GB2187199A - Built non-aqueous liquid laundry detergent compositions - Google Patents

Abstract

A liquid heavy duty detergent laundry composition comprises a suspension of a linear condensed polyphosphate builder salt in liquid nonionic surfactant.

Description

SPECIFICATION Built non-aqueous liquid laundry detergent compositions This invention relatesto nonaqueous liquid fabrictreating compositions. More pasticularly, this invention relates to nonaqueous liquid laundry detergent compositions containing a suspension of a linear condensed polyphosphate builder salt in nonionic surfactants which compositions are stable against phase separation and gelation and are easily pourableandto the use ofthesecompositionsforcleaning soiled fabrics.

Liquid nonaqueous heavy duty laundry detergent compositions are well known in the art. For instance, compositions ofthattype may comprise a liquid nonionic surfactant in which are dispersed particles of a builder, as shown for instance in the U.S.P. Nos. 4,316,812,3,630,929 and 4,264,466 and British Patent Nos.

1,205,711, 1,270,040 and 1,600,981.

The washing power of synthetic nonionic surfactant detergents in laundry detergent compositions can be increased by the addition of builders. Sodium tripolyphosphate is one of the conventionally used builders.

However,the use of sodium polyphosphate in dry powder detergents does involve several disadvantages such as, for example, the tendency of the polyphosphates to hydrolyse into pyro- and ortho-phosphates which represent less valuable builders.

In addition the sodium tripolyphosphatetendsto cake when added to water and has a relatively lowwater solubility and relatively low sequestering capacity for calcium.

Liquid detergents are often considered to be more convenientto employ than dry powdered or particulate products and, therefore, have found substantial favour with consumers. They are readily measurable, speedily dissolved in the wash water, are capable of being easily applied in concentrated solutions or dispersions to soiled areas on garments to be laundered and are non-dusting, and they usually occupy less storage space. Additionally, the liquid detergents may have incorporated in theirformulations materials which could not stand drying operations without deterioration, which materials are often desirably employed in the manufacture of particulate detergent products.Although they are possessed of many advantages over unitary or particulate solid products, liquid detergents often have certain inherent disadvantages too, which have to be overcome to produce acceptable commercial detergent products. Thus, some such products separate out on storage and other separate out on cooling and are not readily redispersed. In some cases the product viscosity changes and it becomes either too thick to pour or so thin as to appear watery. Some clear products become cloudy and others gel on standing.

The conventionally used sodium tripolyphosphate builder salt has the disadvantage oftending to degrade in concentrated nonaqueous liquid nonionic surfactant detergent compositions.

Though hexametaphosphates have been suggested for use in liquid detergent compositions as builder salts they have not been used because they are not current raw material and they are expensive. In addition to the problem of settling or phase separation the nonaqueous liquid laundry detergents based on liquid non ionic surfactants suffer from the drawback that the nonionics tend to gel when added to cold water. This is a particularly important problem in the ordinary use of European houshold automatic washing machines where the user places the laundry detergent composition in a dispensing unit (e.g. a dispensing drawer) of the machine. During the operation of the machine the detergent in the dispenser is subjected to a stream of cold water to transfer itto the main body of wash solution.Especially during the winter months when the detergent composition and watered to the dispenser are particularly cold, the detergent viscosity increases markedly and a gel forms. As a result some ofthe composition is not flushed completely off the dispenser during operation of the machine, and a deposit of the composition builds up with repeated wash cycles, eventually requiring the userto flush the dispenser with hotwater.

The gelling phenomenon can also bea problem whenever it is desired to carry out washing using cold water as may be recommended for certain synthetic and delicate fabrics or fabrics which can shrink in warm or hot water.

The tendency of concentrated detergent compositions to gel during storage is aggravated by storing the compositions in unheated storage areas, or by shipping the compositions during winter months in unheated transportation vehicles.

Partial solutions to the gelling problem in aqueous, substantially builder-free compositions have been proposed, for example, by diluting the liquid nonionic with certain viscosity controlling solvents and gel-inhibiting agents, such as lower alkanols, e.g. ethyl alcohol (see U.S.P. 3,953,380), alkali metal formates and adipates (see U.S.P. 4,368,147), hexylene glycol, polyethylene glycol, etc. and nonionicstructure modification and optimization. As an example of nonionic surfactant modification one particularly successful result has been achieved by acidifying the hydroxyl moiety end group of the nonionic molecule.

The advantages of introducing a carboxylic acid at the end ofthe nonionic include gel inhibition upon dilution; decreasing the nonionic pour point; and formation of an anionicsurfactantwhen neutralized in the washing liquor. Nonionic structure optimization has centered on the chain length ofthe hydrophobic-lipophilic mpietyandthe number and make-up of alkylene oxide (e.g. ethylene oxide) units of the hydrophilic moiety. For example, it has been found that a 0i3 fatty alcohol ethoxylated with 8 moles of ethylene oxide presents only a limited tendencyto gel formation.

Nevertheless, improvements are desired in the dispersibility, pourability, solubility, stability and gel inhibition of polyphosphate buildersalt nonaqueous liquid nonionic surfactantfabrictreating compositions.

In accordance with the present invention a highly concentrated nonaqueous liquid laundry detergent composition is prepared by dispersing a long linear chain condensed polyphosphate builder salt in a liquid nonionicsurfactant detergent.

The long linear chain condensed polyphosphate builder salts used in accordance with the present invention are known compounds. The alkali metal and ammonium salts of linear condensed polyphosphate builder salts are readily water soluble.

The linear condensed polyphosphates used in the present invention have the general formula

wherein M represents a hydrogen atom oran alkali metal, such as sodium or potassium, oran ammonium cation, and n=20 to 30, preferably about 25.

It is preferred that all ofthe M's are alkali metal. A preferred linear condensed polyphosphate is hexametaphosphate in which n=25.

In accordance with the present invention it was found that hexametaphosphate built concentrated nonaqueous liquid nonionic surfactant detergents have improved pourability and dispersibility as compared to sodium tripolyphosphate detergent compositions. The detergent compositions containing hexametaphosphates asthe principle builder salt do not cake when added to water and the hexametaphosphates have a higherwater solubilitythan sodium tripolyphosphate. It was further found that the hexametaphosphate in the concentrated nonaqueous liquid nonionic surfactant detergent compositions did nottendto degrade while in storage.

The hexametaphosphates were also found to be good anti-scaling and anti-encrustation agents and to prevent calcium crystal growth. The hexametaphosphates were formed to act in the nonaqueous liquid nonionic surfactant detergent compositions as superior sequestering agents for calcium. On gram of hexametaphosphate can sequester up to 163 mg. of calcium as compared to 1 gram of sodium tripolyphosphate which can sequester up to 111 mg. of calcium.

In the preferred embodiment of the invention the conventionally used sodium tripolyphosphate builder salt is replaced with the long linear change condensed polyphosphate of the present invention, e.g., alkali metal hexametaphosphate. In the detergent compositions of the present invention the phosphate builder consists essentially of the long linear chain condensed polyphosphate, e.g., alkali metal hexametaphosphate.

In orderto improve the viscosity characteristics of the composition an acid terminated non ionic surfactant can be added. To further improve the viscosity characteristics of the composition and the storage properties ofthe composition there can be added to the composition viscosity improving and anti gel agents such alkylene glycol mono alkyl ethers and anti settling agents such as phosphoric acid esters and aluminium stearate. In preferred embodiment of the invention the detergent composition contains an acid terminated nonionic surfactant and/or an alkylene glycol mono alkyl ether, and an anti settling agent.

Sanitizing or bleaching agents and activators therefor can be added to improve the bleaching and cleansing characteristics of the composition.

In an embodiment of the invention the buildercomponents of the composition are groundto a particlesize of less than 100 microns preferably less than 40 microns and more preferably less than 10 micronstofurther improve the stability ofthe suspension of the builder components in the liquid nonionic surfactant detergent.

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

The presently manufactured washing machines for home use normally operate at washing temperatures up to 10000. Up to 18.5 gallons (70 liters) of water are used during the wash and rinse cycles.

About 175 gms of powder detergent per wash is normally used.

In accordance with the present invention where the highly concentrated liquid detergent is used normally only about 100 gms (77 mi) or less of the liquid detergent composition is required to wash a full load ofdirty laundry.

Accordingly, in one aspect the present invention there is provided a liquid heavy duty laundry composition composed of a suspension of an alkali metal linear condensed polyphosphate builder salt in liquid nonionic surfactant.

According to another aspect, the invention provides a concentrated liquid heavy duty laundry detergent composition which is stable, non-settling in storage and non-gelling in storage and in use. The liquid compositions of the present invention are easily pourable, easily measured and easily put into the washing machine.

According to another aspect, the invention provides a method for dispensing a liquid nonionic laundry detergent composition into and/or with cold water without undergoing gelation. In particular, a method is provided forfilling a container with a nonaqueous liquid laundry detergent composition in which the detergent is composed, at least predominantly, of a suspension of a long linear chain condensed polyphosphate in a liquid non ionic surface active agent and for dispensing the composition from the container into an aqueous wash bath, wherein the dispensing is effected by directing a stream of unheated water onto the composition such that the composition is carried bythe stream of water into the wash bath.

The concentrated nonaqueous liq uid liquid nonionicsurfactantdetergentcompositions containing a long linear chain condensed polyphosphate builder salt have the advantages over sodium tripolyphosphate built detergent composition of having improved pourability and dispersibility ofthe builder salt, the builder salt does nottendto cake on the addition to water and the builder salt has a higherwatersolubility.The compositions of the present invention containing, e.g., alkali metal hexametaphosphate builder salt do not tend to degrade in the liquid nonionic surfactant and exhibit good anti-scaling and anti-encrustation properties and have a high sequestering capacityforcalcium.

The concentrated nonaqueous liquid nonionic surfactant laundry detergent compositions ofthe present invention have the added advantages of being stable, non-settling in storage, and non-gelling in storage. The liquid compositions are easily pourable, easily measured and easily put into the laundry washing machines.

The present invention aims to provide a liquid heavy duty nonaqueous nonionic detergent composition containing an alkali metal hexametaphosphate builder salt suspended in a nonionicsurfactant.

The invention also aims to provide liquid fabric treating compositions which are suspensions of an alkali hexametaphosphate buildersaltin a nonaqueous liquid and which arestoragestable, easily pourableand dispersible in cold, warm or hot water.

This invention further aims to formulate a highly built heavy duty nonaqueous liquid nonionic surfactant laundry detergent compositions which can be poured ata wide range oftemperatures and which can be repeatedly dispersed from the dispensing unit of European style automatic laundry washing machines without fouling or plugging of the dispenser even during the winter months.

This invention also aims to provide a non-gelling, stable suspension of heavy duty built nonaqueous liquid nonionic laundry detergent composition which include an effective amount of an alkali metal hexametaphosphate builder salt.

This invention also aims to provide non-gelling, stable suspensions of heavy duty built nonaqueous liquid nonionic laundry detergent composition which include an amount of phosphoric acid alkanol esterand/or aluminium fatty acid salt anti-settling agent which is sufficientto-increase the stability of the composition, i.e.

prevent settling of builder particles, etc., preferably while reducing or at least without increasing the plastic viscosity ofthe composition.

The detergent composition may be prepared by adding to a nonaqueous liquid nonionicsurfactantan effective amount of an alkali metal hexametaphosphate builder salt and inorganic or organicfabrictreating additives, e.g. viscosity improving and anti-gel agents, anti-settling agents, anti-incrustation agents, bleaching agents, bleach activators, anti-foam agents, optical brighteners, enzymes, anti-redeposition agents, perfume and dyes.

The nonionic synthetic organic detergents employed in the practice of the invention may be any of a wide variety of such compounds, which are well known.

As is well known,the nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophiliogroup and aretypically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature).

Practically any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol,to form a nonionic detergent. The length of the hydrophilic or polyoxy ethylene chain can be readily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups. Typical suitable non ionic surfactants are those disclosed in U.S. patents 4,316,812 and 3,630,929.

Usually, the nonionic detergents are poly-lower alkoxylated lipophiles wherein the desired hydrophile-lipophile balance is obtained from addition of a hydrophilic poly-lower alkoxy group to a lipophilic moiety. A preferred class of the nonionic detergent employed is the poly-lower alkoxylated higher alkanolwherein the alkanol isof9to 18 carbon atoms and wherein the number of moles ofloweralkylene oxide (of 2 or 3 carbon atoms) is from 3 to 12. Of such materials it is preferred to employ those wherein the higheralkanol is a higherfattyalcohol of 9to 11 or 12to 15 carbon atoms and which contain from 5to 8 or5to 9 lower alkoxy groups per mole.Preferably, the lower alkoxy is ethoxy but in some instances, it may be desirably mixed with propoxy, the latter, if present, often being a minor (less than 50%) proportion.

Exemplary of such compounds are those wherein the alkanol is of 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole, e.g. Neodol 25-7 and Neodol 23-6.5, which products are made by Shell Chemical Company, Inc. Theformer is a condensation product of a mixture of higherfatty alcohols averaging about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide and the latter is a corresponding mixture wherein the carbon atom content of the higherfatty alcohol is 12 to 13 and the numberof ethylene oxide groups present averages about6.5. 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 made by Union Carbide Corp. The former is mixed ethoxylation product of 11 to 15 carbon atoms linear secondary alkanol with seven moles of ethylene oxide and the latter is a similar product but with nine moles of ethylene oxide being reacted.

Also useful in the compositions of the present invention as a component of the nonionic detergent are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higherfatty alcohols, with the higherfattyalcohol being of 14to 15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products are also made by Shell Chemical Company.

Other useful nonionics are represented by the commercially well known class of nonionics sold underthe trademark Plurafac. The Plurafacs arethe reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include ProductA (a C13-C15 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide), Product B (a C13-C15fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide), and Product C (a C13-C15 fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide).

Another group of liquid nonionics are commercially available from Shell Chemical Company Inc. underthe Dobanol trademark: Dobanol 91-5 is an ethoxylated Cg-Cll fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12-Cl5 fatty alcohol with an average of 7 moles ethylene oxide per mole of fatty alcohol.

In the preferred poly-lower alkoxylated higher alkanols, to obtain the best balance of hydrophilicand lipophilic moieties the number of lower alkoxies will usually be from 40% to 100% of the number of carbon atoms in the higher alcohol, preferably 40 to 60% thereof and the nonionic detergent will preferably contain at least 50% of such preferred poly-loweralkoxy higheralkanol. Higher molecularweightalkanolsand various other normally solid nonionic detergents and surface active agents may be contributory to gelation of the liquid detergent and consequently, will preferably be omitted or limited in quantity in the compositions ofthe present invention, although minor proportions thereof may be employed fortheir cleaning properties, etc. With respect to both preferred and less preferred nonionic detergents the alkyl groups presenttherein are generally linear although branching may be tolerated, such as at a carbon next to ortwo carbons removed from the terminal carbon of the straight chain and away from the ethoxy chain, if such branched alkyl is not more than three carbons in length. Normally, the proportion of carbon atoms in such a branched configuration will be minor rarely exceeding 20% of the total carbon atom content of the alkyl.Similarly, although linear alkyls which are terminallyjoined to to the ethylene oxide chains are highly preferred and are considered to result in the best combination of detergency, biodegradability and non-gelling characteristics, medial or secondary joinder to the ethylene oxide in the chain may occur. It is usually in only a minor proportion of such alkyls, generally less than 20% but, as is in the cases ofthe mentioned Terigtols, may be greater. Also, when propylene oxide is present in the lower alkylene oxide chain, it will usually be less than 20% thereof and preferably less than 10% thereof.

When greater proportions of non-terminally alkoxylated alkanols, propylene oxide-containing poly-lower alkoxylated alkanols and less hydrophile-lipophile balanced non ionic detergent than mentioned above are employed and when other nonionic detergents are used instead ofthe preferred nonionics recited herein,the product resulting may not have as good detergency, stability, viscosity and non-gelling properties as the preferred compositions but use of the viscosity and gel controlling compounds of the present invention can also improve the properties ofthe detergents based on such nonionics.In some cases, as when a higher molecular weight poly lower alkoxylated higher alkanol is employed, often for its detergency, the proportion thereofwill be regulated or limited in accordance with the results of routine experiments, to obtain the desired detergency and still have the product non-gelling and oT'c]esired of desired viscosity. Also, it has been found that it is only rarely necessary to utilize the higher molecularweight nonionics for their detergent properties since the preferred nonionics described herein are excellent detergents and additionally, permitthe attainment of the desired viscosity in the liquid detergent without gelation at low temperatures.

Another useful group of nonionic surfactants are the "SurfactantT" series of nonionics availablefrom British Petroleum. The Surfactant T nonionics are obtained by the ethoxylation of secondary C13 fatty alcohols having a narrow ethylene oxide distribution. The SurfactantT5 has an average of 5 moles of ethylene oxide; SurfactantT7 an average of 7 moles of ethylene oxide; Surfactant T9 an average of 9 moles of ethylene oxide and Surfactant T1 2 an average of 12 moles of ethylene oxide per mole of secondary C13 fatty alcohol.

In the compositions ofthis invention, preferred nonionic surfactants include the C13-C15 secondaryfatty alcohols with relatively narrow contents of ethylene oxide in the range of from about7 to 9 moles, and the to C11 fatty alcohols ethoxylated with about 5-6 moles ethylene oxide.

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

The viscosity and gel properties of the liquid detergent compositions can be improved by including in the composition an effective amount of an acid terminated liquid nonionic surfactant. The acid terminated nonionic surfactants consist of a nonionic surfactantwhich has been modified to convert a free hydroxyl group thereof to a moiety having a free carboxyl group, such as an esteror a partial ester of a nonionic surfactant and a polycarboxylic acid or anhydride.

As disclosed in the commonly assigned copending application U.S. Serial No. 597,948 filed April 9,1984, corresponding to GB Application No.8509084 Serial No.21 58454A, the disclosure of which is incorporated herein by reference, the free carboxyl group modified nonionic surfactants, which may be broadly characterized as polyether carboxylic acids, function to lowerthe temperature atwhich the liquid nonionic forms a gel with water.

The addition ofthe acid terminated nonionic surfactants to the liquid nonionic surfactant aids in the builder salt.

The alkali metal silicates are useful bilder salts which also function to adjust or control the pH and to make the composition anticorrosive to washing machine parts. Sodium silicates of Na2O/SiO2 ratios offrom 1.6/1 to 1/3.2, especially about 1/2 to 1/2.8 are preferred. Potassium silicates of the same ratios can also be used. A preferred alkali metal silicate is sodium disilicate.

Since the compositions of this invention are generally highly concentrated, and, therefore, may be used at relatively low dosages, it can be desirableto supplement the long linear chain condensed polyphosphate builder with an auxiliary builder such as an alkali metal lower polycarboxylicacid having high calcium and magnesium binding capacity to inhibit incrustation which could otherwise be caused by formation of insoluble calcium and magnesium salts. Suitable alkali metal polycarboxylic acids are alkali metal salts of citric and tartaric acid, e.g., monosodium citrate (anhydrous), trisodium citrate, glutaric acid salt, gluconic acid saltand diacid salt with a longer chain.

Other organic builders are polymers and copolymers of polyacrylic acid and polymaleic anhydride and the alkali metal salts thereof. More specifically such builder salts can consist of a copolymerwhich is the reaction product of about equal moles of methacrylic acid and maleic anhydridewhich has been completely neutralized to form the sodium saltthereof. The builder is commercially available underthetradename of Sokalan CP5. This builderserveswhen used even in small amounts of inhibitincrustation.

Examples of organic alkaline sequestrant buildersalts which can be used with the detergent buildersalts orin admixture with otherorganicand inorganic builders are alkali metal, ammonium orsubstituted ammonium, aminopolycarboxylates, e.g. sodium and potassium ethylene diaminetetraaceatate (EDTA), sodium and potassium nitrilotriacetates (NTA), and triethanolammonium N-(2-hydroxyethyl)nitrilodiacetates. Mixed salts of these aminopolycarboxylates are also suitable.

Other organic builders include the polyacetal carboxylates. The polyacetal carboxylates and their use in detergent compositions are described in application U.S. Serial No.767,579 filed August 19, 1985, assigned to the present applicants and in a U.S.P. Nos. 4,144,226 4,315,092 and 4,146,495.

Other typical suitable builders include, for example, those disclosed in U.S. Patents4,316,812, 4,264,466 and 3,630,929. The inorganic alkaline builder salts can be used with the nonionic surfactant detergent compound or in admixture with other organic or inorganic builder salts.

Thewaterinsolublecrystallineand amorphous aluminosilicatezeolites can be used. The zeolites generally have the formula (M20)x (AI203)y-(SiO2)z wH2O wherein xis 1, y is from 0.8to 1.2 and preferably 1,z is from 1.5to 3.5 or higherand preferably2to 3 andwis from 0 to 9, preferably 2.5 to 6 and M is preferably sodium. Atypical zeolite is type A or similar structure,with type 4A particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents per gram or greater, e.g. 400meq/yg.

Various crystalline zeolites (i.e. alumino-silicates) that can be used are described in British Patent 1,504,168, U.S.P. 4,409,136 and Canadian Patents 1,072,835 and 1,087,477, all of which are hereby incorporated by reference for such descriptions. An example of amorphous zeolites useful herein can be found in Belgium Patent 835,351 and this patent too is incorporated herein by reference.

Other materials such as clays, particularly of the water-insolubletypes, may be useful adjuncts in compositions ofthis invention. Particularly useful is bentonite. This material is primarily montmorillonite which is a hydrated aluminium silicate in which about 1/6th ofthe aluminium atoms may be replaced by magnesium atoms and with which varying amounts of hydrogen, sodium, potassium, calcium, etc., may be loosely combined. The bentonite in its more purified form (i.e. free from any grit, sand, etc.) suitablefor detergents contains at least 50% montmorillonite and thus its cation exchange capacity is at least about 50to 75 meq per 1009 of bentonite. Particularly preferred bentonites are the Wyoming or Western U.S. bentonites which have been sold as Thixo-jels 1,2,3 and 4 by Georgia Kaolin Co.These bentonites are known to soften textiles as described in British Patent 401,413 to Marriott and British Patent 461,221 to Marriott and Duggan.

The inclusion in the detergent composition of an effective amount of low molecularweight amphiphilic compounds which function as viscosity control and gel-inhibiting agents for the nonionic surfactant substantially improves the storage properties of the composition. The amphiphilic compounds can be considered to be analagous in chemical structureto the ethoxylated and/or propoxylated fatty alcohol liquid nonionic surfactants but have relatively short hydrocarbon chain lengths (cato C8) and a low content of ethylene oxide (about 2 to 6 ethylene oxide groups per molecule).

Suitable amphiphilic compounds can be represented by the following general formula RO(CH2CH20)nH where R represents a C2-C5 alkyl group, and n is a number of from about 1 to 6, on average.

Specifically the preferred compounds are lower (cato C3) alkylene glycol mono lower (cato C5) alkyl ethers.

More specifically the compounds are mono di- or tri lower(C2toC3) alkylene glycol mono lower (C1 toy5) alkyl ethers.

Specific examples of suitable amphiphilic compounds include ethylene glycol monoethyl ether dispensibility of the composition, i.e. pourability, and lowers the temperature atwhich the liquid nonionic surfactants form a gel in water without a decrease in their stability against settling. The acid terminated nonionic surfactant reacts in the washing machine water with the alkalinity of the dispersed buildersalt phase ofthe detergent composition and acts as an effective anionic surfactant.

Specific examples include the half-esters of Plurafac RA30 with succinic anhydride,the ester or half ester of Dobanol 25-7 with succinic an hydride, and the ester or half ester of Dobanol 91-5with succinic anhydride.

Instead of succinic anhydride, other polycarboxylic acids or anhydrides can be used, e.g. maleic acid, maleic acid anhydride, citric acid and the like.

The acid terminated nonionic surfactants can be prepared as follows: Acid Terminated Product A. 400 g of Product nonionicsurfactantwhich is a C13 to C15 alkanol which has been alkoxylated to introduce 6 ethyleneoxide and 3 propylene oxide units per alkanol unit is mixed with 329 of succinic anhydride and heated for7 hours at 100 C. The mixture is cooled and filtered to remove unreacted succinic material. Infrared analysis indicated that about one half ofthe nonionic surfactant has been converted to the acidic half-esterthereof.

Acid Terminated Dobanol 25-7.522 g of Dobanol 25-7 nonionic surfactantwhich is the product of ethoxylation of a C12 to C15 alkanol and has about 7 ethylene oxide units per molecule of alkanol is mixed with 1 00g of succinic anhydride and 0.1 g of pyridine (which acts as an esterification catalyst) and heated at260"C for2 hours, cooled and filtered to remove unreacted succinic material. Infrared analysis indicatesthat substantially all the free hydroxyls ofthe surfactant have reacted.

Acid Terminated Dobanol 91-5. 1000 g of Dobanol 91-5 nonionic surfactant which is the product of ethoxylation of a Cgto C11 alkanol and hasabout5 ethylene oxide units per molecule ofalkanol is mixed with 265g of succinic anhydride and 0.1 g of pyridine catalyst and heated at 2600Cfor2 hours, cooled and filtered to remove unreacted succinic material. Infrared analysis indicates that substantially all the free hydroxyls of the surfactant have reacted.

Other esterification catalysts, such as an alkali metal alkoxide (e.g. sodium methoxide) may be used in place of, orin admixturewith,the pyridine.

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

The liquid nonaqueous nonionic surfactant used in the compositions of the present invention has dispersed and suspended therein fine particles of inorganic and/or organic detergent builder salts.

The present invention includes as an essential part ofthe composition long linear chain condensed polyphosphate builder salts.

The long linear chain condensed polyphosphate builder salts used in the detergent compositions ofthe present invention have the following general formula

wherein M represents a hydrogen atom, oran alkali metal oran ammonium cation, and n=20 to 30, preferably about 25. All the M's are preferrably alkali metals orammonium, e.g., sodium and potassium, with sodium being the more preferred. A preferred builder salt is the alkali metal orammonium hexametaphosphate.

Aspecific example of a linear condensed polyphosphate builder salt that can be used is

The detergent compositions containing alkali metal hexametaphosphates provide improved cleaning performance. For example, a 100 gm (77 cc) of 29.6% concentration of sodium hexametaphosate provides cleaning performance equivalentto 100 gm (77 cc) of 30% sodium tripolyphosphate built detergent.

The detergent compositions ofthe present invention include water soluble and/or water insoluble detergent builder salts. Water soluble inorganic alkaline builder salts which can be used alone with the detergent compound or in admixture with other builders are alkali metal carbonates, bicarbonates, borates, phosphates, polyphosphastes, and silicates. (Ammonium or substituted ammonium salts can also be used.) Examples of conventionallyused builder salts are sodium tripolyphosphate, sodium carbonate; sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium and potassium bicarbonate.Sodium tripolyphosphate (TPP) is a commonly used (C2H5-O-CH2CH2OH), diethylene glycol monobutyl ether (C4H9-O-(CH2CH2O)2H), tetraethylene glycol monobutyl ether (C4H7-O-(CH2CH2O)4H) and dipropylene glycol monomethyl ether

Diethylene glycol monobutyl ether is especially preferred.

The inclusion in the composition of the low molecularweight lower alkylene glycol mono alkyl ether decreases the viscosity of the composition, such that it is more easily pourable, improves the stability against settling and improves the dispersibility of the composition on the addition to warm water or cold water.

The compositions of the present invention have improved viscosity and stability characteristics and remain stable and pou rabie at tem peratu res as low as about 5"C.

In an embodiment of this invention the physical stability of the suspension ofthe detergent builder compound or compounds and any other suspended additive, such as bleaching agent, etc., in the liquid vehicle is improved by the presence ofa stabilizing agent which is an alkanol ester of phosphoric acid oran aluminium saltofa higherfattyacid.

Improvements in stability of the composition may be achieved in certain formulations by incorporation of a small effective amount of an acidic organic phosphorus compound having an acidic- POH group, such as a partial ester of phosphorous acid and an alkanol.

As disclosed in the commonly assigned copending application US Serial No.597,948 filed April 9,1984 referred to above the disclosure of which is incorporated herein by reference, the acidic organic phosphorus compound having an acidic - POH group can increase the stability ofthe suspension of builders in the nonaqueous liquid nonionic surfactant.

The acidic organic phosphorus compound may be, for instance, a partial ester of phosphoric acid and an alcohol such as an alkanol which has a lipophiliccharacter, having,forinstance, more than 5 carbon atoms, e.g. 8to 20 carbon atoms.

Aspecificexample is a partial ester of phosphoric acid and a C16to C18alkanol (Empiphos 5632from Marchon); it is made up of about 35% monoesterand 65% diester.

The inclusion of quite small amounts ofthe acidic organic phosphorus compound makes the suspension significantly more stable against settling on standing but remains pourable,while,forthe low concentration of stabilizer, e.g. below about 1%, its plasticviscositywill generally decrease.

Further improvements in the stability and anti-settling properties ofthe composition may be achieved by the addition of a small effective amount of an aluminium salt of a higherfatty acid to the composition.

The aluminium salt stabilizing agents are the subject matter ofthe commonly assigned copending application U.S. Serial No.725,455, filed April 1985, the disclosure of which is incorporated herein by reference.

The preferred higher aliphatic fatty acidswill have from about 8 to about 22 carbon atoms, more preferably from about lOto 20 carbon atoms, and especially preferablyfrom about 12to 18 carbon atoms. Thealiphatic radical may be saturated or unsaturated and may be straight or branched. As in the case of the nonionic surfactants, mixtures of fatty acids may also be used, such as those derived from natural sources, such as tallowfatty acid, coco fatty acid, etc.

Examples of the fatty acids from which the aluminium salt stabilizers can beformed include, decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicosanoic acid, tallow fatty acid, coco fatty acid, mixtures of these acids, etc. The aluminium salts of these acids are generally commercially available, and are preferably used in the triacid form, e.g. aluminium stearate as aluminiumtristearate Al(C,7H35CO0)3. The monoacid salts, e.g. aluminium monostearate, Al(OH)2(C17H35COO) and diacid salts, e.g.

aluminium distearate,Al(OH)(C17H35COO)2, and mixtures of two orthree ofthe mono-, di-andtriacid aluminum salts can also be used. It is most preferred, however, that the triacid aluminum salt comprises at least 30%, preferably at least 50%, especially preferably at least 80% ofthe total amount of aluminium fatty acid salt.

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

Although the applicants do not wish to be bound by any particular theory ofthe manner by which the aluminium saltfunctionsto prevent settling ofthesuspended particles, itis presumed thatthealuminium salt increases the wettability ofthe solid surfaces by the nonionic surfactant. This increase in wettability, it is believed, allows the suspended particles to more easily remain in suspension.

Only very small amounts of the aluminium salt stabilizing agent are required to obtain significant improvements in physical stability.

In addition to its action as a physical stabilizing agent, the aluminum salt has the additional advantages over other physical stabilizing agents that it is non-ionic in character and is compatible with the nonionic surfactant component and does not interfere with the overall detergency of the composition; it exhibits some anti-foaming effect; it can function to boostthe activity offabric softeners, and it confers a longer relaxation time to the suspensions.

The bleaching agents are classified broadly, for convenience, as chlorine bleaches and oxygen bleaches.

Chlorine bleaches aretypified by sodium hypochlorite (NaOCI), potassium dichloroisocyanurate (59% available chlorine), and trichloroisocyanuric acid (95% available chlorine). Oxygen bleaches are preferred and are represented by percompoundswhich liberate hydrogen peroxide in solution. Preferred examples include sodium and potassium perborates, percarbonates, and perphosphates, and potassium monopersulphate. The perborates, particularly sodium perborate monohydrate, are especially preferred.

The peroxygen compound is preferably used in admixture with an activatortherefor. Suitable activators which can lowerthe effective operating temperature of the peroxide bleaching agent are disclosed,for example, in U.S.P. 4,264,466 or in column 1 of U.S.P. 4,430,244, the relevant disclosures of which are incorporated herein by reference. Polyacylated compounds are preferred activators, among these, compounds such as tetraacetyl ethylene diamine ("TAED") and pentaacetyl glucose are particularly preferred.

Other useful activators include, for example, acetylsalicylic acid derivatives, ethylidene benzoate acetate and its salts, ethylidene carboxylate acetate and its salts, alkyl and alkenyl succinic anhydride, tetraacetylglycouril ("TAGU "), and the derivatives ofthese. Other useful classes of activators are disclosed, for example, in U.S.P. 4,111,826,4,422,950 and 3,661,789.

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

Suitable sequestering agentsforthis purpose include sodium salts of nitrilotriaceticacid (NTA), ethylene diamine tetraacetic acid (EDTA), diethylenetriamine pentaacetic acid (DETPA), diethylenetriamine pentamethylene phosphonic acid (DTPMP) sold underthe tradename Dequest 2066; and ethylene diamine tetramethylene phosphonic acid (EDITEMPA). The sequestering agents can be used alone or in admixture.

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

Of special interest as the inhibitor compound, mention can be made of hydroxylamine sulphate and other water-soluble hydroxylamine salts. In the preferred nonaqueous compositions of this invention, suitable amounts of the hydroxylamine salt inhibitors can be as low as about 0.01 to 0.4%. Generally, however, suitable amounts of enzyme inhibitors are upto about 15%, for example, 0.1 to 10%, by weight ofthe composition.

In addition to the detergent builders, various other detergent additives or adjuvants may be present in the detergent product to give it additional desired properties, either offunctional or aesthetic nature. Thus, there may be included in the formulation, minor amounts of soil suspending or anti-redeposition agents, e.g.

polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxy-propyl methyl cellulose. A preferred anti-redeposition agent is sodium carboxymethyl cellulose having a 2:1 ratio of CM/MC which is sold underthetradename Relatin DM 4050.

Optical brighteners for cotton, polyamide and polyester fabrics can be used. Suitable optical brighteners include stilbene, triazole and benzidine sulphone compositions, especially sulphonated substituted triazinyl stilbene, sulphonated naphthotriazole stilbene, benzidene sulphone, etc., most prefered are stilbene and triazole combinations. Preferred brighteners are Stilbene Brightener N4which is a dimorpholino dianilino stilbene sulphonate and Tinopal ATS-Xwhich is well known in the art.

Enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papain,trypsin and pepsin, aswell as amylase type enzymes, lipase type enzymes, and mixtures thereof can be used. Preferred enzymes include protease slurry, esperase slurry and amylase. A preferred enzyme is Esperse SL8 which is a protease.

Anti-foam agents, e.g. silicon compounds, such as Silicane L 7604 can also be added in small effective amounts.

Bactericides, e.g. tetrachlorosalicylanilide and hexachlorophene, fungicides, dyes, pigments (water dispersible), preservatives, ultravoilet absorbers, anti-yellowing agents, such as sodium carboxymethyl cellulose, pH modifiers and pH buffers, colour safe bleaches, perfume, and dyes and bluing agents such as ultramarine blue can be used.

The composition may also contain an inorganic insoluble thickening agent or dispersant of very high surface area such as finely divided silica of extremely fine particle size (e.g. of 5-100 millimicrons diameters such as sold underthe name of Aerosil) or the other highly voluminous inorganic carrier materials disclosed in U.S.P. 3,630,929, in proportions of 0.1-10%, e.g. 1 to 5%. It is preferable, however, that compositions which form peroxyacids in the wash bath (e.g. compositions containing peroxygen compound and activator therefor) be substantially free of such compounds and of other silicates; it has been found, for instance, that silica and silicates promote the undesired decomposition of the peroxyacid.

In an embodiment of the invention the stability ofthe suspension of buildersalts in the composition during storage and the dispersibility of the composition in water is improved by grinding and reducing the particle size of the solid builders to less than 100 microns, preferably less than 40 microns and more preferably to less than 10 microns. The solid builders are generally supplied in particle sizes of about 100,200 or 400 microns.

The nonionic liquid surfactant phase can be mixed with the solid builders prior to or after carrying outthe grinding operation.

In a preferred embodiment ofthe invention, the mixture of liquid nonionic surfactant and solid ingredients Weight% Nonionic surfactant detergent 30-40 Acid terminated nonionicsurfactant 5-15 Alkali metal hexametaphosphate 25-35 Anti-encrustation agent (Sokalan CP-5) 0-10 Alkylene glycol monoalkyl ether 8-12 Alkanol phosphoric acid ester (Empiphos 5632) 0.1-1.0 Anti-redeposition agent (Relatin DM 4050) 0-3.0 Alkali metal perborate bleaching agent 8-15 Bleach activator (TAED) 2-6 Sequestering agent (Dequest 2066) 0-3.0 Optical brightener (ATS-X) 0.05-1.0 Enzymes (Protease-Esperase SL8) 0.5-1.5 Perfume 0.5-1.0 The present invention is further illustrated by the following example.

EXAMPLE A concentrated nonaqueous liquid nonionic surfactant detergent composition is formulated from the following ingredients in the amounts specified in Table 1 below.

TABLE 1 Weight% A mixture of C13-C15 fatty alcohol condensed with 7 moles of propylene oxide and 4 moles ethylene oxide and C13-C15fattv alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide 15.5 SurfactantT7 9.0 SurfactantT9 9.0 Acid terminated Dobanol 91-5 reaction product with succinic anhydride 6.0 Sodium hexametaphosphate 29.6 Diethylene glycol monobutyl ether 9.0 Alkanol phosphoric acid ester (Empiphos 5632) 0.3 Anti-encrustation agent (Sokalan CP-5) 3.0 Sodium perborate monohydrate bleaching agent 10.0 Tetraacetylethylene diamine (TAED) bleach activator 4.5 Sequestering agent(Dequest2066) 1.0 Optical brightener (Tinopal ATS-X) 0.5 Anti-redeposition agent (Relatin DM 4050) 1.0 Esperase scurry (Esperase SL8) 1.0 Perfume 0.5925 Dye 0.0075 100.00 The formulation is ground for about 1 hour to reduce the particle size ofthe suspended builder salts to less than 40 microns. The formulated detergent composition found to be stable and non-gelling in storage and to have a high detergent capacity.

The formulations can be prepared without grinding the builder salts and suspended solid particles to a small particle size, but best results are obtained by grinding the formulation to reducethe particle size ofthe suspended solid particles.

The builder salts can be used as provided, or the builder salts and suspended solid particles can be ground or partially ground prior to mixing them with the nonionic surfactant. The grinding can be carried out in part priorto mixing and grinding completed after mixing or the entire grinding operation can be carried out after mixing with the liquid surfactant. The formulations containing suspended builder and solid particles less than 100 microns in size are preferred.

EXAMPLE2 In order to demonstrate the effect on cleaning and anti-encrustation or anti-scaling performance ofthe substitution of sodium tripolyphosphate by sodium hexametaphosphate detergent builder salt ofthe present invention, the detergent composition formulation of Example 1 containing 29.6% byweightof sodium hexametaphosphate is compared in repeated laundry washing machine cycles with the same composition in which the hexametaphosphate is replaced with 30% by weight of sodium tripolyphosphate.

is subjected to an attrition type of mill in which the particle sizes of the solid ingredients are reduced to less than about 40 microns, preferrablyto less than about 10 microns, e.g. to an average particle size of 2to 10 microns or even lower (e.g. 1 micron). Preferably less than about 10%, especially less than about 5% of all the suspended particles have particle sizes greaterthan 10 microns. Compositions whose dispersed particles are of such small size have improved stability against separation or settling on storage. Addition ofthe acid terminated nonionic surfactant compound aids in the dispersibility ofthe dispersions without a corresponding decrease in the dispersions stability against settling.

In the grinding operation, it is preferred that the proportion of solid ingredients be high enough (e.g. at least about 40% such as about 50%) th at the solid particles are in contact with each other and are not substantially shielded from one another by the nonionic surfactant liquid. Afterthe grinding step any remaining liquid nonionicsurfactantcan be added to the ground formulation. Mills which employgrinding balls (ball mills) or similar mobile grinding elements have given very good results. Thus, one may use a laboratory batch attritor having 8 mm diameter steatite grinding balls.For larger scale work a continuously operating mill in which there are 1 mm or 1.5 mm diametergrinding balls working in a very small gap between a stator and a rotor operating at a relatively high speed (e.g. a CoBall mill) may be employed; when using such a mill, it is desirableto pass the blend ofnonionicsurfactantand solidsfirstthrough a millwhich does not effect such fine grinding (e.g. a colloid mill) to reduce the particle size to less than 100 microns (e.g.

to about 40 microns) prior to the step of grinding to an average particle diameter below about 10 microns in the continuous ball mill.

In the preferred heavy duty liquid laundry detergent compositions ofthe invention, typical proportions (percent based on the total weight of composition, unless otherwise specified) of the ingredients areas follows: Liquid nonionic surfactant detergent in the range of about 10 to 60, such as 20to 50 or 30 to 40 percent.

Acid terminated nonionic surfactant may be omitted, it is preferred howeverthat it be added to the composition in an amount in the range of about 0 to 30, such as 5 to 25 or 5 to 15 percent.

Long linear chain condensed polyphosphate builder salts in the range of about 1 Oto 60, such as 20to 50 or 25 to 35 percent.

Copolymer of polyacrylate and polymaleic anhydride alkali metal salt anti encrustation agent in the range of about0 to 10, such as 2 to 8 or 2 to 6 percent.

Alkylene glycol monoalkyletheranti-gel agent in an amount in the range ofabout0to 20, such as5to 150r 8 to 12 percent.

Phosphoric acid alkanol ester stabilizing agent in the range of to 2.0 orO.1 to 2.0, such as 0.1 to 1.0 percent.

Aluminium salt of fatty acid stabilizing agent in the range of about O to 3.0, such as 0.1 to 2.0 or 0.5 to 1.5 percent.

It is preferred that at least one of phosphoric acid ester or aluminium salt stabilizing agent be included in the composition.

Bleaching agent in the range of about0to 35, such as 5to 30 or 8 to 15 percent.

Bleach activator in the range of about 0 to 20, such as 1 to 15 or 2 to 6 percent.

Sequestering agentfor bleach in the range of about Oto 3.0, preferably 0.5to 2.0 or 0.5 two 1.5 percent.

Anti-redeposition agent in the range of about 0 to 3.0, such as 0.5 to 2.0 or 0.5 to 1.5 percent.

Optical brightener in the range of about 0 to 2.0, such as 0.05 to 1.5 or 0.3 to 1.0 percent.

Enzymes in the range of about 0 to 3.0, such as 0.5 to 2.0 or 0.5 to 1.5 percent.

Perfume in the range of about Oto 2.0, such as 0.1 Oto 1.25 or0.5to 1.0 percent.

Dye in the range of about 0 to 1.0, such as 0.0025 to 0.050 or 0.0025 to 0.0100 percent.

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

Mixtures of the acid terminated nonionic surfactant and the alkylene glyco alkyl ether anti-gel agents can be used and in some cases advantages can be obtained by the use of such mixtures alone, or with the addition to the mixture of a stabilizing and anti settling agent, e.g. phosphoric acid alkanol ester.

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

The concentrated nonaqueous nonionic liquid detergent composition of the present invention dispenses readily in the water in the washing machine. The presently used home washing machines normally use 250 gms of powder detergent to wash a full load of laundry. In accordance with the present invention onlyabout 77 ml or about 100 gms of the concentrated liquid non ionic detergent composition is needed.

In a preferred embodiment ofthe invention the detergent composition of a typical formulation is formulated in the proportions indicated below using the below named ingredients: The repeated wash cycles are carried out at laundry wash water concentrations of each of the detergent compositions of 5 gm/liter ofthe respective detergent compositions.

After each detergent composition is used in twelve wash cycles in a washing machine the amount of encrustation or scaling that results, i.e.,the percent ash deposit is measured. The percent ash deposit measurement is determined by calcination of washed swatches.

The results that are obtained are that the sodium hexametaphosphate detergent composition's cleaning performance is equivalent or better than the sodium tripolyphosphate and the sodium hexametaphosphate detergent composition provides improved anti-encrustation oranti-scaling performance to that of the sodium tripolyphosphate.

As far as the encrustation buildup is concerned, no buildup is observed with the hexametaphosphate, whereas a small buildup is observed with the sodium tripolyphosphate detergent builder salt.

The hexametaphosphate detergent builder salts can also be used to replace the polyphosphate builder salts in concentrated aqueous detergent compositions. At concentrations of 50 to 60%, due to the hexametaphosphate's polymeric structure, a viscous solution is obtained. Because of the viscous nature of the concentrated aqueous solution the physical stability and rheological behavior ofthe aqueous concentrated composition is improved.

It is understood that the foregoing detailed description is given merely byway of illustration and that variations may be made therein without departing from the spirit of the invention.

Claims (20)

1. A heavy duty detergent composition which comprises at least one liquid nonionic surfactant detergent and a long linear chain condensed polyphosphate dispersed therein as the principle detergent builder salt.

2. A composition as claimed in Claim 1 in which the principle detergent builder salt is a hexametaphosphate.

3. A detergent composition as claimed in Claim 1 or Claim 2 comprising at least one of the members of the group consisting of an acid terminated non ionic surfactant anti-gel agent, an alkylene glycol mono ether and an alkanol phosphoric acid ester stabilizing agent.

4. A detergent composition as claimed in Claim 1,2 or 3 comprising one or more detergent adjuvants selected from the group consisting of a bleach agent, a bleach activator, an optical brightener, an enzyme and a perfume.

5. Adetergentcomposition as claimed in Claim 1,2,3 or4comprising 10to 60 percent of a long linear chain detergent builder salt of the formula

wherein M represents a hydrogen atom or an alkali metal or ammonium cation, and n=20 to 30.

6. A detergent composition as claimed in any one of Claims 1 to 5 comprising 5to 25 percent of an acid terminated surfactant.

7. Adetergentcomposition as claimed in any one of claims 1 to 6 comprising 0.1 Oto 2.0 percent of an alkanol phosphoric acid ester.

8. Adetergentoomposition as claimed in anyone of Claims 1 to 7 comprising about5to 15 percentofan alkylene glycol mono-ether.

9. Adetergentcomposition as claimed in any one of Claims 1 to 8 in which the nonionicsurfactanthas dispersed therein detergent builder particles having a particle size of less than about 40 microns.

10. A detergent composition as claimed in any one of Claims 1 to 9 which comprises at leastone iiquid nonionic surfactant in an amount of about 20 to 50 percent, an acid-terminated nonionic surfactant in an amountofabout5to 25 percent, an alkali metal hexametaphosphate (n=25) buildersaltin an amount of about20to 50 percent, an alkylene glycol mono-etherin an amountofabout5to 15 percent, and analkanol phosphoric acid ester in an amount of about 0.1 to 1.0 percent.

11. A detergent composition as claimed in Claim 10 comprising an alkali metal perborate monohydrate bleaching agent in an amount of about 5to 30 percent,tetraacetylethylene diamine bleach activator in an amount of about 1 to 15 percent, and optionally one or more detergent adjuvants selected from the group consisting of anti-encrustation agents, anti-redeposition agents, sequestering agentsforthe bleach, optical brighteners, enzymes and perfumes.

12. A detergent composition as claimed in claim 10, 11 or 12 in which the detergent builder comprisesthe sodium salt of hexametaphosphate (n=25).

13. Adetergentcomposition as claimed in Claim 10,11 or 12 in which the sodium salt of hexametaphosphate has the formula

wherein n=25.

14. A detergent composition as claimed in any one of Claims 10 to 13 in which the alkanol phosphoric acid ester comprises a C16 to C18 alkanol ester of phosphoric acid.

15. Adetergentcomposition as claimed in anyone of Claims lotto 14which is pourableat high and low temperatures, is stable in storage and does not gel when mixed with cold water.

16. A detergent composition as claimed in any one of Claims 10 to 15 which comprises sodium hexametaphosphate (n=25) builder salt in an amounts fabout 25to 35 percent.

17. A concentrated nonaqueous liquid nonionic surfactant heavy duty laundry detergent composition which comprises: Nonionic surfactant in an amount of about 30-40%; Acid terminated surfactant in an amount of about 5-15%; Sodium salt of hexametaphosphate (n=25) in an amount of about 25-35%; Alkylene glycol monobutyl ether in an amount ofabout0.1 -1.0%; Sodium perborate monohydrate bleaching agent in an amount of about 8-15%; and Tetraacetylethylene diamine (TAED) bleach activator in an amount of about 2-6%.

18. A detergent composition as claimed in Claim 16 in which the composition comprises an anti-redeposition agent and anti-encrustation agent, and a sequestering agentforthe bleach.

19. A detergent composition as claimed in Claim 1 substantially as specifically described herein with referenceto Example 1.

20. A method for cleaning solid fabrics which comprises contacting the soiled fabrics with a detergent composition as claimed in any one of claims 1 to 19.