NO863142L - PHosphate-low or phosphate-free detergent mixture. - Google Patents

Description

The invention relates to non-aqueous, liquid mixtures for treating substances. More specifically, the invention relates to phosphate-free or phosphate-poor non-aqueous liquid laundry detergent mixtures which contain a suspension of a heptonate builder salt, a carboxymethyloxysuccinate builder salt or an alginate builder salt in non-ionic surfactants, and which are stable against phase separation and gel formation, and are easily pourable, as well as the use of the mixtures for cleaning soiled substances.

Liquid non-aqueous extra heavy duty laundry detergent compositions are well known in the art. E.g. mixtures of this type may comprise a liquid non-ionic surfactant in which particles of a builder are dispersed, such as e.g. shown in US Patent Nos. 4,316,812, 3,630,929 and 4,264,466, and in British Patent Nos. 1,205,711, 1,270,040 and 1,600,981.

The following related US patent applications are available:

687,815 of 31 December 1984, 597,793 of 6 April 1984,

597,948 of 9 April 1984 and 725,455 of 22 April 1985.

These applications are aimed at liquid non-aqueous,

non-ionic laundry detergent mixes.

The washing strength of synthetic non-ionic surface-active detergents in laundry detergent mixtures 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 entails several disadvantages, such as e.g. the propensity of the polyphosphates to hydrolyse to pyro- and orthophosphates which constitute less valuable builders.

In addition, the polyphosphate content in laundry detergents has been blamed for the undesirably high phosphate content in surface water.

An increased phosphate content in surface water has been found to contribute to greater algae growth with the result that the biological balance in the water can be changed in an unfortunate way.

Legislation that has been passed recently has been aimed at reducing the amount of polyphosphates present in laundry detergents, and in some jurisdictions where polyphosphates have been a problem, laundry detergents have been required to contain no polyphosphate builders.

Liquid detergents are often considered to be more convenient to use than dry powder or particle products, and have therefore won considerable favor with consumers. They are easily measurable, dissolve quickly in the wash water, can be easily added in concentrated solutions or dispersions to soiled areas of clothing to be washed, and are non-dusty, and they usually take up less storage space. In addition, the liquid detergents may contain materials which would not be able to withstand drying operations without destruction, materials which it is often desirable to use in the production of detergent products in particle form. Although they have many advantages over solid products in unitary or particulate form, liquid detergents often have certain inherent disadvantages as well which must be overcome to provide acceptable commercial detergent products. Certain such products thus separate during storage and others separate during cooling and are not easily redispersed. In some cases, the product viscosity changes and it becomes either too thick to pour or so thin that it looks watery. Some clear products become cloudy and others form a gel on standing.

In addition to the problem of precipitation or phase separation, the non-aqueous liquid laundry detergents based on liquid non-ionic surfactants suffer from the disadvantage that the non-ionic compounds tend to gel when added to cold water. This is a particularly important problem in the common use of European automatic household washing machines where the user places the laundry detergent mixture in a dispensing unit (e.g. a dispensing drawer) in the machine. During operation of the machine, the detergent in the dispenser is exposed to a stream of cold water which transfers it to the main part of washing solution. Especially during the winter months, when the detergent mixture and the water supplied to the dispenser are particularly cold, the detergent viscosity increases significantly and a gel is formed. As a result, some of the mixture is not completely flushed out of the dispenser during operation of the machine, and a deposit of the mixture builds up with repeated wash cycles, eventually requiring the user to rinse the dispenser with hot water.

The gel formation phenomenon can also be a problem when it is desired to carry out the washing using cold water, which may be recommended for certain synthetic and finer fabrics or fabrics that may shrink in lukewarm or hot water.

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

Partial solutions to the gel formation problem in aqueous, mainly builder-free mixtures have been proposed, e.g. by diluting the liquid non-ionic agent with certain viscosity-regulating solvents and gel-inhibiting agents, such as lower alkanols, e.g. ethyl alcohol (see US Patent No. 3,953,380), alkali metal formates and adipates (see US Patent No. 4,368,147), hexylene glycol, polyethylene glycol, etc., and nonionic structure modification and optimization. As an example of nonionic surfactant modification, a particularly successful result has been achieved by acidifying the hydroxyl residue in the nonionic molecule. The advantages of introducing carboxylic acid at the end of the nonionic surfactant include gel inhibition after dilution, lowering of the pour point of the nonionic surfactant, and formation of an anionic surfactant upon neutralization in the wash liquor. Nonionic structure optimization has focused on the chain length of the hydrophobic-lipophilic residue and the number and appearance of alkylene oxide units (eg ethylene oxide) in the hydrophilic residue. E.g. it has been found that a C13 fatty alcohol ethoxylated with 8 mol of ethylene oxide gives only a limited tendency to gel formation.

Nevertheless, improvements in both the stability and gel inhibition of phosphate-poor and phosphate-free, non-aqueous liquid mixtures for the treatment of substances are desirable.

According to the present invention, a highly concentrated, phosphate-poor, more specifically a polyphosphate detergent builder-free, non-aqueous liquid laundry detergent mixture is produced by dispersing heptonate builder salts, carboxy-methyloxysuccinate builder salts or alginate builder salts in a liquid non-ionic surfactant detergent.

The heptonic acid salts used according to the present invention are well known. 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

where M is an alkali metal or ammonium cation.

The carboxymethyloxysuccinic acid salts used according to the present invention are known. The alkali metal and ammonium salts of carboxymethyloxysuccinic acid are water soluble.

The carboxymethyloxysuccinic acid salts used in the present invention have the general formula

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

The alginic acid salts used according to the present invention are well known. The alginate is a polysaccharide extract from algae. The alkali metal salts of alginic acid are water-soluble. The alginate is extracted from algae in the form of mixed salts comprising calcium and magnesium.

To improve the viscosity properties of the mixture, an acid-terminated non-ionic surfactant can be added. To further improve the viscosity properties of the mixture, and the storage properties, viscosity-improving and anti-gelling agents can be added to the mixture, such as alkylene glycol monoalkyl ethers and anti-settling agents such as phosphoric acid esters and aluminum stearate. In a preferred embodiment of the invention, the detergent mixture contains an acid-terminated non-ionic surfactant and/or an alkylene glycol monoalkyl ether, and an anti-precipitation agent.

Sanitary or bleaching agents and activators for these can be added to improve the bleaching and cleaning properties of the mixture.

In one embodiment of the invention, the builder components in the mixture are ground up to a particle size of less than 100 µm, and preferably to less than 10 µm, in order to further improve the stability of the suspension of the builder components in the liquid non-ionic surfactant detergent.

In addition, other ingredients can be added to the mixture, such as anti-scale agents, anti-foam agents, optical brighteners, enzymes, anti-redeposition agents, perfumes and dyes.

The washing machines currently manufactured for home use usually work at washing temperatures of up to 100°C. Up to 70 liters of water are used during the wash and rinse cycles.

Usually, approx. 175 g powder detergent per wash.

According to the present invention where the highly concentrated liquid detergent is used, it is normally only required with approx. 100 g (77 ml) or less of the liquid detergent mixture to wash a full load of dirty laundry.

Accordingly, one aspect of the present invention provides a phosphate-builder-free or mainly phosphate-builder-free, liquid extra-strength laundry mixture composed of a suspension of an alkali metal heptonic acid builder salt, an alkali metal carboxymethyloxysuccinic acid builder salt or an alkali metal alginic acid builder salt in liquid non-ionic surfactant.

According to another aspect, the invention provides

a phosphate-free or low-phosphate, concentrated liquid, extra-strength laundry detergent mixture that is stable, non-settling in storage and non-gelling in storage and in use.

The liquid mixtures according to the present invention are easy to pour, easy to measure out and are easily fed into the washing machine.

According to another aspect, the invention provides a method for dispensing a phosphate-free or phosphate-poor, liquid non-ionic laundry detergent mixture in and/or together with cold water without gel formation occurring. In particular, a method is provided for filling a container with a non-aqueous liquid laundry detergent mixture where the detergent consists, at least mainly, of a polyphosphate builder-free, liquid non-ionic surfactant, and for dispensing the mixture from the container into an aqueous wash bath, the dispensing being carried out by directing a flow of unheated water towards the mixture so that the mixture is carried with the flow of water into the wash bath.

The polyphosphate builder-free detergent mixtures overcome the problem of phosphate contamination of surface water.

The polyphosphate-free or polyphosphate-poor, concentrated non-aqueous liquid non-ionic surface-active laundry detergent mixtures according to the present invention have the additional advantages of being stable, non-precipitating during storage and non-gelling during storage. The liquid mixtures are easy to pour, easy to measure out and easy to feed into the washing machines.

It is an object of the present invention to provide a polyphos fat-poor, more specifically a polyphosphate-free, non-polluting liquid extra strong non-aqueous, non-ionic detergent mixture containing heptonate builder salt, carboxymethyloxysuccinate builder salt or alginate builder salt suspended in a non-ionic surfactant.

It is another object of the invention to provide a polyphosphate-free or polyphosphate-poor, liquid mixture for the treatment of substances which are suspensions of heptonate building salt, carboxymethyloxysuccinate building salt or alginate building salt in a non-aqueous liquid, and which is storage-stable, easily pourable and dispersible in cold, lukewarm or warm water.

Another object of the invention is to formulate a polyphosphate-free or polyphosphate-poor, strongly built extra strong non-aqueous liquid non-ionic surfactant laundry detergent mixture which can be poured at all temperatures and which can be dispersed repeatedly from the dispensing unit in automatic European-type laundry machines without re- - growing or clogging of the dispenser even during the winter months.

Another object of the invention is to provide

a polyphosphate-free or polyphosphate-poor, non-gelling, stable suspension of extra heavy duty, non-aqueous liquid non-ionic laundry detergent composition comprising an effective amount of heptonate builder salt, carboxymethyloxysuccinate builder salt or alginate builder salt.

A further object of the invention is to provide non-gelling, stable suspensions of extra heavy duty, non-aqueous liquid non-ionic laundry detergent composition comprising an amount of phosphoric acid alkanol ester and/or aluminum fatty acid salt as anti-precipitating agent sufficient to increase stability to the mixture, i.e. prevent sedimentation of building particles, etc., preferably at the same time as the plastic viscosity of the mixture is reduced or at least not increased.

These and other purposes of the invention, which will become clearer from the detailed description below of preferred embodiments, are generally provided by the production of a polyphosphate-poor or polyphosphate-free detergent builder mixture by adding to the non-aqueous liquid non-ionic surfactant an effective amount of an alkali metal heptonate builder salt, a carboxymethyl-succinate builder salt or an alkali metal alginate builder salt and inorganic or organic additives for treating substances, e.g. viscosity-improving and anti-gel agents, anti-precipitation agents, anti-scale agents, bleaching agents, bleach activators, anti-foaming agents, optical brighteners, enzymes, anti-

redoposition agents, perfumes and dyes.

The non-ionic synthetic organic detergents

used in the practice of the invention may be any of a wide variety of such compounds which are well known.

As is well known, the nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group,

and is usually produced by condensation of an organic aliphatic or alkylaromatic hydrophobic compound with ethylene oxide (hydrophilic in nature). Practically any hydrophobic compound with a carboxy, hydroxy, amido or amino group with a free hydrogen bonded to the nitrogen can be condensed with ethylene oxide or with its polyhydration product, polyethylglycol, to form a nonionic detergent. The length of the hydrophilic chain or polyoxy-ethylene chain can be easily adjusted to achieve the desired equilibrium between the hydrophobic and hydrophilic groups. Typically suitable nonionic surfactants are those described in US Patent Nos. 4,316,812 and 3,630,929.

Generally, the non-ionic detergents are polylower alkylated lipophilic compounds where the desired hydrophilic-lipophilic balance is achieved by adding a hydrophilic polylower alkoxy group to a lipophilic residue. A preferred class of the nonionic detergent used is the polylower alkoxylated higher alkanol, where the alkanol contains 9-18 carbon atoms and where the number of moles of lower alkylene oxide (with 2 or 3 carbon atoms) is from 3 to 12. Among such materials, it is preferred to use those where the higher alkanol is a higher fatty alcohol with 9-11 or 12-15 carbon atoms, and which contain from 5 to 8 or 5 to 9 lower alkoxy groups per mol. The lower alkoxy group is preferably ethoxy, but in some cases it may be mixed with propoxy if desired, the latter, if present, often constituting a minor proportion (less than 50%).

Examples of such compounds are those where the alkanol contains 12 - 15 carbon atoms and which contain approx. 7 ethylene oxide groups per mole, e.g. "Neodol 25-7" and "Neodol 23-6.5", products manufactured by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols with an average of approx. 12 - 15 carbon atoms, and approx. 7 moles of ethylene oxide, and the latter is a corresponding mixture where the carbon atom content in the higher fatty alcohol is 12 - 13 and the number of ethylene oxide groups present, on average, is approx. 6.5. The higher alcohols are primary alkanols.

Other examples of such detergents include Tergi-tol<®>15-S-7 and Tergitol<®>15-S-9, both of which are straight chain secondary alcohol ethoxylates made by Union Carbide Corp. The former is a mixed ethoxylation product of a straight-chain secondary alkanol with 11 - 15 carbon atoms and 7 mol of ethylene oxide, and the latter is a similar product, but where 9 mol of ethylene oxide is converted.

Also useful in the present composition as a component of the nonionic detergent are higher molecular weight nonionic compounds, such as "Neodol 45-11", which are similar ethylene oxide condensation products of higher fatty alcohols, where the higher fatty alcohol contains 14-15 carbon atoms and the number of ethylene oxide groups per mole is approx. 11. Such products are also made by Shell Chemical Company.

Other useful non-ionic compounds are represented by the commercially well-known class of non-ionic compounds sold under the trademark Plurafac®. The Plurafac<®> products are the reaction product between a higher straight-chain alcohol and a mixture of ethylene and propylene oxide, which contains a mixed chain of ethylene oxide and propylene oxide, terminated with a hydroxyl group. Examples include Plurafac<®>RA30 (a C, -,-C, c fatty alcohol condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide), Plurafac<®>RA40 (a c^3~c^5 fatty alcohol condensed, with 7 moles of propylene oxide and 4 mol ethylene oxide), Plurafac<®>D25 (a ci2~ C15 fatty alcohol condensed with 5 mol propylene oxide and 10 mol ethylene oxide.

Another group of liquid nonionic compounds is commercially available from Shell Chemical Company, Inc. under the trade name Dobanol<®>: Dobanol<®>91-5 is an ethoxylated C 8 -C 1 -^ fatty alcohol with an average of 5 moles of ethylene oxide, and Dobanol<®>25-7 is an ethoxylated ci2~ C15 fatty alcohol with an average of 7 mol of ethylene oxide per moles of fatty alcohol.

In order to achieve the best balance between hydrophilic and lipophilic residues, the number of lower alkoxy residues in the preferred polylower alkoxylated higher alkanols will generally be from 40% to 100% of the number of carbon atoms in the higher alcohol, preferably 40-60% thereof, and the non- ionic detergents will preferably contain at least 50% such preferred polylower alkoxy higher alkanol. Higher molecular weight alkanols and various other normally solid non-ionic detergents and surfactants can contribute to gel formation in the liquid detergent and will therefore preferably be avoided or limited in quantity in the present compositions, although smaller amounts thereof may be used due to the cleaning properties, etc. In the case of both preferred and less preferred nonionic detergents, the alkyl groups present are usually straight chain although branching is acceptable, such as on a carbon atom next to or 2 carbon atoms from the terminal carbon atom in the straight chain, and away from the ethoxy chain, if such branched alkyl is not more than 3 carbon atoms in length. Normally, the proportion of carbon atoms in such a branched configuration will be smaller, and rarely exceeds 20% of the total carbon atom content in the alkyl part. Although straight-chain alkyl residues which are attached at the ends to the ethylene oxide chains are highly preferred and are considered to provide the best combination of detergency, biodegradability and non-gelling properties, medial or secondary attachment to the ethylene oxide can also occur in the chain. It is usually only a minor proportion of such alkyl residues, usually less than 20%, but may be greater, as in the cases of the mentioned Tergitol<®> products. When propylene oxide is present in the lower alkylene oxide chain, it will also constitute less than 20% thereof and preferably less than 10% thereof.

When greater proportions of non-terminally alkylated alkanols, propylene oxide-containing polylower alkylated alkanols and non-ionic detergents with a lower degree of hydrophilic-lipophilic equilibrium than mentioned above are used, and when other non-ionic detergents are used instead of the preferred non-ionic detergents which mentioned here, it may be that the resulting product does not have as good washing action, stability, viscosity and non-gelling properties as the preferred compositions, but use of the viscosity and gel regulating compounds according to the invention can also improve the properties of the detergents which are based on such nonionic compounds. In some cases, such as when using a higher molecular weight polylower alkoxylated higher alkanol, often on

due to its washing effect, the proportion thereof will be regulated or limited in accordance with the results of routine tests in order to achieve the desired washing effect and still have the product as non-gelling and with the desired viscosity. Furthermore, it has been found that it is only rarely necessary to use the nonionic compounds having a higher molecular weight, due to their washing properties, since the described preferred nonionic compounds are excellent detergents and in addition allow the maintenance of the desired viscosity in the liquid detergent without gel formation at low temperatures.

Another useful group of nonionic surfactants is the "Surfactant T" series of nonionic compounds available from British Petroleum. The non-ionic "Surfactant 10" is obtained by ethoxylation of secondary fatty alcohols with a narrow ethylene oxide distribution. "Surfactant T5" has an average of 5 mol ethylene oxide, "Surfactant T7" an average of 7 mol ethylene oxide, "Surfactant T" an average of 9 mol ethylene oxide and "Surfactant T 12" an average of 12 mol ethylene oxide per moles of secondary C-^ fatty alcohol.

In the mixtures according to the invention, preferred non-ionic surfactants comprise the c^3-ci5 secondary fatty alcohols with a relatively narrow content of ethylene oxide in the range from approx. 7 to 9 moles, and Cg-C^ fatty alcohols ethoxylated with approx. 5-6 moles of ethylene oxide.

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

Acid-terminated non-ionic surfactants

The viscosity and gelling properties of the liquid detergent compositions can be improved by including in the composition an effective amount of an acid-terminated liquid nonionic surfactant. The acid-terminated nonionic surfactants consist of a nonionic surfactant that has been modified so that a free hydroxyl group is converted to a residue with a free carboxyl group, such as an ester or a partial ester of a nonionic surfactant and a polycarboxylic acid or an anhydride.

As described in US patent application no. 597,948, works

the modified nonionic surfactants with a free carboxyl group, which can generally be characterized as polyether carboxylic acids, so that the temperature at which the liquid nonionic agent forms a gel with water is lowered.

The addition of the acid-terminated non-ionic surfactants to the liquid non-ionic surfactant helps to make the composition more dispensable, i.e. improves pourability, and lowers the temperature at which the liquid non-ionic surfactants form a gel in water without reducing the stability against sedimentation. The acid-terminated non-ionic surfactant reacts in the washing machine water with the alkalinity of the dispersed builder salt phase of the detergent mixture and acts as an effective anionic surfactant.

Specific examples include the half-esters of Plurafac<®>RA30 and succinic anhydride, the ester or half-ester of Dobanol<®>25-7 and succinic anhydride, and the ester or half-ester of Dobanol<®>91-5 and succinic anhydride. Instead of succinic anhydride, other polycarboxylic acids or anhydrides can be used, e.g. maleic acid, maleic anhydride, citric acid and the like.

The acid-terminated non-ionic surfactants can be prepared in the following way: Acid-terminated Plurafac<®>30. 400 g Plurafac<®>30 non-ionic surfactant which is a c^3~ci5<a>lkanol that has been alkoxylated by introducing 6 ethylene oxide and 3 propylene oxide units per alkanol unit, is mixed with 32 g of succinic anhydride and heated for 7 hours at 100°C. The mixture is cooled and filtered to remove unreacted succinic acid material. Infrared analysis indicated that approx. half of the nonionic surfactant had been converted to its acidic half-ester.

Acid terminated Dobanol<®>25-7»522 g Dobanol<®>25-7 non-ionic surfactant which is the product of ethoxylation of a C±2~(~' 15 alkanol, and which has approx. 7 ethylene oxide units per molecule alkanol, was mixed with 100 g of succinic anhydride and 0.1 g of pyridine (which acts as an esterification catalyst) and heated at 260°C for 2 hours, cooled and filtered to remove unreacted succinic material. Infrared analysis indicated that practical counted all the free hydroxyl residues in the surfactant had reacted.

Acid terminated Dobanol<®>91-5. 1000 g Dobanol<®>91-5 non-ionic surfactant which is the product of ethoxylation of Cg-C^ alkanol and has approx. 5 ethylene oxide units per alkanol molecule, was mixed with 265 g of succinic anhydride and 0.1 g of pyridine catalyst and heated at 260°C for 2 hours, cooled and filtered to remove unreacted succinic material. Infrared analysis indicated that virtually all of the free hydroxyl groups of the surfactant had reacted.

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

The acidic polyether compound, i.e. the acid-terminated non-ionic surfactant, is preferably added dissolved in the non-ionic surfactant.

Builder's salts

The liquid non-aqueous non-ionic surfactant used in the compositions according to the present invention contains dispersed and suspended fine particles of organic and/or inorganic detergent builder salts.

The present invention includes as an essential

part of the mixture, an organic heptonate builder salt, an organic carboxymethyloxysuccinate builder salt or an organic alginate builder salt.

Organic building salts

Preferred organic building salts include alkali metal salts of heptonic acid, preferably the sodium and potassium salts. Other monosaccharide acid salts that can be used are any longer chain monosaccharide acid salts. A specific example of monosaccharide acid salts is the sodium salt of heptonic acid.

Other preferred organic building salts include alkali metal or ammonium salts of carboxymethyloxysuccinic acid, preferably the trisodium salt.

The carboxymethyloxysuccinic acid salts used in the detergent mixtures according to the present invention have the following general formula

wherein M is a member of 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, sodium being the most preferred. The mono-, di- and trisodium salts can be used, the trisodium salt being the most preferred. A specific example of carboxymethyloxysuccinic acid salts that can be used is

Further other preferred organic building salts include 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 applications. The sodium alginate is also known as sodium polymannuronate. The polymannuronic acid may have a molecular weight of approximately 240,000.

The alginic acid is extracted from large brown seaweed (brown algae, macrocystis pyrifera (L:) Ag Lessoniaceae) in the form of mixed salts comprising the calcium and magnesium salts of alginic acid. The alginate salts can also be extracted from horsetail seaweed (Laminaria digitata (L.) Lamour, Laminariaceae) and sugar seaweed (Laminaria saccharina (L.) Lamour). The calcium and magnesium salts of alginic acid are readily converted to the alkali metal salts, particularly sodium alginate, by methods well known in the art. The sodium alginate is a cream-colored powder that is soluble in water.

A specific example of alkali metal salts of alginic acid that can be used is

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 building salts can consist of a copolymer which is the reaction product of approx. equal number of moles of methacrylic acid and maleic anhydride, which has been completely neutralized so that the sodium salt thereof is formed. The builder is commercially available under the trade name "Sokalan CP5". This build serves to inhibit crust formation, i.e. as an anti-crusting agent, even when used in small amounts.

As the mixtures according to the present invention are generally highly concentrated, and can therefore be used in relatively small dosages, it is desirable to supplement the builder with an auxiliary builder, such as an alkali metal salt of a lower polycarboxylic acid with a high calcium and magnesium binding capacity to inhibit crust formation as otherwise could be caused by the formation of insoluble calcium and magnesium salts. Suitable alkali metal salts of polycarboxyl acids are alkali metal salts of citric and tartaric acid, e.g. monosodium citrate (anhydrous), trisodium citrate, glutaric acid salt, gluconic acid salt and long chain diacid salt.

Examples of organic alkaline sequestrant builder salts that can be used together with the heptonate builder salts, the carboxymethyloxysuccinate builder salts or the alginate builder salts, or in admixture with other organic and inorganic builders,

are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, e.g. sodium and potassium ethylenediamine tetraacetate (EDTA), sodium and potassium nitriloacetates (NTA)

and triethanolammonium N-(2-hydroxyethyl)nitrile diacetates. Mixed salts of these aminopolycarboxylates are also suitable.

Other suitable builders of the organic type include carboxymethyl succinates, tetranates and glycolates.

Inorganic building salts

The detergent mixtures according to the invention may also comprise inorganic water-soluble and/or water-insoluble detergent building salts. Suitable inorganic alkaline building salts that can be used are alkali metal carbonates, borates, bicarbonates and silicates. Certain examples of such salts are sodium carbonate, sodium tetraborate, sodium bicarbonate, sodium sesquicarbonate and potassium bicarbonate.

The alkali metal silicates are useful building salts that also act to regulate or control pH, and to make the mixture anti-corrosive to washing machine parts. Sodium silicates with a Na20/SiO2 ratio from 1.6/1 to 1/3.2, especially approx. 1/2 to 1/2.8 is preferred. Potassium silicates in the same proportions can also be used.

Although it is preferred that the detergent mixture

is phosphate- or polyphosphate-free, or essentially poly-phosphate-free, small amounts of the usual polyphosphate-building salts can be added where the local legislation allows such use. Certain examples of such building salts are sodium tripolyphosphate (TPP), sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate and sodium hexametaphosphate. Sodium tripolyphosphate (TPP) is a preferred polyphosphate. In the mixtures where the poly-phosphate is added, it is added in an amount from 0 to 50%,

like for example. 0 - 39%, and 5 - 15%. As previously mentioned, however, it is preferred that the mixtures are polyphosphate-free or substantially polyphosphate-free.

Other typical suitable builders include e.g. those described in US Patent Nos. 4,316,812, 4,264,466

and 3,630,929. The inorganic alkaline builder salts can be used together with the nonionic surfactant detergent thor bond or in admixture with other organic or inorganic builder salts.

The water-insoluble crystalline and amorphous aluminum silicate zeolites can be used. The zeolites generally have the formula

where 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 2-3, and w is from 0 to 9, preferably 2.5 to 6, and M is preferably sodium. A typical zeolite is type A or a similar structure, ie

type 4A is particularly preferred. The preferred aluminum silicates have calcium ion exchange capacities of approx. 200 milliequivalents per g or more, e.g. 400 meq./g.

Various crystalline zeolites (ie aluminosilicates) which can be used are described in British Patent No. 1,504,168, US Patent No. 4,409,136 and Canadian Patent Nos. 1,072,835 and 1,087,477. An example of amorphous zeolites as here can be used, can be found in Belgian Patent Document No. 835,351.

Other materials such as clay substances, especially of the water-insoluble types, can be useful additives in the mixtures according to the invention. Bentonite is particularly useful. This material is primarily montmorillonite, which is a hydrated aluminum silicate where approx. one sixth of the aluminum atoms may be replaced by magnesium atoms,

and where varying amounts of hydrogen, sodium, potassium, calcium, etc. may be loosely associated. The bentonite in its more purified form (ie free of sandstone, sand, etc.) suitable for detergents contains at least 50% montomorrillonite and consequently its cation exchange capacity is at least approx. 50 - 75 sq.m. per 100 g bento

nit. Particularly preferred bentonites are Wyoming or Western US bentonites sold as "Thixo-gel" 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften textiles as described in British Patent Nos. 401,413 and 461,221.

Viscosity control and anti-gel agents

The incorporation into the detergent composition of an effective amount of low molecular weight amphiphilic compounds which act as viscosity control and gel inhibiting agents for the nonionic surfactant significantly improves the storage properties of the composition. The amphiphilic compounds can be considered to be analogous in chemical structure to the liquid non-ionic surfactants of the ethoxylated and/or propoxylated fatty alcohol type, but have relatively short hydrocarbon chain lengths (C2-Cg) and a low content of ethylene oxide (approx. 2-6 ethylene oxide groups per molecule).

Suitable amphiphilic compounds can be represented by the following general formula

where R is a C2-C8 alkyl group, and n is a number from approx. 1

to 6, on average.

The compounds are particularly lower (C-^-C^) alkylene glycol monolower (^2-C^) alkyl ethers.

More specifically, the compounds are mono-, di- or tri-lower (C 2 -C 1 ) alkylene glycol monolower (C 2 -C 1 ) alkyl ethers.

Certain examples of suitable amphiphilic compounds include

ethylene glycol monoethyl ether C2H5-0-CH2CH2OH,

diethylene glycol monobutyl ether C4H9"0-(CH2CH20)2H, tetraethylene glycol monobutyl ether C4H_,-0-(CH2CH20)4H and dipropylene glycol monomethyl ether CH^-O-(CH2CH0)2H

CH3

Diethylene glycol monobutyl ether is particularly preferred.

The inclusion in the mixture of the lower alkylene glycol monoalkyl ether of low molecular weight increases the viscosity of the mixture, so that it is easier to pour, improves the stability against sedimentation and improves the dispersibility of the mixture after addition to lukewarm water or cold water.

The mixtures according to the present invention have improved viscosity and stability properties, and remain stable and pourable at temperatures as low as approx. 5°C and lower.

Stabilizers

In one embodiment of the invention, the physical stability of the suspension of the detergent builder compound or compounds and any other slurried additives, such as bleach, etc., in the liquid carrier is improved by the presence of a stabilizer which is an alkanol ester of phosphoric acid, or an aluminum salt of a higher fatty acid.

Improvements in the stability of the mixture can be achieved in certain formulations by the incorporation of a small effective amount of an acidic organic phosphorus compound with an acidic POH group, such as a partial ester of phosphoric acid and an alkanol.

As described in US Patent Application No. 597,948, the acidic organophosphorus compound having an acidic PH group can increase the stability of the suspension of builders in the non-aqueous liquid non-ionic surfactant.

The acidic organic phosphorus-containing compound can e.g. be a partial ester of phosphoric acid and an alcohol, such as an alkanol which has a lipophilic character with e.g. more than 5 carbon atoms, e.g. 8-20 carbon atoms.

A specific example is a partial ester of phosphoric acid and

a C1_6-C18alkanol (Empiphos<®>5632 from Marchon) ; it consists of approx. 35% monoester and 65% diester.

The incorporation of very small amounts of the acid organophosphorus compound makes the suspension significantly more stable against sedimentation after standing, but it remains pourable, while its plastic viscosity due to the low concentration of stabilizer, e.g. under approx. 1%, generally will decrease.

Further improvements in the stability and anti-settling properties of the mixture can be achieved by adding a small effective amount of an aluminum salt of a higher fatty acid to the mixture.

The aluminum salt stabilizers are subject to

US Patent Application 725,455.

The preferred higher aliphatic fatty acids will contain from approx. 8 to approx. 22 carbon atoms, preferably from approx.

10 to 20 carbon atoms, and particularly preferably from approx. 12 more

18 carbon atoms. The aliphatic radical may be saturated or unsaturated, and may be straight chain or branched. As in the case of the nonionic surfactants, mixtures of fatty acids can also be used, such as those derived from natural sources, such as tallow fatty acid, coconut fatty acid, etc.

Examples of the fatty acids from which the aluminum salt stabilizers can be formed include decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicosanoic acid, tallow fatty acid, coconut fatty acid, mixtures of these acids, etc. The aluminum salts of these acids are generally commercially available, and are preferably used in the triacid form, e.g.

aluminum stearate as aluminum tristearate Al (C, -,H0 ,-COO) . Mono-

1 / Jb j the acid salts, e.g. aluminum monostearate, Al(OH)2 (C^H^COO)

and the diacid salts, e.g. aluminum distearate, Al(OH)(C^H^COO)2 i and mixtures of two or three of the mono-, di- and triacid aluminum salts can also be used. However, it is most preferred that the triacid aluminum salt comprises at least 30%, preferably at least 50%, particularly preferably at least 80%, of the total amount of aluminum salt of fatty acid.

As mentioned above, the aluminum salts are commercially available and can be easily prepared, e.g. by saponification of a fatty acid, e.g. animal fat, stearic acid, etc., followed by treatment of the resulting soap with alum, alumina, etc.

Although applicants do not wish to be bound by any particular theory as to the manner in which the aluminum salt acts to prevent settling of the suspended particles, it is believed that the aluminum salt increases the wettability of the solid surfaces by means of the nonionic surfactant. This increase in wettability therefore makes it

enabling the slurried particles to more easily remain in suspension.

Only very small amounts of the aluminum salt stabilizer are required to achieve significant improvements in physical stability.

In addition to its action as a physical stabilizer, the aluminum salt has the additional advantages over other physical stabilizers that it is non-ionic in nature and is compatible with the non-ionic surfactant and does not affect the overall detergency of the mixture; it exhibits some antifoam action; it can act to enhance the activity of fabric softeners and it gives the suspensions a longer relaxation time.

Bleaching agents

The bleaches are generally classified for convenience as chlorine bleaches and oxygen bleaches. Chlorine bleaches are exemplified by sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% available chlorine) and trichloroisocyanuric acid (95% available chlorine). Oxygen bleaches are preferred and are represented by compounds that release hydrogen peroxide in solution. Preferred examples include sodium and potassium perborates, percarbonates and perphosphates, and potassium monopersulfate. The perborates, especially the monohydrate of sodium perborate, are particularly preferred.

The peroxygen compound is preferably used in admixture with an activator. Suitable activators that can lower the temperature for effective action of the peroxide bleach are, for example, described in US Patent No. 4,264,466 or in column 1 of US Patent No. 4,430,244. Polyacetylated compounds

are preferred activators; among these, such compounds as tetraacetylethylenediamine ("TAED") and pentaacetylglucose are particularly preferred.

Other usable activators include e.g. acetyl-salicylic acid derivatives, ethylidene benzoate acetate and its salts, ethylidene carboxylate acetate and its salts, ethylidene carboxylate acetate and its salts, alkyl and alkenyl succinic anhydride, tetra-acetylglycouril ("TAGU") and their derivatives. Other useful classes of activators are described e.g. in US Patent Nos. 4,111,826, 4,422,950 and 3,661,789.

The bleach activator usually reacts with the peroxygen bond to form a peroxyacid bleach in detergents. It is preferred to incorporate a sequestering agent with high complexing strength to inhibit any unwanted reaction between the peroxyacid and the hydrogen peroxide in the washing solution in the presence of metal ions.

Suitable sequestering agents for this purpose include sodium salts of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DETPA), diethylenetriaminepentamethylenephosphonic acid (DTPMP) sold under the trademark Dequest<®>2066; and ethylenediaminetetramethylenephosphonic acid (EDITEMPA). The sequestering agents can be used alone or in combination.

To avoid loss of peroxide bleach, e.g. sodium perborate, due to enzyme-induced decomposition, such as in the case of catalase enzyme, the mixtures may additionally contain an enzyme inhibitor compound, i.e. a compound capable of inhibiting enzyme-induced decomposition of the peroxide bleach. Suitable inhibitor compounds are described in US Patent No. 3,606,990.

Of particular interest as an inhibitor compound, mention may be made of hydroxylamine sulfate and other water-soluble hydroxylamine salts. In the preferred non-aqueous mixtures according to the invention, suitable amounts of the hydroxylamine salt inhibitors can be as small as approx. 0.01 - 0.4%. In general, however, suitable amounts of enzyme inhibitors are up to approx. 15% by weight, e.g. 0.1 - 10%, of the mixture.

In addition to the detergent builders, various other detergent additives and auxiliaries may be present in the detergent product to give it additional desired properties, either of a functional or aesthetic nature. Thus, smaller quantities of anti-fungal or anti-redeposition agents may be included in the mixture, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethylcellulose, hydroxypropylmethylcellulose. A preferred anti-redeposition agent is sodium carboxymethylcellulose with a ratio of

2:1 between CM/MC sold under the trade name Relatin<®>

DM 4050.

Optical brighteners for cotton, polyamide and polyester fabrics can be used. Suitable optical brighteners include stilbene, triazole and benzidine sulfone mixtures, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole-stilbene, benzidine sulfone, etc., stilbene and triazole mixtures being most preferred. Preferred brighteners are stilbene "Brightener N4" which is a dimorpholinodianilinostilbenesulfonate and TinQpal<®>ATS-X which is well known in the art.

Enzymes, preferably proteolytic enzymes, such as subtilisin, bromelain, papain, trypsin and pepsin, as well as amylase type enzymes, lipase type enzymes and mixtures thereof can be used. Preferred enzymes include protease slurry, esperase slurry and amylase. A preferred enzyme is Esperase<®>S18 which is a protease. Anti-foam agents, e.g. silicone compounds, such as Silicane<®>L 7604, may also be added in small effective amounts.

Bactericides, e.g. tetrachlorosalicylanilide and hexa-chlorophene, fungicides, dyes, pigments (water-dispersant-only), preservatives, ultraviolet absorbers, anti-yellowing agents, such as sodium carboxymethyl cellulose, pH modifiers and pH buffers, colorfast bleaches, perfumes and dyes and bluing agents, such as ultra -navy blue, can be used.

The mixture may also contain an inorganic insoluble thickener or dispersant with a very high surface area, such as finely divided silica of extremely small particle size (eg, 5 - 100 µm in diameter, such as that sold under the name Aerosil<®>) or the other very bulky inorganic carrier materials which are described in US Patent No. 3,630,929, in proportions of 0.1 - 10%, e.g. 1-5%. However, it is preferred that mixtures which form peroxyacids in the washing bath (e.g. mixtures containing a peroxygen compound and an activator for this) are essentially free of such compounds and of other silicates; it is e.g. found that silica and silicates promote the undesirable decomposition of the peroxyacid.

In one embodiment of the invention, the stability of the building salts in mixtures during storage and the dispersibility of the mixture in water are improved by grinding and reducing the particle size of the solid builders to less than 100 µm, preferably less than 40 µm and preferably to less than 10 µm. The permanent builders, e.g. alkali metal polyphosphates, usually supplied in particle sizes of approx. 100, 200 and 400 µm. The phase with the non-ionic liquid surfactant can be mixed with the solid builders before or after the coating is carried out.

In a preferred embodiment of the invention, the mixture of liquid non-ionic surfactant and the solid components is subjected to an attrition type mill where the particle sizes of the solid components are reduced to less than approx. 10 µm, e.g. to an average particle size of 2-10 µm or even lower (eg 1 µm). Preferably has less than approx. 10%, especially less than approx. 5%, of all the suspended particles particle sizes greater than 10 µm. Mixtures with dispersed particles having such a small size have improved stability against separation or sedimentation during storage. Addition of the acid-terminated non-ionic surface-active compound improves the dispersibility of the dispersions without causing a corresponding reduction in the stability of the dispersions against sedimentation. During grinding, it is preferred that the proportion of solid components is sufficiently high (e.g. at least approx. 40%, such as approx. 50%) so that the solid particles are in contact with each other and do not separate from each other to any significant extent of the nonionic surfactant liq. After the grinding step, any remaining liquid non-ionic surfactant can be added to the grinding mixture. Mills that use grinding balls (ball mills) or similar moving grinding elements have given very good results. You can thus use a laboratory-scale attrition mill with 8 mm diameter grinding balls made of steatite. For work on a larger scale, a continuously acting mill can be used where there are grinding balls with a diameter of 1 mm or 1.5 mm that work in a very small opening between a stator and a rotor, and which work at a relatively high speed (f .eg a CoBall mill), and when such a mill is used it is desirable to first pass the mixture of non-ionic surfactant and solids through a mill which does not produce such a fine grinding (eg a colloid mill ) to reduce the particle size to less than 100 µm (eg to about 40 µm) before the step of grinding to an average particle diameter below about 10 um in the continuous ball mill.

In the preferred extra heavy duty liquid laundry detergent compositions according to the invention, typical proportions (percentage based on the total weight of the composition, unless otherwise stated) of the ingredients are as follows: Liquid non-ionic surfactant detergent in the range of approx. 10 or 20 to 60%, such as 20 or 25 - 50%, and 30 - 40%.

Acid-terminated non-ionic surfactant may be omitted, however, it is preferred that it is added to the mixture in an amount in the range of approx. 0 - 30%, such as 5 - 25% and 5 - 15%; carboxymethyloxysuccinic acid building salt in the range approx. 5 - 50%, such as 10 - 40% and 25 - 35%; or alginic acid building salt in the area of approx. 5 - 50%, such as 10 - 40% and 25 - 35%.

Heptonic acid building salt, carboxymethyloxysuccinic acid building salt or alginic acid building salt in the area approx. 5 - 50%, such as 10 - 40% and 25 - 35%.

Polyphosphate detergent building salt in the area approx. 0 - 50%, such as 0 - 30% and 5 - 15%.

Alkali metal salt of copolymer of polyacrylate and polymaleic anhydride as an anti-scaling agent in the area of approx. 0 - 10%, such as 2 - 8% and 2 - 6%.

Alkylene glycol monoalkyl ether as an antifreeze agent in an amount in the range of approx. 0 - 20%, such as 5 - 15% and 8 - 12%.

Phosphoric acid alkanol ester stabilizer in the range of 0 - 2.0% or 0.1 - 1.0%, such as 0.10 - 1.5%.

Aluminum salt of fatty acid as a stabilizer in the area approx. 0 - 3.0%, such as 0.1 - 2.0% and 0.5 - 1.5%.

It is preferred that at least one of the phosphoric acid ester or aluminum salt stabilizers is included in the mixture.

Bleach in the area approx. 0 - 35%, such as 5 - 30% and 8 - 15%.

Bleach activator in the area approx. 0 - 25%, such as

3 - 20% and 4 - 8%.

Sequestering agent for bleaching in the area approx. 0 - 3.0%, preferably 0.5 - 2.0% and 0.5 - 1.5%.

Anti-redeposition agent in the area approx. 0 - 3.0%, such as 0.5 - 2.0% and 0.5 - 1.5%.

Optical whitening agent in the area approx. 0 - 2.0%, such as 0.1 - 1.5% and 0.3 - 1.0%.

Enzymes in the area approx. 0 - 3.0%, such as 0.5 - 2.0%

and 0.5 - 1.5%.

Perfume 1 area approx. 0 - 2.0%, such as 0.10 - 1.0% and 0.5 - 1.0%.

Dye in the area approx. 0 - 1.0%, such as 0.0025 - 0.050% and 0.25 - 0.0100%.

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

Mixtures of the acid-terminated non-ionic surfactant and the alkylene glycol alkyl ether anti-gelling agents can be used and in some cases advantageously achieved by the use of such mixtures alone or together with the addition to the mixture of a stabilizing and anti-settling agent, e.g. alkanol esters of phosphoric acid.

When selecting the additives, they will be chosen so that they are compatible with the main components of the detergent mixture. As noted above, all proportions and percentages herein are based on the weight of the entire mixture unless otherwise indicated.

The concentrated non-aqueous non-ionic liquid detergent mixture according to the present invention is easily dispensed into the water in the washing machine. The home washing machines that are currently used use approx. 175 g or 250 g of powder detergent to wash an entire load of laundry. According to the present invention, only 77 ml or approx. 100 g of the concentrated liquid non-ionic detergent mixture.

In a preferred embodiment of the invention, a typical detergent mixture is formulated by using the following components:

The present invention is further illustrated by means of the examples below,

Sodium salt of heptonic acid

Example 1

A concentrated non-aqueous liquid non-ionic surfactant detergent mixture is formulated from the following ingredients in the amounts indicated.

The mixture is ground for approx. 1 hour to reduce the particle size of the slurried building salts to less than 40 µm. The prepared detergent mixture was found to be stable and non-gelling on storage and to have a high detergent capacity.

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

Example 2

To demonstrate the effect on scale formation by replacing sodium polyphosphate with an equivalent detergent builder amount of sodium heptonate, the detergent composition of Example 1 containing 28.7% by weight of sodium heptonate was compared in washing machine use with the same composition where the sodium heptonate had been replaced by 28.7% by weight sodium polyph osph at .

The washing cycles were carried out at concentrations of sodium heptonate and sodium polyphosphate detergent mixtures at laundry water concentrations of each of the detergent mixtures of 1 - 9 g/l of the respective detergent mixtures.

After 6 washing cycles with each detergent mixture had been used in a washing machine, the amount of encrustation obtained, i.e. the percentage of ash deposited, was measured. The measurement of deposited percent ash is determined by calcination of

washing samples.

The observed results are reproduced in the curve which

is illustrated in the drawing in Figure 1, and shows that at detergent mixture concentrations of 1 - 5 g/l wash water, sodium heptonate is significantly better than sodium polyphosphate when it comes to preventing crust formation or ash deposition. At concentrations of detergent mixture of approx. 5-9 g/l wash water, the behavior of sodium heptonate and sodium polyphosphate detergent builder salts is about the same in terms of anti-scaling properties.

Example 3

To demonstrate the effect on scale build-up of replacing sodium polyphosphate with an equivalent detergent builder amount of sodium heptonate, the detergent composition of Example 1 containing 28.7 wt. replaced with 28.7% by weight sodium polyphosphate.

The repeated wash cycles were carried out at concentrations of 5 g/l wash water of each of the detergent mixtures for 12 wash cycles. The crust build-up, i.e. percent ash build-up, was measured in each washing machine after 3, 6, 9 and 12 washes.

The results for crust formation that were obtained,

is reproduced in the curve illustrated in the drawing in figure 2. As regards the crust build-up, no build-up was observed with the sodium heptonate, while a small build-up was observed with the sodium polyphosphate detergent builder salt.

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

Trisodium salt of carboxymethyloxysuccinic acid

Example 4

A concentrated non-aqueous liquid non-ionic surfactant detergent composition was formulated from the following ingredients in the amounts indicated.

The mixture was ground for approx. 1 hour to reduce the particle size of the slurried building salts to less than 40 µm. The prepared detergent mixture was found to be stable and non-gelling on storage and to have a high detergent capacity.

The mixture exhibits a yield stress of 7.5 P.a. and an apparent viscosity of 0.4 P.a. S-l.

Example 5

To demonstrate the effect on encrustation of the replacement of sodium tripolyphosphate with an equivalent detergent builder amount of trisodium carboxymethyloxysuccinate, the detergent composition of Example 4 containing 29.6% by weight of trisodium carboxymethyloxysuccinate was compared in washing machine use with the same composition in which the trisodium carboxymethyloxysuccinate was replaced by 29.6% by weight sodium tripolyphosph at .

The washing cycles were carried out at concentrations of the trisodium carboxymethyloxysuccinate and sodium tripolyphosphate detergent mixtures at laundry water concentrations of each of the detergent mixtures of 1 - 9 g/l of the respective detergent mixtures.

After each detergent mixture was used in a washing machine, the resulting amount of encrustation, i.e., percent ash deposited, was measured. The measurement of the deposited percent ash was determined by calcination of washed samples.

The results that were observed are reproduced in the curve

which is illustrated in the drawing in Figure 3, and shows that with detergent concentrations of 1 - 5 g/l wash water, the tri-sodium carboxymethyl oxysuccinate is significantly better than sodium tripolyphosphat that when it comes to preventing crust formation or ash deposition. At detergent concentrations of approx. 5 - 9 g/l wash water, the behavior of trisodium carboxymethyloxysuccinate and sodium tripolyphosphate detergent builder salts was about the same with respect to the anti-scale properties.

Example 6

To demonstrate the effect on encrustation of replacing sodium tripolyphosphate with an equivalent detergent builder amount of trisodium carboxymethyloxysuccinate, the detergent composition of Example 4 containing 29.6 wt. 6% by weight sodium tripolyphosphate.

The repeated wash cycles were carried out at concentrations of 5 g/l wash water of each of the detergent mixtures for 12 wash cycles. The crust build-up, i.e. percent ash build-up, was measured in each washing machine after 3, 6, 9 and 12 washes.

The obtained results for crust formation are reproduced in the curve illustrated in the drawing in Figure 4. As regards the crust formation, no formation was observed with the trisodium carboxymethyloxysuccinate, while a small formation was observed with the sodium tripolyphosphate detergent builder salt.

The alkali metal carboxymethyloxysuccinate 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.

Sodium salt of alginic acid

Example 7

A concentrated non-aqueous liquid non-ionic surfactant detergent composition was prepared from the following ingredients in the indicated amounts.

The mixture was ground for approx. 1 hour to reduce the particle size of the slurried building salts to less than 40 µm. The prepared detergent mixture was found to be stable and non-gelling on storage, and to have a high detergent capacity.

The mixture exhibits a yield stress of 4.7 P.a. and

an apparent viscosity of 0.45 P.a. S-l.

Example 8

To demonstrate the effect on scale formation of the replacement of sodium tripolyphosphate with an equivalent detergent builder amount of sodium alginate, the detergent composition of Example 7 containing 29.6% by weight of sodium alginate was compared in washing machine use with the same composition where the sodium alginate had been replaced by 29.6% by weight sodium tripolyphosphate.

The wash cycles were carried out at concentrations of the sodium alginate and sodium tripolyphosphate detergent mixtures at fabric-wash water concentrations of each of the detergent mixtures of

1 - 9 g/l of the respective detergent mixtures.

After each detergent mixture was used in a washing machine, the resulting amount of encrustation, i.e., the percent ash deposited, was measured. The measurement of the deposited percent ash was determined by calcination of wash samples.

The observed results are reproduced in the curve illustrated in the drawing in figure 5, and show that at detergent mixture concentrations of 1 - 5 g/l washing water, sodium alginate is significantly better than sodium tripolyphosphate when it comes to preventing crust formation or ash deposition. At concentrations for detergent mixture of approx. 5-9 g/l washing water, the behavior of sodium alginate and sodium tri-polyphosphate detergent builder salts is approximately the same when

applies to anti-crust properties.

Example 9

To demonstrate the effect on scale formation of the replacement of sodium tripolyphosphate with an equivalent detergent builder amount of sodium alginate, the detergent composition of Example 7 containing 29.6 wt. with 29.6% by weight sodium tripolyphosphate.

The repeated wash cycles were carried out at concentrations of 5 g/l wash water of each of the detergent mixtures for 12 wash cycles. Crust build-up, i.e. percent ash build-up, was measured in each washing machine after 3, 6, 9 and 12 washes.

The obtained results for crust formation are reproduced in the curve illustrated in the drawing in Figure 6. As regards crust formation, practically no formation was observed with the sodium alginate, while a small formation 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 mixtures, and in aqueous and creamy detergent mixtures with good effect.

The mixtures according to examples 1, 4 and 7 can be prepared without grinding the building salts and the slurried solid particles to a small particle size, but the best results are obtained by grinding the mixture to reduce the particle size of the slurried solid particles.

The builder salts may be increased as provided, or the builder salts and the suspended solid particles may be ground or partially ground prior to mixing with the nonionic surfactant. The grinding can be carried out partially before mixing and the grinding is completed after mixing, or the whole grinding operation can be carried out after mixing with the liquid surfactant. The mixtures contain slurries and solid particles that are less than 100 µm or preferably less than 40 µm in size.

Claims (12)

1. Non-aqueous, liquid extra-power laundry detergent mixture, characterized in that it comprises at least one liquid non-ionic surfactant and an alkali metal salt of heptonic acid, a carboxymethyloxysuccinate or an alkali metal salt of alginic acid as building salt. 2. Detergent mixture according to claim 1, characterized in that it comprises at least one of the members from the group consisting of an acid-terminated non-ionic surfactant antigelling agent, an alkylene glycol monoether and an alkanol ester of phosphoric acid as stabilizer. 3. Detergent mixture according to claim 1, characterized in that it comprises 5 - 50% of an alkali metal salt of heptonic acid, a carboxymethyloxysuccinate or an alkali metal salt of alginic acid as detergent building salt. 4. Laundry detergent mixture according to claim 1, characterized in that it is polyphosphate-free or polyphosphate-poor, and comprises at least one liquid non-ionic surfactant in an amount of 25 - 50%, an acid-terminated non-ionic surfactant in an amount of 5 - 2 5%, an alkali metal salt of heptonic acid, a carboxymethyloxysuccinate or an alkali metal salt of alginic acid as building salt in an amount of approx. 10 - 40%, an alkylene glycol monoether in an amount of 5 - 15%, a polyphosphate detergent builder in an amount of 0 - 30%, and an alkanol ester of phosphoric acid in an amount of 0.1 - 1.0%. 5. Laundry detergent mixture according to claim 4, characterized in that it comprises an alkali metal perborate monohydrate bleaching agent in an amount of 5 - 30%, tetraacetylethylenediamine bleach activator in an amount of 3 - 20%, and optionally one or more detergent auxiliaries selected from the group consisting of anti-scale agent, anti-redeposition agent, sequestering agent for the bleach, optical brighteners, enzymes and perfume. 6. Detergent mixture according to claim 4, characterized in that the alkali metal salt of heptonic acid has the formula The carboxymethyloxysuccinate has the formula and the alkali metal salt of alginic acid is the sodium salt of alginic acid. 7. Laundry detergent mixture according to claim 4, characterized in that the alkanol ester of phosphoric acid comprises a C2. 6~ C18 alkane° ester of phosphoric acid. 8. Detergent mixture according to claim 4, characterized in that it comprises a polyphosphate builder salt in an amount of 5 - 15%. 9. Phosphate detergent builder-free, non-aqueous liquid extra powerful laundry detergent mixture, characterized in that it comprises 10. Phosphate detergent builder-free, non-aqueous liquid extra powerful laundry detergent mixture, characterized in that it comprises 11. Phosphate detergent builder-free, non-aqueous liquid extra powerful laundry detergent mixture, characterized in that it comprises 12. Detergent mixture according to claim 9, 10 or 11, characterized in that the mixture comprises an anti-redeposition agent and anti-scaling agent, and a sequestering agent for the bleaching agent.