SE468598B - PHOSPHATE-FREE OR PHOSPHATE-DETERGENT COMPOSITION AND ITS APPLICATION IN THE WASHING OF TEXTILES - Google Patents

Description

468,598 10 15 20 25 30 Closely related patent applications to the same applicant are U.S. Patent Application SN 687,815, filed December 31, 1984, USSN 597,793, filed April 6, 1984, USSN 597,948, filed April 9, 1984, and USSN 725,455, filed April 22, 1985.

These applications relate to liquid anhydrous nonionic detergent compositions.

The washing ability of synthetic nonionic surfactants in detergent compositions can be increased by the addition of builders. Sodium tripolyphosphate is one of the preferred builders. However, the use of sodium polyphosphate in dry powdered detergents entails several disadvantages such as e.g. the tendency of polyphosphates to be hydrolyzed to pyro- and orthophosphates, which are less valuable enhancers.

In addition, the polyphosphate content in detergents has been blamed for the undesirably high phosphate content in surface water. An increased phosphate content in surface water has been shown to contribute to increased algae growth, which results in the biological equilibrium of the water changing in a negative direction.

Legislation has recently focused on reducing the amount of polyphosphates contained in detergents, and in some areas where polyphosphates have been a problem, it is required that detergents do not contain any polyphosphate builders.

Liquid detergents are often considered more convenient to use than dry powdered or particulate products and are therefore of great benefit to consumers. They are easy to measure, they dissolve quickly in the washing water, they can easily be applied in concentrated solutions or dispersions to dirty areas on garments to be washed and they do not dust and usually take up less storage space.

In addition, the liquid detergents in their recipes may contain materials which cannot withstand drying operations without decomposition, which materials one would often like to use in the production of particulate detergent products. Although the liquid detergents have many advantages over solid or particulate solid products, the liquid detergents also have certain inherent disadvantages which must be overcome in order to produce commercially acceptable detergent products.

Thus, some such products separate out during storage and others separate out during cooling and they are not easily redispersible. In some cases, the product viscosity changes and the product becomes either too thick to be poured or so thin that it appears watery. Some clear products become cloudy and other gels during storage.

In addition to the problem of sedimentation or phase separation, the anhydrous liquid detergents based on liquid nonionic surfactants suffer from the disadvantage that the nonionic agents tend to gel when added to cold water.

This is a particularly important problem in the normal use of European automatic household washing machines, where the user places the detergent composition in a dosing unit (eg a dosing box) in the machine. During operation of the machine, the detergent in the dosing device is exposed to a stream of cold water for transferring the detergent to the washing solution. Especially during the winter months, when the detergent composition and the water fed to the dosing device are particularly cold, the detergent viscosity increases markedly and a gel is formed. As a result, part of the composition is not completely flushed out of the dosing device during operation of the machine and a deposit of the composition builds up during repeated washing cycles, which eventually requires the user to flush the dosing device with hot water.

The gelation phenomenon can also be a problem as soon as one wishes to carry out washing with cold water, which is recommended for certain synthetic and sensitive textiles or textiles that can shrink in hot or hot water.

The gelling tendency of the concentrated detergent compositions during storage is enhanced by storing the compositions in unheated storage spaces or by shipping the compositions during the winter months in unheated transport containers.

Various partial solutions to the gelation problem have been proposed, such as by diluting the liquid nonionic agent with certain viscosity controlling solvents and gel inhibitors, such as lower alkanols, e.g. ethyl alcohol (cf. U.S. Pat. No. 3,953,380), alkali metal formates and adipates (cf. U.S. Patent Nos. 4,368, 147), hexylene glycol, polyethylene glycol, etc., and by modifying and optimizing the nonionic structure. As an example of modification of nonionic surfactant, a particularly successful result has been obtained by acidifying the hydroxyl end group of the nonionic molecule. The benefits of introducing a carboxylic acid at the end of the nonionic agent include gel inhibition upon dilution, lowering of the pour point of the nonionic agent, and formation of an anionic surfactant upon neutralization in the wash liquor.

Optimization of the nonionic structure has centered on the chain length of the hydrophobic-lipophilic moiety and the number and composition of alkylene oxide moieties (eg, ethylene oxide) in the hydrophilic moiety. For example, it has been found that a C13 fatty alcohol ethoxylated with 8 moles of ethylene oxide shows only a limited tendency to gel.

Nevertheless, improvements are sought both in terms of the stability and gel inhibition of phosphate-poor and phosphate-free anhydrous liquid textile treatment compositions. In accordance with the present invention, a highly concentrated phosphate-poor and more specifically a polyphosphate detergent builder-free anhydrous liquid detergent composition is prepared by dispersing a hydroxyacrylic acid or hydroxyacrylic acid salt polymer builder or polyacetal carboxylic active carboxylic anergic carboxylic ester.

The hydroxyacrylic acid or hydroxyacrylic acid salt polymer detergent enhancers used in accordance with one embodiment of the present invention are well known. The method of preparing the hydroxyacrylic acid and hydroxyacrylic acid salt polymer and its use for stabilizing peracid and peroxyacid bleaches in detergent compositions are described in U.S. Pat. 4,450,089 and 4,455,249, and the disclosures of these two patents are incorporated herein by reference IQIIS.

The lower molecular weight hydroxyacrylic acid and hydroxyacrylic acid salt polymers are readily biodegradable. The hydroxyacrylic acid and hydroxyacrylic acid salt polymers are good bleach stabilizers and act as effective anticrusting agents. The hydroxyacrylate polymers are particularly good detergent builder salts due to their high sequestration capacity for calcium and magnesium ions in the wash water.

The hydroxyacrylate polymer used as a builder in accordance with the present invention contains monomeric units of the formula R OH 11 | CCII R2 COOM 468 10 15 20 25 30 \ 0 03 where R1 and R2 are the same or different groups and represent hydrogen or an alkyl group containing 1 to 3 carbon atoms, and M is hydrogen or an alkali metal, alkaline earth metal or ammonium cation. The degree of polymerization, i.e. the value of n, is generally determined by the limit which is compatible with the solubility of the polymer in water.

The polyacetal carboxylate salts used in accordance with another embodiment of the present invention are also well known. The method for preparing the amplifier salts is described in U.S. Pat. 4,315,092 and 4,144,226 and the use of the polyacetal carboxylates as detergent builder salts are described in U.S. Pat. 4, 146,495, and the disclosure of these three patents is incorporated herein by reference.

The polyacetal carboxylates are water-soluble and they are rapidly polymerized in neutral or non-alkaline medium to form low molecular weight components which are readily biodegradable. The polyacetal carboxylates are thus used in preparations which, when added to washing water, normally have a pH above pH 7, e.g. ca. pH 8 - 10, such as pH 9 - 10. Although the polyacetal carboxylates when used in an alkaline medium are effective detergent builder salts, the polyacetal carboxylates are depolymerized into small fragments that are readily biodegradable when the aqueous wash water is emptied into a sewer or other waste water. - tem and the washing water is neutralized. The polyacetal carboxylates are particularly good detergent builder salts due to their high sequestration capacity for calcium and magnesium ions in the wash water.

The polyacetal carboxylate detergent builder salts used in accordance with the present invention have the general formula R 15 in H 2 R 2 COOM D. where M is an alkali or ammonium cation, n is at least 4 and R 1 and R 2 are selected to be individual stable groups which stabilize the polymer against decomposition in alkaline solution and are selected to be compatible with the ingredients of the nonionic liquid detergent composition of the present invention. A commercially available polyacetal carboxylate detergent builder salt is sold by Monsanto Chemical Company under the trademark Builder U, which is a sodium salt.

To improve the viscosity properties of the composition, an acid-terminated nonionic surfactant may be added.

To further improve the viscosity and storage properties of the composition, viscosity improvers and anti-gelling agents such as alkylene glycol monoalkyl ethers and antisementing agents such as phosphoric acid esters and aluminum stearate may be added to the composition. According to a preferred embodiment of the invention, the detergent composition contains an acid-terminated nonionic surfactant and / or an alkylene glycol monoalkyl ether and an anti-sedimenting agent.

Sanitary or bleaching agents and activators can therefore be added to improve the bleaching and cleaning properties of the composition.

According to one embodiment of the invention, the enhancer components of the composition are ground to a particle size of less than 100 microns and preferably to below 10 microns to further improve the stability of the suspension of the enhancer components in the liquid nonionic surfactant detergent. 468 598 10 15 20 25 30 In addition, other ingredients may be added to the composition such as anti-decongestants, antifoams, optical brighteners, enzymes, antifoulants, perfumes and dyes.

Today's washing machines for home use normally work at washing temperatures of up to 95 ° C. About 75 liters of water were used during the washing and rinsing cycles. About 175 grams of powdered detergent is normally used per wash.

In accordance with the present invention, where the highly concentrated liquid detergent is used, normally only about 80 grams (67 ml) or less of the liquid detergent composition to wash a full load of dirty laundry.

Thus, according to one aspect of the present invention, there is provided a phosphate builder-free or substantially phosphate builder-free liquid high performance detergent composition composed of a suspension of an alkali metal hydroxyacrylate polymer builder or an alkali metal polyacetal liquid carboxylic acid non-carboxylic acid carboxylic acid.

According to another aspect of the invention, there is provided a phosphate-free or phosphate-poor concentrated liquid high performance detergent composition which is stable, non-sedimenting and non-gelling during storage and in use. The liquid compositions of the present invention are easy to pour, easy to measure and easy to insert into the washing machine.

According to another aspect of the invention there is provided a method of dosing a phosphate-free or phosphate-poor liquid nonionic detergent composition in and / or with cold water without undergoing gelation. More particularly, there is provided a method of filling a container with an anhydrous liquid detergent composition in which the detergent is at least predominantly composed of a polyphosphate builder-free liquid nonionic surfactant and for dosing the composition from the container into a aqueous washing bath, the dosing or feeding being effected by directing a stream of unheated water towards the composition so that the composition of the water stream is transported into the washing bath.

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

The polyphosphate-free or polyphosphate-poor concentrated anhydrous liquid nonionic surfactant detergent compositions of the present invention have the additional advantages of being stable, non-sedimenting and non-gelling upon storage. The liquid compositions are easy to pour, easy to measure and can be easily inserted into the washing machines.

An object of the present invention is to provide a phosphate-poor and more specifically a polyphosphate-free non-polluting liquid high-performance anhydrous nonionic detergent composition containing hydroxyacrylate polymer builder or polyacetal carboxylate builder salt suspended in a nonionic surfactant.

Another object of the invention is to provide polyphosphate-free or polyphosphate-poor liquid textile treatment compositions which are suspensions of hydroxyacrylate polymer builder or polyacetal carboxylate builder salt in an anhydrous liquid and which are storage stable, easily pourable or hot water dispersible, easily dispersible.

Another object of the invention is to formulate polyphosphate-free or polyphosphate-poor highly reinforced high-performance anhydrous liquid nonionic surfactant detergent compositions which can be maintained at all temperatures and which can be easily discharged from the dosing unit in European automatic washing machines without coating or clogging of the dosing device even during the winter months.

Another object of the invention is to provide polyphosphate-free or polyphosphate-poor non-gelling stable suspensions of a high performance reinforced anhydrous liquid nonionic detergent composition comprising an effective amount of a hydroxyacrylate polymer builder or a polyacetal carboxylate builder salt.

A further object of the invention is to provide non-gelling stable suspensions of a high performance enhanced anhydrous liquid nonionic detergent composition comprising an amount of phosphoric acid alkanol ester and / or aluminum fatty acid salt sufficient to increase the stability of the composition, i.e. prevent sedimentation of builder particles, etc., preferably while simultaneously reducing or at least without increasing the plastic viscosity of the composition.

These and other objects of the invention, which will become more apparent from the following detailed description of preferred embodiments, are achieved by an anhydrous liquid detergent composition comprising 20 to 60% of at least one liquid nonionic surfactant detergent, in 5 to 50% of an organic polyacetal carboxylate builder. salt, 2 - 30% of a polycarboxylic acid-terminated nonionic surfactant, and 10 - 2.0% of a stabilizing agent in the form of C 1-4 alkanol phosphoric acid ester.

The nonionic synthetic organic detergents utilized 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 are typically prepared by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (which is hydrophilic in nature). Virtually any hydrophobic compound having 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 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.

Typical suitable nonionic surfactants are described in U.S. Pat. 4,316,812 and 3,630,929.

Typically, the nonionic detergents are poly-lower alkoxylated lipophils, where the desired hydrophilic-lipophilic balance is achieved by adding a hydrophilic poly-lower alkoxy group to a lipophilic moiety. A preferred class of the nonionic detergent used is poly-lower alkoxylated-higher alkanol where the alkanol has 9 - 18 carbon atoms ooh where the number of moles of lower alkylene oxide (with 2 or 3 carbon atoms) is 3 - 12. Of these materials are it is preferred to use those in which the higher alkanol is a fatty alcohol having 9 to 11 or 12 to 15 carbon atoms and which contains from 5 to 8 or 5 to 9 lower alkoxy groups per mole. Preferably the lower alkoxy group is ethoxy but in some cases it is preferred that it be mixed with propoxy, the latter often present being a minor moiety (less than 50%).

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

Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates manufactured by Union Carbide Corp.

The former is a mixed ethoxylation product of a linear secondary alkanol having 11 to 15 carbon atoms with 7 moles of ethylene oxide and the latter is a similar product but reacted with 9 moles of ethylene oxide.

In the present composition, as a component of the nonionic detergent, also useful are higher molecular weight nonionic agents such as Neodol 45-111, which are similar to ethylene oxide condensation products of higher fatty alcohols, the higher fatty alcohol having 14 to 15 carbon atoms and the number of ethylene oxide groups per mole amounting to about . ll.

These products are also manufactured by Shell Chemical Company.

Other useful nonionic agents are represented by the commercially well known class of nonionic agents sold under the Plurafac brand. The plurafac agents are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide terminated by a hydroxyl group. Examples include products which are (A) C13-C15 fatty alcohol condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide, (B) C13-C15 fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide, (C) C13-C15 fatty alcohols alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide, and (D) a 1: 1 mixture of (B) and (C).

Another group of liquid nonionic agents is commercially available from Shell Chemical Company Incorporated under the trademark Dobanol: Dobanol 91-5 is an ethoxylated C9-C11 fatty alcohol having an average of 5 moles of ethylene oxide and Dobanol 25-7 is an ethoxylated C12-C15- fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

In the preferred poly-lower alkoxylated-higher alkanols, in order to achieve the best balance between hydrophilic and lipophilic units, the number of lower alkoxy groups usually amounts to 40 - 100% of the number of carbon atoms in the higher alcohol, preferably 40 - 60% thereof, and the nonionic the detergent preferably contains at least 50% of said preferred poly-lower alkoxy-higher alkanol. Higher molecular weight alkanols and various other normally solid nonionic detergents and surfactants can contribute to gel formation in the liquid detergent and are thus preferably omitted or limited in quantity in the present compositions, although smaller proportions thereof may be utilized for their cleaning properties, etc. With respect to both preferred and less preferred nonionic detergents, the alkyl groups present therein are generally linear although branching can be tolerated as in a carbon adjacent to or two carbon atoms from the straight chain end carbon and from the ethoxy chain, if this branched alkyl is not longer than 3 carbon atoms. Normally, the proportion of carbon atoms in such a branched configuration is a minor portion, which seldom exceeds 20% of the total carbon atom content of the alkyl group. Similarly, with the ethylene oxide chains being highly preferred and considered to be linear alkyls which are terminally linked starve in the best combination of cleaning ability, biodegradability and non-gelling properties, medial or secondary bonding to the ethylene oxide in the chain may occur. Usually this occurs only in a small proportion of said alkyls, usually less than 20%, but as in the case of the said Tergitols the proportion may be greater.

Also when propylene oxide is present in the lower alkylene oxide chain, the proportion is usually less than 20% thereof and preferably less than 10% thereof.

When larger proportions of non-terminally alkoxylated alkanols, propylene oxide-containing poly-lower alkoxylated alkanols and less hydrophilic-lipophilic balanced nonionic detergent than above are used, and when other nonionic detergents are used in place of the preferred nonionic agents set forth herein, the resulting the product exhibits a not as good cleaning ability, stability, viscosity and non-gelling properties as the preferred compositions, but use of the viscosity and gel controlling compounds of the invention can also improve the properties of the detergents based on such nonionic agents. In some cases, such as when a poly-lower alkoxylated-higher alkanol having a higher molecular weight is used, often for its cleaning ability, the proportion thereof is regulated or limited in accordance with the results obtained in routine experiments to achieve the desired cleaning ability and still maintain the product non-gelling and with the desired viscosity. It has also been found that it is only rarely necessary to utilize the higher molecular weight nonionic agents for their cleaning properties as the preferred nonionic agents described herein are excellent detergents and, moreover, allow the attainment of the desired viscosity of the liquid detergent without gelation at low temperatures.

Another useful group of nonionic surfactants is the "Surfactant T" series of nonionic agents available from British Petroleum. Surfactant T agents are prepared by the ethoxylation of secondary C13 fatty alcohols with a narrow ethylene oxide distribution. Surfactant T5 has an average of 5 moles of ethylene oxide, Surfactant T7 an average of 7 moles of ethylene oxide, Surfactant T9 an average of 9 moles of ethylene oxide and Surfactant T12 an average of 12 moles of ethylene oxide per mole of secondary C13 fatty alcohol.

In the compositions of the present invention, the preferred nonionic surfactants comprise the C13-C15 secondary fatty alcohols with a relatively narrow content of ethylene oxide in the range of about 7-9 mol, and the C9-C1 fatty alcohols ethoxylated with approx. 5 - 6 moles of ethylene oxide.

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

The viscosity and gel properties of the liquid detergent compositions can be improved by incorporating in the composition an effective amount of an acid-terminated liquid nonionic surfactant. The acid-terminated nonionic surfactants consist of a nonionic surfactant modified by converting a free hydroxyl group therein to a moiety having a free carboxyl group, such as an ester or a partial ester of a nonionic surfactant and a polycarboxylic acid or anhydride.

As described in U.S. Patent Application SN 597,948, filed April 9, 1984, the disclosure of which is incorporated herein by reference, the non-ionic surfactants modified with the free carboxyl group of the boxylene 59s 16, which can generally be characterized as polyethercarboxylic acids, so as to lower that temperature. in which the liquid nonionic agent forms a gel with water. The addition of the acid-terminated nonionic surfactants to the liquid nonionic surfactant contributes to the dosability (dispensability) of the composition, i.e. pourability, and lowers the temperature at which the liquid nonionic surfactants form a gel in water without lowering their stability to sedimentation.

The acid-terminated nonionic surfactant reacts in the washing machine water with the alkalinity of the dispersed builder salt phase in the detergent composition and acts as an effective anionic surfactant. Specific examples include the half esters of product (A) with succinic anhydride, the ester or half ester of Dobanol 25-7 with succinic anhydride and the ester or half ester of Dobanol 91-5 with succinic anhydride. Instead of succinic anhydride, other polycarboxylic acids or anhydrides may be used, e.g. maleic acid, maleic anhydride, citric acid and the like.

The acid-terminated nonionic surfactants can be prepared as follows: Acid-terminated product (A). 400 grams of product (A) nonionic surfactant, which is a C13-C15 alkanol alkoxylated to introduce 6 ethylene oxide and 3 propylene oxide units per alkanol unit, is mixed with 32 grams of sulfuric anhydride and heated for 7 hours at 100 ° C. The mixture is cooled and filtered to remove unreacted succinic acid material. Infrared analysis indicates that approx. half of the nonionic surfactant has been converted to its acidic half ester. 10 15 20 25 30 468 598 17 Acid-terminated Dobanol 25-7. 522 grams of Dobanol 25-7 nonionic surfactant, which is the ethoxylation product of a C12-C15 alkanol and has approx. 7 units of ethylene oxide per molecule of alkanol, mixed with 100 grams of succinic anhydride and 0.1 grams 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 indicates that essentially all of the free hydroxyl groups in the surfactant have been reacted.

Acid-terminated Dobanol 91-5. 1000 grams of Dobanol 91-5-nonionic surfactant, which is the ethoxylation product of a C9-C11 alkanol and has approx. 5 units of ethylene oxide per alkanol molecule, mixed with 265 grams of succinic anhydride and 0.1 gram of pyridine catalyst and heated at 260 ° C for 2 hours, cooled and filtered to remove unreacted succinic material. Infrared analysis indicates that substantially all of the free hydroxyl groups in the surfactant have been reacted. Other esterification catalysts such as 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 nonionic surfactant is preferably added dissolved in the nonionic surfactant.

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

The present invention includes as an essential part of the composition an organic hydroxyacrylic acid or salt polymer builder or an organic polyacetal carboxylate acid builder salt. 116 G 10 15 20 25 5 9E3 18 A preferred organic builder salt comprises alkali metal salts of hydroxyacrylic acid polymer, preferably the sodium and potassium salts. An especially preferred enhancer is the alpha-hydroxyacrylic acid and sodium salt polymers.

Briefly, the hydroxyacrylic acid and salt polymer detergent builder used in accordance with the present invention contains monomer units of the formula wherein R 1 and R 2 may be the same or different groups and represent hydrogen or an alkyl group containing 1 to 3 carbon atoms such as methyl. ethyl and propyl. Preferred substituents for R 1 and R 2 are for both hydrogen. M is hydrogen or an alkali metal such as sodium or potassium or an alkaline earth metal such as calcium, magnesium or barium. The preferred substituent for M is sodium. The terminal or end groups of the polymer are not critical and may be H, OH, CH 3 or a hydrocarbon chain.

The degree of polymerization, i.e. the value of n, is generally determined by the limit which is compatible with the solubility of the polymer in water.

The value of n may be 10 - 10,000, preferably 10 - 1,000 and more preferably 20 - 200. The hydroxyacrylic acid or salt polymer may have a molecular weight of 1,000 - 106, preferably 1.ooo - 105 and more preferably 2.ooo - 2o.ooo. Compare e.g. U.S. Pat. 3,920,570 and 4,07,411 which describe methods for preparing the polymers, and the disclosures of which are incorporated herein by reference.

Other preferred organic builder salts include alkali metal salts of polyacetal carboxylic acid, preferably the sodium and potassium salts.

In general, however, the polyacetalkarboxylate detergent builder salts used in accordance with the present invention have the following general formula R1 'HO R2 COOM n wherein M is selected from the group consisting of alkali metal, ammonium, alkyl groups having 1 to 4 carbon atoms, tetraalkylammonium groups and alkanolamine groups having 1 - 4 carbon atoms in the alkyl chain, with the alkali metals being preferred, e.g. sodium and potassium, n is at least 4, and R 1 and R 2 are individually any chemically stable groups. R1 and R2 can be the same or different groups. The end groups R1 and R2 can be selected from a wide range of materials as long as they stabilize the polyacetal carboxylate polymer against rapid depolymerization in an alkaline solution. The R 1 and R 2 end groups are also selected to be compatible with the ingredients used to prepare the anhydrous liquid nonionic composition of the present invention, in particular the nonionic surfactant and the anti-gel and anti-sedimenting agents.

The number of recurring groups, i.e. the value of n, is an important factor because the efficiency of the polyacetal carboxylate salt as a detergent enhancer is affected by the polymer chain length. When n is 4, the polymer exhibits effectiveness as a sequestering agent, chelating agent and enhancer.

O \ 03 10 15 20 25 30 \ O CO 20 The value of n can be as high as 400. However, no advantage seems to be achieved for n with a value greater than approx. 200.

When the value of n exceeds approx. 100, no significant improvement in sequestering, chelating and amplifying properties can be observed. Thus, the polyacetal carboxylate may contain between 10 and 400 units, i.e. n may be equal to 10 - 400, preferably n is equal to 50 - 200 and more preferably 50 - 100 recurring units.

When n has a value of 50 - 200, very good sequestration ability is obtained for calcium and magnesium ions and very good amplifier properties.

As an example, suitable chemically stable end groups include stable substituent units derived from otherwise stable compounds, such as alkanes, e.g. methane, ethane, propane and butane, alkenes such as ethylene, propylene and butene, branched chain hydrocarbons, both saturated and unsaturated, such as 2-methylbutane and 2-methylbutene, alcohols such as methanol, ethanol, 2-propanol, cyclohexanol, polyvalent alcohols such as 1,2-ethanediol and 1,4-benzenediol, ethers such as methoxyethane methyl ether, ethyl ether, ethoxypropane and cyclic ethers such as ethylene oxide, epichlorohydrin and tetramethylene oxide, aldehydes and ketones such as ethanal, acetone, propanal and methyl ethyl ketone content, and carboxylate content such as the alkali metal salts of carboxylic acids, esters of carboxylic acids and anhydrides. Particularly suitable end groups include alkyl groups and cyclic alkyl groups containing oxygen such as oxyalkyl groups such as methoxy, ethoxy, carboxylic acids, and aldehydes, ethers and other oxygen-containing alkyl groups.

The polyacetal carboxylates may contain polymer fragments and thus the polymer may be a linear homopolymer or copolymer or it may be branched. Any number of chain extenders can be copolymerized with the polyacetal carboxylates. It is only necessary that the chain extender provide at least two reactive sites and not cause depolymerization of the polyacetal carboxylates in alkaline solution and that they be compatible with the nonionic surfactant and anti-gel and anti-disintegrants of the present invention. Suitable chain extenders include: polyhydric alcohols such as ethylene oxide, propylene oxide and epihalohydrin epoxy succinates; aldehydes such as formaldehyde and acetaldehyde. It is particularly advantageous when the chain extender contains substituent carboxy groups. Aliphatic chain extenders having 1 to 4 carbon atoms such as ethylene oxide or propylene oxide are particularly preferred.

When acetalkarboxylate esters are copolymerized with a chain extender, the amount of acetalkarboxylate should be at least about 50% by weight, based on the total weight of the polymer, to ensure that the polymer efficiently sequesters calcium and magnesium ions and retains its builder properties. Preferably the amount of acetalkarboxylate is 50-80% by weight such as approx. 80% by weight, based on the total weight of the polymer, or higher.

According to a preferred embodiment of the invention, R 1 is selected from the group consisting of -OCH 3, -OC 2 5, Ho (cH 2 cH 2 O + ï_4 // CH 2 - CH 2 \\, H 3?, -? OOM - AND CH 2 RC- "CR \ II OíCH HCO COOM 2 5 2 22 and mixtures thereof, and R 2 is selected from the group consisting of - cH 3, - c 2 H 5, - (cH 2cH 2 O) -1-4f1, HC, CH _CH // 2 2 \\ RC- - CH CH 5 HCOO - CH2 and mixtures thereof, and R is hydrogen or an alkyl group having 1 to 8 carbon atoms, and M has the meaning defined above.

It is particularly preferred that R 1 is OCH 2 CH 3 or COOM I - CH 2 C - CH 3 Å I H 3 COOM or mixtures thereof, and R 2 is (1JCH 2 CH 3 --CH CH 3 where M is sodium and n is 50 - 200.

Other organic builders that can be used are polymers and copolymers of polyacrylic acid and polymaleic anhydride and its alkali metal salts. More specifically, these builder salts may consist of a copolymer, which is the reaction product of approximately equal moles of methacrylic acid and maleic anhydride, which has been completely neutralized to form its sodium salt. The amplifier is commercially available under the trademark Sokalan CP5. This amplifier works even when used in small quantities so that it prevents crusting. Since the compositions of the present invention are generally highly concentrated and therefore can be used in relatively low dosages, it is desirable to supplement the builder with an auxiliary builder such as an alkali metal lower polycarboxylic acid with high calcium and magnesium binding capacity for to inhibit crust formation, which would otherwise be caused by the formation of insoluble calcium and magnesium salts. Suitable alkali metal polycarboxylic acids are alkali metal salts of citric acid and tartaric acid, e.g. monosodium citrate (anhydrous), trisodium citrate, monosodium and disodium tartrate and dipotassium tartrate.

The alkali metal polyacetal carboxylic acid builder salts (eg, Builder U), also described herein, can be added to and used with the alkali metal hydroxyacrylic acid polymer builder.

Examples of organic alkaline sequestering builder salts which may be used with the hydroxyacrylic acid polymer builder or hydroxyacrylic acid salt polymer builder or with the polyacetal carboxylate builder salts of the present invention or in admixture with other organic and inorganic builders are ammonium alkyloalkyl amyloalkyl amylalkyl for example sodium and potassium ethylenediaminetetraacetate (EDTA), sodium or potassium nitriloacetates (NTA) and triethanolammonium N- (2-hydroxyethyl) nitrilodiacetates. Mixed salts of these aminopolycarboxylates are also suitable. Other suitable organic type builders include carboxymethyl succinates, tartronates and glycolates.

The detergent compositions of the invention may also include inorganic water-soluble and / or water-insoluble detergent builder salts. Suitable inorganic alkaline builder salts which may be used are alkali metal carbonate, borates, bicarbonates and silicates. (Ammonium or substituted ammonium salts can also be used.) Specific examples of such salts are sodium carbonate, sodium tetraborate, sodium bicarbonate, sodium sesquicarbonate and potassium bicarbonate.

The alkali metal silicates are useful builder salts, which can also be used to adjust or control the pH and make the composition anticorrosive to washing machine parts. Sodium silicates with Na2O / SiO2 ratios of from 1.6 / 1 to 1 / 3.2, especially approx. 1/2 - l / 2.8 are preferred.

Potassium silicates with the same conditions can also be used. Although it is preferred that the detergent composition be phosphate or polyphosphate free or substantially polyphosphate free, minor amounts of the conventional polyphosphate builder salts may be added where local laws allow such use. Specific examples of such builder salts are sodium tripolyphosphate (TPP), sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate and sodium hexametaphosphate. Sodium tripolyphosphate (TPP) is a preferred polyphosphate. In the formulations where the polyphosphate is added, this is added in an amount of 0 - 20 or 30%, such as 5 - 15. As previously mentioned, however, it is preferred that the formulations be polyphosphate free or substantially polyphosphate free.

Other typical suitable amplifiers include e.g. those described in U.S. 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 compound or in admixture with other organic or inorganic builder salts.

The water-insoluble crystalline and amorphous aluminosilicate zeolites can be used. The zeolites have the general formula (Mzmx- (A12o3) y- (S102) z-wnzo where x is 1, y is 0.8 - 1.2 and preferably 1, z is 1 , 5 - 3.5 or higher and preferably 2 - 3 and w is 0 - 9, preferably 2.5 - 6 and M is preferably sodium A typical zeolite is type A or similar structure with type 4A being particularly preferred. The aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents per gram or greater, eg 400 meq per gram.

Various crystalline zeolites (i.e., aluminosilicates) that can be used are described in GB Patent Nos. 1,504,168, U.S. Patent 4,409, 146 and Canadian Patents 1,072,835 and 1,087,477, all of which are incorporated herein by reference for description herein. An example of amorphous zeolites that can be used herein is found in Belgian Patent Specification 835.351 and this patent is also incorporated herein by reference.

Other materials such as clays, especially of the water-insoluble types, may be useful additives in compositions according to the invention. Particularly useful is bentonite. This material is primarily montmorillonite, which is a hydrated aluminum silicate in which approx. 1/6 of the aluminum atoms can be replaced by magnesium atoms and with which varying amounts of hydrogen, sodium, potassium, calcium etc. can be loosely combined. The bentonite in its more purified form (i.e. free from any gravel, sand, etc.) suitable for detergents contains at least 50% montmorillonite and thus its cation exchange capacity is at least approx. 50 - 75 meq. per 100 grams of bentonite. Particularly preferred bentonites are Wyoming or Western U.S. Pat. the bentonites, which have been sold as Thixojels 1, 2, 3 and 4 by Georgia Kaolin co. These bentonites are known to soften textiles, as described in British Pat. Nos. 401, 413 and 461, 221. The incorporation into the detergent composition of an effective amount of low molecular weight alkylene glycol monoalkyl ether amphiphilic compounds, which act as viscosity controlling and gel inhibiting agents for the nonionic surfactant, significantly improves the storage properties of the composition. The amphiphilic compounds can be considered analogous in chemical structure to the ethoxylated and / or propoxylated fatty alcohol-liquid nonionic surfactants, but have relatively short hydrocarbon chain lengths (C2 - C8) and a low content of ethylene oxide (about 2 - 6 ethylene oxide groups per molecular).

Suitable amphiphilic compounds can be represented by the following general formula RO (CH 2 CH 2 O) n H where R is a C 2 -C 8 alkyl group and n is a number of approx. 1 - 6, on average.

Specifically, the compounds are lower (C 2 -C 3) alkylene glycol mono-lower (C 2 -C 5) alkyl ethers.

More specifically, the compounds are mono-, di- or tri-lower (C 2 -C 3) alkylene glycol mono-lower (C 1 -C 5) alkyl ethers.

Specific examples of suitable amphiphilic compounds include ethylene glycol monoethyl ether C 2 H 5 -O-CH 2 CH 2 OH, diethylene glycol monobutyl ether C 4 H 9 O- (CH 2 GH 2 O) 2H, tetraethylene glycol monobutyl ether C 4 H 7 -O- (CH 2 CH 2 O 2 CH 2 O 2 CH

CH3 Diethylene glycol monobutyl ether is especially preferred. Incorporation into the composition of the lower alkylene glycol monoalkyl ether low molecular weight reduces the viscosity of the composition to make it easier to pour, improves stability against sedimentation and improves the dispersibility of the composition when added to hot or cold water.

The compositions of the present invention have improved viscosity and stability properties and remain stable and pourable at temperatures as low as approx. 5OC and lower.

According to one embodiment of the invention, the physical stability of the suspension of detergent builder compound or compounds and any other suspended additives such as bleaching agents, etc., in the liquid vehicle is improved by the presence of a stabilizing agent which is 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 some 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 U.S. Pat. 597,948, filed April 9, 1984, to the same assignee, the disclosure of which is incorporated herein by reference, the acidic organic phosphorus compound having an acidic POH group can increase the stability of the builder suspension in the anhydrous liquid nonionic surfactant.

The acidic organic phosphorus compound can e.g. be a partial ester of phosphoric acid and an alcohol such as an alkanol having a lipophilic character with e.g. more than 5 carbon atoms, e.g. 8 - 20 carbon atoms. 4 8 10 15 20 25 30 598 28 A specific example is a partial ester of phosphoric acid and a C16-C18 alkanol (Empiphos 5632 from Marchon), which is composed of approx. 35% monoester and 65% diester.

The incorporation of very small amounts of the acidic organic phosphorus compound makes the suspension significantly more stable against sedimentation during storage, but it remains pourable while for the low concentration of stabilizer, e.g. under approx. 1% its plastic viscosity is generally reduced.

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

Aluminum salt stabilizers are the subject of U.S. Patent Application No. 725,455, filed April 22, 1985 with the same applicant, the disclosure of which is incorporated herein by reference.

The preferred higher aliphatic fatty acids have approx. 8 - 22 carbon atoms, more preferably approx. 10 - 20 carbon atoms and especially preferred approx. 12 - 18 carbon atoms. The aliphatic radical may be saturated or unsaturated and may be straight or branched. As in the case of the nonionic surfactants, mixtures 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 available. and is preferably used in the triacid form, e.g. aluminum stearate as aluminum tristearate 10 15 20 25 30 468 598 29 Al (C17H35COO) 3. The monoacid salts, e.g. aluminum monostearated Al (OH) 2 (Cl7H35COO) and the diacid salts, e.g. aluminum distearate Al (OH) (C 17 H 35 COO) 2, and mixtures of two or three of the mono-, di- and trisic acid aluminum salts may also be used. However, it is most preferred that the tricurea aluminum salt constitutes at least 30%, preferably at least 50% and especially preferably at least 80% of the total amount of aluminum fatty acid salt.

The aluminum salts are, as mentioned above, commercially available and can be easily prepared by e.g. saponify a fatty acid, e.g. animal fat, stearic acid, etc., followed by treatment of the resulting soap with alum, alumina, etc. Although the applicant does not wish to be bound by any particular theory as to how the aluminum salt prevents sedimentation of the suspended particles, it is assumed that the aluminum salt increases the wettability of the solid surfaces of the nonionic surfactant. This increase in wettability therefore allows the suspended particles to more easily remain in suspension.

Only very small amounts of the aluminum salt stabilizer are required to achieve the 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 in that it is nonionic in nature and is compatible with the nonionic surfactant component and does not interfere with the overall cleaning ability of the composition. It shows some antifoaming effect, it can enhance the effectiveness of fabric softeners and it contributes to a longer relaxation time for the suspensions. Bleaches are generally discarded for convenience such as chlorine bleach and oxygen bleach. The chlorine bleaches can typically be sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% available chlorine), and trichloroisocyanuric acid (95% available chlorine). Oxygen bleaches are preferred and represented by percompounds which release hydrogen peroxide in solution. Preferred examples include sodium and potassium perborates, percarbonates and perphosphates, and potassium monopersulfate. The perborates, especially sodium perborate monohydrate, are particularly preferred. Per bleaching agents can also be used peroxyacid compounds such as diperoxyazelaic acid, diperoxydodecanedioic acid, monoperoxy succinic acid, monoperoxyphthalic acid (MPPA) and diperoxyterephthalic acid.

The peracid compound is preferably used in admixture with an activator therefor. Suitable activators that can lower the effective operating temperature of the peroxide bleach are described, for example, in U.S. Pat. No. 4,264,466 or in column 1 of U.S. Pat. 4,430,244, and the relevant parts thereof are incorporated herein by reference. Polyacylated compounds are preferred activators, and among these, compounds such as tetraacetylethylenediamine ("TAED") and pentaacetyl glucose are particularly preferred.

Other useful activators include e.g. acetylsalicylic acid derivatives, ethylidene benzoate acetate and its salts, ethylidene carboxylate acetate and its salts, alkyl and alkenyl succinic anhydride, tetraacetylglycouril ("TAGU") and their derivatives Other useful classes of activators are described, for example, in U.S. Pat. , 826, 4,422,950 and 3,66l, 789.

The bleach activator usually cooperates with the peracid compound to form a peroxyacid bleach in the wash water.

Preferably, a high complexing agent sequestering agent is incorporated to inhibit any undesirable reaction between said peroxyacid and hydrogen peroxide in the washing solution in the presence of metal ions.

Suitable sequestrants for this purpose include sodium salts of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DETPA), diethylenetriaminepentamethylenephosphonic acid (DTPMP), which is sold under ethylenequinamethylene. can be used alone or in admixture.

Sequestrants To avoid loss of peroxide bleach, e.g. sodium perborate, due to enzyme-induced decomposition such as by catalase enzyme, the compositions may additionally comprise an enzyme inhibitor compound, i.e. a compound capable of inhibiting enzyme-induced decomposition of the peroxide bleach. Suitable inhibitor compounds are described in U.S. Pat. 3,606,990, and the relevant disclosure thereof is incorporated herein by reference.

Of particular interest as an inhibitor compound are hydroxylamine sulfate and other water-soluble hydroxylamine salts. In the preferred anhydrous compositions of the present invention, suitable amounts of the hydroxylamine salt inhibitors may be as low as about 0.01 - 0.4%. In general, however, suitable amounts of enzyme inhibitors amount to approx. 15%, e.g. 0.1 - 10% by weight of the composition.

In addition to the detergent enhancers, various other detergent additives or aids may be present in the detergent product to impart this additional desired properties, of a functional or aesthetic nature. Thus, smaller preparations of soil suspending or anti-precipitating agents can be incorporated into the preparation, e.g. polyvinyl alcohol, fatty amides - hydroxypropyl methylcellulose. A preferred antifoulant sodium carboxymethylcellulose, precipitant is sodium carboxymethylcellulose having a CM / MC ratio of 2: 1, which is sold under the trademark Relatin DM 4050.

Optical brightness enhancer for cotton, polyamide and polyester fabrics can be used. Suitable optical brighteners include stilbene, triazaol and benzidine sulfone compositions, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzide sulfone, etc., with stilbone and triazole being most preferred. A preferred medium is brightness enhancer. Brightener N4, which is a dianilinodimorpholino stilbene polysulfonate. combinations.

Enzymes and preferably proteolytic enzymes such as subtilisin, bromelain, papain, trypsin and pepsin as well as amylase and lipase type enzymes and mixtures thereof may be used. Preferred enzymes include protease slurry, esperase slurry and amylase. A preferred enzyme is Esperase SL8 which is a protease. Antifoams, e.g. Silicone compounds such as Silicane L 7604, which is a polysiloxane can also be added in small effective amounts.

Bacterial sites, e.g. tetrachlorosalicylanilide and hexachlorophene, fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet absorbers, antifungal agents such as sodium carboxymethylcellulose, pH modifiers and pH buffers, and blueing agents such as ultramarine blue may be used. color-safe bleaches, perfumes and dyes The composition may also contain an inorganic insoluble thickener or dispersant with a very high surface area such as finely divided silica with extremely fine particle size (eg the name Aerosil) or other high volume inorganic carriers 5 - 100 nm diameter as sold under materials described in U.S. Pat. 3,630,929, in proportions 10 15 20 25 30 468 598 33 of 0.1 - 10%, e.g. l - 5%. However, it is preferred that compositions which form peroxyacids in the wash bath (eg compositions containing peracid compound and an activator therefor) be substantially free of such compounds and of other silicates as it has been found that e.g. silica and silicates promote the undesired decomposition of peroxyacid.

According to one embodiment of the invention, the stability of the builder 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 below 100 .mu.m, preferably below 40 .mu.m and more preferably to below 10 .mu.m. . The solid amplifiers are generally provided in particle sizes of approx. 100, 200 or 400 Pm. The nonionic liquid surfactant phase can be mixed with the solid enhancers before or after performing the grinding operation.

According to a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid ingredients is subjected to treatment in a friction type mill in which the particle sizes of the solid ingredients are reduced to below approx. 10 / um, e.g. to an average particle size of 2 - 10 μm or t.o.m. lower (eg 1 pm). Preferably less than approx. 10% and especially less than approx. 5% of all suspended particles particle sizes larger than 10 microns. Compositions whose dispersed particles are of such a small size have improved stability to separation or sedimentation during storage. Addition of the acid-terminated nonionic surfactant contributes to the dispersibility of the dispersions without a corresponding decrease in the stability of the dispersions against sedimentation.

During the grinding operation, it is preferred that the proportion of solid ingredients be high enough (eg at least about 40% such as about 50%) for the solid particles to be in contact with each other and not substantially protected from each other by the nonionic surfactant liquid. After the grinding step, any remaining liquid nonionic surfactant can be added to the ground preparation.

Grinders that use grinding balls (ball grinders) or similar mobile grinding elements have given very good results. Thus, a laboratory-type batch of 8 mm diameter steatite molecules can be used. For larger scale work, a continuously operating mill can be used in which 1 mm or 1.5 mm diameter grinding balls operate in a very small gap between a stator and a rotor operating at a relatively high speed (eg a CoBall mill). of such a grinder, it is desirable to first pass the mixture of nonionic surfactant and solid particles through a grinder which does not produce such a fine grind (eg a colloid grinder) to reduce the particle size to below 100. nn (eg to approx.

In use (40 μm) before the grinding step to an average particle diameter of approx. 10 / mn in the continuous ball mill.

In the preferred high performance liquid detergent compositions of the invention, typical proportions of the ingredients are as follows (percent based on the total weight of the composition, unless otherwise indicated): Liquid nonionic surfactant detergent in the range of 20-60, such as 25-50%.

Acid-terminated nonionic surfactant can be omitted Approx. but is preferably added to the composition in an amount in the range of approx. 2 - 30, such as 2 - 20 or 10 - 25%.

Hydroxyacrylic acid or salt polymer builder or polyacetal carboxylic acid builder salt in the range of approx. 5 - 50, such as 10 - 30%.

Polyphosphate detergent builder salt in the range of approx. 0 - 30%, such as 0 - 20% and 5 - 15%. 10 15 20 25 30 468 598 35 Copolymer of polyacrylate and polymaleic anhydride alkali metal salt as anticrusting agent in the range of approx. 0 - 10, such as 2 - 8%.

Alkylene glycol monoalkyl ether as anti-gelling agent can be omitted but is preferably added to the composition in an amount in the range of approx. 0 - 20, e.g. 5 - 30, such as 5 - 15 or 20%.

Phosphoric acid alkanol ester as a stabilizer in the range 0 - 2.0 or 0.1 - 2.0, such as 0.10 - 0.5 or 1.0%.

Aluminum salt of fatty acid stabilizer in the range of approx. 0 - 3.0, e.g. 0.5 - 2.0, such as 0.1 - 1.0%.

Preferably, at least one of the phosphoric acid ester or aluminum salt stabilizers is incorporated into the composition.

Bleach in the range of approx. 0 - 35, e.g. 5 - 40, such as 5 or 10 - 30%.

Bleach activator in the range approx. 0 - 25, e.g. 2 - 25, such as 5 - 20%.

Sequestrants for the bleach in the range of approx. 0 - 3.0, preferably 0.5 - 2.0%.

Anti-precipitating agents in the range of approx. 0 - 3.0, preferably 0.5 - 2.0%.

Optical brightness enhancer within the range of approx. 0 - 2.0, preferably 0.1 - 1.5%.

Enzymes in the range of approx. 0 - 3.0, preferably 0.5 - 2.0% can be incorporated.

Perfume in the range of approx. 0 - 2.0, preferably 0.10 - 1.0% can be incorporated.

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

Mixtures of the acid-terminated nonionic surfactant and the alkylene glycol alkyl ether antagonists may be used and in some cases benefits may be obtained by the use of such mixtures alone or by the addition to the mixture of a stabilizing and antisementing agent.

In the selection of the additives, these must be selected so that they are compatible with the main constituents of the detergent composition.

In this application, as mentioned above, all percentages and percentages express parts by weight of the total formulation or composition unless otherwise indicated.

The concentrated anhydrous nonionic liquid detergent composition of the present invention is rapidly and smoothly distributed in the water of the washing machine. Today's home washing machines normally use 175 grams of powdered detergent to wash a full load of laundry. In accordance with the present invention, only approx. 67 ml or approx. 80 grams of the concentrated liquid nonionic detergent composition.

According to a preferred embodiment of the invention, a typical composition of the detergent composition is composed of the following ingredients stated.

Alkali metal hydroxyacrylic acid polymer builder Weight% Nonionic surfactant detergent 30 - 55 Acid-terminated surfactant 1 - 10 Alkylene glycol monoalkyl ether 3 - 15 Hydroxyacrylate polymer 7 - 22 Alkanol phosphoric acid ester 0,1- 0,9 Alkali metal perborate bleach 0.6 Enzymes 0.5- 1.5 Perfume 0: 1- 0: 8 rJ 10 15 20 468 598 37 According to another preferred embodiment of the invention, the detergent composition having a typical composition is composed of the ingredients listed below: Alkali metal polyacetal carboxylic acid builder salt Weight-Q: Nonionic surfactant detergent 30 - 55 Acid-terminated surfactant 2 - 18 Alkali metal polyacetal carboxylic acid builder salt 5 - 22 Polyphosphate builder salt 0 - 20 Alkanol phosphoric acid ester 0,1- 0,9 Alkali metal perborate bleach 7 - 22 Bleach Nitride active agent , 1- 0.8 Enzymes (Protease-Esperase SL8) 0.5- 1.5 Perfume 0.1- 0.8 Present The invention is further illustrated by the following examples.

Example 1 A concentrated anhydrous liquid nonionic surfactant detergent composition is formulated from the following ingredients in the amounts indicated. 468 598 38% by weight Surfactant T9 20 Surfactant T7 20 Acid-terminated Dobanol 91-5 reaction product with succinic anhydride 4.0 Diethylene glycol monobutyl ether 10 Alpha-hydroxyacrylate polymer-sodium salt 17.0 Alkanol phosphoric acid ester 0.3 Sodium perborate monohydrate Tacetyl ether Ethyl ethate - average activator 10.0 Still life white matter 0.4 Esperase slurry 1.0 Parym 0.3 100.0 Exemgel 2 A concentrated anhydrous liquid nonionic surfactant detergent composition is formulated from the following ingredients in the amounts indicated. 20% by weight Product D nonionic surfactant 40.0 Acid-terminated Dobanol 91-5 reaction product with succinic anhydride 14.0 Sodium salt of polyacetal carboxylic acid 25 (Builder U) 17.0 Alkanol phosphoric acid ester 0.3 Sodium perborate monohydrate bleach 17.0 TetraacetylEDiamediamine bleach activator 10.0 30 Stilbene Brightener N4 0.4 Esperas slurry 1.0 Perfume __2¿§ 100.0 10 15 20 468 598 39 The preparations according to examples 1 and 2 are or can be ground for approx. 1 hour to reduce the particle size of the suspended builder salts to below 10 .mu.m. The formulated detergent compositions are stable and non-gelling during storage and have a high cleaning ability.

The formulations can be prepared without grinding the builder salts and suspended solids to a small particle size, but best results are obtained by grinding the formulation to reduce the particle size of the suspended solids.

The builder salts may be used in the form provided or the builder salts and suspended solids may be ground or partially ground before mixing with the nonionic surfactant. The grinding can be performed partially before mixing and the grinding can be completed after mixing or the entire grinding operation can be performed after mixing with the liquid surfactant.

The formulations of the present invention containing an alkali metal hydroxyacrylic acid polymer builder can be thickened with conventional thickeners such as bentonite and aerosil to form a cream or paste and used as a scouring agent.

Claims (17)

468 10 15 20 25 \ J 40 P a t e n t k r a v Anhydrous, liquid, high performance laundry detergent composition, characterized in that it comprises -20-60% of at least one liquid nonionic surfactant detergent, 5-50% of an organic polyacetal carboxylate builder salt, 2-30% of a polycarboxylic acid terminated nonionic active anti-gel agent, and 0 - 2.0% of a stabilizer in the form of C 2. A composition according to claim 1, characterized in that it comprises one or more detergent additives selected from the group consisting of bleach, bleach activator, optical brightener, enzymes and perfume. A composition according to claim 1 or 2, wherein it comprises 10 - 30% of the polyacetal carboxylate builder salt. k ä n n e t e c k - Composition according to any one of the preceding claims, characterized in that it comprises 10 - 25% of the polycarboxylic acid-terminated anti-gel surfactant. Composition according to any one of the preceding claims, characterized in that it comprises 0.1 - 2.0% of said C8-C20-alkanol phosphoric acid ester in the form of a C6-C18-alkanol phosphoric acid ester. Composition according to any one of the preceding claims, characterized in that the polyacetal carboxylate has the formula: wherein M is selected from the group consisting of alkali metal, ammonium, alkyl groups having 1 to 4 carbon atoms, tetraalkylammonium groups and alkanolamine groups having 1 to 4 carbon atoms in the alkyl chain, n is at least 4, and R 1 and R 2 are selected so as to be individually stable groups which stabilize the polymer against depolymerization in alkaline solution and are compatible with the ingredients of the nonionic liquid detergent composition. Composition according to any one of the preceding claims, characterized in that the detergent builder particles in the nonionic surfactant have such a particle size distribution that no more than about 10% by weight of the particles have a particle size larger than about 10 p.m. Composition according to any one of the preceding claims, characterized in that it is polyphosphate-free or polyphosphate-poor and comprises about 25 - 50% of the liquid nonionic surfactant, about 10 - 25% of the acid-terminated nonionic surfactant, about 10 - 30% of the polyacetalkarboxylate builder, 0 - 20% of the polyphosphate detergent builder and about 0.1 - 1,0% of the alkanol phosphoric acid ester. Composition according to any one of the preceding claims, characterized in that it further comprises an alkali metal perborate monohydrate bleach in an amount of about 5 - 30%, tetraacetylethylenediamine bleach activator in an amount of about 5 - 20% and one or more detergent additives selected from the group consisting of optical brighteners, enzymes and perfumes. 4682598 qa 10 15 20 25 Composition according to any one of the preceding claims, characterized in that the detergent builder comprises the sodium salt of said polyacetal carboxylic acid. ' 11. ll. Composition according to any one of claims 6 to 10, characterized in that in the polyacetal carboxylate of the formula: R1 CHO R COOM M is an alkali metal and n is 50 - 200. Composition according to any one of the preceding claims, characterized in that the alkanol phosphoric acid ester comprises a C16-C18 alkanol ester of phosphoric acid. 13. l3. Composition according to any one of the preceding claims, characterized in that it comprises a polyphosphate builder salt in an amount of about 5 - 15%. 14. l4. Phosphate detergent builder anhydrous liquid high performance laundry detergent composition, characterized in that it comprises nonionic surfactant in an amount of about 30 - 45%, polycarboxylic acid terminated surfactant in an amount of about 2 - 18%, sodium salt of polyacetal carboxylic acid about 5 - 22%, C16-C18 alkanol ester of phosphoric acid in an amount of about 0.1 - 0.9%, sodium perborate monohydrate bleach in an amount of about 7 - 22%, and tetraacetylethylenediamine (TAED) bleach activator in an amount of about 4 - 12%. Composition according to Claim 14, characterized in that the polyacetal carboxylate has the formula: wherein R 1 is selected from the group consisting of sodium and potassium, n is 50 - 200, R 1 is OCH 2 CH 3 or COOM "CIH -Cl 'CH3 CH3 COOM or mixtures thereof and R2 is OCHZCH I CH 3 CH3 and that the polyacetal carboxylate segments comprise 50 - 80% by weight of the total polyacetal carboxylate. 16. A composition according to claim 15, characterized in that the polyacetal carboxylate is the sodium salt. Use of a composition according to any one of claims 1 - 16 for cleaning soiled textiles, wherein said soiled textiles are brought into contact with said composition.