NL8602120A - COMPOSITE DETERGENTS CONTAINING STABILIZERS. - Google Patents

Description

S> if -1 V.0. 8321

Title: Composite detergents containing stabilizing agents.

This invention relates to non-aqueous liquid fabric treatment agents. More particularly, this invention relates to non-aqueous liquid detergents which are stable to phase separation and gelling and are easily pourable, and to the use of these agents for cleaning dirty tissue.

Liquid non-aqueous detergent compositions are known in the art. Agents of that type include, for example, a liquid nonionic surfactant in which particles of a builder are dispersed, such as shown, for example, in U.S. Patent Nos. 4315812, 3630929 and 4264466 and British Patent Nos. 1205711, 127Q04Q, and 1600981.

Applicant's pending U.S. patents are Nos. 687,815, filed December 31, 1984; 15,597,793, filed April 6, 1984; 597,948, filed April 9, 1984; 725,455, filed April 22, 1985, and 687,816, filed December 31, 1984.

These applications are directed to liquid non-aqueous non-20 ionic detergents.

Liquid detergents are often more suitable to use than dry powdered or finely divided products, so they have found much resonance with the consumer. They are easier to measure, quickly dissolve in the wash water, and can easily be applied to dirty garments in concentrated solutions or dispersions on the garments to be washed, and they do not form dust, while usually taking up less storage space.

Furthermore, the liquid detergent compositions may include materials which are not resistant to drying steps without decomposition, which are often desired to be used in the preparation of finely divided detergent compositions. Although the liquid detergents have many advantages over unitary and finely divided solid products, they also have inherent disadvantages which must be overcome in order to produce commercially acceptable detergent products. Thus, some products may curdle on storage, while others will curdle on cooling and are not readily redispersed. In some cases, the product viscosity changes and the agent either becomes too thick to pour or so thin as to resemble water.

5 Some clear products become cloudy and others are assisted.

The inventors have investigated the behavior of non-ionic liquid detergent systems containing finely divided suspended material. Of particular interest are non-aqueous liquid detergent compositions as well as the problem of settling of the suspended builder and other washing additives, as well as the problem of gelling inherent in nonionic actives. These points affect, for example, product stability, pourability and dispersibility.

It is known that one of the main problems for formulated liquid 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 higher than the density of the liquid surfactant.

Therefore, the dispersed particles tend to settle. There are two main solutions to overcome the sag problem: increasing the viscosity of the nonionic liquid and reducing the size of the dispersed solids.

It is known that suspensions can be stabilized against settling by inorganic or organic thickeners or dispersants such as, for example, very high surface area inorganic materials, for example finely divided silica, clays, etc., organic thickeners, such as the cellulose ethers, acrylic and acrylic acrylonide polymers, polyelectrolites, etc.

Of course, such an increase in the suspension viscosity is limited by the requirement that the liquid suspension must remain easily pourable and liquid, even at low temperature. Furthermore, these additives do not contribute to the washing power of the mixture.

By grinding to reduce the particle size, the following advantages are obtained: 8602120

* I

- 3 - 1. The specific surface area of the dispersed particles is increased and therefore the wetting of the particles by the non-aqueous carrier (liquid non-ionic substance) increases proportionately.

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

The yield stress is defined as the minimum stress necessary to effect a plastic deformation (flow) of the suspension. If the suspension is envisioned as a loose network of dispersed particles, the suspension will behave as an elastic gel and no plastic flow will occur. Once the yield strength is overcome, the network breaks at certain 15 points and the sample begins to flow, but without a very high apparent viscosity. If the shear stress is much higher than the yield strength, the pigments are flocculated partially and the apparent viscosity increases.

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

The higher the yield strength of the slurry, the higher the apparent low shear viscosity and the better the physical stability against sagging of the product.

In addition to the sag or phase separation problem, the non-aqueous liquid detergents based on liquid non-ionic surfactants suffer from the drawback that the non-ionic compounds start to gel when added to cold water. This is a particularly important problem in the normal use of European household washing machines where the user places the detergent in a dispenser (eg a dispenser) of the machine. During the operation of the machine, detergent in the tray is subjected to a stream of cold water to transfer it into the main mass of the washing liquid. Especially during the winter months when the detergent and water supplied to the dispenser are particularly cold, the detergent viscosity increases sharply and a gel forms.

As a result, part of the agent is not completely rinsed out of the dispenser during machine operation, and after repeated washing cycles, a deposit of the agent forms causing the user to rinse the dispenser with hot water.

The gelling phenomenon may also be a problem when it is desired to wash in cold water, such as is recommended for certain synthetic and sensitive fabrics or fabrics that can shrink in hot or cold water.

The tendency of the concentrated detergents to gel during storage is enhanced by the detergents being stored in unheated storage areas, or by shipping the agents in non-heated transport vehicles during the winter months.

Partial solutions to the gelling problem have been proposed such as diluting the liquid nonionic with certain viscosity control solvents and gel inhibitors such as lower alkanols, e.g., ethyl alcohol (see U.S. Patent 3,953,380), 20 alkali metal formates and adipates (see U.S. Patent 4,368,147), hexylene glycol, polyethylene glycol etc. and modification and optimization of the nonionic structure.

As an example of a nonionic surfactant modification, a particularly successful result has been achieved by making the hydroxyl end group of the nonionic molecule acidic. The advantages of introducing a carboxylic acid at the end of the nonionic surfactant include the prevention of gelation upon dilution; lowering the pour point of the nonionic and forming an anionic surfactant upon neutralization in the wash.

Optimizing the nonionic structure has focused primarily on the chain length of the hydrophobic hydrophilic unit and the number and shape of the alkylene oxide (e.g., ethylene oxide) units of the hydrophilic unit.

For example, it has been found that the fatty alcohol is ethoxylated 860212e »4.

- 5 - with 3 moles of ethylene oxide shows only a limited tendency to gel.

BRIEF SUMMARY OF THE INVENTION

According to the present invention, a highly concentrated stable non-aqueous liquid detergent composition is prepared by adding to the agent small effective amounts of a urea anti-sag stabilization additive or very small amounts of a quaternary ammonium surfactant as anti-sag stabilization additive .

The agents of the invention contain, as an essential component, a urea anti-sag stabilization additive or a quaternary ammonium surfactant anti-sag stabilization additive.

It is believed that the urea anti-sag stabilizer additive in the detergent acts as a surfactant and makes the phosphate detergent builder more compatible with the nonionic surfactant. The urea is believed to interact with the anionic phosphate detergent builder salts and make the builder salts more compatible with the nonionic surfactant and improve contact between the builder salts and the nonionic surfactant .

By improving the contact between the phosphate and the non-ionic surfactant, the stability of the phosphate suspension in the non-ionic surfactant is improved.

The urea compound even when added to the agent in small amounts improves the dispersibility of the builder salt slurry by inhibiting the gelation of the builder salt slurry.

The urea improves dispersibility by preventing gelation of the slurry of builder salt builder particles when water is added to the agent, for example, in a dishwasher dispenser and / or when the agent is added to water.

The urea compound used in the agents of the invention has the formula H ^ NCONH ^. The urea forms a tautomer of the formula H 2 HNCNHOH and is called carbamide.

1602120 *? - 6 -

The quaternary ammonium anti-settling stabilizing additives are cationic surfactants. The quaternary ammonium cationic surfactants useful in the invention are the compounds which in their molecular structure contain a long hydrophobic carbon group and a hydrophilic group, for example, a water-soluble salt-forming anionic group. The anti-sag stabilizers of the invention are known and commercially available.

The quaternary ammonium compounds have been used as fabric softeners and are also used as surfactant detergents.

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

The quaternary ammonium salts are believed to interact with the anionic phosphate detergent builder salts and coat the anionic phosphate with lipophilic skin. The lipophilic coating makes the anionic phosphate detergent builder salts more compatible with the nonionic surfactant and improves the contact between phosphate and the nonionic surfactant.

By improving the contact between the phosphate and the non-ionic surfactant, the stability of the phosphate suspension in the non-ionic surfactant is improved.

The preferred cationic quaternary ammonium surfactant anti-settling stabilizers of the invention are members of the group consisting of: 1. mono-higher alkyl-tri-lower alkyl-quaternary ammonium salts.

2. di-higher alkyl-di-lower alkyl quaternary ammonium salts.

3. mono-higher alkyl-mono-lower alkyl-diethoxylated quaternary ammonium salts.

4. di-higher alkyl-diethoxylated quaternary ammonium salts.

The cationic quaternary ammonium compound that functions as the anti-settling stabilizer of the invention is briefly described as follows.

The formula 1 compounds are mono-higher alkyl-tri-lower 35 alkyl-quaternary ammonium salts (see the formula sheet), wherein R * is a yy L a & * j 2 »i - 7 - long aliphatic group with 10-22 carbon atoms the R symbols individually are lower alkyl or hydroxyalkyl of 1-4 carbon atoms and X is a water-soluble salt-forming anion.

The formula 2 compounds are-di-higher alkyl-di-lower alkyl-quaternary ammonium salts (see the formula sheet), wherein the R * symbols are independently lower aliphatic groups of 10-22 carbon atoms, 2 the R symbols are independently lower alkyl or hydroxyalkyl with 1-4 are carbon atoms and X is a water-soluble salt-forming anion.

The formula 3 compounds are mono-upper alkyl, mono-lower alkyl, diethoxy quaternary ammonium compounds (see formula sheet),

1 2 where R is a long aliphatic group of 10-22 carbon atoms, R.

a lower alkyl or hydroxyalkyl of 1-4 carbon atoms, x and y are each positive numbers of at least 1 and the sum of x + y is 2-15, where x is a water-soluble salt-forming anion. The compounds of formula 4 of the formula sheet are di-higher alkyl-diethoxylated quaternary ammonium salts (see formula sheet), wherein the b} symbols are independently long aliphatic groups of 10-22 carbon atoms, x and y are each positive numbers of at least 1 and the sum of x + y 2 -15, while X is a water-soluble salt-forming anion.

To improve the viscosity properties of the agent, an acid-terminated nonionic surfactant can be added. To further improve the viscosity and storage properties of the detergent, viscosity improvers and anti-gelling agents, such as alkylene glycols, poly (alkylene glycols) and alkylene glycol monoalkyl ethers, and additional anti-settling agents, such as phosphoric acid ester and / or aluminum stearate, may be added to the agent.

In one embodiment of the invention, the detergent composition comprises an acid-terminated nonionic surfactant, an alkylene-30 glycol monoalkyl ether, and a urea anti-sag stabilizer or a quaternary ammonium anti-sag stabilizer.

Sterilizing or bleaching agents and activators therefor can be added to improve the bleaching and cleaning properties of the detergent.

In one embodiment of the invention, the builder components of the agent are milled to a particle size of less than 100 microns and preferably less than 10 microns to ensure the stability of the dispersion of the builder components in the liquid nonionic further improve surfactant.

Other ingredients may also be added to the agent such as anti-scaling agents, anti-foaming agents, optical brighteners, enzymes, anti-graying agents, perfume and dyes.

The currently manufactured household washing machines normally operate at washing temperatures of up to 95 ° C. About 20 liters of water are used during the washing and rinsing steps.

Usually about 200-250 grams of powdered detergent are used per wash step.

According to the present invention, when using the highly concentrated liquid detergent, normally only 100 grams (78 cc) of the liquid detergent is used to wash a complete batch of soiled laundry.

Thus, in an aspect of the present invention, there is provided a liquid concentrated detergent composition composed of a suspension of a detergent builder salt or of an anionic detergent. builder-20 salt, for example a phosphate builder salt, in the liquid non-ionic surfactant, the agent containing an effective amount of a urea compound to increase the stability of the suspension to sag and the dispersibility of the suspension in water or quaternary ammonium surfactant to increase the stability of the slurry suspension.

In another aspect, the invention provides a concentrated liquid powerful detergent which is stable, non-sagging in storage and non-gelling in storage and in use. The liquid agents of the present invention are easy to pour, easy to measure and easy to machine wash.

In another aspect, the invention provides a method of dispensing a liquid nonionic detergent in and / or with cold water without undergoing gelation. In particular, a method is provided for filling a container with a non-aqueous liquid detergent in which the detergent active substance is at least mainly composed of a liquid nonionic surfactant and for the active substance. dispensing the agent from the container into an aqueous wash bath, wherein dispensing is accomplished by directing a stream of unheated water onto the agent such that the agent is passed through the stream of water into the wash bath.

5 ADVANTAGES OVER THE STATE OF THE ART

The addition of the urea compound to the detergents reduces the problem of dispersed particle sagging and phase separation and improves the dispersibility of the suspended detergent particles in water. The addition of the quaternary ammonium surfactants to the detergents reduces the problem of dispersion of dispersed particles and phase separation.

The concentrated non-aqueous, liquid non-ionic surfactant detergents of the present invention have the advantage of being stable, non-sagging and non-gelling on storage.

The liquids are easy to pour, easy to measure and can be easily applied in household washing machines.

OBJECTS OF THE INVENTION

It is an object of the present invention to provide a stable liquid powerful non-aqueous non-ionic detergent containing at least one urea compound as anti-sag stabilizer and optionally an anionic phosphate detergent builder salt suspended in a non-ionic surfactant .

It is a further object of the invention to provide a stable powerful non-aqueous nonionic detergent containing at least one quaternary ammonium anti-sag stabilizer and at least one anionic phosphate detergent builder salt suspended in a nonionic surfactant contains.

It is a further object of the invention to provide liquid tissue treating agents which are suspensions of insoluble inorganic particles in a non-aqueous liquid and which are stable, easily pourable and dispersible in cold, hot or hot water upon storage.

Sδ0 2 1 2C

0 - 10 -

Another object of the invention is to prepare highly formulated, high performance, non-aqueous liquid nonionic surfactant detergents that are pourable at all temperatures and that can be repeatedly dispensed from the dispenser of a European-style automatic household washing machine. be delivered without deposits forming or without clogging the dispenser, even during the winter months.

It is a specific object of this invention to provide a non-gelling, stable suspension of powerful formulated, non-aqueous liquid, non-ionic detergent compositions containing an effective amount of a urea compound or a quaternary ammonium surfactant contain enough to increase the yield stress of the agent thereby increasing its stability, ie preventing sagging of builder particles etc., preferably under reduction or at least without increasing the plastic viscosity (viscosity under shear conditions) of the agent.

These and other objects of the invention, which will be illustrated by the following description of preferred embodiments, are accomplished by preparing a detergent composition by adding an effective amount of a urea compound as an anti-oxidant to the non-aqueous liquid nonionic detergent sag stabilizer or a quaternary ammonium surfactant anti-sag stabilizer sufficient to prevent sagging of the suspended particles, said agent comprising inorganic or organic tissue treating additives, for example, viscosity improving agents and one or more anti-sagging agents. -gelling agents, anti-scaling agents, pH regulators, bleaching agents, bleach activators, anti-foaming agents, optical brighteners, enzymes, anti-graying agents, perfume and dyes.

DETAILED DESCRIPTION OF THE INVENTION

According to the present invention, the critical stability of the slurry of the anionic phosphate detergent builder compound or the anionic detergent builder compound or compounds and any other suspended additive, such as a bleach, etc., is added in the liquid 8602120. ionic surfactant carrier is greatly improved by the addition of an anti-settling stabilizer consisting of urea or a quaternary ammonium surfactant.

The addition of very small amounts of the urea anti-3 sag stabilizer or the quaternary ammonium surfactant anti-sag stabilizer is sufficient to significantly improve the physical stability of the detergents.

The urea anti-settling agent also greatly improves the dispersibility of the agents in water.

In one embodiment of the present invention, the agents as essential components contain urea anti-sag stabilizer additive. The anti-sag stabilization additive egg may comprise one or more urea compounds.

The urea compounds used in the agents of the invention have the formula R. R_NCNR_R, 1 2 ί 3 4

X

Wherein at least one of R to R is hydrogen and the balance are alkyl / preferably C 1 -C 6 alkyl, aryl, preferably phenyl, hydroxyl or chlorine and X is O or NH. The urea forms a tautomer of the formula H2NCNHOH and is called carbamide. Urea and carbamide compounds and derivative compounds, such as methyl urea, dimethyl urea, ethyl urea, propyl urea, butyl urea, hydroxyl urea and phenyl urea, salts of the foregoing are suitable for use in the present invention.

In addition to acting as a physical stabilizing agent, the urea compounds have the advantage over other physical stabilizing agents that they are compatible with the nonionic surfactant component and that they significantly improve the dosability of the detergent in cold water.

Although the applicant does not wish to commit to any particular theory of how the urea or carbamide compounds function and prevents the suspended anionic phosphate builder from settling washable particles, it is believed that the urea or carbamide compounds interact with the anionic phosphate builder salts and make the phosphate more compatible with the non-ionic 3 δ 0 2 I 2 0 -12 surfactant, improve the contact between the phosphate and the nonionic active agent, and improve the wettability of the dispersed phosphate solid particle surfaces by improve the non-ionic surfactant.

The improvement in the contact between the phosphate and the nonionic surfactant and the improved wettability of the dispersed phosphate particles by the nonionic surfactant increases the stability of the phosphate slurry in the nonionic surfactant thereby suspended phosphate can more easily remain in suspension.

The increased physical stability is demonstrated by an increase in the yield stress of the agent compared to the same agent without the stabilizing agent. As described above, the higher the yield stress, the higher the apparent viscosity at low shear rates and the better the physical stability.

The urea compound, even when added to the agent in small amounts, improves the dispersibility of the builder salt suspension by preventing gelation of the builder suspension upon contact with water.

The urea improves dispersibility by counteracting gel formation of the suspension of detergent builder salt particles when water is added to the agent, for example in the dispenser of a dishwasher and / or when the agent is added to the wash water.

Only small amounts of urea compound are needed to achieve significant improvements in the physical stability of the detergent and the dispersibility of the agent in cold water.

Based on the total weight of the nonionic liquid detergent, suitable amounts of urea range from about 0.1 to about 5%, preferably about 0.2 to about 2.0%, and most preferably about 0 .5-1.5%.

In another embodiment of the invention, the agents as an essential component contain a quaternary ammonium surfactant as an anti-sag stabilizing additive.

The anti-settling stabilizing additive may contain one or more of the quaternary ammonium surfactants.

8602120 - 13 -

The anionic surfactants useful in the invention are those cationic surfactants containing a long hydrophobic hydrocarbon group in their molecular structure and a hydrophilic group, i.e., a water-soluble salt-forming anion group.

The preferred anti-sag stabilizers of the invention based on cationic or quaternary ammonium surfactants are members of the group consisting of 1. Mono-higher alkyl, tri-lower alkyl quaternary ammonium salts.

2. Di-higher alkyl, di-lower alkyl, quaternary ammonium salts.

3. Mono-higher alkyl, mono-lower alkyl, dialkoxylated quaternary ammonium zones.

4. Di-higher alkyl, diethoxylated quaternary ammonium salts.

The anti-sag stabilizers of formula 1 used in the invention are the mono-higher alkyl, tri-lower alkyl, quaternary ammonium compounds wherein R * is a long aliphatic group 2 having 10-22 carbon atoms and the R symbols are independently lower alkyl - or hydroxy lower alkyl groups, X are a water-soluble salt-forming anion, such as a halide, e.g. chloride, bromide, iodide; Sulfate, hydrate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate or similar inorganic or organic solubilizing group.

The R * carbon chain of the aliphatic group is 10-22 carbon atoms, especially 12-20, most preferably 12-13 and especially 25-16-18 carbon atoms, may be straight or branched and saturated or unsaturated.

2

The lower alkyl groups R have 1-4 carbon atoms, for example, methyl, ethyl, propyl and butyl, preferably 1 or 2 carbon atoms, especially methyl, and they may contain a hydroxy group.

The preferred arammonium salt is a mono-higher alkyl trimethyl ammonium chloride in which the alkyl group is derived from tallow acid, hydrogenated tallow acid or stearic acid. Specific examples of quaternary ammonium anti-sag stabilizing agents of formula 1 suitable for use in the agents of the invention include the following:

One can also use the corresponding sulfate; methosulfate; ethosulfate; 10 use bromide or hydroxide salts.

The cationic anti-sag stabilizers of formula 2 used in the invention are the di-higher alkyl, di-lower alkyl, quaternary ammonium compounds, wherein the R * symbols are independently 2

long aliphatic groups with 10-22 carbon atoms and the R.

Symbols are independently lower alkyl or hydroxy alkyl groups, X a water-soluble salt of the anion, such as a halide, i.e. chloride, bromide, iodide; sulfate, nitrate, citrate, acetate, hydroxide methosulfate, ethosulfate, phosphate or a similar inorganic or organic solubising group. The R * carbon chains of the aliphatic groups 20 having 10 to 22 carbon atoms, especially 12-20, preferably 12-18, and especially 16-18 carbon atoms, may be straight or branched or saturated or unsaturated. The R lower alkyl groups have 1-4 carbon atoms, for example methyl, ethyl, propyl and butyl, preferably 1 or 2 carbon atoms, especially preferably methyl and they can contain a hydroxy group.

Typical cationic compounds of Formula 2 include the following: distearyl dimethyl ammonium chloride ditalk dimethyl ammonium chloride 30 dihexadecyldimethyl ammonium chloride distearyl dimethyl ammonium bromide di (hydrogenated talc) dimethyl ammonium bromide 2-alkosyl dimethyl ammonium methethulfropyldi (isopropyl ammonium chloride)

A preferred group of cationic compounds has formula 2 wherein two of the R 1 groups are c 14 -C 18, R 3 is methyl or ethyl and R is methyl, ethyl, isopropyl, n-propyl, hydroxyethyl or hydroxypropyl. Cationic anti-settling stabilizers of formula 3-5 used in the invention are the mono-higher alkyl, mono-lower alkyl, glacio ethoxy-quaternary aimnonium compounds wherein 1 2 R is a long aliphatic group of 10-22 carbon atoms and R is alkyl or hydroxyalkyl group x and y are each positive numbers of at least 1 and the sum of x + y is 2-15 and X is a water-soluble salt-forming anion such as a halide, ie chloride, bromide, iodide; sulfate, nitrate, citrate, acetate, hydroxide, methosulfate and ethosulfate, phosphate or a similar inorganic or organic solubilizing group.

The carbon chain of the aliphatic group, which contains 10-22 carbon atoms, especially 12-20, preferably 12-18, and especially 16-18 carbon atoms, can be straight or branched or saturated or unsaturated 2. The R lower alkyl groups have 1-4 carbon atoms, for example methyl, ethyl, propyl and butyl, preferably one or two carbon atoms, especially methyl, and they may contain a hydroxy group.

Typical examples of cationic quaternary ammonium anti-sag stabilizers of formula 3 which are suitable for use in the agents of the invention include the following: coconut methyl diethoxylated (x + y = 2) ammonium chloride coconut methyl ethoxylated (x + y = 15) ammonium chloride Oleic acid methyl diethyl ethylated (x + y = 2) ammonium chloride oleic acid methyl diethyl ethoxylated (x + y = 15) ammonium chloride stearyl methyl diethyl ethylated (x + y = 2) ammonium chloride stearyl methyl ethoxylated (x + y = 15) ammonium chloride 10-yde methyl ethoxylated ethoxylate sag stabilizers of formula 4 which are used in the invention are the di-higher alkyl diethoxylated quaternary ammonium compounds wherein the R 1 symbols are independently a long aliphatic group having 10-22 carbon atoms, x and y are each positive numbers of at least 1 and the sum of x + y 2-15 is 35 and X is a water-soluble salt-forming anion, such as halide ie

8502120 Chloride, Bromide, Iodide, Sulfate, Nitrate, Citrate, Acetate, Hydroxide, Methosulfate, Ethosulfate, Phosphate or a similar inorganic or -organic-solubilizing group.

The R carbon chains of the aliphatic groups contain 10-22 carbon atoms, especially 12-20, preferably 12-18, and especially 16-18 carbon atoms, and can be straight or branched or saturated and unsaturated.

A specific example of a cationic quaternary ammonium anti-settling stabilizer of formula 4 suitable for use in the inventive agent is di-tallow diethoxylated (x + y = 4) ammonium chloride (Ethoquat 2T / 14).

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

In the compounds of formulas 1-4, the long carbon chains are obtained from long fatty acids, such as those derived from talc and soybean oil. The terms soy and talc, etc. as used herein refer to the origin from which the long fatty alkyl chains are derived. Mixtures of the quaternary ammonium compound anti-sag stabilizers can also be used.

The straight higher alkyl quaternary ammonium salts are readily biodegradable and are preferred.

While the applicant does not wish to commit to any particular theory of how the quaternary ammonium surfactants function and prevent the sagging of the suspended anionic phosphate detergent builder particles, the quaternary ammonium salts are believed to interact with the anionic phosphate detergent builder salts and the anionic phosphate coat with a cationic lipophilic skin making the phosphate more compatible with the nonionic surfactant, improving the contact between the phosphate and the nonionic surfactant and wettability of the dispersed phosphate solid particle surfaces by the nonionic surfactant is improved.

The improvement in the contact between the phosphate and the nonionic surfactant and the improved wettability of the phosphate particles dispersed by the nonionic surfactant increases the stability of the phosphate slurry whereby the suspended phosphate can more easily remain in suspension.

The increased physical stability is manifested by an increase in the yield stress of the agent, for example, from 65 to 260 dynes / cm2, and an increase in the apparent viscosity, from, for example, 2350 to 3250 (DVT, sp. 4, 60 rpm), compared to the same agent without the quaternary ammonium salt stabilizer.

As described above, the higher the yield stress, the higher the apparent low shear viscosity and the better the physical stability.

In addition to acting as a physical stabilizing agent, the higher alkyl quaternary ammonium salts have the additional advantage over other physical stabilizing agents that they are cationic in nature and compatible with the nonionic detergent component.

Only very small amounts of the quaternary ammonium salt stabilizer are required to achieve significant improvements in physical stability. Based on the total weight of the nonionic liquid surfactant, 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 most preferably about 0.5 to 1.5%.

Although the ureas and the quaternary ammonium salts are effective in their physical stabilization activity, other known physical stabilizers can be added to the agent such as, for example, an acidic organic phosphorus compound with an acidic POH group, such as a partial ester of phosphorous acid and an alkanol and / or or an ammonium salt of a fatty acid.

30 NON-IONIC SURFACE-ACTIVE SUBSTANCE

The non-ionic synthetic organic detergents used in the practice of the invention can be selected from a range of known compounds.

As is well known, the nonionic synthetic organic detergents are characterized by the presence of an organic 8602120-18 hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature). Virtually any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to nitrogen can be condensed with ethylene oxide or 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 balance between hydrophobic and hydrophilic groups. Typical suitable nonionic surfactants are those described in U.S. Patent Nos. 4316812 and 3630929.

Typically, the nonionic detergents are poly-lower alkoxylated lipophiles in which the desired hydrophilic-lipophilic balance is obtained by adding a hydrophilic poly-lower alkoxy group to a lipophilic moiety. The preferred group of the nonionic detergent used is the poly-lower alkoxylated higher alkanol wherein the alkanol contains 9-18 carbon atoms, the number of moles of lower alkylene oxide (or 2 or 3 carbon atoms) being 3-12. It is preferred in such materials to use those in which the higher alkanol and higher fatty alcohol is of 9-11 or 12-15 carbon atoms and contains 5-8 or 5-9 low sea alkoxy groups per mole. Preferably, the lower alkoxy group is ethoxy, but in some cases it may advantageously be mixed with propoxy, if the latter is present, often in an unsuitable amount (less than 50%).

Examples of such compounds are those wherein the alkanol contains 12-15 carbon atoms and with about 7 ethylene oxide groups per mole, for example Neodol 25-7 and Neodol 23-6.5 products from Shell Chemical Company Inc. The first is a condensation product of a mixture of higher fatty alcohols having an average of 12-15 carbon atoms, with about 7 moles of ethylene oxide, the latter being a corresponding mixture where the carbon content of the higher fatty alcohol is 12-13 and the number of ethylene oxide groups present is about 6 on average , 5. The higher alcohols are primary alkanols.

35 Other examples of such detergents include 8602120 * ί - 19 -

Tergitol 15-S-7 and Tergitol 15-S-9, both straight secondary alcohol ethoxylates from Union Carbide Corp.

The former is a mixed ethoxylation product of 11-15 carbon atoms with a straight secondary alkanol containing 7 moles of ethylene oxide, while the latter is a similar product but with 9 moles of converted ethylene oxide.

Also used as a component of the nonionic detergent are higher molecular weight nonionics such as Neodol 45-11 which is similar ethylene oxide condensation products of higher fatty alcohols wherein the higher fatty alcohol contains 14-15 carbon atoms and the number of ethylene oxide groups per mole is about 11 is.

Such products are also made by Shell Chemical Company.

Other useful nonionics are represented by the commercially well-known group of nonionics sold under the trademark Plurafac. The Piturafacs are the reaction product of a higher straight alcohol and a mixture of ethylene-propylene oxide containing a mixed chain of ethylene oxide and propylene oxide with hydroxy terminal groups.

Examples include products such as (A) C 1 -C 2 vet fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide (B) C 2 -C 2 fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide (C) C -C. Fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of 10 µl of ethylene oxide, and (D) a product which is a 1: 1 mixture of product B and C.

Another group of liquid nonionics are commercially available from Shell Chemical Company Inc. under the trademark Dobanol: Dobanol 91-5 is a thoxylated C 2 -C 6 fatty alcohol with an average of 5 moles of ethylene oxide and Dobanol 25-7 is an ethoxylated C 2 -C 6 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

In the preferred poly-lower alkoxylated higher alkanols, the number of lower alkoxy groups to achieve the best balance of hydrophilic and lipophilic units will be about 40 to 100% of the number of carbon atoms in the higher alcohol, preferably 40-60% thereof, and the nonionic detergent will preferably contain at least 50% of such a preferred poly-lower alkoxy higher alkanol.

5502120 - 20 -

Higher molecular alkanols and various other normally solid nonionic detergents and surfactants may contribute to the gelation of the liquid detergent and will therefore preferably be omitted from or limited in amount in the present agents, although minor amounts thereof may be used because of their cleaning properties etc.

In both preferred and less preferred nonionic detergent compositions, the alkyl groups contained therein are generally straight although branching can be tolerated, such as at a carbon adjacent to or two carbon atoms away from the terminal carbon of the straight chain and apart from the ethoxy chain, if this branched alkyl does not exceed 3 carbon atoms.

Normally, the amount of carbon atoms in such a branched configuration will seldom exceed 20% of the total carbon atom content of the alkyl. Likewise, while straight-chain alkyls terminated in the ethylene oxide chain are highly preferred and considered to provide the best combination of scrubbing power, biodegradability, and non-gelling properties, intermediate or secondary combinations of the ethylene oxide in the chain take place. This usually involves only a minor amount of such alkyls, generally less than 20%, but as in the case of the listed Tergitols, it may be greater.

When propylene oxide is also present in the lower alkylene oxide chain, it is usually less than 20% thereof and preferably less than 10% thereof.

When using larger amounts of non-terminal alkoxylated alkanols, propylene oxide-containing poly-lower alkoxylated alkanols, and less hydrophilic-hypophilically balanced nonionic detergents than those mentioned above, and when using other nonionic detergents in place of the preferred agents as mentioned herein the product obtained may not have as good washing power, stability, viscosity and non-gelling properties as the preferred agents, but by using the viscosity improving and gel inhibiting compounds of the invention, the properties of the detergents based on such nonionic compounds are improved. In some cases, such as when using a higher molecular poly-lower acoxylated higher alkanol, usually for its washing power, the amount thereof will be controlled or limited according to the results of routine tests, to achieve the desired washing power and still have a product that does not gel and has the desired viscosity.

It has also been found that it is rarely necessary to use the higher molecular weight nonionic compounds because of their washing power since the preferred nonionic compounds described herein are excellent detergents and additionally allow the viscosity desired in the liquid detergent to be without gelation at lower temperatures is achieved.

Another useful group of nonionic surfactants are the Surfactant T series of nonionics available from British Petroleum. The Surfactant T nonionic compounds are obtained by ethoxylation of secondary fatty alcohols with a narrow ethylene oxide distribution. The Surfactant T 5 has an average of 5 moles of ethylene oxide; Surfactant T 7 an average of 7 moles of ethylene oxide; Surfactant T 9 an average of 9 moles of ethylene oxide and Surfactant T 12 an average of 12 moles of ethylene oxide per mole of secondary fatty alcohol.

In the agents of this invention, the preferred nonionic surfactants include the C12 -C15 secondary fatty alcohols with relatively narrow ethylene oxide contents, in the range of about 7-9 moles, and the C8 -C18 fatty alcohols ethoxylated with about 5- 6 moles of ethylene oxide.

Mixtures of 2 or more of the liquid non-ionic surfactants are useful, and in some cases advantages can be achieved with any of these mixtures.

2H-PROVEN NON-IONIC SURFACE-ACTIVE SUBSTANCE

The viscosity and properties of the liquid detergents can be improved by including in the detergent an effective amount of an acid terminated liquid nonionic surfactant 8ac 2120-22. The acid-terminated nonionic surfactant consists of a nonionic surfactant that is modified to convert a free hydroxyl group thereof to a unit with a free carboxyl group, such as an ester or a partial ester of a non-ionic surfactant. ionic surfactant and a polycarboxylic acid or anhydride.

As disclosed in copending U.S. Patent Application No. 597,948 filed April 9, 1984, the disclosure of which is incorporated by reference, the free carboxyl group of modified nonionic surfactants, which may be generally characterized as polyether carboxylic acids, function to maintain the temperature at which the liquid non-ionic compound with water to form a gel.

The addition of the acid-terminated non-ionic surfactants to the liquid non-ionic surfactant 15 promotes the dosability of the agent, ie, the pourability, and lowers the temperatures at which the liquid non-ionic surfactants in water have a gel without a decrease in stability to sag. The acid-terminated nonionic surfactant reacts in the washing water with the alkalinity of the dispersed builder salt phase of the detergent and acts as an effective anionic surfactant.

Specific examples include the half esters of product A with succinic anhydride, the ester or half ester of Dobanol 25-7 with succinic anhydride, and the ester or half ester of Dobanol 91-5 with succinic anhydride. Instead of succinic anhydride, other polycarboxylic acids or anhydrides can be used such as maleic acid, maleic anhydride, glutaric acid, malonic acid, phthalic acid, phthalic anhydride, citric acid e. d.

The acid-terminated nonionic surfactants can be prepared as follows:

Acid-terminated product A. 400 g of product A nonionic surfactant which is a C 1 -C 5 alkanol, alkoxylated to introduce 6 ethylene oxide and 3 propylene oxide units per alcohol unit, is mixed with 32 g succinic anhydride and for 35 Heated at 100 ° C for 7 hours. The mixture is cooled and filtered to remove unreacted succinic acid material. Infrared analysis indicates that about half of the nonionic surfactant has been converted to its acidic half-ester.

Acid-terminated Dobanol 25-7. 522 g Dobanol 25-7 non-ionic surfactant, which is the product of the ethoxylation of a Cl2-Cl5 fatty alcohol, and contains about 7 ethylene oxide units per molecule of alkanol, is mixed with 100 g succinic anhydride and 0.1 g pyridine (which acts as an esterification catalyst) and heated at 260 ° C for 2 hours, cooled and filtered to remove unreacted succinic acid material. Infrared analysis shows that virtually all free hydroxyl groups of the surfactant have been converted.

Acid-terminated Dobanol 91-5. 1000 g of Dobanol 91-5 non-ionic surfactant which is the product of the ethoxylation of a 15 C 8 -C 12 alkanol, and contains about 5 ethylene oxide units per molecule of alkanol, is mixed with 265 g of succinic anhydride and 0, 1 g of pyridine catalyst and heated at 260 ° C for 2 hours, cooled and filtered to remove unconverted succinic acid material.

Infrared analysis shows that almost all free hydroxyl-20 groups of the surfactant have been converted.

Other esterification catalysts, such as an alkali metal alkoxide (e.g. sodium methoxide) can be used in place of or mixed with the pyridine.

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

BUILDER SALTS

The liquid non-aqueous non-ionic surfactant used in the compositions of the invention contains dispersed and suspended fine particles of inorganic and / or organic detergent builder salts. The detergent compositions of the invention include water-soluble and / or water-insoluble detergent builder salts. Water-soluble inorganic alkaline builder salts that can be used only with the detergent compound or mixed with other builders S5Ö2120 - 24 - uses alkali metal carbonates, bicarbonates, borates, phosphates, polyphosphates and silicates (ammonium or substituted ammonium salts are also useful). Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium equicarbonate, sodium mono- and diortho-phosphate and potassium bicarbonate.

Tripolyphosphate (TPP) is particularly preferred.

Since the agents of the invention are generally highly concentrated and are therefore useful at relatively low dosages, it is desirable to supplement any phosphate builder (such as sodium tripolyphosphate) with an auxiliary builder, such as a polylastic carboxylic acid or a polymeric carboxylic acid with high calcium binding capacity. prevent scaling that would otherwise be formed by formation of an insoluble calcium phosphate.

Suitable lower polycarboxylic acids include alkali metal salts of lower polycarboxylic acids, preferably the sodium and potassium salts.

Suitable lower polycarboxylic acids have 2-4 carboxylic acid groups.

The preferred sodium and potassium lower polycarboxylic acid salts are the citric acid and tartaric acid salts.

Most preferred are the sodium citric acid salts, especially trisodium citrate. The monosodium and disodium citrates are also useful. The monosodium and di-sodium tartaric acid salts are also useful. The alkali metal lower polycarboxylic acid salts are particularly good builder salts; because of their high calcium and magnesium binding capacity, they prevent scale formation which would otherwise result from the formation of insoluble calcium and magnesium salts.

Other organic builders are polymers and copolymers of polyacrylic acid and polymaleic anhydride and their alkali metal salts. More particularly, such builder salts may consist of a copolymer which is the reaction product of about equal moles of methacrylic acid and maleic anhydride, which has been completely neutralized to form its sodium salt. The builder is commercially available under the trade name Sokalan CP5. This builder prevents added scale formation even in smaller amounts.

9 i 9 0 V -, «. *» Ie »· '» · - 25 -

Examples of organic alkaline sequential builder salts that are useful with the builder builder salts or mixed with other organic or inorganic builders are alkali metal; ammonium or substituted ammonium aminopolycarboxylates, eg sodium and potassium ethylene diamine tetraacetate (EDTA), sodium and potassium nitrile triacetates (NTA), and triethanol ammonium N- (2-hydroxyethyl) nitrile diacetates. Mixed salts of these aminopolycarboxylates are also suitable.

Other suitable organic type builders include carboxy methyl methyl succinates, carbonates and glycolates. The polyacetal carboxylates are of special value. The polyacetal carboxylates and their use in detergents are described in the pending application of applicant No. (IR 220/221) and U.S. Patent Nos.

4144226, 4315092 and 4146495.

The alkali metal silicates are useful builder salts that adjust or control pH 15 and make the agent anti-corrosion against washing machine parts. Sodium silicates with a Na 2 / SiO 2 ratio of 1.6 / 1 to 1 / 3.2, especially 1/2 to 1 / 2.8, are preferred. Potassium silicates with the same ratio can also be used.

Other typical suitable builders include, for example, those disclosed in U.S. Pat. Nos. 4316812, 4264466, and 3630929. The inorganic builder salts are useful with the nonionic surfactant surfactant and mixed with other organic builder salts or with inorganic builder salts.

Water-insoluble crystalline amorphous aluminosilicate zeolites are useful. Zeolites generally have the formula (M_0) * (A-0) * (SiO,> * wH, 0 2 X 2 3 y 2 z 2 where x is 1, y is 0.8-1.2 and preferably 1, z is 1.5-3.5 or higher and preferably 2-3 and w is 0-9, preferably 2.5-6, and M is preferably sodium A typical zeolite is type A or a similar structure with type 4A being particularly preferred The preferred aluminosilicates have a calcium ion exchange capacity of about 200 milliequivalents per gram or more, for example 400 meq / g.

Various crystalline zeolites (i.e., aluminosilicates) which have been used are described in British Patent 8602120-26-1504168, U.S. Patent 4409136, and Canadian Patent 1072835 and 1087477, all of which are incorporated herein by reference for such descriptions.

An example of amorphous zeolites useful herein can be found in Belgian Patent 835351 and this patent is also incorporated herein by reference.

Other materials such as clay products, especially of the water-insoluble types, may be useful adjuvants in the products of the invention. Bentonite is particularly useful. This material 10 is primarily montmorillonite which is a hydrated aluminum silicate in which about 1/6 of the aluminum atoms can be replaced by magnesium atoms and with which varying amounts of hydrogen, sodium, potassium, calcium etc. can be loosely combined.

The bentonite in its more purified form (i.e., free from any 15 'grit, sand, etc.) suitable for detergents contains at least 50% montmorillonite and thus its cation exchange capacity is at least about 50-75 meq per 100 g bentonite.

Particularly preferred ventonites are the Wyoming or Western Ü.S. bentonites sold as Thixo-jels 1,2,3 and 4 by 20 Georgia Koalin Co. These bentonites are known to soften textile materials, as described in British Patents 401412 and 461221.

VISCOSITY DETERMINATING AND ANTI-RESOURCES

Incorporating an effective amount of a viscosity-determining and gel-inhibiting agent for the non-ionic surfactant into the detergent improves the storage properties of the agent. The viscosity determining and gel inhibitors have the effect of lowering the temperature at which the nonionic surfactant will form a gel upon addition to water.

Such viscosity controlling and gel inhibiting agents may be, for example, a lower alkanol, eg ethyl alcohol (see US patent 3953380), hexylene glycol, polyethylene glycol eg polyethylene glycol having a molecular weight of about 400 (PEG 400) and low molecular weight alkylene oxide lower monoalkyl ether amphiphilic compounds.

3602120 - 27 -

Preferred viscosity determining and gel inhibiting compounds are the low molecular weight amphiphilic compounds. The amphiphilic compounds function as viscosity-determining and gel-inhibiting agents for the nonionic surfactant and significantly improve the storage properties of the agent. The amphiphilic compounds can be considered analogous in chemical structure to the ethoxylated and / or propoxylated fatty alcohol liquid nonionic surfactants but they have relatively short hydrocarbon chain lengths (C2 ~ Cg) and low ethylene oxide content (about 2 to 6 ethylene -10 oxide groups per molecule).

Suitable amphiphilic compounds are represented by the following general formula R30 (CH.CH2 O) H λ l n wherein R3 is a C2 -C8 alkyl group and n is an average number of about 1-6.

The compounds are specifically lower (C 1 -C 2) alkylene glycol mono lower (C 1 -C 2) alkyl ethers.

More specifically, the compounds are mono di- or tri lower (C2-C3) alkylene glycol mono lower alkyl ethers.

Specific examples of suitable amphiphilic compounds include ethylene glycol monoethyl ether (C ^ H ^ -O-CH ^ CH ^ OH), diethylene glycol monobutyl ether (CH-O- (CE.CHO) E), 4 yz ώ 2 tetraethylene glycol monobutyl ether (C ^ H ^ -0- (CH2CH2Q) ^ H) and dipropylene glycol monomethyl ether (CH3-0- (CHCH2O) 2H.

ch3

Diethylene glycol monobutyl ether is particularly preferred.

Incorporation into the low molecular weight lower alkylene glycol monoalkyl ethers lowers the viscosity of the agent so that it is more pourable, improves sag stability, and improves dispersibility of the agent when added to hot or cold water.

The agents of the invention have improved viscosity and stability properties and remain at temperatures of about 5 ° C

8602120 - 28 - or lower are stable and pivotable.

The ureas also act as a stabilizing agent against sagging and improve the dispersibility of the suspension of phosphate detergent builder particles by gel formation of the suspended particles when cold water is added to the agent in the dispenser and / or when the agent is added to the water. .

In an embodiment of this invention, an additional stabilizing agent which is an alkanol ester of phosphoric acid or an aluminum salt of a high fatty acid is added to the agent.

An improvement in the stability of the agent can be achieved by including a small effective amount of an acidic organic phosphorus compound with acidic POH groups, such as a partial ester of phosphorous acid in alkanol.

As disclosed in Pending U.S. Patent Application No. 597948 filed April 9, 1984, the disclosure of which is incorporated herein by reference, the acidic organic phosphorus compounds having an acidic POH group cannot improve the stability of the builders suspension in the non-aqueous liquid improve ionic surfactant 20.

The acidic organic phosphorus compound can be, for example, a partial ester of phosphoric acid and an alcohol, such as an alkanol which has a lipophilic character with, for example, more than 5 carbon atoms, for example 8-20 carbon atoms.

A specific example is a partial ester of phosphoric acid and an alkanol (Empiphos 5632 from Marchonj; it is composed of about 35% monoester and 65% diester.

The incorporation of particularly small amounts of the acidic organic phosphorus compound gives the slurry stability to settle but it remains pourable, while at the lower concentrations of the stabilizer, for example below about 1%, its plastic viscosity will generally decrease.

Improvements in the stability and anti-sag properties of the agent can also be achieved by adding a small effective amount of an aluminum salt of a higher fatty acid to the agent.

3502120 -29 r

The aluminum salt stabilizers are the subject of pending U.S. Application No. 725455 filed April 22, 1985, the disclosure of which is incorporated herein by reference.

The preferred higher aliphatic fatty acids have about 8 to about 22 carbon atoms, preferably about 10 to 20 carbon atoms, especially about 12-18 carbon atoms. The aliphatic group can be saturated or unsaturated and straight or branched. As with the non-ionic surfactants, mixtures of fatty acids can also be used, such as those derived from natural sources, such as tallow fatty acid, coconut fatty acid, etc.

Examples of the fatty acids from which the aluminum salt stabilizers can be formed include decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicosanoic acid, tallow fatty acid, coconut fatty acid, mixtures of these acids, etc.

The aluminum salts of these acids are widely available commercially and are preferably used in the triacid form, for example aluminum stearate as aluminum tristearate Al (C ^ EL ^ COO) ^ · The mono acid salts, for example aluminum monostearate Al (OH) ^ (C ^ H ^ COO And diacid salts, for example, aluminum distearate Al (OH) (C 1 -R 3 COO) 2 and mixtures of 2 or 3 of the mono, di- and tri-acid amine salts are also useful. Most preferably, however, the triacid aluminum salt accounts for at least 30%, preferably at least 50%, especially preferably at least 80%, of the total amount of the aluminum fat acid salt.

The aluminum salts mentioned above are commercially available and can be easily produced by, for example, saponifying the fatty acid such as animal fat, stearic acid, etc., followed by treatment of the obtained soap with alum, alumina, etc.

Only very small amounts of the aluminum salt stabilizer are required to achieve an improvement in physical stability.

8602120 - 30 -

Bleaching agents

The bleaches are generally suitably classified as chlorine and oxygen bleaches.

Chlorine bleaches are typified by sodium hypochlorite (NaOCl), potassium dichloroisocyanylate (59% available chlorine) and trichloroisocyanyl acid (95% available chlorine). Oxygen bleaches are preferred and these are represented by per compounds which release in solution in hydrogen peroxide. Preferred examples include sodium and potassium perborates, percarbonates and perphosphates and potassium monopersulfate.

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

The peracid compound is preferably mixed with an activator used therefor. Suitable activators which can lower the effective operating temperature of the peroxide bleach are described, for example, in U.S. Patent 4,246,466 or in column 1 of U.S. Patent 4,430,244, the latter disclosure of which herein is included as a reference.

Polyacetylated compounds are preferred activators; of these, compounds such as tetraacetylethylenediamine ("TEAD") and pentaacetyl glucose are particularly preferred.

Other useful activators include, for example, acetylsalicylic acid derivatives, ethylidene benzoate acetate and salts thereof, ethylidene carboxylate acetate and sweetening thereof, alkyl and alkenyl succinic anhydride, tetraacetyl glycouryl (TAGU) and the derivatives thereof. Other useful classes of activators have been described as in U.S. Patents 4111826, 4422950, and 3661789.

The bleach activator usually interacts with the peroxygen compound to form the peroxyacid bleach in the wash water. It is preferable to include a high complexing power sequestrant to counteract any undesired reaction between such peroxyacid and hydrogen peroxide in the wash solution in the presence of metal ions. Suitable sequestrants for this purpose include the sodium salts of nitrilotriacetic acid (NTA), ethylene-35 diametetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DETPA), diethylene triamine pentamethylene phosphonic acid (DTPMP) sold under 360.2 1 20 - 31 - ....

trade name Dequest 2066; and ethylenediaminetetramethylene phosphonic acid (EDITEMPA). The sequestrant can be used alone or in mixture.

In order to avoid loss of peroxide bleach, for example sodium 5-perborate, which leads to an enzyme-induced decomposition, such as by catalase enzyme, an enzyme inhibitor compound may additionally be added to the agents, ie a compound capable of enzyme-induced decomposition of the peroxide bleach. to brake.

Suitable inhibitory compounds are described in U.S. Patent 3606990, the relevant description of which is incorporated herein by reference.

As a special inhibitor compound, mention can be made of hydroxylamine sulfate and other water-soluble hydroxylamine proteins. In preferred non-aqueous agents of this invention, suitable amounts of the hydroxylamine salt inhibitors may be as low as 0.01 to 0.4%.

Generally, however, suitable amounts of the enzyme inhibitors are up to about 15%, for example, 0.1-10 weight percent of the agent.

In addition to the detergent builders, various other detergent additives or auxiliaries may be present in the detergent product to give it additional desirable properties, whether of a functional or aesthetic nature. Thus, minor amounts of liquid suspending or anti-graying agents, for example, polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose and hydroxypropylmethyl cellulose, can be included in the agents. A preferred anti-graying agent is sodium carboxymethyl cellulose with a 2: 1 ratio of CM / MC sold under the trade name Relatin DM 4050.

It is also possible to include in the urea compound-containing agent small amounts of an alkyl or alkylene succinic anhydride such as octenyl succinic anhydride which functions as a viscosity controlling and anti-gelling agent.

The octenyl succinic anhydride can be added in amounts such as 0.5-10%, preferably 1-6%, most preferably 1-4% by weight of the agent.

Small amounts of Alcosperse D107, which is sodium polyacrylate and which acts as an anti-scaling agent, can also be included in the quaternary ammonium-containing agent 8602125-32. The Alcosper.se D107 can be included in amounts such as 0.5-8%, preferably 2-6% and most preferably 3-5% by weight of the agent.

5 Optical brighteners for cotton, polyamide and polyester fabrics can be used. Suitable optical brighteners include stilbene, triazole and benzidine sulfone compositions, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzene sulfone, etc., but most preferred are stilbene and triazole 10 compositions. A preferred whitening agent is Stilbene Brightener N4 which is a dianiline dimorpholine stilbene polysulfonate.

Enzymes, preferably proteolytic enzymes such as subtilisin and bromelin, papain, trypsin and pepsin, as well as amylase type enzymes, lipase type enzymes and mixtures thereof can be added. Pre-kerosene enzymes include protease suspension, esperase suspension and amylase.

The preferred enzyme is Esperase SL8 which is a proteolytic enzyme. Anti-foaming agents, for example, silicone compounds such as Silicane L 7604, which is a silicone, can be added in small effective amounts.

Bactericides, for example, tetrachlorosalicylanilide and hexachlorophene, fungicides, dyes, pigments (water soluble), preservatives, ultraviolet absorbers, anti-yellowing agents such as sodium carboxymethyl cellulose, pH modifying agents and pH buffers, colourfast bleaches, perfumes and dyes blue and blue agents such as blue agents. .

The agent may also contain small amounts of pigments to improve discoloration such as TiO2, white pigment. The TiO 2 can be added in amounts such as 0.1-4%, preferably 0.1-2% and most preferably 0.1-1%.

The agent may also contain small amounts of Benton 27 which is an organic derivative of hydrous magnesium aluminum silicate.

The Benton 27 can be used in amounts such as 0.2-3%, preferably 0.5-2%, and most preferably about 1 weight percent.

The agent may also contain an inorganic insoluble thickening agent or dispersant with a very high specific surface such as 6802120 - 33 - finely divided silica with extremely fine particle size (eg 5-100 micrometer diameter as sold under the name Aerosil) or the other high voluminous inorganic carrier materials described in U.S. Patent 3,630,929, in amounts of. 0.1-10%, for example, 1-5%. However, it is preferred that agents which form peroxyacids in the wash bath (for example, agents containing peroxygen compound and activator therefor) are substantially free of such compounds and of other silicates? there is. found, for example, that silica silicates promote the undesirable decomposition of the peroxyacid.

In an embodiment of the invention, the stability of the builder salts in the agent during storage and dispersibility of the agent in water by grinding and reducing the particle size of the solid builders to less than 100 micrometers, preferably less than 40 micrometers and most preferably less than 10 µm improved.

The solid builders, for example sodium tripolyphosphate (TPP), are generally added in particle sizes of about 100, 200 and 400 microns. The nonionic liquid detergent phase can be mixed with the solid detergent actives before or after grinding operation.

In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid components is subjected to a friction type mill in which the particle sizes of the solid ingredients are less than about 10 microns, for example, to an average size of 2-10 micrometers or even lower (e.g. 1 micrometer) are ground. Preferably, less than about 10%, especially less than about 5%, of all the suspended particles have a particle size greater than 10 microns. Agents whose dispersed particles are too small in size have improved stability against separation or settling on storage. The addition of the acid-terminated nonionic surfactant compound allows the yield stress of such dispersions to be reduced and the dispersibility of the dispersions to be promoted without a corresponding reduction in dispersion stabilization relative to settling.

8802120 - 34 -

In the grinding step, it is preferred that the amount of the solid ingredients is so high (e.g., at least about 40%, such as about 50%) that the solids are in contact with each other and therefore are not shielded from each other by the nonionic surface -5 active liquid. After the grinding step, any remaining liquid non-ionic surfactant can be added to the ground mixture. Mills using grinding balls (ball mills) or similar movable grinding elements have given very good results. Thus, one can use a laboratory batch operated grinder with steatite grinding balls with a diameter of 8 mm. For large-scale work, a continuously operating mill can be used in which 1mm or 1.6mm diameter grinding balls operate in a very small gap between a stator and a rotor, which rotate at a relatively high speed (e.g., a CoBall mill); when such a mill is used, it is desirable to first pass the mixture of nonionic surfactant and solid particles through a mill that does not effect such fine grinding (eg, a colloid mill) to reduce the particle size to less than 100 micrometers (eg, about 40 microns) prior to the grinding step to an average particle diameter below about 10 microns in the continuous ball mill. In the preferred high performance liquid detergents of the invention, typical amounts (percentage based on the total weight of the agent, unless otherwise stated) of the ingredients are as follows: Liquid nonionic surfactant in the range of about 10- 60 or 70, such as 20-50 or 60%, for example about 30-40 or 50%.

Acid-terminated nonionic surfactant in an amount in the range of about 0-20, such as 1 or 3 to 15%, for example, about 4-10.

Washing active builder, such as sodium tripolyphosphate (TPP) in the range of about 10-60, such as 15-50%, for example 15 or 25-35.

Alkali metal silicate in the range of about 0-30 such as 5-25%, for example about 10-20.

3602120 - 35 -

Copolymer of polyacrylates and polymalinic anhydride and α-1-limetal salt, e.g. Sokalan CP5, anti-scaling agent in the range of about 0-10, such as 2-8%, e.g. about 3-5.

Alkylene glycol monoalkyl ether anti-gelling agent can be used with the urea-5 additive in an amount in the range of about 5-30, such as 5-20%, e.g. 5-15%.

The alkylene glycol viscosity controlling and gel inhibiting agent can be used with the quaternary ammonium additive in an amount in the range of about 5-30, such as 5-25%, for example 15-25%.

The preferred viscosity controlling and gel inhibiting agents are the alkylene glycol monoalkyl ethers. The urea or quaternary ammonium salt anti-sag stabilizer in the range of 0.1 to 5, preferably 0.2-2.0, and most preferably about 0.5 to 1.5%.

It is an essential feature of the invention that at least one of the urea compounds or at least one of the quaternary ammonium salts is included in the detergent composition.

Phosphoric acid alkanol ester stabilizer in the range of 0-2, or 0.1-2.0 such as 0.10-1.0%.

Aluminum salt of fatty acid stabilizer in the range * from about 0-5.0, such as 0.5-2.0%, for example, about 0.1-1.0%.

Bleach in the range of about 0-30, such as 2-20, e.g. about 5-15%.

Bleach activator in the range of about 0-15, such as 1-8 or 10, for example about 1-8 or 2-6%.

Bleach sequestrant, for example, Dequest 2066 in the range of about 0-3.0, preferably 0.5-2.0%, e.g., about 0.75-1.25%.

Anti-curing agent, for example Relatin DM 4050, in the range of about 0 to 4.0 or 5.0, preferably 0.5-3.0 or 4.0%, for example 1.0-3.0 or 0.5- 1.5%.

Optical brighteners in the range of about 0-2.0, preferably 0.05 or 0.25 to 1.0%, for example, 0.15 or 0.25 to 0.75%.

Enzymes in the range of about 0 to 3.0, preferably 0.5-2.0%, for example 0.75-1.25%.

3SÖ212Ö - 36 -

Perfume in the range of about 0 to 3.0, preferably 0.10 or 0.25 to 1.25%, for example 0.25 or 0.75 to 1.0%.

Color pigment in the range of about 0.1-4.0, preferably 0.1-2.0, and most preferably 0.1-1.0%.

Dyes in the range of about 0-0.10, preferably 0.0025-0.050, for example 0.0025-0.0100%.

Several of the aforementioned additives can be optionally added to achieve the desired function of the added material.

The urea anti-settling stabilizer is preferably used with at least the alkylene glycol monoether or the acid terminated nonionic surfactant viscosity control and anti-gel agents. In some cases, advantages can be achieved by using both the alkylene glycol monoethers and the acid-terminated nonionic surfactants.

Mixtures of the acid-terminated nonionic surfactant and the viscosity controlling and gel inhibiting agents, for example, the alkylene glycol alkyl ether anti-gelling agents, are useful and in some cases advantages can be achieved by using only such mixtures, or by adding to the mixture of the anti-sag stabilizer.

When selecting the additives, they are selected to be compatible with the main detergent ingredients.

In this application, as noted above, all amounts and percentages by weight are of the entire laundry composition or detergent unless otherwise indicated.

The concentrated non-aqueous nonionic liquid detergent of the invention is readily dispersed in the water of the washing machine.

The liquid nonionic detergent compositions of the invention are preferably non-aqueous, for example, they are substantially anhydrous. While minor amounts of water can be tolerated, it is preferred that the detergents contain less than 3%, preferably less than 2%, and most preferably less than 1%.

35 Normally used household washing machines use 8602120 - 37 - 200-250 grams of powdered detergent to wash a complete batch of laundry.

According to the present invention, only 100 cc or 78 grams of the concentrated liquid nonionic detergent is required.

In the embodiment using the urea compound as an additive, the detergent composition of the invention is typically formulated as follows:

Weight percent

Non-ionic surfactant detergent 30-40 10 Acid-terminated surfactant 0-20

Phosphate detergent builder salt 10-60

Anti-tarnishing agent 0-10

Alkylene glycol monoalkyl ether anti-yellowing agent 5-15 urea compound 0.2 - 2.0 15 Anti-graying agent 0-4.0

Alkali metal perborate bleach 5-15

Bleach Activator (TAED) 1.0 - 8.0

Bleach sequestrant 0-3.0

Optical whitener 0.05 - 0.75 20 Enzymes 0.75 - 1.25

Perfume 0.1-1.0

In the embodiment with the quaternary ammonium compound as an additive, the detergent composition of the invention is typically formulated as follows: 25 weight percent

Non-ionic surfactant detergent or mixtures thereof 30 - 50

Acid-terminated surfactant 0-20

Phosphate washative builder salt 15-35 30 Copolymer of polyacrylate and polymaleic anhydrous Me alkali metal salt anti-scaling agent (Sokalan CP-5) 0 - 10

Alkylene glycol viscosity control and gel inhibitor 10 - 25 3502 120 - 38 -

Weight percent

Quaternary ammonium salt anti-gel stabilizer 0.2-2.0

Anti-graying agent 0-5.0 5 Alkali metal perborate bleach 3-15

Bleach Activator (TAED) 1.0-6.0

Sequestrant 0-3.0

Optical whitener (Stilbene whitener N4) 0-2.0

Enzymes (Protease-Esperase SL8) 0-3.0 10 Perfume 0-3.0

The invention is further illustrated by the following examples.

UREA COMPOUND ADDITIVES EXAMPLE I

A concentrated non-aqueous liquid non-ionic surfactant detergent is formulated from the following ingredients in the amounts indicated.

Weight percent

Nonionic surfactant 37.7 20 Acid terminated Dobanol 91-5 reaction product with succinic anhydride 5.0

Sodium tripolyphosphate (TPP) 30

Diethylene glycol monobutyl ether anti-gelling agent 10

Urea 1.0 25 Sodium perborate monohydrate bleach 9.0

Tetracetylethylenediamine (TAED) bleach activator 4.5 (1)

Anti-graying agent (Relatin DM 4096) 1.0

Optical whitener 0.2

Perfume 0.6 30 Enzyme (which is Esperase) 1.0 ^ CMC / MC 2: 1 mixture of sodium carboxymethyl cellulose and hydroxy methyl cellulose.

The addition of 1% urea appears to increase the yield stress of the mixture.

8802120 - 39 -

The mixture is ground for 1.0 hour to reduce the particle size of the suspended builder salts to less than 1.0 micron. The detergent composition appears stable and unreadable on storage and is readily dispersible in water.

EXAMPLE II

A concentrated non-aqueous liquid non-ionic surfactant detergent was formulated from the following ingredients in the amounts indicated.

Weight percent 10 Surfactant T7 18

Surfactant T9 18

Octenyl succinic anhydride ^ 2

Sodium tripolu phosphate (TPP) 29.5

Anti-tarnishing agent (Sokalan CP5) 4.0 15 Diethylene glycol monobutyl ether anti-gelling agent 10

Urea anti-sagging stabilizer 1.0

Sodium perborate monohydrate bleach 9

Tetraacetylethylenediamine (TAED) bleach 4.5

Sequestrant for bleach (Dequest 2066) 1.0 (2) 20 Anti-graying agent (Relatin DM 4096) 1.0

Optical brighteners (ATS-X) 0.2

Enzyme (which is a protease) 1.0

Perfume 0.6

TiO2 (pigment) 0.2 25 ^ Viscosity controlling and anti-gelling agent (2) CMC / MC 2: 1 mixture of sodium carboxymethyl cellulose and hydroxy methyl cellulose.

The addition of 1% urea appears to increase the yield stress of the mixture. The apparent viscosity of the mixture at 100 reciprocal 30 seconds is found to be 1.1 Pa.

The mixture is milled for 1 hour to reduce the particle size of the suspended builder salts to less than 10 micrometers. The detergent composition has been found to be stable and non-gelling 8602120 on storage and is readily dispersible in water.

- 40 -

The mixtures of Examples I and II can be milled without the builder salts and. suspended solid particles to the small particle size are prepared, but best results are obtained by grinding the mixture to reduce the particle size of the suspended solid particles.

The urea anti-sag stabilizer can also be used to improve the compatibility of the nonionic surfactant and the polyphosphate detergent builder salt in the powder detergents.

QUATERARY AMMONIUM COMPOUND AS ADDITIVE EXAMPLE III

A concentrated non-aqueous liquid non-ionic surfactant detergent was prepared from the following ingredients in the amounts indicated

Weight percent

Product D non-ionic surfactant 39

Acid-terminated Dobanol 91-5 reaction product with succinic anhydride 5.0 20 Sodium tripolyphosphate (TPP) 30

Diethylene glycol monobutyl ether anti-gelling agent 10

Quaternary ammonium salt 1.0

Sodium perborate monohydrate bleach 9.0

Tetraacetylethylenediamine (TAED) bleach activator 4.5 25 Stilbene whitener 0.5

Protease (Esperase) 1.0 ^ The quaternary amine salt anti-sag stabilizer used is Arosurf TA 100 (distearyl dimethyl ammonium chloride).

The addition of 1% of the quaternary ammonium salt has been found to increase the yield stress of the mixture from about 2 to about 6 Pa. The apparent viscosity of the mixture appears to have increased from 0.5 to 0.4 Pa.s.

The mixture is milled for about 1 hour to reduce the particle size of the suspended builder salts to less than 10 microns. The detergent formulation appears stable and non-gelling on storage and has high washing power.

EXAMPLE IV

A concentrated non-aqueous liquid non-ionic surfactant detergent is prepared from the following ingredients in the amounts indicated.

Weight percent

Surfactant T7 18.7 10 Surfactant T9 18.7

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

Sodium tripolyphosphate (TPP) 30

Diethylene glycol monobutyl ether anti-gelling agent 10 15 Quaternary ammonium salt ^ 1.0

Sodium perborate monohydrate bleach 9

Tetraacetylethylenediamine (TAED) bleach 4.5

Stilbene whitener. 0.5

Protease (Esperase} 1.0 (2) 20 Relatin DM 4096 (CMC / MC) 1.0

Perfume 0.6 ^ The quaternary amine salt anti-sag stabilizer is Ethoquat 2T14 (di-tallow diethoxylated (x + y = 4) ammonium chloride).

(2)

A 2: 1 mixture of sodium carboxymethyl cellulose and hydroxymethyl-25 cellulose.

The addition of 1% of the quaternary amine salt has been found to increase the yield stress of the mixture from about 3 to 10 Pa. The apparent viscosity of the mixture has been found to increase from about 0.5 to 0.4 Pa.s.

The mixture is milled for about 1 hour to reduce the particle size of the suspended builder salts to less than 10 micrometers. The mixed detergent appears stable and cannot be gelled on storage and has a high washing power.

S § 0 2 1 £ ύ - 42 -

EXAMPLE V

Concentrated non-aqueous liquid non-ionic surfactant detergents from the following ingredients were obtained in the amounts indicated.

A B

5 Plurafac RA50 '35 35

Plurafac B26 9.0 9.0

Sodium tripolyphosphate (TPP) 18 18

Polyethylene glycol (molecular weight 400) anti-gelling agent 20 20 10 Quaternary ammonium salt ^ 1.0

Sodium perborate monohydrate bleach 3.6 4.1

Tetraacetylethylenediamine (TEAD) bleach activator 4.5 5.0 (2)

Relatin DM 4096 (CMC / MC) anti-graying agent 3.0 3.0 15 EDTA sequestrant ^ 0.9 0.9

Benton 27 ^ 1.0 1.0

Alcosperse D107 ^ 4.0 4.0 100.0 100.0 1. Ethoquat 2214 is the di-talc diethoxy (x + y = 4) quaternary ammonium chloride.

2. A 2: 1 mixture of sodium carboxymethyl cellulose and hydroxy methyl cellulose.

3. Ethylenediamine tetraacetic acid. 4. Organic derivative of hydrous magnesium aluminum-silicate which functions as an anti-settling agent.

5. Alcosperse D107 is sodium polyacrylate and functions as an anti-scale agent.

The mixture was ground for about 15 minutes to reduce the particle size of the suspended builder salts to less than 10 µm. The detergent composition A of the invention is found to be stable and non-gelling on storage and has a high washing power.

$ 602 120 - 43 -

A comparison of the agent A of the invention with the anti-settling stabilizing quaternary ammonium salt with respect to the agent B without the quaternary ammonium salt gave the following results.

A B

Apparent viscosity (LVT, Sp.4, 60 rpm) 5 (m Pa.s) 3250 2350

Stability 48 hours: phase separation% 1% 7%

Yield stress: (Pa) 26 6.5

Plastic viscosity (m Pa.s) 400 510

The data obtained shows that the addition to the agent of as little as 1% quaternary ammonium salt as anti-settling stabilizer of the present invention significantly increases the stability of the agent, increases the apparent viscosity, increases the yield stress and increases the plastic viscosity decreases.

The mixtures of Examples III, IV and V can be prepared without grinding the builder salts and suspended solids to a smaller particle size, but the best results are obtained by grinding the mixture to reduce the particle size of the suspended solids.

In Examples I-V, the builder salts can be used as supplied or the builder salts and suspended solid particles can be ground or partially ground before mixing with the nonionic surfactant.

The grinding can be carried out either partially before mixing and the grinding completed after mixing or the entire grinding step can be carried out after mixing with the liquid surfactant.

The mixtures containing suspended builder and solid particles in sizes less than 10 microns are preferred.

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

8602120

Claims (15)

1. Tissue-treating detergent consisting of a suspension of insoluble inorganic detergent builder salt particles in a non-aqueous nonionic liquid surfactant and a urea compound or a cationic quaternary amine salt surfactant anti-sagging agent to enhance the stability of the suspension. Detergent according to claim 1, characterized in that the inorganic detergent builder salt comprises 10-60% of an alkali metal tripolyphosphate detergent builder salt. Detergent according to claim 1, characterized in that the anti-sagging agent is a urea compound. Detergent according to claim 1, characterized in that the cationic quaternary amine salt is at least one of the compounds represented by formulas 1,2, 3 and 4, wherein the R * symbols are independently 2 long aliphatic groups of 10-22 are carbon atoms, the R symbols are independently lower alkyl or hydroxyalkyl groups, x and y are each positive numbers of at least 1, the sum of x + y being 2-15 and X being a water-soluble salt-forming anion. Detergent according to claim 1, characterized in that the agent comprises at least one viscosity controlling and anti-gelling agent selected from the group consisting of acid-terminated non-ionic surfactants and alkylene glycols. Detergent according to claim 1, characterized in that it contains one or more detergent auxiliaries selected from the group consisting of anti-scaling agents, alkali metal silicate, bleaching agents, bleach activators, sequestering agents, anti-graying agents, optical brighteners, enzymes, perfume and colorant . A detergent according to claim 1, characterized in that it contains about 0.1 to about 5 weight percent, based on the total agent, of said urea or said quaternary ammonium salt anti-sag stabilizer selected from the group consisting of from mono-higher alkyl, tri-lower alkyl quaternary amine salt (formula 1), di-higher alkyl, di-lower alkyl, quaternary amine salt (formula 2), mono-higher alkyl, mono-lower alkyl, diethoxylated quaternary ammonium salt 8602120 * - c - 45 - (formula 3 and di-higher alkyl diethoxylated quaternary ammonium salt (formula 4). 8. Non-aqueous high performance, low and low temperature detergent composition which does not gel when mixed with cold water, which consists of at least one liquid nonionic surfactant in an amount of from about 10 to about 60 or 70 weight percent; at least one inorganic detergent builder salt suspended in the nonionic surfactant in an amount from about 10 to about 60 weight percent; an acid-10 terminated nonionic surfactant as a gel inhibitor. additive in an amount of 0 to 20% by weight? at least one alkylene glycol viscosity controlling and gel inhibiting additive in an amount of up to about 5-30 weight percent; and about 0.2-2.0 weight percent of a urea compound additive or a quaternary ammonium salt anti-sag stabilizer selected from the group consisting of a mono-higher alkyl, tri-lower alkyl quaternary ammonium salt (Formula I), di- ' higher alkyl: di-lower "alkyl, quaternary ammonium salt (formula 2), mono-higher alkyl, mono-lower alkyl, diethoxylated quaternary ammonium salt (formula 3) and di-higher alkyl, diethoxylated quaternary ammonium salt (formula 4). A detergent composition according to claim 8 containing about 2-20 weight percent of an acid-terminated nonionic surfactant as a gel-inhibiting additive. 10 Octenyl succinic anhydride in an amount of about 1-6 Sodium tripolyphosphate in an amount of about 25-35 Copolymer of polyacrylate and polymaleic anhydride sodium salt in an amount of about 3-5 15 Diethylene glycol monobutyl ether in an amount of about 5-15 Urea in an amount of about 0.5-1.5 Sodium perborate monohydrate bleach in an amount of about 5-15 Tetraacetylethylenediamine (TAED) bleach activator in an amount of about 2-6.0 Bleach sequestrant in an amount of about 0.75-1.25 Anti-graying agent in an amount of about 0.5-1.5 A non-aqueous liquid powerful detergent according to claim 8, 25 consisting of Wt% Non-ionic surfactant in an amount of about 20-50 Sodium tripolyphosphate (TPP) in an amount of about 15-50 Copolymer of polyacrylate and polymalic anhydride sodium salt in an amount of about 2-8 Diethylene glycol monoalkyl ether in an amount of about 5-20 35 Urea in an amount of about 0.2-2.0 3602120 i * r e - 46 - Wt% Sodium perborate monohydrate bleach in an amount of about 2-20 Tetraacetylethylenediamine (TEAD) in an amount of about 1-10 A non-aqueous liquid powerful detergent according to claim 8 consisting of Wt% Nonionic surfactant in an amount of about 30-40 A non-aqueous liquid powerful detergent according to claim 8 consisting of Wt. % Nonionic surfactant in an amount of about 30-50 30 Acid terminated surfactant in an amount of about 1-15 Sodium tripolyphosphate (TPP) in an amount of about 15-50 Diethylene glycol monobutyl ether in an amount of about 5-25 8602 120 - 47% by weight of Waternair ammonium salt in an amount of about 0.2-2.0 Sodium perborate monohydrate bleach in an amount of about 2-20 Tetraacetylethylenediamine (TEAD) bleach activator in an amount of about 1-8 The non-aqueous liquid powerful detergent according to claim 13, consisting of Wt% Nonionic surfactant in an amount of about 30-50 Sodium polyphosphate in an amount of about 15-50 Polyethylene glycol (molecular weight 400) in an amount of about 5-25 Quaternary ammonium salt in an amount of about 0.2-2.0 Sodium perborate monohydrate bleach in an amount of about 2-20 Tetraacetylethylenediamine (TAED) bleach activator in an amount of about 1-8 14. A method of cleaning soiled fabrics in which said fabrics are contacted with the detergent according to claim 10 or 11. A method for cleaning soiled fabrics, wherein said fabrics are contacted with the detergent according to claim 12 or 13. 8602120