Low phosphate or phosphate free nonaqueous liquid nonionic laundry detergent composition and method of use

DESCRIPTION

This invention relates to liquid, non-aqueous compositions for treating tissues. More particularly, this invention relates to liquid, non-aqueous, phosphate-free or low-phosphate laundry detergent compositions, which contain a suspension of an alkali metal salt of a lower polycarboxylic acid, as a builder. detergency, in a non-ioan surfactant, whose compositions are stable against phase separation and gelation and are easily pourable, as well as the use of these compositions to clean dirty tissues.

Liquid detergent compositions, non-aqueous, of energetic action, for washing clothes, are well known in the art. For example, compositions of this type may comprise a liquid non-ionic surfactant in which particles of a detergency builder are dispersed, as evidenced, for example, by US Patent Nos. 4,316,812, 3,630,929 and 4,264. 466 and the British Patent Numbers 1,205,711,1,270,040 and 1,600,981.

The pending patent applications, related, assigned to the common assignee, are: 550,535, filed on December 31, 1985; 541,940, filed on April 3, 1985; 542,029, filed on April 8, 1985; and, SN 725,455, filed on April 22, 1985.

These patent applications will be directed to non-ionic, liquid, non-aqueous detergent compositions for laundry.

The washing power of detergents with synthetic, non-ioan surfactants, in laundry detergent compositions, can be increased by the addition of detergency builders. Sodium tripolyphosphate is one of the preferred detergency builders. However, the use of sodium polyphosphate in dry, powdered detergents carries several disadvantages, such as, for example, the tendency of polyphosphates to hydrolyse in pyro- and orthophosphates, which represent less valuable detergency builders.

In addition, the polyphosphate content of laundry detergents has been challenged by the undesirably high phosphate content of surface waters. It has been found that an increased phosphate content in surface waters contributes to increased algae growth, with the result that the biological equilibrium of the water can be adversely altered.

Recently enacted government laws have been aimed at reducing the amount of polyphosphates present in laundry detergents and, in some jurisdictions where polyphosphates have been a problem, to require that laundry detergents do not contain builders polyphosphate type detergency.

It is often considered to be more convenient to use liquid detergents than dry, particulate, powdery and particulate products, and therefore have found a substantial favor among the users. These detergents are easily measured, dissolve quickly in the wash water, are able to be easily applied in concentrated solutions or dispersions to areas of dirty garments that have to be washed, and do not give off dust, usually occupying less space for storage . Additionally, liquid detergents may have materials incorporated in their formulations that cannot withstand drying operations without deterioration, the materials of which are desirably employed in the manufacture of particulate detergent products. Even though they possess many advantages over unit products or solids in particulate products, liquid detergents often have certain intrinsic disadvantages as well, which have to be overcome to obtain acceptable commercial detergent products. Thus, some of such products are separated during storage and others are separated upon cooling and are not easily redispersed. In some cases the viscosity of the product changes and becomes either too high to pour or so low that the product appears watery. Some transparent products become cloudy and others gel when left at rest.

In addition to the problem of sedimentation or phase separation, liquid, non-aqueous, laundry detergents, based on liquid non-ioranic surfactants, have the disadvantage that non-ioranic compounds tend to gel when added to cold water . This constitutes a particularly important problem in the ordinary use of domestic automatic washing machines in Europe, where the user places the laundry detergent composition in a distribution unit (for example, a distribution drawer) of the machine. During the operation of the machine the detergent located in the distributor is subjected to a stream of cold water that makes it pass to the main body of the washing solution. Especially during the winter months when the detergent composition and the water that are loaded to the distributor are particularly cold, the viscosity of the detergent increases sharply and a gel is formed. As a result, some of the composition does not flow completely from the distributor during the operation of the machine, and a deposit of the composition is accumulated when carrying out repeated washing cycles, which, finally, requires the user to have You clean the distributor with hot water.

The phenomenon of gelation can also be a problem if washing is desired using cold water, as may be recommended for certain synthetic and delicate fabrics, or for fabrics that can shrink in warm or warm water.

The tendency to gel the concentrated detergent compositions during storage is aggravated by storing the compositions in unheated storage areas, or by transporting them during the winter months in unheated transport vehicles.

Partial solutions to the problem of gelation have been proposed, for example, by dilution of the non-ioan compound, liquid, with certain solvents that control the viscosity.

000 832 and with certain agents that inhibit the formation of gels, such as lower alkanols, e.g. eg, ethyl alcohol (see U.S. Patent 3,953,380), alkali metal formates and adipates (see U.S. Patent 4,368,147), hexylene glycol, polyethylene glycol, etc., and by modification and optimization of the structure of the non-ionic compound. As an example of modification of the non-ioonic surfactant, a result that has been particularly accompanied by success, has been achieved by acidifying the terminal group of the hydroxyl moiety of the non-ionic compound molecule. The advantages of introducing a carboxylic acid at the end of the non-ionic compound include inhibition of gel formation upon dilution; the decrease of the pour point of the non-ioonic compound; and the formation of a non-ionic surfactant by neutralizing in the washing liquid. The optimization of the structure of the non-ioonic compound has focused on the chain length of the hydrophobic-lipophilic moiety and on the nuomer and assembled of alkylene oxide units (eg, ethylene oxide) of the hydrophilic moiety. For example, it has been found that an ethoxylated C13 fatty alcohol with 8 moles of ethylene oxide has only a limited tendency with respect to the formation of gels.

However, improvements in both stability and inhibition of the formation of gels of liquid, non-aqueous, phosphate-free compositions are desired to treat tissues.

In accordance with the present invention, a liquid, non-aqueous, highly concentrated, low-phosphate detergent composition is prepared, particularly free of a polyphosphate type detergent builder, for washing clothes, dispersing an alkali metal salt of a polycarboxylic acid bottom, as a detergency builder, in a liquid, non-ionic surfactant detergent.

In order to improve the viscosity characteristics of the composition, an ionic surfactant terminated in acid is added. To further improve the viscosity characteristics of the composition and the storage properties of the composition, agents that improve viscosity and anti-gel agents, such as alkylene glycol monoalkyl ethers, and anti-sedimentation agents such as oresters can be added to the composition of phosphoric acid and aluminum stearate. In a preferred embodiment of the invention the detergent composition contains an acidic non-ionic surfactant, an alkylene glycol monoalkyl ether and an anti-sedimentation agent.

Disinfection agents or bleaching agents can be added as well as bone activators, 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, to further improve the suspension stability of the builder components. detergency in the liquid non-ionic surfactant detergent.

In addition, other ingredients such as anti-fouling agents, anti-foaming agents, optical brighteners, enzymes, anti-redeposition agents, perfume and dyes can be added to the composition.

Washing machines currently manufactured for domestic use normally operate at wash temperatures of up to 100 ° C. Up to 70 liters of water are used during the wash and rinse cycles.

Normally approximately 250 grams of powdered detergent are used, per wash.

Following the present invention, when using highly concentrated liquid detergent, only 100 grams (77 cc) of the liquid detergent composition is normally required to wash a full load of dirty laundry.

Accordingly, in one aspect the present invention provides a liquid detergent composition, of energy action, free of phosphate type builder or substantially free of phosphate builder, for washing clothes, composed of a suspension of a alkali metal salt of a lower polycarboxylic acid, as a detergency builder, in a liquid non-ionic surfactant.

Following another aspect, the invention provides a liquid, concentrated, phosphorus-free or phosphate-free detergent composition for laundry, which is stable, does not settle during storage and does not gel or during storage. Not during use. The liquid compositions of the present invention can be easily poured, measured easily and easily placed in the washing machine.

Following another aspect, the invention provides a method for distributing a non-ionic, liquid, phosphate-free or low-phosphate detergent composition for washing clothes, in and / or with cold water without suffering gelation. In particular, a method is provided for filling a container with a liquid, non-aqueous, laundry detergent composition, in which the detergent is composed, at least predominantly, of a non-ionic, liquid, improver-free surfactant. of polyphosphate type detergency, and to distribute the composition from the container, in an aqueous washcloth, where the distribution was carried out by directing an unheated stream of water over the composition, such that the composition is transported by the stream of water, to the washbasin.

Detergent builder-free detergent compositions of the polyphosphate type overcome the problem of phosphate surface water contamination.

Detergent contaminations with non-ionic surfactant, liquid, non-aqueous, concentrated, free of polyphosphate or low polyphosphate, for washing clothes, of the present invention, have the additional advantages of being stable, of not sedimenting during storage and not to gel during storage. Liquid compositions can be easily poured, easily measured and easily placed in washing machines

000 832 for washing clothes.

It is an object of the present invention to provide a non-ionic, liquid, non-aqueous, non-polluting, low-polyphosphate, and particularly polyphosphate-free detergent composition that contains an alkali metal salt of a polycarboxylic acid. lower, as a detergency builder, suspended in a non-ioan surfactant.

It is another object of the invention to provide liquid polyphosphate free or low polyphosphate content compositions for treating tissues, which are suspensions of an alkali metal salt of a lower polycarboxylic acid, as a builder, in a non-aqueous liquid, and which are stable during storage, easily pourable and dispersible in cold, warm or hot water.

Another object of this invention is to formulate detergent compositions with non-ionic surfactant, liquid, non-aqueous, energetic action, highly reinforced, free of polyphosphate or low polyphosphate content, for laundry, which can be poured at all temperatures and which can be dispersed repeatedly from the distribution unit of European-style laundry machines, automatic washing machines, without dirtying or sealing the distributor even during the winter months.

Another object of this invention is to provide stable, non-gelling, polyphosphate-free or low-polyphosphate-free suspensions of a non-ioranic, liquid, non-aqueous detergent composition, of vigorous, reinforced action, for washing clothes, including an effective amount of an alkali metal salt of a lower polycarboxylic acid , as a detergency builder.

Another object of this invention is to provide stable, non-gelling, suspensions of a non-ioranic, liquid, non-aqueous detergent composition, of energetic, reinforced action, for washing clothes, including an amount of a phosphoric acid alkanol ester. and / or an aluminum salt of a fatty acid, which is sufficient to increase the stability of the composition, that is, to prevent sedimentation of detergent builder particles, etc., while preferably, the plastic viscosity of the compositions is reduced or at least, without increasing said viscosity.

These and other objects of the invention that will become more apparent from the detailed description of preferred embodiments that follow, which are generally provided by preparing a low polyphosphate or polyphosphate free detergent composition, by adding to the non-ioan surfactant, liquid , non-aqueous, of an effective amount of an alkali metal salt of a lower polycarboxylic acid, as a detergency builder, and other inorganic or organic additives for treating tissues, e.g. eg, agents for improving viscosity and anti-gel, anti-sedimentation agents, anti-fouling agents, pH control agents, bleaching agents, bleaching activators, anti-foam agents, atopic brighteners, enzymes, anti-fouling agents redeposition, perfume, and dyes.

Nonionic surfactant detergent

Synthetic, non-ionic organic detergents, employed in the practice of the invention, can be any of a wide variety of such compounds, which are well known.

As is well known, synthetic, non-ionic organic detergents will be characterized by the presence of an organic hydrophobic group and an organic hydrophilic group, and are typically obtained by the condensation of an aliphatic or alkylaromatic, hydrophalogenic, organo-organic, or ethoxide oxide compound. (hydrophilic in nature). Practically any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen bound to the nitrogen, can be condensed with ethylene oxide or with the product of polyhydration thereof, polyethylene glycol, to form a non-ioanic detergent. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups. Suitable non-ioan surfactants are those described in US Patents 4,316,812 and 3,630,929.

Typically, non-ionic detergents are polyalkoxylated lipophilic with lower alkoxy where the desired hydrophilic-lipophilic balance is obtained by adding hydrophilic lower alkoxy groups to a lipophilic moiety. A preferred class of the non-ionic detergent used is a polyalkoxylated higher alkanol with lower alkoxy, wherein the alkanol has 9 to 18 carbon atoms and where the number of moles of lower alkylene oxide (2 or 3 carbon atoms) it is from 3 to 12. Of such materials it is preferred to employ those in which the upper alkanol is a fatty alcohol greater than 9 to 11 or 12 to 15 carbon atoms and containing 5 to 8, or 5 to 9, groups lower alkoxy per mole. Preferably, the lower alkoxy is ethoxy, but in some cases, it can be desirably mixed with propoxy, the latter constituting, if present, a lower proportion (less than 50%).

Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and containing approximately 7 ethylene oxide groups per mole, e.g., Neodol 25-7 and Neodol 23-6.5, whose products are manufactured by Shell Chemical Company, Inc. The first one is a condensation product of a mixture of higher fatty alcohols which have, on average, approximately 12 to 15 carbon atoms, with approximately 7 moles of ethylene oxide, and the latter is a corresponding mixture in the that the carbon atom content of the higher fatty alcohol is from 12 to 13, and the number of ethylene oxide groups present amounts to approximately 6.5 per mean term. The higher alcohols are primary alkanols.

Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15-S-9, both of which are ethoxylates of linear secondary alcohols manufactured by Union Carbide Corp. 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 latter is a similar product but in which

000 832 nine moles of ethylene oxide have been reacted.

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

Other useful non-ionic compounds are represented by the well-known class of non-ionic compounds, sold under the trademark Plurafac. Plurafacs are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, which contain a mixed chain of ethylene oxide and propylene oxide, terminated in a hydroxyl group. Examples of oysters include Product A (a C13-C15 fatty alcohol condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide), Product B (a C13-C15 fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide), and Product C (a C13C15 fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide).

Another group of liquid non-ionic compounds available from Shell Chemical Company, Inc. under the trademark Dobanol, are: Dobanol 91-5 which is an ethoxylated C9-C11 fatty alcohol, with an average of 5 moles of ethylene oxide, and Dobanol 25-7, which is an ethoxylated C12-C15 fatty alcohol, with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

In preferred, higher alkoxy polyalkoxylated alkanols with lower alkoxy, to obtain the best balance of hydrophilic and lipophilic moieties, the lower alkoxy group number must usually be 40% to 100% of the number of carbon atoms existing in the higher alcohol, preferably from 40 to 60% thereof, and the non-ionic detergent preferably contained at least 50% of such a higher polyalkoxylated alkanol with lower, preferred alkoxy. Higher molecular weight alkanols and various other normally solid non-ionic detergents and surface activity agents may contribute to the gelation of the liquid detergent and therefore, would preferably be omitted or limited in quantity, of the present compositions, even if minor proportions of the same for their cleaning properties, etc. With respect to both preferred and less preferred non-ionic detergents, the alkyl groups present therein are generally linear even when branching can be tolerated, such as in carbon adjacent to the terminal carbon of the linear chain and outside the ethoxy chain, or two carbons separated therefrom, if such branched alkyl does not have a length of more than three carbons. Normally, the proportion of carbon atoms in such a branched configuration will be less, rarely exceeding 20% ​​of the total carbon atom content of the alkyl. Similarly, even when linear alkyls that are terminally linked to ethylene oxide chains are highly preferred and are considered to result in the best combination of detergency, biodegradability and non-gelation characteristics, medium or secondary associations to the oxide may occur. of ethylene in the chain. Usually, only in a smaller proportion of such alkyls, generally less than 20%, as in the cases of the mentioned Tergitoles, can it be greater. Likewise, when propylene oxide is present in the lower alkylene oxide chain, it usually constitutes less than 20% thereof and, preferably, constituted less than 10% thereof.

When higher proportions of non-terminal alkoxylated alkanols, polyalkoxylated lower alkoxy alkanols containing propylene oxide and non-ionic tergent less balanced with respect to hydrophilic and lipophilic groups are used, than those mentioned above, and when other non-ionic detergents are used instead of the preferred non-ionic compounds mentioned herein, the resulting product may not have such good detergency properties, stability, viscosity and non-gelation, as the preferred compositions, but the use of the compounds that control the viscosity and gel formation of the invention can also improve the properties of detergents based on such non-ionic compounds. In some cases, such as when a polyalkoxylated higher alkanol with lower alkoxy, of higher molecular weight, often due to its detergency is used, the proportion thereof will be regulated or limited according to the results of routine experiments, to obtain the desired detergency and have still the product that does not gel and has the desired viscosity. Also, it has been found that it is only rarely necessary to use non-ionic compounds of higher molecular weight for their detergent properties, since the preferred non-ionic compounds described herein are excellent detergents and, additionally, allow to obtain the desired viscosity in the liquid detergent without gelling at low temperatures.

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

In the compositions of this invention, preferred non-ionic surfactants include C13-C15 secondary fatty alcohols with relatively narrow ethylene oxide contents, in the range from about 7 to 9 moles, and ethoxylated C9 to C11 fatty alcohols with approximately 5-6 moles of ethylene oxide.

Mixtures of two or more of the liquid non-ionic surfactants can be used, and in some cases advantages of using such mixtures can be obtained.

000 832

Acid-terminated non-ionic surfactant

The viscosity and gel-forming properties of liquid detergent compositions can be improved by including in the composition an effective amount of a liquid, acidic, non-ionic surfactant. The acid-terminated non-ionic surfactants consist of a non-ionic surfactant that has been modified to convert a free hydroxyl group thereof into a moiety that has a free carboxyl group, such as an oester or a partial oester of a non-ionic surfactant and a polyacid or carboxylic anhydride.

As described in Spanish Patent Application No. 542,029, filed on April 8, 1985, whose description is incorporated herein by reference, non-ionic surfactants modified with free carboxyl group, which can be broadly characterized as polyetherified carboxylic acids, acted lowering the temperature at which the liquid non-ionic compound forms a gel with water.

The addition of non-ionic surfactants terminated in acid to the liquid non-ionic surfactant, helps the compositional distribution capacity, i.e. the pouring capacity, and lowers the temperature at which the liquid non-ionic surfactants form a gel with water, without diminishing its stability against sedimentation. The non-ionic acid-terminated surfactant reacts in the water of the washing machine with the alkalinity of the dispersed salt phase used as a detergency builder, of the detergent composition, and acted as an effective anionic surfactant.

Specific examples include Plurafac RA30 hemi-oesters with succinic anhydride, Dobanol 25-7 oester or hem-oester with succinic anhydride, and Dobanol 91-5 oester or hem-oester with succinic anhydride. Instead of succinic anhydride, other polycarboxylic acids or polycarboxylic acid anhydrides can be used, for example, maleic acid, maleic acid anhydride, citric acid, and the like.

The acidic non-ionic surfactants can be prepared as follows:

Product A finished in acid. 400 g of Product A non-ionic surfactant, which is a C13 aC15 alkanol which has been alkoxylated to introduce 6 units of ethylene oxide and 3 units of propylene oxide per alkanol unit, are mixed with 32 g of succinic anhydride and heat for 7 hours at 100^°C. The mixture is cooled and filtered to separate the unreacted succonic material. The infrared anaolysis showed that approximately half of the non-ionic surfactant had become the acidic hemi-ester thereof.

Dobanol 25-7 finished in acid. 522 g of the non-ionic surfactant Dobanol 25-7, which is the ethoxylation product of a C12 aC15 alkanol and having approximately 7 units of ethylene oxide per alkanol molecule, is mixed with 100 g of succinic anhydride and 0.1 g of pyridine (which acted as esterification catalyst) and heated to 260^°C for 2 hours, it is cooled and filtered to separate the unreacted succonic material. Infrared anaolysis indicates that substantially all of the surfactant free hydroxyl groups have reacted substantially.

Dobanol 91-5 finished in acid. 1,000 g of Dobanol 91-5, a non-ionic surfactant which is the ethoxylation product of a C9 aC11 alkanol and having approximately 5 units of ethylene oxide per alkanol molecule, is mixed with 265 g of succinic anhydride and 0.1 g of pyridine catalyst, and heated to 260^°C for 2 hours, it is cooled and filtered to separate the unreacted succonic material. Infrared anaolysis indicates that substantially all of the surfactant free hydroxyl groups have reacted.

Other esterification catalysts, such as an alkali metal alkoxide (eg, sodium methoxide) may be used instead of, or in admixture with, pyridine.

The acidic polyether compound, that is, the acidic, non-ionic surfactant, is preferably added dissolved in the non-ionic surfactant.

The non-ionic, liquid, non-aqueous surfactant used in the compositions of the present invention is dispersed and suspended in fine particles of orgaonic and / or inorganic salts used as detergent builders.

The present invention includes as an essential part of the composition an organic alkali metal salt of a lower polycarboxylic acid, as a detergency builder.

Organic salts used as a detergency builder

The preferred orgaonic salts used as a detergency builder comprise alkali metal salts of lower polycarboxylic acids, for example, two to four carboxyl groups. The preferred sodium and potassium salts of lower polycarboxylic acids are the salts of the citric acid and tartaric acid.

Sodium salts of citric acid are the most preferred, especially trisodic citrate. Monosodium and disodium citrates can also be used. When monosodium and disodium citrates are used, it is preferred to add as additional detergency builder salts, sodium silicates, e.g. example, disodium silicate, to adjust the pH to approximately the same level as that obtained when trisoodic citrate is used. The monosodium and disodium salts of tartaric acid can also be used. The alkali metal salts of lower polycarboxylic acids are particularly good detergency builders; Due to their high capacity of calcium and magnesium fixation, they inhibit the encrustations that were otherwise caused by the formation of insoluble calcium and magnesium salts.

Other organic detergency builders that can be used are polymers and copolymers of acryl polyacid and maleic polyanhydride, and their alkali metal salts. More specifically, such salts used as a detergency builder may consist of a copolymer that is the reaction product of an approximately equal mole number of methacrylic acid and maleic anhydride that has been completely neutralized to form the sodium salt thereof. The detergency builder can be purchased commercially under the name eat6

000 832 Cial of Sokalan CP5. This detergency builder is used when used even in small amounts, to inhibit scale.

Examples of alkaline organic salts, sequestrants used as a detergency builder, which can be used with the alkali metal salts of lower polycarboxylic acid, used as a detergency builder, or in admixture with other organic and inorganic detergent builders, are metal aminopolycarboxylates alkali, ammonium or substituted ammonium, e.g. eg, sodium and potassium ethylenediaminetetraacetate (EDTA), sodium and potassium nitrilotriacetates (NTA) and N- (2- hydroxyethyl) triethanolammonium nitrilodiacetates. Mixed salts of these aminopolycarboxylates are also suitable.

Other suitable detergency builders of the organic type include carboxymethyl succinates, tartronates and glycolate. Polyacetal carboxylates have a special value. Polyacetal carboxylates and their use in detergent compositions are described in patents 4,144,226, 4,315,092, and 4,146,495. Other patents on similar detergency builders include 4,141,676, 4,169,934, 4,201,858, 4,204,852, 4,224,420, 4,225,685, 4,226,960, 4,233,422, 4,233,423, 4,302,564 and 4,303,777 .

Inorganic salts used as a detergency builder

Zeolites, crystalline and amorphous aluminosilicates, insoluble in water can be used. Zeolites generally have the (M2O) x. (Al2O3) y. (SiO2) z.wH2O where x is 1, and is 0.8 to 1.2 and preferably 1, z is 1, 5-to 3.5 or greater and preferably 2 to 3, and w is 0 to 9, preferably 2.5 to 6, and M is preferably sodium. A typical zeolite is of type A or similar structure, with zeolites of type 4A being particularly preferred. Preferred aluminasilicates have calcium ion exchange capacities of approximately 200 milliequivalents per gram or greater, for example, 400 milliequivalents per gram.

Various crystalline zeolites (ie alumina-silicates) that can be used are described in British Patent 1,504,168, U.S. Patent 4,409,136 and Canadian Patents 1,072,835 and 1,087,477, all of which are incorporated here as a reference for such descriptions. An example of useful amorphous zeolites in this invention can be found in Belgian Patent 835,351 and this patent is also incorporated herein by reference.

The detergent compositions of the invention may also include water soluble and / or water insoluble inorganic salts, such as detergent builders. Suitable alkaline inorganic salts, used as detergency builders, which can be used, are alkali metal carbonates, borates, bicarbonates and silicates. (Ammonium or substituted ammonium salts may also be used). Specific examples of such salts are sodium carbonate, sodium tetraborate, sodium bicarbonate, sodium sesquicarbonate and potassium bicarbonate.

Alkali metal silicates are useful salts to be used as detergency builders, which also act by adjusting or controlling the pH and making the composition anticorrosive for parts of the washing machine. Sodium silicates of Na2O / SiO2 ratios from 1.6 / 1 to 1 / 3.2 are preferred, and especially about 1/2 to 1 / 2.8. Potassium silicates of the same ratios can also be used. When monosodium or disodium citrates are used as the main detergency builder salt, it is preferred to add a sufficient amount of an alkali metal silicate to adjust the pH to approximately that obtained with the trisodium citrate used as a detergency builder.

Although it is preferred that the detergent composition be free of phosphate or polyphosphate or that it is substantially free of polyphosphate, small amounts of the conventional polyphosphate salts, used as a detergency builder, can be added when local legislation permits such use. Specific examples of such salts that are used as a detergency builder are sodium tripolyphosphate (TPP), sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate and sodium hexametaphosphate. Sodium tripolyphosphate (TPP) is a preferred polyphosphate. In formulations in which polyphosphate is added, it is added in an amount of 0 to 50%, such as 0 to 30%, and 5 to 15%. However, as mentioned above, it is preferred that the formulations be free or substantially free of polyphosphate.

Other suitable, typical detergency builders include, for example, those described in US Patents 4,316,812, 4,264,466 and 3,630,929. The alkaline inorganic salts used as detergency builders may be used with the non-ioan surfactant detergent compound or in admixture with other organic or inorganic salts used as detergency builders.

Other materials such as clays, in particular of the water insoluble types, can be useful adjuvants in compositions of this invention. Bentonite is particularly useful. This material is mainly montmorillonite which is a hydrated aluminum silicate in which approximately one sixth of the aluminum atoms can be replaced by magnesium atoms and with which varying amounts of hydrogen, sodium, potassium, calcium, etc. They can be easily combined. Bentonite in its most purified form (i.e., free of roughness, sand, etc.) suitable for detergents, contains at least 50% montmorillonite and therefore its capacity for cation exchange is at least about 50 to 75 milliequivalents per 100 g of bentonite. Particularly preferred bentonites are the bentonites of Wyoming or the Western United States, which have been sold as Thixo-jels 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known as fabric softeners, as described in British patent 401,413 to Marriott and British patent 461,221 to Marriott and Guan. Viscosity control agents and antigel agents

The detergent composition of an effective amount of amphiphilic compounds of

000 832 low molecular weight acting as viscosity control agents and inhibiting the formation of gels for the non-ionic surfactant, substantially improves the storage properties of the composition. The amphiphilic compounds can be considered as chemical-like analogs to the liquid non-ionic surfactants of ethoxylated and / or propoxylated fatty alcohol, but have relatively short hydrocarbon chain lengths (C2 to C8) and a low content of ethylene oxide (approximately 2 to 6 groups of ethylene oxide per molecule).

Suitable amphophilic compounds may be represented by the following general formula:

RO (CH2CH2O) nH where R is a C alkyl group₂-C₈, and n is a number from about 1 to 6, on average.

Specifically, the compounds are lower monoalkyl (C2 aC5) ethers of lower alkylene glycol (C2 aC3).

Specifically, the compounds are lower monoalkyl (C1 to C5) ethers of lower mono-, di- or trialkylene glycol (C2 to C3).

Specific examples of suitable amphiphilic compounds include: ethylene glycol monoetolic ether (C2H5-O-CH2CH2OH), diethylene glycol monobutolic ether (C4H9-O- (CH2CH2O) 2H), tetraethylene glycol monobutolic ether (C4H7-O) (CH2CH2, 4) and dipropylene glycol monometholic ether (CH3-O- (CH2CHO) 2H.

^|

CH3

Diethylene glycol monobutolic ether is especially preferred.

The inclusion in the composition of the lower alkylene glycol monoalkyl ether, of low molecular weight, decreases the viscosity of the composition, so that it can be poured more easily, the stability against sedimentation is improved and the dispersibility of the composition when added to warm water or cold water.

The compositions of the present invention have improved viscosity and stability characteristics and remain stable and can be poured at temperatures as low as about 5 ° C and lower.

Stabilization agents

In one embodiment of this invention, the phosphoric stability of the suspension of the detergent-enhancing compound or compounds and any other suspended additives, such as bleaching agent, etc., in the liquid vehicle, is enhanced by the presence of a stabilizing agent. which is an phosphoric acid alkanol oester ester or an aluminum salt of a higher fatty acid.

Improvements in the stability of the composition can be achieved by incorporating a small, effective amount of an organic phosphorus compound, which has a POH-acid group, such as a partial phosphorous acid ester and an alkanol.

As described in the Spanish patent application 542.029, filed on April 8, 1985, whose description is incorporated herein by reference, the organic acid phosphorus compound, which has a POH-acidic group, can increase the stability of the suspension of detergency builders in the liquid, non-aqueous non-ionic surfactant.

The phosphoric orgaonic phosphorus orgaonic compound may be, for example, a partial phosphoric acid oester and an alcohol such as an alkanol having lipophilic caraócter, which possesses, for example, maos with 5 carbon atoms, e.g., from 8 to 20 carbon atoms.

A specific example is a partial phosphoric acid oester and a C16 aC18 alkanol (Empiphos 5632, from Marchon); It consists of approximately 35% monoester and 65% dioester.

The inclusion of quite small amounts of the organic phosphorus compound, acidic, makes the suspension significantly more stable against sedimentation when left standing, but remains with pouring capacity, while, for the low stabilizer concentration, p. For example, below about 1%, its plastic viscosity generally decreases.

Further improvements in the stability and anti-sedimentation properties of the composition can be achieved by adding a small, effective amount of an aluminum salt of a higher fatty acid to the composition.

Aluminum salt stabilization agents are the subject of the pending, freely available patent application, Ser. 725,455, filed on April 22, 1985, the description of which is incorporated herein by reference.

Preferred higher aliphatic fatty acids have from about 8 to about 22 carbon atoms, more preferably from about 10 to 20 carbon atoms, and especially preferably, from about 12 to 18 carbon atoms. The alifaotic radical can be saturated or unsaturated and can be linear or branched. As in the case of non-ionic surfactants, mixtures of fatty acids may 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 aluminum salt stabilizers may be formed include, decanoic acid, dodecanoic acid, palmotic acid, myriatic acid, stearic acid, oleic acid, eicosanoic acid, tallow fatty acid, fatty acid coconut, mixtures of these acids, etc. The aluminum salts of these acids are commercially available, in general, and are preferably used in the form of trio acid, e.g. eg, aluminum stearate as aluminum triestearate Al (C17H35COO) 3. Monoacid salts, e.g. eg, aluminum monostearate, Al (OH) 2 (C17H35COO) and salts

000 832 diacid, p. eg, aluminum distearate, Al (OH) (C17H35COO) 2, and mixtures of two or three of the aluminum mono-, di- and triaacid salts may also be used. However, it is most preferred that the aluminum triaacid salt comprises at least 30%, preferably at least 50%, and especially preferably, at least 80% of the total amount of aluminum fatty acid salt.

Aluminum salts, as mentioned above, are commercially available and can be easily obtained, for example by saponifying a fatty acid, e.g. eg, animal fat, stearic acid, etc., followed by treatment of the resulting soap with alum, alumina, etc.

Even if it is not desired to join a particular theorem in the way in which the aluminum salt works to prevent sedimentation of the suspended particles, it is presumed that the aluminum salt increases the wetting capacity of the surfaces of the saolids by the non-ioan surfactant. This increase in wetting capacity therefore allows suspended particles to remain in suspension more easily.

Only very small amounts of the aluminum salt stabilizing agent are required to obtain significant advantages in phasic stability.

In addition to its action as a phase stabilizing agent, aluminum salt has the additional advantage over other phase stabilizing agents that has a non-ioanic character and is compatible with the non-ionic surfactant component and does not interfere with the overall detergency of the composicioán; exhibits some anti-foaming effect; It can act by enhancing the activity of fabric softeners, and gives the suspensions a longer relaxation time.

Bleaching agents

Bleaching agents are broadly classified, for convenience, as chlorine bleaching agents and oxygenated bleaching agents. Chlorine bleaching agents are typified by sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% of useful chlorine), and trichloroisocyanaric acid (95% of useful chlorine). Oxygenated bleaching agents are preferred and are represented by percomposites that release hydrogen peroxide in solution. Preferred examples include sodium, potassium perborates, percarbonates and perfosphates, and potassium monopersulfate. Perborates, particularly sodium perborate monohydrate, are especially preferred.

The peroxygenated compound is preferably used in admixture with an activator therefor. Suitable activators that can lower the effective operating temperature of the peroxide bleaching agent are described, for example, in US Patent 4,264,466 or in column 1 of US Patent 4,430,244, whose Relevant descriptions are incorporated herein by reference. Preferred activators are polycylated compounds; Among these, compounds such as tetraacetyl ethylenediamine ("TAED") and pentaacetyl glucose are particularly preferred.

Other useful activators include, for example, derivatives of acetylsalicylic acid, ethylidenebenzoate-acetate and its salts, ethylidene-carboxylatetoacetate and its salts, alkyl anhydride and succanic alkenyl, tetraacetylglyceryl ("TAGU") and the derivatives of esters. Other classes of useful activators are described for example in US Patent 4,111,826, 4,422,950 and 3,661,789.

The bleach activator usually interacts with the peroxygenated compound forming a peroxyacid bleaching agent in the wash water. It is preferred to include a sequestering agent of high complexing power to inhibit any unwanted reaction between such peroxyacid and hydrogen peroxide in the wash solution, in the presence of metal ions.

Suitable sequestering agents for this purpose include the sodium salts of nitrilotriacaetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DETPA), and diethylenetriaminepentamethylene phosphatic acid (DTPMP) under commercial name DTPMP; and that of ethylenediaminetetramethylene phosphoic acid (EDITEMPA). The sequestering agents can be used alone or in admixture.

In order to avoid loss of peroxide bleaching agent, e.g. eg, sodium perborate, resulting from enzyme-induced decomposition, such as the catalase enzyme, the compositions may additionally include an enzyme-inhibiting compound, that is, a compound capable of inhibiting the decomposition of the peroxide bleaching agent, enzyme induced. Suitable inhibitor compounds are described in US Patent 3,606,990, the relevant description of which is incorporated herein by reference.

Mention may be made of hydroxylamine sulfate and other water-soluble hydroxylamine salts, as inhibitors of special interest. In preferred non-aqueous compositions of this invention, suitable amounts of hydroxylamine salt inhibitors may be as low as about 0.01 to 0.4%. However, generally, suitable amounts of enzyme inhibitors are up to about 15%, for example, 0.1 to 10%, of the weight of the composition.

In addition to detergent builders, various other detergent additives or adjuvants may be present in the detergent product to communicate desired additional properties, either functional or static in nature. Thus, smaller amounts of soil suspension agents or anti-redeposition agents may be included in the formulation, for example, vinyl polyalcohol, fatty amides, sodium carboxymethylcellulose or hydroxypropyl methylcellulose. A preferred anti-redeposition agent is sodium carboxymethyl cellulose having a CM / MC ratio of 2: 1, which is sold under the trade name Relatin DM 4050.

Onaptic brighteners for cotton, polyamide and polyester fabrics can be used. Suitable optic brighteners include compositions of stilbene, triazole and benzidine sulfone, especially sulfonated substituted triazinyl-stilbene,

000 832 naphthotriazol-stilbene sulfonated, benzidene sulfone, etc. Preferred maos are combinations of stilbene and triazole. A preferred brightener is Stilbene Brightener N4, which is dimorpholinodianilino-stilbene-sulfonated.

Enzymes, preferably proteolytic enzymes, such as subtilisin, bromelain, papain, trypsin and pepsin, may be used, as well as amylase type enzymes, lipase type enzymes, and mixtures thereof. Preferred enzymes include protease suspension, suspension of Esperase and Amylase. A preferred enzyme is Esperase SL8 which is protease. Anti-foam agents, e.g. eg, silicon compounds, such as Silicane L 7604 can also be added in small effective amounts.

Bactericides can be used, e.g. eg, tetrachlorosalicylanilide and hexachlorophen, fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet absorbers, anti-yellowing agents, such as sodium carboxymethylcellulose, pH modifiers and pH buffers, bleaching agents that ensure color, perfumes, and dyes and sweetening agents, such as ultramarine blue.

The composition may also contain an insoluble, inorganic, thickening or dispersing agent of very high specific surface, such as finely divided silica, of extremely fine particle size (e.g., 5-100 millimeter micrometers, such as sold under the name Aerosil) or the other highly bulky inorgaonic support materials, described in US Patent 3,630,929 in proportions of 0.1-10%, eg, 1 to 5%. However, it is preferable that compositions that form peroxyacids in the washbasin (eg, compositions containing peroxygenated compound and activator for this) are substantially free of such compounds and other silicates; It has been found, for example, that solid and silicates favor the unwanted decomposition of peroxyacid.

In one embodiment of the invention the stability of the detergency builder salts in the composition during storage and the dispersion capacity of the composition in water are improved by grinding and reducing the particle size of the solid detergency builders to less than 100 microns, preferably less than 40 microns, and more preferably less than 10 microns. Solid detergency builders are generally supplied in particle sizes of approximately 100, 200 or 400 microns. The non-ionic liquid surfactant phase may be mixed with the solid detergency builders before or after the milling operation.

In a preferred embodiment of the invention, the mixture of liquid non-ionic surfactant and solid ingredients is subjected to a type of wear mill in which the particle sizes of the solid ingredients are reduced to less than about 10 microns, for example , at an average particle size of 2 to 10 microns or even less (e.g., 1 micron). Preferably less than about 10%, especially less than about 5%, of all suspended particles, have particle sizes greater than 10 microns. Compositions whose dispersed particles have such a small size, have improved stability against separation or sedimentation during storage. The addition of the acidic non-ioin surfactant compound helps the dispersibility of the dispersions without corresponding decrease in the stability of the dispersions against sedimentation.

In the milling operation, it is preferred that the proportion of solid ingredients is sufficiently high (e.g., at least about 40%, such as about 50%), that the solid particles are in contact with each other and are not substantially protected from each other by the non-ionic surfactant liquid. After the grinding stage, the rest of the liquid non-ionic surfactant can be added to the ground formulation. Mills that use grinding balls (ball mills) or similar mobile grinding elements have given very good results. Thus, a discontinuous laboratory mill can be used that has 8 mm diameter soapstone grinding balls. For larger-scale work, a continuous operating mill can be used in which there are 1 mm grinding balls or 1.5 mm diameters, working with a very small separation between a stator and a rotor that operates at a relatively high speed ( e.g., a CoBall mill); when such a mill is used, it is desirable to pass the mixture of non-ioin surfactant and solids first through a mill that does not perform such fine grinding (e.g. eg, a colloidal mill) to reduce the particle size to less than 100 microns (e.g., about 40 microns) before the grinding stage until an average particle diameter of less than about 10 microns is obtained, in the Ball mill that works continuously.

In the liquid detergent compositions, of energetic action, for the laundry, preferred, of the invention, the typical proportions of the ingredients (as many percent based on the total weight of the composition, unless otherwise specified) are the following:

Non-ioin surfactant detergent, liquid, in the range of about 20 to 60, such as 25 to 45 percent.

The acidic non-ioin surfactant can be omitted; it is preferred, however, that it be added to the composition in an amount in the range of about 2 to 20, such as 3 to 15 percent.

Alkali metal builder salt of lower polycarboxylic acid, in the range of about 20 to 60, such as 25 to 45 percent.

Improving salt of phosphate type detergents, in the range of about 0 to 50%, such as 0 to 30% and 5 to 15%.

Alkali metal silicate in the range of about 0 to 30, such as 5 to 25 percent.

Anti-fouling agent of alkali metal salt of a copolymer of polyacrylate and maleic polyanhydride, in the approximate range10

000 832 mind 0 to 10, such as 2 to 8, percent.

The alkylene glycol monoalkyl ether anti-gel agent can be omitted; it is preferred, however, that the composition be added in an amount in the range of about 5 to 20, such as 5 to 15 percent.

Phosphoric acid alkanol ester stabilizer, in the range of 0 to 2.0 or 0.1 to 2.0, such as 0.10 to 1.0 percent.

Stabilizing agents of fatty acid aluminum salt, in the range of about 0 to 3.0, such as 0.5 to 2.0 percent.

It is preferred that at least one of the phosphoric acid or aluminum salt ester stabilization agents be included in the composition.

Bleaching agent, in the range of about 0 to 15, such as 5 to 15 percent.

Bleaching agent activator, in the range of about 0 to 8, such as 2 to 6, percent.

Sequestering agent for bleaching agent, in the range of about 0 to 3.0, preferably 0.5 to 2.0 percent.

Anti-redeposition agent, in the range of about 0 to 3.0, preferably 0.5 to 2.0, percent.

Ooptic brightener, in the range of about 0 to 2.0, preferably 0.25 to 1.0 percent.

Enzymes, in the range of about 0 to 3.0, preferably 0.5 to 2.0, percent.

Perfume, in the range of about 0 to 3.0, preferably 0.25 to 1.25 percent.

Colorant, in the range of about 0 to 0.10, preferably, 0, OO25 to 0.050, percent.

Several of the previously mentioned additives can be optionally added to achieve the desired function of the added materials.

Mixtures of the non-ionic acid-terminated surfactant and the alkylene glycol alkyl ether ether gel can be used and in some cases advantageous can be obtained by using such mixtures alone, or by adding a stabilizing agent and anti-settling agent. .

In the selection of additives, they were chosen to be compatible with the main constituents of the detergent composition. In this patent application, as mentioned above, all proportions and all percentages are by weight with respect to the total formulation or composition, unless otherwise indicated.

The liquid, non-ionic, non-aqueous, concentrated detergent composition of the present invention is easily distributed in the water in the washing machine. Domestic washing machines currently used typically use 250 grams of detergent powder to wash a total load of clothes. Following the present invention, only 77 cc or 100 grams of the non-ionic, liquid, concentrated detergent composition is needed.

In a preferred embodiment of the invention the detergent composition of a topical formulation is formulated using the ingredients indicated below:

<td></td><td>% in weigh</td><td></td><td>% in weigh</td>

<td>TO</td><td> 30-40</td><td>I</td><td> 3,5-5,5</td>

<td>B</td><td> 4-10</td><td>J</td><td> 0,75-1.25</td>

<td>C</td><td> 25-35</td><td>K</td><td> 0,75-1,25</td>

<td>D</td><td> 3-5</td><td>L</td><td> 0,25-0,75</td>

<td>AND</td><td> 0-30</td><td>M</td><td> 0,75-1,25</td>

<td>F</td><td> 8-12</td><td>N</td><td> 0,75-1,0</td>

<td>G H</td><td> 0,1-0,5 8-12</td><td>OR</td><td> 0,0025-0,0100</td>

where:

A = Non-ionic surfactant detergent B = Acid-terminated surfactant C = Lower alkali metal detergent builder salt D = Alkali metal salt and polyacrylate co-alkali metal salt anti-fouling agent (Sokalan CP-5)

E = Detergent builder salt, polyphosphate type

F = Anti-gel agent, alkylene glycol monoalkyl ether

G = Phosphoric acid alkanol ester H = Bleaching agent, alkali metal perborate

I = Bleach Activator (TAED)

J = Sequestering agent (Dequest 2066)

K = Anti-redeposition agent (Relative DM (4050) L = Ooptic brightener (Stilbene Brightener N4) M = Enzymes (Protease-Esperase SL8)

N = Perfume

O = Coloring

The present invention is further illustrated by the following examples.

Example 1

A non-ionic, liquid, non-aqueous surfactant detergent composition is formulated from the following ingredients and in the amounts specified.

<td></td><td>% in weigh</td><td></td><td>% in weigh</td>

<td>TO</td><td> 13,5</td><td>I</td><td> 9,0</td>

<td>B</td><td> 10,0</td><td>J</td><td> 4,5</td>

<td>C</td><td> 10,0</td><td>K</td><td> 1,0</td>

<td>D</td><td> 5,0</td><td>L</td><td> 1,0</td>

<td>AND</td><td> 29,6</td><td>M</td><td> 0,5</td>

<td>F</td><td> 4,0</td><td>N</td><td> 1,0</td>

<td>G</td><td> 10,0</td><td>OR</td><td> 0,5925</td>

<td>H TOTAL</td><td> 0,3</td><td>P</td><td> 0,0075 100,000</td>

where:

A = A mixture of C13-C15 fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide, and C13C15 fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide

B = Surfactant non-ionic surfactant T7 C = Surfactant non-ionic surfactant T9 D = Acid-terminated Dobanol 91-5 reaction product, with succinic anhydride E = Trisodium citrate detergent builder F = Sodium copol sodium salt-inlay agent polyacrylate and maleic polyanhydride

000 832 (Sokalan CP5)

G = Diethylene glycol monobutyl ether anti-gel agent

H = Phosphoric acid alkanol ester

I = Sodium perborate monohydrate bleaching agent

J = Tetraacetylethylenediamine bleaching activator (TAED)

K = Sequestering agent, sodium salt of diethylenetriamine-pentamethylene phosphoric acid (Dequest

2066)

L = Anti-redeposition agent, Relatine DM (4050 mixture of CMC / MC 2: 1 M = Stilbene Brightener N4 N = Protease (Expect SL8)

O = Perfume P = Coloring

The formulation is milled for about an hour to reduce the particle size of the suspended detergency builder salts to less than 40 microns. It is found that the formulated detergent composition is stable and does not gel during storage and that it has a high detergent capacity.

The formulations can be prepared without grinding the detergency builder salts and suspended saolide particles to obtain a small particle size, but better results are obtained by milling the formulation to reduce the particle size of suspended saolide particles.

Detergent builder salts can be used as they are provided, e.g. For example, zeolites of particle sizes of 5 to 10 microns can be obtained, or the detergency builder salts and suspended solid particles can be partially ground or ground before mixing with the non-ioin surfactant. The milling can be carried out in part before mixing and completing the milling after mixing, or the total milling operation can be carried out after mixing with the liquid surfactant. Formulations containing suspended detergency builder and suspended solid particles smaller than 40 microns are preferred.

Example 2

In order to demonstrate the effect on the inlays of the substitution of sodium tripolyphosphate by an equivalent amount of trisoidic citrate detergent builder, the formulation of the detergent composition of Example 1 containing 29.6% by weight of trisoidic citrate, I share in use in a clothes washer with the same composition in which trisodic citrate was replaced by 29.6% by weight of sodium tripolyphosphate.

Washing cycles were carried out with the detergent compositions of trisodic citrate and sodium tripolyphosphate in concentrations in the laundry water of each detergent composition of 1 to 9 grams / liter.

After using each detergent composition in a washing machine, the amount of scale that resulted was measured, that is, the percentage of ash deposited. The measure of the percentage of ash deposited is determined by calcination of samples of washed fabrics.

The observed results are indicated in the graph illustrated in the drawing of Figure 1 and show that at concentrations of the detergent composition of 1 to 5 g / l of wash water, the trisoid citrate is substantially better than the sodium tripolyphosphate to avoid the formation of encrustations or ash deposit. At concentrations of the detergent composition of approximately 5 to 9 g / l of wash water, the behavior of the detergent enhancing salts trisodium citrate and sodium tripolyphosphate are approximately the same in their antifouling properties.

Example 3

In order to demonstrate the effect on the accumulation of inlays of the substitution of sodium tripolyphosphate by an equivalent amount of trisodic citrate, detergent builder, the detergent composition of Example 1 containing 29.6% by weight of trisoid citrate was compared in cycles Repeated washing of the machine with the same composition in which the trisoidic citrate had been replaced by 29.6% by weight of sodium tripolyphosphate.

Repeated wash cycles were carried out at concentrations in the wash water of 5 g / l of each of the detergent compositions for twelve wash cycles. The accumulation of encrustations, that is to say the accumulation of ashes in percent, was measured in each washing machine after 3, 6, 9 and 12 washes.

The results obtained from the accumulation of encrustations are indicated in the graph illustrated in the drawing of Figure 2. As for the accumulation of encrustations, no accumulation was observed with the trisodic citrate, while an accumulation was observed with the improver salt of detergents, sodium tripolyphosphate.

It should be understood that the above detailed description is simply provided as an illustration and that variations may be made therein without departing from the spirit of the invention.

000 832