LU86979A1 - SURFACTIVE ETHOXYL-PROPOXYL FATTY ALCOHOL COMPOUND, DETERGENT COMPOSITION CONTAINING THE SAME, AND METHOD OF USING SAME FOR CLEANING DIRTY TISSUES - Google Patents

Description

r · * '52.684

. ; ~ g £ d d GRAND DUCHY OF LUXEMBOURG

Patent N ...................................... Minister r of August 28, 1987 .. . Economy and the Middle Classes: ¾¾¾ Intellectual Property Service

...................— I gppj LUXEMBOURG

Patent Application ...................: ___________________________________ Π) I. Request

The society known as î -COLGATE — PALMQLIVE-GGMPANYt — 3ÛO Park — Avenue / 2) NEW YORK, ..N. 100 2 2 r United States -JJ-America r — represented-by—

Mr. -Jacques de Muyser-r ~ acting — in-quality-ity- <fe agent— ...................-______________________________________________-_______ r—- (3) deposits ( nt) ce twenty-rhult - august — 19-QQ — four = v-ingt — sept -: - (4) to ...... 15 .............. _______hours , at the Ministry of the Economy and the Middle Classes, in Luxembourg: 1. this request for obtaining a patent of invention concerning: ....... ü Compound-jd ._ '. alcool_gras- ethoxylated ^ propoxy-lé-sur-f active 7- (5) ...... CQmpQsitian-_dêtgenfca-le .. ~ now, —and — process — using ---- ...... this .. .... composition for-cleaning-soiled-fabrics, ---- 2. the description in language - .. French __________________________ of the invention in triplicate; 3 .................... // -................. drawing boards, in triplicate; 4. the receipt of the taxes paid to the Registration Office in Luxembourg, _-27 — August — 1 $ 87-i 5. the delegation of power, dated__________________________ on -----; 6. the successor document (authorization); declare), assuming responsibility for this declaration, that the inventor (s) is (are): (6) 1 · Xrazollah — OUHADXÿ — 5 — Quai — 1Gloessner r_lïeg & t — Belgium -——— 2. Louis ... ... DEHM. "._ 4D-_rue - Curie #„ SERAING # „... Belgium____ 3 · Léopold LAITEM, 2 rue de Merdoro, ORP-LE-GRAND. Belgium_ claim) for the above patent application the priority of one (s) application (s) of (7) ---- patent ------------ filed (s) »n (8 ) in the United States of America on (9) August 28-JLSBB ___________ — _ under N ° (10) 901.339 ____________________________ in the name of (11) s inventors ._________________________________ elect (elect) domicile for him (her) and, if appointed, for its representative, in Luxembourg ------------ ---------------------- ,. · ..35-, .. „boulevard Royal -------------------- (12) requests (s) the issue of a patent for the invention for the object described and represented in the above-mentioned annexes, with postponement of this issue to ____ „6 ---- months. (13)

The agent / agent: _________________________------ (14) MÿsæJ (Π. Minutes of Filing

The above! patent application has been filed with the Ministry of the Economy and the Middle Classes, Intellectual Property Service ^^ ç ^ buxembourg, dated: August 28, 1987

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/U.T '' Z \ Pr. The Minister of the Economy and the Middle Classes, at _____________ At 3 am dd 5d Pd.

\ ^ 16¾¾ 7: / The head of the intellectual property department, CO'fC A68007__ EXPLANATIONS RELATING TO THE DEPOSIT FORM. .

f AAT \ (If applicable "Application for certificate of addition to the main patent, to main patent application No ............ of ........ .... "- (2) enter the surname, first name, profession, V-- JUjL [y address of the applicant, when the applicant is an individual or company name, legal form, address of head office, when the applicant is a legal person - (3) register - Iac nnm nrinnm raHrMO "rti, m ^ nrtnlain" οστέρ mnc ^ îl nmnrî4t £ înrincfri ^ Tti "provided with a nnitvntf cn & rînl. if V9 llfiU!" teoréé OâT _. . ........ flPKftflnf Wl finality dft agent ", .. '·, 52.684

CLAIM OF PRIORITY

! patent application / daxtaasâèiaxlâjtâliés r; 5¾ To the States of America

Of August 28, 1986 (No. 901.339) Brief Description j j filed in support of a request for

PATENT

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Luxembourg on behalf of: colgate-palmolive company NEW YORK, NY 10022 (United States of America) for: "Compound surfactant ethanol-propoxylated fatty alcohol, detergent composition containing it, and process using this composition for cleaning soiled fabrics . "

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NOT

The present invention relates to non-aqueous liquid compositions for the treatment of tissue. The present invention relates in particular to non-aqueous liquid detergent compositions for washing clothes, containing a suspension of detergency builder salt in nonionic surfactants, these compositions being stable against phase separation and gelling and being easy to pour, as well as the use of these compositions for cleaning soiled tissues. More particularly, the present invention relates to detergent compositions based on nonionic surfactants, in which the nonionic surfactant is highly biodegradable.

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 are dispersed JLO particles of a detergency builder, as, for example, is known from U.S. patents. N * 4,316,812, 3,630,929 and 4,264,466, and the British patents N * 1,205,711, 1,270,040 and 1,600,981.

^ '2 îr

The Applicant's related patent applications are as follows: FR-85.19510 filed on December 31, 1985; FR-85.04831 filed March 29, 1985; 5 FR-85.05319 filed April 9, 1985; FR-86.11852 filed August 19, 1986; and FR-86.10918 filed July 28, 1986.

These applications relate to non-aqueous non-ionic liquid detergent compositions for washing clothes. The washing power of synthetic non-ionic detergent surfactants contained in detergent compositions for washing clothes can be increased by the addition of detergency builders.

Liquid detergents are often considered to be 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 washing water and can be easily applied in 2Q concentrated solutions or dispersions on dirty areas of clothes to be washed, and they do not generate dust and usually take up less space. storage. 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 employ 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 in order to obtain commercially acceptable detergent products. Thus, some of these 35> 3 t s products show a low degree of biodegradability, separate during storage, have a high dropping point and foam excessively during use, and others separate by cooling. and are not easy to redisperse. In some cases, the viscosity of the product changes and it becomes either too thick to be poured, or fluid enough to resemble water. Some clear products cloud and others gel on standing.

Conventional detergent synthetic nonionic surfactants conventionally produced and commercially available generally contain only polyethoxy groups, although some of the nonionic surfactants conventionally used contain both polyethoxy groups and polypropoxy groups. The propoxy groups are however generally only present in minor proportions. The ethoxy and propoxy groups are generally randomly distributed in the ethoxy-propoxy chain attached to 2Q fatty alcohol and the ethoxy group is generally attached to the alkyl group of fatty alcohol.

The biodegradability of conventionally used nonionic surfactants varies to a large extent depending on the presence and arrangement of the propoxy group, and on the arrangement and distribution in the polyalkoxy chain of the propoxy and ethoxy groups constituting the chain.

The Applicant has for example found that a non-ionic surfactant corresponding to the formula: R- (OC2H4) y (OC2H6) xOH, that is to say where the polyethoxy group is attached to the alkyl group of fatty alcohol and where the hydroxyl group is attached to the polypropoxy group, has only poor biodegradability of only 20 percent or less.

4 t;

On the other hand, the Applicant has discovered with surprise that if the nonionic surfactant corresponds to the formula:

R- (oc3H6) x (oc2H4) yOH

5 i.e. when the polypropoxy group is attached to the alkyl group of the fatty alcohol and the hydroxyl group is attached to the polyethoxy group, this surfactant is biodegradable at least 60 percent and generally at least 80 percent . Certain particular nonionic surfactants of the present invention have been found to be 90 to 100 percent biodegradable.

The biodegradability of the nonionic surfactants of the present invention is determined by the OECD selection method.

In addition to the problems posed by poor biodegradability and sedimentation or phase separation, non-aqueous liquid detergents for laundry based on liquid nonionic surfactants have the disadvantage that the nonionic surfactant tends to gel when it is added to cold water. This is a problem which is of particularly great importance in the current 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 dispensing drawer). of the machine. During the operation of the machine, the detergent contained 3Q in the dispenser is subjected to a stream of cold water to be transferred into the main mass of the washing solution. It happens in particular during the winter months, when the detergent composition and the water which feeds the dispenser are particularly cold, that the viscosity of the detergent greatly increases and that a gel forms. As a result, part of the composition is not expelled from the dispenser during the operation of the machine, and a deposit of composition accumulates during repeated washing cycles, which ultimately forces 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 the 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.

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 regulating solvents and certain gelation inhibiting agents, such as lower alkanols. , for example ethyl alcohol (see US Pat. No. 3,953,380), alkali metal formates and adipates (see US Pat. No. 3,963,378,147), hexylene glycol, polyethylene glycol, etc .; and by modification and optimization of the structure of the nonionic surfactant. As an example of modification of the nonionic surfactant, a particularly successful result was obtained by acidifying the terminal group of% 6 I. .

* hydroxylated fragment of the nonionic molecule. The benefits of introducing a carboxylic acid to the end of the non-ionic molecule include inhibiting gel setting at dilution, lowering the drop point of the non-ionic surfactant and forming 'an anionic surfactant by neutralization in the washing 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 C 13 fatty alcohol ethoxylated with 8 moles of ethylene oxide exhibits only a limited tendency to gel formation.

1D

Nevertheless, improvements are desirable with respect to the biodegradability, stability and inhibition of gelation of non-aqueous liquid tissue treatment compositions.

2Q In accordance with the present invention, a highly biodegradable concentrated non-aqueous liquid detergent composition for washing clothes is prepared using as main surfactant an ethoxylated-propoxylated fatty alcohol in which the propylene oxide groups are adjacent to the alkyl group and the ethylene oxide groups are adjacent to the hydroxyl group.

We have surprisingly discovered that the non-ionic surfactant is highly biodegradable, for example more than 80 percent biodegradable, when the propylene oxide groups are adjacent to the alkyl group R and the ethylene oxide groups are at the end. of the molecule and adjacent to the OH group. The Applicant has however found that the nonionic surfactant exhibits a low degree of O 9 * i ’7 A..

biodegradability, being for example biodegradable to less than 20 percent, when the ethylene oxide groups are adjacent to the alkyl group R and the propylene oxide groups are at the end of the 2 molecule and adjacent to the OH group.

The highly biodegradable nonionic surfactants of the propoxylated-ethoxylated fatty alkyl alcohol type of the present invention correspond to the general formula:

10 R- (OC3H6) x (OC2H4) yOH

wherein R represents a C8 to C2gf alkyl group preferably a Cg to C ^ g alkyl group, the sum x + y is 20 to 100 percent, preferably 40 to 80 percent, of the number of atoms of carbon of the alkyl group, x is at least 1, preferably at least 2, and y is at least 1, preferably at least 2.

The nonionic surfactants of the propoxylated-ethoxylated fatty alcohol type of the present invention are biodegradable at least 60 percent, preferably at least 80 percent. The nonionic surfactants of the propoxylated-ethoxylated fatty alcohol type of the present invention may be used as the sole detergent nonionic surfactants or they may be used in admixture with conventional commercially available nonionic surfactants. It is preferable that the nonionic surfactants of the propoxylated-ethoxylated fatty alcohol type constitute at least 50 percent, and better still at least 70 percent, of the nonionic surfactants used in the detergent composition.

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 V 9 /./ 8 *; · The composition and its storage properties during storage, it is possible to add to the composition viscosity improving agents and antifreezing agents such as monoalkyl ethers of alkylene glycols and anti-sedimentation agents such as phosphoric acid esters and aluminum stearate. In a preferred embodiment of the invention, the detergent composition contains an acid-terminated nonionic surfactant and / or a monoalkyl ether of alkylene glycol, and an anti-sedimentation agent.

Sanitizers or bleaches and activators for these agents can be added to improve the bleaching and cleaning characteristics exhibited by the composition.

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

In addition, other ingredients can be added to the composition, such as anti-scaling agents, anti-foaming agents, optical brighteners, enzymes, anti-redeposition agents, perfume 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 consumed during the wash and rinse cycles.

35 9 ‘". · *

About 175 grams of powdered detergent is normally used per wash.

In accordance with the present invention, there is provided a liquid detergent composition for heavy laundry work, comprising a highly biodegradable nonionic surfactant which consists of a propoxylated-ethoxylated fatty alkyl alcohol in which the propylene oxide groups are attached to the group. alkyl and ethylene oxide groups are attached on one side to the terminal propylene oxide group and on the other side to the hydroxyl group.

Thus, in one aspect of the present invention, there is provided a liquid laundry detergent composition for heavy laundry work consisting of a suspension of a detergency builder salt in this nonionic surfactant.

In another aspect, the invention provides a liquid detergent composition for heavy laundry work, in which the non-ionic 2Q surfactant is highly biodegradable, and which is stable, does not sediment during storage and does not gel. storage and use. The liquid compositions of the present invention are easy to pour, easy to dose and easy to introduce into the washing machine.

25

In another aspect, the invention provides a method for dispensing a highly biodegradable liquid non-ionic detergent composition for washing laundry, in and / or with cold water without gelation occurring. In particular, there is provided a method of filling a container with a non-aqueous liquid laundry detergent composition in which the detergent is composed at least predominantly of a highly biodegradable liquid nonionic surfactant according to the. 1. The present invention, 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 into the washing bath.

The heavy laundry detergent compositions of the present invention have substantially improved biodegradability as they comprise, as the main and essential constituent of the compositions, a propoxylated-ethoxylated fatty alcohol in which the propylene oxide groups are attached to the alkyl group and the ethylene oxide groups are attached to the hydroxyl group.

The compositions of the present invention have the advantages of having a low flow temperature, being non-gelling on contact with water, being non-foaming and having good detergency.

The nonionic surfactants of the propoxylated-ethoxylated fatty alcohol type of the present invention exhibit a high degree of biodegradability, they are for example more than 80 per 2 g biodegradable, they are not very foaming when used, they have a drop point. low, for example -2 ° C, and they do not gel when contacted with water at 5 ° C. The nonionic active surf of the present invention also exhibits good detergency.

The concentrated non-aqueous liquid detergent compositions based on non-ionic surfactant for washing clothes according to the present invention have the additional advantages of being stable, of not sedimenting during storage and of not being. gel during storage. The liquid compositions are easy to pour, easy to dose and easy to introduce into washing machines.

It is an object of the present invention to provide a highly biodegradable non-ionic detergent surfactant of the propoxylated-ethoxylated fatty alcohol type, in which the propylene oxide groups are attached to the alkyl group and the ethylene oxide groups are attached to the hydroxyl group.

Another object of the invention is to provide liquid tissue treatment compositions which are suspensions of an adjuvant detergency salt in the surfactant of the propoxylated fatty alcohol type ethoxylated g and which are stable in storage and easy pour and disperse in cold, lukewarm or hot water.

Another object of the invention is to formulate non-aqueous liquid detergent compositions based on 2Q non-ionic surfactants and containing detergency builders, for heavy laundry work, which contain the nonionic surfactant of the propoxylated fatty alcohol type. ethoxylated as the main non-ionic surfactant and which can be poured at any temperature and can be dispersed over and over again from the dispensing device of automatic machines for washing European type laundry without clogging or obstructing the dispenser even during the months winter.

Another object of the invention is to provide non-aqueous non-ionic liquid detergent compositions containing a detergency builder, for heavy laundry work, in the form of stable, low-foaming and non-gelling suspensions which contain as surfactant The main surfactant of the propoxylated-ethoxylated fatty alcohol type of the present invention.

Another object of the invention is to provide non-aqueous liquid nonionic detergent compositions containing a detergency builder for heavy laundry use in the form of stable, non-gelling suspensions which contain an alkanolic acid ester. phosphoric acid and / or an aluminum salt of fatty acid as an anti-sedimentation agent in an amount sufficient to increase the stability of the composition, i.e. avoid sedimentation of the detergency builder particles, etc., while preferably reducing or at least not increasing the plastic viscosity of the composition.

These and other objects of the present 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 non-aqueous liquid nonionic surfactant to the composition. present invention an effective amount of an adjuvant detergency salt and organic or mineral additives for tissue treatment, for example agents improving viscosity and antifreezing. 20 anti-sedimentation agents, anti-encrustation agents, bleaching agents, bleach activators, defoaming agents, optical brighteners, enzymes, anti-deposition agents, perfume and colorants.

The highly biodegradable nonionic surfactants of the propoxylated-ethoxylated fatty alkyl alcohol type of the present invention correspond to the general formula:

35 R- (OC3H6) x (OC2H4) yOH

>. * 13 I- in which R represents a C8 to C2g alkyl group, preferably a C9 to C18 alkyl group, and better still a C9 to or C12 to C15 alkyl group. The value of the sum x + y is 20 to 100 5 percent, preferably 40 to 80 percent, and more preferably 45 to 60 percent, of the number of carbon atoms in the alkyl group R. The value of x is at least 1, preferably at least 2, and more preferably x is equal to or greater than 3.

The nonionic surfactants of the propoxylated-ethoxylated fatty alcohol type of the present invention are biodegradable at least 60 percent, preferably at least 80 percent and more preferably at least 90 percent.

The highly biodegradable non-ionic synthetic organic detergents of the present invention are produced by (1) the condensation of a fatty aliphatic alcohol with propylene oxide or polypropylene glycol, followed by (2) the reaction of the former, condensation product obtained with ethylene oxide or polyethylene glycol.

The fatty alkyl alcohol reacts with propylene oxide or polypropylene glycol by fixing a linear chain of low molecular weight, for example where x = 2 to 15, preferably 2 to 8 and better still 3 2 5 to 6, of propylene oxide polymer. The propylene oxide chain normally attaches to the alkyl group on a primary or secondary carbon atom of the fatty alcohol. The condensate of fatty alcohol and propylene oxide is then reacted with ethylene oxide or polyethylene glycol to add the desired number of ethylene oxide groups. The ethylene oxide groups normally join or bind to the terminal propylene oxide group and condense to form a chain of 14.

low molecular weight, for example where y = 2 to 15, preferably 2 to 8 and better still 3 to 6, of ethylene oxide polymer terminated by the hydroxyl group.

By carrying out separate condensation reactions of propylene oxide and ethylene oxide, a low molecular weight linear polymer of propylene oxide binds to the primary or secondary carbon atom of the fatty alcohol and a low molecular weight linear polymer of ethylene oxide binds to the terminal molecule of propylene oxide. The chain end of the ethylene oxide polymer has a hydroxyl group.

The highly biodegradable detergent nonionic surfactants of the present invention are poly (propoxylated-ethoxylated) lipophilic compounds in which the desired hydrophilic-lipophilic ratio is obtained by adding the hydrophilic polypropoxy-polyethoxy groups to the lipophilic aliphatic moiety.

A preferred class of non-ionic detergents is C6 to C18 fatty alkyl alcohols which contain 4 to 16 propylene oxide and ethylene oxide groups, i.e. where x + y = 4 to 16. D Other classes of non-ionic detergents are C6 to C6 fatty alkyl alcohols in which x + y = 5 to 10, and C12 to C12 fatty alkyl alcohols. C15 in which x + y = 5 to 15.

Condensation products of propylene oxide and ethylene oxide on higher molecular weight Cig-C26 fatty alkyl alcohols exhibit a high degree of biodegradability but tend to more readily form gels in the detergent composition concentrated and, in some cases, can be solid at room temperature V, · 15. Although surfactants derived from ci9-c26 fatty alcohols can contribute to gelation of the liquid detergent composition, they can if necessary be added to it. detergent composition 5 in small quantities, in particular in the case where concentrates with low gelling properties are not required.

In the preferred polyalkoxylated higher alkanols, to obtain the best balance between the hydrophilic and lipophilic moieties, the number of lower alkoxy groups, i.e., the sum x + y, is generally 20 to 100 percent, preferably 40 to 80 percent, and more preferably 45 to 60 percent, of the carbon number of the higher alcohol. The total detergent non-ionic surfactant of the composition preferably contains at least 50 percent, of 7% pcéeéœnœæ-ncdns nnt, the surfactant rxxi Icniqje guyed biodegradable of the jxéssite invention.

Suitable highly biodegradable propoxylated-ethoxylated fatty alkyl alcohols of the present invention are:

R- (OC3H6) x (OC2H4) yOH

B xy 1. C12 “C15 3 5 .25 2 * C12“ C15 5 4 3 · Cg "Cn 3 5 4. Cg-Cn 2 4 5. Cg-Cis 3 6 1 6. Cg-Cig 2 4 3Q In this Regarding both nonionic detergents derived from preferred Cg-C18 fatty alcohols and those, less preferred, which are derived from C19-C26 fatty alcohols, the alkyl groups found therein are generally linear although a a low degree of branching can be tolerated, for example at the level of the carbon atom contiguous to the terminal carbon atom, or at the level of the carbon atom distant from two positions of the terminal carbon atom, of the straight chain and opposite of the propoxy chain, provided that the length of this alkyl branch does not exceed three carbon atoms. Normally, the proportion of carbon atoms in such a branched configuration must be minor, for example less than 20 percent of the total number of carbon atoms in the alkyl group. Similarly, although the linear alkyl groups which are joined by the atom of c arbone terminal to the propoxy chains are clearly preferred and are considered to give the best combination of detergency, biodegradability and non-gelling characteristics, there may appear a median or secondary junction of the alkoxy groups, i.e. propoxy chains, to alkyl groups.

Normally there should only be a minor proportion of such alkyl groups, i.e. side chain alkyl groups, for example less than 20 percent, preferably less than 10 percent, of the total alkyl groups.

The non-ionic surfactants of the propoxylated-ethoxylated fatty alkyl alcohol type of the present invention may be used as the sole detergent nonionic surfactants or may be used in admixture with conventional commercially available detergent nonionic surfactants. The nonionic surfactant of the propoxylated-ethoxylated fatty alcohol type of the present invention may constitute 40 to 100 percent, preferably 50 to 100. .

percent, and more preferably 70 to 100 percent, of the total nonionic surfactant of composition 3 g. detergent.

î * * v '17

Non-Ionic Surfactant Classic Detergent

The conventional non-ionic synthetic organic detergents which can be used with the highly biodegradable propoxylated-ethoxylated fatty alcohol type surfactants of the present invention can be any of a wide variety of such compounds which are well known. Typical suitable nonionic surfactants are those described in U.S. patents. Ne 4,316,812 and 3,630,929.

In general, 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 detergents used is that of the higher alkanols polyalkoxylated by lower alkoxy groups in which the alkanol has 9 to 18 carbon atoms and the number of moles of lower alkylene oxide (of 2 or 3 atoms carbon) is 3 to 12. Among these materials, it is preferable to use those in which the higher alkanol is a higher fatty alcohol of 9 to 11 or 12 to 15 25 carbon atoms 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 it can be advantageously mixed with the propoxy group.

2q Representative examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and which contain approximately 7 ethylene oxide groups per molecule, for example Neodol 25-7 and

Neodol 23-6 ^ 5 which are products made by Shell Chemical Company, Inc. The first is a 35 "· * 18" "condensation product of a mixture of higher fatty alcohols having on average about 12 to 15 atoms of carbon, 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 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 secondary linear alcohol ethoxylates manufactured by Union Carbide Corp. The first is the mixed ethoxylation product of a secondary linear alkanol of 11 to 15 carbon atoms with seven 15 moles of ethylene oxide and the second is a similar product but where nine moles of ethylene oxide have reacted.

Higher molecular weight nonionic surfactants are also useful in the present invention as components of nonionic detergent, such as Neodol 45-11, which are similar products of condensation of ethylene oxide on higher fatty alcohols, the higher fatty alcohol having 14 to 15 carbon atoms and the number of 25 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 30 well known in the trade which are sold under the trademark Plurafac. Plurafac series surfactants are the reaction products of a higher linear alcohol and a mixture of ethylene oxide and propylene, containing a mixed chain of ethylene oxide and propylene oxide, W "* * Ό * 19 terminated by a hydroxyl group. Examples are Product A (a C13-C15 fatty alcohol condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide), Product B (a C13-C15 fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide), Product C (a fatty alcohol in c13 “c15 condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide), Plurafac B26 , and Product D (an equal mixture of Product C and 20 of Product B).

Another class of liquid nonionic surfactants is commercially available from Shell Chemical Company, Inc. under the trademark Dobanol: Dobanol 91-5 is a Cq-Ch ethoxylated fatty alcohol with an average of 5 moles of ethylene oxide and Dobanol 25-7 is an ethoxylated fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

If greater proportions than 2Q mentioned above are used of alkanols whose alkoxylation is not terminal, of alkanols polyalkoxylated by lower alkoxy groups containing propylene oxide and of nonionic detergent with poorer hydrophilic-lipophilic ratio, and if other nonionic detergents are used in place of the preferred nonionic surfactants listed herein, the resulting product may not have as good detergency, stability, viscosity and non-gelation than the preferred compositions, but the use of the viscosity regulating and anti-gelation compounds of the invention can also improve the properties of the detergent products based on such nonionic surfactants. In some cases, for example when a higher molecular weight polyalkoxylated higher alkanol is used, often for detergency its proportion may be adjusted or limited according to the results of routine tests for obtain the desired detergent power while the product remains in a gelling agent and of desired viscosity. It has moreover been found that it is only rarely necessary to make use of non-ionic surfactants of higher molecular weight for their detergent properties since the preferred nonionic surfactants described here are excellent detergents and allow in addition to achieving the desired viscosity of the liquid detergent product without gelation at low temperatures.

Another useful class of nonionic surfactants is the series of products called "Surfactant T" available from the company British Petroleum. The nonionic surfactants Surfactant T are obtained by ethoxylation of C13 secondary fatty alcohols with a narrow distribution of 20 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 an average of 9 moles of ethylene oxide and Surfactant T12 contains an average of 12 25 moles of ethylene oxide, per mole of C13 secondary fatty alcohol.

In the compositions of the present invention, the preferred conventional nonionic surfactants include C13-C15 secondary fatty alcohols with relatively narrow ethylene oxide contents, in the range of about 7 to 9 moles, and alcohols fatty Cg-Cj ^ ethoxylated with about 5 to 6 moles of ethylene oxide.

Mixtures of two or more of the conventional liquid nonionic 3g surfactants may be; 21 used with the highly biodegradable surfactant of the propoxylated-ethoxylated fatty alcohol type of the present invention, and in certain cases it is possible to derive advantages from the use of such mixtures.

5 Acid-terminated Non-ionic Surfactant

The viscosity and gelation properties of liquid detergent compositions can be improved by incorporating into 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 a free hydroxyl group of this surfactant into a moiety having a free carboxyl group, for example either an ester or a partial ester of a nonionic surfactant and a polycarboxylic acid or anhydride.

As described in the patent application of the Applicant FR-8505319 filed on April 9, 1985, the 20 nonionic surfactants modified by a free carboxyl group, which can roughly be characterized as polyethercarboxylic acids, act by lowering the temperature at which the liquid non-ionic surfactant forms a Çfel with water.

The addition of the acid-terminated nonionic surfactant to the liquid nonionic surfactant promotes the ability of the composition to be dispensed, i.e., its ability to be poured, 3q and lowers the temperature at which the nonionic surfactant liquid forms a gel in water without reducing its stability against sedimentation. The acid-terminated nonionic surfactant reacts in the water of the washing machine with the alkalinity of the dispersed phase of detergency builder salt of the detergent composition and acts as an effective anionic surfactant.

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

Acid-terminated nonionic surfactants can be prepared as follows:

Acid-terminated Product A: 400 g of Product A are mixed, a nonionic surfactant which is a C 13 to C 15 alkanol which has been alkoxylated so as to introduce therein 6 ethylene oxide units and 3 propylene oxide units per unit of alkanol, with 32 g of succinic anhydride, and the whole is heated for 2Q 7 hours at 100 "C. The mixture is cooled and filtered to remove the unreacted succinic material. Infrared analysis shows that little almost half of the non-ionic surfactant has been transformed into its acid hemi-ester.

2g Dobanol 25-7 with acid termination: 522 g of Dobanol 25-7, nonionic surfactant which is the product of ethoxylation of a C12 to C15 alkanol and contains approximately 7 ethylene oxide units per molecule, are mixed. alkanol, with 100 g of succinic anhydride and 0.1 g of pyridine (which acts as a catalyst

v V

esterification) and the whole is heated to 260 ° C. for 2 hours, cooled and filtered to remove the unreacted succinic material. Infrared t analysis shows that virtually all of the free hydroxyl groups in the surfactant have reacted.

35 * '23 * · *

Acid-terminated Dobanol 91-5: 1000 g of Dobanol 91-5, a nonionic surfactant which is the ethoxylation product of a C 1 -C 1 alkanol, are mixed and contains approximately 5 ethylene oxide units per 5 alkanol molecule, with 265 g of suicin anhydride and 0.1 g of pyridine as catalyst, and the whole is heated to 260 ° C. for 2 hours, cooled and filtered to remove the unreacted succinic material. Infrared analysis shows that virtually all of the free hydroxyl groups in the surfactant have reacted.

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

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

20 ADJUVANT DETERGENCE SALTS

The nonaqueous liquid nonionic surfactant used in the compositions of the present invention contains, in the dispersed or dissolved state, fine particles of organic and / or inorganic detergency builder salts.

Adjuvant organic detergents

Preferred organic detergency builder salts include alkali metal salts of polyacetal carboxylic acids (see application FR-30 86.11852), alkali metal salts of lower polycarboxylic acids (see application FR-86.10973), metal salts nitrilotriacetic acid (NTA) alkalines (see application FR-86.11041) and alkali metal salts of polymers of alpha-hydroxyacrylic acid (see application FR-86.11852), - 24 '* ï'

In certain detergent compositions, the above-mentioned organic detergency builder salts can be used as the main detergency builder salt without the addition of a mineral detergency builder salt, such as a detergency builder polyphosphate, or in combination with only one a small amount of an adjuvant detergent of the polyphosphate type, or polyphosphate may be the main adjuvant detergent.

^ 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 product of the reaction of an approximately equal number of moles of methacrylic acid and maleic anhydride, having been completely neutralized to form its sodium salt. . This detergency builder is commercially available 2q under the trademark Sokalan CP5. This detergency builder is used, even when used in small amounts, to inhibit encrustation, that is, it acts as an anti-encrustation agent.

Since the compositions of this

- M O

are generally very concentrated and therefore can be used in relatively low doses, it is desirable to supplement the detergency builder with an auxiliary detergency builder such as an alkali metal salt of lower polycarboxylic acid having a high capacity for fixing calcium and magnesium in order to inhibit incrustation which, otherwise, could result from the formation of insoluble salts of calcium and magnesium. Alkali metal salts of suitable polycarboxylic acids are the alkali metal salts of citric acid and tartaric acid, for example monosodium citrate (anhydrous), trisodium citrate, an acid salt 5 glutaric, a gluconic acid salt and a longer chain diacid salt.

Examples of sequestering alkaline organic detergency builder salts which can be used in admixture with other organic and mineral detergency builders are alkali metal, ammonium and substituted ammonium aminopolycarboxylates, for example ethylene diaminetetraacetate (EDTA ) of sodium and potassium, the sodium and potassium nitriloacetates (NTA) and the triethanolamine N- (2-hydroxyethyl) nitrilodiacetates. Mixtures of these aminopoly-carboxylates are also suitable.

Other suitable organic type detergency builders include carboxymethyl-2Q succinates, tartronates and glycolates.

Adjuvant Mineral Detergency Adjuvants The detergent compositions of the invention may also contain adjuvant mineral detergency salts soluble in water and / or insoluble in water. Inorganic alkaline detergency builder salts which can be used are alkali metal carbonates, borates, bicarbonates and silicates (ammonium and substituted ammonium salts can also be used). Particular examples of these 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

M V

26 by adjusting or regulating the pH and making the composition anticorrosive with respect to the parts of the washing machine. Sodium silicates, the Na20 / Si02 ratios of which range from 1.6 / 1 to 1 / 3.2, in particular approximately 1/2 to 1 / 2.8, are preferred. Potassium silicates ‘with the same ratios can also be used. The preferred alkali metal silicate is sodium disilicate.

Although the detergent composition may be free of phosphate or polyphosphate or substantially free of polyphosphate, small amounts of conventional detergency builder salts of the polyphosphate type may be added where local law permits. Particular examples of these detergency builder salts are sodium tripolyphosphate (TPP), sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate and sodium hexametaphosphate. The preferred polyphosphate is sodium tripolyphosphate (TPP). In formulations where a polyphosphate is added, this is added in a proportion of 0 to 50%, for example from 0 to 30% or from 5 to 15%. However, as previously mentioned, the formulations may be free or substantially free of polyphosphate.

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

It is also possible to use crystalline and amorphous aluminosilicates insoluble 35 V * * 27 in water of the zeolite type. The zeolites correspond to the general formula: (m20) x. (Ai2o3) y. (Sio2) z.wH2o in which x is 1, y ranges from 0.8 to 1.2 and is preferably 1, z ranges from 1.5 to 3.5 or more and preferably 2 to 3, w is 0 to 9 and preferably 2.5 to 6, and M is preferably sodium. A typical zeolite is a zeolite of type A or of similar structure, type 4A being particularly preferred. Preferred aluminosilicates have calcium ion exchange capacities of about 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. 1,550,168, the U.S. Patent. Ne 4,409,136 and Canadian Patent Nos. 1,072,835 and 1,087,477. An example of the 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 auxiliaries in the compositions of the present invention. Bentonite is 2 g particularly useful. This material consists mainly of montmorillonite which is a hydrated aluminum silicate of which about one sixth 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 purest form (that is to say free of any sand, abrasive particles, etc.) suitable for / detergents, contains at least 50% of montmorillonite and therefore its exchange capacity of cations is 3o 28 * * * of at least about 50 to 75 meq per 100 g of bentonite. Particularly preferred bentonites are bentonites from the western U.S.A. or from Wyoming which have been sold under the designations 5 Thixo-jels 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften textiles as described in British patents Nos. 401,413 and 461,221.

Viscosity Control and Anticelification Agents The preservative properties of the detergent composition during storage can be significantly improved by incorporating into the composition an effective amount of low molecular weight amphiphilic compounds which act as regulating agents viscosity and inhibiting gelation towards the nonionic surfactant. The amphiphilic compounds can be considered analogous by their chemical structure to liquid nonionic surfactants of the ethoxylated fatty alcohol type and / or propoxylated 2Q, but they> have relatively short hydrocarbon chains (C2 to CQ) and a relatively 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: R0 (CH2CH20) nH

wherein R is a C2-C8 alkyl group and n is a number from about 1 to 6 in average value.

In particular, these compounds are lower monoalkyl ethers (C2 to C5) of lower alkylene glycol (C2 to C3).

More particularly, these compounds are ethers of lower monoalkyl (Cj to C5) of mono-, di- or trialkylene-lower glycol (C2 to C3).

35 29.

. · *

Particular examples of suitable amphiphilic compounds include the following: ethylene glycol monoethyl ether (C2H5-0- ch2ch2oh), diethylene glycol monobutyl ether (C4Hg-0- <ch2ch2o) 2h), tetraethylene glycol monobutyl ether (C4H7 -0- (CH2CH20) 4H) f and dipropylene glycol monomethyl ether (CH3-0-10 (CH2CHO) 2H).

ch3 Monobutyl ether of diethylene glycol is very particularly preferred.

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

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 or less.

Stabilizers

In one embodiment of the present invention, the physical stability of the suspension of the detergency builder (s) and any other suspended additives, such as a bleach, etc., in the liquid vehicle is improved by the presence of a stabilizing agent which is an alkanolic ester of phosphoric acid or an aluminum salt of a higher fatty acid.

35 * * * 4 30

Improvements in stability can be made in some formulations by incorporating a small effective amount of an acidic organic phosphorus compound bearing an acid group -ΡΟΗ, for example a partial ester of phosphorous acid and a alkanol.

As described in the patent application of the Applicant FR-85.05319 filed on April 9, 1985, the acidic organic compound of phosphorus carrying an acid group -POH can increase the stability of the suspension of detergency builders in the liquid nonionic surfactant not aqueous.

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

A particular example is a partial ester of phosphoric acid and a C16 to C18 alkanol (Empiphos 5632 from Marchon); this product consists of approximately 35% monoester and 65% diester.

The incorporation of very small amounts of acidic organic phosphorus compounds makes the suspension significantly more stable against sedimentation at rest while leaving it suitable for pouring, however at low concentrations of stabilizing agent, for example less than about 1%, its plastic viscosity generally decreases.

Other improvements can be made to the stability and anti-sedimentation properties of the composition by adding to it a small effective amount of an aluminum salt of a higher fatty acid.

»+ 31

Stabilizers of the aluminum salt type are the subject of the patent application assigned to the Applicant FR-86.02815 filed on February 28, 1986.

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

Examples of the fatty acids from which the stabilizing aluminum salts can be prepared include decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicosanoic acid, tallow fatty acid, coconut fatty acid, mixtures of these acids, etc. The aluminum salts of these acids are generally commercially available, and are preferably used in the form containing three acid residues, for example aluminum stearate in the form of aluminum tristearate Al (C17H35COO ) 3. It is also possible to use the salts with a single acid residue, for example aluminum monostearate Al (OH) 2 (C17H35COO), and the salts with two acid residues, for example aluminum distearate Al ( OH) (C17H35COO) 2 / and mixtures of two or three of these aluminum salts with one, two or three acid residues. It is however preferred at best that the aluminum salt with three acid residues constitutes at least 30%, preferably at least 50%, and better still 35.

»« '32 still at least 80%, of the total amount of aluminum fatty acid salt.

The aluminum salts, mentioned above, are commercially available and can be produced easily, for example by saponifying a fatty acid, such as animal fat, stearic acid, etc., then treating the resulting soap with alum, alumina, etc.

Although we do not wish to be bound by any particular theory as to how the aluminum salt acts to prevent sedimentation of suspended particles, it is believed that the aluminum salt increases the ability of solid surfaces to be wetted with the nonionic surfactant. This increase in wettability therefore allows suspended particles to remain more easily in suspension.

Only very small amounts of the aluminum salt stabilizing agent are required to achieve significant improvements in physical stability.

In addition to its action as a physical stabilizing agent, the aluminum salt has the additional advantages, compared to other physical stabilizing agents, of being of nonionic character and of being compatible with the nonionic surfactant, and not to intervene in the overall detergent action of the composition? it exhibits a certain anti-foam effect; it can act to enhance the activity of tissue sleepers; and it gives the suspensions a longer relaxation time.

Whitening Acrents

Bleaching agents may be broadly classified, for convenience, as chlorine bleaching agents and oxygen bleaching agents. Chlorine bleaches are typically represented by sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% active chlorine) and trichloroisocyanuric acid (95% active chlorine). 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 perphosphates, and potassium monopersulfate. Perborates, especially sodium perborate monohydrate, are particularly preferred.

The peroxygen compound is preferably used in admixture with an activator for this compound. Suitable activators which can lower the effective action temperature of the peroxidized bleach are described, for example, in the U.S. Patent. No. 4,264,466, or in column 120 of the U.S. Patent. No. 4,430,244. Polyacylated compounds are preferred activators; among these, compounds such as tetraacetyl ethylenediamine (TAED) and pentaacetylglucose are particularly preferred.

Other useful activators include, for example, acetylsalicylic acid derivatives, ethylidene benzoate acetate and its salts, ethylidene acetate carboxylate and its salts, an alkyl- or alkenyl succinic anhydride, tetra-30 acetylglycourile (TAGU), and derivatives of these activators. Other useful classes of activators are described, for example, in U.S. patents. Nos. 4,111,826, 4,422,950 and 3,661,789.

The bleach activator usually interacts with the peroxygen compound · · * * 34 to form a bleaching peroxyacid in the wash water. It is preferable to incorporate a sequestering agent of high complexing power 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 nitrilotriacetic acid (NTA), ethylenediamine-10 tetraacetic acid (EDTA), diethylenetriamine-pentaacetic acid (DEPTA), diethylenetriaminepen-tamethylenephosphonic acid (DTPMP) sold under the brand name Dequest 2066, and ethylene diaminetetramethylene phosphonic acid (EDITEMPA). The sequestering agents can be used alone or in admixture.

In order to avoid loss of the bleaching peroxide, for example sodium perborate, as a result of an enzymatic decomposition, for example under the effect of Tine 'catalase type enzyme, the compositions may additionally contain a compound enzyme inhibitor, i.e. a compound capable of inhibiting the enzymatic decomposition of bleaching peroxide. Suitable inhibitors are described 2g in the U.S. Patent. No. 3,606,990.

As particularly interesting inhibiting compounds, mention may be made of hydro-xylamine sulfate and other water-soluble salts of hydroxy-amine. In the preferred nonaqueous compositions of the present invention, suitable proportions of inhibitory hydroxylamine salts can be as low as about 0.01-0.4%. In general, however, suitable proportions of enzyme inhibitors are up to about 15%, for example 0.1-10%, based on the weight of the composition.

'i t »ï 35. * ·

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, it is possible to include in the formulation minor amounts of anti-redeposition or suspending agents for soiling, for example a polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, XO hydroxypropyl methyl cellulose. A preferred anti-redeposition agent is a sodium carboxy-methyl cellulose having a CM / CMC ratio of 2: i, which is sold under the trade name Relatin DM 4050.

Optical brighteners for cotton, polyamide and polyester fabrics can be used. Suitable optical brighteners include compositions of stilbene, triazole and benzidine sulfones, including sulfonated substituted triazinyl-stilbene, naphthotriazole-sulfonated stilbene, benzidine sulfone, etc., the most preferred being combinations of stilbene and triazole . Preferred brighteners are Stilbene Brightener N4 which is a dimorpholino-dianilino-stilbene sulfonate and

Tinopal ATÇ-X which is well known in art.

Enzymes may be used, 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 predease suspension, an esperase suspension and an amylase. A preferred enzyme is Esperse SL8 which is a protease. Antifoaming agents, for example silicone compounds such as Silicane L 7604, can also be added in small effective amounts.

i V

î 36 • * *

It is also possible to use bactericides, for example tetrachlorosalicylanilide and hexachlorophen, fungicides, dyes, pigments (dispersible in water), preservatives, ultraviolet absorbers, anti-rejuvenation agents such as sodium carboxymethyl cellulose, pH modifiers and pH buffers, color preservatives, fragrance and coloring and brightening agents such as ultramarine blue.

The composition can also contain an insoluble mineral thickening or dispersing agent of very large specific surface, such as a finely divided silica of extremely small particle size (for example of 5-100 nm in diameter as sold under the brand Aerosil) or the other very bulky support materials which are described in the US patent Ne 3 630 929, in proportions of 0.1-10%, for example from 1 to 5%. It is preferable, however, that the compositions which form peroxyacids in the washing bath (eg, the compositions which contain a peroxygen compound and an activator for that compound) are substantially free from such compounds and other silicates? for example, it has 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 less than 100 microns, preferably less than 40 microns and more preferably less than 10 microns. The 1 · · '37 solid detergency builders, for example polyphosphates of alkali metals, are generally supplied in particle sizes of about 100, 200 or 400 micrometers. The liquid non-ionic active surfing phase can be mixed with the solid detergency builders before or after performing the grinding operation.

In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid ingredients is subjected to the action of an attrition type mill 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 10 micrometers or even less (for example 1 micrometer). 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 of which the dispersed particles have such small dimensions have better stability against separation or sedimentation during storage. The addition of the acid-terminated nonionic surfactant improves the dispersibility of the dispersions 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%) for the solid particles to come into 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 38% can be added to the milled composition. Grinders which employ grinding balls (ball mills) or similar movable grinding elements have given very good results. Thus, one can use a laboratory mill-attritor working in portions containing grinding balls in steatite of 8 mm in diameter. For a larger scale operation, a mill operating in continuous mode can be used in which there are grinding balls of 1 mm or 1.5 mm in diameter working in a very small interval 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 do not perform such a fine grinding (for example a colloid mill) in order to reduce the particle size 2Q to less than 100 micrometers (for example to about 40 micrometers) before the grinding stage to an average particle diameter. less than about 10 micrometers which takes place in the ball mill operating in continuous mode "

"S JP S

2g 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 as follows: 3Q Liquid nonionic surfactant ^ highly biodegradable detergent of the propoxylated-ethoxylated fatty alkyl alcohol type: in the range of about 10 to 60, for example 20 to 50 or 30 to 40, percent.

Acid-terminated nonionic surfactant: may be omitted, but is preferably added to the composition in a proportion in the range of about 0 to 30, for example 5 to 25 or 5 to 15, percent.

adjuvant organic detergency salt: in the range of about 0 to 50, for example 10 to 40 or 25 to 35, percent.

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

Anti-scaling agent of the alkali metal salt type of polyacrylic acid and polymaleic anhydride copolymer: in the range of about 0 to 10, for example 2 to 8 or 2 to 6, percent.

Antifreezing agent of the alkylene glycol monoalkyl ether type: in the range of about 0 to 20, for example 5 to 15 or 8 to 12, percent.

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

Aluminum salt type fatty acid stabilizer: in the range of about 0 to 3.0, e.g. 0.1 to 2.0 or 0.5 to 1.5, percent.

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

Bleach: in the range of about 0 to 35, for example 5 to 30 or 8 to 15, percent.

Bleach activator: in the range of about 0 to 25, for example 3 to 20 or 4 to 8, percent.

Bleach sequestering agent: in the range of about 0 to 3.0, preferably 3g 0.5 to 2.0 or 0.5 to 1.5, percent.

t 40 »► ·

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

Optical aviator: in the range of about 0 to 5 2.0, for example 0.1 to 1.5 or 0.3 to 1.0, percent.

Enzymes: in the range of about 0 to 3.0, for example 0.5 to 2.0 or 0.5 to 1.5, percent.

Perfume: in the range of about 0 to 2.0, for example 0.10 to 1.0 or 0.5 to 1.0, percent.

10 Dye: in the range of about 0 to 1.0, for example 0.0025 to 0.050 or 0.25 to 0.0100, percent.

Various additives among those previously mentioned can be optionally added to achieve the desired function of these added materials.

Mixtures of the acid-terminated nonionic surfactant and alkylene glycol alkyl ether type antifreezing agents may be used and in some cases advantages may be derived from the use of such mixtures, either alone or by adding to the mixture a stabilizing and anti-sedimentation agent, for example an alkanolic residue of phosphoric acid.

With regard to the content of the additives, these must be chosen to be compatible with the main components 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 non-aqueous non-ionic liquid detergent composition of the present invention is easy to dispense in the water of the washing machine. 25 Household washing machines currently -.- fr l. 41 # * 'used consume 175 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.

COMPARATIVE TESTS

In order to compare the physical properties of the nonionic surfactants of the propoxylated-ethoxylated fatty alcohol type of the present invention with the conventional nonionic surfactants available commercially, the comparative tests described below are carried out.

1. A nonionic surfactant of formula R- (OC3H6) x (OC2H4) yOH where R is a C12-15 alkyl group C15 'x equals 3 and y equals 5, is compared to Product D

with regard to the biodegradability of the respective surfactants. As described above, Product D is an equal mixture of Product B (a C13-C ^ 5 fatty alcohol condensed with 7 moles of propylene oxide and 4 'moles of ethylene oxide) and Product C (a C13-C15 fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide).

In Product B, the propylene oxide molecules are not attached to the alkyl portion of the structure of the surfactant.

In Product C, the propylene oxide molecules are not attached to the alkyl portion of the surfactant structure.

3q Have conducted comparative biodegradability tests using the OECD selection method. Tests show that the active surf of the present invention is degradable to at least 90 percent and that Product D is biodegradable to less than 40 percent. The characteristics of 3 - 42 "* 'biodegradability of the surfactant of the present invention are therefore superior to those of Product D.

2. The nonionic surfactants of the present invention exhibit characteristics of low foaming in use. In order to demonstrate these characteristics of low foaming, the nonionic surfactant of the present invention used in comparative test 1 above is compared with the nonionic surfactant Surfactant T 7/9 conventionally used. The surfactant Surfactant T 7/9 which is used is obtained by ethoxylating a C13 secondary fatty alcohol by an average of 7 to 9 ethylene oxide groups per molecule of fatty alcohol. Conventional foam determination tests are carried out.

The results of the tests show that the nonionic surfactant of the present invention is not very foaming compared to the nonionic surfactant 20 Surfactant T 7/9 '' conventionally used.

3. The nonionic surfactant of the present invention used in Comparative Test 1 above is compared to Surfactant T 7/9 to determine the drip characteristics of each surfactant. The drop point is determined in each case by slowly raising the temperature at a rate of 2 ° C / minute. The drop point or flow temperature is the temperature at which the nonionic surfactant begins to flow. ?

The results of the comparative tests show that the surfactant of the present invention has a flow temperature of -2 ° C., lower than that of Surfactant T 7/9, the flow temperature of which is + 3 ° C.

4. In order to determine the gelation characteristics of the nonionic surfactant of the present invention from comparative test 1 above, it is compared to Product D and to Surfactant T 7/9. The test is carried out by bringing each of the surfactants into contact with water at 5 ° C. and determining the viscosity-concentration relationship.

Comparative tests show that the nonionic surfactant of the present invention does not gel on contact with water at 5 ° C. (although an increase in the viscosity of the surfactant is noted), while Product D and Surfactant T 7/9 gel through contact with water at 5oC.

In a preferred embodiment of the invention, a typical composition is prepared using the ingredients indicated below:% by weight

Non-ionic surfactant highly biodegradable detergent such as 2q fatty alcohol propoxylated-ethoxylated 30-40

Acid-terminated nonionic surfactant 5-15

Sodium tripolyphosphate, adjuvant detergent salt 25-35

Anti-scaling agent (Soka ^ àn CP-5) 0-10 25 Organic detergency builder salt 0-30

Alkylene glycol monoalkyl ether 8-12

Alkanolic phosphoric acid ester (Ernpiphos 5632) 0.1-0.5

Anti-redeposition agent (Relatin DM 4050) 0-3.0 2Φ Alkali metal perborate, bleach 8-15

Whitening Agent Activator (TAED) 4-8

Sequestering Agent (Dequest 2066) 0-3.0

Optical aviator (ATS-X) 0.3-1.0 35 Enzymes 0.5-1.5 ”'' '44.

Perfume 0.5-1.0 The following nonlimiting example further illustrates the present invention.

EXAMPLE 1 A concentrated non-aqueous detergent composition based on non-ionic surfactant is prepared using the following ingredients in the specified proportions.

% by weight 10 Highly biodegradable nonionic surfactant of formula ^ (003 ^) 3 ^ (002¾) ^^ 1) 38.7

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

Sodium tripolyphosphate 26.0 15 Diethylene glycol monobutyl ether 6.0

Alkanolic phosphoric acid ester (Empiphos 5632) 0.3

Anti-scaling agent (Sokalan CP-5) 4.0

Sodium perborate monohydrate, bleaching agent 12.0 Tetraacetylethylenediamine (TAED), bleaching agent activator * ‘4.0

Sequestering Agent (Dequest 2066) 1.0

Opaque aviator (Tinopal ATS- ^ f) 0.5 25 Anti-redeposition agent (Relatin DM 4050) 1.0

Protease (Esperase SL8) 1.0

Perfume 0.5 100.0 (1) R = C1-C15 alkyl, x = 3 and y = 5 3Q The composition is ground for approximately 1 hour to reduce the particle size of the detergency builder salts in suspension to less than 40 micrometers . The nonionic surfactant of the composition is found to be 90 percent biodegradable. It is found that the detergent composition * t ’". 45 prepared is stable and non-gelling during storage and has a strong detergent power and is not foaming when used.

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

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 mixing and can be completed after mixing, or else the grinding operation can be carried out entirely after mixing with the active liquid surfactant. Compositions containing adjuvant detergency salts and solid suspended particles smaller than 100 microns in size are preferred.

The highly biodegradable detergent nonionic surfactants of the propoxylated-ethoxylated alcoholygras type of the present invention can be used to prepare detergent compositions having a high, low or no content of detergency builder of the polyphosphate type, and they can be used as non-surfactant single ionic or as main nonionic surfactants in strong aqueous detergent compositions with or without detergency builders.

♦ 35 - t?

Claims (20)

1. Compound characterized in that it corresponds to the formula: R- (OC3H6) x (OC2H4) yOH in which R represents an aliphatic group in Cg to c2gi the sum x + y is equal to 20 to 100 percent of the number carbon atoms of group R, and x is greater than or equal to 1 and y is greater than or equal to l. 2. Compound according to claim 1, characterized in that R represents a C9 to C18 alkyl group, and x is greater than or equal to 2 and y is greater than or equal to 2. 3. Compound according to claim 1, characterized in that R represents a C9 to C11 # alkyl group and x is greater than or equal to 3 and y is greater than or equal to 3. 4. Compound according to claim 1, characterized in that R represents a C12 to C15 alkyl group, and x is greater than or equal to 3 and y is greater than or equal to 3. 5. detergent composition for heavy laundry work, characterized in that it comprises a highly biodegradable nonionic surfactant corresponding to the formula: R (° C3Hg) χ (° c2h4) y ° H in which R represents an aliphatic group in Cg to C26, and x is a number from 2 to 15 and y is a number from 2 to 15. 6. Detergent composition according to claim 5, characterized in that it comprises at least one detergency builder salt chosen from organic detergency builder salts and mineral detergency builder salts. »47 Λ> * * - 7. Detergent composition according to claim 5, characterized in that it comprises at least one element chosen from an antifreeze agent of the nonionic surfactant type with acid termination, a monoalkyl ether of alkylene glycol and a stabilizing agent of the alkanol ester type of Phosphoric acid. 8. Detergent composition according to claim 5, characterized in that it comprises one or more detergent additives chosen from a bleaching agent, a bleaching agent activator, an optical brightener, enzymes and a perfume. 9. A detergent composition according to claim 5, characterized in that R represents a Cg to C18 alkyl group, x is equal to or greater than 2, y is equal to or greater than 2 and x + y = 4 to 16. 10. A detergent composition according to claim 5, characterized in that R represents a Cg to C11 alkyl group # x is equal to or greater than 2, y is equal to or greater than 2 and x + y = 5 to 10. 11. Detergent composition according to claim 5, characterized in that R represents a C12 to C15 alkyl group, x is equal to or greater than 2, y is equal to or greater than 2 and x + y = 5 to 15. 12. Detergent composition according to claim 5, characterized in that it comprises approximately 20 to 50 percent of a nonionic surfactant of formula: R (OC3H6) x (° ^ 2H4) y0H in which R represents an alkyl group in Cg to C18, x is a number from 2 to 8 and y is a number from 2 to 8, about 10 to 40 percent of a detergency builder salt, about 5 to 25 percent of a surfactant at * 48 * 2 acid termination, about 5 to 15 percent of a monoalkyl ether of alkylene glycol, and about 0.1 to 1.0 percent of an alkanolic ester of phosphoric acid. 13. Detergent composition according to claim 12, characterized in that it comprises approximately 5 to 30 percent of a bleaching agent of the alkali metal perborate type, approximately 3 to 20 percent of tetraacetylethylenediamine as activator of bleaching agent , and optionally one or more detergent additives selected from an anti-encrustation agent, an anti-redeposition agent, a sequestering agent for the bleaching agent, optical brighteners, enzymes and a perfume. 14. A detergent composition according to claim 12, characterized in that it is non-aqueous, in that the surfactant is liquid and in that the detergency builder salt comprises sodium tripolyphosphate. 15. Detergent composition according to claim 5, characterized in that it is non-aqueous and in that it comprises 20 to 50 percent of a highly biodegradable nonionic liquid surfactant of formula: R- (OC3H6) x (OC2H4 ) yOH in which R represents a C9 to C18 alkyl group, the sum x + y is 4 to 16, x is 2 or more and y is 2 or more, about 5 to 25 percent of an acid-terminated surfactant, about 10 to 40 percent sodium tripolyphosphate as a builder salt, about 5 to 15 percent alkylene glycol monoalkyl ether, about 0.1 to 1 percent alkanol ester phosphoric acid, about 8 to 15 percent sodium perborate monohydrate as a bleach, and 49 to 4 to 8 percent tetraacetylethylenediamine as a bleach activator. 16. A detergent composition according to claim 15, characterized in that it can be poured at low and high temperatures, is stable during storage and does not form a gel when mixed with cold water. 17. A detergent composition according to claim 5, characterized in that the nonionic surfactant is biodegradable to at least 80 percent. 18. A method for cleaning soiled fabrics, characterized in that it consists in bringing the soiled fabrics in contact with the detergent composition of claim 5. 19. Method according to claim 18, characterized in that it consists in bringing the soiled fabrics into contact with the detergent composition of claim 12. 20. Method according to claim 18, characterized in that it consists in bringing the soiled fabrics into contact with the detergent composition of claim 15.