GB2178753A - Low phosphate, built, laundry detergent - Google Patents

Abstract

A low polyphosphate or a polyphosphate free liquid heavy duty laundry detergent composition comprises a suspension of an alkali metal heptonic acid builder salt, an alkali metal carboxymethyloxy succinic acid builder salt, or an alkali metal alginic acid builder salt in liquid nonionic surfactant.

Description

SPECIFICATION Phosphate free or low phosphate laundry detergent The present invention relates to non-aqueous liquid fabric treating compositions. More particularly, the present invention relates to phosphate free or low phosphate non-aqueous liquid laundry detergent compositions containing a suspension of a heptonate builder salt, a carboxymethyloxy succinate builder salt, oran alginatebuildersaltin nonionicsurfactants which compositions are easily pourable, are stable against phase separation and gelation and to the use of these compositions for cleaning soiled fabrics.

Liquid non-aqueous heavy duty laundry detergent compositionsarewell known intheart. Forinstance, compositions of that type may comprise a liquid nonionicsurfactant in which are dispersed particles of a builder, as shown for instance in the U.S. Patents Nos. 4,316,812; 3,630,929; 4,264,466; and British Patents Nos. 1,205,711; 1,270,040 and 1,600,981.

The washing power of synthetic non ionic surfactant detergents in laundry detergent compositions can be increased by the addition of builders. Sodium tripolyphosphate is one of the preferred builders. However, the use of sodium polyphosphate in dry powder detergents does involve several disadvantages such as, for example, the tendency ofthe polyphosphates to hydrolyse into pyro-and ortho-phosphates which represent less valuable builders.

In addition the polyphosphate content of laundry detergents has been blamed for the undesirable high phosphate content of surface water. An increased phosphate content in surface water has been found to contributetowards greater a 19 a I growth with the resultthatthe biological equilibrium ofthewatercan be adversely altered.

Recently enacted government legislation has been directed to reducing the amount of polyphosphates present in laundry detergents and in some jurisdictions in which polyphosphates have been a problem to requirethatthe laundry detergents not contain any polyphosphate builders.

Liquid detergents are often considered to be more convenientto employthan dry powdered or particulate products and,therefore, have found substantial favourwith consumers. They are readily measurable, speedily dissolved in the wash water, capable of being easily applied in concentrated solutions or dispersionsto 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 deteriora- tion,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 some cases the product viscosity changes and it becomes either too thick to pour or so thin as to appear watery. Same clear products become cloudy and others gel on standing.

In addition to the problem of settling or phase separation the non-aqueous liquid laundry detergents based on liquid nonionic surfactants sufferfrom the drawbackthatthe nonionics tend to gel when added to cold water. This is a particularly important problem in the ordinary use of European household automatic washing machineswherethe user placesthe laundry detergent composition in a dispensing unit (e.g. a dispensing drawer) ofthe machine. During the operation of the machine the detergent in the dispenser is subjected to a stream of cold waterto transfer itto the main body ofwash 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 ofthe composition is not flushed completely offthe dispenser during operation ofthe machine, and a deposit ofthe 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 of fabrics which can shrink in warm or hot water.

The tendency of concentrated detergent composi tions 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.

Partialsolutionstothegelling problem in aqueous, substantially builder-free compositions have been proposed,forexample, diluting the liquidnonionic with certain viscosity controlling solvents and gelinhibiting agents, such as loweralkanols, e.g. ethyl alcohol (see U.S. Patent 3,953,380), alkali metal formates and adipates (see U.S. Patent 4,368,147), hexylene glycol or polyethylene glycol, and nonionic structure modification and optimisation.

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 anionic surfactant when neutralised in the washing liquor. Nonionic structure optimisation 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 ofthe hydrophilic moiety. For example, it has been found that a C13 fatty alcohol ethoxylated with 8 moles of ethylene oxide presents only a limited tendency to gel formation.

Nevertheless, improvements are desired in the stability, and gel inhibition of phosphate free or low phosphate non-aqueous liquid fabric treating compositions.

In accordance with the present invention a highly concentrated low phosphate, more particularly a polyphosphate detergent builderfree, non-aqueous liquid laundry detergent composition is prepared by dispersing heptonate builder salts, carboxymethyloxy succinate builder salts, oralginate builder salts in a liquid nonionic surfactant detergent.

The heptonic acid salts used in accordance with the present invention are well known. The heptonic acid is an acid derivative of an aldoheptose (monosaccharide). The alkali metal salts of heptonic acid are water soluble.

The alkali metal heptonic acid salts used in the present invention have the general formula

wherein M isan alkali metal orammonium cation.

The carboxymethyloxy succinic acid salts used in accordance with the present invention are known.

The alkali metal and ammonium salts ofcarboxy methyloxy succinic acid are water soluble.

The carboxymethyloxy succinic acid salts used in the present invention have the general formula

wherein Mis hydrogen, an alkali metal, such as sodium or potassium, or ammonium cation, and at least one M is an alkali metal or ammonium cation.

The alginic acid salts used in accordance with the present invention are well known. The alginate is a polysaccharide extract from sea weeds. The alkali metal salts of alginic acid are water soluble. The alginate is extracted from sea weeds in the form of mixed salts comprising calcium and magnesium.

in order to improve the viscosity characteristics of the composition an acid terminated nonionicsurfactant can be added. To further improve the viscosity characteristics of the composition and the storage properties ofthecomposition there can be added to the composition viscosity improving and anti-gel agents such as alkylene glycol monoalkyl ethers and anti-settling agents such as phosphoric acid esters and aluminium stearate. In a preferred embodiment ofthe present invention the detergent composition contains an acid terminated nonionic surfactant and/or an alkylene glycol monoalkyl ether, and an anti-settling agent.

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

In one embodiment ofthe invention the builder components of the composition are ground to a particle size of less than 100 microns and to prefer ably less than 10 microns to further improve the stability ofthe suspension ofthe 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 machinesfor home use normally operate at washing temperatures of up to 100"C. Upto 18.5 gallons (70 litres) of water are used during the wash and rinse cycles.

About 175 grams 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 grams (77 ml) or less ofthe liquid detergent composition is required to wash a full load of dirty laundry.

Accordingly, in one aspect ofthe present invention there is provided a phosphate builder-free or sub stantially phosphate builder-free liquid heavy duty laundry composition comprising a suspension of an alkali metal heptonicacid buildersalt,an alkali metal carboxymethyloxy succinic acid builder salt, or an alkali metal alginicacid buildersaltin liquid nonionic surfactant.

The invention has the advantage of providing a phosphate free or low phosphate concentrated liquid heavy duty laundry detergent composition which is of improvedstability,of lesstendencyto settle in storage and of less tendency to gel in storage and in use. The liquid compositions ofthe present invention are easily pourable, easily measured and easily put into the washing machine.

The invention also provides a method for dispens ing a phosphate free or low phosphate liquid nonionic laundry detergent composition into and/or with cold water with less tendency to undergo gelation. In particular, a method is provided forfilling a container with a non-aqueous liquid laundry detergent composition in which the detergent is composed, at least predominantly, of a polyphos phate builderfree liquid nonionic surface active agent and for dispensing the composition from the contain er into an aqueous wash bath, wherein the dispens ing is effected by directing a stream of unheated water onto the composition such that the composi tion is carried by the stream ofwaterinto the wash bath.

The polyphosphate builder free detergent com positions overcome the problem of phosphate poltu tion of surface water.

The present invention aims to provide a low polyphosphate, more particularly a polyphosphate free non-polluting liquid heavy duty non-aqueous nonionic detergent composition containing hepton ate builder salt, carboxymethyloxy succinate builder salt, or alginate builder salt suspended in a nonionic F surfactant.

The invention also aims to provide polyphosphate free or low polyphosphate liquid fabric treating compositions which are suspensions of heptonate builder salt, carboxymethyloxy succinate builder salt, oralginate builder salt in a non-aqueous liquid and which are storage stable, easily pourable and dis persible in cold, warm or hot water.

The invention also aims to formulate a polyphosphate free or low polyphosphate highly built heavy duty non-aqueous liquid nonionicsurfactantlaundry detergent compositions which can be poured at a wide range oftemperatures and which can be repeatedly dispersed from the dispensing unit of European style automatic laundrywashing machines with less tendency to fouling or plugging ofthe dispenser even during the winter months.

The invention furtheraimsto provide polyphosphate free or low polyphosphate suspensions of heavy duty built non-aqueous liquid nonionic laundry detergent composition of less tendency to gel and of improved stabilitywhich include an effective amount of heptonate builder salt, carboxymethyloxy succin atebuildersalt,oralginatebuildersalt.

The invention also aims to provide suspensions of heavy duty built non-aqueous liquid nonionic laundry detergent composition of less tendency to gel and of improved stability which include an amount of phosphoric acid alkanol ester and/or aluminium fatty acid salt anti-settling agent which is sufficient to further increase the stability ofthe composition, i.e.

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

According to a preferred form ofthe present invention there is prepared a low polyphosphate or polyphosphatefree detergent builder composition by adding to the non-aqueous liquid nonionic surfac tant an effective amount ofan alkali metal heptonate builder salt, a carboxymethyl succinate builder salt, oran alkali metal alginate builder salt and inorganic or organicfabrictreating additives, e.g. viscosity improving and anti-gel agents, anti-settling agents, anti-incrustation agents, bleaching agents, bleach activatores, anti-foam agents, optical brighteners, enzymes, anti-redeposition agents, perfume and dyes.

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

The nonionic synthetic organic detergents employed in the practice ofthe invention may be any of a wide variety of such compounds, which are well known and,for example, are described at length in the text Surface Active Agents, Vol. II, by Schwartz, Perry and Berch, published in 1958 by lnterscience Publishers, and in McCutcheon's Detergents and Emulsifiers, 1969Annual ,the relevant disclosures of which are hereby incorporated by reference.

As is well known, the nonionic synthetic organic detergents are characterised by the presence of an organic hydrophobic group and an organic hydrophi lisgroup and aretypically produced bythe condensa- tion of an organic aliphatic oralkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature). Practically any hydrophobic compound having a carboxy, hydroxy, amido oramino 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 hyd rophile-lipophile balance is obtained by addition of a hydrophilic poly-lower alkoxy group to a lipophilic moiety. A preferred class ofthe nonionic detergent employed is the poly-lower alkoxylated higher alka- nolwherein the alkanol is of 9to 18 carbon atoms and wherein the number of mols of lower alkylene oxide (of 2 or3 carbon atoms) is from 3to 12. Of such materials it is preferred jto employ those wherein the higheralkanol is a higherfatty alcohol of 9 to 11 or 12 to 15 carbon atoms and which contain from 5to 8 or 5 to 9 lower alkoxy groups per mol.Preferably, the lower alkoxy is ethoxy but in some instances, it may bedesirably mixed with propoxy,the latter, if present, usually 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 (Registered Trade Mark) 25-7 and Neodol 23-6.5,which products are made by Shell Chemical Company, Inc. The former is a condensation product of a mixture ofhigherfattyalcohols 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 ofthe higher fatty alcohol is 12to 13 and the number of ethylene oxide groupspresentaveragesabout6.5.The higher alcohols are primary alkanols. Other examples of such detergents includeTergitol (Registered Trade Mark) 15-S-7 and Tergitol 1 5-S-9, both ofwhich are linear secondary alcohol ethoxylates made by Union Carbide Corp.The former is a mixed ethoxylation productof 11 to 15carbon atoms linearsecondary alkanolwithseven molesofehtyleneoxideandthe latter is a similar product but with nine moles of ethylene oxide being reacted.

Also useful in the compositions ofthe 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 higherfatty alcohol being of 14to 15 carbon atoms andthe number of ethyiene oxide groups per mol being about 11. Such products are also made by Shell Chemical Company.

Other useful nonionics are represented hy the commercially well known class of nonionics sold underthetrademark Plurafac (Registered Trade Mark). The Pl u rafacs are the 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 Plurafac RA30 (a C13-C5 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide). Plurafac RA40 (a C13-C15fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide), and Plurafac D25 (a C13-C1sfatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide.

Another group of liquid nonionics are commercial ly available from Shell Chemical Company, Inc. under the Dobanol trade mark: Dobanol 91-5 is an ethyxy lated Cg-C1 1 fatty alcohol with an average of 5 moles ethylene oxide; and Dobanol 25-7 is an ethoxylated C,2-C,5fatty alcohol with an average of 7 moles ethylene oxide.

In the preferredpoly-loweralkoxylated higher alkanols, to obtain the best balance of hydrophilic and lipophilic moieties the number of lower alkoxies will usually be from 40% to 100% of the number of carbon atoms in the higheralcohol, 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 detergents and surface active agents may be con tributoryto 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 employedfortheircleaning properties.With respect to both preferred and less preferred nonionic deter gentsthe alkyl groups present therein are generally linear although branching may be tolerated, such as at a carbon nextto ortwo carbons removedfrom the terminal carbon ofthe straight chain and away from the ethoxychain, if such branched alkyl is not more than three carbons in length. Normally, the proportion of carbon atoms in such a branched configura tin will be minor rarely exceeding 20% of the total carbon atom content of the alkyl group.Similarly, although linear alkyls which areterminallyjoined 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 orsecondary joinderto 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, maybe 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-loweralkoxylated alkanols and less hydrophile- lipophile balanced nonionic detergentsthan 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 ofthe 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 weightpoly-loweralkoxylated higher alkanol is employed, often for its detergency, the proportion thereof will be regulated or limited as in accordance with the results of routine experiments, to obtain the desired detergency and still have the product nongelling and of desired viscosity. Also, it has been found that it is only rarely necessary to utilise the higher molecularweight nonionics fortheir detergent properties since the preferred nonionics described herein are excellent detergents and additionally, permitthe attainment of the desired viscosity in the liquid detergentwithoutgelation atlowtemperatures.

Another useful group of nonionic surfactants are the "Su rfacta nt T" series of nonionics available from British Petroleum. The Surfactant T nonionics are obtained bytheethoxylation ofsecondaryC13fatty alcohols having a narrow ethylene oxide distribution.

The SurfactantT5 has an average of 5 moles of ethylene oxide; SurfactantT7 an average of7 moles of ethylene oxide; Surfacta nt T9 an average of 9 moles of ethylene oxide and SurfactantTl2an averageof12 moles of ethylene oxide per mole of secondary C13 fatty alcohol.

In the compositions of the present invention, preferred nonionic surfactants include the C13-C15 secondary fatty alcohols with relatively narrow contents of ethylene oxide in the range offrom about7to 9 moles, and the Cgto C11 fatty alcohols ethoxylated with about 5-6 moles ethylene oxide.

Mixtures oftwo or more ofthe liquid nonionic surfactants can beusedand insomecasesadvan- tages 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 amountofan acid terminated liquid nonionicsurfactant. The acid terminated nonionic surfactants consist of a nonionic surfactantwhich has been modified to convert a free hydroxyl groupthereofto a moiety having a free carboxyl group, such as an ester or a partial ester of a nonionic surfactant and polycarboxylic acid or anhydride.

As disclosed in the commonly assigned copending application U.S. Serial No. 597,948filed 9th April, 1984, corresponding to G.B. Application No.85.09084 Serial No.21 58454A, the disclosure of which is incorporated herein by reference, the free carboxyl group modified nonionic surfactants, which may be broadly cha racterised as polyether carboxylic acids, function to lowerthetemperature at which the liquid nonionicformsa gel with water.

The addition of the acid terminated nonionic surfactants to the liquid nonionic surfactant aids in the dispensibility ofthe composition, i.e. pourability, and lowersthetemperature at which the liquid nonionic surfactants form a gel in water without a decrease intheir stability against settling. The acid terminated nonionic surfactant reacts in the washing machine water with the alkalinity ofthe dispersed builder salt phase ofthe detergent compositions and acts as an effective anionicsurfactant.

Specific examples include the half-esters of Plurafac RA30 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 polycarboxylic acids or anhydrides can be used, e.g.

maleic acid, maleic acid an hydride, citric acid and the like.

The acid terminated nonionic surfactants can be prepared as follows: Acid Terminated Plurafac RA30. 400g of Plurafac RA30 nonionicsurfactantwhich is a C13to C15 alkanol which has been alkoxylated to introduce 6 ethylene oxide and 3 propylene oxide units peralkanol unit is mixed with 32g of succinic anhydride and heated for 7 hours at 1 00'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-ester thereof.

Acid Terminated Dobanol 25-7. 522g of Dobanol 25-7 nonionic surfactant which is the product of ethoxylation of a C12to C15alkanol and has about7 ethylene oxide units per molecule of alkanol is mixed with 1009 ofsuccinic anhydride a nd 0.1 g of pyridine (which acts as an esterification catalyst) and heated at 2600for 2 hours, cooled and filtered to remove unreacted succinic material. Infrared analysis indicates that substantially all the free hydroxyls of the surfactant have reacted.

Acid Terminated Dobanol 91-5. 10009 of Dobanol 91-5 nonionic surfactantwhich is the product of ethoxylation of a Cg to C11 alkanol and has about 5 ethylene oxide units per molecule ofalkanol is mixed with 2659 or ofsuccinic an hydride and 0.1 g of pyridine catalyst and heated at 260"C for 2 hours, cooled and filteredto remove unreacted succinic material. In frared analysis indicated that substantially all the free hydroxyls ofthe 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.

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

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

The present invention includes as an essential part ofthe composition an organic heptonate builder salt, an organic carboxymethyloxy succinate builder salt, oran organicalginate buildersalt.

Preferred organic builder salts comprise alkali metal salts of heptonic acid, preferablythesodium and potassium salts. Other monosaccharide acid salts that can be used are any monosaccharide acid salts with a longer chain. A specific example of monosaccharide acid salts is heptonic acid sodium salt.

Other preferred organic builder salts comprise alkali metal or ammonium salts of carboxymethyloxy succinic acid, preferablythetrisodium salt.

The carboxymethyloxy succinic acid salts used in the detergent compositions of the present invention have the following general formula

wherein M is a member selected from the group consisting of hydrogen, alkali metal and ammonium cation, and at least one M is an alkali metal or ammonium. The preferred alkali metals are sodium and potassium, with sodium being the more preferred. The mono, di and trisodium salts can be used, with the trisodium salt being the most preferred.

A specific example of a carboxymethyloxy succi nincacidsaltthatcan be used is

Still other preferred organic builder salts comprise alkali metal salts of alginic acid, preferably the sodium and potassium salts. The sodium alginate is a well known product, is readily available and has many known uses. The sodium alginate is also known as sodium polymannuronate. The polymannuronic acid can have a molecular weight of approximately 240,000.

The alginic acid is extracted from giant brown sea weed (giant kelp. macrocystispyrifera (L.) Ag Lessoniaceaeì in the form of mixed salts comprising calcium and magnesium alginic acid salts. The alginate salts can also be extracted from horsetail kelp (Laminaria digitata (L.) Lamour, Laminariaceae) and sugar kelp (Laminaria saccharina (L.) Lamour).

The calcium and magnesium salts ofalginicacid are readily converted to alkali metal salts, particularly sodium alginate by methods well known in the art.

The sodium alginate is a cream coloured powder which is soluble in water.

A specific example of an alkali metal alginic acid saltthatcan be used is

M = Na (Manutex RB Other organic builders that can be used 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 anhydridewhich 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 in small amounts to inhibit encrustation, i.e. as an anti-encrustation agent.

Since the compositions ofthe present invention are generally highly concentrated, and, therefore, may be used at relatively low dosages, it is desirable to supplement the builder with an auxiliary builder such as an alkali metal lower polycarboxylic acid having high calcium and magnesium binding capacity to inhibit incrustation which could otherwise be caused byformation 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 salt and diacid salt with longer chain.

Examples of organic alkaline sequestrant builder salts which can be used with the heptonate builder salts, ca rboxymethyloxy succinate builder salts, or alginate buildersalts, or in admixturewithother organic and inorganic builders are alkali metal, ammonium or substituted ammonium, aminopolycarboxylate, e.g. sodium and potassium ethylene diaminetetraacetate (EDTA), sodium and potassium nitriloacetates (NTA) and triethanolammonium N-(2 hydroxyethyl)nitrilodiacetates. Mixed salts of these aminopolycarboxylates are also suitable.

Other suitable builders ofthe organic type include carboxymethylsuccinates, tartronates and glycolates.

The detergent compositions ofthe present invention also include water soluble and/orwater insoluble detergent builder salts. Suitable inorganic alkaline builder salts which can be used are alkali metal carbonates, borates, bicarbonates and silicates.

(Ammonium or substituted ammonium salts can also be used.) Specific examples of such salts are sodium carbonate, sodium tetraborate, sodium bicarbonate, sodium sesquicarbonate, and potassium bicarbonate.

The alkali metal silicates are useful builder salts which also function to make the composition anti corrosivetowashing machine parts. Sodium silicates of Na2O/SiO2 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.

Though it is preferred that the detergent composition be phosphate or polyphosphate free or substantially polyphosphate free, small amounts ofthe conventional polyphosphate builder salts can be added where the local legislation permits such use.

Specific examples of such builder salts are sodium tripolyphosphate (TPP), sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate and sodium hexametaphosphate.The sodium tripolyphosphate (TPP) is a preferred polyphosphate.

In theformulations where the polyphosphate is added it is added in an amount of Oto 50%, such as O to 30% and 5 to 15. As mentioned previously, however, itis preferred thatthe formulations be polyphosphate free or substantially polyphosphate free.

Other typical suitable builders include,forexam- ple, those disclosed in U.S. Patents 4,316,812, 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.

Thewater-insoluble crystalline and amorphous aluminosilicates can be used.

The zeolites generally have the formula: (M20),.(A1203),.(Si02),WH20 wherein xis 1,yisfrom 0.8 to 1.2 and preferably 1,z is from 1.5 to 3.5 or higher and preferably 2to 3 and w is from 0 to 9, preferably 2.5to 6 and M is preferably sodium. Atypical zeolite is type A or simlarstructure, with type 4A particularly preferred. The preferred aluminosilicates have calcium ion exchange capacitances of about 200 milli-equivalents per gram or greater, e.g.400 meq)g.

Various crystalline zeolites (i.e. aluminosilicates) which can be used are described in British Patent 1,504,168, U.S. Patent4,409,136and Canadian Patents 1,072,835 and 1,087,477, all ofwhich are hereby incorporated by reference for such descriptions. An example of amorphous zeolites useful herein can be found in Belgian Patent 835,351 and this patent, too, is incorporated herein by reference.

Other materials such as clays, particularly of the water insoluble types, may be useful adjuncts in compositions ofthe present invention. Particularly useful is bentonite. This material is primarily mont morillonitewhich is a hydrated aluminium silicate in which about 1/6th ofthe aluminium atoms maybe replaced by magnesium atoms and with which varying amounts of hydrogen, sodium, potassium and calcium, may be loosely combined. The bentonite in its more purified form (i.e. free from any grit, sand or the like) suitable for detergents invariably contains at least 50% montmorillonite 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. bentoniteswhich have been sold asThixojels 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 Dugan.

The inclusion in the detergent compositions of an effective amount of low molecularweight amphiphi lic compounds which function as viscosity control and gel-inhibiting agents for the nonionic surfactant substantially improves the storage properties ofthe composition.

The amph iphilic compounds can be considered to be analogous in chemical structure to the ethoxylated and/or propoxylatedfatty alcohol nonionic surfactants but have relatively short hydrocarbon chain lengths (C2-C8ì and a lowcontent of ethylene oxide (about 2 to 6 ethylene oxide groups per molecule).

Suitable amphiphiliccompounds can berepre- sented bythefollowing general formula: RO(CH2CH2O)nH where R represents a C2-C8 alkyl group, and n is a numberoffrom about 1 to 6, on average.

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

More specifically the compounds are preferably mono di- ortri-lower (C2 to C3) alkylene glycol mono-lower (C1 to C5) alkyl ethers.

Specific examples of suitable amphiphilic compounds include ethylene glycol monoethyl ether (C2H5-O-CH2CH20H), diethylene glycol monobutyl ether (C4H9-O-(CH2CH2O)2H), tetraethylene glycol monobutyl ether (C4H9-O-(CH2CH2O)4H), and dipropylene glycol monomethyl ether

Diethylene glycol monoethyl ether is especially preferred.

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

The compositions ofthe present invention have improved viscosity and stability characteristics and remain stable and pourable attemperatures as low as about 5'C.

The physical stability ofthe suspension ofthe detergent builder compound or compounds and any other suspended additive, such as bleaching agent, etc., in the liquid vehicle in accordance with the present invention may be improved by the presence ofastabilising agentwhich isanalkanol esterof phosphoric acid or an aluminium salt of a higherfatty acid.

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

As disclosed in the commonly assigned co-pending U.S. Application Serial No. 597,793 filed 6th April, 1984, corresponding to British Patent Application No.

85.09083, Serial No.21 58453A, the disclosure of which is incorporated herein by reference, the acidic organic phosphorus compound having an acidic POH group can increase the stability of the suspension of builders in the non-aqueous 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 lipophilic character having, for instance, more than 5 carbon atoms, e.g. to 20 carbon atoms.

A specific example is a partial ester of phosphoric acid and a C16 to C18 alkanol (Empiphos 5632 from Marchon); it is made up of about 35% monoesterand 65% diester.

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

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 higher fatty acid to the composition.

The aluminium saltstabilising agentsarethe subject matter ofthe commonly assigned copending application U.S. Serial No.725,455, filed 22nd April, 1985, corresponding to G.B. Application No.86.04969 Serial No. 2172897A, the disclosure of which is incorporated herein by reference.

The preferred higher aliphatic fatty acids will have fromabout8to about22 carbon atoms, more preferably from about 10 to 20 carbon atoms, and especially preferablyfrom about 12to 18 carbon atoms. The aliphatic radical may be saturated or unsaturated and may be straight or branched. As in the case of the nonionic surfactants, mixtures offatty acids may also be used, such as those derived from natural sources, such as tallow fatty acid, and coco fatty acid.

Examples of the fatty acids from which the alumi niumsaltstabiliserscan be formed include, decanoic acid, dodecanoic acid, palmatic acid, myristic acid, stearic acid, oleic acid, eicosanoic acid, tallow fatty acid, coco fatty acid and mixtures ofthese acids. The aluminium salts ofthese acids are generally commer cially available, and are preferably used in the triacid form, e.g. aluminium stearate as aluminium tristearateAl(C17H35COO)3. The monoacid salts, e.g. aluminiun monostearate (Al(OH)2(C17H35COO) and diacid salts, e.g. aluminium distearate, Al(OH)(C17H35COO)2, and mixtures oftwo orthree ofthe mono-, di- and triacid aluminium salts can also be used.It is most preferred, however,thatthetriacid aluminium salts comprises at least 30%, preferably at least 50%, especially preferably at least 80% ofthe total amount of aluminium fatty acid salt.

The aluminium salts, as mentioned above, are commercially available and can be easily produced by,forexample, 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 particulartheory ofthe manner by which the aluminium salt functions to prevent settling ofthe suspended particles, it is presumed that the alumi niumsaltincreasesthewettabilityofthesolid surfaces by the nonionic surfanctant. This increase in wettability, therefore, allows the suspended particles to more easily remain in suspension.

Only very small amounts ofthealuminium salt stabilising agent are required to obtain the significant improvement in physical stability.

in addition to its action as a physical stabilising agent, the aluminium salt has the additional advantages over other physical stabilising agents that it is nonionicincharacterand is compatible with the nonionic surfactant component and does not inter- fere with the overall detergency of the composition; it exhibits some anti-foaming effect; it can function to boostthe acitivity of fabric 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 are typified by sodium hypochlorite (NaOCl), potassium dichoroisocyanu rate (59% available chlorine), and trichloroisocyanur ic acid (95% available chlorine). Oxygen bleaches are preferred and are represented by percompounds which liberate hydrogen peroxide in solution. Prefer red examples include sodium and potassium perbo rates, percarbonates and perphosphates, and potas sium 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 lower the effective operating tem pera ture ofthe peroxide bleaching agent are disclosed in U.S. Patent 4,264,466 or in column 1 of U.S. Patent 4,430,244, the relevant disclosures of which are incorporated herein by reference. Polyacylated com pounds are preferred activators; among these, com pounds such astetraacetyl ethylenediamine ("TAED") and pentaacetyl glucose are particularly preferred.

Other useful activators include, for example, acety Isalicyclic acid derivatives, ethylidene benzoate acetate and its salts, ethylidene carboxylate acetate and its salts, alkyl and alkyl succinic anhydride, tet raacetylglycouril ("TAGU"), and the derivatives of these. Other useful classes ofactivatorsare disclosed, for example, in U.S. Patents 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 powerto inhibit any undesired reaction between such peroxyacid and hydrogen peroxide in the wash solution in the presence of metal ions. Suitable sequestering agents include, for example, sodium salts of nitrilotriacetic acid (NTA), ethylene diamine tetraacetic acid (EDTA), diethylene triamine pen taaceticacid (DETPA); diethylenetriamine pentamethylene phosphonic acid (DTPMP); and ethylene diaminetetramethylene phosphonic acid (EDITEMPA). The sequestering agents can be used alone or in admixture.

In orderto 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 ofthe peroxide bleaching agent. Suitable inhibitor compounds are disclosed in U.S. Patent 3,606,990, the relevant disclosure ofwhich is incorporated herein by reference.

Of special interest as the inhibitor compound, mention can be made ofhydroxylamine sulphate and other water-insolubie hydroxylamine salts. In the preferred non-aqueous compositions ofthe present 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%, for example, 0.1 to 10%, by weight of the composition.

In addition to the detergent builders, various other detergent additives oradjuvants may be present in the detergent productto give it additionaL desired properties, either of functional or aesthetic nature.

Thus, there may be included in the formulation, minor amounts of soil suspending or anti-redeposition agents, e.g. polyvinyi alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose. A prefered anti-redeposition agent is sodium carboxymethyl cellulose having a 2:1 ratio ofCM/MCwhich is sold underthetrade name 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 sylphonatedsubsti- tutedtriazinyl stilbene,sulphonated naphthotriazole stilbene or benzidine sulphone, most preferred are stilbene andtriazole combinations. Preferred bright eners are stilbene Brightener N4which is a dimorpholino dianilino stilbene su Iphonate and Tinapal ATS-X which are well known in the art.

Enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papain,trypsin and pepsin, as well as amylase type enzymes, lipasetypeenzymes, and mixturesthereofcan be used. Preferred enzymes include protease slurry, esperase slurry and amylase.

A preferred enzyme is Esperase SL8which is a protease. Anti-foam agents, e.g. silicon compouds, such as Silicane L 7604 can also be added in small effective amounts.

Bactericides,e.g.,tetrachlorosalicylanilideand hexachlorophene; fungicides; dyes, pigments (water dispersible); perservatives; ultraviolet absorbers; anti-yellowing agents, such as sodium carboxymethyl cellulose; pH modifiers and pH buffers; colour safe bleaches, perfume and dyes and blueing 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 nameAerosil (Registered Trade Mark)) ortheotherhighlyvoluminous inorga- nic carrier materials disclosed in U.S. Patent 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 activatortherefor) 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.

The stability of the builder salts in the composition during storage and the dispersibility ofthe composition inwater may be 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 su rfactant phase can be mixed with the solid builders priorto or after carrying outthe grinding operation.

In a preferred form ofthe invention, the mixture of liquid nonionic surfactant and solid ingredients is subjected to an attrition type of mill in which the particle sizes of the solid ingredients are reduced to lessthan about 10 microns, e.g.to an average particle size of2 to 10 microns or even lower (e.g. 1 micron).

Preferably less than about 10%, especially less than about 5% ofallthe 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 disperibility ofthe dispersions without a corresponding decrease in the dispersions stability against settling.

In the grinding operation, it is preferred thatthe proportion ofsolid ingredients be high enough (e.g.

at least about 40% such as about 50%) that the solid particles are in contact with each other and are not substantially shielded from one another by the nonionic surfactant liquids. Afterthe grinding step any remaining liquid nonionicsurfactantcan be added to the ground formulation. Millswhich employ grinding balls (ball mills) orsimilar mobile grinding elements have given very good results. Thus, one may use a laboratory batch attritor having 8 mm diameter steatite grinding balls.For largerscale work a continuously operating mill in which there are 1 mm or 1.5 mm diameter grinding balls working in avery 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 nonionicsurfactant and solids first through a mill which does not effect such fine grinding (e.g. a colloid millyto reduce the particle size to less than 100 microns (e.g. to about 40 microns) priortothe step of grinding to an average particle diameter below about 10 microns in the continuous ball mill.

In the preferred heavy duty liquid detergent compositions of the present invention, typical propor tions (based on the total composition, unless other- wise specified) ofthe ingredients are as follows: Liquid nonionic surfactant detergent in the range of about 10 or 20 to 60, such as 20 or 25 to 50 and preferably 30 to 40 percent; Acid terminated nonionic surfactant may be omitted, it is preferred however that it may be added to the compositions in an amountinthe rangeofaboutOto 30, such as 5 to 25 and 5 to 15 percent; Heptonate acid builder salt, carboxymethyloxy succinic acid builder salt oralginic acid builder salt in the range of about 5 to 50, such as 10 to 40 preferably 25to 35 percent; Polyphosphate detergent builder salt in the range of about Oto 50 percent, such as O to 30 preferably 5 to 15 percent;; Copo lymer of po lyacrylate a nd polymaleicanhyd- ride alkali metal salt anti-encrustation agent in the range of about 0 to 10, such as 2 to 8 preferably 2 to 6 percent; Alkylene glycol monoalkylether anti-gelling agent in an amount in the range of about0 to 20, such as 5to 15 preferably8to 12 percent; Phosphoric acid alkanol ester stabilizing agent in the rangeof Oto 2.0 or 0.1 to 1.0, such as 0.10to 0.5 percent; Aluminium salt of fatty acid stablizing agent in the range of about 0 to 3.0, such as 0.1 to 2.0 preferably 0.5to 1.5 percent; (it is preferred that at least one of phosphoric acid ester or aluminium salt stabilizing agents be included in the composition);; Bleaching agent in the range of about 0 to 35, such as to 30 and preferably 8to 15 percent; Bleach activator in the range of about 0 to 25, such as3to 20 preferably4to 8 percent; Sequestering agent for bleach in the range of about O to 3.0, preferably 0.5 to 2.0 more preferably 0.5 to 1.5 percent; Anti-redeposition agent in the range of about 0 to 3.0, such as 0.5 to 2.0 preferably 0.5 to 1.5 percent; Optical brightener in the range of about 0 to 2.0, such as 0.1 to 1.5 preferably 0.3 to 1.0 percent; Enzymes in the range of about 0 to 3.0, such as 0.5 to 2.0 preferably 0.5 to 1.5 percent; Perfume in the range of about 0 to 2.0, such as 0.10 to 1.0 preferably 0.5 to 1.0 percent;; Dye in the range of about 0 to 1.0, such as 0.0025 to 0.050 preferably 0.25 to 0.0100 percent.

Various of the 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 glycol alkyl ether anti-gel agents can be used and in some cases advantages can be obtained by the use of such mixturesalone, 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 of the detergent composition. In this application, as mentioned above, all proportions and percentages are by weight ofthe entire formulation or composition unless otherwise indicated.

The concentrated non-aqueous nonioic liquid detergent composition of the present invention dis penses readily in the water in the washing machine.

The presently used home washing machines normal ly use about 175 grams or 250 grams of powder detergent to wash afull load of laundry. In accord ance with the present invention only about 77 ml or about 100 grams ofthe concentrated liquid nonionic detergent composition is needed.

In a preferred embodiment of the invention the detergent composition of a typical formulation is formulated using the below named ingredients: Weight % Nonionicsurfactantdetergent. 30-40 Acid terminated surfactant. 5-15 Alkali metal heptonic acid builder 25-35 salt; alkali metal carboxymethyloxy succinicacid buidersalt; or alkali metal alginic acid buildersalt.

Anti-encrustation agent (Sokalan CP-5). 0-10 Polyphosphate buldersalt. 0-30 Alkylene glycol monoalkyl ether. 8-12 Alkanol phophoric acid ester 0.1-0.5 (Empiphos 5632).

Anti-redeposition agent (Relatin 0-3.0 Do4050).

Alkali metal perborate bleaching agent. 8-15 Bleach activator (TAED). 4-8 Sequestering agent (Dequest 2066). 0-3.0 Optical brightener (ATS-X). 0.05 or 0.3-1.0 Enzymes (Protease-Esperase SL8). 0.5-1.5 Perfume. 0.5-1.0 The invention may be put into practice in various ways and a number of specific embodiments will be described to illustrate the invention with reference to the accompanying examples and the accompanying drawings, Figures 1 to 6, which are graphs plotting ash content of calcined wash swatchesagainstthe concentration of detergent composition in the bath used to wash the said swatches.

EXAMPLE 1 A concentrated non-aqueous liquid nonionic sur factant detergent composition incorporating a sodium salt of heptonic acid is formulated from the following ingredients in the amounts specified in Tablel below.

TABLE 1 Ingredient Weight % AmixtureofC1 3-C1 Sfattyalcohol 13.5 condensed with 7 moles of propylene oxide and 4 moles ethylene oxide and C13-C15fattyalcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide.

SurfactantT7. 10.0 SurfactantT9. 10.0 Acid terminated Dobanol 91-5 reaction 5.0 productwith succinic anhydride (made as described above).

Sodium saltofheptonicacid. 28.7 Diethylene glycol monobutyl ether. 10.0 Alkanol phosphoric acid ester 0.3 (Empiphos 5632).

Anti-encrustation agent (Sokolan CP-5). 4.0 Sodium perborate monohydrate 9.0 bleaching agent.

Sodium carbonate. 0.9 Tetraacetylethylene diamine (TAED) 4.5 bleach activator Sequestering agent (Dequest 2066). 1.0 Optical brightener(TinopalATS-X). 0.5 Anti-redeposition agent (Relatin DM 4050). 1.0 Enzyme Esperase slurry (Esperase SL8). 1.0 Perfume. 0.5925 Dye .0075 '100.00 The formulation is ground for about 1 hourto reduce the particle size ofthe suspended builder salts to less than 40 microns. The formulated detergent composition is found to be stable and non-gelling in storage and to have a high detergent capacity.

The formulation exhibits yield stress of 5.0 P.a. and an apparent viscosity of 1.1 P.a. S-1.

EXAMPLE 2 In orderto demonstrate the effect on encrustation ofthesubstitutionofsodium polyphosphatebyan equivalent detergent builder amount of sodium heptonate,thedetergentcompositionformulation of Example 1 containing 28.7% byweight of sodium heptonate was compared in laundry washing machine use with the same composition in which the sodium heptonatewas replaced with 28.7% by weight of sodium polyphosphate.

The wash cycles were carried out at concentrations of the sodium heptonate and sodium polyphosphate detergent compositions at laundry wash water cpn centrationsofeach of the detergent compositions of 1 to 9 gm/litre ofthe respective detergent compositions.

After 6 wash cycles of each detergent composition was used in a washing machine the amount of encrustation that resulted, i.e. the percent ash deposited was measured. The percent ash deposited measurement is determined by calcination of wash swatches.

The results observed are reported in the graph illustrated in Figure 1 ofthe drawings and show that at detergent composition concentrations of 1 to 5 g/l of wash waterthe sodium heptonate is substantially betterthan sodium polyphosphate in preventing encrustation as indicated by ash deposit At detergent composition concentrations of about 5 to 9 g/l of wash waterthe behaviour of sodium heptonate and sodium polyphosphate detergent builder salts are aboutthe same in their anti-encrustation properties.

EXAMPLE 3 In orderto demonstrate the effect on encrustation buildup ofthe substitution of sodium polyphosphate by an equivalent detergent builder amount of sodium heptonate, the detergent composition of Example 1 containing 28.7 percent by weight of sodium heptonate was compared in repeated laundry wash machine wash cycles with the same composition in which the sodium heptonate was replaced with 28.7 percent by weight of sodium polyphosphate.

The repeated wash cycles were carried out at 5 g/l wash waterconcentrationsofeach ofthe detergent compositions fortwelve washing cycles. The encrustation buildup, i.e. percent ash buildup, was measured in each washing machine after 3,6,9 and 12 washings.

The results of encrustation buildup obtained are reported in the graph illustrated in Figure 2 ofthe drawings. As far as the encrustation buildup is concerned, no build up was observed with the sodium heptonate, whereas a small buildup was observed with the sodium polyphosphate detergent builder salt.

The alkali metal heptonate detergent buildersalts can also be used replace all orpartofthe polyphosphate builder salts in powder detergent compositions, and in aqueous and cream detergent compositions with good effect.

EXAMPLE 4 A concentrated non-aqueous liquid nonionicsurfactant detergent composition incorporating the trisodium salt ofcarboxymethyloxy succinic acid is formulated from the following ingredients in the amounts specified in Table 2 below.

TABLE 2 Ingredients Weight % A mixture of Ca3-C15fatty alcohol 13.5 condensed with 7 moles of propylene oxideand4 moles ethylene oxide and C13-C15fatty alcohol condensed with Smolespropylene oxide and 10 moles ethylene oxide.

SurfactantT7, 10.0 SurfactantT9. 10.0 Acid terminated Dobanoi 91-5 reaction 5.0 product with succinic anhydride (made as described above).

Trisodium saltofcarboxymethyloxy 29.6 succinic acid.

Diethylene glycol monobutyl ether. 10.0 Alkanol phosphoric acid ester 0.3 tEmpiphos 5632).

Anti-encrustation agent (Sokalan CP-5). 4.0 Sodium perborate monohydrate 9.0 bleaching agent.

Tetraacetylethylene diamine (TAED) 4.5 bleach activator.

Sequestering agent (Dequest 2066j. 1.0 Optical brightener (Tinopal ATS-X). 0.5 Anti-redeposition agent (Relatin DM4050). 1.0 Enzyme Esperase slurry (Esperase SL8). 1.0 Perfume. 0.5925 Dye 0075 100.00 The formulation is groundfor about 1 hour to reduce the particle size of the suspended builder salts to less than 40 microns. The formulated detergent composition is found to be stable and non-gelling in storage and to have a high detergent capacity.

The formulation exhibits a yield stress of 7.5 P.a.

andean apparent viscosity of 0.4 P.a. S-1.

EXAMPLE 5 In order to demonstrate the effect on encrustation ofthe substitution of sodium tripolyphosphate by an equivalent detergent builderamountoftrisodium carboxymethyloxy succinate, the detergent compositionformulation of Example4containing 29.6% by weight oftrisodium carboxymethyloxy succinate was compared in laundry washing machine use with the same composition in which thetrisodium carboxy methyloxy succinate was replacedwith 29.6% by weight of sodium tripolyphosphate.

The wash cycles were carried out at concentrations of the trisodium carboxymethyloxy succinate and sodium tripolyphosphate detergent compositions at laundry wash water concentrations of each of the detergent compositions of 1 to 9 gm/litre of the respective detergent compositions.

After each detergent composition was used in a washing machinetheamount of encrustation that resulted, i.e. the percent ash deposited was measured. The percent ash deposited measurement is determined by calcination ofwashedswatches.

The results observed are reported inthegraph illustrated in Figure 3 of the drawings and show that at detergent composition concentrations of 1 to5g/1 of wash water the trisodium carboxymethytoxy succinate is substantially better than sodium tripolyphosphate in preventing encrustation or ash deposit.

At detergent composition concentrations of about 5 to 9 g/l of wash water the behaviour oftrisodium carboxymethyloxy succinate and sodium tripolyphosphate detergent buildersalts areaboutthesame in their anti-encrustation properties.

EXAMPLE 6 In order to demonstrate the effect on encrustation buildup ofthe substitution of sodium tripolyphosphate by an equivalent detergent builder amount of trisodium carboxymethyloxy succinate, the detergent composition of Example 4 containing 29.6 percent by weight oftrisodium carboxymethyloxy succinate was compared in repeated laundrywash machine wash cycles with the same composition in which the trisodiu m carboxymethyloxy succinate was replaced with 29.6 percent by weight of sodium tripolyphosphate.

The repeated wash cycles were carried out at 5 g/l wash water concentrations of each of the detergent compositions for twelve washing cycles. The encrustation buildup, i.e. percent ash buildupwas measured in each washing machine after 3,6,9 and 12 washings.

The results of encrustation buildup obtained is reported in the graph illustrated in Figure 4 of the drawings. As far as the encrustation buirdup is concerned, no buildup wasobservedwith the trisodium carboxymethyloxy succinate, whereas a small buildup was observed with the sodium tripolyphosphatedetergent builder salt.

The alkali metal carboxymethyloxysuccinate de tergent builder salts can also be used to replace all or part of the polyphosphate builder salts in powder detergent compositions, and in aqueous and cream detergent compositions with good effect.

EXAMPLE 7 A concentrated non-aqueous liquid nonionic surfactant detergent composition incorporating a sodium salt of alginic acid isformulated from the following ingredients in the amounts specified in Table 3 below.

TABLE3 Ingredients Weight % A mixture of C130C15 fatty alcohol condensed 13.5 with 7 moles of propylene oxide and 4 moles ethylene oxide and C13-C15fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide.

SurfactantT7. 10.0 SurfactantT9. 10.0 Acid terminated Dobanol 91-5 reaction 5.0 product with succinic anhydride (made as described above).

Sodium salt of alginic acid. 29.6 Diethylene glycol monobutyl ether. 10.0 Alkanol phosphoric acid ester (Empiphos 0.3 5632).

Anti-encrustation agent (Sokalan CP-5). 4.0 Sodium perborate monohydrate bleaching 9.0 agent.

Tetraacetylethylene diamine (TAED) bleach 4.5 activator Sequestering agent (request 2066). 1.0 Optical brightener (Tinopal ATS-X). 0.5 Anti-redeposition agent (Relatin DM 4050). 1.0 Protease enzyme (Esperase SL8). 1.0 Perfume. 0.5925 Dye. 0.0075 100.00 Theformulation is ground for about 1 hou rto reduce the particle size of the suspended builder salts to lessthan 40 microns. The formulated detergent composition isfoundto bestableand nongelling in storageandto have a high detergent capacity.

The formulation exhibits a yield stress of 4.7 P.a.

and an apparentviscosity of 0.46 P.a. S-i.

EXAMPLE 8 In orderto demonstrate the effect on encrustation of the substitution of sodium tripolyphosphate by an equivalent detergent builder amount of sodium alginate,the detergent composition formulation of Example7 containing 29.6% by weight of sodium alginate was compared in laundry washing machine use with the same composition in which the sodium alginate was replaced with 29.6% by weight of sodium tripolyphosphate.

The wash cycleswere carried out at concentrations ofthe sodium alginate and sodium tripolyphosphate detergent compositions at laundry wash water concentrations of each ofthe detergent compositions of 1 to 9 gm/litre ofthe respective detergent compositions.

Aftereachdetergentcompositionwas used in a washing machine the amount of encrustation that resuited, i.e. the percent ash deposited was measured. The percent ash deposited measurement is determined by calcination of washed swatches.

The results observed are reported in the graph illustrated in Figure5 of the drawings and show that at detergent composition concentrations of 1 to 5 gil of wash water the sodium alginate is substantially betterthan sodium tripolyphosphate in preventing encrustation or ash deposit. At detergent composition concentrations of about 5 to 9 g/l of wash water the behaviourofsodium alginate and sodium tripoly phosphate detergent builder salts are about the same in their anti-encrustation properties.

EXAMPLE 9 In orderto demonstrate the effect on encrustation buildup ofthe substitution of sodium tripolyphosphate by an equivalent detergent builder amount of sodium alginate, the detergent compositidn of Example 7 containing 29.6 percent by weight of sodium alginate was compared in repeated laundry wash machine wash cycles with the same composition in which the sodium alginatewas replaced with 29.6 percent by weight of sodium tripolyphosphate.

The repeated wash cycles were carried out at 5 g/l wash water concentrations of each ofthe detergent compositions fortwelve washing cycles. The encrustation buildup, i.e. percent ash buildup was measured in each washing machineafter3,6,9 and 12 washings.

The results of encrustation buildup obtained is reported in the graph illustrated in Figure 6 ofthe drawings. As far as the encrustation buildup is concerned, substantially no buildup was observed with the sodium alginate, whereas a small buildup was observed with the sodium tripolyphosphate detergent builder salt.

The alkali metal alginate detergent builder salts can also be used to replace all or part of the polyphosphate builder salts in powder detergent compositions, and in aqueous and cream detergent compositions with good effect.

Theformulations ofExamples 1,4 and 7 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, orthe 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 orthe entire grinding operation can be carried out after mixing with the liquid surfactant. The formulations desirably contain suspended builder and solid particles less than 100 microns or preferably less than 40 microns in size.

Reference has been made to USP3606990for inhibitors of enzyme induced decomposition of bleaching agents, and reference made to the use of hydroxylaminesulphateforsuch purpose.

USP 3606990 also lists hydroxylamine hydrochior- ide, hydrazine hydrochloride, 2,4 -dinitrophenolhyd- razine, p - chlorophenol, 4 - chloro - 2 - aminophenol, o - cresol, p - chloro -m - cresol, 2,4- dichlorophenol, resorcinol, pytrocatechol, pyrogallol, betanaphthol, 2,7 -dihydroxynaphthalene, hydroquinone, hydroquinone sulphate, 1,2 - naphthoquinone, 1,2 -cyclohexanediol, aminotriazole, sodium chlorate and sodium nitride.

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.

Claims (16)

1. A non-aqueous liquid heavy duty laundry detergent composition which comprises at least one liquid nonionic surfactant detergent, and an alkali metal heptonic acid, a carboxymethyloxy succinate, or an alkali metal alginic acid builder salt.

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

3. A detergent composition as claimed in Claim 1 or Claim 2 comprising 5 to 50 percent of an alkali metal heptonic acid, a ca rboxymethyloxy succinate, or an alkali metal alginic acid detergent builder salt.

4. A laundry detergent composition as claimed in Claim 1,2 or 3 which is polyphosphate free or of low polyphosphate content.

5. A detergent composition as claimed in any one of claims 1 to 4which comprises at least one liquid nonionic surfactant in an amount ofabout25to 50%, an acid-terminated nonionic surfactant in an amount of about 5 to 25%, an alkali metal heptonic acid, a carboxymethyloxy succinate, oran alkali metal alginic acid builder salt in an amount of about lOto 40%, an alkylene glycol mono-ether in an amount of about5to 15%, a polyphosphate detergent builder in an amount of about0to 30%, and an alkanol phosphoric acid ester in an amount of about0.1 to 1.0%.

6. A laundry detergent compositions as claimed in any one of Claims 1 to 5 comprising an alkali metal perborate monohydrate bleaching agent in an amount of about 5 to 30%, tetraacetylethylene diamine bleach activator in an amount ofabout3to 20%, and optionally one or more detergent adjuvants selected from the group consisting of anti-encrustation agent, anti-redeposition agent, sequestering agentforthe bleach, optical brighteners, enzymes and perfume.

7. A detergent composition as claimed in any one of Claims 1 to 6 inwhichthe alkali metal salt of heptonicacid has the formula

the carboxymethyloxy succinate has the formula

and the alkali metal alginic acid salt isthe sodium salt of alginic acid.

8. A laundry detergent composition as claimed in any one of Claims 2 to 7 when dependent upon Claim 2 in which the alkanol phosphoric acid estercompris esaC16to Cq8alkanol esterof phosphoricacid.

9. A low phosphate or phosphate free detergent composition as claimed in any one ofthe claims 1 to 8 which contains no more than 15% polyphosphate.

10. Adetergentcomposition as claimed in any one of Claims 1 to 9 which comprises a polyphosphate builder salt in an amount of about 5 to 15 percent.

11. A phosphate detergent builder free nonaqueous liquid 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 saltofheptonicacid in an amount of about 25-35%; alkylene glycol monobutyl ether in an amount of about 8-12%; C16to C18alkanol ester of phosphoric acid in an amount of about 0.1-0.5%; sodium perborate monohydrate bleaching agent in an amount of about 8-15%; tetraacetylethylene diamine (TAED) bleach activator in an amount of about4-8%.

12. A phosphate detergent builder free nonaqueous liquid heavy duty laundry detergent composition which comprises: nonionic surfactant in an amount of about30-40 MO; acid terminated surfactant in an amount of about 5-15%; trisodium salt of carboxymethyloxy succinic acid in an amount of about 25-35%; alkyleneglycolmonobutyletherin an amount of about 8-12%; C16to C18aikanol esterof phosphoric acid in an amount ofabout 0.1-0.5%; sodium perborate monohydrate bleaching agent in an amount of about 8-15% tetraacetylethylene diamine (TAED) bleach activator in an amount of about 4-8%.

13. A phosphate detergent builderfree nonaqueous liquid heavy duty laundry detergent composition which comprises: nonionic surfactantin an amount of about30-40%; acid terminated surfactant in an amount of about 5-15%; sodium salt of alginic acid in an amount of about 25-35%; alkylene glycol monobutyl ether in an amount of about 8-12%; C16 to C18 alkanol ester of phosphoric acid in an amountofabout0.1-0.5%; sodium perborate monohydrate bleaching agent in an amount of about8-15%; tetraacetylethylene diamine (TAED) bleach activa tor in an amount of about4-8%.

14. A detergent composition as claimed in any one of Claims to I to 3 in which the eomposition comprises an anti-redeposition agent and anti-encrustation agent and a sequestering agent for the bleach.

15. A detergent composition as claimed in Claim 1 substantially as specifically described herein with reference to the accompanying examples.

16. A method for cleaning soiled fabrics which comprises contacting the soiled fabrics with a iaun- dry detergent composition as claimed any one of Claims 1 to 15.