LU87028A1 - LIQUID DETERGENT COMPOSITIONS CONTAINING HEXYLENE-GLYCOL AND METHODS OF USE THEREOF FOR CLEANING DIRTY TISSUES - Google Patents

Description

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Inventioa Patent Application ............................................ .................................................. .................................................. ............................................. _. il) I. Request -La ...... society ...... known as * ....... COLGAÏE-PALMÔLIVE ...... € QMPAN ¥ -r - 3; 0 & -Park -Aventte # <2> ... NSW ...... YORK, ..... N.-Y, 1002.2 -..... (United States ..- â-LAmériquel-r — represented. .........

by ..... Mister ..... Jacques ...... de_.Muy.ser 4 ...... agi s s ant ...... in ..... q.uality. from .-. mandata ire deposit (s) this twenty-eight October 1909 eighty seven ........— - (4) at .3 5 hours, at the Ministry of Economy and the Middle Classes, in Luxembourg: 1. this request for obtaining a patent for an invention relating to: "Liquid detergent compositions containing - - --------------------- - (5) hexylene glycol and their methods of use for -------------------------- cleaning ...... of. .... soiled fabrics___________________________________________________________________________________________________________________________________________ 2. the description in French _________________________________- of the invention in triplicate; 3. ................ / __________________________ drawing boards, in triplicate; 4 the receipt of the taxes paid to the Luxembourg Registration Office on ..... 28 October 4 93 7-: 5. the delegation of power, dated from New York— ---------- ----------------- the 9 — October-198? '6. the document of aya nt cause (authorization); declare) assuming responsibility for this declaration, that the inventor (s) is (are): (6) - Guy BRO.ZE, ........ rue Claskin 32, S-GRACE- HOLLOGNE (Belgium) ---------------------- ... ”...... Danielle ...... BASTIN f ..... ..rue de-la -Hayoulle y 14 B-SOUMAGNE (Belgium) ........ Leopold ...... LÄITEM ......., ........ rue de ..... Merdorp 12 ........... B-ORP-JAUGEE (Belgium ^ ----- claims! Ntj for the above patent application the priority of one (of) application ( s) of (patent ............................................. ............................................-..... ................... filed in (8) Rfia-ha ..... Tto4s d1 Aroérinus —.........

on (9) ........ 29 ...... October ...... 1.986 ....................... .................................................. ............................- -__________________________________------------------- -------------------------------- under N ° (10) ........... ..924.392 .............. ...................-............. ........ ........................................—- ----------------------------------------.......... ..- in the name of (11 days ... of the inventors ..... -.............................. .................................................. ....................-...........

elect! elect) domicile for him / her and. if appointed, for its representative, in Luxembourg ._......................................- .....— ............... 3.5 ...... boulevard. Royal................................................. .................................................. .................................................. ......; ................— <12) request (s) the grant of a patent for the invention for the subject described and represented in the appendices above, with adjournment of this issue to 6 ......................................... .................................................. .....month. (33)

The ^ exhibitor / agent: ............................................ .......... ........................................ ............... ........................- -4i · "/ \ \ iv 0 V ί (· \ f 1 R · Statement of Deposit

The aforementioned application for a patent for invention has been filed with the Ministry of the Economy and the Middle Classes. Intellectual Property Service Luxembourg, dated: October 28, 1987

Pr. The Minister of Economy and Classes Movenaes- 15 · ’\ i at ............ hours \ p. d.

A) The head of the intellectual property department.

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(I. --N EXPLANATIONS RELATING TO FORM L »L Ut PÛT

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CLAIM OF PRIORITY

of the EK patent application / utility model IN THE UNITED STATES OF AMERICA '

October 29, 1986 (No. 924.392).

11 T ..... 111 I "i / Brief Description filed in support of a request for

PATENT

at

Luxembourg on behalf of: colgate-palmolive company NEW YORK, N.Y. 10022 (United States of America) for: "Liquid detergent compositions containing hexylene glycol and methods of using them to clean soiled fabrics." »* To 'ν' * 1

DETERGENT COMPOSITIONS

05 LIQUIDS_CONTENANT_DE_LgHEXYLENE-

2LIÇQL_ET_LEURS_PR0CEDES_D ^ UTILIZATION

JJETTgYER_DES_TISSy§_SALIS

10

The present invention relates to non-aqueous liquid compositions for the treatment of tissue. More particularly, the invention relates to non-aqueous liquid detergent compositions for washing clothes, which are stable against gelling, easily dispersible and easy to pour, and the use of these compositions for cleaning soiled fabrics. .

Non-aqueous liquid detergent compositions for heavy laundry work are well known in the art. For example, compositions of this type may include a liquid nonionic surfactant in which particles of a detergency builder are dispersed, as described for example in US Pat. Nos. 4,316,812, 3,630,929 and 4,264 466, and British Patent Nos. 1,205,711, 1,270,040 and 1,600,981.

The related French patent applications of the Applicant are as follows: application No. 85.17786, filed on December 2, 1985, describes a stable, concentrated non-aqueous fabric softening composition comprising hexylene glycol alone or in combination with a lower alka-nol or other glycol or glycol ether, or mixtures thereof, as a liquid vehicle for cationic fabric softening agents * * 2 sus, in particular softening agents of ammonium types quaternary and imidazolinium. The concentrated compositions may contain up to 60% by weight of the cationic compound and may further comprise up to 15% by weight of a nonionic surfactant; - Application No. 85.19510, filed on December 31, 1985, describes a non-aqueous liquid detergent composition based on nonionic surfactant, consisting of a suspension of a detergency builder and containing an acid-terminated nonionic surfactant (for example the reaction product of a nonionic surfactant and succinic anhydride) to improve the dispersibility of the composition in an automatic washing machine; This application also describes a non-aqueous liquid detergent composition based on a nonionic surfactant, consisting of a suspension of a detergency builder gel and containing a monoalkyl ether of al-kylene glycol as a viscosity control agent and Antifreezing, in order to improve the dispersibility of the composition in an automatic washing machine; - Application No. 85.05319, filed on August 9, 1985, describes a non-aqueous liquid detergent composition based on nonionic surfactant, consisting of a suspension of a detergency builder polyphosphate and containing an alkenolic ester of phosphoric acid to improve the stability of the suspension against sedimentation during storage.

Liquid detergents are often considered more convenient to use than dry powder or particulate products and consumers have therefore given them great preference. They are easy to dose, dissolve quickly in the washing water and can be easily applied: in solutions or dispersions concentrated on dirty areas of clothes to be washed, and they do not generate dust and occlude “3 usually has less storage space. In addition, it is possible to incorporate into the formulation of liquid detergents materials which cannot withstand drying operations without degradation, materials which it would often be desirable to use in the manufacture of particulate detergent products. Although they have many advantages over solid products in particulate or discrete units, liquid detergents are also often affected by certain inherent disadvantages which must be overcome to obtain commercially acceptable detergent products. Thus, some of these products dissociate during storage and others dissociate on cooling and are not easy to redisperse. In some cases, the viscosity of the product changes and it becomes either too thick to pour, or fluid enough to resemble water. Some clear products cloud and others gel on standing.

The Applicant is interested in studying the behavior of nonionic liquid surfactant systems containing a particulate matter in suspension. Particular attention has been paid to non-aqueous liquid detergent compositions for washing laundry containing a detergency builder, and to the problem of sedimentation of the detergency builder and other laundry washing additives in suspension, as well as 'the problem of gelation which is associated with nonionic surfactants. These considerations have an effect, for example, on the stability and dispersibility of the products and their suitability for pouring.

It is known that one of the major problems encountered with liquid detergents for washing laundry containing detergency builders is that of their physical stability. This problem stems from the “4 • r” * that the density of the solid particles dispersed in the nonionic liquid surfactant is greater than the density of the liquid surfactant.

Therefore, the dispersed particles tend to deposit. Two basic solutions exist to solve the problem of sedimentation: increase the viscosity of the nonionic liquid surfactant and reduce the size of the dispersed solid particles. It is known that the suspensions can be stabilized against sedimentation by the addition of thickeners or mineral or organic dispersants, such as, for example, mineral materials with very large specific surface, such as fine silica. divided, clays, etc., organic thickeners such as cellulose ethers, acrylic polymers and acrylamide polymers, polyelectrolytes, etc. However, such increases in viscosity of the suspensions are naturally limited by the need for the liquid suspension to remain easy to pour and to flow easily, even at low temperatures. In addition, these additives do not contribute to the cleaning action of the composition.

A grinding intended to reduce the particle size offers the following advantages: 1. The specific surface of the dispersed particles increases and, consequently, the wetting of the particles by the nonaqueous vehicle (liquid nonionic surfactant) is proportionally improved. .

2. The average distance between dispersed particles is reduced, resulting in a proportional increase in the interaction between particles. Each of these effects contributes to increasing the resistance to gelling at rest and the flow limit of the suspension while, at the same time, the grinding notably reduces the plastic viscosity.

The flow limit is defined as 5 being the minimum stress necessary to induce plastic deformation (flow) of the suspension. Thus, by representing the suspension as a loose network of dispersed particles, if the applied stress is less than the flow limit, the suspension behaves like an elastic gel and no plastic flow occurs. As soon as the flow limit is exceeded, the network breaks at certain points and the sample begins to flow, but with a very high apparent viscosity. If the stress is sufficiently higher than the flow limit, the particles are partially deflocculated by shearing and the apparent viscosity decreases. Finally, if the shear stress is much greater than the flow limit, the dispersed particles are totally deflocculated by shearing and the apparent viscosity is very low as if there were no interaction between the particles. .

Consequently, the higher the flow limit of the suspension, the higher the apparent viscosity at a low shear rate and the better the physical stability against product sedimentation.

In addition to the problems posed by sedimentation or phase separation, non-aqueous liquid laundry detergents based on liquid nonionic surfactants have the disadvantage that nonionic surfactants tend to gel when added to cold water. This is a problem which is of particular importance in the common use of automatic household washing machines of European type where the user places the detergent composition for washing clothes in a dispensing device (for example a drawer 35 tributor) 'of the machine. During the operation of the machine, the detergent contained in the dispenser "*. 6 is subjected to a stream of cold water to be transferred into the main mass of the washing solution. It happens, especially during the winter months, when the detergent composition and the water which feeds the dispenser-05 are particularly cold, that the viscosity of the detergent increases sharply and that a gel is formed. It follows that a part of the composition is not expelled from the dispenser during the operation of the machine, and that a deposit of composition accumulates during the successive washing cycles, which ultimately obliges the user. sweep the dispenser with hot water.

The gelation phenomenon can also. be a problem whenever it is desired to wash using cold water, as may be recommended for certain synthetic and delicate fabrics or for certain fabrics which may shrink in lukewarm or hot water.

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

Suspensions of adjuvant detergent salts, for example sodium tripolyphosphates, in nonaqueous liquid laundry detergent compositions based on nonionic surfactants are characterized by their plastic viscosity, their flow limit and their · Apparent viscosity,

Compositions which have a high plastic viscosity also have a high flow limit and are physically stable. However, in compositions which have a high plastic viscosity, it is found that the gelation is accentuated when the compositions are added to water. Normally, . Reducing the plastic viscosity lowers the flow limit and reduces the physical stability of the composition. In addition, for the composition to be physically stable, the apparent viscosity must be high. However, a high apparent viscosity generally adversely affects the dispersibility of the composition in cold water.

Partial solutions to the problem of gelation of aqueous compositions substantially free of detergency builders have been proposed, for example by diluting the liquid nonionic surfactant with certain viscosity controlling solvents and certain gelation inhibiting agents, such as al— lower canols, for example ethyl alcohol (see US Pat. No. 3,953,380), alkali metal formates and adipates (see US Patent 3.

A. No. 4,368,147), hexylene glycol, polyethylene glycol, etc., and by modifying and optimizing the structure of the nonionic surfactant. In addition, these two bre-20 garments each make known the use of derivatives of etherification by lower alkyl groups (C -C4) of lower polyols (C ^ C ^), such as ethylene glycol, in these aqueous liquid detergents without detergency additives, replacing a part of the lower alka-25 nol, for example ethanol, used as a viscosity-adjusting solvent. The patents of E. ü, A.

Nos. 4,111,855 and 4,201,686 are interested in similar effects. However, it is by no means revealed or suggested in any of these patents that these compounds, some of which are commercially available under the trademark Cellosolve (registered trademark), can act effectively as viscosity control and antifreeze agents for nonaqueous liquid compositions based on nonionic surfactants, in particular for such compositions which contain detergency builder salts in suspension, 8 such as polyphosphates, and very particularly for such compositions which neither require nor depend on solvents of the type lower alkanol as viscosity control agents.

05 As an example of modification of the surfactant in order to inhibit gelation, a particularly happy result was obtained by acidifying the terminal group of the hydroxyl moiety of the nonionic molecule. The advantages which the introduction of an aci-10 of carboxylic at the end of the nonionic molecule include the inhibition of gel setting. dilution, lowering the drop point of the nonionic surfactant and the formation of an anionic surfactant by neutralization in the wash liquor. The op'-timalisation 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 exhibits only a limited tendency to gel.

Nevertheless, improvements are desired with respect to the stability, inhibition of gelation as well as the dispersibility of the non-aqueous liquid tissue treatment compositions.

According to the present invention, a highly concentrated and stable non-aqueous liquid detergent composition is prepared for washing clothes by adding to the composition hexylene glycol or hexylene glycol and propylene carbonate.

The compositions of the present invention contain hexylene glycol or hexylene glycol and propylene carbonate.

The antifreezing and dispersibility properties of a nonaqueous liquid detergent composition based on nonionic surfactant for washing laundry are improved by the addition of hexylene-glycol to the composition. The addition of hexylene glycol reduces the plastic viscosity of the composition by having little or no adverse effect on the flow limit of the composition or on the physical stability of the composition. The addition of hexylene glycol and propylene carbonate to the composition based on nonionic surfactant significantly reduces the apparent viscosity of the composition and notably improves the dispersibility of the composition.

When added to the composition, hexylene glycol and propylene carbonate improve the dispersibility of the detergency builder suspension by acting to inhibit the gel setting of the detergency builder suspension. Hexylene glycol and propylene carbonate improve dispersibility by inhibiting the freezing of the suspension of particles of detergency builder salt when water is added to the composition, for example in the dispenser drawer. 'a washing machine and / or when the composition is added to water.

In order to improve the viscosity characteristics of the composition, an acid-terminated nonionic surfactant can be added. To improve the storage properties during storage of the composition. one can add to it an anti-sedimentation agent such as a phosphoric acid ester.

Sanitizing or bleaching agents and activators may be added thereto to improve the bleaching and cleaning characteristics of the composition.

In one embodiment of the invention, the detergency builder components of composition 35 can be ground to a particle size of less than 100 microns, for example less than 40 microns and preferably less than 10 microns , to further improve the stability of the suspension of the detergency builder components in the detergent liquid nonionic surfactant.

In addition, other ingredients may be added to the composition, such as anti-fouling agents, defoamers, optical brighteners, enzymes, anti-deposition agents, perfume and colorants, washing machines currently manufactured for domestic use normally operate at washing temperatures up to 90 ° C, approximately 70 liters of water are used during the wash and rinse cycles, 15 are normally used about 200 to 250 grams of powdered detergent per wash.

According to the present invention, where the concentrated liquid detergent is used, normally only 100 grams (78 cc) of the liquid detergent composition is required to wash a full load of dirty laundry.

Thus, in one of its aspects, the present invention provides a liquid composition for heavy laundry work, composed of a suspension of an adjuvant detergency salt, for example a phosphate ad-25 detergency builder, in a surfactant non-ionic, liquid, the composition including hexylene glycol or hexylene glycol and propylene carbonate in an amount effective to inhibit gel formation and to improve water dispersibility of the suspension adjuvant detergent salt.

In another aspect, the invention provides a concentrated liquid detergent composition for heavy laundry work, which is stable, does not dry up during storage and does not gel. storage 35 and use. The liquid compositions of the present invention are easy to pour, easy to dose and easy to introduce into the washing machine, and they disperse easily in water.

In another aspect, the invention provides a method for dispensing a liquid detergent composition based on nonionic surfactant for washing laundry, in and / or with cold water without gelation occurring. . In particular, there is provided a method for filling a container with a non-aqueous liquid detergent composition for washing clothes in which the detergent is composed, at least predominantly, of a liquid nonionic surfactant, and for dispensing the composition by passing it from the container into an aqueous washing bath, process in which the distribution is carried out by directing a stream of unheated water over the composition so that the composition is entrained by the stream of water to '. in the wash bath.

The addition of hexylene glycol to the composition significantly reduces the plastic viscosity of the composition by only slightly or not lowering its flow limit and by only slightly or not reducing its physical stability. The addition of hexylene glycol and propylene carbonate to the composition significantly decreases the apparent viscosity of the composition and notably improves its dispersibility. The addition of hexylene glycol or hexylene glycol and propylene carbonate to the composition prevents the formation of gel which generally occurs when the composition is contacted with cold water, and the dispersibility of the compo-30 sition is thereby improved.

The concentrated non-aqueous liquid detergent compositions based on non-ionic surfactant for washing clothes according to the present invention have the advantages of being stable, of not becoming sedentary during storage and of not gelling during storage. · ^ Ge. The liquid compositions are easy to pour, 12 easy to dose and easy to put in washing machines and they disperse easily in water.

An object of the present invention is to provide a non-aqueous liquid detergent composition based on non-ionic surfactant for heavy laundry work, containing hexylene glycol or hexylene glycol and carbonate of propylene, as well as an anionic detergency builder salt of the phosphate type 10 suspended in the nonionic surfactant.

Another object of the invention is to provide liquid tissue treatment compositions which are suspensions of mineral particles insoluble in a non-aqueous liquid and which are stable on storage, easy to pour and easy to use. disperse in cold, lukewarm or hot water.

Another object of the present invention is to formulate non-aqueous liquid detergent compositions based on non-ionic surfactant, with a high content in detergency builder, for heavy laundry work, which can be poured at any temperature and which can be dispersed repeatedly from the dispenser device of automatic washing machines of the European type 25 without clogging or obstructing the dispenser even during the winter months.

Another object of the present invention is to provide non-aqueous liquid detergent compositions based on nonionic surfactant and detergency builder for heavy laundry work, in the form of suspensions; Stable and non-gelling which contains hexylene glycol in an amount effective to significantly decrease the plastic viscosity of the compositions while lowering their flow limit only slightly or not at all.

Another object of the present invention is to provide non-aqueous liquid detergent compositions to. non-ionic active surfactant base and detergency builder for heavy laundry work, in the form of stable, non-gelling and easily dispersible suspensions which contain hexylene glycol and propylene carbonate in an amount effective for significantly reduce the apparent viscosity of the compositions and significantly improve their dispersibility.

These and other objects of the invention will become more apparent from the following detailed description of its preferred embodiments and are generally achieved by preparing a detergent composition by adding to the non-aqueous liquid nonionic surfactant hexylene glycol or hexylene glycol and propylene carbonate in an effective amount sufficient to inhibit gelation of the composition while maintaining its physical stability, said composition comprising mineral or organic additives for treating tissues, e.g. viscosity enhancing agents and one or more antifreeze agents, anti-scaling agents, pH adjusting agents, bleaches, bleach activators, agents defoamers, optical brighteners, enzymes, anti-repellants, fragrance, dyes and pigments.

In accordance with the present invention, the antifreeze properties and the dispersibility properties of the non-aqueous liquid composition based on nonionic surfactant for washing clothes are significantly improved by adding hexylene glycol or hexylene glycol and propylene carbonate.

When added to the composition, hexylene glycol or hexylene glycol and propylene carbonate improve the dispersibility of the detergent builder salt suspension by acting to inhibit gelation of the suspension when it is brought into contact with water.

Hexylene glycol or hexylene glycol and propylene carbonate improve dispersibility by inhibiting gelation of the suspension of particles of detergency builder salt when water is added to the composition, for example in the dispenser drawer of a washing machine, and / or when the composition is added to the washing water.

The antifreezing and dispersibility properties of a non-aqueous liquid detergent composition based on non-ionic surfactant for washing clothes are improved when hex-glycylene glycol is added to it. The addition of hexylene glycol lowers the plastic viscosity of the composition with little or no adverse effect on the flow limit of the composition and on its physical stability. The addition of hexylene glycol and propylene carbonate to the composition based on nonionic surfactant decreases the apparent viscosity of the composition and appreciably improves its dispersibility. Hexylene glycol can be used alone or as a mixture with a C 1 -C 4 alkanol, for example ethanol or propanol, a C 2 -C 4 glycol, such as diethylene glycol or propylene glycol, or a mono- or di-alkyl ether C ^ -C ^) of these glycols or mixtures of them. In its commercial form, hexylene glycol mainly consists of 2-methyl-pentane-2,4-diol, The term "hexylene-glycol" 30 is understood to include 2-methyl-pentane-2,4- diol as well as the other isomeric diols corresponding to the generic formula CgH12 (OH) 2f, for example hexane-1,3-diol, hexane-1,4-diol, etc.

The propylene carbonate used according to the present invention corresponds to the formula: 15 f Ο

II

/ \ ο ο

05 I I

CH2 - CH —CHg

The lower alkyl carbonates 10 corresponding to the formula can also be used in accordance with the present invention:

O

II

o o 15 | |

Rl — CH ---- CH — R2 and in which R ^ and R2 are H, CH ^ -, <- '2H5 ~ / or C4Hg / and R2 can be identical or different. When added to the composition, even in small amounts, propylene carbonate increases the polarity of the matrix and promotes dispersibility in water. Propylene carbonate is also a gelling inhibitor. Propylene carbonate is essential in the presence of ben-tones for which it acts as a polarity enhancer by promoting their swelling. The recommended level of propylene carbonate is about one third of that of Bentone on a weight basis, for example about 0.5 g of propylene carbonate per about 1.5 g of Bentone.

Active Surf - Non-Ionic Detergent

The non-ionic synthetic organic detergents employed in the practice of the invention may be any of a wide variety of known compounds.

16

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

Generally, nonionic detergents are lipophilic compounds polyalkoxylated by lower alkoxy groups, in which the desired hydrophilic-lipophilic ratio is obtained by adding a hydrophilic poly (lower alkoxy) group to a lipophilic moiety. A preferred class of the nonionic detergent used is that of the higher alkanols polyalkoxylated by lower alkoxy groups where the alkanol have from 9 to 18 carbon atoms and where the number of moles of lower alkylene oxide (to 2 or 3 carbon atoms) is from 3 to 12. Among these products, it is preferable to use those whose 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 molecule. Preferably, the lower alkoxy group is the ethoxy group, but in some cases this may be advantageously mixed with the propoxy group which, if present, often constitutes only a minor proportion (less than 50 %) of lower alkoxy groups.

Representative 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 molecule, for example Neodol 25-7 and Neodol 23-6.5 which are products manufactured by Shell Chemical Company, Inc. The former 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 where the number of carbon atoms in the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups present is on average about 15 6.5. Higher alcohols are primary alcohols.

Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15-S-9 which are both ethoxylates of secondary linear alcohols, manufactured by Union Carbide Corp. The first is the mixed product of ethoxylation of a secondary linear 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 oxide of ethylene reacted.

Higher molecular weight nonionic surfactants are also useful in the present invention as a component of nonionic detergent, such as Neodol 45-11, and are similar products of condensation of ethylene oxide on higher fatty alcohols , the higher fatty alcohol having 14 or 15 carbon atoms and the number of ethylene oxide groups being approximately 11 per molecule. These products are also manufactured by Shell Chemical Company.

Other useful nonionic surfactants are represented by the class of nonionic surfactants 35 well known in the trade sold under the trademark Plurafac. Plurafac 18 series surfactants are the reaction products of a higher linear alcohol and a mixture of ethylene oxides and pro-1 pylene, containing a mixed chain of ethylene oxide and d propylene oxide, terminated by a hydro-05 xyl group. Examples are the following products: (A) a C ^ gC ^ fatty alcohol, - condensed with 6 mol of ethylene oxide and 3 moles of propylene oxide, (B) a condensed fatty alcohol with 7 moles of propylene oxide and 4 moles of ethylene oxide, 10 (C) a fatty alcohol - C ^ -C ^ ,. condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide, and (D) a mixture in equal parts of the products (B) and (C).

Another class of liquid nonionic surfactants is commercially available from Shell Chemical Company, Inc., under the trademark Dobanol: Dobanol 91-5 is a CQ-C fatty alcohol ethoxylated with an average of 5 moles of oxide y 11 of ethylene and Dobanol 25-7 is a fatty alcohol in Cl2-20 c ^ ethoxylated with an average of 7 moles of ethylene oxide, per mole of fatty alcohol.

In the higher polyaloxyl alcohols preferred, to obtain the best ratio between the hydrophilic and lipophilic moieties, the number of lower alkoxy groups is usually 40% to 100% of the number of carbon atoms present in the higher alcohol, preferably 40 to 60% of this number, and the nonionic detergent preferably contains at least 50% of such a preferred polyalkoxylated higher alkanol. The higher molecular weight alkanols and various other normally solid detergents and surfactants may contribute to the gelation of the liquid detergent and, therefore, are preferably omitted or incorporated in limited amounts in the present compositions, although that minor proportions can be used for their cleaning properties, etc. With respect to both preferred and less preferred nonionic detergents / the alkyl groups present therein are generally linear although a low degree of tree structure may have been tolerated, for example at the level of the carbon atom contiguous to the carbon atom-terminal, or distant from two positions of the carbon atom terminal ',' from the straight chain and opposite from the ethoxy chain, provided that the length of this alkyl-10 branching does not exceed three carbon atoms. Normally, the proportion of carbon atoms in such a branched configuration should be minor and rarely exceed 20% of the total number of carbon atoms in the alkyl group. Likewise, although the linear alkyl groups which are joined by the terminal carbon atom to the ethylene oxide chains are greatly preferred and are considered to give the best combination of detergency, biodegradability and characteristics. non-gelation, there may appear in the chain a median or secondary junction with ethylene oxide. There is normally only a minor proportion, generally less than 20%, of such alkyl groups, but this proportion may be greater, as is the case with the mentioned Tergitol. In addition, when the propylene oxide is present in the lower alkylene oxide chain, it generally constitutes less than 20% and preferably less than 10%,

If larger proportions than those mentioned above are used of alkanols the alkoxylation of which is not terminal, alkanols polyalkoxy-damaged by lower alkoxy groups containing propylene oxide. ; and non-ionic detergent to. poorer hydrophilic-lipophilic ratio, and if other nonionic detergents are used in place of the preferred nonionic surfactants listed herein, the. · I, 20 resulting product may not have as good detergency, stability, viscosity and non-gelling properties as the preferred compositions, but the use of viscosity regulating and gelling inhibiting compounds The present invention can also improve the properties of detergent products based on such nonionic surfactants. In some cases, for example when using a higher molecular weight coxylated polyalsf alkanol, often for its detergency, the proportion may be adjusted or limited according to the results of routine tests to obtain the desired detergency. while still keeping a non-gelling product and the desired viscosity. We have also 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 also make it possible to obtain the desired viscosity for the liquid detergent product without undergoing gelation at low temperatures.

Another useful class of non-ionic surfactants is the series of "Surfactant T" products available from British Petroleum. The non-ionic Surfactant T-Surfactants T are obtained by ethoxy-lation of C13 secondary fatty alcohols and have a narrow distribution of ethylene oxide contents. Surfactant T5 contains on average 5 moles of ethylene oxide; Surfactant T7 contains on average 7 moles of ethylene oxide; Surfactant T9 contains on average 9 moles of ethylene oxide and Surfactant T12 contains on average 12 moles of ethylene oxide, per mole of C13 secondary fatty alcohol.

In the compositions of the present invention, the preferred nonionic surfactants include ethoxylated C 1 -C 4 secondary fatty alcohols with relatively narrow ethylene oxide contents, ranging from about 7 to 9 moles, and the fatty alcohols in C ^ -C. ^ Ethoxyles with about 5 to 6 moles of ethylene oxide.

05 Mixtures of two or more of the liquid nonionic surface active agents can be used and in some cases benefits can be derived from the use of such mixtures.

Sur facti Non-Tonic - Termination · Acid 10 The viscosity and gelation properties of liquid detergent compositions can be improved by incorporating into the composition an effective amount of a nonionic surfactant - acid terminated liquid. The acid-terminated nonionic surfactants consist of a nonionic surfactant which has been modified to transform a free hydroxyl group of this surfactant into a moiety having a free carboxyl group, for example an ester or a partial ester of a nonionic surfactant and a polycarboxylic acid or anhydride.

As described in French patent application 85.05319, filed April 9, 1985, non-ionic surfactants modified by a free carboxyl group, which can roughly be characterized as polyether-carboxylic acids, act by lowering the temperature at which the surfactant non-ionic liquid forms a gel with water.

The addition of acid-terminated nonionic surfactants to the liquid nonionic surfactant fa-30 enhances the ability of the composition to be dispensed, i.e., its ability to be poured, and lowers the temperature at which the surfactants . non-ionic liquids form a gel in water, without reducing their stability against sedimentation. The non-ionic acid-terminated surfac-tif reacts in the water of the washing machine with alkalinity. of the dispersed phase 22 of detergency builder salt 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 the succinic anhydride, and the ester or hemi-ester of Dobanol 91 -5 "with succinic anhydride. Instead of succinic anhydride, other anhydrides or polycarboxylic acids can be used, for example maleic acid, maleic anhydride, acid glutaric, malonic acid, phthalic acid, phthalic anhydride, citric acid, etc.

Acid-terminated nonionic surfactants can be prepared as follows;

Acid-terminated product (A): 400 g of the nonionic surfactant are mixed. Product (A) which is an alkanol having been alkoxylated so as to introduce therein 6 ethylene oxide units and 3 propylene-20 unit units not by alkanol motif, with 32 g of succinic anhydride, and the whole is heated for 7 hours. 100 ° C, The mixture is cooled and filtered to remove the unreacted succinic material. Infrared analysis shows that about half of the nonionic surfactant has been transformed into its acid hemi-ester.

Dobanol 25-7 acid terminated; 522 g of non-ionic surfactant Dobanol 25-7, which is the ethoxylation product of a C 12 to C 15 alkanol and contains approximately 7 ethylene oxide units per molecule of alkanol, are mixed with 100 g of anhydride succinic and 0.1 g of pyridine (which acts as a catalyst for es ter if ica · * tion) and the whole is heated to 260 ° C for 2 hours, cooled and filtered to remove the unreacted succinic material. Infrared analysis shows that almost all of the free hydroxyl groups in the surfactant have reacted.

23

Acid-terminated Dobanol 91-5; 1.000 g of non-ionic surfactant Dobanol 91-5, which is the product of ethoxylation of an alkanol in CQ S C. 265 g of succinic anhydride and 0.1 g of pyridine serving as catalyst, and the whole is heated to 260 ° C. for 2 hours, cooled and filtered to remove the unreacted succinic material, the infrared analysis shows that practically 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 as pyridine mix with it.

The acidic polyether, i.e., the acid-terminated nonionic surfactant, is preferably added in the dissolved state to the nonionic surfactant.

Detergency Builder Salts The nonaqueous 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 detergent compositions of the invention include water soluble and / or water insoluble builder salts. Water-soluble alkaline mineral detergent builder salts which can be used alone with the detergent compound or in admixture with other detergency builders are carbonates, bicarbonates, borates, phosphates, polyphosphates and alkali metals (ammonium or substituted ammonium salts can also be used). Particular examples of these salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbon ** 24 te, potassium tripolyphosphate, hexa -sodium metaphosphate, sodium sesquicarbonate, sodium mono- and di-orthophosphates and potassium bicarbonate. Sodium tripolyphosphate (TPP) 05 is particularly preferred.

Since the compositions of the present invention are generally very concentrated and therefore can be used in relatively low doses, it is desirable to supplement any detergency builder of the phosphate type (such as sodium tripolyphosphate ) by an auxiliary detergency builder such as a lower polycarboxylic acid or a polymeric carboxylic acid having a high calcium binding capacity in order to inhibit incrustation which, if not, could be caused by the formation of an insoluble calcium phosphate.

Suitable lower polycarboxylic acids include the alkali metal salts of lower polycarboxylic acids, preferably the sodium and potassium salts. Suitable lower polycarboxylic acids have two to four carboxylic acid groups. The preferred sodium and potassium salts of lower polycarboxylic acids are the salts of citric and tartaric acids.

The sodium salts of citric acid are the most appreciated, in particular trisodium citrate. It is also possible to use the non-sodium and di-sodium citrates. It is also possible to use the monosodium and disodium salts of tartaric acid. The alkali metal salts of lower polycarboxylic acids are particularly good detergency builder salts; thanks to their strong capacity for fixing calcium and magnesium, they inhibit encrustation which, without them, could be caused by the formation of insoluble salts of calcium and magnesium.

Other organic detergency builders 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 product of the reaction of an approximately equal number of moles of methacrylic acid and maleic anhydride, having been completely neutralized to form its salt. sodium. This detergency builder is commercially available under the trademark Sokalan CP5. This detergency builder is used, even when used in small amounts, to inhibit incrustation.

Examples of sequestering alkaline organic detergency builder salts which may be used with the detergency builder salts or in admixture with other organic and inorganic detergency builders are alkali metal, ammonium and substituted ammonium aminopolycarboxylates, for example sodium and potassium ethylenediaminetetraacetate (EDTA), sodium and potassium nitrilotriacetates (NTA), and triethanolamine N- (2-hydroxyethyl) nitrilodiacetates, Mixtures of these aminopolycarboryl xylates are also suitable , 25 Other suitable organic type detergency builders include carboxymethÿlsuccina-tes, tartronates and glycolates. Polyacetal carboxylates are particularly interesting. The polyacetal carboxylates and their use in detergent compositions are described in French patent application of the Applicant No. 86.11852 filed on August 19, 1986, and in the patents of E, ü. A, N ° 4 144 226, 4 315 092 and 4 146 495,

The alkali metal silicates are useful as detergency builder salts and also act by adjusting or adjusting the pH and rendering the composition anticorrosive to parts of the washing machine. Sodium silicates whose Na 2 O / SiC> 2 ratios range from 1.6 / 1 to 1 / 3.2, in particular approximately 1/2 to 1 / 2.8, are preferred. Silicates of potas-05 sium of the same ratios can also be used.

Other suitable typical detergency builders include, for example, those described in US Pat. Nos. 4,316,812, 4,264,466 and 3,630,929. Mineral detergent builders can be used with the nonionic surfactant detergent or in admixture with other mineral detergency builder salts or with organic detergency builder salts.

One can also use aluminosilica-é your crystalline: and amorphous insoluble in water ty-15 pe zeolite. The zeolites correspond to the general formula: (M20> x- <A1203> y · (Si ° 2) z.wH20 in which x is 1, y is 0.8 to 1.2 and preferably-20 rence 1, z is 1.5 to 3.5 or more and preferably 2 to 3 and w is 0 to 9 and preferably 2.5 to 6, and II is preferably sodium. A typical zeolite is a zeolite of the type A or of similar structure, the type .4A being particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of approximately 200 milliequivalents per gram or more, for example 400 meq / g,

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

Other matins such as clays, particularly water insoluble types, may be useful auxiliaries in the compositions of the invention. Bentonite is particularly useful * This material consists mainly of montmorillo'-nite mistletoe is a hydrated aluminum silicate of which.

05 about the sixth of the aluminum atoms can be replaced by magnesium atoms / and with legua! various quantities of hydrogen, sodium / potassium * calcium / etc., can be weakly combined, bentonite, in its purest form (that is to say free of any sand, abrasive particles, etc.) suitable for detergents ·, contains at least 50% montmorillonite and, therefore, its cation exchange capacity is at least about 50 to 75 meq per 100 g of bentonite, Particularly preferred bentonites are bentonites from western E, UA or Wyoming which were sold under the designations Thi'xo-jel 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften textiles, as described in the British patents No. 401 413 and 461 221, 20 It is also possible to add to the compositions of the present invention small amounts of Bentones, for example Bentona-27 which is an organic derivative of magnesium aluminum silicate and which acts in the composition as an anti-sedimentation agent, 25 Bentones, e.g. Like Behtone-27, can be added in proportions of 0.05 to 3 I, as from 0.2 to 2%, for example about 0.5 to 1.5%.

The compositions of the present invention have improved viscosity and stability characteristics and remain stable and suitable for pouring at temperatures as low as about 5oC and below.

The hexylene glycol or hexylene glycol and propylene carbonate act to improve the dispersibility of the suspension of the phosphate-like detergency builder particles by inhibiting the gel setting of the suspended particles when cold water is added to the composition in the dispenser drawer and / or when the composition is added to water.

In one embodiment of the present invention, a stabilizing agent which is an alkanolic ester of pho-phoric acid may be added to the composition. Improvements can be made to the stability of the composition by incorporating a small effective amount of an acidic organic phosphorus compound bearing an acid group -POH, for example a partial ester of phosphorous acid and a alkanol.

As described in patent application assigned to Applicant 597,948 filed April 9, 1984, the organic phosphorus acid compound carrying an acid group -POH. may increase the stability of the detergency builder suspension in the non-aqueous liquid nonionic surfactant.

The acidic organic phosphorus compound may be, for example, a partial ester of phosphorous acid and an alcohol such as an alkanol having a lipophilic character since it has, for example, more than 5 carbon atoms, for example 8 to 20 carbon atoms. 25 A particular example is a partial ester of phosphoric acid and a C 6 to C 8 alkanol (tEm-piphos 5632 from Marchdn), · this product consists of approximately 35% monoes'ter and 65% dies -ter.

The incorporation of very small amounts of the acidic organic phosphorus compound makes the suspension stable against sedimentation at rest while leaving it capable of; be paid.

Another additive which can be added to the composition is Arosurf TA 100 which is distearyl dimethyl ammonium chloride, Arosurf TA 100 acts in the composition as a rheological additive to improve physical stability. of the product. Arosurf TA 100 can be added in proportions of 0.05 to 4%, as from 0.5 to 1.5%, for example from about 0.1 to 1.0%.

05 Bleaching Agents

Bleaching agents are broadly classified for convenience as chlorine bleaching agents and oxygen bleaching agents. Chlorine bleaches are typically represented by sodium hypochlorite (NaOCl), potassium dichlo-isocyanurate (59% active chlorine) and trichloroisocyanuric acid (95% chlorine active). Oxygen 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 monopersul potassium potassium Perborates, in particular the sodium perbo-rate monohydrate, are particularly preferred.

The peroxygen compound is preferably used in admixture with an activator for this compound. Appropriate activators can lower the effective action temperature of the peroxide bleach.

Are polyacylated compounds preferred activators? among these, compounds such as tetraacetyl ethylenediamine (TAED) and pentaacetyl glucose are particularly preferred.

Other useful activators include, for example, acetylsalicylic acid derivatives, ethylidene benzoate and its salts, an ethylidene carboxylate acetate and its salts, an alkyl- or ale® anhydride. "nyl-succinic, tetraacetylglycouril (TAGU), and derivatives of these activators. Other useful classes of activators are described, for example, in E, U, A, Patent Nos. 4,111,826,4 422,950 and 3,661,789, 30 The bleach activator usually interacts with the peroxygen compound to form a bleaching peroxyacid in the wash water. It is preferable to incorporate a high potency sequestering agent 05 complexing agent to inhibit any undesirable reaction between this peroxyacid and hydrogen peroxide in the washing solution in the presence of metal ions,

Sequestering agents suitable for this purpose include the sodium salts of nitrilotriacetic acid 10 (NTA), ethylene diaminetetraacetic acid (CEDTA), diethylenetriaminepentaacetic acid (DEP'TA), diethylenetriaminepentamethylenephosphonic acid (DTPMP) sold under the trade mark Dequest 2066, and acid, ethylenediaminetetramethylenephosphonic · (EDITEMPA) “15 The sequestering agents can be used alone or as a mixture.

In order to avoid a loss of the bleaching peroxide, for example sodium perborate, as a result of an enzymatic decomposition, for example under the effect of a catalase type enzyme, the compositions may additionally contain a compound inhibiting d 'enzyme, that is to say a compound capable of inhibiting the enzymatic decomposition of bleaching peroxide. Suitable inhibitors are described in E, U, A, Patent No. 3,606,990.

As particularly advantageous inhibiting compounds, mention may be made of hydroxylamine sulphate and other water-soluble salts of hydroxylamine,

In the preferred nonaqueous compositions of the present invention, suitable proportions of hydroxylamine salts used as inhibitors may be as low as about 0.01-0.4%, however, in general, appropriate proportions of inhibitors enzymes range up to about 15%, for example from 0.1 to 10%, by weight relative to the weight of the composition,

In addition to detergency builders, various other additives or builders may be present in the detergent product to provide it with additional desired properties, whether functional or aesthetic in nature. Thus, 05 can be included in the composition of the minor amounts of anti-redeposition or suspending agents for soiling, for example a polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose. A preferred antireposition agent is a sodium carboxymethyl cellulose having a CM / CMC ratio of 2: 1, which is sold under the trademark Relatin DM 4050.

Optical brighteners for cotton, polyamide and polyester fabrics can be used. Suitable optical carriers include compositions of stilbene, triazole and benzidine sulfone, including sulfonated substituted triazinyl-stilbene, naphthotri-azole-sulfonated stilbene, benzidine sulfone, etc., the most preferred being combinations of stilbene 20 and triazole.

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

Bactericides, for example tetrachlorosalicylanilide and hexachlorophen, fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet absorbers, yellowing 32 such as, sonic carboxymethyl cellulose, pH modifiers and pH buffers, color preservatives, fragrance, dyes and brighteners such as overseas blue, 05 The composition may also contain an insoluble mineral thickening or dispersing agent with a very large specific surface such as finely divided silica having an extremely small particle size (for example 5-100 nanometers in diameter / 10 as sold under the brand Aerosil) or the other very bulky mineral support materials described in the patent of E, U ,. A. No. 3 630 929, in proportions of 0.1-10%, for example from i to 5;. however preferable that the es compositions which. form peroxyacids in the washing bath (e.g. compositions containing a peroxygen compound and an activator therefor) are substantially free of such compounds and other silicates? it has for example been found that silica and silicates promote undesirable decomposition of the peroxyacid.

In one embodiment of the invention, the stability of the adjuvant detergency salts in the composition during storage and the dispersibility of the composition in water are improved by grinding and reduction of the particle size of the adjuvants. solid detergents to less than 100 microns, preferably to less than 40 microns and more preferably to less than 10 microns. Solid detergency builders, for example sodium tripolyphosphate (TPP), are generally supplied in particle sizes of about 100, 200 or 400 microns, The liquid nonionic surfactant phase can be mixed with solid detergency builders before or after the grinding operation has been carried out, In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid ingredients is subjected to the action of a grinder. of the attrition type in which the particle dimensions of the solid ingredients are reduced to less than about 10 microns, for example to an average particle size of 2 to 10 microns or even less (for example 1 micron), Preferably less than approximately 10%, and in particular less than approximately 5%, of all the particles in suspension have dimensions greater than 10 micrometers. The compositions 10 of which the dispersed particles have such small dimensions exhibit better stability at. against separation or sedimentation during storage. The addition of nonionic active surfactant terminated with its acid can decrease the flow limit of these dispersions and improve their dispersibility without causing a correlative reduction in the stability of the dispersions against sedimentation.

In the grinding operation, it is preferable that the proportion of solid ingredients is high enough (for example at least about 40%, such as about 50%) so that the solid particles are in contact with them and are not substantially isolated from each other by the liquid nonionic surfactant. After the milling step, any remaining liquid nonionic surfactant can be added to the milled composition. Grinders which use grinding balls (ball mills) or similar movable grinding elements have given very good results. Thus, one can use a laboratory mill-attritor 30 working by loads, containing grinding balls in steatite of 8 mm in diameter. For a larger scale operation, one can use a mill operating in continuous mode in which ' find grinding balls of 1 mm or 1.5 · dia-35 meter working in a very small gap between a stator and a rotor rotating at a relatively high speed (for example a CoBall mill); when using such a mill, it is advantageous to first pass the mixture of nonionic surfactant and solid ingredients through a mill which does not perform such a fine milling (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 10 micrometers in approximately 10 which takes place in the ball mill operating in continuous mode .

In the liquid detergent compositions for heavy laundry work according to the invention, typical proportions (in percent based on the total weight of the composition, unless otherwise indicated) of the ingredients are the following: - Liquid nonionic surfactant detergent: in the range of about 10 to 80 percent, such as from 20 to 70 percent, for example about 30 to 70 percent. 20 - Detergency builder, for example sodium tripolyphosphate (TPP): in the range of about 10 to 60 percent, such as 15 to 50 percent, for example about 20 to 35 percent.

- Hexylene glycol in a proportion of about 5 to 25 percent, or from 5 to 30 percent, such as from 10 to 30 percent, for example about 20 to 30 percent.

- Propylene carbonate: in a proportion of about 0 to 5 percent, such as 0.1 to 1.0 or 0.1 to 2.0 percent, for example 0.2 to 0.8 percent.

- Acid-terminated nonionic surfactant in an amount in the range of about 0 to 20 percent, such as 3 to 15 percent, for example about 4 to 10 percent.

- Alkali metal silicate; in the range 35 from about 0 to 30 percent, such as from 5 to 25 for caritr for example about 10 to 20 percent, 35 - Alkali metal salt of copolymer of polyacrylic acid and polymaleic anhydride, for example So-kalan CP5, as an anti-scaling agent: in the range of about 0 to 10 percent, like from 2 to 8 05 percent, for example about 3 § 5 percent.

- Alkanolic ester of phosphoric acid as stabilizing agent: in the range from 0 to 2.0 or 0.1 to 2.0 percent, for example 0.10 to 1.0 percent.

- Bleaching agent: in the range of about 10 to 0 to 30 percent, such as from 2 to 20 percent, for example about 5 to 15 percent.

- Bleach activator: in the range of about 0 to 15 percent, such as from 1 to 8 percent, for example about 2 to 6 percent.

15 - Sequestering agent for the bleaching agent, for example Dequest 2066: in the range of about 0 to 3.0 percent, preferably 0.5 to 2.0 percent, for example about 0.75 at 1.25 percent.

- Anti-redeposition agent, for example Relatin DM

405050: in the range of about 0 to 4.0 percent, preferably 0.5 to 3.0 percent, e.g. 0.5 to 1.5 percent, - Optical brightener: in the range of about 0 to 2.0 percent, preferably 0.05 to 1.0 percent, e.g. 0.15 to 0.75 percent, - Enzymes: in the range of about 0 to 3.0 percent, preferably 0.5 to. 2.0 percent, for example 0.75 to 1.25 percent, - Perfume: in the range of about 0 to 3.0 per 30 percent, preferably 0.10 to 1.25 percent, for example 0.25 to 1.0 percent.

- Colorant: in the range of about 0 to 4.0 percent, preferably 0.1 to 2.0 percent, more preferably 0.1 to 1.0 percent, 35 Various additives among those previously mentioned can be added optionally to obtain the desired function of these added materials.

Hexylene glycol is preferably used with propylene carbonate.

With regard to the choice of additives, these must be chosen so as to be compatible with the main constituents of the detergent composition. In the present specification, as mentioned above, all the proportions and all the percentages are expressed by weight relative to the weight of the total composition or formulation, unless otherwise indicated.

The concentrated nonaqueous liquid nonionic detergent composition of the present invention is. easy to dispense in the washing machine water.

15 Household washing machines currently in use normally consume 200 to 250 g of powdered detergent to wash a full load of laundry. According to the present invention, only 78 cm or 100 grams of the concentrated liquid nonionic detergent composition is required.

In a preferred embodiment of the invention, a detergent composition of typical formulation is prepared using the following designated ingredients: 25% by weight

Nonionic detergent surfactant30-80

0-20 acid-terminated surfactant

Phosphate detergency builder salt 10-60 30 Hexylene glycol 5-30

Propylene carbonate 0-5.0

Bentone 27 0-1.5

Arosurf TA 100 0-1.5

Phos-35 phoric acid alkanolic ester 0-1.0

Anti-scaling agent 0-10 37

Anti-redeposition agent 0-4.0

Alkali metal perborate as a bleach 5-15

Bleaching agent activator 05 (TAED) 1.0-8.0

Bleach sequestering agent 0-3.0 ·

Optical aviator 0.05-0.75

Enzymes 0.75-1.25 10 Perfume 0.1 -1.0

The following examples further illustrate the present invention, EXAMPLE 1

A non-aqueous liquid detergent composition based on non-ionic surfactant is prepared from the ingredients in the specified proportions.

% by weight 20 Non-ionic surfactant 37.7

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

Sodium tripolyphosphate (TFP) 25 25 Hexylene glycol 15

Alkanolic ester of phosphoric acid 1.0

Sodium perborate monohydrate (bleach) 9.0 30 Tetraacetylethylenediamine (TAED), bleach activator 4, 5

Anti-redeposition agent (Relatin DM

4096) 1.0 '35 Optical aviator 0r2'

Perfume 0 * 6 38

Enzyme (Esperase) 1/0 ~ 100.0 (1) mixture of CMC / MC = 2: 1 (of sodium carboxymethylcellulose and hydroxymethylcellulose).

05

The composition 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 10 prepared is stable and non-gelling during storage and that it disperses easily in water.

EXAMPLE 2.

A concentrated non-aqueous detergent composition based on non-ionic surfactant is prepared from the following ingredients in the specified proportions.

% in weight

Surfactant T7 17 20 Surfactant T9 17

Acid-terminated reaction product of Dobanol 91-5 with succinic anhydride 4

Sodium tripolyphosphate (TPP) 24.5 25 Hexylene glycol 15.0

Propylene carbonate 0.3

Anti-scaling agent (Sokalan CP5) 4.0

Alkanolic phosphoric acid ester 1.0

Sodium perborate monohydrate bleach 9 Tetraacetylethylenediamine (TAED), bleach activator 4f5

Sequestering agent for bleach 39 (Dequest 2066) 1.0

Anti-redeposition agent (Relatin DM 4096) 1.0 Optical brighteners (ATS-X) 0.2 05 Enzyme (Protease) 1.0 'Fragrance 0.5 (1) Mixture of CMC / MC = 2; 1, of carboxymate -sodium cellulose and hydroxymethylcellulose.

10

The composition is ground for about an hour to reduce the particle size of the detergency builder salts to the suspension to less than 40 micrometers. It is found that the composition prepared 15 is stable and not gelling at. storage and easily dispersed in water.

EXAMPLE LE- 3

In order to demonstrate the effect of the addition of hexylene glycol to detergent compositions based on nonionic surfactant, compositions A and B are prepared and tested to determine their flow limit. and plastic viscosity,

A B

25 Non-ionic surfactant, Product C 69% -58.5%

Sodium tripolyphosphate 30% 30%

Hexylene glycol - 10.5%

Arosurf ta 100 i% 1% 30 The two compositions are ground for 1 hour in order to reduce the particle size to. less than 40 micrometers.

When testing the compositions, the following results are obtained,

35 A B

Flow limit (pascals) 15f5 13.0 '40

Plastic viscosity (Pa, s) 0.500 0.265 £ The above results show that the addition of 10.5% of hexylene glycol to composition B 05 significantly reduces the plastic viscosity from 5.0 to 2.65, all by lowering the flow limit from 15.5 to 13.0 pascals, for example by only about 12.9%. The physical stability of the composition is not adversely affected.

10 EXAMPLE 4

In order to demonstrate the effect of the addition of hexylene glycol and of propylene carbonate on the apparent viscosity and on the dispersibility of the detergent compositions with nonionic surfactant, compositions C to F are prepared and they are varied the proportion of hexylene glycol from 0 to 30%.

C (%) D (%) E (%) F (%) • 20 Non-ionic surfactant,

Product C 47.9 47.9 47.9 47.9

Non-ionic surfactant,

Product D 30 20 10 -

Sodium tripolypho'sphate 25 21 21 21 21

Hexylene glycol - 10 20 30

Propylene carbonate 0.3 0.3 0.3 0.3

Bentone 27 0.8 0.8 · 0.8 0.8 30 Each composition is ground for 1 hour to reduce the particle size to less than 40 micrometers.

The compositions are tested to determine their apparent viscosity and their dispersibility. The dispersibility test is carried out by pouring 100 g of detergent composition into the dispenser of a washing machine and measuring the quantity of detergent composition which remains in the dispenser after a washing cycle.

The results obtained for each of the 05 detergent compositions are as follows:

C D E ’F

Apparent viscosity (mPa, s) (LVT, 60 rpm, Bro- 10 ehe NQ 4) 350 900 650 530

Dispersibility (% remaining in the dispenser) 24 17 7 5

The above results show that the addition of 10 to 30% of hexylene glycol to compositions D, E and F substantially reduces the apparent viscosity and appreciably improves the dispersibility of the compositions. The addition of hexylene glycol or hexylene glycol and propylene carbonate does not have an adverse effect on the physical stability of the compositions.

The compositions of Examples 1 to 4 can be prepared without grinding detergency builder salts and / or suspended solid particles to a small particle size, but best results are obtained by grinding the composition to reduce the particle size of the suspended solids.

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 performed in part before the mëlan-35 ge operation and to be completed after the mixing operation, well the entire grinding operation can be carried out after mixing with the liquid surfactant. Compositions which contain detergency builders and suspended solid particles whose particle size is less than 40 micro-05 meters are preferred.

Claims (19)

1. A detergent composition comprising a suspension of insoluble mineral particles of detergency builder salt in a non-aqueous nonionic liquid detergent surfactant and hexylene glycol to improve the anti-gelling properties and the dispersibility of the composition. 2. Composition according to claim 1, characterized in that the insoluble mineral particles consist of adjuvant detergency of phosphate type. 3. Composition according to claim 2, characterized in that the phosphate-type detergency builder salt consists of an alkali metal polyphosphate. 4. Composition according to claim 1, characterized in that the mineral particles comprise 10 to 60 percent of a detergency builder salt of the polyphosphate type. 5. Composition according to claim 1, characterized in that it comprises 0 to 5.0 percent of carbonate of formula; I? 0 0 1 1 R1 — CH —- CH — R2 30 in which Rj ^ and R2 are chosen from the group formed by H and a lower alkyl radical in C1 to C4, and R2 being identical or different. 6. A detergent composition according to claim 1, characterized in that it contains 5 to 40% of hexylene glycol and 0.1 to 2 percent of propylene carbonate. 44 "ι 7. Detergent composition according to claim 1, characterized in that it contains one or more detergent additives chosen from the group formed by an anti-encrustation agent, a bleaching agent, a bleaching agent activator , a sequestering agent, an anti-redeposition agent, an optical brightener, enzymes, a perfume and a pigment, 8. Compositior according to claim 1, characterized in that it contains 20 to 70 percent 10 of a nonionic liquid detergent surfactant, 9. A detergent composition according to claim 1, characterized in that it contains 5 to 30 percent of hexylene glycol, 10. Composition according to claim 1 ,. 15 characterized in that the mineral particles have a particle size of less than 40 micrometers. 11. Composition according to claim 1, characterized in that it contains approximately 0.1 to approximately 1.0 percent by weight, based on the whole of the composition, of propylene carbonate, 12. A non-aqueous detergent composition reinforced with a detergency builder for heavy duty laundry which can be poured at high and low temperatures and does not gel when mixed with cold water, including an at least one nonionic liquid surfactant in a proportion of about 20 to about 70% by weight, · at least one mineral salt, detergency builder, suspended in the nonionic active surfactant, in a proportion of about 10 to about 50 percent by weight, * and hexylene glycol in a proportion of about 5 to 30 percent, 13. Detergent composition according to claim 12, characterized in that it optionally contains one or more additives for detergent chosen from the following: enzymes, corrosion inhibitors, defoamers, foam suppressants, agents! i * 45 for suspending or anti-redeposition of dirt, anti-yellowing agents, dyes, perfumes, optical brighteners, brighteners, pH modifiers, pH buffers, bleaching agents, bleaching agent stabilizers, bleach activators, enzyme inhibitors and sequestering agents, 14, A non-aqueous liquid detergent composition for heavy laundry work according to claim 12, characterized in that it contains approximately 20 10 to 70 percent by weight of nonionic surfactant, approximately 20 to 35 percent by weight of tripolypho sodium phosphate (TPP), about 10 to 30 percent by weight of hexylene glycol, about 0 to 20 percent by weight of acid-terminated non-ionic overbite, about 0 to 2 15 percent by weight weight of alkanolic phosphoric acid ester, about 2 to 20 percent by weight of sodium perborate monohydrate as a bleaching agent, and about 1 to 8 percent by weight of tetraacetylethylenediamine (TAED). 15. A non-aqueous liquid detergent composition for heavy laundry work according to claim 12, characterized in that it contains about 20 to 70 percent by weight of nonionic surfactant, about 20 to 35 percent by weight of tripolypho sodium phosphate, about 10 to 30 percent by weight of hexylene glycol, about 0.1 to 1.0 percent by weight of propylene carbonate, about 0 to 20 percent by weight of non-surfactant acid-terminated ionic, about 0 to 2 percent by weight of alkanolic ester of phosphoric acid, about 2 to 20 percent by weight of sodium perborate monohydrate as a bleaching agent, and about 1 to 8 percent by weight tetraacetylethylenene diamine (TAED) as an activator of the bleaching agent. 16. A method for cleaning soiled fabrics, characterized in that it consists in bringing the r 46 "" -¼ „k soiled fabrics into contact with the detergent composition of the laundry according to claim 1. 17. Method for cleaning soiled fabrics> characterized in that it consists in bringing the soiled fabrics 05 in contact with the detergent composition of the laundry according to claim 12, 18. A method for cleaning soiled fabrics * characterized in that it consists in bringing the soiled fabrics in contact with the detergent composition of the "laundry" according to claim 14, 19. A method for cleaning soiled fabrics, characterized in that it consists in bringing the soiled fabrics in contact with the detergent composition for the laundry washing according to claim 15,