LU86992A1 - NON-IONIC AND NON-AQUEOUS LIQUID DETERGENT COMPOSITIONS CONTAINING PERSON AS A WHITENING AGENT AND METHODS OF USE THEREOF FOR CLEANING DIRTY TISSUES - Google Patents

Description

f l 0 i ’L Q Γ û 0Π 9 GRAND-DUCHY OF LUXEMBOURG 52,690

Patent No. ii ü U J.

dicvclin yj Mr. Minister | * of . 5 ....... September 1987 of the Economy and the Middle Classes _, Department of Intellectual Property

Ί ^ issued -.............................- I gp LUXEMBOURG

Patent Application ..........-................................. .........; - (1) I. Request

Xa society-jditer.XOLGATE ^ ÂLMOLI ^ E COMEMY-r- ^ tXO-îiark-Avenue, (2) NEW YORK..N * X. — 10022 r._Eta ts-Un is of America r-represented by—. .Mr. Jacques-de-Muyser-r-agant. En qiaLité -de-roandataire ________________________________ ___________________ (3) deposit (s) this new-september. 1900-quatre = twenty-sept -; - (4) at 3 p.m., at the Ministry of the Economy and the Middle Classes, in Luxembourg: 1. this request for obtaining a patent for invention concerning: - There are aqueous detergents and non-ionic and non-ionic (5) liquids containing a persalt as a bleach agent and their processes. _d * use-for- -cleaning— of —fabrics-— salis. "_____________________________ 2. the description in language ... French _____ of the invention in triplicate; 3 ............ / _ / ---------------------------- _____________ drawing boards, in triplicate; 4. receipt of the fees paid to the Office of the 'Registration in Luxembourg, 9 September, 1987 ï 5. the delegation of power, dated_NoW — York ______________ 29.—.' J ui llet —19S7 ----; 6. the successor document (authorization ); declares (s) assuming responsibility for this declaration, that the inventor (s) is (are): (6) ..... 1 ........ Guy ..... BrQZE, ....... 3 2., .- rue-Claskin, -X = .433Q_jGRACE = HOLLOGNE, - Belgium ..... 2 ........ Danielle ..... BASTIN, 14 rue rte .1 a -H ^ youlle-B ^ 4- & 22-SQUMAGNEf ............

Belgium __________________________________________________: ._______________ claims (s) for the above patent application the priority of one (s) application (s) of (7) .................... .-................................- patent -------------- ----- filed (s) in (8) in the United States of America on (9) ......... 9 ....... September ...... 19 .. 8..6 _______________________________________________________ under No. (10). 905 * 210 _________________________________________________________________________________________________________________________ on behalf of (he) s ....... inventors .___________________________________________________________________ elect (elect) domicile for him (her) and, if designated, for his proxy, in Luxembourg ___________ ........ ..3.5, ....... boulevard ..... Royal ................................ ................................ (12) seeks (s) the grant of a patent for the invention for the 'object described and represented in the abovementioned appendices, with postponement of this delivery to ____________ & __________________ months. (13) The exhibitor / agent: ______________________________________________________________________ (14) / Π. Deposit Minutes

The above patent application has been filed with the Ministry of Economy and Middle Classes, Servicè'dfijla Intellectual Property in Luxembourg, dated: September 9, 1987 - · 'f, .v-t-fit. V c / - ¾ \ f *> ft gf *. X, v Pr. The Minister of Economy and the Middle Classes, at _____________________ hours ;: £ / p. d.

i \ \ "Éj / jf The head of the intellectual property department, v> - Γ \. A68007_? g’f (_ L · 11 l) EXPLANATIONS RELATING TO FORMUÏÂIR & BEOÎPÔT.

* -US (1) if applicable "Application for certificate of addition to the main patent, to the main patent application No ........... of ........ .... (2) enter the last name, first name, profession.

address of the applicant, when the latter is an individual or your corporate name, legal form, address of the head office, when the applicant is a legal person- (3) enter / Λ - ^ f the surname, first name, address of the authorized representative , eD industrial property council, with special powers, if applicable: "represented by .......... acting as agent ** *., *., '., 52.690 CLAIM OF PRIORITY ✓ of patent application /

In the United States of America '

Of September 9, 1986 (No. 905.210) Brief Description filed in support of a request for

PATENT

at

Luxembourg on behalf of: colgate-palmolive company NEW YORK, NY 10022 (United States of America) for: "Non-ionic and non-aqueous liquid detergent compositions containing parsley as a bleaching agent and methods of using them for cleaning soiled fabrics. " 'tv · j î.

1 1, '1

NON-IONIC AND NON-AQUEOUS LIQUID DETERGENT COMPOSITIONS CONTAINING PERSON AS A WHITENING AGENT AND METHODS OF USING SAME FOR CLEANING

SALIS FABRICS

"

The present invention relates to non-aqueous liquid compositions for the treatment of fabrics. The invention relates more particularly to non-ionic liquid detergent compositions for washing clothes, which contain, as a bleaching agent, a mineral persalt and, as activator bleaching agent, calcium cyanamide, i.e. calcium cyanamide. The compositions are stable against phase separation and gelation and are capable of being easily poured. The compositions are used for cleaning soiled fabrics.

Non-aqueous liquid detergent compositions for heavy laundry use are well known in the art. For example, compositions of this type can comprise a liquid nonionic surfactant in which particles of a detergency builder are dispersed, as disclosed, for example, in United States patents No. 4,416,812, 3,630,929 and 4,264,466 and British patents Nos. 1,205,711, 1,270,040 and 1,600,981.

Related French patent applications of the Applicant are as follows: Λ -., - '*' i * 2 86 044 68 filed March 27, 1986, describes a non-ionic liquid detergent composition for washing clothes, containing a perborate as bleach, bleach activator and hydroxylamine sulfate as a bleach stabilizer and, in particular as a catalase inhibitor, 85 048 31 filed March 29, 1985, discloses a non-aqueous liquid detergent composition based on a non-ionic surfactant, comprising a suspension of a detergency builder salt and containing an acid-terminated nonionic surfactant (for example the reaction product of a nonionic surfactant and succinic anhydride) to improve the dispersibility of 15 the composition in an automatic washing machine.

85 19 510 deposited on December 31, 1985, describes a non-aqueous liquid detergent composition based on nonionic surfactant, comprising a suspension of a detergency builder salt and containing a monoalkyl ether of alkylene glycol as viscosity control agent and anti-gelation, in order to improve the dispersibility of the composition in an automatic washing machine.

85 05 319 deposited on April 9, 1985, describes a nonaqueous liquid detergent composition based on nonionic surfactant, comprising a suspension of a detergency builder salt of polyphosphate type and containing an alkanolic ester of phosphoric acid to improve the stability suspension at en-30 against sedimentation during storage.

These applications relate to non-aqueous non-ionic liquid detergent compositions for washing clothes.

Liquid detergents are often considered to be more convenient to use than 3: 3Τ dry products! .

j ί * Ί.

in powder or particles and consumers have therefore given them great preference. They are easy to dose, dissolve quickly in washing water and can be easily applied in concentrated solutions or dispersions on areas of the garment to be washed, and they do not generate dust and usually occupy less than place for 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 use in the manufacture of particulate detergent products. Although they enjoy 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 products separate on storage and others separate on 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. 25 Some clear products cloud and others gel on standing.

The applicant has studied the behavior of nonionic liquid surfactant systems containing suspended particulate matter. Particular attention was 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 over-board laundry washing additives, as well as 'to the problem of gelation which t 4 ·> * * is associated with nonionic surfactants. These considerations have an impact, for example, on the stability and dispersibility of products and their suitability for pouring.

5 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 arises from the fact that the density of the solid particles dispersed in the nonionic liquid surfactant is greater than the density of the liquid surfactant.

As a result, the dispersed particles tend to settle. 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 silica finely split, clays, etc., organic thickeners such as cellulose ethers, acrylic polymers and acrylamide polymers, polyelectrolytes, etc. However, such an increase in the viscosity of the suspensions is naturally limited by the need for the liquid suspension to be 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.

The 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 5% t 4; particles by the nonaqueous vehicle (nonionic liquid surfactant) is proportionally improved.

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

The flow limit is defined as the minimum stress necessary to induce plastic deformation (flow) of the suspension. Thus, in representing the suspension as a loose bucket 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 shear stress is sufficiently greater than the flow limit, the particles are partially deflocculated by shear and the apparent viscosity decreases. Finally, if the shear stress is much higher 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. Therefore, 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 sedimentation of the product.

35 In addition to the problems posed by imentation 6 4 / ί sedimentation or phase separation, non-aqueous liquid detergents for laundry based on liquid non-ionic surfactants have the disadvantage that non-ionic surfactants tend to gel during that they are 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 10 in a dispensing device (for example a dispensing drawer). of the machine. During the operation of the machine, the detergent contained in the dispenser is subjected to a stream of cold water 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 increases sharply and that it forms a gel. As a result, 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 repeated washing cycles, which ultimately forces the user sweep the dispenser with hot water.

The phenomenon of gelation 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 water warm or hot.

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 months of storage. winter in unheated transport vehicles.

Partial solutions to the problem of gelation of aqueous compositions substantially free of detergency builders have been proposed, and consist for example of a dilution of the liquid nonionic surfactant with certain viscosity-regulating solvents and certain gelation-inhibiting agents, such as lower alkanols, for example ethyl alcohol (see US Patent No. 3,953,380), alkali metal formates and adipates (see United States Patent No. 4,368,147), hexylene glycol, polyethylene glycol, etc., and modification and optimization of the structure of the nonionic surfactant. As an example of modification of the nonionic surfactant, a particularly happy result was obtained by acidifying the terminal group of the hydroxylated fragment of the nonionic molecule. The advantages of intro-duction of a carboxylic acid at the end of the nonionic molecule include the inhibition of freezing at dilution, the lowering of the drop point of the nonionic surfactant and the formation of 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 has only a limited tendency to gel.

It is desirable to improve the bleaching properties and the stability and inhibition of gelation of non-aqueous liquid laundry treatment compositions containing a bleaching agent and a bleaching agent activator.

According to the present invention, a non-aqueous, stable and highly concentrated liquid detergent composition 5 is prepared for washing clothes, containing a parsley · as a bleaching agent and calcium cyanamide calcium cyanamide as a bleaching agent activator. . A preferred parsley as a bleaching agent is sodium perborate mono-10 hydrate.

Calcium cyanamide, which is the bleach activator, is used to replace commonly used organic bleach activators such as tetraacethyl ethylene diamine (TAED), which release an acid detrimental to detergent action.

Calcium cyanamide acts as an activator against bleaching parsley, it increases the alkalinity of the aqueous washing liquor and it improves detergency.

The system consisting of bleaching persalt and calcium cyanamide (bleach activator) of the present invention can be used in compositions containing low phosphate phosphate detergency builder salts.

In order to improve the viscosity characteristics of the composition, an acid-terminated nonionic surfactant can be added. To further improve the viscosity characteristics of the composition and 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 glycol and an anti-aging agent. sedimentation such as an alkanolic ester of phosphoric acid. In a preferred embodiment of the invention, the detergent composition contains sodium perborate monohydrate as a bleach, calcium cyanamide as a bleach activator, an acid-terminated nonionic surfactant, a alkylene glycol monoalkyl ether and an alkanolic ester of phosphoric acid as anti-gelling stabilizing agent.

The commonly used peroxygen bleaching compounds, for example perborate, percarbonate, perphosphate and sodium persulfate, can be used as a bleaching agent.

In one embodiment of the invention, the detergency builder components of the composition may 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 adjuvant components of detergency in the liquid nonionic surfactant detergent.

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

Therefore, in one of its aspects, the present invention provides a liquid composition for heavy laundry work, consisting of a suspension of a peroxy-30 bleaching compound and a detergency builder salt, for example an adjuvant detergency of the phosphate type, in a liquid nonionic surfactant, the composition containing as activator of bleaching agent an effective amount of calcium cyanamide.

In another aspect, the invention provides a

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10 concentrated liquid detergent composition for heavy laundry work, which has good bleaching properties at low temperature, which is stable, does not settle out during storage and does not gel during storage and employment. The liquid compositions of the present invention are easy to pour, easy to dose and easy to put in the washing machine, and are easily dispersed in water.

In another aspect, the invention provides a method for dispensing a nonionic liquid laundry detergent composition, into 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 liquid non-ionic surfactant, and for dispensing the composition by passing it from the container into an aqueous washing bath, method 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 the wash bath.

The use of calcium cyanamide as a bleach activator in the composition in place of the commonly used organic bleach activators, for example TAED, provides good bleaching properties at low temperatures while increasing the alkalinity of the aqueous washing liquor, and increasing the detergent power of the composition.

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

An object of the present invention is to provide a stable non-aqueous nonionic liquid detergent composition for heavy work, containing a per-salt as a bleaching agent and cal-10 cyanamide as a bleaching agent activator, at least one agent for viscosity adjustment and antifreezing, an anti-sedimentation stabilizing agent and an anionic detergency adjuvant salt of the phosphate type suspended in a nonionic surfactant.

Another object of the invention is to provide liquid tissue treatment compositions which have good detergent properties at low temperature, better detergency and which are suspensions of mineral particles insoluble in a non-aqueous liquid and are stable in storage, easy to pour and disperse in cold, lukewarm or hot water.

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

A particular object of the present invention is to provide non-aqueous nonionic liquid detergent compositions containing a detergency builder for heavy duty laundry applications in the form of stable, non-gelling suspensions which contain persalts as a cleaning agent. bleaching and an effective amount of calcium cyanamide as a bleach activator.

These and other objects of the invention will emerge more clearly from the following detailed description of its preferred embodiments and are generally achieved by preparing a detergent composition comprising a non-aqueous liquid nonionic surfactant, a parsley as a bleaching agent and a calcium cyanamide as a bleaching agent activator, said composition comprising mineral or organic tissue treatment additives, for example viscosity improving agents and one or more antifreeze agents, anti-scaling agents, pH adjusting agents, defoamers, optical brighteners, enzymes, anti-deposition agents, perfume and colorants.

20 Whitening Persels

The non-aqueous liquid nonionic detergent compositions for washing clothes of the present invention contain, as essential ingredients of the composition, a parsley as a bleaching agent and calcium cyanamide as a bleaching agent activator.

Whitening persalts are well known in the art; they are dispersed in the form of solids in the nonionic surfactant and they are easily soluble at the time of the addition of the detergent composition to the aqueous washing bath. Persalts, or oxygenated bleaches, are per-compounds that release hydrogen peroxide in aqueous solution. Preferred examples include perborates, percarbonates, sodium and potassium perphosphates, 11-13 and potassium monopersulfate. Perborates, in particular sodium perborate monohydrate, are particularly preferred.

Hydrogen peroxide and its precursors which release hydrogen peroxide are good oxidizing agents for removing stains from clothing, especially stains from wine, tea, coffee, cocoa, fruit, etc. It has generally been found that hydrogen peroxide and its precursors exert a quick and more effective whitening action at a relatively high temperature, for example from about 80 ° to 100 ° C.

In order to take advantage of the effective low temperature detergents and low temperature washing cycles which are now commonly used for temperature sensitive fabrics, parsley or peroxygen bleach is used in admixture with an activator. bleaching agent.

Organic bleach activators have hitherto been used, such as tetraacethyl ethylene diamine (TAED). The use of such organic bleach activators increases the acidity of the aqueous wash liquor and therefore adversely affects the detergent action of the composition.

Calcium cyanamide is used as an activator for bleaching persalts. The calcium cyanamide reacts in the aqueous washing liquor with the hydrogen peroxide generated by the bleaching persalt, producing a fragment endowed with bleaching activity at low temperature.

The calcium of calcium cyanamide contained in the aqueous washing liquor increases the alkalinity of the washing liquor and improves the detergency of the detergent composition. The addition of cyan

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14 calcium amide as a bleach activator with a detergent composition can lower the effective action temperature of bleaching peroxides to values as low as about 60 ° C.

In detergent compositions for which lower working temperatures are desired, small amounts of commonly used bleach activators such as TAED can be added. In the preferred embodiment of the invention, calcium cyanamide is the only bleach activator, or the major constituent, i.e., it represents more than 50%, of the activator of total bleaching agent used in the detergent composition.

Only small amounts of calcium cyanide amide are required as a bleach activator to activate the peroxygen bleach compound. For example, based on the total weight of the nonionic liquid surfactant composition, suitable proportions of calcium cyanamide are in the range of about 1 to about 15%, preferably about 8%, and better still about 2 to 6%.

The bleach activator usually interacts with HA-25 with the peroxygen compound 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 include the sodium salts of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DEPTA), diethylenetriaminepentamethylene phosphonic acid (DTPMP) sold under the trademark Dequest 2066, and ethylenediaminetetramethy-lenephosphonic acid (EDITEMPA). The sequestering agents can be used alone or as a mixture.

In order to avoid loss of the bleaching perxide, 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 enzyme inhibitor compound, i.e. a compound capable of inhibiting the enzymatic decomposition of bleaching peroxide. Suitable inhibitors are described in the U.S. Patent. No. 3,606,990.

As particularly useful inhibitory compounds, there may be mentioned hydroxylamine sulfate and other water-soluble hydroxylamine salts. In the preferred nonaqueous compositions of the present invention, suitable proportions of inhibitory hydroxylamine salts may 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.

Stabilizers can also be added to the composition, such as, for example, an acidic organic phosphorus compound having an acid group -POH, such as a partial ester of phosphorous acid and an alkanol.

Non-ionic detergent surfactants can be reinforced by detergency builder salts which are entirely of the polyphosphate type or have a low polyphosphate content.

Non-Ionic Surfactant Detergent The non-ionic synthetic organic detergents used in the practice of the invention can be any of a wide variety of known compounds.

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 10 with ethylene oxide (hydrophilic in nature). Almost 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 polyhydration product, polyethylene glycol , to form a non-ionic detergent. The length of the polyoxyethylene hydrophilic chain can be easily adjusted to achieve the desired ratio between the hydrophobic and hydrophilic groups. Typical suitable nonionic surfactants are those described in U.S. patents. N ° A 316 812 and 3 630 929.

Generally, nonionic detergents are lipohilic compounds polyalkoxylated by lower alkoxy groups, in which the desired hydrophilic-lipophilic ratio is obtained by addition of a hydrophilic poly (lower alkoxy) group to a lipophilic moiety. A preferred class of the nonionic detergent used is that of the lower alkanols polyalkoxylated by lower alkoxy groups where the alkanol has from 9 to 18 carbon atoms and where the number of moles of lower alkylene oxide (at 2 or 3 carbon atoms) is 3 to 12. Among these materials, it is preferable to use those in which the higher alkanol is a fatty alcohol higher than 9 to 11 or 35 to 15 carbon atoms and which contain 5 to 8 17 or 5 to 9 lower alkoxy groups per mole. Preferably, the lower alkoxy group is the ethoxy group but, in some cases, it can be advantageously mixed with the propoxy group which, if present, often constitutes only a minor proportion (less than 50¾).

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 10 per molecule, for example Neodol 25-7 and Neodol 23-6.5 which are manufactured products. by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols with an average of about 12 to 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 6.5. Higher alcohols are primary alca-20 nols.

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 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 a component of a nonionic detergent, such as Neodol 45-11, which are similar products of condensation of ethylene oxide with higher fatty alcohols, higher fatty alcohol having 14 to 15 carbon atoms and the number of ethylene oxide groups 18 being approximately 11 per molecule.

These products are also manufactured by Shell Chemical Company.

Other useful nonionic surfactants are represented by the class of commercially known nonionic surfactants which are sold under the trademark Plurafac. Plurafac series surfactants are the reaction products of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples are the products (A) a C - ^ - C ^ fatty alcohol condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide, (B) a C ^ fatty alcohol - C ^ condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide, (C) a fatty alcohol in C ^ g - 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 trade name Dobanol: Dobanol 91-5 is a C 8 -C 8 ethoxylated fatty alcohol with an average of 5 moles. of ethylene oxide and Dobanol 25-7 is a Cyl ^ 2 "fatty alcohol ethoxylated with an average of 7 moles of ethylene oxide, per mole of fatty alcohol.

In preferred alkanols polyalkoxylated with preferred lower alkoxy groups, to obtain the best ratio between 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 this preferred polyalkoxylated higher canol. Higher molecular weight alkanols and various other normally solid detergents and surfactants can 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 regard to both preferred and less preferred nonionic detergents, the alkyl groups present therein are generally linear although a low degree of tree structure can be tolerated, for example at the level of carbon atom contiguous to the terminal carbon atom, or distant from two positions of the terminal carbon atom, of the straight chain and opposite of the ethoxy chain, provided that the length of this branch alkyl 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 non-characteristics. gelation, a median or secondary junction with ethylene oxide may appear in the chain. There is normally only a minor proportion of such alkyl groups, generally less than 20%, but this proportion may be greater, as is the case with the mentioned tert-gitols. In addition, when propylene oxide is present in the lower alkylene oxide chain, it generally constitutes less than 20% and preferably less than 10%.

20

If greater proportions than alkanols whose alkoxylation is not terminal are used than those mentioned above, alkanols polyalkoxylated by lower alkoxy groups containing propylene oxide and nonionic detergent with poorer hydrophilic-lipophilic ratio, and if other non-ionic detergents are used in place of the preferred non-ionic over-fillers listed herein, the resulting product may not have as good detergency properties, 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 polyalkoxy alkanol higher is used, often for its detergency, its proportion can be adjusted or limited according to the results of routine tests to obtain the detergency. desired while the product still remains non-gelling and of desired viscosity. It has moreover been found that it is only rarely necessary to use higher molecular weight nonionic surfactants for their detergent properties since the preferred nonionic surfactants described here are excellent detergents and allow further to achieve the desired viscosity of the liquid detergent product without gelation at low temperatures.

Another useful class of non-ionic surfactants is the series of "Surfactant T" products available from the company British Petroleum. The non-ionic surfactants Surfactant T are obtained by ethoxylation of secondary fatty alcohols in C 4 with a narrow distribution of ethylene oxide contents. Surfactant T5 contains on average 5 moles of oxide ethylene; Surfactant T7 contains an average of 7 moles of ethylene oxide; Surfactant T9 contains an average of 9 moles of ethylene oxide and Surfactant T12 5 contains an average of 12 moles of ethylene oxide per mole of secondary fatty alcohol C13 *

In the compositions of the present invention, the preferred conventional non-ionic surfactants include the secondary fatty alcohols in C · 10 “with relatively narrow contents of ethylene oxide, ranging in the range of about 7 to 9 moles, and the C9 "C11 fatty alcohols ethoxylated with about 5 to 6 moles of ethylene oxide.

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

Acid-terminated Non-Ionic Surfactant The viscosity and gelation properties of liquid detergent compositions can be improved by 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 an ester or partial ester of a non-surfactant ionic and a polycarboxylic acid or anhydride.

As described in patent application FR-85 05 319 filed on April 9, 1985, non-ionic surfactants modified by a free carboxyl group, which can roughly be characterized as polyether-carboxylic acids, act by lowering "ï" 22 la temperature at which the liquid nonionic surfactant gel with water.

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

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

Acid-terminated nonionic surfactants can be prepared as follows:

Acid-terminated product (A): 400 g of non-ionic surfactant (A), which is a C 4 alkanol, have been alkoxylated so as to introduce therein 6 ethylene oxide units and 3 propylene oxide units by alkanol motif, with 32 g of succinic anhydride, and the whole is heated for 7 hours at 100 ° C. The mixture is cooled and filtered to remove unreacted succinic material.

'S r' 23 Infrared analysis shows that roughly half of the nonionic surfactant has been transformed into its acid hemi-ester.

Acid-terminated Dobanol 25-7: 522 g of Dobanol 25-7, a nonionic surfactant which is the ethoxylation product of an alkanol at 12 12 ^ 15 and contain approximately 7, are mixed. ethylene oxide units per molecule of alkanol, with 100 g of succinic anhydride and 0.1 g of pyridine (which acts as an esterification catalyzer) and the whole is heated at 260 ° C. for two hours, cools and filters to remove unreacted succinic material. Infrared analysis shows that virtually all of the free hydroxyl groups in the surfactant have reacted.

15 Acid-terminated Dobanol 91-5: 1000 g of Dobanol 91-5, a non-ionic surfactant which is the ethoxylation product of a Gg alkanol, are mixed together and contains approximately 5 ethylene oxide units per molecule of alkanol, with 265 g of succinic anhydride and 0.1 g of pyridine as catalyst, and the whole is heated at 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 admixture with, pyridine.

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

Adjuvant Detergency Salts 35 The liquid nonaqueous liquid surfactant used! "24 in the compositions of the present invention contains, in the dispersed and suspended state, fine particles of organic and / or mineral detergency builder salts.

The detergent compositions of the invention include water soluble and / or water insoluble detergent 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 bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate , Sodium sesquicarbonate, sodium mono- and di-ortho-phosphates and potassium bicarbonate.

Sodium tripolyphsophate (TPP) 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 to inhibit incrustation which could otherwise be caused by the formation of an insoluble calcium phosphate.

25

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 citric and tartaric acid salts.

The sodium salts of citric acid are the most ap-10 specified, in particular trisodium citrate. You can also use monosodium and disodium 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 incrustation which could, without them, be caused by the formation of insoluble salts of calcium and magnesium.

In order to obtain a phosphate-free detergent composition, the whole polyphosphates can be replaced by one or more of the auxiliary detergency builder salts.

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 sodium salt. 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 aminopolycarboxylates substituted ammonium, for example sodium and potassium ethylenediaminetetraacetate (EDTA), sodium and potassium nitriloacetates (NTA) and triethanolamine N- (2-hydroxyethylnitril-odiacetates). Mixtures of these aminopolycarboxylates are also suitable .

Other suitable detergency builders or auxiliary detergency builders of the organic type include carboxymethylsuccinates, tartro-nates and glycolates. Polyacetal carboxylates are particularly interesting. The polyacetal-carboxylates and their use in detergent compositions are described in patent application 20 of the Applicant FR 86 11 852 filed on August 19, 1985, and in the patents of the USA. N ° 4 144 226, 4 315 092 and 4 146 495.

The alkali metal silicates are useful detergent builder salts which also act by adjusting or regulating the pH and making the composition anticorrosive to parts of the washing machine. Sodium silicates whose Na 2 O / SiO 2 ratios range from 1.6 / 1 to 1 / 3.2, in particular from approximately 1/2 to 1 / 2.8, are preferred. Potassium silicates of the same ratios can also be used.

Other typical suitable detergency builders include, for example, those described in U.S. patents. Nos. 4,316,812, 4,264,466 and 35,630,929. The 27 w mineral alkaline detergency builder salts can be used with the nonionic surfactant detergent or in admixture with other organic or mineral detergency builder salts.

It is also possible to use crystalline and amorphous alumi-5 nosilicates insoluble in water, of the zeolite type. The zeolites correspond to the general formula: (Μ20) χ · (Al203) y · (Si02) z wH20 in which x is 1, y ranges from 0.8 to 1.2 and is preferably 10, z ranges from 1 , 5 to 3.5 or more and preferably from 2 to 3, w ranges from 0 to 9 and preferably from 2.5 to 6, and H is preferably sodium. A typical zeolite is a zeolite of type A or of similar structure, type 4A being particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of around 200 milli-equivalents per gram or more, for example 400 meq / g.

Various crystalline zeolites (i.e., aluminosilicates) that can be used are described in British Patent No. 1,504,168, United States Patent No. 4,409,136 and Canadian Patents Nos. 1,072,835 and 1,087,477. An example of the amorphous zeolites useful herein 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 particularly useful. This material consists mainly of montmorillonite which is a hydrated aluminum silicate of which roughly one sixth of the aluminum atoms can be replaced by mag-35ium atoms and with which various quantities of hydrogen, sodium, potassium, calcium, etc. . can be weakly combined. Bentonite, in its purest form (i.e. free of any sand, abrasive particles, etc.) suitable for detergents, contains at least 50% of montmorillonite and therefore its exchange capacity of cations is at least about 50 to 75 meq per 100 g of bentonite. Particularly preferred ben-tonites are the bentoni-tes from the western United States of America or Wyoming which have been sold under the names 10 Thixo-jels 1,2,3 and 4 by Georgia Kaolin Co. These ben- tonites tonites are known to soften textiles as described in British Patents Nos. 401,413 and 462,221.

Viscosity Adjusters and Antifreezing Agents The storage 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 agents. regulating viscosity and inhibiting gelation towards the nonionic surfactant. Viscosity adjusting and gelling inhibiting agents work to lower the temperature at which the nonionic surfactant forms a gel when added to water. These viscosity adjusting and inhibiting gelling agents can be, for example, amphiphilic compounds of the lower monoalkyl ether type of low molecular weight alkylene oxide.

Amphiphilic compounds can be considered analogous in their chemical structure to liquid nonionic surfactants of the ethoxylated and / or propoxylated fatty alcohol type, but they have relatively short hydrocarbon chains (C2 to Cg) and a relatively low content of oxide ethylene (about 2 to 6 ethylene oxide groups per molecule).

29 r.,.,

Suitable amphiphilic compounds can be represented by the following general formula: R2

1 I

ΈΓ 0 (CHCH20) nH

wherein R "* · is a C2 - C6 alkyl group, R2 is hydrogen or a methyl group and n is a number from 1 to 6 on average.

In particular, these compounds are lower monoalkyl ethers (C2 to C8) of lower alkylene glycol (C2 to C8).

More particularly, these compounds are lower monoalkyl ethers (C1 to C8) of lower mono-, di- or trialkylene glycol (C2 to C8).

Particular examples of suitable amphiphilic compounds include the following: ethylene glycol monoethyl ether (C2Hg-0-CH2CH20H) diethylene glycol monobytyl ether (c4h9-o- (ch2ch2o) 2h) tetraethylene glycol monobutyl ether (c4h7-o - (ch2ch20) 4h) 20 and dipropylene glycol rrarmethyl ether (CHg-O- (CHCH20) 2H.

CH3 Monobutyl ether of diethylene glycol is especially 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. composition when added ¥ 30 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 5 ° C or less.

In one embodiment of the present invention, a stabilizing agent which is an alkanolic ester of phos-phoric acid may be added to the formulation. Improvements in the stability of the composition can be made 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 FR-85.053 19 filed on April 9, 1985, the organic phosphorus acid compound carrying an acid group -POH can increase the stability of the suspension of detergency builders in the nonionic non-aqueous liquid surfactant . 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 nature because 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 C 1 -C 4 alkanol (Empiphos 5632 from Marchon); this product consists of approximately 35¾ of monoester and 65¾ of diester.

The incorporation of very small amounts, for example 0.3% by weight of the organic phosphorus acid compound makes the suspension more stable against sedimentation at rest while leaving it capable of being poured, however only at low concentrations of agent. 35 stabilizer, for example less than about H, its visc ψ * * • * 31 plastic viscosity generally decreases.

Other useful bleach activators can be added to the composition: among them, mention can be made of bleach-5 activators such as tetraacetyl ethylene diamine t (TAED) and pentaacetyl glucose , acetylsalicylic acid derivatives, ethylidene benzoate-acetate and its salts, an ethylidene carboxylate-acetate and its salts, an ethylidene carboxylate-acetate and its salts, an alkyl- or alkenyl-succinic anhydride , tetraacetylglycourile (TAGU), and derivatives of these activators. Other useful classes of activators are described, for example, in U.S. patents. N ° 4 111 826, 4 422 950 and 3 661 789.

The second bleach activator or auxiliary bleach activator can be added to supplement the calcium cyanamide bleach activator and to further lower the temperature, for example below about 60 ° C, at which the per-oxygenated compound whitening becomes effective.

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, minor amounts of anti-deposition or soil suspending agents can be included in the formulation, for example polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose. A preferred anti-redeposition agent is a sodium carboxy-methyl cellulose having a CM / CMC ratio of 2: 1, which is sold under the trademark Relatin DM 4050.

It is also possible to incorporate into the composition 35 small quantities of Duet 787 which is a fragrance fr 32 and which is supplied by International Flavors and Fragrances, Inc., Union Beach, New Jersey 07735 USA Duet 787 can be added in proportions, by example 0.3 to 1.0 percent, preferably 0.2 5 to 2.0 percent, especially 0.5 to 2 percent, "such as 0.3 to 1.0 percent by weight of the composition.

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. A favorite brightener is

Stilbene Brightener N4 which is a dimorpholino-dianilino-stilbene polysulfonate.

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 Esperase SL8 which is a proteolytic enzyme. Defoamers, for example silicon compounds such as Silicane L 7604, can also be added in small effective amounts.

It is also possible to use bactericides, for example tetrachlorosalicylanilide and hexa-chlorophene, fungicides, dyes, pigments (dispersible in water), preservatives, ultraviolet absorbers, anti-yellowing agents such as than sodium carboxymethyl cellulose, pH modifiers and pH buffers, color preserving bleaches, perfume, coloring agents and brighteners such as ultramarine blue.

In one embodiment of the invention, the stability of the detergency builder salts in the composition during storage and the dispersibility of the composition in water are improved by grinding and reducing the particle size of the builders solid detergents to less than 100 micrometers, preferably to less than 40 micro-10 meters and better still to less than 10 micrometers. Solid detergency builders, for example sodium tri-polyphosphate (TPP) are generally supplied in particle sizes of about 100, 200, or 400 microns. The liquid non-ionic surfactant phase can be mixed with the solid detergency builders before or after the grinding operation is carried out.

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. less than about 10 micrometers, for example at an average particle size of 2 to 10 25 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 whose dispersed particles have such small dimensions have better stability against separation or sedimentation during storage. The addition of the acid-terminated nonionic surfactant can decrease the flow limit of these dispersions and improve their dispersibility without causing a correlative reduction (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%, about 50%) so that the solid particles are in contact between them and are not substantially isolated from each other by the liquid nonionic over-charge. 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, it is possible to use a laboratory mill-attritor working in portions containing grinding balls made of soapstone 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 gap between a stator and a rotating rotor. 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 micro-30 meters) before the grinding step to an average particle diameter of less than about 10 micrometers which takes place in the ball mill operating in continuous mode .

In 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) ingredients are as follows:

Liquid nonionic surfactant detergent: in the range of about 10 to 60 percent, such as from »20 to 50 percent, for example about 30 to 40 percent.

Acid-terminated nonionic surfactant as a viscosity enhancing agent: in the range from 10 to about 0 to 20 percent, such as from 3 to 15 percent, for example about 4 to 10 percent.

Detergency builder, e.g. tripoly sodium phosphate (TPP): in the range of about 10 to 60 percent, such as 15 to 50 percent, 15 for example about 25 to 35 percent.

Copolymer of metal salt of polyacrylic acid and polymaleic anhydride, for example Sokalan CP5, as anti-scaling agent: in the range of about 0 to 10 percent, such as from 2 to 8 percent, for example about 3 to 5 percent.

Alkylene glycol monoalkyl ether as anti-gelling agent: in the range of about 5 to 30 percent, such as 5 to 20 percent, for example about 5 to 15 percent.

25 Alkanolic ester of phosphoric acid as stabilizer: in the range of 0 to 2.0 percent or 0.1 to 1.0 percent, such as 0.2 to 0.5 percent.

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

Cyanamide calcium as a bleach activator: in the range of about 1 to 15 percent, like 1 to 8 percent, for example about 2 to 6 percent.

ψ ♦ »· • '36

Sequestering agent for the bleach, 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 to 1 , 25 percent.

5 Anti-redeposition agent, for example Relatin DM 4050: in the range of about 0 to 4.0 percent, preferably 0.5 to 3.0 percent, for example 0.5 to 1.5 percent hundred.

Optical brightener: in the range of about 10 0 to 2.0 preferably 0.05 to 1.0 percent, for example 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 percent, preferably 0.10 to 1.25 percent, for example 0.25 to 1.0 percent.

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

The calcium bleach activator calcium cyanamide is preferably used with at least one of the viscosity control and antifreezing agents that are the alkylene glycol monoethers and the acid-terminated nonionic surfactants.

In some cases, benefits can be derived from the simultaneous use of alkylene glycol monoethers and nonionic acid-terminated surfactants.

As regards 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 non-aqueous non-ionic liquid detergent composition of the present invention is easy to dispense in the water of the washing machine.

In one embodiment of the invention, a detergent composition of typical formulation is prepared using the ingredients designated below:% by weight 10 Nonionic surfactant detergent 30 - 40

Acid-terminated surfactant, viscosity improving agent 0-20

Phosphate, detergency builder salt 10-60

Anti-scaling agent 0-10 15 Monoalkyl ether of alkylene glycol, antifreeze agent 5-15

Alkanolic ester of phosphoric acid, stabilizing agent 0-2.0

Anti-redeposition agent 0-4.0 20 Alkali metal perborate, bleaching parsley 5-15

Calcium cyanamide, bleach activator 1.0 - 8.0

Sequestering agent for bleach 0 - 3.0

Duet 787 0 - 3.0

Optical aviator 0.15 - 0.75

Enzymes 0.75-1.25

Perfume 0 - 3.0 The following examples further illustrate the present invention.

EXAMPLE 1

A concentrated non-aqueous liquid detergent composition based on non-ionic surfactant is prepared only from the following ingredients,

jiF

38 specified conditions.

% in weight

Non-ionic surfactant 38.8 "

Dobanol 91-5 acid-terminated reaction product with succinic anhydride 5.0 t

Sodium tripolyphosphate (TPP) 29.6

Diethylene glycol monobutyl ether, antifreezing agent 10 10 Alkanolic phosphoric acid ester (Emphiphos 5632) 0.3

Sodium perborate monohydrate, bleach 9.0

Calcium cyanamide, bleach activator 4.5

Anti-redeposition agent (Relation DM 4050) ^ 1.0

Optical aviator 0.2

Perfume (Duet 787) 0.6

Enzyme (Esperase) 1.0 20 100.0 (1) mixture CMC / MC = 2: 1 of sodium carboxymethyl cellulose and hydroxymethyl cellulose.

The composition is ground for about 1.0 hour to reduce the particle size of the detergency builder salts in suspension to less than 40 microns. It is found that the detergent composition prepared is stable and non-gelling during storage, that it disperses easily in water and that it has good whitening properties and better detergent power.

EXAMPLE 2

A concentrated nonaqueous liquid detergent composition based on nonionic surfactant is prepared from the following ingredients in the proportions specified.

39 ψ I »'% by weight

Non-ionic surfactant, Product D 13.5

Surfactant T7 10

Surfactant T9 10 5 Acid-terminated reaction product of Dobanol 91-5 with succinic anhydride 5 Sodium tripolyphosphate (TPP) 29.6

Anti-scaling agent (Sokalan CP5) 4.0

Diethylene glycol monobutyl ether, 10 antifreeze agent 10

Alkanolic phosphoric acid ester (Emphiphos 5632) 0.3

Sodium perborate monohydrate, bleach 9 9 Calcium cyanamide, bleach activator 4.5

Bleach sequestering agent (Dequest 2066) 1.0

Anti-redeposition agent (Relatin DM 4050) ^ 1.0 20 Optical brighteners (Stilbene) 0.5

Enzyme (Esperase suspension) 1.0

Duet 787 (2) 0.6 100.0 (1) mixture CMC / MC = 2: 1 of sodium carboxymethylcellulose and hydroxymethylcellulose.

(2) Duet 787 which is a fragrance from IFF, Inc.

The composition is ground for about 1 hour to reduce the particle size of the detergency builder salts to less than 40 microns. It is found that the detergent composition prepared is stable and non-gelling during storage and that it disperses easily in water. The bleach is active at 60 ° C on the immediate dark. The 4.5% concentration of calcium cyanamide gives a value Rd = 5.3, in comparison with a value I * m 40 - ^ Rd of 0.8 without activator. The pH of the aqueous washing liquor without bleach activator is 9.6, it is 9.9 with 4.5% calcium cyanamide activator, and it is 9.0 with 4.5% 5 TAED as activator.

4

The compositions of Examples 1 and 2 can be prepared without grinding detergency builder salts and suspended solid particles to a small particle size, but the best results are obtained by grinding the composition to reduce the particle size of the solid particles. in suspension.

The detergency builder salts can be used as supplied, or the detergency builder salts and suspended solid particles can be ground or partially ground before being mixed with the nonionic surfactant. The grinding can be carried out in part before the mixing operation and can be completed after the mixing operation, or else the entire grinding operation can be carried out after mixing with the liquid surfactant. Compositions which contain a detergency builder and suspended solid particles having a particle size of less than 40 microns are preferred.

The bleaching persalt and calcium cyanamide bleach activator system of the present invention can also be used in detergent compositions based on nonionic surfactant for washing dishes, cream scourers, and other compositions in which a bleaching is necessary like dry powder and granular detergent compositions.

Claims (19)

1. A detergent fabric treatment composition comprising a liquid nonionic detergent surfactant, a peroxygen mineral compound as a bleaching agent and calcium cyanamide as a bleaching agent activator. 2. Detergent composition according to claim 1, characterized in that it comprises an agent for adjusting the viscosity and anti-gelling. 3. A detergent composition according to claim 10 1, characterized in that it comprises at least one agent for adjusting the viscosity and anti-gelling chosen from a monoalkyl ether of alkylene glycol and a nonionic surfactant with acid termination. 4. Detergent composition according to claim 1, characterized in that it comprises a suspension of insoluble mineral salts detergency adjuvants. 5. A detergent composition according to claim 20 4, characterized in that the adjuvant salt of detergency comprises an alkali metal polyphosphate. 6. Detergent composition according to claim 4, characterized in that the adjuvant insoluble mineral detergency salt comprises 10 to 60 per cent of a detergency adjuvant polyphosphate. 7. Detergent composition according to claim 1, characterized in that it comprises one or more detergent additives chosen from an anti-encrustation agent, a sequestering agent, an anti-redeposition agent, an optical brightener, enzymes and a perfume. 8. Detergent composition according to claim 1, characterized in that it comprises 10 to 60 percent of nonionic liquid detergent surfactant. 42 · * r ‘« * * 9. A detergent composition according to claim 3, characterized in that it comprises 5 to 30 percent of a monoalkyl ether of alkylene glycol. 10. Detergent composition according to CLAIMS 5 tion 4, characterized in that the adjuvant salt of mineral detergency j has a particle size less than 40 micrometers. 11. Detergent composition according to claim 1, characterized in that it contains approximately 0.1 10. approximately 0.5 percent by weight, relative to the weight of the total composition, of an alkanolic ester of phosphoric acid such as anti-sedimentation stabilizer. 12. Non-aqueous liquid detergent composition containing a detergent builder for heavy laundry work, which can be poured at low and high temperatures and does not gel when mixed with cold water, comprising at least one surfactant non-ionic liquid in a proportion of about 20 to 10 to 60 percent by weight; at least one adjuvant mineral detergency salt suspended in the nonionic surfactant in an amount of about 10 to about 60 percent by weight; an inorganic peroxy-bleaching agent in a proportion of about 5 to 15 percent by weight; calcium cyanamide as bleach activator, in a proportion of about 1 to 8 percent by weight, an acid-terminated nonionic surfactant as a gelling inhibiting additive, in a proportion of about 0 to 20 percent by weight; and a compound of the formula: 1 l2 R ± 0 (CHCH90) H 1. n 2 where R is a C'2 - Cg alkyl group, R is hydrogen or a methyl group and n is a number having a> (- * 'I «* T · 43 average value of about 1 to 6, as an additive inhibiting gelation, in a proportion of up to about 5 to 30 percent by weight. 13. Detergent composition according to claim 5 tion 12, characterized in that it contains one or more detergent additives chosen from an anti-encrustation agent, a sequestering agent, an anti-redeposition agent, an optical brightener, an enzyme and a perfume . 14. Detergent composition according to claim 12, characterized in that it comprises: approximately 20 to 50% by weight of nonionic surfactant, approximately 3 - 15 1 by weight of acid-terminated nonionic surfactant as viscosity-improving agent, about 15 - 50% by weight of sodium tripolyphosphate, about 2 - 8% by weight of sodium polycrylic acid sodium hydroxide and polymaleic anhydride, about 5 - 20 1 by weight of diethylene glycol monoalkyl ether, about 0.1 - 1.0% by weight of alkanolic ester of phosphoric acid, approximately 2 - 20% by weight of sodium perborate monohydrate as a bleaching agent, and approximately 1 - 8% by weight of calcium cyanamide. 15. Detergent composition according to CLAIMS-25 tion 12, characterized in that it comprises: about 30 - 40% by weight of nonionic surfactant, about 3 - 15% by weight of nonionic surfactant acid-terminated as agent improving the viscosity, approximately 25 - 35 1 by weight of sodium tripolyphosphate, approximately 3 - 5% by weight of sodium salt of copolymer of polyacrylic acid and polymaleic anhydride, approximately 5 - 15% by weight of mono- ether diethylene glycol butyl, about 0.2 - 0.5 1 by weight of alkanolic ester of phosphoric acid, about 5 - 15 1 by weight of sodium perborate mono- mr γ * f, «. V 44 · hydrated as a bleaching agent, approximately 2 - 6.0% by weight of calcium cyanamide, approximately 0.75 - 1.25% by weight of sequestering agent for the bleaching agent, and approximately 0.5 - 1.5 t by weight of anti-5 deposition agent. 16. A method for cleaning soiled fabrics, characterized in that it consists in bringing the soiled fabrics in contact with the detergent composition of claim 1. 17. A method for cleaning soiled fabrics, it is characterized in that it consists in bringing the soiled fabrics in contact with the detergent composition for washing the laundry of claim 12. 18. Method for cleaning soiled fabrics according to claim 17, characterized in that it consists in bringing the soiled fabrics in contact with the detergent composition for washing the laundry of claim 14. 19. Method for cleaning soiled fabrics according to claim 17, characterized in that it consists in bringing the soiled fabrics in contact with the detergent composition for washing the laundry of claim 15.