LU86783A1 - POLYPHOSPHATE CONTAINING NON-AQUEOUS LIQUID LIQUID DETERGENT COMPOSITIONS AND METHODS FOR CLEANING DIRTY TISSUES USING THE SAME - Google Patents

Description

* 4 Λ

The present invention relates to non-aqueous liquid compositions for the treatment of tissue. More particularly, the present invention relates to nonaqueous liquid laundry detergent compositions, containing a suspension of a linear condensed polyphosphate detergency builder in nonionic surfactants, which compositions are stable against phase separation and gelation and can be easily poured. It also relates to the use of these compositions for cleaning soiled fabrics.

Non-aqueous liquid detergent compositions for heavy duty laundry are well known in the art. For example, compositions of this type may include a nonionic liquid surfactant in which particles of a detergency builder are dispersed, as described, for example, in U.S. patents. N * 4 316 812, 3 630 929 and 20 4 264 466 and in the British patents N * 1 205 711, 1 270 040 and 1 600 981.

Previous related patent applications are as follows;

Application FR-85.19510, filed on December 25, 1985, describes an aqueous liquid detergent composition containing a nonionic surfactant, comprising a suspension of an adjuvant detergency salt and containing an acid-terminated nonionic surfactant (for example the product reaction of a nonionic surfactant and succinic anhydride) to improve the dispersibility of the composition in an automatic washing machine.

This application also describes a monoalkyl ether of alkylene glycol as agent for adjusting the viscosity and anti-gelation in order to improve the dispersibility of the composition in an automatic washing machine.

^ Application FR-85.04831, filed March 29, 1985, describes a non-aqueous liquid detergent composition with nonionic surfactant, comprising a suspension of polyphosphate detergency builder and containing an alkanol ester of phosphoric acid in order to improve the stability of the suspension against sedimentation during storage.

Application FR-86.02815, filed on February 28, 1986, describes a non-aqueous liquid detergent composition with a nonionic surfactant, comprising a suspension of an adjuvant detergency salt and containing an aluminum stearate in order to improve the stability of the suspension with respect to sedimentation and to improve the flow limit of the composition while at the same time improving or lowering the plastic viscosity of the composition.

The washing power of the nonionic synthetic surfactant detergents contained in the laundry detergent compositions can be increased by the addition of detergency builders. Sodium tripolyphos-phate is one of the commonly used detergency builders. However, the use of poly sodium phosphate in dry powder detergents has several drawbacks, such as for example the tendency of polyphosphates to hydrolyze into pyro- and ortho-phosphates which represent less attractive detergency builders.

In addition, sodium tripolyphosphate tends to solidify when added to water and has relatively low solubility in water and a relatively low capacity for calcium sequestration.

Liquid detergents are often considered to be more convenient to use than dry powder or particulate products and have therefore met with widespread acceptance by consumers. They are easy to dose, dissolve quickly in washing water, can be easily applied in concentrated solutions or dispersions on dirty areas of clothes to be washed and do not produce dust, and they usually take up less space during storage. In addition, it is possible to include in the formulations of liquid detergents materials which cannot withstand drying operations without deterioration, materials which it would often be desirable to use in the manufacture of particulate detergent products. Although they offer many advantages over particulate or unitary solid products, liquid detergents often also have certain inherent drawbacks which must be remedied to obtain commercially acceptable detergent products. Thus, some of these products separate during storage and others separate by cooling and are not easily dispersed again. In some cases, the viscosity of the product changes and it becomes either too thick to pour, or so fluid that it appears aqueous. Some clear products become cloudy and others gel on standing.

Sodium tripolyphosphate, adjuvant detergency salt commonly used, has the disadvantage of having a tendency to degrade in concentrated nonaqueous liquid detergent compositions based on nonionic surfactant.

Although hexametaphosphates have been proposed for use in liquid detergent compositions as detergency builder salts, they have not been used since they are not common raw materials and they are expensive.

In addition to the problem of sedimentation or phase separation, nonaqueous liquid laundry detergents based on liquid nonionic surfactants have the disadvantage that nonionic surfactants tend to gel when added to water. Cold water. This is a particularly important problem in the current use of automatic household washing machines of the European type in which the user puts the detergent laundry composition in a dispenser compartment (for example a dispenser drawer) of the f machine. During the operation of the machine, the detergent contained in the dispenser is subjected to a stream of cold water used to transport it into the main body of the washing solution. Particularly during the winter months when the detergent composition and the feed water arriving at the dispenser are particularly cold, the viscosity of the detergent increases sharply and a gel is formed. As a result, a certain amount of the composition 25 is not completely expelled from the dispenser during the operation of the machine, and a deposit of composition accumulates during the successive washing cycles, which ultimately forces the user to clean the dispenser with hot water.

The gelation phenomenon can also be a problem whenever it is desired to wash using cold water, as may be recommended for certain synthetic and delicate fabrics or for fabrics which may not be used. wind shrink in warm or hot water.

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

Partial solutions to the problems of gelation in compositions substantially free of detergency builders have been proposed, for example by diluting the liquid nonionic surfactant with certain viscosity controlling solvents and certain gelation inhibiting agents, such as lower alkanols such as ethyl alcohol (see US Patent No. 3,953,380), formates and adi-alkali metal pastes (see US Patent No. 4,368,147 ), Hexylene glycol, polyethylene glycol, etc., and by modifying and optimizing the structure of nonionic surfactants. As an example of modification of nonionic surfactants, a particularly advantageous result has been obtained by acidifying the terminal group of the hydroxyl portion of the nonionic molecule. The advantages of introducing a carboxylic acid at the end of the nonionic surfactant include inhibition of gelling upon dilution, lowering of the drop point of the nonionic surfactant, and formation of an anionic surfactant by neutralization in the washing liquor. Optimization of the nonionic structure focused on the chain length of the hydrophobic-lipophilic moiety and the number and constitution of the alkylene oxide units (eg, ethylene oxide) of the hydrophilic moiety. For example, it has been found that a fatty alcohol ethoxylated with 8 moles of ethylene oxide * 6 exhibits only a limited tendency to gel formation.

However, it is desirable to improve dispersibility, pourability, solubility, stability, and inhibition of gel formation of non-aqueous liquid detergency adjuvant polyphosphate tissue compositions and non-ionic surfactant.

In accordance with the present invention, a highly concentrated non-aqueous liquid laundry detergent composition is prepared by dispersing a linear long chain condensed detergency builder polyphosphate in a liquid nonionic surfactant detergent.

The linear long chain condensed polyphosphates used as detergency builders according to the present invention are known compounds. Linear condensed polyphosphates of alkali metal and ammonium builders are readily soluble in water.

The linear condensed polyphosphates used in the present invention are represented by the general formula: 0

25 MO- (1-0) -M

1 n

OM

in which M is hydrogen, an alkali metal cation, for example sodium or potassium, or ammonium, and n = 20 to 30, preferably about 25.

It is preferable that all of the M's be an alkali metal. A preferred linear condensed polyphosphate is hexametaphosphate in which n = 25.

According to the present invention, it has been found that concentrated nonaqueous liquid detergents based on nonionic surfactant reinforced with hexa-metaphosphate have better dispersibility and better pourability than detergent compositions containing sodium tripolyphosphate. 5 Detergent compositions containing hexametaphosphates as the main detergency builder salts do not solidify when added to water and hexametaphosphates have greater water solubility than sodium tripoly-10 phosphate . It has also been found that the hexametaphosphate contained in the concentrated nonaqueous liquid detergent compositions with nonionic surfactant does not tend to degrade during storage.

It has also been found that hexameta- phosphates are good anti-scale and anti-scaling agents and prevent the development of calcium crystals. Hexametaphosphates have been formed to act in non-aqueous non-aqueous surfactant detergent compositions as agents with high calcium sequestering capacity. One gram of hexametaphosphate can sequester up to 163 mg of calcium, while 1 g of sodium tripolyphosphate can sequester up to 111 mg of calcium.

In the preferred embodiment of the invention, the sodium tripolyphosphate commonly used as a detergency builder is replaced by the long straight chain condensed polyphosphate of the present invention, for example an alkali metal lined hexametaphos. In the detergent compositions of the present invention, the detergency builder phosphate consists essentially of the condensed polyphosphate with a long straight chain, for example k 8 t an alkali metal hexametaphosphate.

In order to improve the viscosity characteristics of the composition, an acid-terminated nonionic over-faction can be added. To further improve the viscosity characteristics of the composition and its storage properties during storage, antifreeze and viscosity improving agents such as monoalkyl ethers of alkylene glycols and agents may be added to the composition. anti-sedimentation such as phosphoric acid esters and aluminum stearate. In one embodiment of the invention, the detergent composition contains an acid-terminated nonionic surfactant and / or an alkylene glycol monoalkyl ether and an anti-sedimentation stabilizer.

Sanitizers or bleaches and activators therefor can be added to improve the bleaching and sanitizing 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, preferably less than 40 microns, and more preferably less than 10 microns, to further improving the stability of the suspension of the detergency builder components in the liquid nonionic surfactant detergent.

Other ingredients can additionally be added to the composition, for example anti-scaling agents, anti-foaming agents, optical brighteners, enzymes, anti-redeposition agents, perfume and colorants.

- Washing machines currently manufactured for domestic use normally operate at washing temperatures of at most 100’C. A maximum of about 70 liters of water is used during the wash and rinse cycles.

Normally about 175 grams of powdered detergent is used per wash.

In accordance with the present invention, where a highly concentrated liquid detergent is used, normally only 100 grams (77 cm) or less of the liquid detergent composition is required to wash a full load of dirty laundry. Therefore, in accordance with one aspect of the present invention, there is provided a liquid composition for heavy duty laundry, consisting of a suspension of a linear condensed polyphosphate of alkali metal as a detergency builder salt in a liquid surfactant = - non-ionic.

In another aspect, the invention provides a concentrated liquid detergent composition for heavy duty laundry which is stable, does not settle out during storage and does not gel during storage and use. The liquid compositions of the present invention can be easily poured, easily dosed and easily introduced into the washing machine.

In another aspect, the invention provides a method for dispensing a nonionic liquid laundry detergent composition in and / or with cold water, without undergoing gelation. In particular, a method is provided for filling a container with a non-aqueous liquid laundry detergent composition, the detergent of which consists, at least in large part, of a suspension of a condensed polyphosphate with a long linear chain in an agent liquid nonionic surfactant, and for dispensing the composition by passing it from the container into an aqueous washing bath, in which the distribution is carried out by directing a stream of unheated water over the composition so that the composition is transported in the washing bath by the stream of water.

Concentrated nonaqueous liquid detergent compositions with nonionic surfactant containing a condensed polyphosphate with a long linear chain as a detergency builder have the advantages, compared to a detergent composition reinforced with sodium tripolyphosphate, of having a greater ability to be poured and better dispersibility, that the detergency builder salt does not tend to solidify when added to water, and that the detergency builder salt has greater solubility in water. 'water. The compositions of the present invention containing, for example, an alkali metal hexameta-phosphate as a detergency adjuvant, do not tend to degrade in the liquid nonionic sur-charge and have good anti-scale and anti-encrustation properties. and have a great capacity for sequestering calcium.

The concentrated non-aqueous liquid laundry detergent compositions based on non-ionic factif according to the present invention offer the advantages of being stable, of not settling during storage and of not gelling during storage. The liquid compositions can be easily poured, easily dosed and easily introduced into washing machines.

An object of the present invention is to provide a non-aqueous liquid detergent composition based on nonionic surfactant, for heavy work, containing as detergency builder salt an alkali metal hexa-metaphosphate suspended in a nonionic surfactant.

Another object of the invention is to provide liquid tissue treatment compositions which are suspensions of an alkali metal hexametaphosphate detergency builder in a non-aqueous liquid and which are storage stable and can be easily poured and dispersed in cold, lukewarm or hot water.

Another object of the invention is to formulate highly reinforced non-aqueous liquid detergent compositions, based on non-ionic surfactant, for heavy laundry work, which can be poured at any temperature and which can be dispersed in any way. repetitive from the dispenser compartment of automatic washing machines of the European type without clogging or obstructing the dispenser even during the winter months.

Another object of the present invention is to provide stable, non-gelling suspensions of reinforced non-aqueous liquid detergent composition based on non-ionic surfactant, for heavy laundry work, which comprise an effective amount of an alkali metal hexametaphosphate such as adjuvant detergent salt.

Another object of the present invention is to provide stable non-gelling suspensions of reinforced non-aqueous liquid detergent composition based on nonionic surfactant, for large laundering jobs, which contain an alkanolic ester of phosphoric acid and / or a salt aluminum fatty acid as an anti-sedimentation agent, in an amount sufficient to increase the stability of the compound 12

: / J

tion, i.e. to prevent sedimentation of the detergency builder particles, etc., preferably by reducing or at least not increasing the plastic viscosity of the composition.

These and other objects of the invention will become more apparent from the following detailed description of preferred embodiments and are generally achieved by preparing a detergent composition by adding to a nonionic liquid surfactant. non-aqueous an effective amount of an alkali metal hexametaphosphate detergency builder and mineral or organic tissue treatment additives, for example viscosity improving and anti-gelling agents, anti-sedimentation agents, anti-encrustation agents, bleaching agents, activators for bleaching agents, anti-foaming agents, optical brighteners, anti-redeposition agents, a perfume and colorants.

20 Non-ionic surfactant detergent

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

As is known, non-ionic synthetic organic detergents are characterized by the presence of a hydrophobic organic group and a hydrophilic organic group and they are generally produced by the condensation of a hydrophobic aliphatic or alkyl-aromatic organic compound. with ethylene oxy (hydrophilic in nature). Practically any hydrophobic compound comprising a carboxy, - hydroxy, amido or amino group having a free hydrogen atom linked to nitrogen can be condensed with 13 * ethylene oxide or with its polyhydration product, polyethylene -glycol, to form a nonionic detergent. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to achieve the desired ratio between the hydrophobic and hydrophilic groups. Representative examples of suitable nonionic surfactants are those described in U.S. patents. N * 4,316,812 and N * 3,630,929.

In general, nonionic detergents are lipophilic compounds alkoxylated by a poly- (lower alkoxy) group in which the desired hydrophilic / lipophyl ratio is obtained by the addition of a hydrophilic poly (lower alkoxy) group to a lipophilic fragment. A preferred class of nonionic detergents used is the higher alkanols alkoxylated by poly (lower alkoxy) groups, in which the alkanol has 9 to 18 carbon atoms and in which the number of moles of oxide 20 of Lower alkylene (of 2 or 3 carbon atoms) is from 3 to 12. Among these materials, it is preferred to use those in which the higher alkanol is a higher fatty alcohol of 9 to 11 or 12 to 15 carbon atoms, and which contain 5 to 8 or 5 to 9 lower alkoxy groups per mole. Preferably, the lower alkoxy group is the ethoxy group, but in some cases it can be advantageously mixed with the propoxy group which, if present, often represents only a minor proportion (less than 50%).

Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups ώ per mole, for example Neodol 25-7 and Neodol 23-6.5, which are products manufactured by Shell Chemical 14

Company, Inc. The first is a condensation product of a mixture of higher fatty alcohols having on average about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide, and the second is one; 5 corresponding mixture in which the carbon atom content of the higher fatty alcohol is from 12 to 13, and the number of ethylene oxide groups present represents an average of about 6.5. Higher alcohols are primary alkanols.

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

Also useful in the composition of the invention, as a component of the non-ionic detergent, non-ionic surfactants of higher molecular weight, such as Neodol 45-11, which are similar condensates of ethylene oxide on higher fatty alcohols, the higher fatty alcohol com-25 having 14 or 15 carbon atoms, and the number of ethylene oxide groups per mole being about 11. These products are also manufactured by Shell Chemical Company.

Other useful nonionic surfactants are represented by the well-known trade class of nonionic surfactants sold under the trademark Plurafac. Plurafac products are the product. reaction of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include Product A (a 3 “c-d5 fatty alcohol con densed with 6 moles of ethylene oxide and 3 moles of o; 5 propylene xene), Product B (a 3-C15 fatty alcohol condensed with 7 moles of propylene oxides and 4 moles of ethylene oxide), and Product C (a fatty alcohol in ^ 3- ^ 5 condensed with 5 moles of propylene oxide and 10 moles of oxide ethylene).

Another group of liquid nonionic surfactants are commercially available from Shell Chemical Company, Inc., under the trade name Dobanol: Dobanol 91-5 is a C 8 -C 8 ethoxylated fatty alcohol with an average of 5 moles. of ethylene oxide and Dobanol 25-7 is an ethoxylated C 1 -C 2 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

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

When using proportions greater than those mentioned above of alkanols whose alkoxylation is not terminal, of alkanols alkoxylated by poly (lower alkoxy) groups containing 11 propylene oxide and of non-ionic detergent with a lower water-lipid ratio, and when 17 other non-ionic detergents are used in place of the preferred nonionic detergents listed herein, the resulting product may not have as good detergency, stability properties viscosity and non-gelling than the preferred compositions, but the use of the compounds of the invention acting on the viscosity and inhibiting gelling can also improve the properties of detergents based on such nonionic compounds. In some cases, for example when a higher molecular weight poly (lower alkoxy) alkanol is used, often for its detergency, its proportion is adjusted or limited in accordance with the results of routine experiments, to obtain the detergent power desired and to obtain at the same time a non-gelling product and desired viscosity. Also, it has been found that it is only rarely necessary to use higher molecular weight nonionic surfactants for their detergent properties, since the preferred nonionic surfactants described herein are excellent detergents and, moreover, achieve viscosity in liquid detergent without gelation at low temperatures.

Another useful group of nonionic surfactants is the "Surfactant T" series of nonionic surfactants from British Petroleum. The nonionic surfactants Surfactant T are obtained by ethoxylation of C13 secondary fatty alcohols with a narrow distribution of ethylene oxide. Surfactant T5 has an average of 5 moles of ethylene oxide; Surfactant T7 has an average of 7 moles of ethylene oxide; Surfactant T9 has an average of 9 moles of ethylene oxide and Surfactant T12 has an average of 12 moles of ethylene oxide, per 18 moles of C13 secondary fatty alcohol.

In the compositions of the present invention, preferred nonionic surfactants include. C13-C ^ 5 secondary fatty alcohols having relatively limited contents of ethylene oxide of about 7 to 9 moles, and Cg fatty alcohols to ethoxylated with about 5 to 6 moles of oxide ethylene.

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

Acid-terminated nonionic surfactant

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

As described in patent application FR-85 25 05319 filed on April 9, 1985, non-ionic surfactants modified by a free carboxyl group, which can roughly be characterized as being polyether-carboxylic acids, act so as to lower the temperature to which the nonionic surfactant liqui-30 forms a gel with water.

The addition of acid-terminated nonionic surfactants to the liquid nonionic surfactant enhances the ability of the composition to be dispensed, i.e., to be poured, and reduces the temperature to • f 19 which the Liquid nonionic surfactants form a gel in water without reducing their stability to sedimentation. The acid-terminated nonionic surfactant reacts in water of the ma-; 5 china to wash with the alkalinity of the dispersed phase of detergency builder salt of the detergent composition and acts as an effective anionic surfactant.

Particular examples include the hemi-esters of Plurafac RA30 with succinic acid, the ester or hemi-ester of Dobanol 25-7 with the succinic anhydride, and the ester or hemi-ester of Dobanol 91 -5 with succinic anhydride. Instead of succinic anhydride, other polycarboxylic acids or anhydrides can be used, for example maleic acid, maleic acid anhydride, citric acid, etc.

Acid-terminated nonionic surfactants can be prepared as follows:

Acid-terminated Product A: 20,400 g of nonionic surfactant Product A is mixed, which is an alkanol having been alkoxylated to introduce 6 ethylene oxide units and 3 propylene oxide units per alkanol unit, with 32 g of succinic anhydride and the mixture is heated for 7 hours at 100 ° C. The mixture and the filter are cooled to separate the unreacted succinic material. Infrared analysis shows that about half of the nonionic surfactant has been converted to its acid hemi-ester.

Acid-terminated Dobanol 25-7: 522 g of non-ionic surfactant Dobanol 25-7, which is the ethoxylation product of a C12 ~ C15 alkanol and contains approximately 7 ethylene oxide units per mo, are mixed. - the alkanol molecule, with 100 g of succinic anhydride and 0.1 g of pyridine (which acts as an esterification catalyst) and heated to 260 ° C for 2 hours, cooled and filtered to separate the unreacted succinic material. Infrared analysis shows that almost all of the free hydroxyl groups of the surfactant ~ 5 have reacted.

Acid-terminated Dobanol 91-5: 1000 g of non-ionic surfactant Dobanol 91-5 are mixed, which is the ethoxylation product of a C 8 alcohol with and has approximately 5 ethylene oxide units per 10 N alkanol molecule , with 265 g of succinic anhydride and 0.1 g of pyridine as catalyst, and the mixture is heated at 260 ° C. for 2 hours, cooled and filtered to separate the unreacted succinic material. Infrared analysis shows that almost all of the free hydroxyl groups in the surfactant have reacted.

Other esterification catalysts, such as an alkali metal alcoholate (for example sodium methylate), can be used in place of or mixed with pyridine.

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

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

The present invention includes, as an essential part of the composition, condensed polyphosphates with a long linear chain, detergency builders.

The linear long chain condensed polyphosphates used as detergency builders in the detergent compositions of the present invention have the following general formula:

O

II

MO- (P-O) -M

5 1

5 OM

in which M is chosen from hydrogen, an alkali metal or ammonium cation, and n = 20 to 30, preferably about 25. The M are preferably all alkali metals or ammonium, for example the sodium or potassium, sodium being more preferred. A preferred detergency builder salt is an alkali metal or ammonium hexame-taphosphate.

A particular example of a linear condensed polyphosphate which can be used as a detergency builder is represented by the formula: 0

II

NaO- (P-O) -Na 1 n 20 O 'n = 25

N / A

Detergent compositions containing alkali metal hexametaphosphates provide better cleaning performance. For example, 3,100g (77cm) of a reinforced detergent containing 29.6% sodium hexametaphosphate provides cleaning performance equivalent to 100g (77cm) of reinforced detergent containing 30% tripolyphosphate 30 sodium.

The detergent compositions of the invention may also contain adjuvant mineral detergency salts soluble in water and / or insoluble in water. Suitable water-soluble alkaline inorganic detergency builder salts which can be used alone or in admixture with other detergency builders are carbonates, bicarbonates, borates, phosphates, polyphosphates and alkali metal silicates. (It is also possible to use ammonium or substituted ammonium salts). Examples of commonly used detergency builder salts are sodium tri-polyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, bicarbonates sodium and potassium. Sodium tripolyphosphate (TPP) is a commonly used detergency builder salt.

The alkali metal silicates are useful detergency builder salts which also act to adjust or adjust the pH and to make the composition anticorrosive to parts of the washing machine. Sodium silicates having Na 2 O / SiC> 2 ratios of 1.6: 1 to 1: 3.2, in particular about 1: 2 to 1: 2.8, are preferred. It is also possible to use potassium silicates with the same ratios. A preferred alkali metal silicate is sodium disilicate.

Since the compositions of the present invention are generally very concentrated and, therefore, can be used in relatively small amounts, it is advantageous to supplement the condensed polyphosphate with long straight chain, detergency builder using an auxiliary adjuvant such as an alkali metal salt of lower polycarboxylic acid having a large capacity for fixing calcium and magnesium, making it possible to inhibit incrustation which could otherwise be caused by formation insoluble calcium and magnesium salts. Suitable alkali metal salts of polycarboxylic acids are alkali metal salts of citric and tartaric acids, for example monosodium citrate (anhydrous), trisodium citrate, a salt of glutaric acid, a salt of gluconic acid and a longer chain diacid salt.

Other organic detergency builders are polymers and copolymers of polyacrylic acid and polymaleic anhydride and their alkali metal salts. More particularly, these detergency builder salts can consist of a copolymer which is the reaction product of an approximately equal number of 15 moles of methacrylic acid and of a maleic hydride, which has been completely neutralized to form its salt of sodium. The detergency builder is commercially available under the trademark Sokalan CP5. This detergency builder 20 serves, when used in even small amounts, to inhibit encrustation.

Examples of sequestering alkaline organic detergency builder salts that can be used with detergency builder salts or in admixture with other organic and inorganic detergency builders are alkali metal ammonium or aminopolycarboxylates substituted ammonium, for example sodium and potassium ethylenediaminetetraacetate (EDTA), sodium and potassium nitriloacetates (NTA) and triethanolammonium N- (2-hydroxyethyl) nitrilodiacetates. The mixed salts of the corresponding ami-nopolycarboxylic acids are also suitable.

Other organic detergency builders 24 include polyacetal carboxylates. Polyaceous-tal-carboxylates and their use in detergent compositions are described in U.S. patents. N * 4 144 226, 4 315 092 and 4 146 495.

Other representative examples of suitable detergency builders include, for example, those described in US Pat. Nos. 4,316,812, Nos. 4,264,466 and 3,630,929. Alkaline mineral salts detergency builders can be used with the non-ionic detergent surfactant or in admixture with other organic salts or inorganic detergency builders.

The water-insoluble crystalline and amorphous zeolytic aluminosilicates can be used. Zeolites generally have the formula: (M2 ° V (â12 ° 3Y (Si ° 2Y WH2 ° in which x is equal to 1, y is a number from 0.8 to 1.2 and is preferably equal to 1, z is a number from 1.5 to 3.5 or more, and preferably is 2-3, and 20 w is a number from 0 to 9, preferably 2.5 to 6, and M is preferably A representative example of a zeolite is a type A or similar structure zeolite, with type 4A being particularly preferred The preferred aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents per gram or more, for example 400 milliequiva-slow per gram.

Various crystalline zeolites (i.e., aluminosilicates) that can be used are described in British Patent Nos. 1,504,168, the U.S. Patent. N * 4,409,136 and in Canadian patents N * 1,072,835 and N * 1,087,477. An example of amorphous zeolites useful here can be found in Belgian patent N * 835,351.

Other materials such as clays, particularly water-insoluble types, may be useful additives in the compositions of the present invention. A particularly useful clay "5 is bentonite. This material is mainly 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 various amounts of hydrogen, sodium, potassium, calcium, etc. can be poorly combined. Bentonite, in its more purified form (that is to say completely free of sand, abrasive particles, etc.), suitable for detergents contains at least 50% montmorillonite and thus its cation exchange capacity is at least about 50 to 75 milliequivalents per 100 g of bentonite. Particularly preferred bentonites are bentonites from Wyoming or from Western United States of America which sold under the designations 20 of Thixo-jel 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften textile materials, as described in the British patents N * 401,413 and 461,221.

Viscosity Adjusters and Anti-Gelling The incorporation into the detergent composition of an effective amount of low molecular weight amphiphilic compounds acting as viscosity adjusting and gelling inhibiting agents for non-surfactant ionic significantly improves the. storage properties during storage of the composition. Amphiphilic compounds can be considered to have a chemical structure analogous to that of liquid nonionic surfactants derived from ethoxylated and / or propoxylated fatty alcohols, but they have relatively short hydrocarbon chain lengths (C2 to Cg) and a low content. into ethylene oxide (approximately 2 to 6 ethylene-Ξ 5 lene groups per molecule).

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

RO (CH-CH-O) H

2. 2 n where R is a C2-C6 alkyl group and n is a number of about 1 to 6 on average.

In particular, the compounds are lower monoalkyl ethers (C2 to C8) of lower alkylene glycols (C2-C3).

More particularly, the compounds are ~ 15 lower monoalkyl ethers (C ^ -Cg) of lower mono-, di- or trialkylene glycols (C2-C3).

Particular examples of suitable amphiphilic compounds include the ethylene glycol monoethyl ether (C2Hg-O-CH2CH20H), the diethylene glycol mono-butyl ether (C ^ Hg-O- (CH2CH20) 2H), the monobutyl ether of tetraethylene glycol (C ^ H ^ -0- (CH2CH20) ^ H) and the monomethyl ether of di-propylene glycol (CH3-0- (CHjCHO) 2H). Particular preference is given to CH3 for the monobutyl ether of diethylene glycol col.

By incorporating low molecular weight lower alkylene glycol monoalkyl ether into the composition, the viscosity of the composition is decreased, so that it is easier to pour, the stability is improved vis-à-vis sedimentation and the dispersibility of the composition is improved when it is added to lukewarm or cold water.

27

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

Stabilizers

In one embodiment of the present invention, the physical stability of the suspension of the detergent builder compound (s) and any other suspended additive, e.g. bleach, etc., in the liquid vehicle is improved by the presence of a stabilizing agent which is an alkanol ester of phosphoric acid or an aluminum salt of a higher fatty acid.

~ 15 In certain formulations, the stability of the composition can be improved by incorporating a small but effective amount of an acidic organic phosphorus compound comprising an acid group -POH, for example a partial ester of phosphorous acid and 20% an alkanol.

As described in the aforementioned patent application FR 8505319, the acidic organic phosphorus compound comprising an acidic -POH group can increase the stability of the suspension of detergency builders in the nonaqueous nonionic liquid surfactant.

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

A particular example is a partial ester; phosphoric acid and a C ^ to C ^ g alkanol (Empiphos 5632 from Marchon); it consists of approximately * 28 35% monoester and 65% diester.

The incorporation of very small quantities of the organic phosphorus acid compound makes the suspension clearly more stable with respect to a sediment; 5 at rest, while leaving it suitable for pouring, while at this low concentration of stabilizer, for example less than about 1%, its plastic viscosity generally decreases.

The stability and anti-sedimentation properties of the composition can be further improved by adding to the composition a small and effective amount of an aluminum salt of a higher fatty acid.

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

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

Examples of fatty acids from which stabilizing aluminum salts can be formed include 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 generally commercially available, and they are preferably used in the form of three acid residues, for example aluminum stearate in the form of aluminum tristearate Al (C ^ H ^ COO) 3 · Salts with an acid residue, for example aluminum monostate-5, A1 (OH) (C1? H35COO) 2 and salts with two acid residues, for example aluminum distearate, A1 (OH) (C ^ H3gCOO) 2 and mixtures of two or three of the aluminum salts with one, two or three acid residues can also be used. However, it is particularly preferable that the aluminum salt with three acid residues constitutes at least 30%, preferably at least 50%, more preferably at least 80%, of the total amount of aluminum salt of fatty acid.

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

Although the Applicant does not wish to be bound by any particular theory on how the aluminum salt acts to prevent sedimentation of the suspended particles, it assumes that the aluminum salt increases the wettability of solid surfaces by the nonionic surfactant. This increase in wettability therefore allows the particles in suspension to remain more easily in suspension.

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

In addition to its action as a physical stabilizer, aluminum salt has the additional advantages over other physical stabilizers that it is non-ionic in character and is compatible with the non-ionic surfactant and does not disturb the detergent action. overall composition; it has a certain anti-foam effect; it can ren-5 force the action of fabric softeners and it gives suspensions a longer duration of relaxation.

Bleaching Agents 10 Bleaching agents are broadly classified by convenience into chlorine-based bleaching agents and oxygen-based bleaching agents. Chlorinated bleaches are represented by sodium hypochlorite (NaOC1), potassium dichloroisocyanurate ~ 15 (59% active chlorine) and trichloroisocyanuric acid (95% active chlorine). Oxygenated bleaches are preferred and are represented by co-compounds which release hydrogen peroxide in solution. Preferred examples include per-borates, percarbonates and perphosphates of sodium and potassium and potassium monopersulfate. Perborates, in particular sodium perborate mo-nohydrate, are particularly preferred.

The peroxygen compound is preferably used in admixture with an activator. Suitable activators that can lower the effective activity temperature of the peroxide bleach are described, for example, in the U.S. Patent. No. 4,264,466 or in column 1 of the U.S. Patent No. 4 30 430 244. Polyacylated compounds are the preferred activators; among them, compounds such as tetraacetylethylene diamine ("TAED") and pentaacetylglucose are even more preferred.

Other useful activators include, for example, derivatives of acetylsalicylic acid, ethylidene benzoic acetic acid and its salts, ethylidene carboxylic acetic acid and its salts, alkyl- and alkenyl succinic anhydrides , 5-traacetylglycourile ("TAGU"), and their derivatives.

Other useful classes of activators are described, for example, in U.S. patents. N * 4 111 826, N * 4 422 950 and N * 3 661 789.

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

Suitable sequestering agents for this purpose include the sodium salts of nitri-lotriacetic acid (NTA), ethylene-diamine-tere-traacetic acid (EDTA), diethylene-triamine-pentaacetic acid (DETPA) ), diethylene triamine pentamethylene phosphonic acid (DTPMP) sold under the trademark Dequest 2066; and ethylene diamine-tetramethylene phosphonic acid (EDITEMPA). The sequestering agents can be used alone or in admixture.

In order to avoid a loss of the bleaching peroxide, for example sodium perborate, resulting from a decomposition under the action of enzymes, for example catalase, the compositions can also contain an enzyme inhibitor , that is to say a compound capable of inhibiting the decomposition, under the action of enzymes, of bleaching peroxide. Suitable inhibitors are described in the U.S. Patent. N * 3 32 606 990.

As a particular inhibitor of interest, mention may be made of hydroxylamine sulfate and other water-soluble hydroxylamine salts. In the preferred nonaqueous compositions of the present invention, suitable amounts of the inhibitory hydroxylamine salts may be as low as about 0.01-0.4%. However, in general, suitable amounts of inhibitors of enzymes range up to about 15%, for example 0.1 to 10% by weight of the composition.

In addition to detergency builders, various other additives or auxiliaries for detergents may be present in the detergent product to provide it with other desired properties, functional or aesthetic in nature. Thus, one can include in the formulation of minor quantities of agents of suspension or of anti-redeposition of the stains, for example polyvinyl alcohol, fatty amides, sodium carboxymethylcellulose, hydroxypropyl methyl -cellulose. A preferred anti-redeposition agent is sodium carboxymethylcellulose having a CM / MC ratio of 2: 1, which is sold under the trade name Relatin DM 4050.

Optical brightening agents can be used only for cotton, polyamide and polyester fabrics. Suitable optical brightening agents include compositions of stilbene, triazole and benzidine sulfone, in particular substituted sulfonated triazinyl-stil-bene, sulfonated naphthotriazolestilbene, benzidene sulfone, etc., those which are preferred being combinations of stilbene and * triazole. Preferred brightening agents are Stilbene

Brightener N4 which is a dimorpholino-dianilino-stil-bene-sulfonate and Tinapal ATS X which is well known in the art.

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

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

The composition may also contain an insoluble mineral thickener or dispersant with a very large contact surface, for example finely divided silica of extremely small particle size (for example with a diameter of 5 to 100 nanometers, such as that sold under the name Aerosil) or the other very bulky mineral supports described in the US patent N * 3,630,929, in proportions of 0.1 to 10%, for example from 1 to 5%. However, it is preferable that the compositions which form peroxyacids in the wash bath (for example compositions containing a peroxygen compound and an activator therefor) are substantially free of such compounds and others if k 34 licates; it has been found, for example, that silica and silicates promote undesirable decomposition of the peroxyacid.

In one embodiment of the invention, the stability of the detergency builder salts in the composition during storage and the dispersibility of the composition in water are improved by grinding and reducing the particle size of the solid detergency builders 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 about 100, 200, or 400 microns. The liquid nonionic surfactant phase can be mixed with the solid detergency builders before or after the grinding operation.

In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid ingredients is subjected to attrition milling in which the particle sizes of the solid ingredients are reduced to less than about 40 micrometers , preferably to less than about 10 microns, for example to an average particle size of 2 to 10 microns or even less (for example 1 micron). Preferably, less than about 40%, in particular less than about 5% of all of the suspended particles have particle sizes greater than 10 microns. Compositions whose dispersed particles are of such small size have better stability with respect to separation or sedimentation during storage. The addition of the acid-terminated nonionic surfactant compound promotes dispersibility of the dispersions without a corresponding decrease in the stability of the dispersions against sedimentation.

For the grinding operation, it is preferable that the proportion of solid ingredients is sufficiently high (for example at least about 40%, such as about 50%) so that the solid particles are at contact with each other and are not too isolated from each other by the nonionic liquid surfactant. After the grinding step, any remaining liquid nonionic surfactant to be incorporated can be added to the milled formulation. Grinders which use grinding balls (ball mills) or similar movable grinding elements have given very good results. Thus, it is possible to use a laboratory attrition mill working with batch loads, comprising grinding balls made of soapstone 8 mm in diameter. For a larger scale operation, one can use a continuously working grinder in which there are 20 grinding balls with a diameter of 1 mm or 1.5 mm operating in a very small interval between a stator and a rotor operating at a relatively high speed (for example a CoBall mill); when using such a mill, it is advantageous to pass the mixture of nonionic surfactant and solids first through a mill which does not perform such a fine grinding (for example a colloid mill) in order to reduce the particle size to less than 100 micrometers (for example to about 40 mi-30 crometers) before the grinding step to an average particle diameter less than about 10 micrometers in the continuously working ball mill.

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

The acid-terminated nonionic surfactant can be omitted; however, it is preferable to add it to the composition in a proportion in the range of about 0 to 30, for example 5 to 25, and especially 5 to 15 percent.

Linear long chain condensed polyphosphates, detergency builders: in the range 15 of about 10 to 60, for example 20 to 50, and especially 25 to 35 percent.

Copolymer of polyacrylic acid and polymaleic anhydride, alkali metal salt, as an anti-scaling agent: in the range of about 0 to 20 10, for example 2 to 8, especially 2 to 6 percent.

Alkylene glycol monoalkyl ether as anti-gelling agent: in a proportion in the range of about 0 to 20, for example 5 to 15, especially 8 to 12 percent.

Stabilizing agent of the alkanolic ester type of phosphoric acid: in the range from 0 to 2.0 or 0.1 to 2.0, for example 0.10 to 1.0 percent.

Stabilizing agent of the fatty acid aluminum salt type: in the range of about 0 to 3.0, for example 0.1 to 2.0 and especially 0.5 to 1.5 percent.

: It is preferable that at least one of the stabilizing agents of the ester type of phosphoric acid or aluminum salt is present in the composition.

37

Bleaching agent: in the range of about 0 to 35, for example 5 to 30, and especially 8 to> 15 percent.

? Bleach activator: in the range of about 0 to 20, for example 1 to 15 and especially 2 to 6 percent.

Sequestering agent for the bleaching agent: in the range of about 0, to 3.0, preferably 0.5 to 2.0 and especially 0.5 to 1.5 percent.

Anti-redeposition agent: in the range of about 0 to 3.0, for example 0.5 to 2.0, and especially 0.5 to 1.5 percent.

Optical brightener: in the range - from about 0 to 2.0, for example 0.05 to 1.5, and especially 0.3 to 1.0 percent.

Enzymes: in the range of about 0 to 3.0, for example 0.5 to 2.0, and especially 0.5 to 1.5 percent.

Perfume: in the range of about 0, to 2.0, for example 0.10 to 1.25, and especially 0.5 to 1.0 percent.

Colorant: in the range of about 0 to 1.0 for example 0.0025 to, 0.050, and especially 0.0025 to 0.0100 percent.

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

It is possible to use mixtures of the acid-terminated nonionic surfactant and of anti-gelation agents of the alkyl ether alkylene glycol type and, - in certain cases, it is possible to benefit from the use of such mixtures alone, or with the addition to the mixture of a stabilizing and anti-sedimentation agent, for example an alkanol ester of phosphoric acid.

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

The concentrated non-aqueous liquid detergent composition based on the nonionic surfactant of the present invention is easy to dispense into the water of the washing machine. Household washing machines currently in use normally use about 250 grams of powdered detergent to wash a full load of laundry. According to the present invention, only about 77 cm or about 100 grams of the concentrated liquid detergent composition with nonionic surfactant is required.

In a preferred embodiment of the invention, a typical detergent composition is formulated using the ingredients listed below:% by weight Non-ionic surfactant 30-40 25 Acid-terminated surfactant 5-15

Alkali metal hexametaphosphate 25-35

Anti-scaling agent (Sokalan CP 5) 0-10

Alkylene glycol monoalkyl ether 8-12

Alkanolic ester of phosphoric acid 30 (Empiphos 5632) 0.1-1.0 - Anti-redeposition agent (Relatin DM 4050) 0-3.0 “Perborate of alkali metal bleaching 8-15“

Bleaching agent activator (TAED) 2-6 Sequestering agent (Dequest 2066) 0-3.0 y 39

Optical brightening agent (ATS X) 0.05-1.0

Enzymes (Protease Esperase SL8) 0.5-1.5

Perfume 0.5-1.0

The following nonlimiting examples illustrate the present invention.

EXAMPLE 1

A non-aqueous concentrated liquid detergent composition based on non-ionic active surfactant is prepared from the following ingredients in the indicated pro portions:% by weight

A mixture of fatty alcohol condensed with 7 moles of ~ 15 propylene oxide and 4 moles of ethylene oxide "and fatty alcohol of 3-C ^ 5 condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide 15.5

Surfactant T7 9.0 20 Surfactant T9 9.0

Acid-terminated reaction product of Dobanol 91-5 with succinic anhydride 6.0

Sodium hexametaphosphate 29.6

Diethylene glycol monobutyl ether 9.0 25 Alkanolic ester of phosphoric acid (Empiphos 5632) 0.3

Anti-scaling agent (Sokalan CP 5) 3.0

Sodium perborate bleach monohydrate 10.0 30 Tetraacetylethylene diamine (TAED) as an activator of the bleach 4.5

Sequestering agent (Dequest 2066) 1.0 1 Optical brightening agent (Tinopal ATS X) 0.5

Anti-redeposition agent (Relatin DM 4050) 1.0 40

Esperase suspension (Esperase SL8) 1.0

Perfume 0.5925 - Colorant 0.0075 100.00, 5 The formulation is ground for approximately 1 hour to reduce the particle size of the detergency builder salts in suspension to less than 40 micrometers. The prepared detergent composition is shown to be stable and non-gelling upon storage and has great detergency.

The formulations can be prepared without grinding the detergent builder salts and the suspended solid particles to a small particle size, but best results are obtained by grinding the composition to reduce the particle size of the suspended solid particles.

The detergency builder salts can be used as supplied, or the detergency builder salts and suspended solid particles can be ground or partially ground before being mixed with the nonionic surfactant. The grinding can be carried out in part before mixing and can be completed after mixing, or else all the grinding can be carried out after mixing with the liquid surfactant. Preference is given to compositions containing, in suspension, particles of detergency builder and solids of dimension less than 100 micrometers.

EXAMPLE 2

In order to demonstrate the effect on the cleaning and anti-scaling or anti-scaling performance of the substitution of tripolyphspohate by sodium hexametaphosphate as adjuvant detergency salt of the present invention, one compares, during cycles washing machine, the detergent composition of Example 1 containing 29.6% by weight of sodium hexametaphosphate with the same composition in which the hexametaphosphate is replaced by 30% by weight of sodium tripolyphosphate sodium.

Wash cycles are repeated at concentrations in the wash water of 5 g / liter of each of the respective detergent compositions.

After each detergent composition has been used in a washing machine for twelve washing cycles, the degree of incrustation or scale formation, that is to say the percentage of: 15 ash deposited, is measured. The percentage of ash deposited is measured by calcining the washed parts.

As a result, the cleaning performance of the sodium hexametaphosphate detergent composition is equivalent to or better than that containing sodium tripolyphosphate and the detergent composition of sodium hexametaphosphate provides anti-scaling or anti-scaling performance improved by compared to that containing sodium tripolyhosphate.

With regard to the build-up of build-up, no build-up was observed with hexametaphosphate, while a slight build-up was observed with sodium tripolyphosphate as adjuvant detergency.

Detergent builder hexametaphosphates can also be used to replace detergent builder polyphosphates in concentrated aqueous detergent compositions. At concentrations of 50 to 60%, due to the polymer structure of hexametaphosphate, a viscous solution is obtained. Due to the viscous nature of the concentrated aqueous solution, the physical stability and rheological behavior of the concentrated aqueous composition are improved.

v "k l -

Claims (13)

2. A detergent composition according to claim 1, characterized in that it contains at least one of the elements of the group formed by an anti-gelling agent of the acid-terminated nonionic surfactant type, an alkylene mono-ether. glycol and a stabilizing agent of the alkanolic ester type of phosphoric acid. 3. Detergent composition according to claim 1, characterized in that it contains one or more detergent additives chosen from the group formed by a bleaching agent, a bleaching agent activator, an optical brightening agent. enzymes and a scent. 4. A detergent composition according to claim 1, characterized in that it contains 10 to 60 percent of a long-chain detergency builder salt of formula: O 11 MO- (PO) -M 25. n OM in which M is chosen from the group formed by - hydrogen and alkali metal cations and * - * 30 ammonium, and n = 20 to 30. 5. Detergent composition according to claim 1, characterized in that it contains 5 to 44 percent of an acid-terminated surfactant. 6. A detergent composition according to claim 1, characterized in that it contains 0.10 to * 2.0 percent of an alkanolic ester of phosphoric acid. 7. A detergent composition according to claim 1, characterized in that it contains about 5 to 1-5 percent of an alkylene glycol mono-ether. 8 - Detergent composition according to claim 1, characterized in that the nonionic surfactant contains, in the dispersed state, particles of detergency builder having a particle size of less than about 40 micrometers. 9 - Detergent composition according to claim 1, characterized in that it contains at least * one liquid nonionic surfactant in a proportion of about 20 to 50%, a nonionic surfactant with acid termination in a proportion of '' about 5 to 25%, an alkali metal hexametaphosphate (n = 25) as detergency builder salt in a proportion of about 20 to 50%, an alkylene glycol mono-ether in a proportion of about 5 at 15%, and an alkanolic ester of phosphoric acid in a proportion of about 0.1 to 1.0%. 10. Detergent composition according to claim 9, characterized in that it contains an alkali metal monohydrate perborate as a bleaching agent in a proportion of about 5 to 30%, of tetraacetylethylene diamine as activator of agent L bleach in a proportion of about 1 to 15%, and J optionally one or more detergent additives chosen from the group formed by an anti-encrustation agent, an anti-redeposition agent, a sequestering agent * 45 for the bleaching agent , brightening agents, enzymes and a fragrance. - 11 Detergent composition according to claim 9, characterized in that the detergency builder consists of sodium hexametaphosphate (n = 25). 12. Detergent composition according to claim 9, characterized in that the sodium hexametaphosphate is represented by the formula: 10 O II NaO- (P-O) -Na I n ONa * 5 in which n = 25. 13. Detergent composition according to claim 9, characterized in that the alkanolic ester of phosphoric acid consists of an ester of al-canol in C ^ g-C ^ of phosphoric acid. 14 - Detergent composition according to claim 9, characterized in that it can be poured at low and high temperatures, it is stable during storage and does not gel when mixed with cold water. 15 - Detergent composition according to claim 9, characterized in that it contains as detergency builder salt sodium hexametaphosphate (n = 25) in a proportion of about 25 to 35 percent. 30. 16 - Concentrated non-aqueous liquid detergent composition with nonionic surfactant for large laundering works, characterized in that it contains approximately 30 to 40% of nonionic surfactant, approximately 5 to 15% of acid-terminated surfactant, Μ 46 λ about 23 to 35% of sodium hexametaphosphate, about 8 to 12% of monobutyl alkylene glycol ether, “about 0.1 to 0.5% of C 1 -C 4 alkanolic ester of phosphoric acid about 8 to 15% sodium perborate monohydrate as a bleaching agent, and about 4 to 8% tetraacetylethylene diamine (TAED) as an activator of the bleaching agent. 17. A detergent composition according to claim 16, characterized in that it comprises an anti-redeposition agent, an anti-encrustation agent and a sequestering agent for the bleaching agent. 18. A method for cleaning soiled fabrics, characterized in that it consists in bringing the soiled fabrics in contact with the detergent composition according to claim 1. 19. A method for cleaning soiled fabrics, characterized in that it consists in bringing the soiled fabrics in contact with the detergent composition according to claim 9. 20 - A method for cleaning soiled fabrics, characterized in that it bringing the soiled fabrics into contact with the laundry detergent composition according to claim 16.