GB2195125A - Nonaqueous liquid nonionic laundry detergent compositions containing a persalt bleach and a liquid organic bleach activator - Google Patents

Description

1 1 10 GB2195125A 1

SPECIFICATION

Nonaqueous liquid nonionic laundry detergent compositions containing a persalt bleach and a liquid organic bleach activator and method of use The present invention relates to nonaqueous liquid fabric treating compositions. More particularly, this invention relates to liquid nonionic laundry detergent compositions which contain an organic persalt bleach compound and a liquid organic bleach activator, and to the use of these compositions for cleaning soiled fabrics. The compositions are stable against phase separation and gelation and are easily pourable.

Liquid nonaqueous heavy duty laundry detergent compositions are well known in the art. For instance, compositions of that type 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.

Liquid detergents are often considered to be more convenient to employ than dry powdered or 15 particulate products and, therefore, have found substantial favour with consumers. They are readily measurable, speedily dissolved in the wash water, 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 their formulations materials which could not stand drying operations without 20 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 others separate out on cooling and are not readily redispersed. In 25 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 present inventors have been involved in studying the behaviour of nonionic liquid surfac tant systems with particulate matter suspended therein. Of particular interest has been nonaque ous built laundry liquid detergent compositions and the problem of settling of the suspended 30 builder and other laundry additives as well as the problem of gelling associated with nonionic surfactants. These considerations have an impact on, for example, product stability, pourability and dispersibility.

It is known that one of the major problems with built liquid laundry detergents is their physical stability. This problem stems from the fact that the density of the solid particles dispersed in the 35 nonionic liquid surfactant is higher than the density of the liquid surfactant.

Therefore, the dispersed particles tend to settle out. Two basic solutions exist to solve the settling out problem: increase nonionic liquid viscosity and reduce the dispersed solid particle size.

It is known that suspensions can be stabilized against settling by adding inorganic or organic 40 thickening agents or dispersants, such as, for example, very high surface area inorganic ma terials, e.g. finely divided silica, clays, etc., organic thickeners, such as the cellulose ethers, acrylic and acrylamide polymers, polyelectrolytes, etc. However, such increases in suspension viscosity are naturally limited by the requirement that the liquid suspension be readily pourable and flowabieve, even at low temperature. Furthermore, these additives do not contribute to the cleaning performance of the formulation.

Grinding to reduce the particle size provides the following advantages:

1. Specific surface area of the dispersed particles is increased, and, therefore, particle wetting by the nonaqueous vehicle (liquid nonionic) is proportionately improved.

2. The average distance between dispersed particles is reduced with a proportionate increase 5G in particle-to-particle interaction. Each of these effects contributes to increase the rest-gel strength and the suspension yield stress while at the same time, grinding significantly reduces plastic viscosity.

The yield stress is defined as the minimum stress necessary to induce a plastic deformation (flow) of the suspension. Thus, visualizing the suspension as a loose network of dispersed particles, if the applied stress if lower than the yield stress, the suspension behaves like an elastic gel and no plastic flow will occur. Once the yield stress is overcome, the network breaks at some points and the sample begins to flow, but with a very high apparent viscosity. If the shear stress is much higher than the yield stress, the pigements are partially shear-deflocculated and the apparent viscosity decreases. Finally, if the shear stress is much higher than the yield 60 stress value, the dispersed particles are completely shear-deflocculated and the apparent visco sity is very low, as if no particle interaction were present.

Therefore, the higher the yield stress of the suspension, the higher the apparent viscosity at low shear rate and the better is the physical stability against settling of the product.

In addition to the problem of settling or phase separation, the nonaqueous liquid laundry 65 GB 2 195 125A detergents based on liquid nonionic 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 household 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 it to the main body of wash solution. Especially during the winter months when the detergent composition and water fed to the dispenser are particularly cold, the detergent viscosity increases markedly and a gel forms. As a result some of the 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 user to flush the dispenser with hot water.

The gelling phenomenon can also be a 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 aggrevated by 15 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 builderfree compositions have been proposed and include, for example, diluting the liquid nonionic with certain viscosity controlling solvents and gel-inhibiting agents, such as lower alkanols, e. g. ethyl alcohol (see 20 U.S.P. 3,953,380), alkali metal formates and adipates (see U.S.P. 4,368, 147), hexylene glycol, polyethylene glycol, etc. and nonionic structure 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 of the nonionic include gel inhibition upon dilution; decreasing the 25 nonionic pour point; and formation of an anionic surfactant when neutralized in the washing liquor. Nonionic structure optimization has centred on the chain length of the hydrophobic lipophilic moiety and the number and make-up of alkylene oxide (e.g. ethylene oxide) units of the hydrophilic moiety. For example, it has been found that a C,, fatty alcohol ethoxylated with 8 moles of ethylene oxide presents only a limited tendency to gel formation.

Improvements are desired in the bleach properties and the stability and gel inhibition of nonaqueous liquid fabric treating compositions containing a bleach and bleach activator.

In accordance with the present invention a highly concentrated stable nonaqueous liquid laun dry detergent composition is prepared containing a persalt bleach compound and a liquid organic compound bleach activator. A preferred persalt bleach compound is sodium perborate monohy- 35 drate and a preferred liquid organic compound bleach activator is ethylidene benzoate acetate.

The liquid organic compound bleach activator is used to replace the conventionally used solid bleach activators, such as tetraacetyl ethylene diamine (TAED), and to thereby reduce the solids content of the concentrated detergent composition and to improve the pourability and dispersibil ity of the composition.

The persalt bleach and organic liquid bleach activator system of the present invention can be used in phosphate and in low phosphate detergent builder salt compositions.

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 the storage properties of the composition there can be added to the composition viscosity improving and antigel agents such alkylene glycol mono alkyl ethers and an anti-settling agent such as an alkanol ester of phosphoric acid. In a preferred embodiment of the invention the detergent composition contains sodium perborate monohydrate bleach, ethylidene benzoate ace tate bleach activator, an acid terminated nonionic surfactant, an alkylene glycol mono alkyl ether and an alkanol ester or phosphoric acid anti-settling stabilizing agent.

The conventionally used peroxygen bleach compounds, e.g. sodium perborate, percarbonate, perphosphate and persulphate can be used as the bleaching agent.

In an embodiment of the invention the builder components of the composition can be ground to a particle size of less than 100 microns, for example, to less than 40 microns, and to preferably less than 10 microns to further improve the stability of the suspension of the builder components in the liquid nonionic surfactant detergent. I In addition other ingredients can be added to the composition such as anti-incrustation agents, sequestering agents, anti-foam agents, optical brighteners, enzymes, anti- redeposition agents, perfumes and dyes.

Accordingly, in one -aspect the present invention provides a liquid heavy duty laundry compo- 6G sition composed of a suspension of a peroxygen bleach compound and a detergent builder salt, e.g. a phosphate builder salt, in a liquid nonionic surfactant wherein the composition includes as the bleach activator an effective amount of a liquid organic bleach activator compound, e.g.

ethylidene benzoate acetate.

According to another aspect, the invention provides a concentrated liquid heavy duty laundry 65 &' 1 1 V 3 GB2195125A 3 detergent composition which has good low temperature bleach properties, 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 and are readily dispersible in water.

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 for filling a container with a non-aqueous liquid laundry detergent composition in which the detergent is composed, at least predominantly, of a liquid nonionic 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 10 composition such that the composition is carried by the stream of water into the wash bath.

The use of the liquid organic compound bleach activator in the composition in place of the solid bleach activator reduces the problem of dispersed particle settling and improves the pourability of the composition.

The substitution of a liquid organic bleach activator for the prior art solid activators, such as 15

TAED reduces the total solids content of the composition and provides the bleach activator in a dispersed liquid form in which it can more readily react with the persalt bleach compound.

The concentrated nonaqueous liquid nonionic surfactant laundry detergent compositions of the present invention have the 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 machins and are readily dispersible in water.

The present invention aims to provide a stable liquid heavy duty nonaqueous nonionic detergent composition containing a persalt bleach compound and a liquid organic bleach activator compound, at least one viscosity control and anti-gel agent, an anti-settling stabilizing agent and an anionic phosphate detergent builder salt suspended in a nonionic surfactant.

The invention also aims to provide liquid fabric treating compositions which have good low temperature bleach properties which are suspensions of insoluble inorganic particles in a nona queous liquid and which are storage stable, easily pourable and dispersible in cold, warm or hot water.

This invention also aims to formulate a highly built heavy duty nonaqueous liquid nonionic 30 surfactant laundry detergent compositions which can be poured at a wide range of temperatures and which can be repeatedly dispersed from the dispensing unit of European style automatic laundry washing machines with less tendency to fouling or plugging of the dispenser even during the winter months.

This invention aims to provide a non-gelling, stable suspensions of heavy duty built nonaque- 35 ous liquid nonionic laundry detergent composition which contain a persalt bleach compound and include an effective amount of a liquid organic bleach activator compound.

In a preferred embodiment of the present invention a detergent composition comprises a nonaqueous liquid nonionic surfactant, a persalt bleach compound and a liquid organic persalt bleach activator, and may include inorganic or organic fabric treating additives, e.g. viscosity improving agents and one or more anti-gel agents, anti-incrustation agents, pH control agents, anti-foam agents, optical brighteners, enzymes, anti-redeposition agents, perfumes, dyes and colouring pigments.

The nonaqueous liquid nonionic laundry detergent compositions of the present invention con tain a persalt bleach compound and a liquid organic bleach activator as essential ingredients of 45 the composition.

The persalt bleach compounds, which are well known in the art, are dispersed as solids in the nonionic surfactant and are readily soluble on the addition of the detergent composition to the aqueous wash water. The persalt compounds, or oxygen bleaches are percompounds which liberate hydrogen peroxide in aqueous solution. Preferred examples include sodium and potas sium perborates, percarbonates and perphosphates, and potassium monopersulphate. The perbo rates, particularly sodium perborate monohydrate, are especially preferred.

Hydrogen peroxide and the precursors which liberate hydrogen peroxide are good oxidizing agents for removing stains from cloth, especially strains caused by wine, tea, coffee, cocoa, fruits, etc. Hydrogen peroxide and its precursors have been found in general to bleach quickly 55 and most effectively at a relatively high temperature, e.g. about 80' to 100'C.

In order to take advantage of the low temperature effective detergents and low temperature washing cycles now commonly used for temperature sensitive fabrics, the persalt or peroxygen bleach compound is used in admixture with a bleach activator.

Heretofore solid bleach activators have been used, such as tetraacetyl ethylene diamine 60 (TAED). The use of the solid activators increased the solids content of the particles dispersed in the nonionic surfactant detergent and required that the solid bleach activators dissolve in the aquous bath liquid prior to the activators being able to react with the persalt bleach compound.

In accordance with the present invention clear fluid liquid organic bleach activator compounds are used to activate the persalt bleach compound. Because the organic bleach activators are 4 GB2195125A 4 liquid they are readily dispersed in the nonionic liquid surfactant detergent and because the organic bleach activators are liquid they more readily react with the persalt bleach compounds in the aqueous wash liquor. The addition of the liquid organic bleach activator compounds can lower the effective operating temperature of the peroxide bleaching agents to temperatures as 5 low as 30 to 4WC.

The preferred organic liquid bleach activator compounds have the general formula 0 10 11; O-C-R2 R' -CH O-C-R3 0 wherein W, R2 and R3 are hydrocarbon radicals. W, R2 and R3 can each independently be Cl to 20 C12 alky], e.g. Cl to C, alkyl such as Cl-C2 alkyl; aromatic, e.g. phenyl and lower alkyl aromatic, such as Cl-C3 substituted phenyl; and C, to C, heterocyclic, wherein the hetero atom is oxygen, nitrogen or sulphur, such as furane, tetra hydrofurane, thiophene, tetrahydrothiophene, oxazine, pyridine, pyrrolidine and pyrrolidone.

In the preferred embodiment R' is Cl-C, alkyl, preferably CH3, R2 'S ClC4 alkyl, preferably CH3, and R3 is phenyl and phenyl substituted with 1 to 3 methyl groups, preferably phenyl, or heptanoyl, ethylidene heptanoate acetate, ethylidene octanoate acetate and ethylidene dodeca noate acetate. Each perform well, but the heptanoate is the best, probably because the hydro philic-lipophilic balance is right to absorb on fabric and remain hydrophilic enough to react with hydrogen peroxide.

The preferred organic liquid bleach activator compound is ethylidene benzoate acetate which is a clear fluid liquid and which is readily commercially available.

Only small amounts of liquid organic bleach activator compound, e.g. ethylidene benzoate acetate, are required to activate the peroxygen bleach compound. For example, based on the total weight of the nonionic liquid surfactant composition, suitable amounts of ethylidene benzo- 35 ate acetate are in the range of from about 1% to about 15%, preferably from about 1% to about 8.0% and more preferably about 2% to 6%.

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 40 peroxide in the wash solution in the presence of metal ions.

Suitable sequestering agents for this purpose include the sodium salts of nitrilotriacetic acid (NTA), ethylene diamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DETPA), diethylene triamine pentamethylene phosphonic acid (DTPMP) sold under the tradename Dequest 2066; and ethylene diamine tetramethylene phosphonic acid (EDITEMPA). The sequestering 45 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 50 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 an embodiment of the 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 up to about 15%, 55 for example, 0.1 to 10% by weight of the composition.

There can also be added to the formulation stabilizers, such as, for example, an acidic organic phosphorous compound having an acidic -POH group, such as a partial ester of phosphorous acid and an alkanol.

The nonionic surfactant detergents can be built with only polyphosphate builder salts or can 60 be low in polyphosphates.

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

As is well known, the nonionic synthetic organic detergents are characterised by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by 65 -1 10 GB2195125A 5 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 nonionic 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 hydrophilelipophile 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 alkanol wherein the alkanol is of 9 to 18 carbon atoms and wherein the number of moles of lower alkylene oxide (of 2 or 3 carbon atoms) is from 3 to 12. Of such materials it is preferred to employ those wherein the higher alkanol is a higher fatty alcohol of 9 to 11 or 12 to 15 carbon atoms and which contain from 5 to 8 or 5 to 9 lower alkoxy groups per mol. Preferably, the lower alkoxy is ethoxy but in some instances, it may be desirably mixed 15 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 mol, e.g. Neodol 25-7 and Neodol 23-6.5, which products are made by Shell Chernial Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols averaging about 12 to 15 carbon atoms, with about 7 20 moles of ethylene oxide and the latter is a corresponding mixture wherein the carbon atom content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups present averages about 6.5. The higher alcohols are primary alkanols.

Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15S-9, both of which are linear secondary alcohol ethoxylates made by Union Carbide Corp. The former is a mixed ethoxylation product of 11 to 15 carbon atoms linear secondary alkanol with seven mols of ethylene oxide and the latter is a similar product but with nine mols 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 higher fatty alcohols, with the higher fatty alcohol being of 14 to 15 carbon atoms and the number of ethylene oxide groups per mol 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 under the trademark Plurafac. The plurafacs are the reaction product of a higher linear alcohol 35 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 products which are (A) C13-Cl. fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide, (B) (C13-Cl. fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide, (C) C13-ClS fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide, and 40 (D) which is a 1: 1 mixture of products (B) and (C).

Another group of liquid nonionics are commercially available from Shell Chemical Company, Inc. under the Dobanol trademark: Dobanol 91-5 is an ethoxylated C,-C,, fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 which is an ethoxylated C12-ClI 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 hydro- philic and 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-lower alkoxy higher alkanol. Higher molecular weight alkanols and various other normally solid nonionic deter- 50 gents 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 present compositions, although minor proportions thereof may be employed for their cleaning properties, etc. With respect to both preferred and less preferred nonionic detergents the alkyl groups present therein are generally linear although branching may be tolerated, such as at a carbon next to or two 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 terminally joined to the ethylene oxide chains are highly preferred and are considered to resuhit in the best combina- 60 tion 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 case of the mentioned Tergitols, may be greater. Also, when propylene oxide is present in the lower alkylene oxide chain, it will usually 65 be less than 20% thereof and preferably less than 10% thereof.

6 GB2195125A 6 When greater proportions of non-terminally alkoxylated alkanols, propylene oxide-containing poly-lower alkoxylated alkanols and less hydrophile-lipophile balanced nonionic detergent than mentioned above are employed and when other nonionic detergents are used instead of the 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 invention can also improve the properties of the detergents based on such nonionics. In some cases, as when a higher molecular weight polylower alkoxylated higher alkanol is employed, often for its detergency, the proportion thereof will 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 of desired viscosity. Also, it has been found that it is only rarely necessary to utilize the higher molecular weight nonionics for their detergent properties since the preferred nonionics described herein are excellent detergents and additionally, permit the attainment of the desired viscosity in the liquid detergent without gelation at low temperatures.

Another useful group of nonionic surfactants are the "Surfactant T" series of nonionics 15 available from British Petroleum. The Surfactant Tnonionics are obtained by the ethoxylation of secondary C, fatty alcohols having a narrow ethylene oxide distribution. The Surfactant T5 has an average of 5 moles of ethylene oxide; Surfactant T7 an average of 7 moles of ethylene oxide; Surfactant T9 an average of 9 moles of ethylene oxide and Surfactant T12 an average of 12 moles of ethylene oxide per mole of secondary C1, fatty alcohol.

In the compositions of this invention, preferred nonionic surfactants include the C,2_C15 secon dary fatty alcohols with relatively narrow contents of ethylene oxide in the range of from about 7 to 9 moles, and the C, to C1, 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 an acid terminated liquid nonionic surfactant.

The acid terminated nonionic surfactants consist of a nonionic surfactant which has been modi fied to convert a free hydroxyl group thereof to a moiety having a free carboxyl group, such as an ester or a partial ester of a nonionic surfactant and a polycarboxylic acid or anhydride.

As disclosed in the common assigned copending application U.S. Serial No. 597,948 filed April 9, 1984, corresponding to G.B. Application No. 8509084 Serial No. 2158454 the disclo sure 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 lower the temperature at which the liquid nonionic forms a gel with water.

The addition of the acid terminated nonionic surfactants to the liquid nonionic surfactant aids in the dispensibility of the composition, i.e. pourability, and lowers the temperature at which 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 builder salt phase of the detergent composition and acts as an 40 effective anionic surfactant.

Specific examples include the half-esters of nonionic surfactant product (A) with succinic anhydride, the ester or half ester of Dobanol 25-7 with succinic anhydride, and the ester or half ester of Dobanol 91-5 with succinic anhydride. Instead of succinic anhydride, other polycarboxy lic acids or anhydrides can be used, e.g. maleic acid, maleic acid anhydride, glutaric acid, 45 malonic acid, phthalic acid, phthalic anhydride, citric acid and the like.

The acid terminated nonionic surfactants can be prepared as follows:

Acid Terminated product (A). 400g of nonionic surfactant product (A) (which is a C1. to C, alkanol which has been alkoxylated to introduce 6 ethylene oxide and 3 propylene oxide units per alkanol unit) is mixed with 32g of succinic anhydride and heated for 7 hours at 100'C. The 50 mixture is cooled and filtered to remove unreacted succinic material. Infrared analysis indicated that about one half of the nonionic surfactant has been converted to the acidic half-ester thereof.

Acid Terminated bobanol 25-7. 522g of Dobanol 25-7 nonionic surfactant (which is the product of ethoxylatlon of a C1. to C,5 alkanol and has about 7 ethylene oxide units per molecule of alkanol) is mixed with 100g of succinic anhydride and 0.1g of pyridine (which acts as an esterification catalyst) and heated at 2600C for 2 hours, cooled and filtered to remove unreacted succinic material. Infrared analysis indicates that substantially all the free hydroxyls of the surfac tant have reacted.

Acid Terminated Dobanol 91-5. 10OOg of Dobanol 91-5 nonionic surfactant (which is the product of ethoxylation of a C, to C1, alkanol and has about 5 ethylene oxide units per molecule of alkanol) is mixed with 2659 of succinic anhydride and 0.1g of pyridine catalyst and heated at 260'C for 2 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, or in admixture with, the pyridine.

-1 c 7 GB2195125A 7 The acidic polyether compound, i.e. the acid terminated nonionic surfactant is preferably added dissolved in the nonionic surfactant.

The liquid nonaqueous nonionic surfactant used in the compositions of the present invention preferably has dispersed and suspended therein fine particles of inorganic and/or organic deter5 gent builder salts.

The detergent compositions of the present invention may 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, polyphosphates, and silicates. (Ammonium or substituted ammonium salts can also be used). Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono- and diorthophosphate, and potassium bicarbonate. Sodium tripolyphosphate (TPP) is especially preferred.

Since the compositions of this invention are generally highly concentrated, and, therefore, may be used at relatively low dosages, it is desirable to supplement any phosphate builder (such as sodium tripolyphosphate) with an auxiliary builder such as a poly lower carboxylic acid or a polymeric carboxylic acid having high calcium binding capacity to inhibit incrustation which could otherwise be caused by formation of an insoluble calcium phosphate.

A suitable lower poly carboxylic acid comprises alkali metal salts of lower polycarboxylic acids, 20 preferably the sodium and potassium salts. Suitable lower polycarboxylic acids have two to four carboxylic acid groups. The preferred sodium and potassium lower polycarboxylic acid salts are the citric and tartaric acid salts. The sodium citric acid salts are the most preferred, especially trisodium citrate. The monosodium and disodium citrates can also be used. The monosodium and disodium tartaric acid salts can also be used. The alkali metal lower polycarboxylic acid salts 25 are particularly good builder salts; because of their high calcium and magnesium binding capacity they inhibit incrustation which could otherwise be caused by formation of insoluble calcium and magnesium salts.

In order to obtain a non-phosphate detergent composition the polyphosphates can be replaced entirely by one or more of the auxiliary builder salts.

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 copolymer which is the reaction product of about equal moles of methacrylic acid and maleic anhydride which has been completely neutralized to form the sodium salt thereof. The builder is commercially available under the tradename of Sokalan CP5. This builder serves when used even 35 in small amounts to inhibit incrustation.

Examples of organic alkaline sequestrant builder salts which can be used with the detergent builder salts or in admixture with other organic and inorganic builders are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, e.g. sodium and potassium ethylene diaminetetraacetate (EDTA), sodium and potassium nitrilotriacetates (NTA), and triethanolammonium N-(2- 40 hydroxyethyl)nitrilodiacetates. Mixed salts of these aminopolycarboxylates are also suitable.

Other suitable builders of the organic type include carboxymethylsuccinates, tartronates and glycollates. Of special value are the polyacetal carboxylates. The polyacetal carboxylates and their use in detergent compositions are described in application U.S. Serial No. 767,570, filed August 19, 1985, corresponding to G.B. Application No. 8619793 Serial No. 2179365 assigned 45 to applicants' assignee and in a U.S.P. Nos. 4,144,226, 4,315,092 and 4, 146,495.

The alkali metal silicates are useful builder salts which also function to adjust or control the pH and to make the composition anticorrosive to washing machine parts. Sodium silicates of Na2O/S'02 ratios of from 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.

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

The water insoluble crystalline and amorphous aluminosilicate zeolites can be used. The zeol- 55 ites generally have the formula (M,0), (A1,0J,. (Si0J, wH,0 wherein x is 1, y is from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3. 5 or higher and preferably 2 to 3 and w is from 0 to 9, preferably 2.5 to 6 and M is preferably sodium. A typical 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. 400 meq/g.

Various crystalline zeolites (i.e. aluminosilicates) that can be used are described in British 65 8 GB 2 195 125A 8 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 incorpor ated herein by reference.

Other materials such as clays particularly of the water-insoluble types, may be useful adjuncts in compositions of this invention. Particularly useful is bentonite. This material is primarily montmorillonite which is a hydrated aluminium silicate in which about 1/6th of the aluminiurn 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.) suitable for detergents contains at least 50% montmori lonite and thus its cation exchange capacity is at least about 50 to 75 meq per 100g 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 molecular weight amphiphilic compounds which function as viscosity control and gel. inhibiting agents for the nonionic surfactant substantially improves the storage properties of the composition. The visco sity control and gel inhibiting agents act to lower the temperature at which the nonionic surfactant will form a gel when added to water. Such viscosity control and gel inhibiting agents 20 can be, for example, low molecular weight alkylene oxide lower mono-alkyl ether amphilic compounds. The amphiphilic compounds can be considered to be analogous in chemical struc ture to the ethoxylated and/or propoxylated fatty alcohol liquid nonionic surfactants but have relatively short hydrocarbon chain lengths (C, to Q and a low content of ethylene oxide (about 2 to 6 ethylene oxide grups per molecule).

Suitable amphiphilic compounds are represented by the following general formula R2 R' 0 (CHCH 20) nH 30 where RI represents a C,-C, alkyl group, R2 represents a hydrogen atom or a methyl group and n is a number of from about 1 to 6, on average.

Specifically the compounds are lower (C2 to C3) alkylene glycol mono lower (C2 to C,) alkyl ethers.

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

Specific examples of suitable amphiphilic compounds include ethylene glycol monoethyl ether 40 C2H,-O-CH2CH2OH, diethylene glycol monobutyl ether C,H,-O-(CH2CH20)2H, tetraethylene glycol monobutyl ether C,H,-O-(CH2CH20),H and dipropylene glycol monomethyl ether CH 3-0-(CHCH 20)2H CH, Diethylene glycol monobutyl ether is especially preferred.

The inclusion in the composition of the low molecular weight 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 55 and remain stable and pourable at temperatures as low as about 5'C.

In an embodiment of this invention a stabilizing agent which is an alkanol ester of phosphoric acid can be added to the formulation. Improvements in stability of the composition may be achieved by incorporation of a small effective amount of an acidic organic phorphorous com pound having an acidic -POH group, such as a partial ester of phosphorous acid and an alkanol. 60 As disclosed in the commonly assigned copencling application U.S. Serial No. 597,948 filed April 9, 1984 corresponding to G.B. Application No. 8509084 Serial No. 2158454 the disclosure of which is incorporated herein by reference, the acidic organic phosphorous compound having an acidic -POH group can increase the stability of the suspension of builders in the nonaqueous liquid nonionic surfactant. The acidic organic phosphorous compound may be, for instance, a 65 Z 6 1 9 GB2195125A 9 partial ester of phosphoric acid and an alcohol such as an alkanol which has a lipophilic character, having, for instance, more than 5 carbon atoms, e.g. 8 to 20 carbon atoms.

A specific example is a partial ester of phosphoric acid and a C, to C,, alkanol (Empiphos 5632 from Marchon); it is made up of about 35% monoester and 65% diester.

The inclusion of quite small amounts, e.g. 0.3% by weight of the acidic organic phosphorous compound makes the suspension stable against settling on standing but remains pourable, while, for the low concentration of stabilizer, e.g. below about 1%, its plastic viscosity will generally decrease.

Other bleach activators can optionally be added to the composition: among these are bleach activator compounds such as tetraacetyl ethylene diamine (TAED) and pentaacetyl glucose, 10 acetylsalicylic acid derivatives, alkyl and alkenyl succinic anhydride, tetraacetylglycouril ("TAGU"), and the derivatives of these.

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 of functional or aesthetic nature. Thus, there may be included in the formulation, minor amounts of soil suspend- 15 ing 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 CMC/MC which is sold under the tradename Relatin DM 4050. 20 There may also be included in the composition small amounts of Duet 787 which is a laundry 20 detergent perfume, and which is supplied by International Flavours and Fragrances, Inc., Union Beach, NJ 07735. The Duet 787 can be added in amounts such as 0 to 3, preferably 0.2 to 2. 0 percent, e.g. 0.5 to 2 percent, such as 0.3 to 1.0 percent by weight of the composition. Optical brighteners for cotton, polyamide and polyester fabrics can be used. Suitable optical brighteners include stilbene, triazole and benzidine sulphone compositions, especially sulphonated 25 substituted triazinyl stilbene, sulphonated napthotriaolze stilbene, benzidene sulphone, etc., most preferred are stilbene and triazole combinations. A preferred brightener is Stilbene Brightener N4 which is a dianilinodimorphalino stilbene polysulphonate.

Enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papin, trypsin and pep sin, as well as amylase type enzymes, lipase type enzymes, and mixtures thereof can be added. 30 A preferred enzyme is Esperase SL8 which is a proteolytic enzyme. Anti- foam agents, e.g.

silicon compound, such as Silicane L 7604, which is a polysiloxane, can also be added in small effective amounts.

Bactericides, e.g. tetrachlorosalicylanilide and hexachlorophene, fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet absorbers, anti-yellowing agents, such as sodium 35 carboxymethyl cellulose, pH modifiers and pH buffers, colour safe bleaches, perfume, and dyes and bluing agents such as ultramarine blue can be used.

In an embodiment of the invention the stability of the builder salts 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 40 and more preferably to less than 10 microns. The solid builders, e.g. sodium tripolyphosphate (TPP), 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 out the grinding operation. 45 In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid 45 ingredients is subjected to an attrition type of mill in which the particle sizes of the solid ingredients are reduced to less than about 10 microns, e.g. to an average particle size of 2 to 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 greater than 10 microns. Compositions whose dispersed particles are of such small size have improved stability against separa- 50 tion or settling on storage. Addition of the acid terminated nonionic surfactant compound can decrease the yield stress of such dispersions and aid in the dispersibility of the 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%) that the solid particles are in contact with each 55 other and are not substantially shielded from one another by the nonionic surfactant liquid. After the grinding step any remaining liquid nonionic surfactant can be added to the ground formula tion. Mills which employ grinding 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 60 1.5 mm diameter grinding 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 desirable to pass the blend of nonionic surfactant and solids first through a mill which 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 - 65 GB2195125A 10 below about 10 microns in the continuous ball mill.

In the preferred heavy duty liquid laundry detergent compositions of the invention, typical proportions (percent based on the total weight of composition, unless otherwise specified) of the ingredients are as follows:

Liquid nonionic surfactant detergent in the range of about 10 to 60, such as 20 to 50 percent, e.g. about 30 to 40 percent; Acid terminated nonionic surfactant viscosity improving agent in an amount in the range of about 0 to 20, such as 1 to 10 percent, e.g. about 2 to 5; Detergent builder, such as sodium tripolyphosphate (TPP), in the range of about 10 to 60, such as 15 to 50 percent, e.g. about 25 to 35 percent; Copolymer of acrylic acid and maleic anhydride, alkali metal salt, e.g. Sokalan CP5, anti incrustation agent in the range of about 0 to 10, such as 1 to 8 percent, e.g. about 2 to 4 percent; Alkylene glycol monoalkylether anti-gel agent in an amount in the range of about 5 to 30, such as 5 to 20 percent, e.g. about 5 to 15 percent; Phosphoric acid alkanol ester stabilizing agent in the range of 0 to 2.0 or 0.1 to 1.0, such as 0.2 to 0.5 percent; Persalt bleaching agent in the range of about 5 to 30, such as 2 to 20, e. g. about 5 to 15 percent; Liquid organic bleach activator compound, e.g. ethylidene benzoate acetate in the range of about 1 to 15, such as 1 to 8, e.g. about 2 to 6 percent; Sequestering agent for bleach, e.g. Dequest 2066, in the range of about 0 to 3.0, preferably 0.5 to 2.0 percent, e.g. about 0.50 to 1.25 percent; Anti-redeposition agent, e.g. Relatin DM 4050, in the range of about 0 to 4.0, preferably 0.5 to 3.0 percent, e.g. 0.5 to 1.5 percent; Optical brightener in the range of about 0 to 2.0, preferably 0.05 to 1.0 percent, e.g. 0.15 to 0.75 percent; Enzymes in the range of about 0 to 3.0, preferably 0.5 to 2.0 percent, e. g. 0.75 to 1.25 percent; and Perfume in the range of about 0 to 3.0, preferably 0.10 to 1.25 percent, e.g. 0.25 to 1.0 30 percent.

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

The liquid organic bleach activator compound is preferably used with at least one of the alkylene glycol mono-ether or the acid terminated nonionic surfactant viscosity control and anti- 35 gel agents. In some cases advantages can be obtained by using both the alkylene glycol mono ethers and the acid terminated nonionic surfactants.

In the selection of the additives, they will be chosen to be compatible with the main constitu ents of the detergent composition. In this application 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.

In an embodiment of the invention the detergent composition of a typical formulation is formulated using the below named ingredients:

45 Weight % Nonionic surfactant detergent, or mixture. 20-45 Acid terminated surfactant viscosity improving agent. 0-20 Phosphate detergent builder salt. 10-60 50 Anti-incrustation agent. 0-10 Alkylene glycol monoalkylether anti-gel agent. 5-15 Phosphoric acid alkanol ester stabilizing agent. 0-2.0 55 Anti-redeposition agent. 0-4.0 Alkali metal perborate bleaching agent. 5-15 Liquid organic bleach activator compound, e.g. ethylidene benzoate acetate. 1.0-8.0 Sequestering agent for bleach. 0-3.0 60 Perfume (Duet 787). 0-3.0 Optical brightener..0.15-0.75 Enzymes. 0.75-1.25 The present invention is further illustrated by the following examples.

4 ;1 11 GB2195125A 11 -5 EXAMPLE 1 A concentrated nonaqueous liquid nonionic surfactant detergent composition is formulated from the following ingredients in the amounts specified.

Nonionic surfactant.

Acid terminated Dobanol 91-5 reaction product with succinic anhydride. 10 Sodium tripolyphosphate (TPP).

Diethylene glycol monobutylether anti-gel agent.

Phosphoric acid alkanol ester (Empiphos 5632).

Sodium perborate monohydrate bleaching agent 15 Ethylidene benzoate acetate bleach activator.

Anti-redeposition agent (Relatin DIV1 4050)0).

Optical brightener (Tinopal ATSX).

Perfume.

Enzyme (which is Esperase).

Weight % 37.0 5.0 31.4 10.0 0.3 9.0 4.5 1.0 0.2 0.6 1.0 100.0 (1) CIVIC/MC 2:1 mixture of sodium carboxymethyl cellulose and hydroxymethyleellulose.

The formulation is ground for about one hour to reduce the particle size of the suspended builder salts to less than 40 microns. The formulated detergent composition is found to be 25 stable and non-gelling in storage and readily dispersible in water and to have good bleaching properties.

EXAMPLE 2

A concentrated nonaqueous liquid nonionic surfactant detergent composition was formulated 30 from the following ingredients in the amounts specified.

Surfactant Product D. Surfactant T7.

Surfactant T9. Acid terminated Dobanol 91-5 reaction product with succinic anhydride. Sodium tripolyphosphate (TPP). Anti-incrustation agent (Sokalan CP5).

Diethylene glycol monobutylether anti-gel agent. Phosphoric acid alkanol ester (Empiphos 5632). Sodium perborate monohydrate bleaching agent. Ethylidene benzoate acetate bleach activator. Sequestering agent for bleach (Dequest 2066). Anti-redeposition agent (Relatin DIVI 4050)(1). Optical brighteners (Stilbene). Enzyme (Esperase slurry). Duet 787(2).

Weight % 13.5 10.0 10.0 5.0 29.6 4.0 10.0 0.3 9.0 4.5 1.0 1.0 0.5 1.0 0.6 100.0 (1) CIVIC/MC 2:1 mixture of sodium carboxymethyl cellulose and hydroxymethylcellulose. (2) Duet 787 which is a perfume, i.e. fragrance from IFF, Inc.

The formulation is ground for about one hour to reduce the particle size of the suspended builder salts to less than 40 microns. The formulated detergent composition is found to be 55 stable and non-gelling in storage and readily dispersible in water. The bleach is active at 400C on both wine and immedial black soils.

The formulations of Examples 1 and 2 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 reduce the particle size of the 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 prior to 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 40 microns in size are preferred. 65 12 GB2195125A 12 The persalt bleach compound and the liquid organic bleach activator compound system of the present invention can also be used in nonionic surfactant detergent dishwashing compositions, cream scourers, and other compositions in which bleaching is required.

It is understood that the foregoing detailed description is given merely by way of illustration and that variations may be made therein without departing from the spirit of the invention. 5

Claims (19)

1. A detergent composition which comprises a nonionic surfactant detergent, an inorganic peroxygen compound bleaching agent and a liquid organic bleach activator compound.

2. A detergent composition as claimed in Claim 1 in liquid form comprising a liquid nonaqueous nonionic surfactant detergent.

3. A composition as claimed in Claim 2 in which the composition comprises a viscosity control and anti-gel agent.

4. A detergent composition as claimed in Claim 2 or Claim 3 in which the composition comprises at least one viscosity control and anti-gel agent selected from the group consisting of 15 an alkylene glycol monoalkyl ether and an acid terminated nonionic surfactant.

5. A composition as claimed in any one of Claims 2 to 4 which comprises a suspension of insoluble inorganic detergent builder salt.

6. A composition as claimed in Claim 5 in which the insoluble inorganic builder salt corn- prises a polyphosphate detergent builder and is present in an amount of 10 to 60 percent.

7. A detergent composition as claimed in any one of Claims 1 to 6 comprising one or more detergent adjuvants selected from the group consisting of anti-incrustation agents, sequestering agents, antiredeposition agents, optical brighteners, enzymes and perfumes.

8. A composition as claimed in any one of Claims 1 to- 7 in which the composition corn- prises 10 to 60 percent of a nonionic liquid surfactant detergent.

9. A detergent composition as claimed in Claim 4 or any one of Claims 5 to 8 when appendant to Claim 4 comprising 5 to 30 percent of an alkylene glycol monoalkyl ether.

10. A composition as claimed in Claim 5 or any one of Claims 6 to 9 when appendant to Claim 5 in which the inorganic builder salt has a particle size of less than 40 microns.

11. A composition as claimed in any one of Claims 1 to 10 which contains from about 0. 1 30 to about 0.5 percent by weight, based on the total composition, of a phosphoric acid alkanol ester anti-settling stabilizing agent.

12. A composition as claimed in any one of Claims 1 to 11 in which the liquid organic bleach activator compound has the general formula 0 O-C-R2 10.1 R' -CH 40 O-CR3 0 wherein R', R2 and R3 represent hydrocarbon radicals and the hydrocarbon radicals are selected such that the organic compound is a liquid.

13. A composition as claimed in Claim 12 in which the liquid organic bleach activator is 50 ethylidene benzoate acetate.

14. A nonaqueous heavy duty, built laundry detergent composition which is pourable at high and low temperatures and does not gel when mixed with cold water, the said composition comprising at least one liquid nonionic surfactant in an amount of from about 10 to 60 percent by 55 weight; at least one inorganic detergent builder salt suspended in the nonionic surfactant in an amount of from about 10 to about 60 percent by weight; an inorganic peroxygen bleaching agent in an amount of about 5 to 15 percent; ethylidene benzoate acetate bleach activator in an amount of about 1 to 8. 0 percent; an acid terminated nonionic surfactant as a gel inhibiting additive, in an amount of about 0 to percent by weight; and a compound of the formula 1 13 GB2195125A 13 R2 R'O(CHCH20)nH where R' represents a C2 to C. alkyl group, R2 represents a hydrogen atom or a methyl group and n is a number having an average value in the range of from about 1 to 6, as a gel inhibiting additive in an amount up to about 5 to 30 percent by weight.

15. A detergent composition as claimed in Claim 14 which contains one or more detergent adjuvants selected from the group consisting of anti-incrustation agents, sequestering agents, anti-redeposition agents, optical brighteners, enzymes and perfumes.

16. A nonaqueous liquid heavy duty laundry detergent composition as claimed in Claim 14 or Claim 15 which comprises in percent by weight:

Nonionic surfactant in an amount of about 20-50; Sodium tripolyphosphate (TPP) in an amount of about 15-50; Copolymer of acrylic acid and maleic anhydride sodium salt in an amount of about 1-8; Diethylene glycol monoalkylether in an amount of about 5-20; Phosphoric acid alkanol ester in an amount of about 0.1-1.0; Sodium perborate monohydrate bleaching agent in an amount of about 2-20; and Ethylidene benzoate acetate bleach activator in an amount of about 1-8.

17. A nonaqueous liquid heavy duty laundry detergent composition as claimed in Claim 14, or 16 which comprises in percent by weight:

Nonionic surfactant in an amount of about 30-40; Acid terminated nonionic surfactant viscosity improving agent in an amount of about 1-10; Sodium tripolyphosphate in an amount of about 25-35; Copolymer of acrylic acid and maleic anhydride sodium salt in an amount of about 2-4; Diethylene glycol monobutylether in an amount of about 5-15; Phosphoric acid alkanol ester in an amount of about 0.2-0.5; Sodium perborate monohydrate bleaching agent in an amount of about 5-15; Ethylidene benzoate acetate bleach activator in an amount of about 2-6.0; Sequestering agent for bleach in an amount of about 0.50-1.25; and Anti-redeposition agent in an amount of about 0.5-1.5.

18. A composition as claimed in Claim 1 substantially as specifically described herein with 35 reference to the Examples.

19. A method for cleaning soiled fabrics which comprises contacting the soiled fabrics with a detergent composition as claimed in any one of Claims 1 to 18.

Published 1988 at The Patent Office, State House, 66/71 High Holborn, London WC1R 4TP. Further copies may be obtained from The Patent Office, Sales Branch, St Mary Cray, Orpington, Ke nt BR5 3RD. Printed by Burgess & Son (Abingdon) Ltd. Con. 1/87.