ethoxylation product of a linear secondary alkanol of 11 to 15 carbon atoms with seven moles of ethylene oxide, and the second is a similar product but where nine moles of ethylene oxide have reacted.

* 27

Also useful in the composition of the invention, as a component of the non-ionic detergent, non-ionic surfactants of higher molecular weight, such as Neodol 45-11, which are similar condensation products of ethylene oxide on higher fatty alcohols, the higher fatty alcohol having 14 or 15 carbon atoms, and the number of ethylene oxide groups per mole being about 11. These products are also manufactured by Shell Chemical Company.

Other useful nonionic surfactants are represented by the well known trade class of nonionic surfactants sold under the trademark Plurafac. Plurafac products are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a group hydroxyl. Examples include the products which are: (A) C - ^ - C ^ s fatty alcohol condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide, (B) C fatty alcohol ^ -C ^ s condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide and (C) a fatty alcohol in C ^ -C ^ j. condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide and (D) a product which is a 1: 1 mixture of products (B) and (C).

Another group of nonionic liquid surfactants are commercially available from Shell Chemical Company, Inc., under the trademark Dobanol: Dobanol 91-5 is an ethoxylated C 4 -C 30 fatty alcohol with an average of 5 moles of ethylene oxide and Dobanol 25-7 is a C12 “ci5 fatty alcohol ethoxylated with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

In the higher alkanols alkoxylated by poly (lower alkoxy) groups, to obtain the best ratio between the hydrophilic and lipophilic portions, the number of lower alkoxy groups is generally equal to 40% to 100% of the number of carbon atoms higher alcohol, preferably 40 to 60% of this number, and the nonionic detergent preferably contains at least 50% of such preferred lower polyalkoxy-preferred alkanol. The higher molecular weight alkanols and various other normally solid nonionic detergents and surfactants may contribute to the gelation of the liquid detergent and, therefore, will preferably be removed or will be limited in the present compositions, although that they can be used in minor proportions for their cleaning properties, etc. As regards the preferred and less preferred nonionic detergents, the alkyl groups which they contain are generally linear, although branching can be tolerated, for example at the level of a carbon atom close to the carbon atom terminal 20 of the straight chain or two carbon atoms distant from this terminal carbon atom and opposite the ethoxylated chain, provided that such a branched alkyl group is not more than three atoms in length carbon. Normally, the proportion of carbon atoms in such a branched configuration is minor and rarely exceeds 20% of the total content of carbon atoms in the alkyl group. Similarly, although the linear alkyl groups which are linked at the end to the ethylene oxide chains are very preferable and are considered to give the best combination of detergency, biodegradability and non-gelling characteristics , a median or secondary junction with the ethylene oxide of the chain may appear. In general there is only a minor proportion of 29 such alkyl groups, generally less than 20%, but, as in the case of the Tergitol mentioned, this proportion can be higher. Also, when the lower alkylene oxide chain contains propylene oxide, the proportion of this propylene oxide is generally less than 20%, and preferably less than 10%, of this chain.

When using proportions higher than those mentioned above of alkanols whose alkoxy-lation is not terminal, of alkanols alkoxylated by poly- (lower alkoxy) groups containing propylene oxide and of nonionic detergent with a lower hydro-lipophilic ratio and when other nonionic detergents are used in place of the preferred nonionic detergents listed herein, the resulting product may not have as good detergency properties, stability, viscosity and non-gelation than the preferred compositions, but the use of the compounds of the invention acting on the viscosity and inhibiting gelation can also improve the properties of detergents based on such nonionic compounds. In some cases, for example when using a higher poly (lower alkoxy) alkanol of higher molecular weight, often for its detergency, its proportion is adjusted or limited according to the results of routine experiments, to obtain the power desired detergent and to obtain at the same time a non-gelling product and, of desired viscosity. Also, it has been found that it is only rarely necessary to use the higher molecular weight nonionic surfactants for their detergent properties, since the preferred nonionic surfactants described herein are excellent detergents and furthermore they achieve the desired viscosity in the liquid detergent without gelation at low temperatures.

Another useful group of nonionic surfactants is the "Surfactant T" series of nonionic surfactants offered by British Petroleum. The non-ionic surfactants of Surfactant T are obtained by ethoxylation of secondary fatty alcohols with a narrow distribution of ethylene oxide. Surfactant T5 has an average of 5 moles of ethylene oxide; Surfactant T7 has an average of 7 moles of ethylene oxide; Surfactant 10 T9 has an average of 9 moles of ethylene oxide and Surfactant T12 has an average of 12 moles of ethylene oxide, per mole of C13 secondary fatty alcohol.

In the compositions of the present invention, preferred nonionic surfactants include the secondary fatty alcohols having relatively limited ethylene oxide contents of about 7 to 9 moles, and the fatty alcohols in to ethoxylated with about 5 to 6. moles of ethylene oxide.

Mixtures of two or more of the liquid nonionic surfactants can be used and, in some cases, benefit can be obtained from the use of such mixtures.

Non-Ionic Surfactant with Acid Termination.

The viscosity and gelation properties of liquid detergent compositions can be improved by including in the composition an effective amount of an acid-terminated liquid nonionic surfactant. Acid-terminated nonionic surfactants consist of a nonionic surfactant which has been modified to transform one of its free hydroxyl groups into a moiety having a free carboxyl group, such as an ester or partial ester of a nonionic surfactant and a polycarboxylic acid or anhydride.

As described in French patent application 31 No. 85 05319 filed on April 9, 1985, non-ionic surfactants modified by a free carboxyl group, which can roughly be characterized as being acids; polyethercarboxylates, act to lower the temperature at which the nonionic liquid surfactant forms a gel with water.

Addition of the acid-terminated nonionic surfactants to the liquid nonionic surfactant promotes the ability of the composition to be dispensed, i.e., to be poured, and reduces the temperature at which the liquid nonionic surfactant forms a gel in water without reducing their stability against sedimentation. The acid-terminated nonionic surfactant reacts in the washing machine water with the alkalinity of the dispersed detergency builder salt phase of the detergent composition and acts as an effective anionic surfactant.

Particular examples include the hemiesters of product (A) with succinic anhydride, the ester or hemi-ester of Dobanol 25-7 with succinic anhydride, and the ester or hemi-ester of Dobanol 91- 5 with succinic anhydride. In place of succinic anhydride, other polycarboxylic acids or anhydrides can be used, for example maleic acid, maleic acid anhydride, glutaric acid, malonic acid, phthalic acid, 25 phthalic acid anhydride, citric acid, etc.

Acid-terminated nonionic surfactants can be prepared as follows:

Acid-terminated product A: 400 g of nonionic surfactant (A) are mixed, which is a 30 alkanol to which has been alkoxylated to introduce 6 ethylene oxide units and 3 propylene oxide units per alkanol unit, with 32 g of succinic anhydride and the mixture is heated for 7 hours at 100 ° C. The mixture and the filter are cooled to separate the unreacted succinic material. Infrared analysis shows that about half of the nonionic surfactant has been converted to its acidic hemiester.

p Acid-terminated Dobanol 25-7: 522 g of non-ionic surfactant Dobanol 25-7 are mixed, which is the product of ethoxylation of a C12 to C15 alkanol and contains approximately 7 ethylene oxide units per alkanol molecule, - with 100 g of succinic anhydride and 0.1 g of pyridine (which acts as an esterification catalyst) and heated to 260 ° C for 2 hours, cooled and filtered to separate the material unreacted succinic. Infrared analysis shows that almost all of the free hydroxyl groups of the surfactant have reacted.

Acid-terminated Dobanol 91-5: 1000 g of non-ionic surfactant Dobanol 91-5 is mixed, which is the ethoxylation product of a C6 alkanol with and has about 5 ethylene oxide units per alkanol molecule , with 265 g of succinic anhydride and 0.1 g of pyridine as catalyst, and heated to 260 ° C for 2 hours, cooled and filtered to remove unreacted succinic material. Infrared analysis shows that almost all of the free hydroxyl groups in the surfactant have reacted.

Other esterification catalysts, such as an alkali metal alcoholate (e.g. sodium methylate) may be used in place of or in admixture with pyridine.

The acidic polyether, i.e., the acid-terminated nonionic surfactant, is preferably added dissolved in the nonionic surfactant.

Adjuvant Detergent Salts .:

The non-aqueous liquid nonionic surfactant used in the compositions of the present invention contains, in the dispersed and suspended state, fine particles of organic and / or inorganic detergency builder salts.

The detergent compositions of the invention include adjuvant detergency salts soluble in water and / or insoluble in water. The water-soluble alkaline mineral salts detergency builders which can be used alone with the detergent compound or in admixture with other detergency builders are carbonates, bicarbonates, borates, phosphates, polyphosphates and alkali metal silicates. (It is also possible to use ammonium or substituted ammonium salts).

Particular examples of such salts are sodium tripoly-phosphate, sodium carbonate, sodium tetra-borate, sodium pyrophosphate, potassium pyro-phosphate, sodium bicarbonate, potassium tri-polyphosphate , Sodium hexametaphosphate, sodium sesquicarbonate, sodium mono- and di-orthophosphates and potassium bicarbonate. Particular preference is given to sodium tripolyphosphate (TPP).

Since the compositions of the present invention are generally very concentrated, and can therefore be used in relatively low doses, it is desirable to supplement any phosphate-type detergency builder (e.g. sodium tripolyphosphate) with a detergency builder auxiliary such as a lower polycarboxylic acid or a polymeric carboxylic acid with high calcium binding capacity to inhibit incrustation which could otherwise be caused by the formation of an insoluble calcium phosphate.

Suitable lower polycarboxylic acids include the alkali metal salts of lower polycarboxylic acids, preferably sodium and potassium salts. Suitable lower polycarboxylic acids have two to four carboxylic acid groups. The preferred sodium and potassium salts of lower polycarboxylic acids are the citric acid and tartaric acid salts.

The sodium salts of citric acid are those which are preferred, in particular trisodium citrate. Monosodium and disodium citrates can also be used. The monosodium and disodium salts of tartaric acid can also be used.

The alkali metal salts of lower polycarboxylic acids are particularly satisfactory detergency builder salts; due to their high calcium and magnesium binding power, they inhibit incrustation which could otherwise be caused by the formation of insoluble calcium and magnesium salts.

Other organic detergency builders are polymers and copolymers of polyacrylic acid and polymaleic anhydride and their al-cuddly metal salts. More particularly, these detergency builder salts can consist of a copolymer which is the reaction product of an approximately equal number of moles of methacrylic acid and maleic anhydride having been completely neutralized to form its sodium salt.

The detergency builder is commercially available under the trademark Sokalan CP5. This detergency builder, when used even in small amounts, is used to inhibit encrustation.

Examples of sequestering alkaline organic detergency builder salts which can be used with the detergency builder salts or in admixture with other organic and inorganic detergency builders are the aminopolycarboxylates of alkali metals, ammonium or of substituted ammonium, for example sodium and potassium edetate (EDTA), sodium and potassium nitrilotriacetates (NTA) and triethanolammonium N- (2-hydroxy-✓ ethyl) nitriloacetates. Mixed salts of these aminopolycarboxylates are also suitable.

Other suitable detergency builders of the organic type include carboxymethylsuccinates, tartronates and glycollates. The polyacetal-carbo-10 xylates are of particular interest. Polyacetal carboxylates and their use in detergent compositions are described in the U.S. Patents.

N ° 4 144 226, N ° 4 315 092 and N ° 4 146 4-95.

36

The alkali metal silicates are useful detergency builder salts which also act to regie or adjust the pH and to make the composition anticorrosive for parts of the machine to be washed. Sodium silicates of NaO / ^ si02 ^ ratios 6: 1 to 1: 3.2, in particular about 1: 2 to 1: 2.8 are preferred. Potassium silicates can also be used in the same ratios.

Other representative examples of suitable detergency builders 10 include, for example, those described in the brevets patents. UA No. 4,316,812, No. 4,264,466 and No. 3,630,929. The mineral detergency builder salts can be used with the nonionic surfactant or in admixture with other mineral builder detergents or with organic detergency builder salts.

The water-insoluble crystalline and amorphous zeolytic aluminosilicates can be used.

Zeolites generally have the formula: 20 (M20) x- (A12 ° 3y in which x is equal to 1, y ranges from 0.3 to 1.2, and is preferably equal to 1, z is located from 1, 5 to 3.5 or more, and preferably 2.3, and w is 0 to 9, preferably 2.5 to 6, and A1 is preferably sodium. A representative example of a zeolite is a zeolite of type A or of similar structure, type 4A being particularly preferred The preferred aluminosilicates have a calcium ion exchange power of about 200 milliequivalents per gram or more, for example 400 milliequivalents per gram.

Various crystalline zeolites (i.e., aluminosilicates) which can be used are described in British Patent Nos. 1,504,168, US Patent No. 4,409,136 and in Canadian Patents N No. 1,072,835 and 10,087,477. An example of 37 amorphous zeolites useful here can be found in Belgian Patent No. 835,351.

Other materials such as clays, particularly water insoluble types, may be useful additives in the compositions of the present invention. A particularly useful clay is bentonite. This material is mainly montmorillonite which is a hydrated aluminum silicate in which approximately 1/6 of the atoms of α-10 luminium can be replaced by atoms of magnesium and with which various quantities of hydrogen, sodium, potassium, calcium, etc. can be weakly combined. Bentonite in its most purified form (that is to say free from any sandstone, sand, etc.) suitable for detergents contains at least 50% of montmorillonite and thus its cation exchange power is at least minus about 50 to 75 milliequiva-slow for 100 g of bentonite. Particularly preferred bentonites are bentonites from Wyoming or 20 from the western United States of America which have been sold under the designations of Thixo-jel 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known for soften textile materials, as described in British Patents No. 401,413 and No. 461,221.

25 Viscosity Adjusting and Anti-Gelling Agents The incorporation into the detergent composition of an effective amount of viscosity adjusting and gelling inhibiting agents for the non-ionic overactive significantly improves the properties 30 composition conservation tees. Viscosity control agents and gelation inhibitors work to lower the temperature at which the nonionic surfactant forms a gel when added to water. Such viscosity control agents and gelation inhibitors can be, for example, a lower alkanol, for example ethyl alcohol (see U.S. Patent, A. No. 3,953,380), hexyl- 38 ene- glycol, a polyethylene glycol, for example polyethylene glycol having a molecular weight of about 40Ö (PEG 400) and amphiphilic compounds of the type * lower monoalkyl ether of low molecular weight alkylene oxide.

The preferred compounds controlling viscosity and inhibiting gelation are low molecular weight amphiphilic compounds. The amphiphilic compounds act as viscosity adjusting and gelling inhibiting agents for the nonionic surfactant and significantly improve the preservative properties of the composition. Amphiphilic compounds can be considered to have a chemical structure analogous to that of liquid nonionic surfactants derived from ethoxylated and / or pro-poxylated fatty alcohols, but they have relatively short hydrocarbon chain lengths (C2 to Cg) and a few low ethylene oxide content (approximately 2 to 6 ethylene oxide groups per molecule).

Suitable amphiphilic compounds can be represented by the following general formula;

R3 (CH2CH20) nH

Where R3 is a C2-6alkyl group and a is a number of about 1 to 6 on average.

In particular, the compounds are lower monoalkyl ethers (Cg to C ^) of lower alkylene glycols (C ^ -Cg).

More particularly, the compounds are lower monoalkyl ethers (C1-C8) of lower mono-, di- or trialkylene glucols (Cg-Cg).

Particular examples of suitable amphiphilic compounds include the ethylene glycol monoethyl ether (Cgli-O-CHgCHgOH), the diethylene glycol monobutyl ether (C ^ H ^ -O- (CHgCHgO) 2H) , the monobutyl ether of tetraethylene glycol (C ^ H ^ -0- 39 (CH, CH, 0) H) and the monomethyl ether of dipropylene glycol (CH3-0- (CH2CHO) 2H). Particular preference is given to CH3 05 monobutyl ether of diethylene glycol.

The incorporation into the composition of low molecular weight lower alkylene glycol monoalkyl ether decreases the viscosity of the composition, so that it is easier to pour, improves the stability against sedimentation and improves the dispersibility of the composition when added to lukewarm or cold water.

The compositions of the present invention have better viscosity and stability characteristics and remain stable and able to be poured at temperatures as low as about 5 ° C or less.

Urea compounds, in addition to acting as an anti-sedimentation stabilizing agent, improve the dispersibility of the suspension of phosphate particles as detergency builder by inhibiting the gel formation of suspended particles in water. cold is added to the composition in the dispenser drawer and / or when the composition is added to the water.

In one embodiment of the present invention, an additional stabilizing agent which is an al-canolic ester of phosphoric acid or an aluminum salt of a higher fatty acid may be added to the composition.

The stability of the composition can be improved by incorporating a small but effective amount of an acidic organic phosphorus compound having an acid group -PQH, for example a partial ester of phosphorous acid and an alkanol.

As described in the aforementioned French patent application 85 05 319, the acidic organic phosphorus compound comprising an acid -POH group can increase the stability of the suspension of detergency builders in the non-aqueous non-ionic liquid surfactant. .

The organic phosphorus acid compound can be, for example, a partial ester of phosphorus acid and an alcohol such as an alkanol having a lipophilic character, comprising for example more than 5 carbon atoms, for example 8 to 20 carbon atoms.

A particular example is a partial ester of phosphoric acid and a C1 (- to C ^ g) alkanol (Em-piphos 5632 from Marchon); it consists of approximately 35% monoester and 65% diester .

The incorporation of very small quantities of the organic phosphorus acid compound makes the suspension stable against sedimentation at rest, while remaining pourable, while for a low concentration of stabilizer, for example less than about 1%, its plastic viscosity generally decreases ^ 41 „The stability and the anti-sedimentation properties of the composition can be further improved by the addition of a small effective amount of an aluminum salt of an acid. higher fat 5 than the composition.

Stabilizing agents of the aluminum salt type are the subject of French patent application 86 02 815 filed on February 28, 1986.

Preferred higher aliphatic fatty acids have about 8 to about 22 carbon atoms, preferably about 10 to 20 carbon atoms, and more preferably about 12 to 18 carbon atoms. The aliphatic radical can be saturated or unsaturated, and it can be straight or branched chain. As in - * - 5 cases of nonionic active surf, it is also possible to use mixtures of fatty acids, such as those from natural sources, such as tallow fatty acid, coconut fatty acid, etc. .

Examples of fatty acids from which stabilizing aluminum salts can be formed include decanolque acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid , eicosanoxque acid, tallow fatty acid, coconut fatty acid, mixtures of these acids, etc. The aluminum salts of these acids are generally commercially available, and are preferably used in the form of three acid residues, for example aluminim stearate in the form of aluminum tristearate (Al ( C ^ H ^ COO).

Salts with an acid residue, for example aluminum monostearate, Al (OH) 2 (C ^ H ^ COO) and salts with two acid residues, for example aluminum distearate, Al (OH) (Cl7H35COO) 2 and mixtures of two or three of the aluminum salts with one, two or three acid residues can also be used. However, it is particularly preferable that the aluminum salt with three acid residues constitutes at least 30%, preferably at least 50%, more preferably at least 80%, of the total amount of aluminum salt. fatty acid.

Aluminum salts, as mentioned above, are commercially available and can be easily produced, for example by saponification of a fatty acid, for example animal fat, stearic acid, etc., then treatment of the resulting soap with alum, alumina, etc.

Only very small amounts of the stabilizing aluminum salt are required to achieve a marked improvement in physical stability.

Bleaching Agents

Bleaches are broadly classified, for convenience, into chlorinated bleaches and oxygenated bleaches. Chlorine bleaches are represented by sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% available chlorine) and trichloroisocyanuric acid (95% available chloride). Oxygenated bleaches are preferred and are represented by co-compounds which release hydrogen peroxide in solution. Preferred examples include sodium and potassium perborates, percarbonates and per-phosphates and potassium monoper-sulfate. Perborates, in particular sodium perborate monohydrate, are particularly preferred.

The peroxygen compound is preferably used in admixture with an activator. Suitable activators which can lower the effective activity temperature of the peroxidic bleach are described, for example, in US Patent No. 4,264,466 or in column 1 of US Patent No. 4,430,244 Polyacetylated compounds are the preferred activators; among them, more preferred are compounds such as tetra "acetylethylene diamine (" TAED ") and pentaacetyl glucose.

Other useful activators include, for example, derivatives of acetylsalicylic acid, ethylidene-benzoate-acetate and its salts, ethylidene-20-carboxylate and its salts, alkyl- and alkenyl-succinic anhydrides, tetraacetylglycourile ("TAGU") and their derivatives. Other useful classes of activators are described, for example, in the US patents. A. N ° 4 111 826, N ° 4 422 950 and N ° 3 661 789.

The bleach activator generally reacts with the peroxygen compound to form a bleaching peroxyacid in the wash water. It is preferable to include a sequestering agent with high complexing power in order to inhibit any undesirable reaction between this peroxyacid and hydrogen peroxide in the washing solution in the presence of metal ions.

Suitable sequestering agents for this purpose include the sodium salts of nitrilo-triacetic acid (NTA), ethylene-diamine-tetra-acetic acid (EDTA), diethylene-triamine-penta-acetic acid (DETPA), diethylene triamine-pen-tamethylene phosphonic acid (DTPMP) sold under the trademark Dequest 2066; and ethylene diamine-tetramethylene phosphonic acid (SDITEMPA). The sequestering agents can be used alone or as a mixture.

In order to avoid loss of the bleaching peroxide, for example sodium perborate, resulting from a decomposition under the action of enzymes, for example the enzyme catalase, the compositions may also contain an inhibitor of enzyme, i.e. a compound capable of inhibiting the decomposition, under the action of enzyme, of bleaching peroxide. Suitable inhibitors are described in the U.S. patent.

A. No. 3,606,990.

As a particularly useful inhibitor, mention may be made of hydroxylamine sulfate and other water-soluble hydroxylamine salts. In the preferred nonaqueous compositions of the present invention, suitable amounts of the inhibitory hydroxylamine salts may be as low as about 0.01 to 0.4%. In general, however, suitable amounts of enzyme inhibitor are up to about 15%, for example 0.1-10% by weight of the composition.

In addition to detergency builders, various other additives or auxiliaries for detergents may be present in the detergent product to provide it with other desired properties, functional or aesthetic in nature. Thus, minor amounts of soil suspending or anti-redeposition agents, for example polyvinyl alcohol, fatty amides, sodium carboxymethylcellulose, hydroxypropylmethyl- can be included in the formulation. cellulose. A preferred anti-redeposition agent is sodium carboxymethylcellulose having a ratio of 2.1 to CM / MC, which is sold under the trade name Relationship DM 4050.

One can also include in, the composition 45 containing the urea compound of small amounts of alkyl- or alkylene-succinic anhydride, like octenyl-succinic anhydride which acts as agent of regulation of viscosity and anti-gelation. Octe-05 nyl succinic anhydride can be added in amounts, for example, from 0.5 to 10 percent, preferably from 1 to 6 percent, and more preferably from 1 to 4 percent based on the weight of the composition.

It is also possible to include in the composition containing the quaternary ammonium, small amounts of Alcosperse D107 which is a sodium polyacrylate and which acts as an anti-scale agent. Alcosperse D107 can be incorporated in amounts for example from 0.5 to 8%, preferably from 2 to 6%, and better still from 3 to 5%, relative to the weight of the composition.

Optical brighteners can be used for cotton, polyamide and polyester fabrics. Suitable optical brightening agents include compositions of stilbene, triazole and benzidine sulfone, in particular substituted triazinyl-stil-bene, naphthotriazole-sulfonated stilbene, benzidene sulfone, etc., such as we prefer being the combinations of stilbene and triazole. A preferred brightener is "Stilbene Brightener N4" which is a dianilino-dimorpholino-stilbene-polysulfonate.

Enzymes can be added, preferably proteolytic enzymes, such as subtilisin, bromelain, papain, trypsin and pepsin, as well as amylase and lipase enzymes and mixtures thereof. Preferred enzymes include a protease suspension, an esperase suspension and amylase. A preferred enzyme is Espéras SL8 which is a proteolytic enzyme. Antifoaming agents can also be added, for example silicone compounds, such as Silicane L 7604 which is a polygiloxane and can be used in small effective amounts.

Bactericides can be used, for example tetrachlorosalicylanilide and hexachlorophene, fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet absorbers, anti-yellowing agents , such as sodium carboxymethylcellulose, pH modifiers and pH buffers, color preservatives, fragrances, dyes and brighteners such as ultramarine blue.

The composition may also contain small amounts of paint pigments to give a color, for example TiO2 / a white pigment. TiO2 can be added in amounts, for example, 0.1 to 4 percent, preferably 0.1 to 2 percent, and more preferably 0.1 to 1 percent.

The composition may also contain small amounts of Bentone 27 which is an organic derivative of magnesium silicate and hydrated aluminum.

Bentone 27 can be used in amounts, for example, 0.2 to 3%, preferably 0.5 to 2%, and more preferably about 1% by weight.

The composition may also contain an insoluble mineral thickener or dispersant with a very large contact surface, for example finely divided silica of extremely small particle size (for example with a diameter of 5 to 100 micrometers, such as that sold under the name Aerosil) or the other very bulky mineral supports described in the patent for Ξ. U. A. No. 3,630,929, in proportions of 0.1 to 10%, for example from 1 to 5%. However, it is preferable that the compositions which form peroxyacids in the wash bath (for example compositions containing a peroxygen compound and an activator therefor) are substantially free of such compounds and other silicates; it has been found, for example, that silica and silicates promote undesirable decomposition of the pero-xyacid.

47

In one embodiment of the invention, the stability of the detergency builder salts in the composition during storage and the dispersibility of the composition in water are improved by grinding 05 and reducing the particle size of the solid detergency builders less than 100 micrometers, preferably less than 40 micrometers and more preferably less than 10 micrometers. Solid detergency builders, for example sodium tripolyphosphate (TPP), are generally supplied in particle sizes of about 100, 200 or 400 microns. The liquid nonionic surfactant phase can be mixed with builders. solid detergency before or after the grinding operation.

In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid ingredients is subjected to attrition milling in which the particle sizes of the solid ingredients are reduced to less than about 10. micrometers, for example to an average particle size of 2 to 10 micrometers or even less (for example 1 micrometer). Preferably, less than about 10%, in particular less than about 5% of all of the suspended particles, have particle sizes greater than 10 microns. Compositions with dispersed particles of such small dimensions have better stability against separation or sedimentation during storage. The addition of the nonionic surfactant compound to acidic ter-30 mination can decrease the flow limit of such dispersions and promote the dispersibility of the dispersions, without corresponding reduction in the stability of the dispersions with respect to sedimentation.

For the grinding operation, it is preferable that the proportion of solid ingredients is sufficiently high (for example at least about 40%, especially about 50%) for the solid particles to be brought into contact with from each other and are not too isolated from each other by the nonionic surfactant. After the grinding step, any remaining liquid nonionic surfactant to be incorporated can be added to the milled formulation.

Grinders which use grinding balls (ball mills) or similar movable grinding elements have given very good results. Thus, it is possible to use a laboratory attrition mill working by batch loads comprising grinding balls made of soapstone 8 mm in diameter. For a larger scale operation, one can use a continuously working grinder in which there are grinding balls with a diameter of 1 mm or 1.5 mm operating in a very small interval between a stator and a rotor operating at a relatively high speed (eg a CoBall mill)? when using such a mill, it is advantageous to pass the mixture of nonionic surfactant and solid materials first through a mill which does not perform such a fine grinding (for example a colloids) in order to reduce the particle size to less than 100 micrometers (for example to about 40 micrometers) before the grinding step to an average particle diameter of less than about 10 micrometers in the continuously working ball mill.

In the preferred liquid detergent compositions for heavy duty laundry of the invention, typical proportions (the percentages being based on the total weight of the composition, unless otherwise specified) of the ingredients are as follows: Nonionic liquid surfactant detergent; in the range of about 10 to 60 or 70, for example 20 to 50 or 60 percent, especially about 30 to 40 or 50 percent; 49

Acid-terminated nonionic surfactant: in the range of about 0 to 20, e.g. 1 to 3 to 15 percent, including about 4 to 10;

Detergency builder, for example tripolyphos-05 sodium phate (TPP): in the range of about 10 to 60, for example 15 to 50 percent, especially about 15 or 25 to 35;

Alkali metal silicate: in the interlayer of about 0 to 30, for example 5 to 25 percent, especially about 10 to 20;

Copolymer of polyacrylate and alkali metal salt of polymaleic anhydride, for example Sokalan CP5, anti-scaling agent: in the range of about 0 to 10, for example 2 to 8 percent, especially about 3 to 5; The alkylene glycol monoalkyl ether, anti-gelling agent, can be used with the urea compound (additive) in an amount of about 5 to 30, for example 5 to 20 percent, especially about 5 to 15 20 percent ; The alkylene glycol, a viscosity control agent and gelation inhibitor, can be used with the quaternary ammonium additive in an amount of about 5 to 30, for example 5 to 25 percent, including about 15 to 25. The preferred viscosity control agents and gelation inhibitors are monoalkyl ethers of alkylene glycols.

. Compound of urea or quaternary ammonium salt used as anti-sedimentation stabilizer: in the range of 0.1 to 5, preferably 0.2 to 2.0, and more preferably about 0.5 to 1.5 percent. An essential characteristic of the invention is that at least one of the urea compounds or at least one of the quaternary ammonium salts is included in the composition; Alkanolic ester of phosphoric acid, stabilizing agent: in the range from 0 to 2.0 or 0.1 to 2.0, especially 0.10 to 1.0 percent; ✓ 50

Aluminum salt of fatty acid as stabilizing agent: in the range of about 0 to 5.0, for example 0.5 to 2.0 percent, especially about 0.1 to 1.0 percent; 05 Bleaching agent: in the range of about 0 to 30, for example 2 to 20, especially about 5 to 15 percent;

Activator of the bleaching agent: in the range of about 0 to 15, for example 1 to 8 or 10 10, especially about 1 to 8 or 2 to 6 percent; Sequestering agent for bleach, for example Dequest 2066; in the range of about 0 to 3.0, preferably 0.5 to 2.0 percent, especially about 0.75 to 1.25 percent; Anti-redeposition agent, for example Relatin DM 4050: in the range of about 0 to 4.0 or 5.0, preferably 0.5 to 3.0 or 4.0 percent, especially 1.0 to 3.0 or 0.5 to 1.5 percent;

Optical brightener: in the range 20 from about 0 to 2.0, preferably 0.05 or 0.25 to 1.0 percent, especially 0.15 or 0.25 to 0.75 percent ;

Enzymes: in the range of about 0 to 3.0, preferably 0.5 to 2.0 percent, especially 0.75 to 1.25 percent; Perfume: in the range of about 0 to 3.0, preferably 0.10 or 0.25 to 1.25 percent, especially 0.25 or 0.75 to 1.0 percent;

Coloring pigment: in the range of about 0.1 to 4.0, preferably 0.1 to 2.0, and more preferably 0.1 to 1.0 percent;

Colorant: in the range of about 0 to 0.10, preferably 0.0025 to 0.050, for example 0.0025 to 0.0100 percent;

Various additives previously mentioned may optionally be added to achieve the desired function of the added materials.

The urea compound is used as an anti-sedimentation stabilizing agent 51 preferably with at least one of the viscosity control and anti-gelling agents that are the alkylene glycol monoether or the nonionic surfactant with termination. acid. In some cases, benefit can be derived from the simultaneous use of alkylene glycol monoethers and acid-terminated nonionic surfactants.

Mixtures of the acid-terminated nonionic surfactant and viscosity adjusting agents and gelation inhibitors may be used, for example anti-gelation agents of the alkylene glycol alkyl ether type, and in some cases, may benefit from the use of such mixtures alone, or with the addition of the anti-sedimentation stabilizer to the mixture.

The additives will be chosen so that they are compatible with the main constituents of the detergent composition. In the present description, as mentioned above, all the proportions and all the percentages are expressed by weight relative to the whole of the formulation or composition, unless otherwise specified.

The concentrated non-aqueous non-ionic liquid detergent composition of the present invention is easy to dispense into the water of the washing machine.

The liquid nonionic detergent compositions of the present invention are preferably nonaqueous; for example, they are substantially anhydrous. Although small amounts of water can be tolerated, it is preferable that the compositions contain less than 3%, preferably less than 2%, and more preferably less than 1% water.

Household washing machines currently in use normally use 200 to 250 grams of powdered detergent to wash a full load of laundry. According to the present invention, only 52,100 cm 3 or 78 g of the concentrated non-ionic liquid detergent composition is required.

In the embodiment of the invention: where a urea compound is used as an additive, a detergent composition of typical formulation is prepared using the ingredients listed below:% by weight Non-ionic surfactant detergent 30-40 10 Acid-terminated surfactant 0-20

Adjuvant detergent of the phosphate type · 10-60

Anti-encrustation agent 0-10

Alkylene glycol monoalkyl ether 15 (anti-gelling agent) 5-15

Compound of urea 0.2-2.0

Anti-redeposition agent 0-4.0

Alkali metal perborate (bleach) 5-15 20 Bleach activator (TAED) 1.0-8.0

Bleach sequestering agent 0-3.0

Optical brightener 0.05-0.75 25 Enzymes 0.75-1.25

Perfume 0.1-1.0

In the embodiment of the invention where a quaternary ammonium compound is used as an additive, a detergent composition of typical formulation is prepared using the ingredients listed below:% by weight Non-ionic surfactant detergent (or 35 such detergent mix) 30-50

0-20 acid-terminated surfactant

Adjuvant detergent type phos- 53 it phate 15-35

Copolymer of polyacrylate and alkali metal salt of polymaleic anhydride as anti-scaling agent - 05 (Sokalan CP-5) 0-10

Alkylene glycol (viscosity control agent and gelling inhibitor 10-25

Quaternary ammonium salt (anti-gelling sta-10 stabilizing agent) 0.2-2.0

Anti-redeposition agent 0-5.0

Whitening alkali metal perborate 3-15

Bleaching agent activator (TAED) 1.0-6.0 15 Sequestering agent 0-3.0

Optical brightening agent (Stilbene Brighener N4) 0—2.0

Enzymes (Protease-Esperase SL8) 0-3.0

Perfume 0-3.0 20

The following nonlimiting examples illustrate the present invention.

Additive: Urea Compound EXAMPLE 1 A concentrated non-aqueous detergent composition containing nonionic surfactant is prepared from the following ingredients in the amounts indicated:% by weight 30 Nonionic surfactant 37.7

Acid-terminated Dobanol 91-5 reaction product with succinic anhydride 5.0

Sodium tripolyphosphate (TPP) 30 35 Diethylene glycol monobutyl ether (antifreeze agent) 10

Urea 1.0 54

Sodium perborate monohydrate (bleach) 9.0 Tetraacetylethylene diamine (TAED) „(bleach activator 05) 4.5

Anti-redeposition agent (Relatin DM

4096) 1.0

Optical brightening agent 0.2

Fragrance 0.6 10 Enzyme (Esperase) 1.0 (1) mixture at CMC / MC = 2: 1 of sodium carboxymethylcellulose and hydroxymethylcellulose.

The addition of 1% urea has been found to increase the flow limit of the composition.

The composition is ground for about 1.0 hour to reduce the particle size of the detergency builder salts in suspension to less than 1.0 micrometer. The prepared detergent composition has been found to be stable and non-gelling upon storage and readily dispersible in water.

EXAMPLE 2

A concentrated non-aqueous detergent composition with nonionic surfactant is prepared from the following ingredients in the quantities indicated:% by weight * Surfactant T7 13 30 Surfactant T9 18

Octenyl succinic anhydride ^ 2

Sodium tripolyphosphate (TPP) 29.5

Anti-scaling agent (Sokalan CP5) 4.0

Diethylene glycol monobutyl ether 35 (anti-gelling agent) 10

Urea (anti-sedimentation stabilizing agent) 1.0 55

Sodium perborate monohydrate (bleaching agent) 9 Tetraacetylethylenediamine (TAED) (activator of bleaching agent 05 chiment) 4.5 t Sequestering agent for bleaching agent (Dequest 2066) lf0

Anti-redeposition agent (Relatin DM

4096) (2) 1.0 10 Optical brightening agents (ATS-X) 0.2

Enzyme (protease) 1.0

Perfume 0.6

Ti02 (pigment) 0.2 15 (1) Viscosity control and anti-gelling agent, (2) Mixture at CMC / MC = 2: 1 of sodium carboxymethylcellulose and hydroxymethylcellulose. The addition of 1 percent urea had increased the flow limit of the composition.

The apparent viscosity of the composition at 100 reverse seconds was found to be 1.1 Pa.

The composition is ground for about 1 hour to reduce the particle size of the suspended detergency builder salts to less than 10 microns. The prepared detergent composition has been shown to be stable and non-gelling during storage and easy to disperse in water.

The compositions of Examples 1 and 2 can be prepared without grinding the detergency builder salts or suspended solid particles to a small particle size, but best results are obtained by grinding the composition to reduce the particle size of the particles. suspended solids.

Urea (anti-sedimentation stabilizing agent) can also be used to improve the compatibility of the nonionic surfactant and of the adjuvant detergency of the polyphosphate type in powdered detergent compositions - 05 Additive: Quaternary ammonium compound EXAMPLE 3

A concentrated nonaqueous liquid detergent composition with nonionic surfactant is prepared from the following ingredients in the amounts indicated; % in weight

Non-ionic surfactant, product D 39

Acid-terminated reaction product of Dobanol 91-5 with succinic anhydride 5.0

Sodium tripolyphosphate (TPP) 30

Diethylene glycol monobutyl ether (anti-gelling agent) 10

Quaternary ammonium salt 1.0 20 Sodium perborate monohydrate (bleaching agent) 9.0 Tetraacetylethylene diamine (TAED) (activating bleaching agent) 4.5

Stilbene-type brightening agent 0.5 Protease (Esperase) 1.0 (1) the quaternary ammonium salt used as an anti-sedimentation stabilizing agent is Arosurf TA 100 (distearyl dimethyl ammonium chloride).

The addition of 1% of the quaternary ammonium salt has been found to increase the flow limit of the composition from about 2 Pa to about 6 Pa. The apparent viscosity of the composition has been found to be increased by '' about 0.5 Pa.s to 0.4 Pa.s.

The composition is ground for about 1 hour to reduce the particle size of the detergency builder salts to less than 10 micrometers. The prepared detergent composition was found to be stable and non-gelling during storage and demonstrated high detergency.

EXAMPLE 4 u A concentrated, nonaqueous liquid detergent composition with nonionic surfactant is prepared from the following ingredients in the quantities indicated: 10% by weight

Surfactant T7 18.7

Surfactant T9 18.7

Acid-terminated reaction product of Dobanol 91-5 with succinic anhydride 5.0

Sodium tripolyphosphate (TPP) 30

Diethylene glycol monobutyl ether (anti-gelling agent) 10

Quaternary ammonium salt (* ·) 1.0 20 Sodium perborate monohydrate (bleaching agent) 9 Tetraacetethylenediamine (TAED) (activating bleaching agent) 4.5 25 Brightening agent of the stilbene type 0 , 5

Protease (Esperaæ) 1.0

Relatin DM 4096 (CMC / MC) (2) 1.0

Perfume 0.6 £ 30 (1) the quaternary ammonium salt used as anti-sedimentation stabilizing agent is Ethoquat 2T14 (di-tallow-ammonium chloride diethoxylé (x + y = 4)).

(2) a 2: 1 mixture of sodium carboxymethylcellulose and hydroxymethyl cellulose.

The addition of 1% of the quaternary ammonium salt has been found to increase the flow limit of the composition from about 3 Pa to 10 Pa. The apparent viscosity of the composition has been found to increase from about 0/5 Pa.s to 0.4 Pa.s.

The composition is ground for about ^ 1 hour to reduce the particle size of the? 05 adjuvant detergency salts suspended within 10 micrometers. The prepared detergent composition has been shown to be stable and non-gelling during storage and has demonstrated high detergency.

10 3 SAMPLE 5

Concentrated nonaqueous liquid detergent compositions with nonionic surfactant are prepared from the following ingredients in the amounts indicated: A3

Plurafac RA50 35 35

Plurafac B26 9.0 9.0

Sodium tripolyphosphate (TPP) 18 18

Polyethylene glycol (molecular weight-20 re 400) (anti-gelling agent) 20 20

Quaternary ammonium salt (D 1.0 ---

Sodium perbotate monohydrate (bleaching agent) 3.6 4.1 25 Tetraacetylethylenediamine (TAED) (activator of bleaching agent) 4y5 5.0. Relatin DM4096 (CMC / MC) ^ (anti-L-redeposition agent) 3.0 3.0 30 EDTA (sequestering agent) (3) 0.9 0.9

Bentone 27 ^) 1.0 1.0

Alcosperse D1074.0 4.0 100.0 100.0 35 1, Ethoquat 2T14 is diethoxymethyl diethoxylated chloride (x + y = 4), 2. A 2: 1 mixture of carboxymethyl- cellulose 59 sodium and hydroxymethyl cellulose, 3. ethylene diamine tetraacetic acid, 4. organic derivative of magnesium silicate ^ and hydrated aluminum acting as anti-sedimentation agent, 5. Alcosperse D107 is a polyacrylate of so dium acting as an anti-tartar agent.

The composition is ground for about 15 minutes to reduce the particle size of the detergency builder salts in suspension to less than 10 microns. The prepared detergent composition A of the invention has been shown to be stable and not gelling during storage and has demonstrated high detergency.

A comparison of the composition A of the invention containing the quaternary ammonium salt as an anti-sedimentation stabilizing agent with the composition B devoid of the quaternary ammonium salt gave the following results:

20 AB

Apparent viscosity (LVT, spindle; j ° 4, SO rpm) (mPa.s) 3250 2350

Stability after 48 h:% of phase separation: 1 7 25 Flow limit (Pa) 26 6.5

Plastic viscosity (mPa.s) 400 510 ^ The results obtained show that the addition to the composition of as little as 1% of quaternary ammonium salt as anti-sedimentation stabilizing agent for the present invention greatly increases the stability of the composition, increases the apparent viscosity, increases the flow limit and decreases the plastic viscosity.

The compositions of Examples 3, 4 and 5 can be prepared without grinding the detergency builder salts and solid particles in suspension 60 *, to a small particle size / but the best results are obtained by grinding the composition to reduce the size particulate of suspended Solist particles.

C 05 In Examples 1 to 5, the detergency builder salts can be used as supplied or the detergency builder salts and suspended solid particles can be ground or partially ground before being mixed with the non-ionic surfactant. The grinding can be carried out partially before mixing and can be completed after mixing, or the whole grinding operation can be carried out after mixing with the liquid surfactant. Compositions of which the detergency builder 15 and the solid particles are less than 10 microns in size are preferable.

S.

Claims (15)

61 1. Detergent composition for the treatment of tissues, characterized in that it comprises a suspension of insoluble mineral particles of salt adju-05 before detergency in a non-ionic surfactant detergent that non-aqueous liquid and urea or one. urea derivative or a cationic quaternary ammonium surfactant salt as an anti-sedimentation agent to increase the stability of the suspension. 2. Composition according to claim 1, ca acterized in that the detergency builder mineral salt comprises 10 to 60 percent of a detergency builder salt of the alkali metal tripolyphosphate type. 3. Composition according to claim 1, ca-15 acted in that the anti-sedimentation agent is urea or urea derivative. 4. Composition according to claim 1, characterized in that the cationic quaternary ammonium salt is at least one of the compounds represented by the formulas: R2 Ί + î 1 2 - R - N - R * X (I) '2 RZ 25. i Ί R + 1 1 2 - R1 - N -R * X (II)' 2 ^ LR l- Γ R2 + 30 .1 R -N - (CH2CH20) xH X (III) (CH2CH20) yH R1 +! IR - N - (CH, CH „0) fi X (IV) 35, 2 2 x (CH2CH20) yH 62 Ci in which the radicals R1 are independently of the long-chain aliphatic radicals of 10 to 22 carbon atoms 2, the radicals R are independently lower alkyl or lower hydroxyalkyl radicals, x and y are each 05 a positive number at least equal to 1 and the sum h x + y ranges from 2 to 15, and X is a water-soluble salt-forming anion . 5. A detergent composition according to claim 1, characterized in that it comprises at least one viscosity control and anti-gelling agent, chosen from a nonionic surfactant with acid termination and an alkylene glycol. 6. Detergent composition according to claim 1, characterized in that it comprises one or more detergent additives, chosen from an anti-scaling agent, an alkali metal silicate, a bleaching agent, a bleaching agent activator. , a sequestering agent, an anti-redeposition agent, an optical brightening agent, enzymes, a perfume and a dye. 7. Composition according to claim 1, characterized in that it contains approximately 0.1 to approximately 5 percent by weight, on the basis of the total composition, of said anti-sedimentation stabilizing agent of the urea type or derived from urea or quaternary ammonium salt, the latter being chosen from a mono (upper alkyl) - tri (lower alkyl) ammonium craterate-nary salt (I), a di (higher alkyl) di (lower alkyl [ = laughing) quaternary ammonium (II), a mono (higher alkyl) mono (lower alkyl) salt diethoxylated quaternary ammonium (III) and a salt of di (higher alkyl) diethoxylated quaternary ammonium (IV). 8. Reinforced non-aqueous detergent composition for heavy laundry work, which can be poured at high and low temperatures and does not gel when mixed with cold water, characterized in that it comprises at least one non-ionic liquid surfactant 63 ta in an amount of about 10 to about 60 or 70 percent by weight; at least one detergent builder mineral salt suspended in the nonionic surfactant, in an amount of about 10 to about 05 60 percent by weight; an acid-terminated nonionic surfactant as a gelling inhibitor additive, in an amount of about 0 to 20 percent by weight; at least one viscosity controlling and gelling inhibitor of the alkylene glycol type in an amount of about 5 to 30 percent by weight; and about 0.2 to 2.0 percent by weight of an additive of the urea or urea derivative type or of an anti-sedimentation stabilizing agent of the quaternary ammonium salt type which is chosen from a mono salt (higher alkyl) tri (lower alkyl) -15 quaternary ammonium (I), a salt of di (higher alkyl) di (lower alkyl) quaternary ammonium (II), a salt of mono (higher alkyl) -mono (lower alkyl) diethoxylated quaternary ammonium (III) and a di (higher alkyl) salt diethoxylated quaternary ammonium (IV). 9. Detergent composition according to claim 8, characterized in that it comprises approximately 2 to 20 percent by weight of a nonionic surfactant with acid termination as a gelling inhibitor additive. 10. Non-aqueous liquid detergent composition for heavy laundry work according to the claim; tion 8, characterized in that it comprises a nonionic surfactant S "in an amount of about 20 to 50% by weight, sodium tripolyphosphate (TPP) in an amount of about 15 to 50% in by weight, a copolymer of polyacrylate and sodium salt of polymale anhydride in an amount of 2 to 8% by weight, a monoalkyl ether of di-ethylene glycol in an amount of about 5 to 20% by weight, of urea in an amount of about 0.2 to 2.0% by weight, sodium perborate monohydrate as a bleaching agent in an amount of 2 to 20% by weight, and tetraacetylethylenediamine (TAED) in an amount 64 of about 1.1 to 10% by weight. 11. A non-aqueous liquid detergent composition for large laundering works according to claim 8, characterized in that it comprises: a nonionic surfactant in an amount of about 30 to 40% by weight, octenyl succinic anhydride in an amount of about 7% by weight of sodium tripolyphosphate in an amount of about 25 to 35% by weight, a copolymer of polyacrylate and sodium salt of anhy-10 polymaleic dride in an amount of about 3 to 5% by weight, monobutyl ether of diethylene glycol in an amount of about 5 to 15% by weight, urea in an amount of about 0.5 to 1.5% by weight, sodium perbo-rate monohydrate as a bleaching agent in an amount of about 5 to 15% by weight, t-traacetylethylene diamine (TAED) as an activator The bleach in an amount of about 2 to 6.0% by weight, a sequestering agent for the bleach in an amount of about 0.75 to 1.25% by weight by weight, and an anti-redeposition agent in an amount of about 0.5 to 1.5% by weight. 12. A non-aqueous liquid detergent composition for large laundering works according to claim 8, characterized in that it contains a nonionic surfactant in an amount of about 30 to 50% by weight, an acid-terminated surfactant in an amount about 1 to 15% by weight, sodium tripolyphosphate (TPP) in an amount of about 15 to 50% by weight, 7 'of the monobutyl ether of diethylene glycol in a quan 30 about 5 to 25% by weight, a quaternary ammonium salt in an amount of about 0.2 to 2.0% by weight, sodium perborate monohydrate as a bleaching agent in an amount of about 2 at 20% by weight, tetraacetylethylene diamine (TAED) as activator of the bleaching agent in an amount of about 1 to 8% by weight. 13. A non-aqueous liquid detergent composition for large laundering works according to claim 8, characterized in that it comprises a nonionic over-charge in an amount of approximately 30 to 50%, by weight, of tripolyphosphate. sodium in an amount of about 15 to 50% by weight, polyethylene gly- (h col (molecular weight 400) in an amount of about 5 to 25% by weight, a quaternary ammonium salt in an amount of about 0.2 to 2.0% by weight, sodium perborate monohydrate as a bleach, in an amount of about 2 to 20% by weight, and tetraecetylethylene diamine (TAED) as activator of the bleaching agent, in an amount of about 1 to 8%. 14. Method for cleaning soiled fabrics, characterized in that it consists in bringing the soiled fabrics in contact with the detergent laundry composition according to claim 10 or 11. 15. Method for cleaning soiled fabrics, characterized in that it consists in bringing the soiled fabrics in contact with the laundry detergent composition according to claim 12 or 13. MM.