BE1001722A5 - POLYPHOSPHATE CONTAINING NON-AQUEOUS LIQUID LIQUID DETERGENT COMPOSITIONS AND METHODS FOR CLEANING DIRTY TISSUES USING THE SAME. - Google Patents

Abstract

Non-aqueous liquid detergent composition for heavy laundry work. Said composition comprises at least one liquid nonionic surfactant and, in the dispersed state, as the main detergency builder salt, a condensed alkaline polyphosphate with a long straight chain, in particular sodium hexametaphosphate.

Description

       

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  Non-aqueous liquid laundry detergent compositions containing a polyphosphate and methods for cleaning soiled fabrics using them
The present invention relates to non-aqueous liquid compositions for the treatment of tissue. More particularly, the present invention relates to non-aqueous liquid laundry detergent compositions, containing a suspension of a linear condensed polyphosphate detergency builder in nonionic surfactants, which compositions are stable with respect to separation of phases 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 large laundering jobs 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. Pat. Nos. 4,316,812.3 630,929 and
4,264,466 and in British patents Nos. 1,205, 711, 1,270,040 and 1,600,981.



   Previous related patent applications are as follows:
Request FR-85. 19510, filed December 31, 1985, describes an aqueous liquid detergent composition containing a nonionic surfactant, comprising a suspension of a detergency builder salt and containing an acid-terminated nonionic surfactant (for example the reaction product 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 glycot as a regulating agent.

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 viscosity and anti-gelation in order to improve the dispersibility of the composition in an automatic washing machine.



   Request FR-85. 04831, filed March 29, 1985, describes a detergent composition, a non-aqueous liquid with a nonionic surfactant, comprising a suspension of detergency adjuvant polyphosphate and containing an alkanol ester of phosphoric acid in order to improve the stability of the suspension. -to sedimentation during storage.



   Request FR-86. 02815, filed 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 vis a sedimentation and improve the flow limit of the composition while improving or lowering at the same time 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 tripolyphosphate is one of the commonly used detergent builders. However, the use of sodium polyphosphate in dry powder detergents has several drawbacks, such as for example the tendency of polyphosphates to hydrolyse into pyro- and ortho-phosphates which represent less interesting detergency builders.



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

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   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 soiled areas of clothes to be washed and do not produce dust, and they usually take up less storage space . 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 solid particulate or unitary products, liquid detergents often also have certain inherent disadvantages which must be remedied in order 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 be poured, or so fluid that it seems watery. Some clear products become cloudy and others gel on standing.



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



   Although hexametaphosphates have been

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 proposed to be used in liquid detergent compositions as detergency builder salts, they have not been used because 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 cold water. .

   This is a particularly important problem in common use of automatic household washing machines of the European type in which the user puts the laundry detergent composition in a dispenser compartment (for example a dispenser drawer) of the 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 quantity of the composition 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 obliges the user to clean the dispenser with hot water.



   The gelation phenomenon can also be a problem every time you want to wash using cold water, as may be recommended for certain synthetic and delicate fabrics or for fabrics that may

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 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 the winter months in unheated transport vehicles .



   Partial solutions to the problems of gelation in compositions substantially free of detergency builder have been proposed, for example by diluting the liquid nonionic surfactant with certain viscosity adjusting solvents and certain gelation inhibiting agents, such as lower alkanols such as ethyl alcohol (see US Patent No. 3,953,380), alkali metal formates and adipates (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 the formation of an anionic surfactant. by neutralization in the washing liquor. Optimization of the nonionic structure focused on the chain length of the hydro-
 EMI5.1
 phobic-lipophilic and the number and constitution of the alkylene oxide units (for example ethylene oxide) of the hydrophilic moiety.

   For example, we found that a fatty alcohol in C-ethoxyl per 8 moles of oxide

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   ethylene exhibits only a limited tendency to gel.



   Nevertheless, it is desirable to improve dispersibility, pourability, solubility, stability and inhibition of gel formation of non-aqueous liquid fabric treatment compositions with detergency builder polyphosphate and non-ionic surfactant. .



   According to the present invention, a highly concentrated non-aqueous liquid laundry detergent composition is prepared by dispersing a polyphosphate adjuvant with long linear chain condense in a detergent based on liquid nonionic surfactant.



   Long chain condensed polyphosphates
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 linear used as divergence adjuvants according to the present invention are known compounds. Linear condensed polyphosphates of alkali metal and ammonium builders are easily soluble in water.



   The linear condensed polyphosphates used in the present invention are represented by the general formula:
 EMI6.2
 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 the M 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 the nonaqueous liquid detergents concentrated in

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 Non-ionic surfactant base reinforced with hexametaphosphate have better dispersibility and better pourability than detergent compositions containing sodium tripolyphosphate.



  Detergent compositions containing hexametaphosphates as the main detergency builder salts do not set in bulk when added to water and hexametaphosphates have greater water solubility than sodium tripolyphosphate. It has also been found that the hexametaphosphate contained in concentrated non-aqueous liquid detergent compositions with non-ionic surfactant does not tend to degrade during storage.



   It has also been found that hexametaphosphates are good anti-scale and anti-scaling agents and prevent the development of calcium crystals. The hexametaphosphates have been formed to act in non-aqueous non-aqueous surfactant detergents with nonionic surfactants as high calcium sequestering agents. 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 hexametaphosphate. In the detergent compositions of the present invention, the detergent builder phosphate consists essentially of the long straight chain condensed polyphosphate, for example

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 an alkali metal hexametaphosphate.



   In order to improve the viscosity characteristics of the composition, an acid-terminated nonionic surfactant can be added. To further improve the viscosity characteristics of the composition and its storage properties during storage, antifreeze and viscosity improving agents such as monoalkyl ethers of alkylene glycols and anti-sedimentation agents may be added to the composition. 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 a monoalkyl ether of alkylene glycol 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 micrometers, preferably less than 40 micrometers, and more preferably less than 10 micrometers, to further improve the stability of suspending the detergency builder components in the liquid nonionic surfactant detergent.



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



   Washing machines currently manufactured for domestic use normally operate at times.

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   Wash peratures of up to 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 are used per wash.
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  In accordance with the present invention, where a highly concentrated liquid detergent is used, normally only 100 grams (77 cc) or less of the liquid detergent composition is required to wash a full load of dirty laundry. Consequently, according to one aspect of the present invention, there is provided a liquid composition for large laundering works, consisting of a suspension of a linear condensed polyphosphate of alkali metal as adjuvant detergency in a nonionic liquid surfactant.



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



   In another aspect, the invention provides a method for dispensing a non-ionic liquid laundry detergent composition in and / or with cold water, without undergoing gelation. In particular, there is provided a method of filling a container with a non-aqueous liquid laundry detergent composition, the detergent of which consists, at least for the most part, of a suspension of a polyphosphate condensed with a long linear chain in a surfactant. -liquid nonionic active, and for

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 distributing 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 adjuvant divergence salt does not tend to solidify when added to
 EMI10.1
 water, and that the detergency builder salt has greater water solubility.

   The compositions of the present invention containing, for example, an alkali metal hexametahosphate as a detergency builder do not tend to degrade in the liquid nonionic surfactant and have good anti-scaling and anti-scaling properties and have great calcium sequestration capacity.



   The concentrated non-aqueous liquid laundry detergent compositions based on non-ionic surfactant 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,

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 containing as an adjuvanting salt an alkali metal hexametaphosphate 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 stable on storage 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 nonionic surfactant, for large laundering jobs, which can be poured at any temperature and which can be dispersed repeatedly 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 nonionic surfactant, for large laundering jobs, which comprise an effective amount of an alkali metal hexametaphosphate as adjuvant salt detergent.



   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 thereof. aluminum fatty acid as an anti-sedimentation agent, in an amount sufficient to increase the stability of the compound

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 tion, that is, 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 non-aqueous liquid nonionic surfactant a effective amount of an alkali metal hexametaphosphate detergency builder and mineral or organic tissue treatment additives, for example viscosity enhancing and anti-gelling agents, anti-sedimentation agents, anti-encrustation agents, bleaching agents, activators for bleaching agents, defoamers, optical brighteners, anti-redeposition agents, perfume and colorants.



   N2n ionia surfactant
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 l ethylene oxide (hydrophilic in nature). Virtually any hydrophobic compound having a carboxy, hydroxy, amido or amino group having a free hydrogen atom attached to nitrogen can be condensed with

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   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. Pat. Nos. 4,316,812 and N # 3,630,929.



   In general, nonionic detergents are lipophilic compounds alkylated 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 of a lipophilic moiety. A preferred class of nonionic detergents used is the higher alkanols alkoxylated by poly (lower alkoxy) groups, in which the alkanol has 9 to 18 carbon atoms and in which the number of moles of oxide 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 methoxy 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 per mole, for example Neodol 25-7 and Neodol 23-6. 5, which are products manufactured by Shell Chemical

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 Company, Inc. The first is a condensation product of a mixture of higher fatty alcohols having an average of about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide, and the second is a mixture a correspondent in which the carbon atom content of the higher fatty alcohol is 12 to 13, and the number of ethylene oxide groups present represents an average of about 6.5. 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 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 has moles of oxide
 EMI14.1
 ethylene reacted.



   Also useful in the composition of the invention, as a component of the nonionic detergent, are nonionic surfactants of molecular weight suparior, such as Neodol 45-11, which are similar condensation products of ethylene oxide on alcohols higher fatty acids, the higher fatty alcohol having 14 or 15 carbon atoms, and the number of ethylene oxide groups per mole being approximately 11.



  These products are also manufactured by Shell Chemical Company.



   Other useful nonionic surfactants are represented by the well-known class of trade in nonionic surfactants sold under the trademark Plurafac. Plurafac products are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing

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 a mixed chalne of ethylene oxide and propylene oxide, terminated by a hydroxyl group.

   Examples 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 oxides propylene and 4 moles of ethylene oxide), and Product C (an alcohol
 EMI15.1
 fatty C13-C15 condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide).



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



   In the higher alkanols alkoxylated by preferred poly (interior alkoxy) groups, to obtain the best ratio between the hydrophilic and lipophilic portions, the number of lower alkoxy groups is generally equal to 40% to 100% of the number of carbon atoms of carbon. higher alcohol, 40 to 60% of this number, and the nonionic detergent preferably contains at least 50% of such a preferred higher poly (lower alkoxy) alkanol.

   Higher molecular weight alkanols and various other normally solid detergents and nonionic surfactants may contribute to the gelation of the liquid detergent and therefore will preferably be removed or will be present in limited amounts in the present compositions, although they can be used in minor proportions for their cleaning properties, etc.

   In what

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 relates to preferred and less preferred nonionic detergents, the alkyl groups which they contain are generally linear, although branching can be tolerated, for example at a carbon atom close to the terminal carbon atom of the chalne straight or two carbon atoms away from this terminal carbon atom and opposite the
 EMI16.1
 ethoxylated chain, provided that such a branched alkyl group is not more than three carbon atoms in length. 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 gel-forming characteristics, it may appear middle or secondary junction with ethylene oxide of the chain. There is generally 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 higher than those mentioned above of alkanols of which
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 the alkylation is not terminal, of alkanols alkoxylated by poly (lower alkoxy) groups containing propylene oxide and of nonionic detergent with lower hydrolipophilic ratio, and when using

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 other nonionic detergents in place of the preferred nonionic detergents listed here, the resulting product may not have as good detergency, viscosity stability and non-gelling properties as the preferred compositions,

   but the use of the compounds of the invention acting on the viscosity and inhibiting gelation can also improve the properties of detergents based on such nonionic compounds. In some cases, for example when using a higher poly (lower alkoxy) alkanol of higher molecular weight, often for its detergent power, its proportion is adjusted or limited in accordance with the results of routine experiments, to obtain the detergent power required and to obtain at the same time a non-gelling product of desired viscosity.

   Also, it has been found that it is only rarely necessary to use nonionic surfactants of higher molecular weight for their detergent properties, since the preferred nonionic surfactants described here are excellent detergents and, moreover, they allow achieve viscosity in liquid detergent without gelation at low temperatures.



   Another useful group of nonionic surfactants is the 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 mole

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 EMI18.1
 of secondary fatty alcohol in C.-.



  In the compositions of the present invention, preferred nonionic surfactants include C13-C15 secondary fatty alcohols having relatively limited ethylene oxide contents of about 7 to 9 moles, and Cq to C11 fatty alcohols ethoxylated with about 5 to 6 moles of ethylene oxide.



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



   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 of a polycarboxylic acid or anhydride.



   As described in patent application FR-85 0319 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 which the nonionic liquid surfactant forms a gel with water.



   The addition of acid-terminated nonionic surfactants to the liquid nonionic surfactant promotes the ability of the composition to be dispensed, i.e. poured, and reduces the temperature Åa

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 which liquid nonionic surfactants form a gel in water without reducing their stability against sedimentation. The acid-terminated nonionic surfactant reacts in the washing machine water with the alkalinity of the dispersed detergent builder salt phase 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 succinic anhydride, and the ester or hem-ester of Dobanol 91-5 with succinic anhydride. In place of succinic anhydride, other acids or can be used. polycarboxylic anhydrides, for example maleic acid, maleic acid anhydride, citric acid, etc.



   Acid-terminated nonionic surfactants can be prepared as follows: Acid-terminated Product A: 400 g of Product A nonionic surfactant is mixed, which is a C 1 -C alkanol. <E 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 acidic hem-ester.



   Acid-terminated Dobanol 25-7: 522 g of non-ionic surfactant Dobanol 25-7 are mixed, which is the ethoxylation product of a C12-C15 alkanol and contains approximately 7 ethylene oxide units per alkanol molecule , with 100 g of succinic anhydride and 0.1 g of pyridine (which acts as an ester-

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 fication) 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 in the
 EMI20.1
 surfactant reacted. , t Acid-terminated Dobanol 91-5: 1000 g of non-ionic surfactant Dobanol 91-5, which is the product of ethoxylation of a C9 9 C11 alcohol and has approximately 5 ethylene oxide units per N molecule, are mixed. alkanol, with 265 g of succinic anhydride and 0.1 g of pyridine as catalyst, and heated to 260 ° C for 2 hours, cooled and filtered to 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 (eg sodium methylate), can be used in place of or in mixture with pyridine.



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



   The non-aqueous liquid nonionic surfactant used in the compositions of the present invention contains, while dispersed and in suspension, 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 adjuvants.



   The linear long chain condensed polyphosphates used as detergency builders in the detergent compositions of the present invention

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 have the following general formula:
 EMI21.1
 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 sodium or potassium, sodium is still available. A preferred detergency builder salt is an alkali metal or ammonium hexane-taphosphate.



   A particular example of a linear condensed polyphosphate which can be used as a detergency builder is represented by the formula:
 EMI21.2
 
Detergent compositions containing alkali metal hexametaphosphates provide better cleaning performance. For example, 100q (77 cm3) of a reinforced detergent containing 29.6% sodium hexametaphosphate provides cleaning performance equivalent to 100 g (77 cm3) of reinforced detergent containing 30% sodium tripolyphosphate.



   The detergent compositions of the invention may also contain adjuvant mineral detergency salts soluble in water and / or insoluble in water. Adjuvant salts of mineral divergence

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 suitable water-soluble alkalines which can be used alone or in admixture with other detergency builders are the carbonates, bicarbonates, borates, phosphates, polyphosphates and silicates of alkali metals. (It is also possible to use ammonium or substituted ammonium salts).

   Examples of adjuvant detergency salts commonly used are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium bicarbonates 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
 EMI22.1
 Na2O / Sio2 ratio of 6: 1 to 1: 3.2, especially 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 linear chain, detergency builder using an adjuvant auxiliary such as an alkali metal salt of lower polycarboxylic acid having a high capacity for fixing calcium and magnesium, making it possible to inhibit incrustation which could otherwise be pr-

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 dedicated to the formation of 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 l 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 adjuvant detergency salts may consist of a copolymer which is the reaction product of an approximately equal number of moles of methacrylic acid and maleic anhydride, 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 is used, when used in even small amounts, to inhibit encrustation.
 EMI23.1
 



  Examples of sequestering alkaline organic detergent builder salts which can be used with detergent builder salts or in admixture with other organic and mineral detergency builders are ammonium or ammonium alkali metal aminopolycarboxylates substituted, for example ethylene diaminetetraacetate (EDTA) of sodium and
 EMI23.2
 potassium, the nitriloacetates (NTA) of sodium and potassium and the N- (2-hydroxyethyl) nitrilodiacetates of triethanolammonium. Mixed salts of the corresponding amino polycarboxylic acids are also suitable.



   Other organic divergence adjuvants

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 include polyacetal-carboxylates. Polyacetal-carboxylates and their use in detergent compositions are described in U.S. Pat. Nos. 4,144,226.4 315,092 and 4,146,495.



   Other representative examples of suitable detergency builders include, for example, those described in U.S. patents. N + 4 316 812, N + 4 264 466 and 3 630 929. The alkaline mineral salts with detergency builders can be used with the non-ionic detergent surfactant or in mixture with other organic salts or mineral builders with detergency builders.



   The water insoluble crystalline and amorphous zeolitic aluminosilicates can be used.



  Zeolites generally have the formula:
 EMI24.1
 (M20) (AlOy- (SiO-wHO 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 w is a number from 0 to 9, preferably 2.5 to 6, and M is preferably sodium. A representative example of a zeolite is a zeolite of the type A or of similar structure, type 4A being particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of approximately 200 milliequivalents per gram or more, for example 400 milliequivalents 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 the beige patent N * 835,351.

  <Desc / Clms Page number 25>

 



   Other materials such as clays, in particular types insoluble in water, can be useful additives in the compositions of the present invention. A particularly useful clay is bentonite. This material is mainly montmorillonite which is a hydrated aluminum silicate in which approximately 1/6 of the aluminum atoms can be replaced by magnesium atoms and with which various quantities of hydrogen, sodium, potassium, calcium, etc. can be weakly combined.

   Bentonite, in its most purified form, that is to say 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 the western United States of America which have been sold under the designations of Thixo-jel 1,2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften textile materials, as described in British patents Nos. 401,413 and 461,221.



   Viscosity and Anti-Gelling Agents
The incorporation into the detergent composition of an effective amount of low molecular weight amphiphilic compounds which act as viscosity adjusting and gelling inhibiting agents for the nonionic surfactant appreciably improves the storage properties. of the composition.

   Amphiphilic compounds can be considered to have a chemical structure analogous to that of liquid nonionic surfactants derivat

  <Desc / Clms Page number 26>

 
 EMI26.1
 ethoxylated and / or propoxylated fatty alcohols, but they have relatively short hydrocarbon chain lengths (C2 to Cg) and a low content of ethylene oxide (approximately 2 to 6 ethylene oxide groups per molecule).



   Suitable amphiphilic compounds can be represented by the following general formula:
 EMI26.2
 RO (CHCHO) H where R is a C2-Ca alkyl group and n is a number of about 1 to 6 on average.



   In particular, the compounds are lower monoalkyl ethers (C to C5) of alylene glycols
 EMI26.3
 lower (C2-C3).



   More particularly, the compounds are lower monoalkyl ethers (C-Ce) of mono-, diou trialkylene-lower glycols (C2-C3).



   Particular examples of amphi-
 EMI26.4
 suitable philes include ethylene glycol monoethyl ether (C2HS-O-CH2CH20H), diethylene glycol monobutyl ether (CH-O- (CHCHO) H), tetraethylene glycol monobutyl ether (C4H7 -O- (CH2CH2O) 4H) and the monomethyl ether of dipropylene glycol (CH3-0- (CH2CHO) 2H). We prefer in
 EMI26.5
 CH3 in particular the monobutyl ether of diethylene glycol.



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

  <Desc / Clms Page number 27>

 



   The compositions of the present invention have better viscosity and stability characteristics and remain stable and suitable for pouring at temperatures as low as about 5 ° C or less.



    Aaents ätabilisänts
In one embodiment of the present invention, the physical stability of the suspension of the detergent builder compound (s) and any other suspended additive, such as 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.



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



   As described in the patent application FR 8505319 cited above, the acidic organic phosphorus compound comprising an acidic -POH group can increase the stability of the suspension of detergency builders in the non-aqueous non-ionic liquid surfactant.



   The acidic organic phosphorus 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 of phosphoric acid and a C16 to C18 alkanol (Empiphos 5632 from Marchon); it is made up of about

  <Desc / Clms Page number 28>

 35% monoester and 65% diester.



   The incorporation of very small quantities of the organic phosphorus acid compound makes the suspension significantly more stable with respect to sedimentation at rest, while leaving it capable of being poured, while at this low concentration of stabilizer, for example less than about 1 t, its plastic viscosity generally decreases.



   The stability and the 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.



   Stabilizers 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 better still about 12 to 18 carbon atoms. The aliphatic radical can be saturated or unsaturated, and it can be straight or branched. 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 decanolque acid, dodecanolque acid, palmitic acid, myristic acid, steric 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

  <Desc / Clms Page number 29>

 are preferably used in the form of three acid residues, for example aluminum stearate in the form of aluminum tristearate Al (C17H35COO) 3.



   The salts with an acid residue, for example aluminum monostearate, Al (OH) (C 7H35COO) 2 and the salts with two acid residues, for example aluminum distearate, Al ( OH) (C17H35COO) 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% better still at least 80%, of the total amount of aluminum salt of fatty acid .



   Aluminum salts, as mentioned above, are commercially available and can be produced easily, 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 the surfaces solids by the nonionic surfactant. This increase in wettability therefore makes it possible for 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 additional advantages over other stabilizers

  <Desc / Clms Page number 30>

 physical, that it is of nonionic character and is compatible with the nonionic surfactant and does not disturb the overall detergent action of the composition; he senses a certain anti-foam effect; it can reinforce the action of fabric softeners and it gives suspensions a longer duration of relaxation.



   Whitening Aaents
Bleaches are broadly classified for convenience into chlorine bleaches and oxygenated bleaches. Chlorine bleaches are represented by sodium hypochlorite (NaOC1), potassium dichloroisocyanurate (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 sodium and potassium perborates, percarbonates and perphosphates and potassium monopersulfate. Perborates, in particular sodium perborate monohydrate, are particularly preferred.



   The peroxygen compound is preferably used in admixture with an activator. Suitable activators which can lower the effective activity temperature of the peroxide bleach are described, for example, in US Patent No. 4,264,466 or in column 1 of US Patent No. 4,430,244. pOlyacy1és are the preferred activators. among them, compounds such as tetraacetylethylene diamine ('TAED') and pentaacetylglucose are even more preferred.



   Other useful activators include, for example

  <Desc / Clms Page number 31>

 
 EMI31.1
 for example, derivatives of acetylsalicylic acid, ethylidene-benzolic acetic acid and its salts, ethylidene-carboxylic-acetic acid and its salts, alkyl- and aicenyl-succinic anhydrides, tetraacetylglycourile ("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 typically reacts with the peroxygen compound to form a bleaching peroxyacid in the wash water. It is preferable to include a sequestering agent with a 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.



   Sequestering agents suitable for this purpose include the sodium salts of nitri-lotriacetic acid (NTA), ethylene-diamine-tetraacetic acid (EDTA), diethylene-triamine-pentaacetic acid (DETPA) , diethylene-triamine-pentamethylene-phosphonic acid (DTPMP) sold under the trademark Dequest 2066; and ethylenediamine-tetramethylene phosphonic acid (EDITEMPA). The sequestering agents can be used alone or as a mixture.



   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 may also contain an enzyme inhibitor, this that is to say a compound capable of inhibiting the decomposition, under the action of enzymes, of bleaching peroxide. Appropriate inhibitors are described in U.S. Patent A.A. N'3

  <Desc / Clms Page number 32>

 606,990.



   As a particular interesting inhibitor, mention may be made of hydroxylamine sulfate and other water-soluble hydroxylamine salts. In the preferred nonaqueous compositions of the present invention, suitable amounts of the inhibiting hydroxylamine salts may be as low as about 0.01 to 0.4%. However, in general, suitable amounts of enzyme inhibitors. 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 in order to give it other desired properties, of a functional or aesthetic nature. Thus, one can include in the formulation of minor quantities of suspending agents or anti-redeposition of soiling, for example polyvinyl alcohol, fatty amides, sodium carboxymethylecululose, hydroxypropylmethyl-cellulose. A preferred anti-redeposition agent is sodium carboxymethylcellulose having a CM / MC ratio of 2: 1, which is sold under the trademark Relatin DM 4050.



   Optical brightening agents can be used for cotton, polyamide and polyester fabrics. Suitable optical brighteners include compositions of stilbene, triazole and benzidine sulfone, especially substituted triazinyl-stil-bene sulfon6, sulfonated naphtotriazolestilbene, benzidine sulfone, etc., the preferred ones 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

  <Desc / Clms Page number 33>

 in the technique.



   Enzymes may be used, preferably proteolytic enzymes, such as subtilisin, bromelain, paapine, 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 tetrachlorosalicylamide and hexachlorophene, fungicides, dyes, pigments (dispersible 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 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 of Aerosil) or other very bulky mineral supports
 EMI33.1
 described in U.S. Patent No. 3,630,929, in proportions of 0.1 to 10%, for example 1 to 5%.

   However, it is preferable that the compositions which form peroxyacids in the washing bath (for example the compositions containing a pe-oxygenated compound and an activator for it) are substantially free from such compounds and others.

  <Desc / Clms Page number 34>

 licates; it has been observed, for example, that silica and silicates promote an 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 micrometers, preferably less than 40 micrometers and more preferably less than 10 micrometers. 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 grinding in which the particle sizes of the solid ingredients are reduced to less than about 40 micrometers, preferably has less than about 10 micrometers, for example an average particle size of 2 to 10 micrometers or even less (for example 1 micrometer). Preferably, less than about 10 \, in particular less than about 5 \ of all of the suspended particles have particle sizes greater than 10 microns.

   The compositions whose dispersed particles are so small have better stability with respect to separation or sedimentation during storage.



  The addition of the acid-terminated nonionic surfactant compound promotes the dispersibility of the dispersants.

  <Desc / Clms Page number 35>

 without any corresponding reduction in the stability of the dispersions with respect to sedimentation.



   For the grinding operation, it is preferable that the proportion of solid ingredients is sufficiently high (for example at least about 40%, such as about 50) so that the solid particles are in contact with each other and are not too isolated from each other by the nonionic liquid surfactant. After the grinding step, all of the liquid nonionic surfactant remaining 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, one can use a laboratory attrition mill working by batch loads, comprising grinding balls in steatite of 8 mm in diameter.

   For an operation on a larger scale, one can use a continuously working grinder in which there are grinding balls with a diameter of 1 mm or 1.5 mm operating in a very small interval between a stator and a rotor operating at a relatively high speed (for example a CoBall mill);

   when using such a mill, it is advantageous to pass the mixture of non-ionic surfactant and solids first through a mill which does not perform such a fine grinding (for example a colloidal mill) in order to reduce the particle size to less than 100 micrometers (for example Åa about 40 micrometers) before the grinding stamp 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 laundering

  <Desc / Clms Page number 36>

 Note, typical proportions (the percentages being based on the total weight of the composition, unless otherwise specified) of the ingredients are as follows:
Liquid nonionic surfactant detergent: 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.



   Long linear condensed polyphosphates, detergency builders: in the range of about 10 to 60, e.g. 20 to 50, and especially
 EMI36.1
 25 to 35 percent.



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



   Monoalkyl ether of alkyl glycol 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.

  <Desc / Clms Page number 37>

 



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



   Activator of the bleaching agent: in the range of approximately 0 to 20, for example 1 to 15 and in particular 2 to 6 percent.



   Sequestering agent for bleaching agent
 EMI37.1
 ment: 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, especially 0.5 to 1.5 percent.



   Optical brightening agent: in the range of about 0 to 2.0, for example 0.05 to 1.5, and in particular
 EMI37.2
 0.3 to 1.0 percent.



  Enzymes: in the range of about 0.3 to 3.0, for example 0.5 to 2.0, and especially 0.5 to 1.5 percent.



   Perfume: in the range of about 0.2 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 obtain the desired function of the added materials.



   Mixtures of the acid-terminated nonionic surfactant and anti-gelling agents of the alkyl glycol alkyl ether type can be used and, in some cases, the use of such mixtures can be used alone, or with the addition of mixture of a stabilizing and anti-sedimentation agent, for example an alkanol ester of phosphoric acid

  <Desc / Clms Page number 38>

 than.



   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 whole of the formulation or composition, unless otherwise specified.



   The concentrated nonaqueous liquid detergent composition based on nonionic surfactant of the present invention is easy to dispense into the water of the washing machine. Household washing machines currently in service normally use approximately 250 grams of powdered detergent to wash a full load of laundry. According to the present invention, only about 77 cm3 or about 100 grams of the concentrated liquid detergent composition Åa nonionic surfactant is required.



   In a preferred embodiment of the invention, a typical detergent composition is formulated using the ingredients listed below:
 EMI38.1
 % by weight Non-ionic surfactant detergent 30-40 Surfactant & acid termination 5-15 Alkali metal hexametaphosphate 25-35 Anti-scaling agent (Sokalan CP 5) 0-10 Monoalkyl ether of alkylene glycol 8-12 Alkanol ester of Phosphoric acid
 EMI38.2
 (Empiphos 5632) 0, 1-1, 0 Anti-redeposition agent (Relatin DM 4050) 0-3, 0 Alkali metal perborate for bleaching 8-15 Bleaching agent activator (TAED) 2-6 Sequestering agent ( Dequest 2066) 0-3, 0

  <Desc / Clms Page number 39>

 Optical brightening agent (ATS X) 0, 05-1, 0 Enzymes (Protease Espérase SL8) 0, 5-1, 5 Perfume 0, 5-1,

   0
The following nonlimiting examples illustrate the present invention.



   EXAMPLE 1
A concentrated nonaqueous liquid detergent composition based on nonionic surfactant is prepared, from the following ingredients in the proportions indicated:% by weight A mixture of C13-C15 fatty alcohol condensed with 7 moles of propylene oxide and 4 moles ethylene oxide, and C13-C15 fatty alcohol condensed with 5 moles of propylene oxide and 10 moles
 EMI39.1
 ethylene oxide 15.5 T7 surfactant 9.0 T9 surfactant 9.0 O-terminated reaction product of Dobanol 91-5 with succinic anhydride 6.0 sodium hexametaphosphate 29.6 Monobutyl ether of diethylene glycol 9 0 Alkanolic phosphoric acid ester (Empiphos 5632) 0, 3 Anti-scaling agent (Sokalan CP 5) 3, 0 Sodium perborate bleached nonohydrate 10,

   0 Tetraacetylethylene diamine (TAED) as activator of the bleaching agent 4, 5 Sequestering agent (Dequest 2066) 1, 0 Optical brightening agent (Tinopal ATS X) 0, 5 Anti-redeposition agent (Relatin DM 4050) 1, 0

  <Desc / Clms Page number 40>

 Suspension of espérasse (Esperase SL8) 1, 0 Parfum 0, 5925
 EMI40.1
 Dye 0. 9075
100, 00
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 partly before mixing and can be finished 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 size less than 100 micrometers.



   EXAMPLE 2
In order to demonstrate the effect on cleaning and anti-scaling or anti-scale performance of the substitution of tripolyphspohate by

  <Desc / Clms Page number 41>

   sodium hexametaphosphate as adjuvant divergence salt of the present invention, the detergent composition of Example 1 containing 29.6% is compared during repeated washing cycles
 EMI41.1
 weight of sodium hexametaphosphate with the same composition in which the hexametaphosphate is replaced by 30% by weight of sodium tripolyphosphate.



   Repeated washing cycles are carried out at concentrations in the washing water of 5 g / l 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 ash deposited, is measured. The percentage of ash deposited is measured by calcining the washed parts.



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



   As regards the accumulation of incrustation, no accumulation is observed with hexametaphosphate, while a slight accumulation is observed with sodium tripolyphosphate as
 EMI41.2
 adjuvant detergent salt.



   Detergency builder hexametaphosphates can also be used to replace detergency builder polyphosphates in concentrated aqueous detergent compositions. At concentrations of 50 to 60%, due to the structure

  <Desc / Clms Page number 42>

 
 EMI42.1
 hcxamts rolnre. phosphate, a viscous solution is obtained. Given the viscous nature of the concentrated aqueous solution, the physical stability and the rheological behavior of the aqueous composition
 EMI42.2
 concentrated are improved.


    

Claims (20)

 EMI43.1   FVFNtATJONS  EMI43.2  1. C <-'rnposition dt; 't: ergunt. n)) uur gross trvux. t ii ti ta um 0 i (1 su fi su if- "i tz fi f li u 1 L 0 ni ci 1) HL i. C-1 1) ic 1 z- containing at least $ one urfachLf nun Loniq'JH Li. Which.) Detergent and, in a dispersed state, a polyphosphat o condensed with a long linear flesh as the main adjuvant detergency salt, characterized in that the adjuvant detergency salt is a hexametaphosphate.  EMI43.3   2. detergent composition according to claim 1. Caracterisce t'n co it cont. have an alkali metal monohydrate perborate as a bleaching agent in a proportion of about 5 to 30%, tetraacetylethylene diamine as a bleaching activator in a proportion of about 1 to 15 $. and optionally one or more detergent additives chosen from the group formed by an anti-encrustation agent, an anti-redeposition agent, a sequestering agent for the bleaching agent, optical brightening agents. enzymes and a scent.  3. Detergent composition according to claim 1. characterized in that the detergency adjuvant comprises a sodium hexametaphosphate (n 25).  4. detergent composition according to claim 3, characterized in that the hexametapnosphate  EMI43.4  of sodium is represented by the formula:  EMI43.5    EMI43.6  where n = 25. 5. A detergent composition according to claim 1, characterized in that it contains as an adjuvant detergency salt sodium hexametaphosphate (n = 25) in a proportion of about 25 to 35 percent.  <Desc / Clms Page number 44>    6 - Detergent composition according to claim 1, characterized in that it contains 0.10 to 2.0 per cent of an alkanolic ester of phosphoric acid.  7 - Detergent composition according to claim 1, characterized in that it contains approximately '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, detergency builder particles 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 nonionic liquid surfactant in a proportion of about 20 to 50t, a nonionic surfactant with acid termination in a proportion of about 5 to 25 \ , an alkali metal hexametaphosphate (n = 25) as an adjuvant detergency in an amount of about 20 to 50%, an alkylene glycol mono-ether in an amount of about 5 to 1six, and an alkanolic ester  EMI44.1  phosphoric acid in a proportion of about 0.1 1 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 approximately 5 to 30 t, tetraacetylethylene diamine as a bleaching agent activator in a proportion of approximately 1 to 15%, and optionally one or more detergent additives chosen from the group formed by an anti-fouling agent, an anti-redeposition agent, an agent  <Desc / Clms Page number 45>    squcstrant for bleach, optical brighteners, 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:  EMI45.1  where n = 25.   13 - Detergent composition according to claim 9, characterized in that the alkanolic ester of phosphoric acid consists of a C16-C18 alkanol ester of phosphoric acid.  14 - Detergent composition according to claim 9, characterized in that it can be poured at 4 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  EMI45.2  adjuvant detergent for sodium hexametaphosphate (n = 25) in a proportion of about 25 to 35 percent.  16 - Concentrated nonaqueous 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,  <Desc / Clms Page number 46>  about 23 to 35% sodium hexametaphosphate, about 8 to 12% alkylene glycol monobutyl ether,  EMI46.1  about 0.1 a. 0.5 to C <g-C <alkanolic ester of phosphoric acid about 8 to 15% sodium perborate monohydrate as a bleaching agent, and. about 4 to 8% tetraacetylethyldne diamine (TAED) as activator of the bleaching agent.    I 17 - 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 - process 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 - Process 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 - process for cleaning soiled fabrics, characterized in that it consists in bringing the soiled fabrics in contact with the detergent laundry composition according to claim 16.