NL8601998A - PHOSPHATE-LESS OR PHOSPHATE-FREE DETERGENT. - Google Patents

Description

'*' *? - VO 8317

Low-phosphate or phosphate-free detergent.

The invention relates to non-aqueous liquid compositions for the treatment of fabrics. The invention relates in particular to phosphate-free or low-phosphate, non-aqueous liquid laundry detergent compositions containing a suspension of a hepto-5-nate build-up salt, a carboxymethyl oxysuccinate build-up salt or an alginate build-up salt in nonionic surfactants, which compositions are stable to gel formation and easily pourable, as well as using these compositions for cleaning dirty fabrics.

Liquid non-aqueous laundry detergent compositions are well known. Compositions of that type may include, for example, a liquid nonionic surfactant in which particles of a builder salt are dispersed, as described, for example, in U.S. Patents 4,316,812, 3,630,929 and 4,264,466 and British Patents 1,205,711, 1,270,040 and 1,600,981.

Related U.S. patent applications pending and assigned to the applicant are Nos. 687,815 filed December 31, 1984, 597,793 filed April 6, 1984, 597,948 filed April 9, 1984, 725,455 filed April 22, 1985.

These patent applications are directed to liquid non-aqueous non-ionic laundry detergent compositions.

The washing power of synthetic nonionic surfactant detergents in detergents can be increased by adding builders. Sodium tripolyphosphate is a preferred builder salt. However, the use of sodium polyphosphate in dry powder detergents has several drawbacks, for example the tendency of the polyphosphates to hydrolyze to pyro and orthophosphates which are less valuable building materials.

In addition, the polyphosphate content of detergents can cause an undesirably high phosphate content in surface water. An increased phosphate content in surface water appears to promote algae growth, which can adversely change the biological balance of the water.

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Legislation in some countries is aimed at reducing the amount of polyphosphates in detergents and in some legislations detergents must not contain polyphosphate builders.

Liquid detergents are often considered easier to use than dry powdered or particulate products and are therefore favored by the consumer. They are easy to dose, dissolve quickly in the wash water, can be easily applied to dirty garments to be washed in concentrated solutions or dispersions and do not cause dust, and they usually take up less storage space. Furthermore, liquid detergents in their compositions may contain materials which cannot be dried without damage, while such materials are often just desired in the preparation of particulate detergent products. Although they have many advantages over unitary or particulate solid products, liquid detergents often also have certain drawbacks that must be overcome to obtain acceptable commercial detergent products. For example, some products show phase separation on storage and others on cooling, after which they cannot be easily redispersed. In some instances, the viscosity of the product changes, which either becomes too thick for pouring or so thin that it appears to be watery. When standing, some clear products become cloudy, while others gel.

Furthermore, the non-aqueous liquid detergents based on liquid non-ionic surfactants have the drawback that the non-ionic material has a tendency to gel when added to cold water. This is a particularly important problem in the ordinary use of European automatic household washing machines, where the user places the detergent in a dispenser (e.g. a dispenser drawer) of the machine. During the operation of the machine, the detergent 30 in the doser is exposed to a stream of cold water, which carries it to the main mass of the washing solution. Especially during the winter months, when the detergent composition and the water supplied to the doser are particularly cold, the viscosity of the detergent drops significantly and a gel forms. As a result, a portion of the composition is not completely rinsed out of the doser, so that a deposit of the composition is built up on repeated washes, 3 6.0 1 9 9 8 fc * -3-, so that ultimately the user dispenses the doser rinse with hot water.

Gelling can also be a problem when it is desired to perform the cold water wash, such as is recommended for certain synthetic and delicate fabrics or fabrics that can shrink in hot or hot water.

The tendency of concentrated detergent compositions to gel during storage is enhanced by storage of the compositions in unheated spaces or by transportation of the compositions during winter 10 months in unheated vehicles.

Partial solutions to the gel-forming problem in aqueous, substantially builder-free compositions have already been proposed, for example, diluting the liquid non-ionic material with certain viscosity-controlling solvents and gel-inhibiting agents, such as low alkanols, for example ethyl alcohol (see the

U.S. Patent 3,953,380), alkali metal formates and adipates (see U.S. Patent 4,368,147), hexylene glycol, polyethylene glycol and the like, and modification and optimization of the nonionic structure. A successful example of modification of a nonionic surfactant is acidification of the terminal hydroxy group-containing molecular portion of the nonionic molecule. The advantages of introducing a carboxyl group at the end of the nonionic molecule are inhibition of dilution gel formation, reduction of the pour point of the nonionic material and formation of an anionic surfactant upon neutralization in the wash. Optimization of the nonionic structure is directed to the chain length of the hydrophobic-lipophilic molecular moiety and the number of alkylene oxide (e.g., ethylene oxide) groups of the hydrophilic molecular moiety. For example, it has been found that a 30 C 3 fatty alcohol ethoxylated with 8 moles of ethylene oxide has only a limited tendency to gel.

Nevertheless, improvements are desirable in both the stability and the gel inhibition of low-phosphate and phosphate-free non-aqueous liquid compositions for the treatment of fabrics.

According to the invention, a highly concentrated phosphate-free, more in particular a polyphosphate-free, non-aqueous liquid detergent is

880 1 SH

? ? - Gentle laundry composition prepared by dispersing heptonate build-up salts, carboxymethyl oxysuccinate build-up salts or alginate build-up salts in a liquid nonionic surfactant detergent.

The heptonic acid salts used according to the invention are generally known. Heptonic acid is an acid derivative of an aldo-heptose (monosaccharide). The alkali metal salts of heptonic acid are water-soluble.

The alkali metal salts of heptonic acid used according to the invention comply with formula 1 (see formula sheet), in which M represents an alkali metal or ammonium cation.

The salts of carboxymethyloxy succinic acid used according to the invention are known. The alkali metal and ammonium salts of carboxymethyloxy succinic acid are water soluble. They satisfy the general formula 2, wherein M represents hydrogen, an alkali metal, such as sodium or potassium, or ammonium cation, at least one M being an alkali metal or ammonium cation.

The salts of alginic acid used according to the invention are generally known. The alginate is a seaweed polysaccharide extract. The alkali metal salts of alginic acid are water-soluble. The alginate is extracted from seaweeds in the form of mixed salts containing calcium and magnesium.

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

Bleaching agents and activators therefor can be added to improve the bleaching and cleaning properties of the composition.

In one embodiment of the invention, the build-up components of the composition are milled to a particle size of less than 100 µm, preferably less than 10 µm, to further improve the particle size. stability of the suspension of the build-up components in the liquid, non-ionic surfactant.

Furthermore, various other ingredients can be added to the composition, such as anti-crusting agents, anti-foaming agents, optical brighteners, enzymes, anti-redeposition agents, perfume and dyes.

Current household washing machines normally operate at washing temperatures up to 100 ° C. Up to 70 liters of water are used during the wash and rinse cycle 10, while about 175 g of powdered detergent is normally used per wash.

When the highly concentrated liquid detergent of the invention is used, normally only about 100 g (77 cm 3) or less of the liquid detergent composition is required to wash a full load of soiled laundry.

In one aspect, the invention provides a phosphate-free or substantially phosphate-free liquid detergent composition composed of a suspension of an alkali metal heptate build-up salt, an alkali carboxymethyl oxysuccinate build-up salt, or an alkali metal alginate build-up salt in a liquid nonionic surfactant.

In another aspect, the invention provides a phosphate-free or low-phosphate concentrated liquid detergent composition which is stable and which does not settle and form a gel during storage and use. The liquid compositions according to the invention are easy to pour, easy to dose and easy to place in the washing machine.

In another aspect, the invention provides a method of dosing a phosphate-free or low-phosphate liquid nonionic detergent in and / or with cold water without undergoing gel formation. In particular, a method is provided for filling a vessel with a non-aqueous liquid detergent composition, wherein the detergent is at least mainly composed of a polyphosphate-free liquid nonionic surfactant and for dispensing the composition from the detergent composition. vessel in an aqueous wash bath, the metering being effected by directing a stream of unheated water onto the composition such that the composition is fed through the stream of water into the wash bath.

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The polyphosphate-free detergent compositions of the invention eliminate the problem of surface water contamination with phosphate.

The polyphosphate-free or polyphosphate-poor concentrated non-aqueous liquid non-ionic surfactant detergent compositions according to the invention have the further advantages that they are stable and do not settle and gel on storage. The liquid compositions are easy to pour, easy to measure and can easily be placed in the washing machine.

An object of the invention is to provide a polyphosphate-low phosphate, in particular a polyphosphate-free, non-polluting liquid non-aqueous nonionic detergent composition containing a heptonate build-up salt, a carboxymethyl oxysuccinate build-up salt or an alginate build-up salt, suspended in a nonionic surfactant contains.

Another object of the invention is to provide a polyphosphate-free or low-polyphosphate liquid fabric treatment composition, which composition is a suspension of a heptonate build-up salt, carboxymethyl oxysuccinate build-up salt, or alginate build-up salt in a non-aqueous liquid and is stable in storage, easily 20 is pourable and dispersible in cold, warm or hot water.

A further object of the invention is to formulate a polyphosphate-free or polyphosphate-poor, highly built-up non-aqueous liquid nonionic surfactant detergent composition, which can be poured at any temperature and can be dispersed repeatedly from the dispenser of European automatic washing machines without contamination or blockage of the doser, even during the winter months.

Another object of the invention is to provide a polyphosphate-free or low-polyphosphate non-gelling stable suspension of a built-up non-aqueous liquid nonionic detergent composition containing an effective amount of a heptonate build-up salt, carboxymethyl oxysuccinate build-up salt or alginate build-up salt.

A further object of the invention is to provide non-gelling, stable suspensions of non-aqueous liquid non-ionic detergent compositions containing an amount of a phosphoric alkanol ester and / or aluminum fatty acid salt as an anti-settling agent, 8 5.0 1 9 9 8 mi -7- which amount is sufficient to increase the stability of the composition, i.e. sufficient to prevent reflection of build-up salt particles and the like, preferably while decreasing or at least without increasing the plastic viscosity of the composition, 5 and other objects of the invention, which will become apparent from the following description of preferred embodiments, are generally provided by preparing a polyphosphate-free or polyphosphate-free detergent composition by adding to the non-aqueous liquid nonionic surfactant an effect of active amount of an alkali metal heptate builder salt, a carbo xymethyl succinate builder salt or an alkali metal alginate builder salt, as well as inorganic or organic additives for tissue treatment, for example, viscosity improvers, anti-gelling agents, anti-settling agents, anti-crusting agents, bleaches, bleach activators, anti-foaming agents, optical brighteners, enzymes, anti-redeposition agents , perfume and dyes.

The nonionic synthetic organic detergents used in the present invention can be selected from a wide variety of such compounds which are well known.

As is known, nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group, and are typically prepared by condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature) . Practically any hydrophobic compound having a carboxyl, hydroxyl, amido or amino group with a free hydrogen bonded to the nitrogen can be condensed with ethylene oxide or with its polyhydration product, polyethylene glycol, to form a nonionic detergent.

The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups. Suitable non-ionic surfactants are described in U.S. Patents 4,316,812 and 3,630,929.

Usually, the nonionic detergents are poly-lower alkoxylated lipophiles in which the desired hydrophilic-lipophilic balance is obtained by addition of a hydrophilic poly-lower alkoxy group to a lipophilic molecular moiety. A preferred class of the sao19 ^ used? . 1-8 nonionic detergent is formed by the poly-lower alkoxylated higher alkanols, in which the alkanol contains 9-18 carbon atoms and in which the number of molecules of the lower alkylene oxide (having 2 or 3 carbon atoms) is 3-12. Preferably, such materials are used such that the higher alkanol is a higher fatty alcohol of 9-11 or 12-15 carbon atoms and contains 5-8 or 5-9 lower alkoxy groups per mole. Preferably, the lower alkoxy group is an ethoxy group, but in some cases the ethoxy group may be mixed with propoxy, which then, when present, often forms a minor (less than 50%).

Examples of such compounds are those in which the alkanol contains 12-15 carbon atoms and which contain about 7 ethylene oxide groups per mole, for example Neodol 25-7 and Neodol 23-6.5, which are marketed by Shell Chemical Company . Neodol 15 25-7 is a condensation product of a mixture of higher fatty alcohols having an average of 12-15 carbon atoms with about 7 moles of ethylene oxide; Neodol 23-6.5 is an analog mixture in which the carbon content of the higher fatty alcohol is 12-13 and the number of ethylene oxide groups present is on average about 6.5. The higher alcohol-20 caves are primary alkanols.

Other examples of such detergents are Tergitol 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates, sold by Union Carbide Corporation. Tergitol 15-S-7 is a mixed ethoxylation product of a linear secondary alkanol of 11-15 carbon atoms with 7 moles of ethylene oxide; Tergitol 15-S-9 is a similar product, but with 9 moles of ethylene oxide.

Also useful as a component of the nonionic detergent in the present composition are higher molecular weight nonionic materials, such as Neodol 45-11, which are condensation products of higher fatty alcohols having 14-15 carbon atoms and containing about 11 ethylene oxide groups per mole . These products are also marketed by Shell Chemical Company.

Other suitable nonionic materials are commercially available under the brand name Plurafac. These materials are reaction products of higher linear alcohols and mixtures of ethylene and propylene oxide; they contain a mixed chain of ethylene oxide and 86-0 1998-9 propylene oxide with a terminal hydroxyl group. Examples are Plurafac Ra30 (a C 1 -C 2 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide), Plurafac RA.40 (a C 1 -C 2 fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide 5 Plurafac D25 (a C 1 -C 2 fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide).

Another group of liquid nonionic materials is marketed by Shell Chemical Company under the brand name Dobanol: Dobanol 91-5 is an ethoxylated C.-C .. fatty alcohol with medium

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5 moles of ethylene oxide and Dobanol 25-7 is an ethoxyated C 12 -C 15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

To obtain the best balance of hydrophilic and lipophilic molecular moieties, the number of lower alkoxy groups is usually 40-100% by number of carbon atoms in the higher alcohol, preferably 40-60% thereof, and especially at least 50%. Higher molecular alkanols and various other normally solid nonionic detergents and surfactants may contribute to the gelation of the liquid detergent and are therefore preferably omitted or used in a limited amount at most, although minor amounts may be used in connection with their cleaning properties and the like. In the nonionic detergents, both preferred and less preferred, the alkyl groups present are generally linear, although some branching may be permitted, such as with a carbon atom next to or two carbon atoms away from the terminal carbon of the straight chain and away from the ethoxy chain, provided that such branched alkyl has a length of no more than three carbon atoms. Normally, the amount of carbon atoms in such a branched configuration is minor and rarely more than 20% of the total carbon atom content of the alkyl-30 group. Although linear alkyl groups terminally bonded to the ethylene oxide chains are particularly preferred and are believed to provide the best combination of detergent, biodegradability and non-gel-forming properties, medial or secondary bonding to the ethylene oxide can also occur in the chain. This is usually 35 in only a minor number of such alkyl groups, generally less than 20%, but the percentage may also be greater, such as those mentioned in the Tergitols. When propylene oxide is present in the lower alkylene oxide chain, it is usually in less than 20% thereof, preferably less than 10% thereof.

When larger amounts of non-terminal alkoxylated alkanols, propylene oxide-containing poly-lower alkoxylated alkanols and less hydrophilic-lipophilically balanced nonionic detergents than those mentioned above are used and when other nonionic detergents are used in place of the above mentioned non- Preferred ionic materials, the resulting product may not have the good detergent, stability, viscosity and non-gelling properties as the preferred compositions, but nevertheless the properties of detergents which are on such nonionic materials based, are improved by the viscosity and gel control compounds of the invention. In some instances, such as when a higher molecular weight poly-lower alkoxylated higher alkanol is used, often because of its detergent, the amount thereof can be regulated or limited by routine testing to obtain the desired detergent, while the product is then non-gelling and has the desired viscosity. It has also been found that it is only rarely necessary to use the higher molecular weight nonionic materials because of their detergent properties, as the preferred nonionic materials described herein are excellent detergents and additionally allow the desired viscosity in the liquid detergent without gel formation at low temperatures.

Another useful group of nonionic surfactants are the "Surfactant T" series of nonionic materials sold by British Petroleum.

The Surfactant T non-ionic materials are obtained by ethoxylation of secondary C 2-6 fatty alcohols without a narrow ethylene oxide distribution. Surfactant T5 contains an average of 5 moles of ethylene oxide; Surfactant T7 contains an average of 7 moles of ethylene oxide; Surfactant T9 contains an average of 9 moles of ethylene oxide and Surfactant T12 contains an average of 12 moles of ethylene oxide per mole of secondary C 2 fatty alcohol.

In the compositions of the invention, the preferred nonionic surfactants include the S δ-ο 1 9 S 8 -11-C12-C C-secondary fatty alcohols with about 7-9 moles of ethylene oxide and the CQ -C-fatty alcohols, ethoxylated with about 5-6 moles of ethylene oxide.

Mixtures of two or more liquid non-ionic surfactants can also be used and in some cases this even offers an advantage.

The viscosity and gelling properties of the liquid detergent compositions can be improved by including in the composition an effective amount of liquid nonionic surfactant with terminal acid group. These materials consist of a nonionic surfactant, which has been modified by converting a free hydroxyl group into a molecular moiety with a free carboxyl group, such as an ester or partial ester of a nonionic surfactant and a polycarboxylic acid or anhydride thereof.

As disclosed in U.S. Patent Application 597,948, filed April 9, 1984, the modified nonionic surfactants having free carboxyl group, which may be referred to as polyether carboxylic acids, lower the temperature at which the liquid nonionic material with a gel forms.

The addition of the nonionic surfactant with terminal acid group to the liquid nonionic surfactant promotes the dosability of the composition, i.e., pourability, and lowers the temperature at which the liquid nonionic surfactant in water gels without reducing stability against settling. The nonionic surfactant with terminal acid group reacts in the washing water with the alkalinity of the dispersed build-up salt phase of the detergent composition and acts as an effective anionic surfactant.

Specific examples are 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 thereof can also be used, for example maleic acid, maleic anhydride, citric acid and the like.

The nonionic surfactants with terminal acid group can be prepared as follows: 5501998 -12-

Plurafac 30 with terminal acid group. 400 g of Plurafac 30, a C 1 -C 2 -alcanol, which has been alkoxylated by introducing 6 ethylene oxide and 3 propylene oxide units per alkanol unit, is mixed with 32 g succinic anhydride and heated at 100 ° C for 7 hours. The mixture is cooled and filtered to remove unconverted succinic acid material. Infrared analysis shows that about half of the nonionic surfactant has been converted to its acidic half-ester.

Dabanol 25-7 with terminal acid group. 522 g Dobanol 25-7, the ethoxylation product of a C 1 -C 2 alkanol and about 7 ethylene oxide units per molecular alkanol, is mixed with 100 g succinic anhydride and 0.1 g pyridine (esterification catalyst) and left for 2 hours Heated at 260 ° C. The reaction product is cooled and filtered to remove unconverted succinic acid material. Infrared analysis shows that virtually all free hydroxy groups of the surfactant have reacted.

Dobanol 91-5 with terminal acid group. 1000 g Dobanol 91-5, the product of ethoxylation of a C 1 -C 3 -alkanol, which is about

7 -L-L

ethylene oxide units per molecule of alkanol, is mixed with 265 g of succinic anhydride and 0.1 g of pyridine catalyst, the mixture is heated at 260 ° C for 2 hours and then cooled and filtered to remove unconverted succinic acid material. Infrared analysis shows that virtually all free hydroxy groups have reacted.

Other esterification catalysts, such as an alkali metal alkoxide (eg sodium methoxide) can be used in place of or in conjunction with pyridine.

The acidic polyether compound, ie the nonionic surfactant with terminal acid group, is preferably added as a solution in the nonionic surfactant.

Fine particles of organic and / or inorganic detergent build-up salts are dispersed and suspended in the liquid non-aqueous nonionic surfactant used in the compositions of the invention.

An essential part of the composition according to the invention is an organic heptonate build-up salt, an organic carboxymethyl oxysuccinate build-up salt or an organic alginate build-up salt.

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

Other preferred organic builder salts are alkali metal or ammonium salts of carboxy methyl oxy succinic acid, preferably the trisodium salt.

The carboxymethyl oxysuccinates used in the compositions of the invention comply with the general formula 2, wherein M represents hydrogen or an alkali metal or ammonium cation, at least one M being an alkali metal or ammonium cation. The alkali metals are preferably sodium and potassium, with sodium being most preferred. The mono, di and trisodium salts can be used, preferably the trisodium salt.

A specific example of such salts is the compound of formula 3.

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

Alginic acid is extracted from giant brown seaweed (macro-25 cystis pyrifera (L.) Ag Lessóniaceae) in the form of mixed salts, including calcium and magnesium alginates. The alginate salts can also be extracted from horsetail (Laminaria digitata (L.) Lamour, Laminariaceae) and sugarweed (Laminaria saccharina (L-) Lamour). The calcium and magnesium alginates can easily be converted in known manner into alkali metal salts, in particular sodium alginate. Sodium alginate is a cream-colored powder that is soluble in water.

A specific example of alkali metal alginate is Manutex RH of Formula 4, wherein M represents sodium.

Other organic building materials which can be used are polymers and copolymers of polyacrylic acid and polymaleic anhydride and the alkali metal salts thereof. Such builder salts, in particular, consist of a copolymer, which is the reaction product of approximately equal molar amounts of methacrylic acid and maleic anhydride, which is completely neutralized to form its sodium salt. The builder is commercially available under the brand-5 name Sokalan CP5. This builder acts even in small quantities as an anti-crusting agent.

Since the compositions of the invention are generally highly concentrated and are therefore used in relatively small doses, it is desirable to supplement the builder with an auxiliary builder such as an alkali metal salt of a low polycarboxylic acid with high calcium binding capacity. and magnesium, which inhibits crusting that would otherwise be caused by the formation of insoluble calcium and magnesium salts. Suitable salts are the alkali metal salts of citric and tartaric acid, for example, monosodium 15 citrate (anhydrous), trisodium citrate, glutaric acid salts, gluconic acid salts and long chain diacid salts.

Examples of organic alkaline sequestering builder salts which can be used with the heptonate builder salts, carboxymethyl oxysuccinate builder salts or alginate builder salts, or mixed with other organic and inorganic builder salts are alkali metal, ammonium or substituted ammonium aminopolycarboxyl ethyl, e.g. (EDTA), sodium and potassium nitriloacetates (NTA) and triethanolammonium N- (2-hydroxyethyl) nitrilodia acetates. Mixed salts of these aminopolycarboxylates can also be used.

Other suitable organic builder salts are carboxymethyl succinates, tartranates and glycolates.

The compositions of the invention may also contain inorganic water-soluble and / or water-insoluble detergent build-up salts. Examples are the alkali metal carbonates, borates, bicarbonates and silicates. (Likewise, ammonium or substituted ammonium salts can be used.) Specific examples of such salts are sodium carbonate, sodium tetraborate, sodium bicarbonate, sodium sesquicarbonate, and potassium bicarbonate.

The alkali metal silicates are suitable builder salts, which can also adjust or control the pH and make the composition anti-corrosive for 8 S 0 1 Q Q 9 f * -15 washing machine parts. Sodium silicates with O / SiO2 ratios from 1.6 / 1 to 1 / 3.2, preferably about 1/2 to 1 / 2.8. Potassium silicates with the same proportions can also be used.

Although the detergent composition is preferably phosphate or polyphosphate-free or substantially polyphosphate-free, smaller amounts of conventional polyphosphate builder salts can be added, if local laws allow. Specific examples of such builder salts are sodium tripolyphosphate (TPP), sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate and sodium hexametaphosphate.

Sodium tripolyphosphate (TPP) is preferred. The polyphosphate is then added in an amount of 0-50%, such as 0-30% and 5-15%,

As mentioned previously, however, it is preferred that the compositions be polyphosphate free or substantially polyphosphate free.

Other suitable building materials are described, for example, in US Patents 4,316,812, 4,264,466 and 3,630,929. The inorganic alkaline build-up salts can be used alone or in admixture with other organic or inorganic build-up salts.

Water-insoluble crystalline and amorphous alumino-silicate zeolites can also be used. They generally have the formula 20 (M_0) · (Al.0_) · (SiO_) * wH_0 2x 2 3 y 2z 2 where x * 1, y = 0.8-1.2 and preferably = 1.z = 1.5-3.5 or higher and preferably = 2-3 and w = 0-9, preferably = 2.5-6, and M = preferably sodium. A typical zeolite is type A or analogous structure, with particular preference for type 4A. The preferred aluminosilicates have calcium ion exchange capacities of about 200 milliliters equivalent per gram or more, for example, 400 milliliters equivalent per gram.

Various crystalline zeolites (i.e., aluminosilicates) which can be used are described in British Patent 1,504,168, U.S. Patent 4,409,136, and Canadian Pat. Nos. 1,072,835 and 1,087,477. An example of suitable amorphous zeolites can be found in Belgian patent 835,351.

Other materials, such as clays, especially of the water-insoluble types, may be suitable adjuvants in compositions of the invention. Bentonite is particularly suitable. This mate- 860193? The material is mainly montmorillonite, which is a hydrated aluminum silicate, in which about 1/5 of the aluminum atoms can be replaced by magnesium atoms and with which varying amounts of hydrogen, sodium, potassium, calcium and the like can be loosely combined. Bentonite in its purer form (i.e., free from grit, sand and the like), which is suitable for detergents, contains at least 50% montorillonite and has a cation exchange capacity of at least about 50-75 milliequivalents per 100 grams of bentonite. Particularly preferred bentonites are the Wyoming or Western U.S. ben-10 tonites, produced by Georgia Kaolin Co. are marketed as Thixo gels 1, 2, 3 and 4. These bentonites can soften textiles, as described in British Pat. Nos. 401,413 and 461,221.

The inclusion in the detergent composition of an effective amount of low molecular weight amphiphilic compounds, which act as viscosity regulators and gel inhibitors for the nonionic surfactant, significantly improves the storage properties of the composition. The amphiphilic compounds may be considered analogous in chemical structure to the ethoxylated and / or propoxylated fatty alcohol liquid non-ionic surfactants, but have relatively short hydrocarbon chain lengths (C-CQ) and low Z ethylene oxide content (about 2-6 ethylene oxide groups per molecule).

Suitable amphiphilic compounds can be represented by the general formula

RO (CH CH-O) H

2 2 n where R represents a C 1 -C 8 alkyl group and n is a number having an average value of 1-6.

The compounds are in particular C 1 -C 2 -alkylene glycol mono-C 1 -C 2 -alkyl ethers.

More specifically, the compounds are mono-, di- or tri-C 2 -C 3 alkylene glycol mono-C 1 -C 8 alkyl ethers.

Specific examples of suitable amphiphilic compounds are ethylene glycol monoethyl ether C ^ E ^ -O-CE ^ CE ^ OE, diethylene glycol monobutyl ether C ^ H ^ -O- (CH2CH20) 2H, tetraethylene glycol monobutyl ether C4H7 ~ 0-35 (CH2CH20) 4H and dipropylene glycol monometh -O- (CH2C (CH2) HO) 2H.

Diethylene glycol monobutyl ether is particularly preferred.

8801998 4, -17-

The inclusion in the composition of such a low molecular weight alkylene glycol monoalkyl ether lowers the viscosity of the composition so that it is more pourable, improves settling stability, and improves dispersibility of the composition when added to hot water or cold water.

The compositions of the invention have improved viscosity and stability properties and remain stable and pourable at temperatures as low as about 5 ° C and below.

In one embodiment of the invention, the physical stability of the suspension of the detergent builder or substances and any other suspended additive, such as a bleach and the like, is enhanced in the liquid carrier by the presence of a stabilizing agent, being an alkanol ester of phosphoric acid or an aluminum salt of a higher fatty acid.

Improvements in the stability of the composition can be achieved in certain compositions by adding a small effective amount of an acidic organic phosphorus compound with an acidic POH group, for example, a partial ester of phosphoric acid and an alkanol.

As disclosed in US patent application 597,948, filed April 9, 1984, the acidic organic phosphorus compound having an acidic -POH group can increase the stability of the builder suspension in the non-aqueous liquid nonionic surfactant.

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

A specific example is a partial ester of phosphoric acid and a C 1 -C 3 -alkanol (Empiphos 5632, sold by Marchon);

Xo Xo 30 the product consists of about 35% monoester and 65% diester.

The addition of relatively small amounts of the acidic organic phosphorus compound makes the suspension considerably more stable against settling on standing, but the suspension remains pourable, while at the low stabilizer concentration, for example below about 1%, its plastic viscosity generally decreases .

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

The stabilizers based on aluminum salts are described in U.S. Patent Application 725,455, filed April 22, 1985.

The preferred higher aliphatic fatty acids have about 8-22 carbon atoms, preferably about 10-20 carbon atoms, especially about 12-18 carbon atoms. The aliphatic group can be saturated or unsaturated and branched or unbranched. Mixtures of fatty acids can also be used, such as derived from natural sources, such as tallow fatty acid, coco fatty acid, and the like.

Examples of fatty acids from which the aluminum salt stabilizers can be formed are decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicosanoic acid, tallow fatty acid, coco fatty acid, mixtures of such acids and the like. The aluminum salts of these acids are generally commercially available. They are preferably used in the triacid form, for example aluminum stearate as aluminum tristearate Al (CL_H._C00). The mono acid salts, 1 / Jb 3 for example aluminum monostearate, Al (OH) (C ^ H ^ COO) and diacid salts, for example aluminum distearate, Al (OH) (C ^ H COO) 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 accounts for at least 30%, preferably at least 50%, and especially at least 80%, of the total amount of aluminum fatty acid salt.

The aluminum salts are commercially available, but can also be easily prepared, for example, by saponification of a fatty acid, for example, animal fat, stearic acid and the like, followed by treatment of the soap formed with alum, alumina, and the like. Although it is not intended to bind the invention to any particular theory regarding the manner in which the aluminum salt prevents settling of the suspended particles, it is believed that the aluminum salt increases the wettability of the solid surfaces by the nonionic surfactant. This increased wettability allows the suspended particles to remain in suspension more easily.

86-0 19 PT.

-19-

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

Furthermore, the aluminum salt has the advantages over other physical stabilizers that it is nonionic, compatible with the nonionic surfactant and does not harm the total detergent of the composition. It exhibits some anti-foaming effect, can promote the activity of fabric softeners and gives the suspensions a longer relaxation time.

Bleaches are generally classified as chlorine bleaches and oxygen bleaches. Typical chlorine bleaches are sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% available chlorine) and trichloroisocyanuric acid (95% available chlorine). Oxygen bleaches are preferred and are represented by per compounds which release hydrogen peroxide in solution.

Preferred examples of oxygen bleaches are sodium and potassium perborates, percarbonates and perphosphates, and potassium monopersulfate. The perborates, in particular sodium perborate monohydrate, are particularly preferred.

The peroxygen compound is preferably used in combination with an activator therefor. Suitable activators, which can lower the effective working temperature of the peroxide bleach, are described, for example, in U.S. Patents 4,264,466 and 4,430,244 (column 1). Preferred activators are polyacetylated compounds; among them, compounds such as tetraacetylethylene diamine (TAED) and pentaacetyl glucose are particularly preferred.

Other examples of suitable activators are acetylsalicylic acid derivatives, ethylidene benzoate acetate and its salts, ethylidene carboxylate acetate and its salts, alkyl and alkenyl succinic anhydride, tetraacetyl glycouril (TAGU), and the derivatives thereof.

Other suitable classes of activators are described, 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 bleach 35 in the wash water. Preferably, a high complexing ability sequestrant is added to inhibit undesired reactions between the peroxide and hydrogen peroxide in the wash solution in the presence of metal ions.

Examples of suitable sequestrants for this purpose include sodium salts of nitrilotriacetic acid (NTA), ethylenediamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DETPA), diethylene triamine pentamethylene phosphonic acid (DTPMP) sold under the trade name Dequest 2066; and ethylenediaminetetramethylene phosphonic acid (EDITEMPA). The sequencing agents can be used alone or mixed with one another.

In order to prevent loss of peroxide bleach, eg, sodium perborate, due to enzyme-induced decomposition, eg, by catalase enzyme, the compositions may further contain an enzyme inhibitor compound, ie, a compound capable of inhibiting enzyme-induced decomposition of the peroxide bleach. -15 tars. Suitable inhibitor compounds are described in U.S. Patent 3,606,990.

Hydroxy amine sulfate and other water-soluble hydroxylamine salts can be mentioned as particularly important inhibitor compounds. Suitable amounts of the hydroxylamine salt inhibitors can be as low as about 0.01-0.4%. Generally, however, enzyme inhibitors can be used in amounts up to about 15%, for example 0.1-10%, by weight of the composition.

In the composition of the invention, various other additives or auxiliary substances may be present to impart further desirable properties to the composition, whether of a functional or aesthetic nature. For example, minor amounts of soil-suspending or anti-redeposition agents can be added, for example, polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxypropylmethyl cellulose. A preferred anti-redeposition agent is sodium carboxymethyl cellulose with a CM / MC ratio of 2: 1, marketed under the trade name Relatin DM 4050.

Optical brighteners for cotton, polyamide and polyester fabrics can also be used. Suitable optical brighteners are stilbene, triazole and benzidine sulfone compositions, especially 35 sulfonated substituted triazinyl stilbene, sulfonated naphthriazole stilbene, benzidene sulfone, and the like; most preferred are 8601998 »Λ -21- stilbene and triazole combinations. Preferred brighteners are stilbene Brightener N4, a dimorpholinodianilino stilbene sulfonate, and Tinapal ATS-X, which products are well known.

In addition, enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papain, trypsin and pepsin, as well as amylase and lipase type enzymes, as well as mixtures thereof, can be used. Preferred enzymes are protease suspension, esperase suspension and amylase. A preferred enzyme is Esperase SL8, a protease. Furthermore, anti-foaming agents, for example silicon compounds, such as Silicane L 7604 can be added in small effective amounts.

Further additives are bactericides, for example tetrachlorosalicylanilide and hexachlorophene, fungicides, dyes, pigments (dispersible in water), preservatives, ultraviolet absorbers, anti-yellowing agents, such as sodium carboxymethyl cellulose, pH modifiers and pH buffers, color-safe bleaching agents, perfume, dyes and bluing agents, such as ultramarine fowl.

The composition may also contain a very large surface inorganic insoluble thickener or dispersant, such as finely divided silica of extremely fine particle size (eg, with diameters of 5-100 millimicron, as marketed under the trade name Aerosil) or the other highly bulky inorganic support materials, described in U.S. Pat. No. 3,630,929, in amounts of 0.1-10%, e.g., 1-5%. Preferably, however, compositions that form peroxyacids in the wash water (e.g., compositions containing a peroxygen compound and an activator therefor) are substantially free of such compounds and of other silicates? For example, silica and silicates have been found to promote undesirable decomposition of the peroxyacid.

In an embodiment of the invention, the stability of the build-up salts in the composition during storage and the dispersibility of the composition in water are improved by grinding and reducing the particle size of the solid builders to less than 35 µm, preferably less 40 ym and in particular to less than 10 ym. The solid builders, for example, alkali metal polyphosphates, 85019 ° -22- are generally supplied in particle sizes of about 100, 200 or 400 µm. The nonionic liquid surfactant phase can be mixed with the solid builders before or after milling.

In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid ingredients is ground in a friction type mill, in which the particle size of the solid ingredients is reduced to less than about 10 µm, for example to an average particle size of 2-10 µm or even less (eg 1 µm). Preferably less than about 10%, especially less than about 5%, of all suspended particles has a particle size greater than 10 µm. Compositions in which the dispersed particles are of such small size have improved stability against settling on storage. Addition of a nonionic surfactant with an acidic terminal group promotes dispersibility without correspondingly reducing the stability of the dispersion against settling.

During grinding, the amount of solid ingredients is preferably sufficient (eg, at least about 40%, such as about 50%) to ensure that the solid particles are in contact with each other and are not separated by the nonionic surfactant liquid shielded. After grinding, any remaining amount of liquid nonionic surfactant can be added to the ground product. Mills, in which balls (ball mills) or analog mobile grinding elements are used, give very good results. For example, a laboratory mill with steatite balls with a diameter of 8 mm can be used. For larger scale work, a continuously operating mill can be used, in which balls with a diameter of 1 mm or 1.5 mm are present in a very small gap between a stator and a rotor rotating at a relatively high speed (eg a CoBall mill) ; if such a mill is used, it is desirable that the mixture of nonionic surfactant and solid material is first passed through a mill in which no such fine grinding is effected (eg a collold mill) for particle size reduction to less than 100 µm (eg, to about 40 µm), before the material is ground to an average particle diameter of less than about 10 µm in the continuous ball mill.

Preferred in the detergent compositions of the invention are typical amounts (in%, based on the total weight of the composition, unless otherwise stated) of the ingredients as follows: 5 Liquid non- ionic surfactant, 10 or 20 to 60%, such as 20 or 25 to 50%, especially 30 to 40%.

A nonionic surfactant with a terminal acid group can be omitted, but is preferably added in an amount of about 0 to 30%, such as 5 to 25%, especially 5 to 15%.

Carboxymethyl oxysuccinate build-up salt, 5 to 50%, such as 10 to 40%, especially 25 to 35%, or alginate build-up salt, 5 to 50%, such as 10 to 40%, especially 25 to 35%, or heptonate build-up salt, 5 to 50% such as 10 to 40%, especially 25 to 35%.

Polyphosphate build-up salt, 0 to 50%, such as 0 to 30%, especially 5 to 15%.

Copolymer of polyacrylate and polymaleic anhydride alkali metal salt anti-encrusting agent, 0 to 10%, such as 2 to 8%, especially 2 to 6%.

Alkylene glycol monoalkyl ether anti-gelling agent, 0 to 20%, such as 5 to 15%, especially 8 to 12%.

Phosphoric acid alkanol ester stabilizer, 0 to 2.0% or 0.1 to 1.0%, such as 0.10 to 0.5%.

Aluminum salt of fatty acid stabilizer, 0 to 3.0%, such as 0.1 to 2.0%, especially 0.5 to 1.5%.

Preferably at least one of the stabilizers phosphoric acid ester or aluminum salt is included in the composition.

Bleach, 0 to 35%, such as 5 to 30%, especially 8 to 15%.

Bleach activator, 0 to 25%, such as 3 to 20%, especially 4 to 8%.

Bleaching sequestrant, 0 to 3.0%, preferably 0.5 to 2.0%, especially 0.5 to 1.5%.

Anti-redeposition agent, 0 to 3.0%, such as 0.5 to 2.0%, especially 0.5 to 1.5%.

8601998 -24-

Optical brightener, 0 to 2.0%, such as 0.1 to 1.5%, especially 0.3 to 1.0%.

Enzymes, 0 to 3.0%, such as 0.5 to 2.0%, especially 0.5 to 1.5%.

Perfume, 0 to 2.0%, such as 0.10 to 1.0%, especially 0.5 to 1.0%.

Dye, 0 to 1.0%, such as 0.0025 to 0.050%, especially 0.25 to 0.0100%.

If desired, various of the aforementioned additives 10 can be added to perform their function.

Mixtures of the nonionic surfactant with a terminal acid group and the alkylene glycol alkyl ether anti-gelling agents can be used, and in some cases advantages can be achieved by using such mixtures alone or by adding to the mixture a stabilizing agent and anti-settling agent, for example phosphoric acid alkanol ester.

The additives should be chosen to be compatible with the main ingredients of the detergent composition.

In a preferred embodiment of the invention, the detergent composition is composed as follows:

Non-ionic surfactant 30-40 wt% surfactant with terminal acid group 5-15 wt% builder's salt: alkali metal heptate, alkali metal carboxymethyl oxysuccinate or alkali metal alginate 25-35 wt% 25 anti-encrustant (Sokalan CP-5) 0-10 wt% polyphosphate builder salt 0-30 wt% alkylene glycol monoalkyl ether 8-12 wt% phosphoric alkanol ester (Empiphos 5632) 0.1-0.5 wt% anti-redeposition agent (Relatin DM 4050) 0-3.0 wt% 30 alkali metal perborate bleach 8-15 wt% bleach activator (TAED) 4-8 wt% sequestrant (Dequest 2066) 0-3.0 wt% optical brightener (ATS-X) _ 0.05 or 0.3-1.0 wt % enzymes (Protease-Esperase SL8) 0.5-1.5 wt% perfume 0.5-1.0 wt% 8801938.

-25-

The invention is further illustrated by the following examples.

EXAMPLE I

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

A mixture of -C ^ fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide, and C ^ - C ^ - fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide 13.5 wt%

Surfactant T 7 10.0 wt%

Surfactant T9 10.0 wt%

Dobanol 91-5 with terminal acid group, reaction product with succinic anhydride 5.0 wt.% Sodium heptate 28.7 wt.% Diethylene glycol monobutyl ether 10.0 wt.% Phosphoric acid alkanol ester (Empiphos 5632) 0.3 wt.% Anti-encrusting agent (Sokalan CP -5) 4.0 wt% sodium perborate monohydrate, bleach 9.0 wt% sodium carbonate 0.9 wt% tetraacetylethylenediamine (TAED) bleach activator 4.5 wt% sequestrant (Dequest 2066) 1.0 wt% optical brightener (Tinopal ATS-X) 0.5 wt% anti-redeposition agent (Relatin DM 4050) 1.0 wt% Esperase suspension (Esperase SL8) 1.0 wt% perfume 0.5925 wt% dye 0, 0075 wt%.

100.00

The mixture was ground for about 1 hour, reducing the particle size of the suspended builder salts to less than 40 µm. The composition was found to be stable on storage and not to gel and to have a high detergent capacity.

EXAMPLE II

To demonstrate the effect of the replacement of sodium polyphosphate on an encrustation with an equivalent amount of sodium heptate 35, the composition of Example I, containing 28.7% w / w sodium heptate, was compared in a washing machine to the same composition, wherein 3 3 δ 1 9 However, the sodium heptate was replaced with 28.7% by weight sodium polyphosphate.

The wash cycles were performed at concentrations of both compositions in the wash water, ranging from 1 to 9 g / liter.

After 6 wash cycles with each of the two compositions, the amount of crusting, ie the percentage of ash deposited, was measured.

The percentage of ash deposited was measured by calcination of wax samples.

* The observed results are shown in the graph of Fig. 1. They show that at concentrations of the compositions of 1 to 5 g / liter wash water, the sodium heptate significantly prevents the crusting or deposition of ash over the sodium polyphosphate.

At concentrations of about 5 to 9 g / liter of wash water, both compositions behaved about the same in their anti-scaling properties.

EXAMPLE III

To demonstrate the effect of the replacement of sodium polyphosphate on an equivalent amount of sodium heptate on the rind construction, the composition of Example I, containing 28.7% w / w sodium heptate 20, was compared in repeated washing cycles in a washing machine with the same composition, however. sodium heptate was replaced by 28.7% by weight sodium polyphosphate.

12 wash cycles were performed with both compositions, each at a concentration of the composition in the wash water of 5 g / liter. The crust build-up, ie the percentage of ash build-up, was always measured after 3, 6, 9 and 12 washes.

The results are shown in the graph of Fig. 2. With regard to the crust build-up, no build-up was observed with the sodium heptate, while a low build-up was observed with the sodium polyphosphate.

The alkali metal heptate builder salts may also be used to replace, in whole or in part, the polyphosphate builder salts in powder detergent compositions and in aqueous and cream detergent compositions with good effect.

3501998 -27-

EXAMPLE IV

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

A mixture of -C1-fatty alcohol condensed with 7 Bral propylene oxide and 4 moles of ethylene oxide, and C 1 -C 2 fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide 13.5 wt%

Surfactant T 7 10.0 wt% 10 Surfactant T9 10.0 wt%

Dobanol 91-5 with a terminal acid group, reaction product with succinic anhydride 5.0 wt% trisodium salt of carboxymethyloxy succinic acid 29.6 wt% diethylene glycol monobutyl ether 10.0 wt% 15 phosphoric alkanol ester (Empiphos 5632) 0.3 wt% anti-encrusting agent (Sokalan CP-5) 4.0 wt% sodium perborate monohydrate, bleach 9.0 wt% tetraacetylethylenediamine (TAED) bleach activator 4.5 wt% sequestrant (Dequest 2066) 1.0 wt% optical brightener (Tinopal ATS- X) 0.5 wt% anti-redeposition agent (Relatin DM 4050) 1.0 wt%

Esperase suspension (Esperase SL8) 1.0 wt% perfume 0.5925 wt% dye 0.0075 cew% 100.00 The mixture was ground for 1 hour reducing the particle size of the suspended build-up salts to less than 40 µm . The composition was found to be stable on storage and not to gel and to have a high washing capacity.

EXAMPLE V

To evaluate the effect of the replacement of sodium tripolyphosphate by an equivalent amount of trisodium carboxymethyl oxysuccinate on the. to show crusting, the composition of Example IV, containing 29.6 wt. % trisodium carboxymethyl oxysuccinate, in a washing machine compared to the same composition, wherein the trisodium carboxymethyl-35 was oxysuccinate. replaced with 29.6 wt% sodium tripolyphosphate.

86-01 938 -28-

Each of the two compositions was tested at various concentrations of the composition in the wash water, ranging from 1 to 9 g / liter.

The results are shown in the graph of Figure 3 and show that at composition concentrations of 1 to 5 g / liter of wash water the tri-5 sodium carboxymethyl oxysuccinate significantly prevented crusting or ash deposition than sodium tripolyphosphate. At concentrations of about 5 to 9 g / liter of wash water, the trisodium carboxy methyl oxysuccinate and sodium tripolyphosphate behaved about the same in their anti-crusting properties.

EXAMPLE VI

To demonstrate the effect of replacing sodium tripolyphosphate with an equivalent amount of trisodium carboxymethyloxysuccinate on encrustation, the composition of Example IV, containing 29.6% by weight trisodium carboxymethyl oxysuccinate, was compared with the same composition in repeated washing cycles in a washing machine, wherein however the trisodium carboxymethyl oxysuccinate was replaced by 29.6% by weight sodium tripolyphosphate.

With each of the two compositions, 12 wash cycles were performed at a concentration of the composition in the wash water of 5 g / liter.

20 The short build, ie the percentage of ash build up, was measured in each washing machine after 3, 6, 9 and 12 washes.

The results are shown in the graph of Fig. 4. No crust build-up was observed with the trisodium carboxymethyl oxysuccinate, while low build-up was observed with the sodium tripolyphosphate.

The alkali metal carboxymethyl oxysuccinate build-up salts can also partially or fully replace the polyphosphate build-up salts in powder detergent compositions and in aqueous and cream detergent compositions with good effect.

EXAMPLE VII

From the following ingredients in the indicated amounts, a concentrated non-aqueous liquid nonionic surfactant detergent composition was formulated.

6601998 -29-

A mixture of C 1 -C 15 fatty alcohol, condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide, and C 1 -C 15 fatty alcohol, condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide 13.5% by weight 5 Surfactant T 7 10 .0 wt%

Surfactant T9 10.0 wt%

Dobanol 91-5 with a 2-hour end group, reaction product with succinic anhydride 5.0 wt% sodium alginate 29.6 wt% 10 diethylene glycol monobutyl ether 10.0 wt% phosphoric alkanol ester (Empiphos 5632) 0.3 wt% anti-encrusting agent (Sokalan CP-5) 4.0 wt% sodium perborate monohydrate, bleach 9.0 wt% tetraacetylethylenediamine (TAED) bleach activator 4.5 wt% 15 sequestrant (Dequest 2066) 1.0 wt% optical brightener (Tinopal ATS-X) 0.5 wt% anti-redeposition agent (Relatin DM 4050) 1.0 wt%

Protease (Esperase SL8) 1.0 wt% perfume 0.5925 wt% dye 0.0075 wt% 100.00

The mixture was ground for about 1 hour, reducing the particle size of the suspended build-up salts to less than 40 µl. The composition was found to be stable on storage and not to gel and to have a high washing capacity.

EXAMPLE VIII

To demonstrate the effect of replacing sodium tripolyphosphate with an equivalent amount of sodium alginate on crusting, the composition of Example VII, containing 29.6 wt% sodium alginate, was compared in a washing machine to the same composition, however, the sodium alginate being replaced with 29.6 wt% sodium tripolyphosphate.

Both cycles performed wash cycles at different concentrations ranging from 1 to 9 g of each composition per liter of wash water.

35 After each composition was used in a washing machine, the amount of crusting, i.e. the percentage of ash deposited, was 35-01938

v A

-30- measured. The percentage of ash deposited was measured by calcination of wax samples.

The results are shown in the graph of Fig. 5. They show that at composition concentrations of 1 to 5 g / liter wash water, the sodium alginate significantly inhibits crusting or ash deposition than the sodium tripolyphosphate. At concentrations of about 5 to 9 g / liter of washing water, the behavior of both build-up salts was approximately the same with regard to crusting.

EXAMPLE IX

To demonstrate the effect of replacing sodium tripolyphosphate with an equivalent amount of sodium alginate on the rind build, the composition of Example VII, containing 29.6 wt% sodium alginate, was compared with the same composition in repeated washing cycles in a washing machine, wherein however the sodium alginate was replaced with 29.6 wt% sodium tripolyphosphate.

12 wash cycles were performed at a concentration of the compositions in the wash water of 5 g / liter. The short build, i.e. the percentage of ash build up, was measured in each washing machine after 3, 6, 9 and 12 washes.

The results are shown in the graph of Fig. 6.

Virtually no short-build-up was observed with the sodium alginate, while low build-up was observed with the sodium tripolyphosphate.

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

The compositions of Examples I, IV and VII can be prepared without grinding the build-up salts and suspended solids to a small particle size, but the best results are obtained by grinding the composition to reduce the particle size of the suspended solid material.

8501993

Claims (15)

A non-aqueous liquid laundry detergent composition, characterized by at least a liquid nonionic surfactant detergent and an alkali metal heptate, a carboxymethyl oxysuccinate or an alkali metal alginate builder salt. Composition according to claim 1, characterized by a nonionic surfactant anti-gel-forming agent having an acid terminal group, an alkylene glycol monoether and / or a phosphoric acid alkanol ester stabilizing agent. Composition according to claim 1, characterized by 5 to 50% of an alkali metal heptate, carboxymethyl oxysuccinate or alkali metal buildinate salt. 4. Composition according to claim 1, which is polyphosphate-free or low-polyphosphate and characterized by at least one liquid non-ionic surfactant in an amount of 25 to 50%, a non-ionic surfactant with an acid terminal group in an amount from 5 to 25%, an alkali metal heptate, carboxymethyl oxysuccinate or alkali metal alginate build-up salt in an amount of 10 to 40%, an alkylene glycol monoether in an amount of 5 to 15%, a polyphosphate build-up salt in an amount of 0 to 20%, and a phosphoric acid alkanol ester from 0.1 to 1.0%. 5. A composition according to claim 4, characterized by an alkali metal perborate monohydrate bleach in an amount of 5 to 30%, a tetraacetyl ethylene diamine bleach activator in an amount of 3 to 20% and optionally one or more auxiliaries selected from anti-encrustants, anti-redeposition agents, bleach sequestrants, optical brighteners, enzymes, and perfume. 6. A composition according to claim 4, characterized in that the alkali metal heptate conforms to formula 5 (see formula sheet), the carboxymethyl oxysuccinate satisfies formula 3 and the alkali metal alginate is the sodium salt of alginic acid. Composition according to claim 4, characterized in that the phosphoric acid alkanol ester is a C 1 -C 6 alkanol ester of phosphoric acid. 16 18 860 1 9 Ö C -32- Composition according to claim 4, characterized by a polyphosphate build-up salt in an amount of 5 to 15%. 9. Non-aqueous liquid laundry detergent composition, free from phosphate build-up salt, characterized by a nonionic surfactant in an amount of 30 to 40%, a surfactant with an acidic terminal group in an amount of 5 to 15% sodium heptate in an amount of 25 to 35%, alkylene glycol monobutyl ether in an amount of 8 to 12%, C. -C. alkanol ester of phosphoric acid in an amount of 0.1 to 0.5%, sodium perborate monohydrate bleach in an amount of 8 to 15% and tetraacetylethylenediamine (TAED) bleach activator in an amount of 4 to 8%. 10. Non-aqueous laundry detergent composition, free of phosphate build-up salt, characterized by a nonionic surfactant in an amount of from 30 to 40%, a surfactant with a terminal acid group in an amount of 5 to 15%, trisodium -carboxymethyl oxysuccinate in an amount of 25 to 35%, alkylene glycol monobutyl ether in an amount of 8 to 12%, C 1 -C 3 alkanol ester of phosphoric acid in an amount of 0.1 to 0.5%, sodium 20 perborate monohydrate bleach in an amount of 8 to 15%, tetraacetylethylenediamine (TAED) bleach activator in an amount of 4 to 8%. 11. Non-aqueous liquid laundry detergent composition, free of phosphate build-up salt, characterized by a nonionic surfactant in an amount of 30 to 40%, a surfactant with an acidic terminal group in an amount of 5 to 15 %, sodium alginate in an amount of 25 to 35%, alkylene glycol monobutyl ether in an amount of 8 to 12%, C 1 g C 2 g alkanol ester of phosphoric acid in an amount of 0.1 to 0.5%, sodium perbo- 30 monohydrate bleach in an amount of 8 to 15%, tetraacetylethylenediamine (TAED) bleach activator in an amount of 4 to 8%. 12. A composition according to any one of claims 9, 10 or 11, characterized in that the composition contains an anti-redeposition agent and an anti-encrustation agent and a bleach sequestrant. 8801998 -33- Method for cleaning dirty fabrics, characterized in that the dirty fabrics are brought into contact with the composition according to claim 9. 14. Method for cleaning dirty tissues, characterized in. S that the soiled fabrics are brought into contact with the composition according to claim 10. Method for cleaning dirty tissues, characterized in that the dirty tissues are brought into contact with the composition according to claim 11. 10 2501998