LU86380A1 - LIQUID DETERGENT AND WHITENING COMPOSITION AND METHOD FOR CLEANING AND WHITENING DIRTY TISSUES USING THE SAME - Google Patents

Description

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The present invention relates to liquid laundry detergent compositions - More particularly, the present invention relates to non-aqueous liquid laundry detergent compositions which can be easily poured and which do not gel when they are added to water, as well as the use of these compositions for cleaning soiled fabrics.

Non-aqueous liquid detergent compositions for laundering coarse laundry are well known in the art. For example, compositions of this type may include a nonionic liquid surfactant in which particles of a detergency builder are dispersed, as indicated, for example, in U.S. patents. No. 4,316,812; No. 3,630,929; No. 4,264,466 and British Patents No. 1,205,711; N ° 1 270 040 and NQ 1 600 981.

Liquid detergents are often considered to be more convenient to use than dry powder or particulate products and are therefore very popular with consumers.

They can be easily dosed, they dissolve quickly in washing water, they can be easily applied in concentrated solutions or dispersions on soiled parts of garments to be laundered, they do not generate dust, and they occupy generally less storage space. In addition, liquid detergent formulations may contain materials which could not withstand drying without deterioration, materials which it is often desirable to use in the manufacture of particulate detergent products. Although they have many advantages over discrete or particulate solid products, liquid detergents often have some inherent disadvantages which must be overcome to obtain commercially acceptable detergent products. Thus, μ i ^ • i / î * 2 some of these products separate during storage and others separate on cooling and do not readily re-disperse. In some cases, the cosiness screw of the product changes and this product becomes 05 either too thick to be poured, or so fluid that it looks like water. Some clear products become cloudy and others gel on standing.

The Applicant has intensively studied the rheological behavior of nonionic liquid surfactant systems, whether or not containing particulate matter in suspension. Of particular interest are the enhanced non-aqueous liquid laundry detergent compositions and the gelation problems associated with nonionic surfactants as well as the deposition of suspended detergency builder and other laundry additives. These considerations have repercussions for example on the aptitude of the product to be poured, its dispersibility and its stability.

The rheological behavior of reinforced non-aqueous laundry detergents * can be compared to the rheological behavior of paints, so that the particles of detergency builder in suspension correspond to the mineral pigment and the nonionic liquid surfactant corresponds to the non-aqueous paint vehicle.

To simplify, in the description which follows, the particles in suspension, for example of detergency builder, will sometimes be designated by "pigment".

It is known that one of the main problems with reinforced laundry paints and liquid detergents is their physical stability. This problem arises from the fact that the density of the solid pigment particles is greater than the density of the liquid matrix. As a result, particles tend to settle under Stoke's law. Two basic solutions exist to solve. * '„Λ' 3 the problem of sedimentation: increase the viscosity of the liquid matrix and reduce the dimension m ~ of solid particles.

For example, it is known that such suspensions can be stabilized against deposition by the addition of mineral or organic thickening or dispersing agents such as, for example, mineral materials with very large specific surface , such as finely divided silica, clays, etc., organic thickeners such as cellulose ethers, acrylic and acrylamide polymers, polyelectrolytes, etc. However, these increases in viscosity of the suspensions are naturally limited by the need that the liquid suspension can be poured easily and can flow, even at low temperatures. In addition, these additives do not contribute to the cleaning action of the formulation.

Grinding, aimed at reducing the particle size, is more advantageous and has two major consequences: 1. The specific surface area of the pigment is increased, and, consequently, the wetting of the particles by the non-aqueous vehicle (non-ionic surfactant 25 liquid) is improved proportionally.

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

Nonaqueous liquid suspensions of the particles of detergency builders, for example polyphosphate type detergency builders, especially sodium tripolyphosphate (TPP), in a nonionic surfactant have been found to have a composition. '4 <rheological behavior, substantially in accordance with Casson's equation: € I / 2 9 S o ^ 1 + 2 Ç 05 oö β is the shear rate, CT is the shear stress, (T is the limit of flow, and <\ 0> is the "plastic viscosity" (viscosity 10 apparent at an infinite shear rate).

The flow limit is the minimum stress necessary to cause plastic deformation (flow) of the suspension. Thus, if the suspension is represented in the form of a loose network of pigment particles, if the applied stress is less than the flow limit, the suspension behaves like an elastic gel and no plastic flow. 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 much higher than the flow limit, the pigment particles are partially deflocculated by shear and the apparent viscosity decreases. Finally, if the shear stress is much higher than the flow limit value, the pigment particles are completely deflocculated by shear and the apparent viscosity is very low, as if there were no particle interaction.

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

In addition to the problem of depositing phase separation, non-aqueous liquid detergents of β * = '5 r bleaching based on liquid non-ionic surfactants have the disadvantage that non-ionic compounds tend to gel when they are added to cold water. This is a particularly important problem during the normal use of European domestic automatic washing machines in which the user places the laundry detergent composition in a dispensing device (for example a dispenser drawer) of the machine.

During the operation of the machine, the detergent contained in the dispenser is subjected to the action of a stream of cold water which transfers it into the main mass of the washing solution. In particular during the winter months when the detergent composition and the water introduced into the dispenser are particularly cold, the viscosity of the detergent increases markedly and a gel is formed. As a result, a part of the composition is not entirely drawn out of the dispenser during the operation of the machine, and a deposit of composition accumulates as the washing cycles are repeated, which ultimately forces the user to sweep the dispenser with hot water.

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

Partial solutions to the problem of gelation in aqueous compositions substantially free of detergency builder have been proposed and include, for example, dilution of the liquid nonionic overbite with certain viscosifying solvents and inhibiting agents. gelling agents, such as lower alkanols, eg ethyl alcohol (see US Pat. No. 3,953,380), alkali metal formates and adipates. "E lins (see US patent Np 4,368,147), hexylene glycol, polyethylene glycol, etc., * In addition, these two patents each describe the use of a maximum of approximately 2, 5% of 05 derived from the lower alkyl ethyer type (C ^ -C ^) of the lower polyols (C ^ -C ^) "for example ethylene glycol, in these aqueous liquid detergents free of adjuvant detergency in place of part of the lower alkanol, for example ethanol, as a viscosity-acting solvent. U.S. Pat. Nos. 4,111,855 and NQ 4,201,686 deal with the same effect. None of these patents, however, describes or suggests that these compounds, some of which are commercially available under the trademark Cellosolve®, can act effectively as viscosity regulators and gelation inhibitors for nonaqueous compositions. liquid nonionic surfactants, in particular such compositions containing adjuvanted detergency salts, for example - polyphosphates, and in particular such compositions which do not depend on or require solvents of the lower alkanol type as regulating agents the viscosity.

In addition, British Patent No. 1,600,981 mentions that in non-aqueous non-ionic detergent compositions containing detergency builders suspended with the aid of certain dispersants for the detergency builder, such as finely divided silica 30 and / or compounds containing a polyether group having molecular weights of at least 500, it may be advantageous to use mixtures of nonionic surfactants, one of which fulfills the function of surfactant and the other fulfills the function of surfactant and also reduces the drop point of the compositions. Examples of the first surfactant are fatty alcohols in 0 - ^^ 15 having 5 to 15 moles of oxide 7 "1 j 4 f of ethylene and / or propylene per mole. Examples of the other surfactant are linear fatty alcohols in cg-cg or branched in Cg-C. ^ Having 2 to 8 moles ^ of ethylene oxide and / or propylene per mole. Again w 05, it is not mentioned that these low carbon chain compounds can adjust the viscosity and prevent gelation of nonaqueous compositions of liquid nonionic surfactants for large laundering jobs, or to a deter-10 adjuvant gence is suspended in the., active non-ionic liquid surf.

It is also known to modify the structure of nonionic surfactants in order to optimize their resistance to gelation in contact with water, in particular cold water. As an example of modification of the structure of nonionic surfactants, a particularly satisfactory result has been achieved by acidifying the hydroxyl terminal group of the nonionic molecule. The advantages of introducing a carboxylic acid at the end of the nonionic surfactant include the inhibition of gel formation at the time of dilution; a decrease in the drop point of the nonionic surfactant; and forming an anionic surfactant when neutralized in the wash liquor. Optimization of the non-ionic structure to minimize gelation is also known, for example by adjusting the chain length of the hydrophobic-lipophilo portion and the number and constitution of the alkylene oxide units (e.g. 'ethylene) of the hydrophilic portion.

For example, it has been found that a fatty alcohol in Cl3 * ethoxylated with 8 moles of ethylene oxide only exhibits a tendency limited to the formation of gel. However, it is still desired to improve the stability, viscosity control and inhibition of gelation of non-aqueous liquid detergent compositions.

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It is therefore an object of the invention to provide non-aqueous liquid bleach detergents which do not gel when they come into contact with water or when they are added to water, in particular cold water.

Another object of the invention is to provide reinforced non-aqueous liquid laundry detergent compositions which are storage stable, can be easily poured and are dispersible in cold, lukewarm or hot water.

Another object of the present invention is to formulate non-aqueous liquid detergent compositions with highly ionic surfactant, for heavy laundry laundering jobs, which can be poured at all temperatures and which can be dispersed in a way repeated from the dispenser device of automatic washing machines of the European type without clogging or obstructing the dispenser even during the winter months.

A particular object of the present invention is to provide suspensions of low viscosity, stable, non-gelling, of non-aqueous liquid detergent composition with nonionic surfactit, reinforced with tripolyphosphate, for large laundering works, which comprise an amount of an amphiphilic compound of low molecular weight sufficient to reduce the viscosity of the composition in the absence of water and in contact with cold water.

These objects of the invention, as well as others which will emerge from the following detailed description of preferred embodiments, are achieved in general by the addition to the surfing composition. liquid nonionic active ingredient of an amount 3 of a low molecular weight amphiphilic compound, in particular a mono (lower alkyl (C ^ to C5)) ether of mono-, di- or tri (lower alkylene (C ^ to C ^)) - glycol, effective in inhibiting gelation of non-ionic sur- factive in the presence of cold water.

Consequently, according to one of its aspects, the present invention provides a composition for large laundering works consisting of a suspension k 05 of a detergency builder salt in a liquid nonionic surfactant, the composition comprising an amount of an ether mono (lower alkyl (C ^ to C, _)) of (lower alkylene (C ^ to C ^)) glycol. able to. reducing the viscosity of the composition in the absence of water and on bringing the composition into contact with water.

In a more particular embodiment, the present invention provides a non-aqueous liquid cleaning composition, which remains suitable for pouring at temperatures below about 5 ° C and which does not gel when contacted with water. or added to water at temperatures below about 20 ° C, the composition consisting of a liquid nonionic surfactant and a mono (C5 to C5 alkyl) alkylene glycol C2 ether ~ C3 and ®tant substantially free of water.

According to yet another aspect, the invention provides a method for dispensing a nonionic liquid laundry detergent composition in and / or with cold water. Without undergoing gelation.

In particular, there is provided a method for filling a container with a non-aqueous liquid laundry detergent composition in which the detergent consists, at least predominantly, of a liquid non-ionic surfactant, and for dispensing the composition from the container into an aqueous washing bath, in which the dispensing is effected by directing a stream of unheated water over the composition so that the composition is entrained by the stream of water in the washing bath. By virtue of the incorporation of a low molecular weight amphiphilic compound, that is to say a mono (lower alkyl (C1-C6) ether) of C2-C3 lower alkylene glycol , the composition can be easily poured into the container even when it is at a temperature below room temperature. In addition, the composition does not undergo gelation 05 when it comes into contact with the stream of water and it disperses easily on entering the washing bath.

As will be seen below, liquid detergent compositions often include, in addition to the active detergent ingredient, one or more detergent additives or auxiliaries. The most important of these, in terms of consumer appeal and real interest in cleaning, belong to the class of bleaching agents, in particular the oxygenated bleaching agents, a particularly example of which preferred is sodium perborate monohydrate. It is well known in practice that in solution, the oxygenated bleaching agent of the persal type releases hydrogen peroxide which constitutes the active oxidizing agent. However, hydrogen peroxide is easily broken down by catalase, an enzyme that is always present in soil and natural stains. This decomposition takes place even in the presence of activators of bleaches, since the reaction rate between hydrogen peroxide and the activator is slower than the decomposition of hydrogen peroxide by catalase. The activity of the catalase is very high, even at room temperature, and a substantial amount of active oxygen is lost before the catalase can be deactivated by raising the temperature of the washing bath.

* An attempt to solve this problem has been to use an excess amount of perborate or other peroxidic bleach, for example an amount of generally 2 to 4 times that which would be necessary to effectively whiten dirt or stains in l lack of decomposing enzyme 4

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the peroxide and also in molar excess of 2 to 4 times relative to the number of moles of activator of the bleaching agent.

“It has also been proposed to carry out bleaching with an aqueous solution of peroxide bleach in the presence of a compound capable of inhibiting the decomposition of the bleaching agent by the enzyme. Thus, US Pat. No. 3,606,10,990, assigned to the Applicant, describes a relatively wide range of inhibitory compounds, including for example a hydroxylamine salt, hydrazine and Phenylhydrazine and their salts, phenols and substituted polyphenols, and the like, as well as various detergent compositions containing the water-soluble mineral peroxide bleach and the inhibitor compound. However, there is no mention of liquid detergent compositions which contain the compounding agents and neither is it said that the bleaching agent inhibiting compounds in addition to the bleaching peroxide. In addition, this patent establishes in column 7, lines 25-29, that in the case of hydroxylamine sulfate, the effective amount of inhibitor compound is from about 0.5 to about 2 percent by weight. of the total composition.

It has now been discovered that in the liquid detergent compositions of the present invention, containing a water-soluble mineral peroxide as a bleaching agent of the persal type, the incorporation of very limited quan-tites of less than about 0.5%, for example from 0.01 to about 0.45%, can effectively prevent a breakdown of the bleach caused by the enzyme. It has been further discovered that hydroxylamine sulfate is very stable in composition and in no way interferes with activation of the bleaching system by activators of the persalt bleach.

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Therefore, in yet another aspect of the present invention, there is provided a liquid detergent composition for laundering coarse laundry, which comprises a water-soluble mineral peroxide 05 as a bleaching agent and an effective amount of a compound which can inhibiting the decomposition of the bleaching agent caused by an enzyme, in particular in a proportion of less than about 5% by weight of the composition, and preferably an activator for activating the bleaching agent.

Other particular characteristics and embodiments of the invention will emerge from the detailed description which follows.

The non-ionic synthetic organic detergents used in the practice of the invention can be any of a wide variety of such compounds, which are well known and, for example, are described in detail in the book Surface Active Agents, Vol. il, by Schartz, Perry and Berch, 20 published in 1958 by Interscience Publishers, and in Detergents and Emulsifiers, by McCutcheon, 1969, Annual, the relevant descriptions of which are cited here for reference. In general, nonionic detergents are lipophilic compounds alkoxylated by a poly (lower alkoxy) group in which the desired hydrophilic-lipophilic ratio is obtained by the addition of a hydrophilic poly (lower alkoxy) group to a lipophilic portion. . A preferred class of the nonionic detergent used is that of the higher poly (lower alkoxy) alkanals in which the alkanol has 10 to 18 carbon atoms and in which the number of moles of lower alkylene oxide (2 or 3 carbon atoms) is 3 to 12. Among these materials, it is preferred to use those in which the higher alkanol is a fatty alcohol greater than 10 to 11 or 12 to 15 carbon atoms and which contains 5 to 8 or 5 to 9 lower alkoxy groups per mole. Of

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13 * “preferably, the lower alkoxy group is the efchoxy group but, in certain cases, it can be advantageously mixed with a propoxy group, the latter, if present, generally but not necessarily representing only one minor proportion (less than 50%). Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and which contain about 7 ethylene oxide groups per mole, for example Neodol 25-7 and Neodol XO 23-6.5, which are products manufactured by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols having on average about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide, and the latter is a corresponding mixture in which the number of carbon atoms of the higher fatty alcohol is 12 or 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, both of which are ethoxylated linear secondary alcohols manufactured by Union Carbide Corporation. The first is a product of mixed ethoxylation of linear secondary alkanols of 11 to 15 carbon atoms with seven moles of ethylene oxide and the second is a similar product, but where nine moles of ethylene oxide have reacted.

Also useful in the compositions of the invention, as a component of the nonionic detergent, are higher molecular weight nonionic surfactants, such as Neodol 45-11, which are similar condensates of ethylene oxide. and higher fatty alcohols, the higher fatty alcohol s having 14 or 15 carbon atoms and the number of ethylene oxide groups per mole being about 11. Such products are also manufactured by Shell Chemical Company . Other useful nonionic surfactants 14 s φ * are represented by the well known and commercially available Plurafac series, each compound in this series being the reaction product of a higher linear alcohol and a mixture of oxides ethylene and propylene oxide and containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include Plurafac RA30 (a C ^ -C ^ fatty alcohol) condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide 10 ne), Plurafac RA40 (a C ^ -C fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide), Plurafac D25 (a fatty alcohol in C ^ 3 “C ^ condensed with 5 moles of propylene oxide and 10 moles of oxide ethylene), and Plurafac B26.

In general, the condensation products of fatty alcohols and mixed oxides of ethylene and propylene can be represented by the general formula RO (C2H ^ O) x (C3HgO) yH or R is a primary or secondary aliphatic hydrocarbon with straight or branched chain 20, preferably an alkyl or alkenyl group of 6 to 20 carbon atoms, preferably of 10 to 18, and better still of 14 to 18 carbon atoms, x is a number from 2 to 12, preferably 4 to 10, and y is a number from 2 to 7, preferably 3 to 6. Another group of liquid nonionic surfactants are available from Shell Chemical Company, Inc., under trademark Dobanol: Dobanol 91-5 is a C 1 -C 4 ethoxylated fatty alcohol with an average of 5 moles of ethylene oxide; Dobanol 25-7 is a C 1 -C 4 fatty alcohol ethoxylated with an average of 7 moles of ethylene oxide; etc.

In poly (lower alkoxy) alkanols s. which are preferred, in order to obtain the best hydrophilic / lipophilic ratio, the number of lower alkoxy groups is generally from 40% to 100% of the number of carbon atoms = '15 * * higher alcohol, preferably from 40 to 60% of this number, and the nonionic detergent preferably contains at least 50% of such a lower polyfalkoxy) -alkanol. Higher molecular weight 05 alkanols and various other normally solid detergents and nonionic surfactants may contribute to the gelation of the liquid detergent and, therefore, will preferably be omitted or their quantity will be limited in the compounds-10 tions of the invention, although minor proportions can be used for their cleaning properties, etc. As regards the preferred and less preferred detergents, the alkyl groups which they contain are generally linear, although branching can be tolerated, for example at the level of the carbon atom neighboring or separated by two carbon atoms of the terminal carbon atom of the straight chain and opposite of the ethoxylated chain, provided that this branched alkyl group has a length of not more than three carbon atoms. Normally, the proportion of carbon atoms in such a branched configuration will be minor, rarely exceeding 20% of the total content of carbon atoms in the alkyl group. Likewise, although the linear alkyl groups which are linked at the end to the oxyethylene chains are highly preferred and are considered to offer the best combination of detergency, biodegradability and non-gelling characteristics, it may appear, in the chain, a median or secondary junction with ethylene oxide. There are generally; than a minor proportion of such alkyl groups, generally less than 20% but, as in the case of the s · Tergitol mentioned, it may be higher. Also, when the lower alkylene oxide chain contains propylene oxide, this generally, but not necessarily, represents less than 20% * 16% of this chain and preferably less than 10%. %.

When higher proportions of al-canols whose alkoxylation is not terminal / of poly (lower alkocy) -alkanols containing propylene oxide and non-ionic detergent with a lower hydrophilic-lipophilic ratio than mentioned above above are used and when other nonionic surfactants are used in place of the preferred nonionic surfactants described herein / the resulting product may not exhibit as good properties of detergency, stability, viscosity and than the preferred compositions, but the use of the viscosity controlling and gelling inhibiting compounds of the invention can also improve the properties of detergents based on such nonionic surfactants. In some cases, for example when using a higher molecular weight poly (lower alkoxy) alkanol, often for its detergency, its proportion will be adjusted or limited according to the results of various experiments, in order to obtain the detergent power desired, while still obtaining a non-gelling product and desired viscosity. It has also been found that it is only rarely necessary to use nonionic surfactants of higher molecular weight for their detergent properties, since the preferred nonionic surfactants described here are excellent detergents and, moreover, they make it possible to obtain the desired viscosity in the liquid detergent without gelling at low temperatures. Mixtures of two or more of these liquid nonionic surfactants can also be used and, in some cases, benefit can be obtained from the use of such mixtures.

c. As mentioned above, the structure of liquid nonionic surfactants can be optimized with regard to the length of their carbon chain and its configuration (for example linear chains 4 ”17 instead of branched chains, etc.) and the number and distribution of their alkylene oxide units. Intensive research has shown that these structural features can and do have a marked ef-05 effect on properties of the nonionic surfactant such as drop point, cloud point, viscosity, tendency to gel. , as well as naturally, on the detergent power.

In general, the most commercially available nonionic surfactants have a relatively wide distribution of the ethylene oxide (EO) and propylene oxide (OP) units and the length of the lipophilic hydrocarbon chain, the EO and OP contents. and the lengths of the hydrocarbon chain indicated being global averages. This "polydispersity" of hydrophilic chains and lipophilic chains can have a great influence on the properties of the product, in the same way as the specific values of the average values. The relationship between the "polydispersity" and the lengths of specific chain and the properties of the product for a well-defined surfactant can be demonstrated by the following results concerning the "Surfactant T" series of nonionic surfactants available from the British firm Petro-25 leum. Surfactant T surfactants are obtained by ethoxylation of 'secondary fatty alcohols in Cl3, with a narrow distribution of EO, and they have the following physical characteristics:

Content Cloud Point Point (solu-30 in EO drop (° C) content at 1%) (° C)

Surfactant T5 5 <-2 <25

Surfactant T7 7 -2 38? T9 surfactant 9 6 58 35 Tl2 surfactant 12 20 88

In order to determine the influence of the distribution of 5, 18 Λ "" OE bution, an "Surfactant T8" was artificially prepared in two ways: ** a. mixture l; l of T7 and T9 (T8a) b. 4: 3 mixture of T5 and Tl2 (T8b).

05 The following properties have been observed:

Content Cloud point point (EO solution drop (° C) to 1 I) (° C) (average) 10 Surfactant T8a 82 48

Surfactant T8b 8 15 <20 According to these results, the following general observations can be made: 15 1. T8a corresponds closely to a real surfactant T8, because it fits well between T7 and T9 for the drop point and the point of trouble.

2. T8b which is highly polydispersed would be generally unsatisfactory given its high drop point and its low cloud point.

3. The properties of T8a are basically additive between T7 and T9, while for T8b, the drop point is close to that given by the long chain OE (T12) while the cloud point 25 is close to that given by short OE chain (T5).

The viscosities of the nonionic surfactants Surfactant T were measured at concentrations of nonionic surfactant of 20%, 30%, 40%, 50%, 60%, 30 80% and 100% for T5, T7, T7 / T9 (1 : 1), T9 and T12 at 25 ° C and gave the following results (when a gel is obtained, the viscosity is the apparent viscosity) at 100 s "· * · .; 1 * 19

Non-ionic surfactant Viscosity (mPa.s) type τ5 τ7 T7 / T9 T9 Tl2

05% N

100 36 63 61 149 80 65 104 112 165 60 750 78 188 239 32 200 10 50 4000 123 233 634 89 100 40 2050 96 149 211 187 30 630 58 38 27 20 170 78 28 100 15 From these results, we can conclude that Surfactant T7 is less sensitive to gelation than T5, and that T9 is less sensitive to gelation than Tl2; moreover, the mixture of T7 and T9 (T8) does not gel, and its viscosity does not exceed 225 mPa.s.

~ T5 and T12 do not form the same gel structure.

Although we do not wish to be linked to any particular theory, we suppose that these results can be explained by the following hypothesis: For T5: with only 5 EO, the hydrodynamic volume of the EO chain is almost the same as the hydrodynamic volume of the fatty chain. Surfactant molecules can therefore organize themselves to form a lamellar structure.

30 For T12: with 12 EO, the hydrodynamic volume of the EO chain is greater than that of the fatty chain. When the molecules try to organize themselves together, an interfacial curvature appears and sticks are obtained. The superstructure is then hexagonal; with a longer OE chain or with greater hydration, the interfacial curvature can be such that one ob- '*. 20 holds real spheres, and the lowest energy arrangement is a face-centered cubic lattice.

* From T5 to T7 (and T8), the interfacial curvature increases and the energy of the lamellar structure - 05 increases. As the lamellar structure loses its stability, its melting temperature decreases.

From T12 to T9 (and T8), the interfacial curvature decreases and the energy of the hexagonal structure increases (the rods become larger and larger), As there is loss of stability, the melting temperature of the structure also decreases.

Surfactant T8 seems to be at the critical point at which the lamellar structure is destabilized, that is to say that the hexagonal structure is not yet sufficiently stable and no gel is obtained during dilution. In fact, a 50% solution of T8 finally gels after two days, but the formation of the superstructure is delayed enough to allow easy dispersibility in water.

The effects of molecular weight on the physical properties of non-ionic surfactants were also considered. Surfactant T8 (1: 1 mixture of T7 and T9) represents a good compromise between the lipophilic chain (Cl3) and the hydrophilic chain (OEg), although the drop point and the maximum viscosity at dilution at 25 ° C. are still high.

The equivalent compromise of OE for the 0oph0 and Cg lipophilic chains was also determined using the Dobanol 91-x series from Shell Chemical Co., which are ethoxylated derivatives of fatty alcohols in = C9-Cll (m yenne : c10) 'and the Alfonic 610-y series from

Conoco which are ethoxylated derivatives of Cg to C10 fatty alcohols (average Cg); x and y represent the percentage by weight of OE.

The following table indicates the · physical characteristics of the Alfonic 610-y and Dobanol series * * · 4 * 21 91-x: ψ

Active surfing no Number of Œ Point of Point from maximum ^ to. the ionic (medium) cloudy drop dilution at 25 ° C

05 (° C) (° C) (mPa.s)

Alfonic 610-50R 3 -15 Gel (60%)

Alfonic 610-60 4.4 -4 41 36 (60%)

Dobanol 91-5 5 -3 33 Gel (70%) 10 Dobanol 91-5T 6 +2 55 126 (50%)

Dobanol 91-8 8 +6 81 Gel (50%)

Dobanol 91-5 and Dobanol 91-8 are commercially available products; Headed Dobanol 91-5 (T) is a laboratory scale product: Dobanol 91-5 from which free alcohol has been removed. When the lower ethoxylation components are also removed, the average number of EOs is 6.

Dobanol 91-5T provides the best v results.

20 lipophilic chain C ^ q, because it does not gel at c 25 ° C. The cloud point in 1% solution (55 ° C) is higher than that of Surfactant T8 (48 ° C). This is probably due to the lower molecular weight, since the entropy of the mixture is greater. Alfonic 25 610-60 provides the best results from the Cg lipophilic chain series.

A summary of the best EO contents for each length of lipophilic chain tested is given in the following table: 30

Active surfing no Ato-Nanbre Point Point of ^ max. at ionic mes of car- of OE drop cloudy dilute bone (° C) (solution tion (%) at

at 1%) 25 ° C

35__ÇC) _ (mPa.s)

Surfactant T8 13 8 +2 48 223 (50%)

Dobanol 91-5T 10 6 +2 55 126 (50%)

Alfonic 610-60 8 4.4-4 41 36 (60%)

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u «« t '22 From these results, we can draw the following conclusions:

Drop Points: As the molecular weight of the nonionic surfactant decreases, its 05 drop point also decreases. The relatively high dropping point of Dobanol 9I-5T can be explained by the higher polydispersity. This is also noted for T8a and T8b, that is to say that the polydispersity of the chains increases the drop point.

Cloud points: theoretically, as the number of molecules increases (if the molecular weight decreases), the entropy of the mixture is greater, so that the cloud point increases as the molecular weight decreases. This is actually the case with the Surfactant T8 at Donanol 91-5T, but this has not been confirmed by Alfonic 610-60.

It is assumed, in this case, that the polydispersity of the lipophilic hydrocarbon chain is responsible λ 20 for the cloud point which is too low compared to the theory. The relatively large amount of C ^ -OE present reduces the solubility.

Maximum viscosity at dilution at 25 ° C: none of these nonionic surfactants gels 25 to 25 ° C when diluted with water. The maximum viscosity abruptly decreases with molecular weight. As the molecular weight of the nonionic superfactives decreases, the hydrogen bridges become less efficient. Unfortunately, the non-ionic surfactants of too low molecular weight are not suitable for washing clothes: their critical micelle concentration (CMC) is too high, and this would be obtained under conditions. laundering practices a true solution, having only a limited detergent power.

With this information, the Applicant continued its research on the effects

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9 * \ 23 exerted by low molecular weight amphiphilic compounds on the rheological properties of liquid nonionic detergent cleaning compositions. These investigations have revealed that although it is possible to lower the drop point of the composition and achieve some degree of gelation inhibition using a short chain hydrocarbon, e.g., about Cg, with a substitution of short-chain ethylene oxide, for example about 4 moles, as an amphiphilic additive, such as Alfonic 6X0-60, these additives do not greatly contribute to the overall action of cleaning the laundry and do not provide satisfactory overall viscosity setting under all normal conditions of use.

The present invention is, therefore, based, at least in part, on the discovery that low molecular weight amphiphilic compounds, which can be considered analogous, by their chemical structure, to non-ionic surfactants of the ethoxylated and / or propoxylated fatty alcohol type, but having short lengths of hydrocarbon chain (C 1 -C 4) and a low content of alkylene oxide, that is to say oxide of ethylene and / or propylene oxide (about 1 to 4 EO / OP units per molecule), act effectively as viscosity adjusting and gelling inhibiting agents for liquid nonionic surfactants of cleaning.

The amphiphilic compounds regulating the viscosity and inhibiting gelation used in the present invention can be represented by the following general formula: (

P

* 35 I

RO (CHCH.O) H 2 n in which R is a C ^ -Cg alkyl group, 24 * \ 5 * preferably in C ^, in particular in C2 t C4 / and better still in C ^, R ' is H or CH3, preferably H, and n is a number of about 1 to 4, preferably 2 to 4 on average.

Preferred examples of suitable amphiphilic compounds include the ethylene glycol monoethyl ether (C2H5-0-CH2CH20H), and the diethylene glycol monobutyl ether (C ^ Hg-O- (CH2CH20) 2H). The monoethyl ether of diethylene glycol is particularly preferred and, as will be seen later, is remarkably effective in controlling viscosity.

Although the amphiphilic compound, in particular the monobutyl ether of diethylene glycol, may be the only additive controlling the viscosity and inhibiting gelation in the compositions of the invention, it is possible to further improve the rheological properties of the anhydrous liquid compositions of nonionic surfactants by incorporating into the composition a small amount of a nonionic surfactant-W 20 which has been modified to transform one of its free hydroxyl groups into a unit having a free carboxyl group, for example an ester partial of a nonionic surfactant and a polycarboxylic acid and / or an acidic organic phosphorus compound having an acidic POH group, such as a partial ester of phosphorous acid and an alkanol.

As described in French patent application No. 85 05 319, filed on April 9, 1985, by the Applicant, nonionic surfactants modified by a free carboxyl group, which can roughly be characterized as polyether carboxylic acids. , act to lower the temperature at which the liquid nonionic surfactant forms a gel with water. The acidic polyether can also decrease the flow limit of such dispersions, by promoting their distributability, without corresponding decrease in their stability against a deposit. Suitable polyether carboxylic acids contain a group of formula: -K> CH0-CH0) - -fCH-CH0) - -Y-Z-COOH, in which z z p | z q

05 CH

2 ^ 3 R is hydrogen or methyl, Y is oxygen or sulfur, Z is an organic bond, p is a positive number:; from about 3 to about 50, and q is zero or is a positive number up to 10. Special examples include the Plurafac RA30 hemi-ester with succinic anhydride, Dobanol 25-7 hemi-ester with succinic anhydride, the hemi-ester of Dobanol 91-5 with succinic anhydride, etc. In place of succinic acid anhydride, other polycarboxylic acids or anhydrides can be used, for example maleic acid, maleic anhydride, glutaric acid, malonic acid, succinic acid , phthalic acid, phthalic anhydride, '• ί 20 citric acid, etc. In addition, one can use

other bonds such as ether, thioether or urethane bonds, formed by conventional reactions. For example, to form an ether bond, the nonionic surfactant can be treated with a strong base (to transform its OH group into an ONa group for example), then react it with a halocarboxylic acid such as chloracetic acid. or chloropropionic acid or the corresponding brominated compound. Thus, the resulting carbo-xylic acid may have the formula R-Y- ZCOOH

where R is the residue of a nonionic surfactant (after elimination of a terminal OH), Y is oxygen or sulfur and Z represents an organic bond such as a hydrocarbon group, having for example 1 to 10 35 carbon atoms, which can be linked to the oxygen (or sulfur) of the formula directly or by means of an intermediate bond such as an oxygen bond 26, for example a 0 0 * "or" bond, etc. .

* -C- -C-NH- 05 Polyether carbaxylic acid can be produced from a polyether which is not a nonionic surfactant .; for example it can be prepared by reaction with a polyalkoxylated compound such as polyethylene glycol or a monoester or monoether thereof, which does not have the long alkyl chain characteristic of nonionic surfactants. Thus, R can have the formula: R1 15 1 R1 (OCH-CEL ·) -2 n in which R is hydrogen or methyl group, R1 is an alkyl or alkylphenyl group or another? 20 chain termination group and "n" is at least 3, for example 5 to 25. When the alkyl group of R "* · is a higher alkyl group, R is a residue of a nonionic surfactant. indicated above, R1 may, on the contrary, be hydrogen or an alkyl group (for example methyl, ethyl, propyl, butyl), or a lower acyl group (for example acetyl, etc.). , if present in the detergent composition, is preferably added in the dissolved state in the nonionic surfactant.

Another useful class of additional antifreeze agents is the C 1-6 alkyl- or alkenyl-dicarboxylic anhydrides such as, for example, octenylsuccinic anhydride, octenylmaleic anhydride, dodecylsuccini anhydride -that, etc. These compounds can be used with anti-gelling agents of the polyether-carbo- »* * \ xylic acid type or as a partial or total replacement for these agents.

As described in French patent application 85.04.831, filed on March 29, 1985 by the Applicant, the acidic organic phosphorus compound having an acidic POH group can increase the stability of the detergency builder suspension, in particular: polyphosphate type detergency builders in non-aqueous liquid nonionic surfactant.

The organic phosphorus acid compound can, for example, be a partial ester of phosphoric acid and an alcohol such as an alkanol which has a lipophilic character, for example having more than 5 15 carbon atoms, for example 8 to 20 carbon atoms.

A particular example is a partial ester of phosphoric acid and a C16 * C ^ alkanol (Empiphos 5632 from Marchon); it consists of about 35% monoester and 65% diester.

The incorporation of very small quantities, for example approximately 0.05 to 0.3% relative to the weight of the composition, of the organic phosphorus acid compound makes the suspension appreciably more stable with respect to rest while leaving it suitable for pouring, probably due to the increase in the flow limit of the suspension, but decreases its plastic viscosity. It is believed that the use of the phosphorus acid compound can result in the formation of a high energy physical bond between the -POH portion of the molecule and the surfaces of the mineral polyphosphate detergency builder such that these surfaces ac-. which become organic and become more compatible with the nonionic surfactant.

The organic phosphorus acid compound can be selected from a wide variety of materials, in addition to the partial esters of phosphorus-guiding acid and alkanols mentioned above. Thus, a partial ester of phosphoric or phosphorous acid can be used with a mono- or di-alcohol such as hexylene glycol, ethylene glycol, di- or tri-ethylene glycol or polyethylene- higher glycol, polypropylene glycol, glycerol, sorbitol, mono- or diglycerides of fatty acids, etc., in which one, two or more of the alcoholic groups of the molecule OH can be esterified with the phosphorous acid. The alcohol can be a nonionic surfactant such as an ethoxylated or ethoxylated-propoxylated higher alkanol, a (higher alkyl) phenol, or a (higher alkyl) amide. The -POH group need not necessarily be linked to the organic portion of the molecule by an ester bond; on the contrary, it can be directly linked to carbon (as in a phosphonic acid such as a polystyrene in which part of the aromatic rings carry phosphonic acid or phosphinic acid groups; or an alkylphosphonic acid such as propyl- or laurylphosphonique) or it can be linked to carbon by another intermediate bond (for example bonds passing through atoms 0, S or N). Preferably, the carbon: phosphorus atomic ratio in the organic phosphorus compound is at least about 3: 1, for example 5: 1, 10: 1, 20: 1, 30: 1.or 40: 1.

The detergent composition of the invention may also include, and preferably comprises, water-soluble builder adjuvant salts. Representative examples of suitable detergency builders include those described in US Pat. Nos. 4,316,812, No. 4,264,466 and No. 3,630,929. Water soluble mineral alkaline detergency builder salts which can be used alone with the detergent compound or mixed with other detergency builders are carbonates, borates, phosphates, polyphosphates, bicarbonates and alkali metal silicates. (The ammonium and substituted ammonium salts can also be used). Particular examples of such salts are sodium tripolyphosphate 05, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate / sodium bicarbonate, potassium tripoly phosphate, sodium hexametaphosphate, sodium sesguicarbonate, sodium mono- and di-orthophosphates and potassium bicarbonate. Sodium tripolyphosphate (TPP) is particularly preferred. The alkali metal silicates are useful detergency builder salts which also act to make the composition anti-corrosive to parts of the washing machine. Sodium silicates having Na ^ O / SiO ^ ratios of 1.6 / 1 to 1 / 3.2, in particular about 1/2 to 1 / 2.8 are preferable. It is also possible to use potassium silicates having the same ratios.

Another class of detergency builders useful here are the water-insoluble aluminosilicates, both crystalline and amorphous. Various crystalline zeolites (i.e., aluminosilicates) are described in British Patent No. 1,504,168, US Patent No. 4,409,136 and Canadian Patents No. 1,072,835 and No. 1,087,477. An example of amorphous zeolites useful here can be found in Belgian Patent No. 835,351. The zeolites are generally represented by the formula: (M20) x. (Al203) y. ( si02) z.WH20 in which x is equal to 1, y is 0.8 to 1.2, preferably equal to 1, z is 1.5 to 3.5 or more, and preferably 2 to 3 , w is 0 to 9, preferably 2.5 to 6 and H is preferably sodium. A typical zeolite is type A or of similar structure, type 4A being particularly preferable. Preferred alumi-nosilicates have calcium ion exchange powers of about 200 milliequivalents per 05 gram or more, for example 400 meq / g.

Other materials such as clays, particularly water-insoluble types, may be other additives useful in the compositions of the present invention. Bentonite is particularly useful. This material is mainly montmorillonite which is a hydrated aluminum silicate in which approximately 1/6 of the aluminum atoms can be replaced by magnesium atoms and with which various quantities of hydrogen, sodium, potassium, calcium, etc. can be weakly combined. Bentonite, in its more purified form (i.e. free of sandstone, sand, etc.) suitable for detergents, invariably contains at least 50% montmorillonite and thus its cation exchange power is at least about 50 to 75 meq. per 100 g of bentinite. Particularly preferred bentonites are bentonites from Wyoming or the western USA which have been sold under the designations of Thixo-jels 1, 2, 3 and 4 by Georgia 25 Kaolin Co. These bentonites are known to soften textile materials, as described in the British patents Nw 401 413 and N9 461 221.

Examples of sequestering alkaline organic detergency builder salts which may be used alone with the detergent or in admixture with other organic and inorganic detergency builders are the alkali metal, ammonium or substituted ammonium aminopolycarhoxylates, for example sodium and potassium tetylene diaminetetraacetate (EDTA), sodium and potassium nitrilotriacetates (NTA) and triethanolammonium N- (2-hydroxyethyl) nitrilodiacetate. The mixed salts of these pèly-. “31 carboxylates are also suitable.

Other suitable organic type detergency builders include carboxymethylsuc-cinates, tartronates and glycollates. The polyacetal-05 carboxylates are of particular interest. The po-lyacetal-carboxylates and their use in detergent compositions are described in US Pat. Nos. 4,144,226; Nos. 4,315,092 and No. 4,146,495. Other patents dealing with similar detergency XO builders include the following US patents: Νς 4,141,676? N ° 4 169 934; N ° 4 201 858; N ° 4 204 852; N ° 4 224 420; Nu 4 225 685; N ° 4 226 960? N ° 4 233 422; Nv 4 233 423? N ° 4 302 564; and Np 4 303 777. The applications for European bre-15 vet N ° 0015024; N "0021491 and NQ 0063399 are also relevant.

Since the compositions of the present invention are generally highly concentrated. and therefore can be used in relatively low doses, it is advantageous to supplement the action of any detergency builder phosphate (eg sodium tripolyphosphate) with an auxiliary detergency builder such as a carboxylic acid polymer having a high calcium binding power in order to inhibit incrustation which could otherwise be caused by the formation of an insoluble calcium phosphate. Such auxiliary detergency builders are also well known in the art.

Various other additives or adjuvants for detergents may be present in the detergent product to give it other desirable properties, functional or aesthetic. Thus, minor amounts of soil suspending or anti-redeposition agents can be incorporated into the formulation, for example polyvinyl alcohol, fatty amides, carboxymethyl- 32 * "I, * cellulose sodium, hydroxypropyl methylcellulose? * ^ Optical brightening agents, for example cotton, polyamide and polyester brightening agents, for example stilbene, triazole and benzidine-sulfone compositions, in particular triazinyl-stil-bene substituted sulfone, sulfonated naphthotriazole-stilbene, benzidene sulfone, etc., those which are preferred being the combinations of stilbene and triazole.

X0 Brightening agents such as ultramarine blue can also be used; enzymes, preferably proteolytic enzymes such as subtilisin, bromelain, papain, trypsin and pepsin, as well as amylase-like enzymes, X5 lipase-like enzymes, and mixtures thereof; bactericides, for example tetrachlorosalicylani-lide, hexachlorophene; fungicides; dyes; pigments (dispersible in water); preservatives; ultraviolet absorbers; anti-yellowing agents such as sodium carboxymethylcellulose, a C12 to C22 alkyl alcohol complex and ae (C1 to C12 alkyl) sulfate; pH modifiers and pH buffers; color preservatives, fragrance, and defoamers or foam suppressants, for example silicone compounds.

Bleaches are classified broadly, for convenience, as chlorinated bleaches and oxygenated bleaches. The chlorinated bleaches are represented by sodium hypchlorite (NaOCL), potassium dichloroisocyanurate (59% available chlorine) and trichloroisocyanuric acid (85% available chlorine). Oxygenated bleaches are preferable and are represented by per-compounds which release hydrogen peroxide in solution, i.e. compounds containing hydrogen peroxide or mineral perhydrates, when dissolved, release the hydrogen peroxide which they contain in their crystal lattice. Preferred examples include sodium and potassium perborates, percarbonates and per-05 phosphates, and potassium monoper sulfate. Perborates, in particular sodium perborate monohydrate, are particularly preferred.

Hydrogen peroxide and the precursors which release it in solution are good oxidizing agents for removing certain stains from clothing, in particular stains from wine, tea, coffee, cocoa, fruit, etc.

It has been found that in general hydrogen peroxide and its precursors whiten quickly and more effectively at a relatively high temperature, for example about 80 "C to 100" C. However, these compounds tend to decompose and release gaseous oxygen at lower temperatures. The release of gaseous oxygen, which is not involved in the oxidation of dyed articles, unnecessarily consumes a measurable amount of hydrogen peroxide or the precursors releasing it, all of which are expensive products. In addition, it has been found that various stains on clothing, etc., greatly accelerate the decomposition of hydrogen peroxide to gaseous oxygen during washing at room temperature.

In general, washing clothes, whether by machine, by hand, or in washing machines or tubs, is accomplished by dissolving a bleach or detergent composition (containing perborate, for example) in water. cold or lukewarm water, adding to the solution thus formed the dirty clothes (from which some of the stains have often already been removed by soaking or pre-washing), and by heating, often just at boiling point.

However, it has been found that, by a phenol - 34 which leads similar to that previously mentioned, all or part of the perborate decomposes during heating and more particularly during the rise in temperature, that is to say say that 05 perborate breaks down before the actual effective temperature is reached.

It is assumed that this rapid decomposition of hydrogen peroxide, perborate, or other precursors of hydrogen peroxide, to gaseous oxygen at low temperatures is due to the extremely powerful catalytic action of certain enzymes which are always present in stains , which are found on washing materials, and especially dirty clothes, such as shirts, these enzymes coming from secretions or being of bacterial origin.

Hydroperoxidases are a particularly active group of enzymes in this regard, in particular catalase, which is well known as a very effective catalyst for the decomposition of hydrogen peroxy-20 into gaseous oxygen. These enzymatic substances, whether called "redox" or otherwise, are nevertheless uniformly characterized by the pronounced tendency which they exhibit to cause decomposition of the bleaching peroxide, the decomposing products thus released being made up of species ineffective for bleaching.

In order to take advantage of the effective detergents at low temperatures and the low temperature washing cycles currently in use for temperature sensitive fabrics, the peroxygen compound is preferably used in admixture with an activator. Suitable activators which can lower the effective operating temperature of the peroxide bleach to about 40 ° C or less are described, for example, in US Pat. No. 4,264,466 or in column 1 of US Pat. E. ü. A. No. 4,430,244. Polyacylated compounds are the preferred activators; among them, compounds such as tetraacetyl-ethylene-diamine (TAED) and pentaacetyl-glucose are particularly appreciated. Other useful activators include, for example, acetylsalicylic acid and its salts, ethylidene aceto-benzoate (ABE) and its salts, ethylidene aceto-carboxylate and its salts, anhydride al-kyl- and alcênylsuccinique, tétraacétylglycourile (TAGü) and their derivatives. See also US Patents 10 ü. A. No. 4 111 826, No. 4 422 950 and No. 3 661 789 for other classes of activators useful here.

The bleach activator generally reacts with the peroxygen compound to form a bleaching peroxyacid in the wash water. It is preferable to include a sequestering agent with high complexing power in order to inhibit any undesirable reaction between this peroxyacid and the hydrogen peroxide in the washing solution in the presence of metal ions. Preferred sequestering agents are capable of forming a complex with Cu2 + ions, such that the stability constant (pK) of the complexation is equal to or greater than 6, at 25 ° C, in water at a force ionic content of 0.1 mole / liter, pK being conventionally defined by the formula: 25 pK = -log K where K represents the equilibrium constant. Thus, for example, the pK values for the complexing of the copper ion with NTA and EDTA under the conditions fixed are 12.7 and 18.8, respectively. Preferred sequestering agents include, for example, in addition to those mentioned above, diethylenene triamine pentaacetic acid (ADEPT); diethylenene triamine pentamethylene phosphonic acid (DTPMP); and ethylene diamine-tetramethylene phosphonic acid (AEDITEMP).

However, even in the presence of bleach activators, and even at temperatures as low as room temperature, there is a decomposition of Persian! in the presence of stained clothing because the reaction rate between the bleaching agent and the activator is slower than the rate of decomposition of hydrogen peroxide 05 by catalase.

In order to avoid loss of bleach resulting from decomposition by an enzyme, the compositions of the present invention preferably additionally contain an effective amount of a compound capable of inhibiting this decomposition of the agent whitening caused by an enzyme. Suitable inhibitor compounds are described in the U.S. patent. A. No. 3,606,990.

As an inhibitor compound, hydroxylamine sulfate and other hydroxylamine hydroxylamine salts including, for example, hydrochloride, hydrobromide, etc., are of particular interest and importance. It has now been found that the hydroxylamine salts, in particular the sulphate, effectively inhibit the harmful effect of the catalase itself - when they are present in the composition in very limited quantities, for example less than 0.5 %, such as from 0.01 to 0.4%, preferably from 0.04 to 0.2%, and more preferably about 0.1%, based on the weight of the total composition.

In addition, the hydroxylamine acting as an inhibitor is very stable in the composition: less than 20% loss after aging for two months at 43 ° C. The hydroxylamine salts are very quickly dissolved in water and can therefore react with the catalase before the dissolution of the perborate or other bleaching peroxide. Another advantage of the hydroxylamine salts is that they are quickly destroyed in the wash liquor and therefore no nitrosamine derivatives are detected.

When the bleaching system is activated by one of the bleach activators, for example TAED, the activator is used more effectively, and therefore, the appropriate bleach-to-bleach / activator ratios bleached-n, ment can be maintained at values much closer to the weights of stoichiometric equivalent or in a small molar excess only of the bleaching agent.

The composition may also contain an insoluble mineral thickener or dispersant with a very large specific surface, for example finely divided silica of very small particle size (for example with a diameter of 5-100 nanometers, such as that sold under the name Aerosil) or the other very bulky mineral support materials described in US Pat. No. 3,630,929, in proportions of 0.1-10%, for example 1-5%. It is preferable, however, that the compositions which form peroxyacids in the washing bath (for example the compositions containing a peroxygen compound and an activator for this compound) are substantially free of such compounds and other silicates; it has been found, for example, that silica and silicates promote the undesirable decomposition of the peroxyacid.

In a preferred form 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 about 10 micrometers * for example at an average particle size of 2 to 10 micrometers or even less (for example 1 micrometer). The compositions v whose dispersed particles have such a small dimension have better stability against separation or deposit during storage.

In the grinding operation, it is preferable that the proportion of solid ingredients is sufficiently large (for example at least about 40%, no- ► *.

38 approximately 50%), so that the solid particles are in contact with each other and? are not substantially isolated from each of the very μ by the nonionic surfactant. ’05 grinders using grinding balls: (ball mills) or similar mobile grinding elements have given very good results. Thus, one can use a laboratory attrition mill operating by loads, having XO balls grinding in steatit with a diameter of 8 mm. For work on a larger scale, one can use a continuously operating mill in which there are balls with a diameter of X or 1.5 mm working in a very small interval between a stator and a rotor 15 operating at relatively high speed (eg CoBall)? when using such a grinder, it is advantageous to first pass the mixture of non-ionic surfactant and solid matter through a grinder which does not perform such a fine grinding (for example a grinder col-loïds) in order to reduce the particle size to less than X00 micrometers (for example to about 40 micrometers) before the grinding stage to an average particle diameter of less than about 10 mi-25 crometers in the ball mill operating continuously.

In the preferred liquid detergent compositions for heavy laundering according to the invention, representative examples of proportions (based on the total composition, unless otherwise specified) of the ingredients are as follows:

Suspended detergency builder: in the range of about 10 to 60%, for example about 20 to 50%, especially about 25 to 40%; 35 Nonionic surfactant constituting the liquid phase and dissolved amphiphilic compound regulating the viscosity and inhibiting gelation: in the range 39 of approximately 30 to 70%, for example approximately 40 to 60%; this phase may also contain minor amounts of a diluent such as a glycol, for example polyethylene glycol (for example PEG 400), hexylene glycol, etc., for example up to 10%, preferably up to 5%, for example 0.5 to 2%. The weight ratio of the nonionic surfactant to the amphiphilic compound is from about 100: 1 to 1: 1, preferably from about 50: 1 to about 2: 1, and more preferably from about 25: 1 to 25 about 3: 1.

Polyether-carboxylic acid as gelling inhibitor compound: in a proportion capable of providing approximately 0.5 to 10 parts (for example approximately 1 to 6 parts, in particular approximately 2 to 5 parts) 15 of -COQH (molecular weight 45) per 100 parts of a mixture of such an acidic compound and a nonionic surfactant. In general, the amount of polyether carboxylic acid is approximately 0.01 to 1 part per part of nonionic surfactant, for example approximately 0.05 to 0.6 parts, in particular approximately 0 , 2 to 0.5 part;

Acid compound of the organic phosphoric acid type, as an anti-depositing agent: up to 5%, for example in the range of 0.01 to 5%, especially around 0.05 to 2%, for example around 0.1 at 1%.

Suitable ranges of other optional detergent additives are: enzymes - 0 to 2%, especially 0.7 to 1.3-%; corrosion inhibitors - about 0 to 40%, and preferably 5 to 30%? anti-foaming agents and foam suppressants - 0 to 15%, preferably 0 to 5%, for example 0.1 to 3%; thickener and dispersants -0 to 15%, for example 0.1 to 10%, preferably 1 to 5%; soil suspending or anti-deposition agents and anti-yellowing agents - 0 35 to 10%, preferably 0.5 to 5%; colorants, perfumes, brighteners and brighteners - total weight: 0% to about 2%, and preferably 0% to about 1%; 40 pH modifiers and pH buffers - 0 to 5%, preferably 0 to 2%? bleaching agent - 0% to about 40%, and preferably 0% to about 25%, for example 2 to 20%; inhibiting compound intended to inhibit the breakdown of the bleaching agent by enzymes - up to approximately 0.5%, preferably 0.01 to 0.4 or 0.5%, better still 0.04 to 0, 2%? bleach stabilizers and bleach activators - 0 to about 15%, preferably 0 to 10%, for example 0.1 to 8%? sequestering agent with high complexing power - in a range of at most about 5%, preferably 0.25 to 2%. The additives will be chosen so that they are compatible with the main constituents of the detergent composition.

All proportions and percentages are expressed by weight, unless otherwise specified.

It goes without saying that the invention is not limited to the above detailed description and that various variants can be made to it without departing from its scope.

In order to demonstrate the effects of the agents regulating the viscosity and inhibiting gelation, various of its compositions were prepared using the active surfactant T8 described above (C ^ g, OEg) (50/50 mixture by weight of surfactant T7 and Surfactant T9) as a non-aqueous liquid non-ionic surfactant cleaning agent. Formulations containing 5%, 10%, 15% 30 or 20% of amphiphilic additive were prepared and were tested at 5QC, 10 ° C, 15 ° C, 20 ° C and 25 ° C for different dilutions with water, that is to say at total concentrations of 100%, 83%, 67%, 50% and 33% v in non-ionic T8 surfactant and additive, that is to say 35 after dilution with water. The additives tested were Alfonic 610-60 (Cg-OE ^ ^), monoethyl ether of ethylene glycol ^ -OEj) and monobutyl ether ", 41 of diethylene glycol (C ^ -OE ^. results of the behavior of the viscosity at the dilution of each composition tested at each temperature are illus-- very on the graphs of Figures 1 to 3.

> - 05 For Alfonic 610-60, an addition of 5% was sufficient to inhibit gelation at 25 ° C; however, on the plot of the viscosity as a function of the concentration of the nonionic surfactant, an accentuated maximum of viscosity was observed at a concentration of approximately 67% and a shoulder at a concentration of approximately 55% to 35 % of non-ionic surfactant. At 5QC, an addition of 15% was necessary to avoid the formation of a gel. Viscosity decreased to a minimum at a concentration of non-ionic sur-factif of about 83% at all rates

of additive addition at 5 ° C., while at higher temperatures, minimum viscosities were observed for the undiluted formulations, that is to say at concentrations of 100% of nonionic surfactant. AT

£ 20 for each temperature and for each tested concentration of additive (with the exception of the 20% additive at 25 ° C), there is a relatively sharp peak in viscosity which is found at a concentration of 75 to 50 % of nonionic surfactant (that is to say a dilution of 25 to 25 50%).

For the ethylene glycol monoethyl ether, 5% of additive could inhibit gel formation even at 5 ° C. However, sharp peaks and / or viscosity maxima were again observed at each temperature and at each concentration of additive, although the effects were not as pronounced as for Alfonic 610-60, and for some applications, maximum viscosities, particularly at the highest additive concentrations and / or at the highest temperatures, may be acceptable for commercial application.

On the other hand, no increased peaks in viscosity were observed for the monobutyl ether of di-ethylene glycol at any temperature down to 5 ° C. at the rate of 20% of additive. lower additive levels v, the viscosity peaks and the viscosity values at practically all dilutions (concentrations of non-ionic surfactants) were lower than those for the additive C8 ~ OE4.4 or C2 ~ 0E1 *

The following table is representative of the 10 results obtained for the various concentrations of additives, dilutions, and temperatures, but these results are given for 20% of additive and a temperature of 5 ° C.

Viscosity at Point of 15 Compositions_5- ° C (Pa.s) _ drip (0C) _ without water 50% water

Surfactant T8 only 1.140 1.240 5 80% of Surfactant ς 20 T8 + 20% A 0.086 0.401 -10 ι80% of Surfactant T8 + 20% B 0.195 0.218 -2 80% of Surfactant T8 + 20% C 0.690 0.936 3 25 A = monoethyl ether of ethylene glycol, B = monobutyl ether of diethylene glycol, C = Alfonic 610-60 (Cg-OE ^ 4).

30 EXAMPLE 1

A reinforced non-aqueous nonionic liquid cleaning composition is prepared for washing heavy iron, having the following formula: * 43

Ingredients% by weight

Surfactant T7 17.0

Surfactant T8 17.0 '05 Dohanol 91-5 Acid1 5.0

Diethylene glycol monobutyl ether 10.0

Dequest 2066 ^ 1.0 TPP NW (sodium tripolyphosphate) 29.0925

Sokolan CP53 (calcium sequestering agent) 4.0 10 Perborate H ^ O (sodium perborate monohydrate 9.0 TAED (tetraacethylethylene diamine 4.5

Emphiphos 5632 ^ 0.3

Stilbene 4 (optical brightening agent) 0.5 15 Esperase (proteolytic enzyme) 1.0

Duet 787 ^ 0.6

Relatin DM 4050® (anti-redeposition agent) 1.0 w Bleu Foulan Sandolane (colorant) 0.0075 / 20 _

It the esterification product of Dobanol 91-5 (a fatty alcohol C 1 -C 4 ethoxylated with 5 moles of ethylene oxide) with succinic anhydride - the hemi-ester, 2) diethylene acid - triamine-pentamethylene-phosphoric, sodium salt, 3) a copolymer of approximately equimolar amounts of methacrylic acid and maleic anhydride, completely neutralized to form its sodium salt, 4) partial ester of phosphoric acid and a C.,. to C .. alkanol. ~ 16 χ8) about 1/3 of monoester and 2/3 of dies ter),] 5) perfume, 6) mixture of sodium carboxymethylcellulose and 35 of hydroxymethylcellulose.

44

This composition is a liquid, non-gelling, reinforced, fluid, stable nonionic cleaning composition in which the polyphosphate used “as a detergency builder is in stable suspension 05 in the liquid nonionic surfactant phase, EXAMPLE 2

In the same way as in Example 1, a nonionic cleaning composition li ~ 10 quide nonaqueous reinforced for heavy washes is prepared, containing an enzyme inhibitor:

Ingredients% by weight 15 Plurafac RA 30 37.5

Diethylene glycol monobutyl ether 10.0

Octenylsuccinic anhydride 2.0 TPP NW 28.4 w Sokolan CP5 4.0 - 20 Dequest 2066 1.0

Perborate HjO 9.0 TAED 4.5

0.1 hydroxylamine sulfate

Emphiphos 5632 0.3 25 ATS-X (optical brightening agent) 0.2

Esperas 1.0

Perfume 0.6

Relatin DM 4050 1.0

Ti02 0.4 30

This composition has the same characteristics. ques advantageous than the composition of Example 1, i and, moreover, it provides a better bleaching effect.

Claims (14)

45 1 A- *, 46 aqueous. 1. Liquid detergent and whitening composition for laundry, characterized in that it comprises a liquid nonionic surfactant, a water-soluble mineral peroxide salt as a bleaching agent, and an effective amount of a compound which inhibits the decomposition caused by an enzyme of the peroxygen bleaching salt. 2. Composition according to claim 1, 10 characterized in that the bleaching agent is a perborate, percarbonate, perphosphate or persulfate and the compound inhibiting the decomposition by an enzyme of the bleaching agent is one. hydroxylamine salt, 3. Composition according to claim 2, characterized in that the hydroxylamine salt is hydroxylamine sulfate, hydroxylamine hydrochloride or hydroxylamine hydrobromide. 4. Composition according to claim 2, characterized in that the amount of hydroxylamine salt is from approximately 0.01 to approximately 0.5 I by weight of the composition. 5. Composition according to claim 2, characterized in that the amount of hydroxylamine salt is approximately 0.01 to 0.4% by weight of the composition. 6. Composition according to claim 1, characterized in that it further comprises an activator of the bleaching agent which reacts with the bleaching agent in an aqueous washing bath to form a bleaching peroxyacid at a temperature d '' about 40 ° C or less. 7. Composition according to claim 6, characterized in that the activator of the bleaching agent is Ν, Ν, Ν ', N'-tetraacetyl-ethylene diamine. 8. Composition according to claim 1, characterized in that it is substantially non 9. A nonaqueous liquid detergent composition capable of washing and bleaching soiled fabrics at temperatures as low as about 40 ° C. or less, characterized in that it comprises a liquid nonionic surfactant, a mono ether ( (C 1 -C 4) alkyl of mono- or poly (C 1 -C 4 alkylene) a bleaching agent of the water-soluble mineral peroxide type, an activator of the bleaching agent to lower the temperature at which the bleaching agent releases hydrogen peroxide in aqueous solution, and about 0.01 to 0.4% by weight, based on the total composition, of a hydroxylamine salt capable of inhibiting the decomposition of the bleaching agent by an enzyme, said enzyme being present in soiled tissue. 10. Composition according to claim 9, characterized in that the bleaching agent comprises sodium perborate monohydrate, the activator * of the bleaching agent is N, N, Ν ', N' -te- M traacetyl-ethylene-diamine and the hydroxylamine salt is hydroxylamine sulfate or hydroxylamine hydrochloride and is present in a proportion of about 0.02 to 0.2%. 25 11- Composition according to claim 9, characterized in that it further comprises an adjuvant detergency salt suspended in the liquid nonionic surfactant. 12. Method for cleaning and bleaching soiled fabrics, characterized in that it consists in bringing the soiled fabrics in contact with the composition according to claim 1 in an aqueous washing bath. 13. Method for cleaning and bleaching soiled fabrics, characterized in that it consists in bringing the soiled fabrics in contact with the composition according to claim 9 in a washing bath *, 47 ′ A aqueous. 14. The method of claim 13, ^ characterized in that the aqueous washing bath is at a temperature of 40QC or less. ! v i