LU86558A1 - NON-AQUEOUS LAUNDRY LIQUID DETERGENT COMPOSITIONS AND METHODS FOR CLEANING DIRTY TISSUES USING THE SAME - Google Patents

Description

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The present invention relates to non-aqueous liquid compositions for the treatment of tissue. More particularly, the present invention relates to non-aqueous liquid detergent compositions without phosphate or with low phos content for laundry laundering, containing a suspension of a polymer of hydroxy acrylic acid or a salt of a such acid as detergent builder or a polyacetalcarboxylate as builder detergency salt in nonionic surfactants, which / compositions are stable with respect to phase separation and gelling and can easily be and the use of these compositions for cleaning soiled fabrics.

Liquid non-aqueous detergent compositions for heavy laundering are well known in the art. For example, compositions of this type may include a nonionic liquid surfactant in which particles of a detergency builder are dispersed, as described, for example, in U.S. patents. N * 4 316 812, N * 3 630 929 and N * 4 264 466 and in the British patents N * 1 205 711, N * 1 270 040 and ΙΓ 1 600 981.

The U.S. Patent No. 4,450,089 discloses a particulate bleach detergent composition comprising an inorganic bleach of the pe-oxygenated type and a hydroxy acrylate polymer to stabilize the bleach, and the U.S. Patent. No. 4,445,249 describes a detergent composition for particulate bleaching comprising an organic bleaching agent of the peroxyacid type and a hydroxy-acrylate polymer for stabilizing the bleaching agent.

The U.S. Patent No. 3,825,498 describes in i 2 the use of a polyhydroxycarbo-xylic acid polymer as a substitute for adjuvant detergents of the phosphate or polyphosphate type used in aqueous or particulate powdered detergent compositions for washing dishes.

The U.S. Patent No. 3,706,672 and the U.S. Patent No. 3,922,230 describe the use of polyacrylic polymers as substitutes for adjuvant detergency salts of the phosphate or polyphosphate type in detergent compositions.

The cleaning power of synthetic nonionic surfactant detergents of laundry detergent compositions can be increased by the addition of detergency builders. Sodium tripolyphosphate is one of the preferred detergency builders. However, the use of sodium polyphosphate in dry powder detergents has some drawbacks such as, for example, the tendency of polyphosphates to hydrolyze into pyro- and ortho-phosphates which constitute less attractive detergency builders .

In addition, the polyphosphate content of laundry detergents has been held responsible for the excessively high phosphate content of surface water. Higher phosphate content in surface water has been shown to contribute to increased algae growth resulting in an adverse change in the biological balance of the water.

30 Recently, government legislation, -Λτ - enacted has aimed to reduce the amount of polyphosphates present in laundry detergents and, in some jurisdictions where polyphosphates have been a problem, have demanded that they be detected! 3 4 laundry bleaches do not contain any detergent builder polyphosphates.

Liquid detergents are often considered to be more convenient to use than particulate or dry powder products and, therefore, have found great success with consumers. They can be dosed easily, they dissolve quickly in the washing water, they can be easily applied in solutions or concentrated dispersions on its parts; - / clothing lees to be cleaned and do not give off dust, and they generally take up little storage space. In addition, liquid detergents may contain, in their formulation, materials which could not withstand drying operations without deteriorating, which materials would often be advantageously used in the manufacture of particulate detergent products. Although they have many advantages over solid unitary or particulate products, liquid detergents often have certain inherent disadvantages which must be overcome to obtain commercially acceptable detergent products. Thus, some of these products separate on storage and others separate on cooling and cannot easily be redispersed. In some cases, the viscosity of the product changes and the product becomes either too thick to be poured, or so liquid that it looks like water. Some clear products become cloudy and others gel on standing.

In addition to the problem of sedimentation or phase separation, non-aqueous liquid laundry detergents based on liquid surfactants! 4 non-ionic quides have the disadvantage that non-ionic surfactants tend to gel when added to cold water. This is a particularly aiqu problem during common use of automatic European household washing machines in which the user places the laundry detergent composition in a dispensing device (for example a dispensing drawer). of the machine. During the operation of the machine, the detergent contained in the dispenser is subjected to a stream of cold water which transfers it into the main body of the washing solution. Particularly during the winter months, when the detergent composition and the water introduced into the dispenser are particularly cold, the viscosity of the detergent increases sharply and a gel is formed. As a result, a part of the composition is not completely swept out of the dispenser during the operation of the machine, and a deposit of composi-tion accumulates during repeated washing cycles, ultimately forcing the user to sweep the distributor with hot water.

The phenomenon of gelation can also be a problem when it is desired to carry out washing in cold water, as may be recommended for certain synthetic and delicate fabrics or fabrics which can shrink in lukewarm or hot water.

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

0 i 5 /

Partial solutions to the problems of praise have been proposed, for example by diluting the ionic liquid surfactant with certain solvents acting on the viscosity and certain gelling inhibiting agents, such as lower alkanols, for example alcohol. ethyl (see US patent N * 3,953,380), formates and adipates of, alkali metals (see US patent N * 4,368,147), 11hexylene glycol, polyethylene glycol, etc., and 10 by modification and an optimization of the / structure of nonionic surfactants. As an example of modification of nonionic surfactants, a particularly advantageous result has been obtained by acidifying the hydroxyl terminated portion of the nonionic molecule. The advantages of introducing a carboxylic acid at the end of the nonionic surfactant include an inhibition of gelation at the time of dilution; a decrease in the drop point of nonionic surfactants; and forming an anionic surfactant by neutralization in the wash liquor. Optimization of the nonionic structure related to the chain length of the hydrophobelipophilic fragment and to the number and the constitution of the alkylene oxide units (for example ethylene oxide) of the hydrophilic fragment. For example, it has been found that a C 13 fatty alcohol ethoxylated with 8 moles of ethylene oxide exhibits only a limited tendency to form a gel.

30 Nevertheless, it is desired to improve both the stability and the inhibition of the gelling of non-aqueous, phosphate-free and low-phosphate liquid compositions for the treatment of tissues.

According to the present invention, a very concentrated non-aqueous laundry detergent composition 6 with a low phosphate content, and more particularly free of polyphosphate type detergency builder, is prepared by dispersing a polymer of hydroxy acrylic acid or of a salt of such an acid as a detergency builder or a polyacetal carboxy-late as a adjuvant of detergency in a liquid nonionic surfactant detergent.

Polymers of hydroxy acrylic acid or a salt of such an acid as detergency builders used in accordance with an embodiment of the present invention are well known. The process for making the polymer of hydroxy acrylic acid and the salt of such an acid and its use for stabilizing peroxygen bleaches or bleaching peroxyacids in detergent compositions are described in the US Patents. AT. N * 4,450,089 and N * 4,455,249, which are cited here for reference.

The lower molecular weight polymers of hydroxy acrylic acid or salt of such an acid are readily biodegradable. The polymers of hydroxy acrylic acid and of a salt of such an acid are good stabilizers for bleaching agents and serve as effective anti-scaling agents. Hydroxyacrylate polymers are particularly good detergent builder salts due to their high sequestering power of calcium and magnesium ions in the wash water.

The hydroxy-acrylate polymer used as detergency builder according to the present invention T contains monomer units of formula: R, 011

I1 I

-,_vs -

L · C00M

- J nt 7 in which and ^ are the same or different and represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and M represents hydrogen, or an alkali metal cation, of alkaline earth metal or ammonium. The degree of polymerization, i.e. the value of n, is generally determined by the limit compatible with the solubility of the polymer in water.

The polyacetal carboxylates used according to another embodiment of the present invention are also well known. The manufacturing process for detergency builder salts is described in U.S. patents. Nos. 4,315,092 and H * 4,144,226 and the use of polyacetal carboxylates as adjuvant detergency salts is described in the U.S. Patent. N * 4 146 495.

Polyacetal carboxylates are water soluble and rapidly depolymerize in neutral or non-alkaline media to form low molecular weight components which are readily biodegradable. Polyacetal carboxylates are therefore used in formulations which, at the time of addition to the washing water, normally have a pH greater than 7, for example around 8 to 10, for example 9 to 10. Although The polyacetal carboxylates as they are used in an alkaline medium are effective detergency builder salts, when the waste water from the aqueous washing bath is discharged into the sewer or other waste water collection system and 1 washing water is neutralized, the polyacetal carboxylates are depolymerized into small fragments which are easily biodegradable. Polyacetal carboxylates are particularly satisfactory detergency builder salts because of their high sequestering power of calcium and magnesium ions in the washing water.

The adjuvant builder polyacetal carboxylates used in the present invention are represented by the general formula: —TcHO “J- - LH.

... 10 wherein N is an alkali metal cation oty ammonium, n is at least 4, and and Rj are chosen so as to be individually stable groups which stabilize the polymer against a depolymerization in alkaline solution and are chosen so as to be compatible with the ingredients of the nonionic liquid detergent composition of the present invention. A commercially available builder adjuvant polyacetal carboxylate is sold by Monsanto Chemical Company under the trademark 20 Commercial Builder U and is a sodium salt.

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

9

Sanitation agents or. bleaching and their activators can be added to improve the bleaching and cleaning characteristics of the composition.

In one embodiment of the invention, the detergency builder components of the composition are ground to a particle size of less than 100 microns and preferably less than 10 microns in order to further improve the suspension stability of the components adjuvants / detergency in liquid nonionic surfactant detergent.

In addition, other ingredients can be added to the composition, such as anti-fouling agents, anti-foaming agents, optical brightening agents, enzymes, anti-redeposition agents, perfumes and dyes.

Washing machines currently manufactured for home use normally operate at washing temperatures up to 95 ° C. About 20 liters of water are used during the wash and rinse cycles.

Normally about 175 grams of powdered detergent is used per wash.

According to the present invention, when using the highly concentrated liquid detergent, only about 80 grams (67 ml) or less of liquid detergent compositions are required to wash a full load of dirty laundry.

Therefore, in one aspect, the present invention provides a heavy duty laundry composition free of or substantially free of a phosphate-like detergency builder, consisting of a suspension of a alkyd metal hydroxyacrylate polymer detergency builder or an alkali metal salt of polyacetal carboxylic acid detergency builder in a nonionic liquid surfactant.

According to another aspect, the invention provides a concentrated liquid detergent composition with little or no phosphate content for large laundering jobs, which is stable, does not settle during storage and does not gel during storage and in use. The liquid compositions of the present invention can easily be poured, they are easily dosed and are easy to introduce into the washing machine.

In another aspect, the invention provides a method for dispensing a non-ionic liquid laundry detergent composition with little or no phosphate content in and / or with cold water without causing gelation. In particular, there is provided a method of filling a container with a non-aqueous liquid laundry detergent composition in which the detergent consists, at least predominantly, of a liquid non-ionic surfactant agent free of adjuvant polyphosphate for detergency and for dispensing the composition from the container into an aqueous wash bath, dispensing being effected by directing a stream of unheated water over the composition so that the composition is entrained by the stream of water in the wash bath.

Detergent compositions free of detergency builder polyphosphate eliminate the problems of surface water pollution by phosphates.

The concentrated non-aqueous liquid detergent compositions of non-ionic surfactant laundering, with little or no polyphosphate content, in accordance with the present invention, combine the advantages of being stable, and of not being sedimented. storage or gelation at storage. The liquid compositions are easy to pour, easy to dose and easy to introduce into washing machines.

An object of the present invention is to provide a liquid non-polluting non-aqueous non-ionic detergent composition, with a low content, and in particular with zero polyphosphate content, for large laundering works, containing a hydroxy polymer. acrylate as a detergency builder or a polyacetal-tal-carboxylate as a detergency builder salt in a nonionic surfactant.

Another object of the invention is to provide liquid compositions for the treatment of tissues, with little or no polyphosphate content, which are suspensions of hydroxy-acrylate polymer as detergency builder or of polyacetal-carbon xylate as a detergency builder salt in a non-aqueous liquid and which are stable in storage, and are easy to pour and disperse in cold, lukewarm or hot water.

Another object of the present invention is to formulate highly reinforced non-aqueous liquid detergent compositions with non-ionic surfactant, with little or no polyphosphate content, for large laundering jobs, which can be poured at all temperatures and which can be dispersed repeatedly from the European-style automatic washing machine dispensing device without clogging or obstructing the dispenser even during the winter months.

Another object of the present invention is to provide stable suspensions, non-gelling, low or zero polyphosphate content, of non-ionic liquid non-ionic detergent composition forced ren for large laundering work, which include an effective amount of 'a hydroxy-acrylate polymer as a detergency builder or a polyacetal-carboxylate as a detergency builder salt.

Another object of the present invention is to / provide stable non-gelling suspensions of reinforced non-ionic liquid non-ionic detergent composition for heavy laundry work, which comprise an alkanolic ester of phosphoric acid and / or an acid salt aluminum fat in an amount sufficient to increase the stability of the composition, i.e. to prevent sedimentation of the detergency builder particles, etc., preferably while reducing or at least not increasing the plastic viscosity of the composition.

These objects of the invention as well as others which will emerge from the detailed description which follows of preferred embodiments are generally achieved by preparing a deter-gent composition with low or zero polyphosphate content, by adding to the nonionic surfactant. non-aqueous liquid an effective amount of an alkali metal hydroxy acrylate polymer as a detergency builder or an alkali metal polyacetal carboxylate as an adjuvant detergency salt and additives for treating "tissue, organic or minerals, for example anti-gelling and viscosity improving agents, anti-sedimentation agents, anti-encrustation agents, bleaching agents, activators of a / 13 bleaching agents, anti-foaming agents, Optical brightening agents, enzymes, anti-redeposition agents, perfumes and dyes.

Nonionic Surfactant Detergent The nonionic synthetic organic detergents used in the practice of the invention can be any of a wide variety of such compounds, which are well known.

As is known, non-ionic synthetic 1Θ organic detergents are characterized by the presence of a hydrophobic organic group and a hydrophilic organic group and they are generally produced by the condensation of a hydrophobic aliphatic or alkyl-aromatic organic compound. with ethylene oxy-15 (hydrophilic in nature). Virtually any hydrophobic compound having a carboxy, hydroxy amido or amino group having a free hydrogen atom attached to nitrogen can be condensed with ethylene oxide or with its polyhydration product, polyethylene glycol, to form non-ionic detergent. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to achieve the desired ratio between the hydrophobic and hydrophilic groups. Representative examples of suitable nonionic surfactants are those described in U.S. Patents. N * 4,316,812 and N * 3,630,929.

In general, nonionic detergents are lipophilic compounds alkoxylated by a poly-30 (lower alkoxy) group in which the desired hydrophilic / lipophilic ratio is obtained by the addition of a hydrophilic poly (lower alkoxy) group to a lipophilic fragment. A preferred class of non-ionic detergents used is constituted by the higher alkanols alkoxylated by poly (lower alkoxy) groups in which the alkanol contains 9 to 18 carbon atoms and in which the number of moles of oxide d the lower alkylene (of 2 or 3 carbon atoms) is 5 from 3 to 12. Among these materials, it is preferred to use those in which the higher alkanol is a higher fatty alcohol of 9 to 11 or 12 to 15 carbon atoms, and which contain 5 to 8 or 5 to 9 lower alkoxy groups per mole. Preferably, the lower alkoxy group is the ethoxy group, but in this case it can in any case be advantageously mixed with the propoxy group, the possible presence of which often only represents a minor proportion (less than 50%).

Examples of such compounds are those in which the alkanol has 12 to 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 manufactured products. by Shell Chemical 20 Company, Inc. The first is a condensation product of a mixture of higher fatty alcohols having on average about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide, and the second is a corresponding mixture in which the carbon atom content of the higher fatty alcohol is 12 to 13, and the number of ethylene oxide groups present represents an average of about 6.5. Higher alcohols are primary alkanols.

Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15-S-9, which are both "ethoxylates of linear secondary alcohols manufactured by Union Carbide Corporation. The former is a product of mixed ethoxylation of a linear secondary alkanol of 11 to 15 carbon atoms with seven moles of ethylene oxide, and the second is a similar product but where nine moles of ethylene oxide have reacted.

Also useful in the composition of the invention, as a component of the non-ionic detergent, non-ionic surfactants of higher molecular weight, such as Neodol 45-11 which are similar condensation products of ethylene oxide on alcohols higher fatty acids, the higher fatty alcohol com-10 having 14 or 15 carbon atoms, and the number of ethylene oxide groups / per mole being about 11. These products are also manufactured by Shell Chemical Company.

Other useful nonionic surfactants are represented by the well known trade class of nonionic surfactants sold under the trademark Plurafac. Plurafac products 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 group hydroxyl. Examples include products which are (A) a C13-C15 fatty alcohol condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide, (B) a C13-C15 fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide, (C) a fatty alcohol C13 ~ C15 condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide and (D) a mixture 1: 1 of (B) and (C).

Another group of liquid nonionic surfactants are commercially available from Shell Chemical Company, Inc., under the trade name Dobanol: Dobanol 91-5 is a C 8 -C 8 ethoxylated fatty alcohol with an average of 5 moles. of oxide 16! \ *, 1

U

ethylene and Dobanol 25-7 is a C12-C15 fatty alcohol ethoxylated with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

In the higher alkanols alkoxylated by poly (lower alkoxy) groups, preferred in order to obtain the best ratio between the hydrophilic and lipophilic portions, the number of lower alkoxy groups is generally equal to 40% to 100% of the number of atoms. carbon of the higher alcohol, preferably 40 to 60% of this number, and the nqh / ionic detergent preferably contains at least 50% of such a preferred higher poly (lower alkoxy) -alkanol. The higher molecular weight alkanols and various other normally solid nonionic detergents and surfactants may contribute to the gelation of the liquid detergent and therefore will preferably be removed or will be in limited amounts in the present compositions, although they can be used in minor proportions for their cleaning properties, etc. As regards the preferred and less preferred nonionic detergents, the alkyl groups which they contain are generally linear, although branching can be tolerated, for example at a carbon atom close to the atom. terminal carbon of the straight chain or two carbon atoms distant from this terminal carbon atom and opposite the ethoxylated chain, provided that such a branched alkyl group is not more than three atoms in length 30 carbon. Normally, the proportion of carbon atoms in such a branched configuration is minor and rarely exceeds 20% of the total carbon atom content of the alkyl group. Similarly, although the linear alkyl groups which are terminally linked to the ethylene oxide chains are very preferable and are considered to give the best combination of detergency, biodegradability and non-gelling characteristics, '5 there may appear a median or secondary junction with the ethylene oxide of the chain. There is generally only a minor proportion of such alkyl groups, generally less than 20%, but, as in the case of the Tergitols mentioned, this proportion may be higher. Also, when the oxide chain /! f of lower alkylene contains propylene oxide, the proportion of this propylene oxide is generally less than 20%, and preferably less than 10 of this chain.

When higher proportions are used than those mentioned above of alkanols whose alkoxylation is not terminal, of alkanols alko-xylated by poly- (lower alkoxy) groups containing propylene oxide and nonionic detergent with lower hydro-lipophilic ratio, and when other nonionic detergents are used in place of the preferred nonionic detergents listed herein, the resulting product may not have as good potency properties detergent, viscosity stability and non-gelation than the preferred compositions, but the use of the compounds of the invention acting on the viscosity and inhibiting gelation can also improve the properties of detergents based on such nonionic compounds. . In some cases, for example when a lower polyialkoxy is used) higher alkanol of higher molecular weight, often for its detergency, its proportion is adjusted or limited in accordance with the results of routine experiments, in order to obtain detergent desired and to obtain at the same time a non-gelling product and of desired viscosity. Also, it has been found that it is only rarely necessary to use nonionic surfactants of higher molecular weight for their detergent properties, since the preferred nonionic surfactants described here are excellent detergents and, more, they allow to reach the desired viscosity in the liquid detergent without gelation at 1 o low temperatures. / “Another useful group of nonionic surfactants is the" Surfactant T "series of nonionic surfactants offered by British Petroleum. The non.ionic surfactants Surfactant T 15 are obtained by ethoxylation of C 13 secondary fatty alcohols with a narrow distribution of ethylene oxide. Surfactant T5 has an average of 5 moles of ethylene oxide; Surfactant T7 has an average of 7 moles of ethylene oxide; Surfactant T9 has an average 20% of 9 moles of ethylene oxide and Surfactant T12 has an average of 12 moles of ethylene oxide, per mole of C13 secondary fatty alcohol.

In the compositions of the present invention, preferred nonionic surfactants include C 1 -C 4 secondary fatty alcohols having relatively limited ethylene oxide contents of about 7 to 9 moles, and fatty alcohols Cg to ethoxylated with about 5 to 6 moles of ethylene oxide.

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

Acid-terminated non-ionic surfactant

The viscosity and gelation properties of liquid detergent compositions can be improved by including in the composition an effective amount of an acid-terminated liquid nonionic surfactant. Acid-terminated nonionic surfactants consist of a nonionic surfactant which has been modified to transform one of its free hydroxyl groups into a moiety having a free carboxyl group, such as an ester or partial ester of a surfactant non-ionic and a polycarboxylic acid or anhydride. / ~ As described in French patent application 85 05 319 filed on April 9, 1985, the nonionic surfactants modified by a free carboxyl group, which can roughly be characterized as being polyether-carboxylic acids, act so lowering the temperature at which the nonionic liquid surfactant forms a gel with water.

The addition of acid-terminated nonionic surfactants to the liquid nonionic surfactant promotes the ability of the composition to be dispensed, i.e., to be poured, and reduces the temperature at which the liquid nonionic surfactant forms a gel in water without reducing their stability against sedimentation. The acid-terminated nonionic surfactant reacts in the washing machine water with the alkalinity of the dispersed detergency builder salt phase of the detergent composition and acts as an effective anionic surfactant.

Particular examples include the hemi-esters of product (A) with succinic anhydride, the ester or hemi-ester of Dobanol 25-7 with succinic anhydride, and the ester or hemi-ester of Dobanol 91-5 with succinic anhydride. Instead of succinic anhydride, other polycarboxylic acids or anhydrides can be used, for example maleic acid, maleic acid anhydride, citric acid, etc.

Acid-terminated non-ionic surfactants can be prepared as follows:

Acid-terminated product (A): 400 g of nonionic surfactant are mixed. Product (A) which is a C 15 alkanol which has been alkoxylated to introduce 6 ethylene oxide motifs and 3 propylene oxide units in per d motif. 'alkanol, with 32 g of succinic anhydride' / <~ and heated for 7 hours at 100 ° C. The mixture and the filter are cooled to separate the unreacted suckinic material. Infrared analysis shows that about half of the nonionic surfactant has been converted to its acid hemi-ester.

Acid-terminated Dobanol 25-7: 522 g of non-ionic surfactant Dobanol 25-7 are mixed, which is the ethoxylation product of a C 15 alkanol and comprises approximately 7 ethylene oxide units per molecule 20 d alkanol, with 100 g of succinic anhydride and 0.1 g of pyridine (which acts as an esterification catalyst) and heated to 260 ° C for 2 hours, cooled and filtered to separate the succinic material having no not reacted. Infrared analysis shows that almost all of the free hydroxyl groups in the surfactant have reacted.

Acid-terminated Dobanol 91-5: 1000 g of non-ionic surfactant Dobanol 91-5 is mixed, which is the ethoxylation product of a C 8 alkanol with and has about 5 ethylene oxide units per alkanol molecule *, with 265 g of succinic anhydride and 0.1 g of pyridine as catalyst, and heated to 260 ° C for 2 hours, cooled and filtered to separate the unreacted succinic material. Infrared analysis shows that almost all of the free hydroxyl groups of the surfactant have reacted. Other esterification catalysts, such as an alkali metal alcoholate (eg sodium methylate) can be used in place of or in mixture with pyridine. The acidic polyether, i.e. the acid-terminated nonionic surfactant, is preferably added in the dissolved state to the nonionic surfactant.

Adjuvanted Detergency Salts The non-aqueous liquid nonionic surfactant used in the compositions of the present invention contains, in dispersed and suspended form, fine particles of organic and / or mineral detergency builder salts.

The present invention encompasses, as an essential part of the composition, an organic detergency builder of the polymeric type hydroxyacrylic acid or a salt of such acid or an organic detergency builder salt of the polyacetal carboxylate type.

20 organic adjuvant detergency salts

Hydroxv-Acrylic Acid Polymer Type Detergency Additive

A preferred organic detergency builder salt is among the alkali metal salts of hydroxy acrylic acid polymer, preferably the sodium and potassium salts.

Briefly, the polymer of hydroxy acrylic acid and salt of such an acid, used in the present invention as a detergency builder, contains monomer units of the formula: [R ·. OH "

• AT

- Ç - ç - r2 coom L n 22 in which and Rj may be identical or different and represent hydrogen or an alkyl group containing 1 to 3 carbon atoms, such as methyl, ethyl and propyl. The preferred substituents for R, j and R2 are both hydrogen. It represents hydrogen or an alkali metal, such as sodium or potassium, or an alkaline earth metal such as calcium, magnesium or barium. The preferred substitute for M is sodium. The terminal groups of the polymer are not critical and may / may be H, OH, CH3 or a hydrocarbon chain.

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

The value of n can be from 10 to 10,000, preferably from 10 to 1000, and more preferably from 20 to 200. The polymer of hydroxy acrylic acid or salt of such an acid can have a molecular weight of 1000 to 10 preferably from 1000 to 10, and better still from 20 2000 to 20 000. See for example the patents of the USA

N * 3,920,570 and N * 4,107,411 which describe processes for manufacturing polymers.

Salts P-olv_acétal-carboxvligue detergency builder Other preferred organic detergent builder salts include the alkali metal salts of polyacetal-carboxylic acid, preferably the sodium and potassium salts.

In general, the detergency builder polyacetal-carbo-xylates used in the present invention are represented by the following general formula:

C00M

L - * n 5 23 in which N is chosen from an alkali metal, ammonium, alkyl groups of 1 to 4 carbon atoms; tetralkylammonium groups and alkanolamine groups having 1 to 4 carbon atoms in the alkyl chain; alkali metals, for example sodium and potassium, are preferred; n is at least 4; and and R2 are individually all chemically stable groups. and R2 can be the same or different groups. j 10 The terminal groups and Rj can be chosen from a wide range of materials, provided that they stabilize the polyacetal-carboxylate against rapid depolymerization in alkaline solution. The terminal groups R1 and R2 are also chosen so as to be compatible with the ingredients used to formulate the nonaqueous nonionic liquid composition of the present invention, in particular the nonionic surfactant and the anti-gelling and anti-gelling agents. sedimentation.

The number of recurring groups, i.e., the value of n, is an important factor, since the effectiveness of the polyacetal carboxylate as a detergency builder is affected by the length of the polymer chain. When n = 4, the polymer exhibits efficacy as a sequestering agent, chelating agent and detergency builder. The value of n can be as high as 400. However, there does not seem to be any advantage in having n having a value greater than about 200.

When the value of n exceeds about 100, no significant improvement in sequestering, chelating and adjuvant detergency properties is observed. Thus, the polyacetal-carboxylate can contain 10 to 400 units, that is to say that n can be equal to 10-400, preferably n * 50 to 200, and better still n = 50 to 100 recurring units. .

When n has a value of 50 to 200, the efficiency of sequestration of the calcium and magnesium ions is very satisfactory and the adjuvant detergency properties are very good.

For example, suitable chemically stable end groups include stable substituent moieties derived from otherwise stable compounds, such as alkanes, such as methane, ethane, propane and butane; alkenes such as ethylene, propylene and butylene; branched chain hydrocarbons, both saturated and unsaturated, such as 2-methylbutane and 2-methylbutene; alcohols such as methanol, ethanol, 2-propanol, cyclohexanol, polyalcohols such as 1,2-ethanol-diol and 1,4 benzene-diol; 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; and compounds containing carboxylate groups such as alkali metal salts of carboxylic acids, esters of carboxylic acids and anhydrides. Particularly suitable end groups include alkyl groups and oxygen-containing cyclic alkyl groups such as oxyalkyl groups such as methoxy, ethoxy, carboxylic acids; and aldehydes, ethers and other oxygen-containing alkyl groups.

The polyacetal carboxylates can contain polymeric moieties, and therefore the polymer can be a linear homopolymer or copolymer, or it can be branched. A number of chain extenders can be copolymerized with the polyacetalcarboxylates. It is sufficient that the chain extender agent provides at least two reactive sites and does not cause the depolymerization of polyacetal carboxylates in alkaline solution and that it is compatible with the nonionic surfactant and anti-gelling agents and / anti-sedimentation of the present invention.

Suitable chain extenders include: polyalcohols such as ethylene oxide, propylene oxide and epihalohydrin epoxysuccinates; aldehydes such as formaldehyde and acetaldehyde. It is particularly advantageous for the chain extender to contain substituent carboxy groups. Aliphatic chain extenders having 1 to 4 carbon atoms, such as ethylene oxide and propylene oxide, are particularly preferred.

When acetal-carboxylic esters are copolymerized with a chain extender, the amount of acetal-carboxylate should be at least about 50 percent by weight, based on the total weight of the polymer, to ensure that the polymer effectively sequesters calcium and magnesium ions and retains its detergency builder properties. It is preferable that the amount of acetal carboxylate is 50 to 80 percent, for example about 80 percent by weight, based on the total weight of the polymer, or even greater.

In a preferred embodiment of J ”4 26 the invention, R1 is chosen from: —OCH„ - OC, H., HO (CH, CH2Cm -

/ Ch2-chk. H3ç *, "m - / 1 J | I

- OCH CH, RC— - CR

\ / * 1

0 - ch2 h5c2o COOH

10 and mixtures thereof, and R2 is chosen from: -CH3, -c2h5, - (ch2ch20> -, _4H, h3?>, CH2-CH, 15 SC / 2 \

Rfj '-CH CH2 H5C2 ° ο — οαζ 20 and mixtures thereof, where R is hydrogen or an alkyl group of 1 to 8 carbon atoms, and M is as defined above.

It is particularly preferable that R ^ is:

25 OCH, CH, COOM

I 4 Λ I

-ÇH OR -C —CH,

I I J

CH3 COOH

30 or their mixtures, and that R2 is: 1 OCH, CH, I 2 3

-CH

^ 3 y * "Λ fc 27 where Μ is sodium and that n is equal to 50-200.

Other organic detergency builders which can be used are polymers and copolymers of polyacrylic acid and polymaleic anhydride and their alkali metal salts. More particularly, these detergency builder salts may consist of a copolymer which is the reaction product of an approximately equal number of moles of methacrylic acid and maleic anhydride, which has been completely neutralized to form its salt. sodium. The detergency builder is commercially available under the trademark Sokalan CP5.

. This detergency builder is used, when used in even small amounts, to inhibit encrustation. Since the detergent compositions of the present invention are generally very concentrated, and therefore can be used in relatively small amounts, it is advantageous to supplement the detergency builder with an auxiliary builder such as an alkali metal salt of lower polycarboxylic acid having a high calcium and magnesium fixing power making it possible to inhibit encrustation which could otherwise be caused by the formation of insoluble calcium and magnesium salts. Suitable alkali metal salts of polycarboxylic acids are the alkali metal salts of citric and tartaric acids, for example monosodium citrate (anhydrous), monosodium, disodium and dipotassium tartrates.

They can be added to, and used with, the acidic alkali metal salt polymer. hydroxy-acrylic detergency builder and alkali metal salts of polyacetal-carboxylic acid i ".

28

T

detergency builders (eg Builder. U), which are also described here.

Examples of sequestering alkaline oragnetic detergency builder salts which can be used with the detergency builder polymer of hydroxy acrylic acid or salt of such acid or with the detergency builder polyacetal carboxylates of the present invention, or in admixture with other organic and mineral detergency builders are the aminopolycarboxylates of alkali metal, ammonium or substituted ammonium, for example sodium and potassium edetate (EDTA), the nitrilotriacetates (NTA) of sodium and potassium * and trietha-nolammonium N- (2-hydroxyethyl) nitrilodiacetates. Mixed salts of these aminopolycar boxylates are also suitable.

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

20 Mineral Adjuvant Detergent Salts

The detergent compositions of the invention may also contain inorganic detergency builder salts soluble in water and / or insoluble in water. Suitable alkaline inorganic detergency builder salts which can be used are alkali metal carbonates, borates, bicarbonates and silicates. (It is also possible to use ammonium or substituted ammonium salts). Particular examples of such salts are sodium carbonate, sodium tetraborate, sodium bicarbonate, sodium sesquicarbonate and potassium bicarbonate.

Alkali metal silicates are useful detergency builder salts that work. ” · 29 also to adjust or adjust the pH and to make the composition anticorrosive for the parts of the washing machine. Sodium silicates with an Na 2 O / SiO 2 ratio of 1.6: 1 to 1: 3.2, in particular of approximately 5 1: 2 to 1: 2.8 are preferred. Potassium silicates can also be used in the same ratios.

Although it is preferable that the detergent composition be free of phosphate or polyphosphate or substantially free of polyphosphate, small amounts of the conventional / polyphosphate can be added as detergency builder salts when local regulations permit this use. Particular examples of such detergency builder salts are sodium tripolyphosphate (TPP), sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate and sodium hexa-metaphosphate. Sodium tripolyphosphate (TPP) is the preferred polyphosphate. In formulations in which the polyphosphate is added, it is added in a proportion of 0 to 20 or 30 *, for example 5 to 15¾.

As mentioned previously however, it is preferable that the formulations are free of polyphosphate or substantially free of polyphos-phate.

Other representative examples of suitable detergency builders include, for example, those described in U.S. patents. N * 4 316 812, N * 4 264 466 and N * 3 630 929. The alkaline mineral salts with detergency builders can be used i with the nonionic detergent surfactant or in admixture with other organic salts or mineral builders with detergency builders .

The water insoluble crystalline and amorphous zeolite aluminosilicates can be used. Zeolites generally have the formula: (Μ20) χ * (Al203) y · (Si02) 'ZwH20 in which x is equal to 1, y ranges from 0.8 to 1.2, and · 5 is preferably equal to 1 , z is 1.5 to 3.5 or more, and preferably is 2-3, and w is 0 to 9, preferably 2.5 to 6, and M is preferably sodium . A representative example of a zeolite is a zeolite of type A or of similar structure, type 4A being particularly preferred. The preferred aluminosilicates have a calcium ion exchange power of about 200 milliequivalents per gram or more, for example 400 milliequivalents per gram.

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

Other materials such as clays, particularly water-insoluble types, can be useful additives in the compositions of the present invention. A particularly useful clay is bentonite. This material is mainly montmorillonite which is a hydrated aluminum silicate in which about 1/6 of the aluminum atoms can be replaced by magnesium atoms and with which various amounts of hydrogen, sodium, potassium, calcium, etc., can be weakly combined. Bentonite in its more purified form (that is to say free from any sandstone, sand, etc.) suitable for detergents contains at least 50% of montmorillonite and thus its cation exchange power 31 is d '' at least about 50 to 75 milliequivalents per 100 g of bentonite. Particularly preferred bento-nites are bentonites from Wyoming or the western United States of America which * 5 were sold under the designations of Thixo-jel 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften textile materials, as described in British patents N * 401,413 and N * 461,221.

10 Viscosity Adjusters and Anti-Gelling / Incorporation in the detergent composition of an effective amount of low molecular weight amphiphilic compounds of the monoalkyl ether alkylene glycol type acting as viscosity adjusting agents and inhibiting gelation for the nonionic surfactant appreciably improves the preservation properties of the composition.

Amphiphilic compounds can be considered to have a chemical structure analogous to that of liquid nonionic surfactants derived from ethoxylated and / or propoxylated fatty alcohols, but they have relatively short hydrocarbon chain lengths (C2 to Cg) and a low content. into ethylene oxide (about 2 to 6 ethylene oxide groups per molecule).

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

In particular, the compounds are lower monoalkyl ethers (C2 to C8) of lower alkylene glycols (C2-C3).

More particularly, the compounds are 32 »k Λ lower monoalkyl ethers (C1 to C5) of lower mono-, di- or trialkylene glycols (C2-C3).

Particular examples of suitable amphiphilic compounds include the ethylene glycol C2H5 "®" CI2CH2OH 'monoethyl ether of diethylene glycol C4H9-0- (CH2CH20) 2H, the monobutyl ether of tetraethylene -glycol C ^ Hy-O-ÎCHg. CH20) 4H and the monomethyl ether of dipropylene-> glycol (CH ^ -O-tCH ^ CHO ^ H). Particularly preferred is 10 k monobutyl ether of diethylene glycol.

The incorporation into the composition of low molecular weight lower alkylene glycol monoalkyl ether decreases the viscosity of the composition, so that it is easier to pour, improves the stability towards -vis sedimentation and improves the dispersibility of the composition when added to lukewarm or cold water.

The compositions of the present invention have better viscosity and stability characteristics and remain stable and pourable at temperatures as low as about 5’C or less. Stabilizers

In one embodiment of the present invention the physical stability of the suspension of the detergent builder compound (s) and any other suspended additive, for example bleach, 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.

The stability of the composition can be improved by incorporating a small but effective amount of an acidic organic phosphorus compound 33 having an acid group -POH, for example a partial ester of phosphorous acid and an alkanol.

As described in the aforementioned French patent application No. 85 05 319, the acid organic phos- * 5 phore compound comprising an acid -POH group can increase the stability of the suspension of detergency builders in the nonionic non-ionic liquid surfactant. aqueous.

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

A particular example is a partial ester of phosphoric acid and a alkanol (Empiphos 5632 from Marchon); it consists of approximately 35% monoester and 65% diester.

The incorporation of very small amounts of the organic phosphorus acid compound makes the suspension significantly more stable with respect to sedimentation at rest, while remaining pourable, while for a low concentration of stabilizer, for example lower at about 1%, its plastic viscosity generally decreases.

The stability and anti-sedimentation properties of the composition can be further improved by the addition of a small effective amount of an aluminum salt of a higher fatty acid than the composition.

Stabilizing agents of the aluminum salt type are the subject of French patent application 86 02 815 filed on February 28, 1986.

Preferred higher aliphatic fatty acids i to 34 have about 8 to about 22 carbon atoms, preferably about 10 to 20 carbon atoms, and most preferably about 12 to 18 carbon atoms. The aliphatic radical can be saturated or unsaturated, and it can be straight or branched chain. As in the case of nonionic surfactants, it is also possible to use mixtures of fatty acids, such as those from natural sources, such as tallow fatty acid, coconut fatty acid, etc.

Examples of fatty acids from which stabilizing aluminum salts can be formed include decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid , eicosanoic acid, tallow fatty acid, coconut fatty acid, mixtures of these acids, etc. The aluminum salts of these acids are generally commercially available, and they are preferably used in the form of three acid residues, for example aluminum stearate 20 in the form of aluminum tristearate A1 (C ^ H ^ gCOO)

Salts with an acid residue, for example aluminum monostearate, A1 (OH) 2 (C17H35COO) and salts with two acid residues, for example aluminum distearate, A1 (OIDC ^ H ^ COO and mixtures of two or three of the aluminum salts with one, two or three acid residues can also be used, however it is particularly preferable that the aluminum salt with three acid residues constitutes at least Preferably 30% at least 50%, more preferably at least 80% of the total amount of aluminum salt of fatty acid.

> Aluminum salts, as mentioned above, are commercially available and can be produced easily, for example by saponification of a fatty acid, for example animal fat, stearic acid, etc., then treatment of the soap resulting with alum, alumina, etc.

Although the Applicant does not wish to be bound by any particular theory on the way in which the aluminum salt acts to prevent sedimentation of the particles in suspension, it is assumed that the aluminum salt increases the wettability of solid surfaces by the nonionic surfactant. This increase in wettability therefore allows suspended particles to remain more easily in suspension.

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

In addition to its action as a physical stabilizer, aluminum salt has the additional advantages over other physical stabilizers that it is non-ionic in character and is compatible with the non-ionic surfactant and does not alter the overall detergent power of the composition; it has a certain anti-foam effect; it can reinforce the action of fabric softeners and it gives suspensions a longer duration of relaxation.

25 Bleaching Agents

Bleaches are broadly classified for convenience into chlorine bleaches and oxygenated bleaches. The chlorinated bleaching agents are represented by sodium hypochlorite (NaOC1), potassium dichloroisocyanurate (59% available chlorine) and trichloroisocyanuric acid (95% available chloride). Oxygenated bleaches are preferred and are represented by co-compounds which release hydrogen peroxide 36 in solution. Preferred examples include sodium and potassium perborates, percarbonates and perphosphates and potassium monopersulfate. Perborates, in particular sodium perborate * 5 monohydrate, are particularly preferred.

Peroxyacids such as diperoxyazelaic acid, diperoxydodecanedioic acid, monoperoxy-succinic acid, monoperoxyphthalic acid (MPPA) and can also be used as bleaches. 10 diperoxytererephthalic acid.

u The peroxygen compound is preferably used in admixture with an activator. Suitable activators which can lower the effective activity temperature of the peroxide bleach are described, for example, in the U.S. Patent. No. 4,264,466 or in column 1 of the U.S. Patent No. 4,430,244. Polyacetylated compounds are the preferred activators; among them, compounds such as tetraacetylethyl-lene diamine ("TAED") and pentaacetyl-glucose are even more preferred.

Other useful activators include, for example, derivatives of acetylsalicylic acid, ethylidene benzoate acetate and its salts, ethyli-dene carboxylate and its salts, alkyl- and alkenyl succinic anhydrides, tetraacetylglycourile ("TACU") and their derivatives. Other useful classes of activators are described, for example, in U.S. patents. N * 4 111 826, N * 4 422 950 and N * 3 661 789.

The bleach activator 30 generally reacts with the peroxygen compound to form a bleaching peroxyacid in the wash water. It is preferable to include a sequestering agent with high complexing power in order to inhibit any undesirable reaction between this peroxyacid and the hydrogen peroxide in the washing solution in the presence of metal ions.

Suitable sequestering agents for this purpose include the sodium salts of nitri-lotriacetic acid (NTA), ethylene diamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DETPA) , diethylene triamine pentamethylene phosphonic acid (DTPMP) sold under the trademark Dequest 2066; and ethylene diamine-tetramethylene phosphonic acid (EDITEMPA). The sequestering agents can be used alone or as a mixture.

In order to avoid loss of bleaching peroxide, for example sodium perborate, resulting from decomposition by the action of enzymes, for example the enzyme catalase, the compositions may further contain an enzyme inhibitor , that is to say a compound capable of inhibiting the decomposition, under the action of an enzyme, of bleaching peroxide. Suitable inhibitors are described in the U.S. Patent. N * 3,606,990.

As a particular interesting inhibitor, mention may be made of hydroxylamine sulfate and other water-soluble hydroxylamine salts. In the preferred nonaqueous compositions of the present invention, suitable amounts of the inhibitory hydroxylamine salts may be as low as about 0.01-0.4%. In general, however, suitable amounts of enzyme inhibitor are up to about 15%, for example 0.1-10% by weight of the composition.

In addition to detergency builders, various other additives or auxiliaries for detergents may be present in the detergent product to provide it with other desired properties of a functional or aesthetic nature. Thus, it is possible to include, in the formulation, minor amounts of suspending agents or anti-redeposition of soiling, for example polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydro-xypropylmethyl-cellulose. A preferred anti-redeposition agent is sodium carboxymethylcellulose having a 2: 1 CM / MC ratio, which is sold under the brand name? Relatin DM 4050.

Optical brighteners can be used for cotton, polyamide and polyester fabrics. Suitable optical brightening agents include compositions of stilbene, triazole and benzidine sulfone, in particular substituted sulfonated triazinyl-stilbene, sulfonated naphthotriazole-stylbene, benzidene sulfone, etc. 'we' prefer being the combinations of stilbene and triazole. A preferred brightening agent is "Stilbene Brightener N4M which is a dianilino-dimorpholino-20 stilbene-sulfonate.

Enzymes may be used, preferably proteolytic enzymes, such as subtilisin, bromelain, papain, trypsin and pepsin, as well as amylase and lipase enzymes and mixtures thereof. Preferred enzymes include a protease suspension, an esperase suspension and amylase. A preferred enzyme is Esperase SL8 which is a protease. Antifoaming agents, for example silicone compounds, such as Silicane L7604, can also be added in small effective amounts.

Bactericides can be used, for example tetrachlorosalicylanilide and hexchlorophene, fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet absorbers, anti-yellowing agents , such as sodium carboxymethylcellulose, pH modifiers and pH buffers, color preservatives, fragrances, dyes and brighteners such as ultramarine blue.

The composition may also contain an insoluble mineral thickener or dispersant with a very large contact surface, for example finely divided silica 10 with an extremely small particle size (for example with a diameter of 5 to 100 micrometers, such as that sold under the name Aerosil) or the other very bulky mineral supports described in the US patent N * 3,630,929, in proportions of 0.1 to 10%, for example from 1 to 5t. However, it is preferable that the compositions which form peroxyacids in the washing bath (for example the compositions containing a peroxygen compound and an activator for it) are substantially free of such compounds and other silicates, it has been found, for example, that silica and silicates promote undesirable decomposition of the peroxyacid.

In one embodiment of the invention, the stability of the detergency 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 detergency builders solids less than 100 microns, preferably less than 40 microns ΟΠ -> and more preferably less than 10 microns. Solid detergents are generally supplied in particle sizes of about 100, 200 or 400 micrometers. The liquid nonionic surfactant phase can be mixed with the solid detergency builders before or after the grinding operation.

In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid ingredients is subjected to attrition milling in which the particle sizes of the solid ingredients are reduced to less than about 10 micrometers, for example to an average particle size of 2 to 10 micrometers or even lower (for example 1 micrometer). Preferably, / less than about 10%, in particular less than about 5 \ of all of the suspended particles have particle sizes greater than 10 microns. Compositions with dispersed particles of such small size have better stability against separation or sedimentation during storage. The addition of the acid-terminated nonionic surfactant compound promotes dispersibility of the dispersions, without a corresponding decrease in the stability of the dispersions against sedimentation.

For the grinding operation, it is preferable that the proportion of solid ingredients is sufficiently high (for example at least about 40%, especially about 50% so that the solid particles are brought into contact with each other and are not too isolated from each other by the nonionic surfactant liquid After the grinding step, all of the liquid nonionic surfactant remaining to be incorporated can be added to the milled formulation.

Grinders which use grinding balls (ball mills) or similar movable grinding elements have given very good results. Thus, it is possible to use a laboratory attrition mill 41 working by batch loads comprising grinding balls made of soapstone 8 mm in diameter. For a larger scale operation, one can use a continuously working grinder in which there are grinding balls with a diameter of 1 mm or 1.5 mm operating in a very small interval between a stator and a rotor operating at a relatively high speed (for example a CoBall mill); when using such a mill, it is advantageous to pass the mixture of nonionic surfactant and cUÿ solids first through a mill which does not perform such a fine grinding (for example a colloid mill) in order to reduce the particle size to less than 100 microns (for example to about 40 microns) before the grinding step to an average particle diameter of less than about 10 microns in the continuously working ball mill.

In the preferred liquid laundry detergent compositions for heavy laundry of the invention, typical proportions (the percentages being based on the total weight of the composition, unless otherwise specified) of the ingredients are as follows: Liquid nonionic surfactant: in the range of about 20 to 60, for example 25 to 50 percent.

The acid-terminated nonionic surfactant can be omitted; however, it is preferable to add it to the composition in an amount in the range of about 2 to 30, for example 2 to 20 or 10 to 25 percent.

Polymer of hydroxy acrylic acid or salt of such adjuvant acid or polyacetal carboxylate of 42 detergency in the range of about 5 to 50, for example 10 to 30 percent.

Polyphosphate type detergency builder salt: in the range of about 0 to 30 percent, 5 for example 0 to 20, and especially 5 to 15 percent.

Polyacrylate copolymer and alkali metal salt of polymaleic anhydride as an anti-scaling agent: in the range of about 0 to 10, for example 2 to 8 percent.

^ 10 Monoalkyl ether of alkylene glycol as an anti-gelling agent: can be omitted; however, it is preferable to add it to the composition in an amount in the range of about 0 to 20, for example 5 to 30 percent, especially 5 to 15 or 20 to 15 percent.

Stabilizing agent of the alkanolic ester type of phosphoric acid: in the range from 0 to 2.0 or 0.1 to 2.0, for example 0.10 to 0.5 or 1.0 percent.

Stabilizing agent of the aluminum salt type of fatty acid in the range of about 0 to 3.0, for example 0.5 to 2.0 percent, especially 0.1 to 1.0 percent.

It is preferable that at least one of the stabilizing agents of the phosphoric acid ester or aluminum salt type is present in the composition.

Bleach in the range of about 0 to 35, for example 5 to 40 percent, especially 5 or 10 to 30 percent.

Bleach activator: in the range of about 0 to 25, for example 2 to 25 percent, especially 5 to 20 percent.

Bleach sequestering agent: in the range of about 0, to 3.0, preferably 0.5 to 2.0 percent.

43

Anti-redeposition agent: in the range of about 0 to 3.0 preferably 0.5 to 2.0 percent.

Optical brightener: in the range of about 0 to 2.0, preferably 0.1 to 1.5 percent.

5 Enzymes: in the range of about 0 to 3.0, preferably 0.5 to 2.0 percent.

Perfume in the range of about 0 to 2.0, preferably 0.10 to 1.0 percent.

~ The various additives previously mentioned "can optionally be added to achieve.

u the desired function of the added materials.

Mixtures of acid-terminated nonionic surfactant and alkylene glycol-type anti-gelation agents can be used and, in some cases, the use of such mixtures alone can be benefited , or with the addition of a stabilizing and anti-sedimentation agent to the mixture.

The additives will be chosen so that they are compatible with the main constituents of the detergent composition. In the present application, as mentioned above, all the proportions and all the percentages are expressed by weight relative to the whole of the formulation or composition, unless otherwise specified.

25

The concentrated non-aqueous non-ionic liquid detergent composition of the present invention is easy to dispense in the water of the washing machine. Household washing machines currently in use normally use about 175 grams of powdered detergent to wash a full load of laundry. According to the present invention, only about 67 ml or about 80 grams of the concentrated liquid nonionic detergent composition is required.

In a preferred embodiment of the invention, the typical detergent composition is formulated using the ingredients listed below: 5 Hydroxyacrylic acid alkali metal salt polymer Detergency builder \ by weight

Non-ionic detergent surfactant 30-55 - Acid-terminated surfactant 1-10 ^ 10 Alkylene glycol monoalkyl ether 3-15, / i Hydroxyacrylate polymer 7-22

Alkanolic phosphoric acid ester 0.1-0.9 Alkaline bleaching metal perborate 10-22 Bleaching agent activator (TAED) 4-15 15 Optical brightening agent 0.1-0.6

Enzymes 0.5-1.5

Perfume 0.1-0.8

In another preferred embodiment of the invention, the detergent composition of typical formulation is formulated using the ingredients listed below:

Alkaline Salt of Polvacetal-Carboxylic Acid Detergency% by weight 25 Non-ionic surfactant detergent 30-55

Acid-terminated surfactant 2-18

Polyacetal-carboxylic acid alkali metal salt detergency builder 5-22

Polyphosphate detergency builder 0-20 - 30 Alkanolic phosphoric acid ester 0.1-0.9

Bleaching Alkali Metal Perborate 7-22

Bleaching Agent Activator (TAED) 4-12

Optical brightening agent (Stilbene Brightener N4)) 0.1-0.8 45

Enzymes (Protease-Esperase SL8) 0.5-1.5

Perfume 0.1-0.8

The following nonlimiting examples illustrate the present invention.

5 EXAMPLE 1

A concentrated nonaqueous liquid detergent composition with nonionic surfactant is prepared from the following ingredients in the amounts indicated.

^ 10 * by weight, Surfactant T9 20

Surfactant T7 20

Dobanol 91-5 acid-terminated reaction product with succinic anhydride 4.0 15 Diethylene glycol monobutyl ether 10

Sodium alpha-hydroxyacrylate polymer, 17.0

Alkanolic ester of phosphoric acid 0.3

Sodium perborate monohyrate bleach 17.0 Tetraacetylethylene diamine (TAED) as activator of bleach 10.0

Stilbene type brightener 0.4

Suspension of Esperase 1.0 25 Perfume 0.3 100.0 EXAMPLE 2 „A concentrated non-aqueous liquid detergent composition with nonionic surfactant is prepared from the following ingredients in the quantities indicated: 46% by weight

Non-ionic surfactant, product D 40.0

Acid-terminated reaction product of Dobanol 91-5 with succinic anhydride 14.0 Sodium salt of polyacetal carboxylic acid 5 (Builder U) 17.0

Alkanolic ester of phosphoric acid 0.3

Bleaching sodium perborate monohydrate 17.0 w Tetraacetylethylene diamine (TAED) as u 10 bleach activator 10.0

Stilbene Brightener N4 0.4

Suspension of Esperase 1.0

Perfume 0.3 15 100.0

The compositions of Examples 1 and 2 are or can be ground for about an hour to reduce the particle size of the detergency builder salts in suspension to less than 10 microns.

It is found that the detergent compositions prepared are stable and do not gel on storage and have high detergency.

The compositions can be prepared without grinding the detergency builder salts and solid particles in suspension to a small particle size, but best results are obtained by grinding the composition to reduce the particle size of the solid particles in suspension -to sion.

The detergency builder salts can be used as supplied, or the detergency builder salts and suspended solid particles can be ground or partially ground before being mixed with the nonionic surfactant. The grinding can be carried out partly before mixing and the grinding can be completed after mixing, or else all the grinding can be carried out after mixing with the liquid surfactant.

The compositions of the present invention, containing an alkali metal hydroxyacrylate polymer as a detergency builder, can be thickened with conventional thickeners such as Bentonite and Aerosil to form a * v '' cream, or paste and be used as a degreasing cleaning agent.

Claims (16)

1. A nonaqueous liquid detergent composition for large laundering works, characterized in that it contains: at least one nonionic liquid surface-active detergent, a detergency builder of the type 5 polymer of hydroxy acrylic acid or acid salt hydroxy-acrylic or an adjuvant salt of organic detergency of the polyacetal-carboxylate type, at least one component chosen from an anti-gelling agent of the anionic surfactant type with acid termination and uhl '10 monoalkyl ether of alkylene glycol, and a anti-sedimentation agent. 2. A detergent composition according to claim 1, characterized in that it comprises 5 to 50 percent of a detergency builder of the polymeric type of hydroxy acrylic acid or salt of hydroxy acrylic acid or of a adjuvant detergency of the polyacetal-carboxylate type. 3. A detergent composition according to claim 1, characterized in that the detergency builder hydroxy-acrylic acid polymer contains monomer units of the formula: ’r, oh” 1 I - C —C '- _à2 Îoom. in which and Rg may be the same or different and are chosen from hydrogen and alkyl groups of 1 to 3 carbon atoms, and M is chosen from hydrogen, an alkali metal, alkali metal cation - earthy and ammonium. * <* 49 4. Detergent composition according to claim 1, characterized in that it comprises at least one nonionic liquid surfactant in an amount of about 25 to 50%, a nonionic surfactant with its acid terminal in an amount of about 2 to 20%, a monoalkyl ether of alkylene glycol in an amount of about 5 to 20 a polymer of detergency builder hydroxy-acrylate in an amount of about 10 to 30 V and an alkanolic acid ester phosphoric acid, an amount of about 0.1 to 1.0 w / v; 5. Detergent composition according to claim 4, characterized in that the detergency builder hydroxy-acrylic acid polymer contains monomer units of formula: 15 TR, 0H '1 _.r_è - L C00M * J tt- in which and R2 can be the same or different and are chosen from hydrogen, methyl, ethyl and propyl, M is chosen from sodium and potassium, and the value of n is chosen so that the polymer is soluble in water. 6. Non-aqueous liquid detergent composition free of detergency builder phosphate, characterized in that it comprises approximately 30 to 55% of nonionic surfactant, approximately 1 to 10% of acid-terminated surfactant, approximately 3 to 15% of alkylene glycol monoalkyl ether, approximately 7 to 22% of sodium hydroxy-acrylate polymer, detergency builder, approximately 0.1 to 0.9% of C 16 to C 18 alkanolic ester. * 50 of phosphoric acid, approximately 10 to 22 * of sodium perborate monohydrate for bleaching, and approximately 4 to 15% of tetraacetylethylene diamine as activator of bleaching agent. ^ 7. Detergent composition according to claim 6, characterized in that the hydro-xy-acrylate polymer has a molecular weight of 2000 to 20000. 8. A detergent composition according to claim 1, characterized in that the polyacetal carbonate xylate is represented by the formula: V. “lf? HOi * 2 IqoohJ n 15 in which M is chosen from an alkali metal , ammonium, alkyl groups of 1 to 4 carbon atoms; tetralkylammonium groups and alkanolamine groups of 1 to 4 carbon atoms in the alkyl chain: na has a value of at least 4, and and R2 are chosen to be individually stable groups which stabilize the polymer against of a depolymerization in alkaline solution and are chosen to be compatible with the ingredients of the nonionic liquid detergent composition. 9. laundry detergent composition according to claim 1, characterized in that it has a low or zero or polyphosphate content and in that it comprises at least one liquid nonionic surfactant in an amount of about 25 to 50 a nonionic acid-terminated surfactant in an amount of about 10 to 25%, a detergency builder polyacetal carboxylate in an amount of about 10 to 30%, a detergency builder polyphosphare in a quan- * j 51 tity of about 0 to 20%, and an alkanolic ester of phosphoric acid in an amount of about 0.1 to 1.0 V 10. Detergent composition according to claim 9; characterized in that the polyacetal-carboxylate is represented by the formula: - - Rx - CHO Rj - in COOM -In \ in which M is an alkali metal; na has a value of 50 to 200, and and R2 are selected to be individually stable groups which stabilize the polymer against depolymerization in alkaline solution and are chosen to be compatible with the ingredients of the detergent composition non-ionic liquid. 11. A non-aqueous liquid detergent composition free of detergency builder phosphate, characterized in that it comprises approximately 30 to 45% of nonionic surfactant, approximately 2 to 18% of acid-terminated surfactant, approximately 5 to 22 of sodium salt of polyacetal carboxylic acid, about 0.1 to 0.9% of C16 to C18 alkanolic ester of phosphoric acid, about 7 to 22% of sodium perborate bleaching monohydrate, and about 4 to 12% tetraacetylethylene diamine (TAED) as an activator of bleaching agent. 12. Detergent composition according to Claim 11, characterized in that the polyacetal carboxylate is represented by the formula: ^ —ÎCHO 3 “R2 C00M. J e a i «i 52 in which M is chosen between sodium and potassium; n has a value of 50 to 200; is 0CH, CH- "COOM 5. Z 3 ° tt | -CH -C -CH- i i 3 CH3 cooh s, ke. 2 ^ 10 or mixtures thereof, and R is OCH-CH-I 2 3 -CH I CH3 and the polyacetal-carboxylate segments constitute 50 to 80 percent by weight of the entire polyacetal-tal-carboxylate. 13. A detergent composition according to claim 12 characterized in that the polyacetal carboxylate is the sodium salt and the groups R ^ are stabilizing end groups. 14. Detergent composition according to claim 3 or 11, characterized in that it comprises an alkali metal perborate monohydrate bleaching l, in an amount of about 5 to 30%, tetraacetyl- * ethylene diamine as activator bleach, in an amount of about 5 to 20%, and optionally, one or more detergent additives selected from optical brighteners, enzymes and a perfume. 53 15. Method for cleaning soiled fabrics, characterized in that it consists in bringing the soiled fabrics in contact with the detergent laundering composition according to claim 6. 16. Method for cleaning soiled fabrics, characterized in that it consists in bringing the soiled fabrics in contact with the laundry detergent composition according to claim 11. V y \ 'u —v