LU86545A1 - PHOSPHATE-FREE NON-AQUEOUS LIQUID DETERGENT COMPOSITIONS AND METHODS FOR CLEANING DIRTY TISSUES USING THE SAME - Google Patents

Description

! '/ 52.560 1 Patent application of ... 5 ..... a.Q.ût .... l.9.8.6 .................

Designation of the Inventor (1) The undersigned ...... Jacques ..... de..Muys.er ...................... .................................................. .................................................. ...................

.................................................. .......:. 3..5. / ....... bQule.Y.ar.d .... RQy.al .... à ..... LUXEMBOURG_______________________________________________________________________ acting in ctecâéposaat quality: - of the depositor's representative - '' (*) ......... CQLG.ÄTE.r: .P.ALMOLIWE ..... COMRÄN.Y ......... .................................................. .................................................. ...................................

300 Park Avenue ...............:.: NEW - YORK-r — Ν.Χ, · 1 · ΰΟ · 22 ............ .................................................. ............-............. ··· ..................... .................................................. ....

(United States of America) (8) of the intent regarding: "Non-aqueous liquid phosphate-free laundry detergent compositions and methods for cleaning soiled fabrics using them." designates as inventor (s): 1. Name and first names .... T.raZ.Q.ll.ah ..... D.UHAD.I _____________________________________________________________________________________________________________________________________

Address ^ 'üua ^ Gl ° esener' LIEGE (Belgium) 2. Name and first names .... Louis ..... DEKAN ..................... .................................................. .................................................. ..................................

Address .1 ° ... '. SERAING (Belgium) .............................................. .................................................. ..

3. Name and first names ... Lucie ..... FELLEN ................................... .................................................. .................................................. ....................

Address 72 · route <3e Liège, ·· J-UPILLE (Belgium)

He affirms the sincerity of the above indications and declares to assume full responsibility for them.

Luxembourg ^ August 20 | g86 SESŸICE MOüRfiHlIS DE U PSOPfilETÉ IHDUSIRIEtifl f *.

fcnfcÂXitK -, _ * \ \ i ^,

Upifpüt ..... J \ / \ \ \; \ ^ _ - (signature) - (1) Last name, first names, company, address.

(*) Surname, first names and address of the depositor.

86 / B 52 560

CLAIM OF PRIORITY

of the patent application / utility model * "_ in the United States of America From August 5, 1985 (No. 762.162) and (No. 762.163) and (No. 762.167) Brief Description filed in support of a request of

! PATENT

at

Luxembourg on behalf of: Colgate-Palmolive company

New York (United States of America) for: "Non-aqueous liquid phosphate-free laundry detergent compositions and methods for cleaning soiled fabrics using them." * Λ ϊ »

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 with 05 phosphate-free or low phosphate content for laundry laundering, containing a suspension * of a detergent adjuvant salt of the heptonate type, a salt detergency builder of the carboxymethyl-oxy-succinate type or a builder salt of type alginate in nonionic surfactants, which compositions are stable against phase separation and gelation and can be easily poured, and the use of these compositions for cleaning soiled tissues.

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. No. 4,316,812, No. 3,630,929 and No. 4,264,466 and in British patents No. 1,205,711, No. 1,270,040 and No. 1,600,981.

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 detergency builders interesting.

35 In addition, the polyphosphate content of laundry detergents has been held responsible for the excessively high phosphate content in i 2 i water.

V

Â, surface. 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.

05 Recently / laws promulgated by governments have aimed to reduce the amount of po-lyphosphates present in laundry detergents and, in some jurisdictions where polyphosphates have been a problem, have required that deter-10 laundry agents do not contain detergency builder po-lyphosphates at all.

Liquid detergents are often considered to be more convenient to use than particulate or powdered, dry products and, therefore, have met with significant success with consumers. They can be poured easily, they dissolve quickly in washing water, they can be easily applied in concentrated solutions or dispersions on soiled parts of garments to be cleaned and do not generate dust, and they generally occupy little space. 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 during storage and others separate during cooling and cannot easily be persisted. In some cases, the viscosity of the product changes and the product becomes either too thick to be poured, or liquid to the point of resembling water.

3 1, ι ί 'i

Some clear products become cloudy and others gel on standing.

In addition to the problem of sedimentation or phase separation, nonaqueous liquid laundry detergents based on nonionic liquid surfactants have the disadvantage that nonionic surfactants tend to gel when added to water. 'Cold water. This is a particularly acute problem during common use of 10 European household automatic washing machines in which the user places the laundry detergent composition in a dispensing device (e.g. a dispensing drawer). the machine. During the operation of the machine, the detergent 15 contained in the dispenser is subjected to a stream of cold water which transfers it into the main body of the washing solution. In particular, 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 composition accumulates during repeated washing cycles, ultimately forcing the user to sweep the hot water dispenser.

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.

λ 1 - 'ϊ 4

Partial solutions to the problem of the gelling of aqueous compositions substantially without detergency builder have been proposed, for example by diluting the nonionic liquid surfactant 05 with certain solvents acting on the viscosity and certain gelling inhibiting agents, such as lower alkanols. , for example ethyl alcohol (see US Patent No. 3,953,380), alkali metal formates and adipates (see US Patent No. 4,368,147), hexylene glycol, polyethyl- ene-gly-col, etc., and by modifying and optimizing the structure of nonionic surfactants. As an example of modification of nonionic surfactants, a particularly advantageous result was 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 including 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 hydrophobic-lipophilic 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 fatty alcohol ethoxylated with 8 moles of ethylene oxide only exhibits a limited tendency to form a gel.

Nevertheless, there is a desire to improve both the stability and the gelation inhibition of non-aqueous, low-phosphate, low-phosphate liquid compositions for tissue treatment.

According to the present invention, a highly concentrated non-aqueous liquid detergent composition with a low phosphate content, and more particularly free of polyphosphate type detergency builder, is prepared by dispersing detergent builder salts of the heptonate type, carboxymethyloxysuccinate type, or alginate type in a liquid nonionic surfactant detergent.

The heptonic acid salts used according to the present invention are well known. Heptonic acid is an acid derivative of an aldoheptose (mono-saccharide). The alkali metal salts of heptonic acid are water-soluble.

The alkali metal salts of heptonic acid used in the present invention are represented by the general formula:

H

15 H-C-OH

(H-C-OH) _

0 = C-0M

Wherein M is an alkali metal or ammonium cation.

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

The carboxymethyloxysuccinic acid salts used in the present invention are represented by the general formula: i 6

MOOC-CH-COOM

f

CH30-CH-C00M

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

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

In order to improve the viscosity characteristics of the composition, an acid-terminated nonionic surfactant can be added. To further improve the viscosity characteristics of the composition and the storage properties of the composition, viscosity improvers and antifreeze agents may be added to the composition.

7 such as monoalkyl ethers of alkylene glycol and anti-sedimentation agents such as esters of phosphoric acid and aluminum stearate. In 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-sedimentation agent.

Sanitizers or bleaches 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 micrometers and preferably less than 10 micrometers in order to further improve the stability of the suspension of the components detergency builders in liquid nonionic surfactant detergent.

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

Washing machines currently manufactured for home use normally operate at washing temperatures up to 100 ° C. Up to 70 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 100 grams (77 ml) or less of liquid detergent composition is required to wash a full load of dirty laundry.

Consequently, according to one aspect, the present invention provides a composition-liquid "for ·. 8% fat ί laundering work free of detergency builder of phosphate type or substantially free of such a builder builder, consisting of a suspension of an alkali metal salt of detergency builder adjunct acid, of alkali metal salt of detergency builder carboxymethyloxy-succinic acid, or of an alkali metal salt of detergency builder alginic acid a nonionic liquid surfactant.

In another aspect, the invention provides a concentrated liquid detergent composition with little or no phosphate content for heavy laundering work, 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 for filling a container with a nonaqueous liquid laundry detergent composition in which the detergent consists, at least predominantly, of a liquid nonionic surfactant free of polyphosphate detergency builder and for dispensing the composition from the container into an aqueous washing bath, the distribution 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 washing bath.

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

9

The concentrated nonaqueous liquid detergent compositions for laundering with nonionic surfactant, with little or no polyphosphate content, in accordance with the present invention, combine the advantages of being stable, and of not being sedimented during storage. no gelation during 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 non-ionic liquid non-aqueous detergent composition, non-polluting, with a low content, and in particular with no polyphosphate content, for large laundering works, containing as an adjuvant detergency salt , a heptonate, a carboxyraethyl-oxysuccinate or an alginate suspended 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 an adjuvant detergency of the heptonate, carboxymethyloxy-succinate or alginate 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 repeatedly dispersed from the dispenser of European-style automatic washing machines without fouling or obstructing the dispenser even during the winter months.

Another object of the present invention is to provide stable, non-gelling suspensions, with little or no polyphosphate content, of non-aqueous liquid nonionic detergent composition reinforced for large laundering jobs / which comprise an effective amount of heptonate, carboxymethyloxy-suc-05 cinate or alginate as adjuvant detergency salt.

Another object of the present invention is to provide stable non-gelling suspensions of reinforced nonaqueous liquid nonionic detergent composition for large laundering jobs, which include an alkanolic ester of phosphorous acid and / or an acid salt aluminum fat as an anti-sedimentation agent, in an amount sufficient to increase the stability of the composition, i.e. to prevent sedimentation of detergency builder particles, etc., preferably while reducing or at least not increasing the plastic viscosity of the composition.

These and other objects of the invention which will become apparent from the following detailed description of preferred embodiments are generally achieved by preparing a detergency builder composition with little or no polyphosphate content by adding to the non-surfactant. non-aqueous liquid ionic an effective amount of an alkali metal heptonate, carboxymethyloxy-suc-cinate, or alkali metal alginate detergency builder and tissue treatment additives, organic or inorganic, for example gelling and viscosity improving agents, anti-sedimentation agents, anti-encrustation agents, bleaching agents, activators of bleaching agents, anti-foaming agents, optical brightening agents, enzymes, anti-redeposition agents, perfumes and dyes.

Non-ionic active detergent Non-ionic 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 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 oxide (hydrophilic in nature). Practically, any hydrophobic compound comprising a carboxy, hydroxy, amido or amino group having a free hydrogen atom linked to. 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 ratio between the hydrophobic and hydrophilic groups. Representative examples of suitable nonionic surfactants are those described in US patents. A. No. 4 316 812 and No. 3 630 929.

In general, nonionic detergents are lipophilic compounds alkoxylated by a poly (lower alkoxy) group in which the desired hydrophilic / lipophilic ratio is obtained by the addition of a hydrophilic poly (lower alkoxy) group to a moiety 25 lipophilic. A preferred class of nonionic detergents used is constituted by the alkoxylated higher alkanols by poly (lower alkoxy) groups in which the alkanol has 9 to 18 carbon atoms and in which the number of moles of al-30 oxide Lower kylene (of 2 or 3 carbon atoms) is 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 35 per mole. Preferably, the lower alkoxy group is the ethoxy group, but in certain cases, it can be advantageously mixed with the propoxy group, the possible presence of which often represents only a minor proportion (less than 50%).

Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and 05 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 Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols with an average of about 12 to 10 15 carbon atoms, with about 7 moles of ethylene oxide, and the latter is a corresponding mixture in which the carbon atom content of the higher fatty alcohol is 12 or 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 linear secondary alcohol ethoxylates manufactured by Union Carbide Corporation. The first 20 is a mixed ethoxylation product 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 nonionic detergent, are higher molecular weight nonionic surfactants, such as Neodol 45-11, which are similar condensates of ethylene oxide on 30 higher fatty alcohols, the higher fatty alcohol 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 trade mark 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. hydro-xyle. Examples include Plurafac RA30 (a C ^ -C ^ fatty alcohol condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide), Plurafac RA40 (a C ^ gC ^ fatty alcohol condensed with 7 moles 10 propylene oxide and 4 moles of ethylene oxide), Plurafac D25 (a fatty alcohol in C ^ -C 5 condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide).

Another group of liquid nonionic surfactants are commercially available from Shell Chemical Company, Inc., under the trade name Dobanol: Dobanol 91-5 is an ethoxylated C 8 -C fatty alcohol with an average of 5 moles of ethylene oxide and Dobanol 25-7 is a C 1 -C 20 Cl5 fatty alcohol ethoxylated with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

In higher alkanols alkoxylated by poly (lower alkoxy) groups, to obtain the best ratio between hydrophilic and li-pophile moieties, the number of lower alkoxy groups is generally 40% to 100% of the number of atoms. carbon of the higher alcohol, preferably 40 to 60% of this number, and the nonionic 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 - * 14 fl toyage, etc- In this. as regards the preferred and less preferred nonionic detergents, the al-kyle groups which they contain are generally linear, although one can tolerate branching, for example-05 pie at the level of a carbon atom neighboring the terminal carbon atom in 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 not have a length of 10 more than three carbon atoms. 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 group! eg alkyl. 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 , there may appear a median or secondary junction with the ethylene oxide of the chain. In general there is only a minor proportion of such alkyl groups, generally less than 20%, but, as in the case of the Tergitol mentioned, this proportion can be higher. Also, when the lower alkylene oxide chain contains propylene oxide, the proportion of this propylene oxide is generally less than 20% and preferably less than 10% of this chain.

When using higher proportions than those mentioned above of alkanols of which? the alkoxylation is not terminal, of alkanols alkoxylated by poly- (lower alkoxy) groups containing propylene oxide and of nonionic detergent with lower hydro-lipophilic ratio, and when 35 d Other nonionic detergents in place of the preferred nonionic detergents listed herein, the resulting product may not have as good detergency, stability and non-gelling properties as the preferred compositions, but the use of compounds of the invention which act on viscosity and inhibit gelation can also improve the properties of detergents based on such nonionic compounds. In certain cases, for example when a poly (lower alkoxy) is used higher alkanol of higher molecular weight, often for - its detergent power, its proportion is adjusted or limited in accordance with the results of routine experiments, to obtain the desired detergent power and to obtain at the same time emps a non-gelling product of desired viscosity. Also, it has been found that it is only rarely necessary to use higher molecular weight nonionic surfactants for their detergent properties, since the preferred nonionic surfactants described herein are excellent detergents and, moreover, , they make it possible to reach the desired viscosity in the liquid detergent without gelling at low temperatures.

Another useful group of nonionic surfactants is the "Surfactant T" series of nonionic surfactants offered by British Petroleum. The nonionic surfactants Surfactant T are obtained by ethoxylation of secondary fatty alcohols in Cl3 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 of 9 mol of ethylene oxide and Surfactant T12 has an average of 12 moles of ethylene oxide, per mole of C 4 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 from about 7 to 9 moles, and the ethyl alcohol to - h 16 xylated with approximately 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.

Non-Ionic Surfactant · Acid Termination

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 nonionic surfactant and a po-lycarboxylic acid or anhydride.

As described in French patent application No. 85 05319 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. poured, and reduces the temperature at which the liquid nonionic surfactant forms a gel 30 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 Plurafac RA30 with succinic acid, the ester or hemi-ester of Dobanol 25-7 with succinic anhydride, and the ester or hemi-ester of Dobanol 91-5 with succinic anydride. Instead of succinic anhydride, other polycarboxylic acids or anhy-05 can be used, for example maleic acid, maleic anhydride, citric acid, etc.

Acid-terminated nonionic surfactants can be prepared as follows: 10 Acid-terminated Plurafac 30: 400 g of Plurafac 30 nonionic surfactant is mixed, which is an al-canol to which has been alkoxylated to introduce 6 oxide units. ethylene and 3 propylene oxide units per alkanol unit, with. 32 g of succini-15 anhydride and heated for 7 hours at 100 ° C. The mixture and the filter are cooled to separate the unreacted succinic material. Infrared analysis shows that about half of the nonionic surfactant has been converted to its acid hemi-ester.

20 Dobanol 25-7 with acid termination: 522 g of non-ionic surfactant Dobanol 25-7 are mixed, which is the product of ethoxylation of an alkanol in to and comprises approximately 7 ethylene oxide units per molecule of 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 n ' having 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 C8 alkanol with and has approximately 5 ethylene oxide units per mol-35 cule of alkanol, with 265 g of succinic anhydride and 0.1 g of pyridine as catalyst, and the mixture is heated at 260 ° C. for 2 hours, cooled and filtered for - *. t. i%> 18 separate the unreacted succinic material. Infrared analysis shows that almost all of the free hydroxyl groups in the surfactant have reacted.

Other esterification catalysts, such as an alkali metal alcoholate (e.g. sodium methylate) can be used in place of or in admixture with pyridine.

The acidic polyether, that is to say the acid-terminated nonionic over-factive, is preferably added in the dissolved state in the nonionic surfactant.

Adjuvanted Detergency Salts The nonaqueous liquid nonionic surfactant used in the compositions of the present invention contains, in the dispersed and suspended state, fine particles of organic and / or mineral detergency adjuvant salts.

The present invention encompasses, as an essential part of the composition, an adjuvant salt of organic detergency of the heptonate type, of the carboxy-methyloxysuccinate type or of the alginate type.

Adjuvant Detergent Organic Salts

Preferred organic detergency builder salts include the alkali metal salts of heptonic acid, preferably the sodium and potassium salts. Other acid salts of monosaccharides which can be used are the acid salts of monosaccharides formed with a longer chain. A particular example of acid salts of monosaccharides is the sodium salt of heptonic acid.

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

The carboxymethyloxysuccini acid salts used in the detergent compositions of the present invention are represented by the following general formula:

MOOC-CH-COOM

CH30 - (! H-C00M

05 in which M is chosen from hydrogen / an alkali metal and ammonium cation / and at least one M is an alkali metal or ammonium. The preferred alkali metals are sodium and potassium, with sodium still being preferred. The mono-, di- and trisodium salts can be used, the trisodium salt being more preferred.

A particular example of carboxymethyloxysuccinic acid salts which can be used is that represented by the formula:

Na-00C-CH-C00-Na

15 I

CH ^ O-CH-COO-Na Other preferred organic detergency builder salts include the alkali metal salts of alginic acid, preferably the sodium and potassium salts. Sodium alginate is a well known product, it is readily available and has many known uses. Sodium alginate is also known as sodium polymannuronate. Polymannuronic acid can have a molecular weight of about 240,000.

Alginic acid is extracted from giant brown seaweed (giant kelp macrocystis pyrife-ra (L.) Ag Lessoniaceae) in the form of mixed salts comprising calcium and magnesium salts of alginic acid. Alginates can also be extracted from digested kelp (Laminaria digitata (L.) La-mour, Laminariaceae) and sugar kelp (Laminaria saccharina (L.) Lamour). The calcium and magnesium salts of alginic acid are readily converted to alkali metal salts, particularly sodium al-ginate, by methods well known in the art. Sodium alginate is a powder of

P

20 cream color which is soluble in water.

A particular example of alkali metal salts of alginic acid which can be used is represented by the formula: 05

COOM COOM

OH T "-Y COOM COOM OH

10 M = Na (Manutex RH) Other organic detergency builders that 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 serves, when used in even small amounts, to inhibit encrustation, that is, it serves as an anti-encrustation agent.

Since the 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 alkali metal salt of lower polycarboxylic acid having a high calcium and magnesium binding power to inhibit incrustation 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), trisodium citrate, a salt of glutaric acid, a gluconic acid salt and a longer chain diacid salt.

Examples of sequestering alkaline organic detergent builder salts which can be used with detergent builder salts of the heptonate, carboxymethyloxy succinate or alginate type, or in admixture with other organic and mineral detergency builders are alkali metal, ammonium or substituted ammonium aminopolycarboxylates, for example sodium and potassium edetate (EDTA), sodium and potassium nitri-loacetates (NTA) and N- (2-hydroxy- ethyl) nitrilodiacetates of triethanolammonium.

Mixed salts of these aminopolycarboxylates are also suitable.

Other suitable organic type detergency builders include carboxymethylsuccina-tes, tartranates and glycollates.

20 Mineral Adjuvant Detergent Salts

The detergent compositions of the invention may also contain adjuvant mineral detergency salts soluble in water and / or insoluble in water. Adjuvant mineral detergent salts 25. suitable alkalines 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.

The alkali metal silicates are useful detergency builder salts which also act to adjust or adjust the pH and to make the composition anticorrosive to parts of the washing machine. Sodium silicates with Na20 / 22 ratios

SiO, from 1.6: 1 to 1: 3.2, especially about 1: 2

4M

at 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 polyphosphates can be added as detergency builder salts; when local regulations allow this use. Particular examples of such detergency builder salts are sodium tripolyphosphate (TPP), sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate and sodium hexametaphosphate. Sodium tripolyphosphate (TPP) is the preferred polyphosphate. In the formulations in which the polyphosphate is added, it is added in a proportion of 0 to 50% / for example 0 to 30%, and in particular from 5 to 15%. As previously mentioned, however, it is preferable that the formulations are free of polyphosphate or substantially free of polyphosphate.

Other representative examples of suitable detergency builders include, for example, those described in US Pat. Nos. 4,316,812, Nos. 4,264,466 and No. 3,630,929. Alkaline mineral salts detergency builders can be used with the non-ionic detergent surfactant or in mixture with other organic salts or mineral detergency adjuvants.

The water-insoluble crystalline and amorphous zeolite aluminosilicates can be used. Zeolites generally have the formula: (M20) x. (A1203). (Si ° 2) z.wH20 in which x is equal to 1, y ranges from 0.8 to 1.2, and is preferably equal to 1 , z is 1.5 to 3.5 or 35

V V

23 plus, 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.

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) that can be used are described in British Patent Nos. 1,504,168, the U.S. Patent. A. No. 4,409,136 and in Canadian Patents No. 1,072,835 and No. 1,087,477. An exera-pie of amorphous zeolites useful here can be found in Belgian Patent No. 835,351.

Other materials such as clays, particularly water-insoluble types, may 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 of any sandstone, sand, etc.) suitable for detergents contains at least 50% of montmorillonite and thus its cation exchange power is at least minus about 50 to 75 milliequivalents per 100 g of bentonite. Particularly preferred bentoni-tes are bentonites from Wyoming or from the western United States of America which have been sold under the designations of Thixo-jel 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften textile materials, such as.

k 24 described in British patents No. 401,413 and No. 461,221.

Viscosity Adjusting and Anti-Gelling Agents The incorporation into the deter-05 gente composition of an effective amount of low molecular weight amphiphilic compounds acting as viscosity adjusting and gelling inhibiting agents for non-surfactant ionic significantly improves "the storage 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 of ethylene oxide (approximately 2 to 6 ethylene oxide groups per molecule).

Suitable amphiphilic compounds can be represented by the following general formula:

RO (CHoCHo0) H

2. λ n where R is a C2-C6 alkyl group and n is a number of about 1 to 6 on average.

In particular, the compounds are lower mono-alkyl ethers (C 1 -C 4) of lower alkylene glycols (C 1 -C 4).

More particularly, the compounds are lower monoalkyl ethers (C ^ to C ^) of mono-, di-30 or lower trialkylene glycols.

Particular examples of suitable amphiphilic compounds include the ethylene glycol monoethyl ether C2H5-0-CH2CH £> H, the diethylene glycol monobutyl ether C ^ H ^ -O- (CH2CH20) 2H, the ether monobu-35 tetraethylene glycol C ^ H ^ -0- (CH2CH20) and dipropylene glucol monomethyl ether CH3 ~ 0- (CH2 -. »25 CHO), H. Particular preference is given to the monobutyl ether CH2 of diethylene glycol.

05 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 sedimentation and 10. 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 they remain stable and versalbes 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 detergency builder compound (s) and any additive in suspension, such as 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.

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

As described in the above-mentioned French patent application 85.05319, the acidic organic phosphorus compound having an acidic -POH group can increase the stability of the suspension of detergency builders in the nonaqueous nonionic liquid surfactant.

The acidic organic phosphorus compound can be, for example, a partial ester of phosphoric acid 26 and of an alcohol such as an alkanol having a lipophilic character, comprising for example more than 5 carbon atoms, for example 8 to 20 carbon atoms.

A particular example is a partial ester 05 of phosphoric acid and a C16 to C18 alkanol (Empiphos 5632 from Marcho'n); it consists of approximately 35% monoester and 65% diester.

The incorporation of very small quantities of the organic phosphorus acid compound makes the suspension clearly more stable with respect to sedimentation at rest, while remaining pourable, while for a low concentration of stabilizer, for example less than about Z%, its plastic viscosity generally increases.

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

Stabilizing agents of the aluminum-20 minium salt type are the subject of French patent application 85.02815 of February 28, 1986.

Preferred higher aliphatic fatty acids 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 non-ionic 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 27 acids, etc. The aluminum salts of these acids are generally commercially available, and are preferably used in the form of three acid residues, for example aluminum stearate 05 in the form of aluminum tristearate Al (C ^ H ^ COO)

Salts with an acid residue, for example aluminum monostearate, Al (OH) ^ C ^ H ^ COO) and salts with two acid residues, for example aluminum distearate, Al (OH) (C ^ yH ^ COO) 2 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 30%, preferably at least -50%, more preferably at least 80%, of the total amount of aluminum salt d '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 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 acts to prevent sedimentation of the suspended particles, it is assumed that the aluminum salt increases the wettability of solid surfaces by the non-ionic surfactant. This increase in wettability therefore allows the particles in suspension 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 j it has a certain anti-foam effect? it can reinforce the action of fabric softeners and it gives suspensions a longer duration of relaxation.

Bleaching Agents

Bleaches are broadly classified, for convenience, into chlorinated bleaches and oxygenated bleaches. The chlorinated bleaches are represented by sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% available chlorine) and trichlo-roisocyanuric acid (95% available chloride). Oxygenated bleaches are preferred and are represented by per-compounds which release hydrogen peroxide in solution. Preferred examples include sodium and potassium perborates, percarbonates and per-phosphates and potassium monopersulfate. Perborates, in particular, sodium perborate monohydrate, are particularly preferred.

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 tetraacetyl ethylene 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, ethylidenecarboxylate and its salts, alkyl and alkenyl succinic anhydrides, tetraacetylglycourile ("TAGU") • * 29 and their derivatives. Other useful classes of activators are described, for example, in the US patents.

A. N ° 4 1X1 826, N ° 4 422 950 and N ° 3 661 789.

The bleach activator 05 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 hydrogen peroxide in the washing solution in the presence of metal ions.

Suitable sequestering agents for this purpose include the sodium salts of ni-trilotriacetic acid (NTA), ethylene diaminer 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 decomposition under the action of enzyme, bleaching peroxide. Suitable inhibitors are described in U.S. Patent No. 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 05 may be present in the detergent product in order to give it other desired properties, of a functional or aesthetic nature. Thus, minor amounts of suspending or anti-redeposition agents may be included in the formulation, such as polyvinyl alcohol, fatty amides, sodium carboxymethylcellulose, hydroxypropylmethyl- cellulose. A preferred anti-redeposition agent is sodium carboxymethylcellulose (CMC) having a 2: 1 ratio of CM / MC, which is sold under the trademark Relatin DM 4050.

Optical brightening agents can be used for cotton, polyamide and polyester fabrics. Suitable optical brighteners include compositions of stilbene, triazole and benzidine sulfone, in particular substituted sulfonated triazinyl-stilbene, naphthotriazole-stilbene sulfone, benzidene sulfone, etc. prefers being the combinations of stilbene and triazole. Preferred brighteners are Brithtener N4 which is a dimorphilino-dianilino-stilbene sulfonate and Tinapal ATS-X which are well known in the art.

Enzymes may be used, preferably proteolytic enzymes, such as subtilisin, bromelain, papain, trypsin and pepsin, as well as amylase, lipase type enzymes and mixtures thereof. Preferred enzymes include a protease suspension, an esperase suspension and amylase. A preferred enzyme is Esperas SL8 which is a protease. Antifoaming agents, for example silicone compounds, such as Silicane L 7604, can also be added in small effective amounts.

Bactericides can be used, for example tetrachlorosalicylanilide and hexchlorophen, fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet absorbers, anti-jaundice agents-05 ment, such as carbosymethÿlcellulose sodium, pH modifiers and pH buffers, color preservatives, fragrances 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 of extremely small particle size (for example with a diameter of 5 to 100 micrometers, such as that sold under the name 15 Aerosil) or the other very bulky mineral supports described in US Pat. No. 3,630,929, in proportions of 0.1 to 10%, for example from 1 to 5%. However, it is preferable that the compositions which form peroxyacids in the wash bath (for example compositions containing a peroxygenic compound and an activator therefor) are substantially free from such compounds and other silicates; it has been found, for example, that silica and silicates promote undesirable decomposition of pe-roxyacid.

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 and more preferably less than 10 microns. Solid detergency builders, for example polyphosphates of alkali metals, are generally supplied in particle sizes of about 100, 200 or 400 microns. 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 nonionic surfactant liqui-05's and solid ingredients is subjected to attrition grinding in which the particle sizes of the solid ingredients are reduced to less than about 10 micrometers , for example at an average particle size of 2 to 10 micrometers or even less (for example 1 micrometer). Preferably, less than about 10%, in particular less than about 5% of the total 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%, for example about 50%) so that the solid particles are brought into contact with each other. from each other and are not too isolated from each other by the nonionic surfactant. After the grinding step, any 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 working with batch loads comprising 35 grinding balls made of soapstone 8 mm in diameter.

For a larger scale operation, one can v use a continuously working grinder 33 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); 05 when using such a mill, it is advantageous to pass the mixture of nonionic surfactant and 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 micrometers (for example to about 40 micrometers) before the grinding step to an average particle diameter of less than about 10 micrometers in the continuously working ball mill.

In the preferred liquid detergent compositions for heavy duty 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 ï in the range of about 10 or 20 to 60, for example 20 or 25 to 50 and especially 30 to 40 percent.

The aci-25 terminated nonionic surfactant may be omitted; however, it is preferable to add it to the composition in an amount in the range of about 0 to 30, for example 5 to 25, and especially 5 to 15 percent; builder salt of carboxymethyloxysuccinic acid in the range of about 5 to 50, for example 10 to 40, and especially 25 to 35 percent; or detergency builder salt of alginic acid in the range of about 5 to 50, for example 10 to 40, especially 25 to 35 percent.

Adjuvant detergent salt of heptonic acid, carboxymethyloxysuccinic acid or alginic acid: in the range of about 5 to 50, for example 10 to 40, and in particular 25 to 35 percent.

’1 34

Polyphosphate type detergency builder salt: in the range of about 0 to 50 percent, for example 0 to 30 and especially 5 to 15 percent.

Copolymer of polyacrylate and polymaleic anhydride 05 and salt in the form of alkali metal cane-1 anti-scaling agent: in the range of approximately 0 to 10, for example 2 to 8, and in particular 2 to 6 percent.

Alkylene glycol monoalkyl ether as anti-gelling agent: in an amount in the inter-valle of about 0 to 20, for example 5 to 15, especially 8 to 12 percent.

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

Stabilizing agent of the fatty acid aluminum salt type: in the range of about 0 to 3.0, for example 0.1 to 2.0, and especially 0.5 to 1.5 percent.

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

Bleaching agent: in the range of about 0 to 35, for example 5 to 30, and especially 8 to 15 percent.

25 Bleach activator: in the range of about 0 to 25, e.g. 3 to 20, and especially 4 to 8 percent.

Bleach sequestering agent: in the range of about 0 to 3.0, preferably ~ 0.5 to 2.0, including 0.5 to 1.5 percent.

Anti-redeposition agent: in the range of about 0 to 3.0, for example 0.5 to 2.0, and especially 0.5 to 1.5 percent.

Optical brightener: in the range 35 to about 0 to 2.0, for example 0.1 to 1.5, and in particular 0.3 to 1.0 percent.

Enzymes: in the range of about 0 to 4 35 3.0, for example 0.5 to 2.0, and especially 0.5 to 1.5 percent.

Perfume; in the range of about 0 to 2.0, for example 0.10 to 1/0, and especially 0.5 to 1.05 percent.

Colorant: in the range of about 0 to 1.0, for example 0.0025 to 0.050, and especially 0.25 to 0.0100 percent.

The various additives previously mentioned can optionally be added to achieve the desired function of the added materials.

Mixtures of acid-terminated nonionic surfactant and antifreezing agents of the alkyl ether-alkylene glycol-15 col type can be used and, in some cases, the use of such mixtures can be benefited alone, or with the addition to the mixture of a stabilizing and anti-sedimentation agent, for example an alkanol ester of phosphoric acid.

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.

The concentrated, non-aqueous, non-ionic liquid detergent composition of the present invention is easy to dispense into the water of the worm machine. Household washing machines currently in use normally use approximately 175 grams or 250 grams of powdered detergent to wash a full load of laundry. According to the present invention, only about 77 ml or about 100 grams of the concentrated liquid nonionic detergent composition is required.

In a preferred embodiment of the invention, a typical detergent composition is formulated using the ingredients listed below:% by weight Non-ionic surfactant 30-40 05 Surfactant. acid termination 5-15

Alkaline metal salt heptonic acid detergency builder; alkali metal salt of carboxymethyloxysuccini acid as detergency builder; or alkali metal salt of alginic acid detergency builder 25-35

Anti-scaling agent (Sokalan CP-5) 0-10

Polyphosphate (detergency builder salt) 0-30 15 Alkylene glycol monoalkyl ether 8-12

Alkanolic phosphoric acid ester (Empiphos 5632) 0.1-0 / 5

Anti-redeposition agent (Relatine DM 4050) 0-3.0 20 Alkali metal perborate for bleaching 8-15

Bleaching Agent Activator (TAED) 4-8

Sequestering agent (Dequest 2066) 0-3.0 25 Optical brightening agent (ATS-X) 0.05 or 0.3-1.0

Enzymes (Protease Esperase SL8) 0.5-1.5

Perfume 0.5-1.0

The following nonlimiting examples illustrate the present invention.

30 Sodium Salt of Heptonic Acid EXAMPLE 1

A liquid, non-aqueous nonionic surfactant detergent composition is concentrated from the following ingredients in the amounts indicated: 37% by weight

A mixture of fatty alcohol in Cl3-Cl5 condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide and fatty alcohol 05 in C ^ 3-C ^ ç. condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide 13.5

Surfactant T7 10.0 · * Surfactant T9 10.0 10 Acid-terminated reaction product of Bobanol 91-5 with succinic anhydride 5.0

Sodium salt of heptonic acid 28.7

Diethylene glycol 15.0 monobutyl ether 10.0

Alkanolic phosphoric acid ester (Empiphos 5632) 0.3

Anti-scaling agent (Sokalan CP-5) 4.0

Sodium perborate monohydrate blan-20 chiment 9.0

Sodium carbonate 0.9 Tetraacetylethylene diamine (TAED) as a bleach activator 4.5

Sequestering agent (Dequest 2066) 1.0 25 Optical brightening agent (Tinopal ATS-X) 0.5

Anti-redeposition agent (Relatin DM 4050) 1.0

Esperase suspension (Esperase SL8) 1.0

Perfume 0.5925

Dye 0.0075 30 100.00

The formulation is ground for approximately 1 hour to reduce the particle size of the detergency builder salts in suspension to less than 40 micrometers. The formulated detergent composition is shown to be stable and non-gelling during storage and has great detergency.

The formulation has a listening limit.

* V V

38 only 5.0 Pa and an apparent viscosity of 1.1 Pa.s “1.

EXAMPLE 2

In order to demonstrate the effect on incrustation of the substitution of sodium polyphosphate with an equivalent amount of detergency builder of the sodium heptonate type, the formulation of the detergent composition of Example 1, containing 28, 7% by weight of sodium heptonate is compared in a washing machine with the same composition in which 1 * sodium heptonate is replaced by 28.7% by weight of sodium polyphosphate.

The washing cycles are carried out with concentrations of 1 to 9 g / liter of each of the detergent compositions containing respectively sodium heptonate and sodium polyphosphate.

After having carried out 6 washing cycles with each of the detergent compositions in a washing machine, the degree of incrustation, that is to say the percentage of resulting ash deposited, is measured. The measurement of the percentage of ash deposited is determined by calcination of washed parts.

The results observed are indicated on the graph illustrated in FIG. 1 of the drawings and show that at detergent composition concentrations of 1 to 5 g / 1 of washing water, sodium heptonate is appreciably superior to polyphosphate. sodium to prevent encrustation or deposit of ash. At concentrations of detgen-30 te composition of approximately 5 to 9 g / l of washing water, the behavior of sodium heptonate and sodium polyphosphate detergency builders is roughly equivalent in terms of their anti - inlay.

EXAMPLE 3 In order to demonstrate the effect on the accumulation of incrustation of the substitution of sodium polyphosphate by an equivalent amount of sodium heptonate + detium builder, the detergent composition of Example 1, containing 28.7 percent by weight of sodium heptonate is compared in repeated washing cycles in a washing machine with the same composition in which the sodium heptonate is replaced by 28.7 percent by weight of sodium polyphosphate.

Repeat wash cycles are carried out at concentrations in the wash water of 5 g / l of each of the detergent compositions during twelve wash cycles. The accumulation of encrustations, i.e. the percentage of ash accumulation, is measured in each washing machine after 3, 6, 9 and 12 washes.

The results obtained concerning the accumulation of incrustations are indicated on the graph illustrated in FIG. 2. As regards the accumulation of incrustations, no accumulation with sodium heptonate is observed, while a slight accumulation is observed with the sodium polyphosphate detergency builder.

Alkaline metal heptonates can also be used as detergency builder salts to replace all or part of the polyphosphates in powdered detergent compositions, and in aqueous and cream detergent compositions, while obtaining good results.

Trisodigue Salt of Carboxymethyloxysuccinic Acid EXAMPLE 4 A liquid, non-aqueous, nonionic surfactant detergent composition is formulated from the following ingredients in the amounts indicated.

% by weight 35 Mixture of fatty alcohol in c ^ 3 ~ c ^ 5 condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide and fatty alcohol

* -H

40 in C-p-C · ^ condens ^ with 5 moles of propylene oxide and 10 moles of ethylene oxide 13.5

Surfactant T 7 10.0 05 Surfactant T 9 10.0

Acid-terminated reaction product of Dobanol 91-5 with succinic anhydride 5.0

Trisodium salt of 10-carboxymethyloxy-succinic acid 29.6

Diethylene glycol monobutyl ether 10.0

Alkanolic phosphoric acid ester (Empiphos 5632) 0.3

Anti-scaling agent (Sokalan CP-5) 4.0 15 Sodium perborate bleach monohydrate 9.0 Tetraacetylethylene diamine (TAED) as bleach activator 4.5

Sequestering agent (Dequest 2066) 1.0 20 Optical brightening agent (Tinopal ATS-X) 0.5

Anti-redeposition agent (Relatin DM 4050) 1.0

Esperase suspension (Esperase SL8) 1.0

Perfume 0.5925

Dye 0.0075 25: 100.00

The formulation is ground for about 1 hour to reduce the particle size of the detergency builder salts in suspension to less than 40 micrometers. It is found that the detergent composition formulated is stable and does not gel during storage and that it has great detergent power.

The formulation has a flow limit of 7.5 Pa and an apparent viscosity of 0.4 Pa.s “* ·.

35 EXAMPLE 5

In order to demonstrate the effect on the incrustation of the substitution of sodium tripolyphosphate by

'· V

41 an amount equivalent to the detergency builder effect of trisodium carboxymethyloxy succinate, the formulation of the detergent composition of Example 4 containing 29/6% by weight of trisodium carboxy-05 methyloxy succinate is compared for use in a washing machine with the same composition in which the trisodium carboxymethyloxy-succinate is replaced by 29/6% by weight of sodium tripolyphos-phate.

Wash cycles are carried out at wash water concentrations of 1 to 9 mg / l of each of the respective detergent compositions.

After having used each detergent composition in a washing machine, the resulting incrustion degree, that is to say the percentage of ash deposited, is measured. The measurement of the percentage of ash deposited is determined by calcination of washed parts.

The results observed are indicated on the graph in FIG. 3 and show that at concentrations of the detergent composition of 1 to 5 g / 1 in the washing water, the trisodium carboxymethyloxy succinate is appreciably superior to the tripolyphos-phate of sodium to prevent encrustation or deposit of ash. At detergent composition concentrations of about 5 to 9 g / l in the wash water, the behavior of the trisodium carboxymethyloxy succinate and the sodium tripolyphosphate detergency builders is about the same with regard to the properties anti-encrustation.

EXAMPLE 6 In order to demonstrate the effect on the accumulation of incrustation of the substitution of sodium tripolyphosphate by an equivalent amount to the action of detergency builder of trisodium carboxymethyloxy-succinate, the detergent composition of the Example 4 containing 29.6 percent by weight of trisodium boxymethyloxy succinate in machine wash cycles with the same composition in which the carboxymethyloxy trisodium succinate is replaced by 29/6 parts by weight of sodium tripolyphosphate -05 dium-

The repeated washing cycles are carried out at. concentrations of 5 g / l in the washing water T of each of the detergent compositions for twelve washing cycles. The accumulation of incrustation, that is to say the percentage of accumulation of ash is measured in each washing machine after 3, 6, 9 and 12 washes.

The results of the accumulation of incrustation obtained are indicated on the graph of fig. 15 re 4. With regard to the accumulation of incrustation, no accumulation with the carboxymethyl-oxy-succisate trisodium is observed. , while a slight accumulation with sodium tripolyphosphate is observed.

The metal carboxymethyloxy succinate al-20 cuddle detergency builders can also be used to replace some or all of the polyphosphates in powdered detergent compositions, and in aqueous and creamy detergent compositions, giving good results.

25 Sodium Salt of Alginic Acid EXAMPLE 7

A non-ionic, liquid, non-aqueous detergent surfactant composition is formulated, concentrated from the following ingredients in the amounts indicated:% by weight Mixture of fatty alcohol in C con densified with 7 moles of propylene oxide and 4 moles of ethylene oxide and fatty fatty al-35 condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide 13.5 43

Surfactant T 7 10.0

Surfactant T 9 10.0

Acid-terminated reaction product of Dobanol 91-5 with succi-05 anhydride 5.0

Alginic acid sodium salt 29.6

Diethylene-gly-col monobutyl ether 10.0

Alkanolic phosphoric acid ester 10 (Empiphos 5632) 0.3

Anti-scaling agent (Sokalan CP-5) 4.0

Sodium perborate bleach monohydrate 9.0 Tetraacetylethylene diamine (TAED) as a bleach activator 4.5

Sequestering Agent (Dequest 2066) 1.0

Optical brightening agent (Tinopal ATS-S) 0.5

Anti-redeposition agent (Relatin DM 4050) 1.0

Protease (Esperase SL8) 1.0 20 Fragrance 0.5925

Dye 0.0075 100.00

The formulation is ground for about 1 hour to reduce the particle size of the suspended detergency builder salts to less than 40 microns. It is found that the detergent composition formulated is stable and does not gel during storage and has a high detergent power.

The formulation has a flow limit of 4.7 Pa and an apparent viscosity of 0.46 Pa · s.

EXAMPLE 8

In order to demonstrate the effect on the incrustation of the substitution of sodium tripolyphosphate 35 by an equivalent amount with adjuvant effect of detergency of sodium alginate, the formulation of detergent composition of Example 7, containing 44 29, is compared. 6% by weight of sodium alginate for use in a machine. wash with the same composition in which the sodium algi.nate is replaced by 29.6% by weight of sodium tripolyphosphate.

05 The washing cycles are carried out at concentrations in the washing water of 1 to 9 g / liter of; respective detergent compositions, c. After having used each detergent composition in a washing machine, the degree of resulting incrustation, that is to say the percentage of ash deposited, is measured. The measurement of the percentage of ash deposited is determined by calcination of washed parts.

The results observed are indicated on the graph in FIG. 5 and show that at detergent composition concentrations of 1 to 5 g / l in the washing water, the sodium alginate is appreciably superior to the sodium tripolyphosphate for prevent encrustation or deposit of ash. At concentrations of detergent composition of about 5 to 9 g / day in the wash water, the behavior of sodium alginate and sodium tripolyphosphate detergency builders is about the same with regard to the properties anti-encrustation.

25 EXAMPLE 9

In order to demonstrate the effect on the accumulation of incrustation of the substitution of sodium tripolyphosphate by an equivalent amount, with the effect of detergency builder, of sodium alginate, the detergent composition of Example 7 is compared. containing 29.6 percent by weight of sodium alginate during repeated machine wash cycles with the same composition in which the sodium alginate is replaced by 29.6 percent by weight of tri-35 sodium polyphosphate.

The repeated washing cycles are carried out at concentrations of 5 g / l of washing water from each of the detergent compositions during twelve washing cycles. The accumulation of incrustation, i.e. the percentage of accumulation of ashes, is measured for each washing machine after 3, 6, 9 and 12 05 washes.

The results concerning the accumulation of incrustation obtained are indicated on the graph - of FIG. 6. With regard to the accumulation of incrustation, substantially no accumulation with the alginate is observed. sodium, while a slight accumulation is observed with sodium tripolyphosphate.

The alkali alginates detergency builders can also be used to replace, in whole or in part, the polyphosphate builders in the detergent powder compositions, and in the aqueous and cream detergent compositions, providing good results.

The formulations of Examples 1, 4 and 7 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 formulation to reduce the size of the solid particles. in addition to 25 pension.

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 in part before the end of the mixing and can be carried out after mixing, or else the whole grinding operation can be carried out after mixing with the liquid surfactant.

The formulations contain detergency builder particles and suspended solids of less than 100 microns, or preferably less than 46 microns. 40 micrometers in diameter.

It goes without saying that the invention is not limited to the embodiments described and that it is capable of various variants without departing from its scope.

Claims (15)

47 1. Non-aqueous liquid detergent composition for large laundering works, characterized in that it comprises: 05 at least one nonionic surfactant detergent liqui de and an adjuvant detergency salt of the alkali metal salt type <heptonic acid , carboxymethyloxy-suc cinate or alkali metal salt of alginic acid. 2. Detergent composition according to claim 1, characterized in that it comprises at least one of the elements of the group formed by: an anti-gelling agent of the nonionic surfactant type with acid termination, an alkylene monoether- glycol, and a stabilizing agent of the alkanolic ester type of phosphoric acid. 3. A detergent composition according to claim 1, characterized in that it comprises 5 to 50 percent of an alkali metal salt of heptonic acid, a carboxymethyloxy succinate, or an alkali metal salt d alginic acid as detergency builder salt. 4. Laundry detergent composition according to claim 1, characterized in that it has a low or zero polyphosphate content and in that it comprises: at least one liquid nonionic surfactant in an amount of about 25 to 50 %, An acid-terminated nonionic surfactant in an amount of about 5 to 25%, an alkali metal salt of heptonic acid, a carboxymethyloxy succinate or an alkali metal salt of alginic acid as a detergency builder salt in an amount of about 10 to 40%, an alkylene glycol monoether in an amount of about 5 to 15%, • Λ 48 a detergency builder polyphosphate in an amount of about 0 to 30%, · and an alkanolic ester of phosphoric acid in an amount of about 0.1 to 1.0%. 5. A detergent laundering composition according to claim 4, characterized in that it comprises: an alkali metal perborate monohydrate bleaching agent in an amount of about 5 to 30%, 10 of tetraacetylethylene diamine as activator bleach in an amount of about 3 to 20%, and optionally one or more additives for detergents, selected from the group consisting of an anti-scaling agent, an anti-redeposition agent, a sequestering agent for the whitening, optical brightening agents, enzymes and a perfume. 6. Detergent composition according to claim 4, characterized in that the alkali metal salt of heptonic acid is represented by the formula: 8 PM H-C-0H! (H-C-0H) 5 23 L 0 = C-0Na the carboxymethyloxy-succinate is represented by the formula: 30 NaOOC-CH-COONa CH3-CH-COONa 35 and the alkali metal salt of alginic acid is the sodium salt of alginic acid. 7. Detergent laundry composition '3 49 according to 1¾ claim 4, characterized in that the alkanolic ester of phosphoric acid comprisesun alkanolic ester C of phosphoric acid. 8. Detergent composition according to Reven-05 Dication 4, characterized in that it contains a detergency adjuvant polyphosphate in an amount> of about 5 to 15 percent. 9. Liquid detergent composition not l. aqueous phosphate-free detergency builder 10 for heavy laundering, characterized in that it comprises approximately 30 to 40% of nonionic surfactant, approximately 5 to 15% of acid-terminated surfactant, approximately 23 to 35% of sodium of heptonic acid, approximately 8 to 12% of alkylene glycol monobutyl ether, approximately 0.1 to 0.5% of C 1 -C 4 alkanolic ester of phosphoric acid, approximately 8 to 15% sodium perborate monohydrate for bleaching, approximately 4 to 8% of tetraacetylethylene diamine (TAED) as a bleach activator. 10. A non-aqueous liquid detergent composition free of detergency builder phosphate for heavy laundry work, characterized in that it comprises approximately 30 to 40% of nonionic surfactant, approximately 5 to 15% of acid-terminated surfactant, approximately 25 35% of trisodium salt of carboxymethyloxy-succinic acid, approximately 8 to 12% of monobutyl ether of alkylene glycol, approximately 0.1 to 0.5% of C 1 -C 4 alkanolic ester of acid phosphoric, about 8 to 15% sodium perborate monohydrate bleach 30, about 4 to 8% tetraacetylethylenene diamine (TAED) as a bleach activator. 11. Non-aqueous liquid detergent composition free of detergency builder phosphate for large laundering work, characterized in that it comprises approximately 30 to 40% of nonionic surfactant, approximately 5 to 15% of acid-terminated surfactant, approximately 25 at 35% sodium salt of alginic acid, about 8 to 12% of monobutylether of alkylene glycol, about 0, there 0/5% of C 1 -C 4 alkanol ester g of phosphoric acid, approximately 8 to 15% of sodium perborate monohydrate for bleaching / 05 approximately 4 to 8% of tetraacetylothylene diamine (TAED) as activator of bleaching. ς 12. Detergent composition according to claims 9, 10 or 11, characterized in that it comprises an anti-redeposition agent, an anti-encrustation agent and a sequestering agent for the bleaching agent. 13. Method for cleaning soiled fabrics, characterized in that it consists in bringing the soiled fabrics into contact with the laundry detergent composition according to claim 9. 14. 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 10. 15. A 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. .j V,