NL8600798A - LIQUID DETERGENT BLEACHING COMPOSITION. - Google Patents

Description

* i ^ λ »VO 8115

Liquid detergent bleaching composition.

The invention relates to liquid detergent compositions for laundry, in particular non-aqueous liquid detergent compositions, which are easily pourable and do not form a gel when added to water, as well as the use of these compositions for cleaning dirty fabrics.

Heavy duty liquid non-aqueous laundry detergent compositions are well known. For example, U.S. Pat. Nos. 4,316,812, 3,630,929, 4,264,466 and British Pat. Nos. 1,205,711, 1,270,040 and 1,600,981 are compositions of the type envisaged which contain a liquid nonionic surfactant contain material in which builder particles are dispersed.

Liquid detergents are often thought to be easier to use than dry powdered or granular products, and are therefore quite favored by consumers. They are easy to dose, dissolve quickly in the wash water, can be applied with concentrated solution or dispersion on dirty parts of garments to be washed, do not cause dust formation and usually take up less space. Furthermore, liquid detergents may contain materials which cannot be dried without undergoing a deterioration, which materials are often preferably used in the preparation of granular detergent products. Although they have many advantages over unitary or granular solid products, liquid detergents often exhibit certain inherent drawbacks which must be eliminated in order to make acceptable commercial detergent products. Some such products exhibit demixing on storage and others on cooling and are not readily redispersible. In some cases, the viscosity of the product changes, either becoming too thick to be poured or so thin as to appear watery. Some clear products become cloudy and others gel on standing.

An in-depth investigation was conducted into the theological behavior of non-ionic liquid surfactant systems 35 with and without granular material suspended therein.

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Particular attention has been paid to builder containing non-aqueous liquid laundry detergent compositions and the problems of gelation associated with nonionic surfactants, as well as settling of the suspended builder and other additives.

These phenomena affect, for example, the pourability, dispersibility and stability of the product.

The Theological behavior of the builder containing non-aqueous liquid laundry detergents is similar to the Theological behavior of paints, where the suspended builder-10 particles correspond to the inorganic pigment and the non-ionic liquid surfactant corresponds to the non- aqueous paint carrier. For convenience, the suspended particles, for example the builder, will sometimes be referred to as the "pigment" hereinafter.

It is known that one of the major problems with paints and builder-containing liquid laundry detergents is their physical stability. This problem arises from the fact that the specific gravity of the solid pigment particles is greater than that of the liquid phase. Therefore, in accordance with Stoke's law, the particles tend to sink. There are basically two ways to solve this settling problem: increasing the viscosity of the liquid phase and decreasing the particle size of the solid particles.

It is known, for example, that such settling suspensions can be stabilized by adding inorganic or organic thickening agents or dispersing materials, such as very large surface inorganic materials, for example finely divided silica, clay, and the like, organic thickening agents, such as the cellulose ethers, acrylic and acrylamide polymers, polyelectrolytes and the like. The increase in the viscosity of the suspension is, of course, limited by the condition that the liquid suspension must be easily pourable and flowable even at low temperature. Furthermore, these additives do not contribute to the cleaning effect of the composition.

Particle size reduction by grinding is more beneficial 35 and has two main consequences: Ό $ · Λ 1 1 -0 # * i -3- 1. The surface area of the pigment is increased, thereby wetting the particles by the non-aqueous carrier (liquid non-ionic surfactant) is improved proportionately.

2) The average distance between pigment particles is reduced, so that the interaction between the particles increases proportionally.

Each of these effects helps to increase the residual gel strength and the yield strength of the suspension, while at the same time significantly reducing the plastic viscosity.

The non-aqueous liquid suspension of the builder particles, such as particles of polyphosphate builders, in particular sodium tripolyphosphate (TPP), in nonionic surfactant, appear to behave rheologically substantially according to the Casson equation: 15.

i l \ \ σ * σ ° + η »γ where γ represents the shear, σ the shear stress, σ ° the yield stress and n» the “plastic viscosity” (apparent viscosity at infinite shear).

The shear stress is the minimum stress required to cause a plastic deformation (flow) of the suspension. If the suspension is considered to be a loose network of pigment particles, if the applied tension is lower than the yield stress, the suspension will behave as an elastic gel and no plastic flow will take place. However, if the yield stress is overcome, the network breaks at a number of points and the sample starts to flow, but with very high apparent viscosity. If the shear stress is much higher than the yield stress, the pigments are partially flocculated and the apparent viscosity drops. If the shear stress is much higher than the yield stress, the pigment particles are ultimately completely flocculated and the apparent viscosity is very low, as if no interaction between the particles is present.

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Therefore, the higher the yield stress of the slurry, the higher will be the apparent low shear viscosity and the better the physical stability of the product.

The non-aqueous liquid laundry detergents based on liquid non-ionic surfactants also have the drawback that the non-ionic surfactants exhibit a gelling tendency when added to cold water. This is a particularly important problem in the normal use of European automatic household washing machines, where the user places the detergent composition in a dosing unit (eg a dosing drawer) of the machine. During the operation of the machine, the detergent in the dosing unit is exposed to a stream of cold water, which transfers it to the main mass of the washing solution.

Especially during the winter months, when the detergent composition and the water supplied to the dosing unit are quite cold, the viscosity of the detergent increases markedly and a gel forms. As a result, the composition is not completely rinsed out of the dosing unit, so that after a number of washings, a build-up of composition residues is formed, which may have to be rinsed off with hot water.

The gel form can also cause problems when washing with cold water, as recommended for certain synthetic and delicate fabrics, or fabrics that can shrink in warm or hot water.

Partial solutions to the problem of gel formation in aqueous, substantially builder-free compositions have already been proposed, for example, dilution of the liquid nonionic material with certain viscosity-controlling solvents and gel inhibitors, such as low alkanols, for example ethanol (see U.S. Patent 3,953,380), alkali metal formates and adipates (see U.S. Patent 4,368,147), hexylene glycol, polyethylene glycol, and the like.

Furthermore, each of the two patents cited discloses the use of up to 2.5% of the C 1 -C 4 ether derivatives of 35 ^ 2 - <3 PO3 ^ and "for example ethylene glycol, in these aqueous liquid liquids. v? * -5- builder-free detergents in place of a portion of the lower alkanol, such as ethanol, as a viscosity controlling solvent. Reference may also be made in this regard to U.S. Patents 4,111,855 and 4,201,686. However, there is no mention or suggestion anywhere in these patents that these compounds, some of which are commercially available under the name Cellosolve, could effectively function as viscosity regulators and gel inhibitors for non-aqueous liquid non-ionic surface active compositions, in particular such compositions containing suspended builder salts, such as the polyphosphate compounds, and most particularly such compositions which do not rely on or require low alcohols as viscosity control agents.

Furthermore, British Patent 1,600,981 discloses that in non-aqueous nonionic detergent compositions containing builders suspended therein using certain builder dispersants, such as finely divided silica and / or polyether group containing compounds with molecular weights of at least 500, advantageous use can be made of mixtures of non-ionic surfactants, one of which acts as a surfactant and the other also acts as a surfactant, but also as a pour point depressant means of composition. Examples of the former material are fatty alcohols with 5-15 moles of ethylene oxide and / or propylene oxide per mole of 25 and examples of the latter compound are linear

Cg-Cg or branched Cg-C 2 fatty alcohols with 2-8 moles of ethylene oxide and / or propylene oxide per mole. Again, it is not stated that these compounds could control the viscosity and gelation of the non-aqueous liquid nonionic surfactant compositions for heavy purposes containing builder in the nonionic liquid surfactant in suspension, could occur.

It is known to modify the structure of nonionic surfactants to optimize their resistance to gelling on contact with water, especially cold water. For example, a particularly successful result is obtained by conversion of the terminal hydroxyl portion>.

-6- * »of the non-ionic molecule in an acid group. The advantages of introducing a carboxylic acid group at the end of the nonionic molecule are that it inhibits gelation upon dilution, decreases the pour point of the nonionic material and forms an anionic surfactant upon neutralization in the wash water . It is also known to optimize the structure of the non-ionic material to minimize gel formation, for example by control. . the chain length of the hydrophobic-lipophilic molecular moiety and the number of alkylene oxide (e.g., ethylene-oxide) units of the hydrophilic molecular moiety. For example, it has been found that a fatty alcohol ethoxylated with 8 moles of ethylene-oxide has only a limited tendency to gel. Nevertheless, further improvements are desired in the stability, viscosity control and gel inhibition of non-aqueous liquid detergent compositions.

It is therefore an object of the invention to provide non-aqueous liquid laundry detergents which do not gel upon contact with or upon addition to water, especially cold water.

A further object of the invention is to provide builder-containing non-aqueous liquid laundry detergent compositions which are stable in storage, are easily pourable and can be dispersed in cold, warm or hot water.

Another object of the invention is the preparation of many builder-containing laundry detergent compositions based on non-aqueous liquid non-ionic surfactants, which compositions are pourable at all temperatures and can be repeatedly dispersed from the metering unit of European automatic washing machines without pollution or blockage of the dosing unit, even during the winter months.

A specific object of the invention is to provide non-gelling, stable, low viscosity suspensions of tripolyphisophate builder containing non-aqueous liquid nonionic laundry detergent compositions containing a sufficient amount of a low molecular weight amphiphilic compound to the viscosity of the composition. in the absence of water and on contact with cold water.

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These and other objects of the invention are accomplished by adding to the liquid nonionic detergent composition an amount of a low molecular weight amphiphilic compound, especially mono-, di- or tri-C 1 -alkylene glycol mono C 1 -C 4 alkyl-5 ether, which is effective for inhibiting gelation of the nonionic surfactant in the presence of cold water.

In one aspect, therefore, the invention relates to a heavy-duty liquid washing composition composed of a suspension of a builder salt in a liquid non-ionic surfactant, which composition comprises a sufficient amount of a C2-C3 alkylene glycol mono-C 1 -C ^ alkyl ether to reduce the viscosity of the composition in the absence of water and on contact of the composition with water. * 15 In a more specific embodiment, the invention relates to a non-aqueous liquid cleaning composition pourable at temperatures below 5 ° C and which does not gel on contact with or upon addition to water at temperatures below 20 ° C, which composition is composed of a liquid, nonionic surfactant and over the alkylene glycol mono over the C 1 -C 6 alkyl ether and virtually no water.

In another aspect, the invention relates to a method of dispensing a liquid nonionic laundry detergent composition into and / or with cold water without undergoing gel formation. In particular, a method is provided for filling a vessel with a non-aqueous liquid laundry detergent composition, wherein the detergent is at least predominantly composed of a liquid non-ionic surfactant, as well as for dispensing the composition from the container in an aqueous washing liquid, the dosing being effected by directing a strip of unheated water onto the composition such that the composition is fed through the water flow into the washing liquid. By incorporating a low molecular weight amphiphilic compound, especially a C 2 -C 3 alkylene glycol mono C 1 -C 2 alkyl ether, the composition can be easily poured into the container even when the temperature of the composition is below room temperature.

-8-

The composition does not gel on contact with the water flow and disperses smoothly in the wash water.

Liquid detergent compositions often contain one or more detergent additives or additives in addition to the active detergent.

One of the most important of these in terms of consumer attractiveness and actual cleaning benefit is the class of bleaches, especially the oxygen bleaches, of which sodium perborate monohydrate is a particularly preferred example. It is known that hydrogen peroxide is formed from such persalts in solution as an active oxidizing agent. However, hydrogen peroxide is decomposed by catalase, an enzyme which is always present in natural dirt and stains. This decomposition takes place even in the presence of bleach activators, since the rate of the reaction between hydrogen peroxide and the activator is less than the decomposition of hydrogen peroxide by catalase. The activity of catalase is very high, even at room temperature, and a significant amount of active oxygen is lost before the catalase can be deactivated by raising the temperature of the wash water.

One possibility to solve the problem is to use an excessive amount of perborate or other peroxide bleach, for example an amount 2-4 times the amount that would be needed to effectively bleach the dirt or stain in the absence of peroxide-decomposing enzyme, and also a 2-4 fold molar excess over the number of moles of bleach activator.

It has also been proposed to perform bleaching with an aqueous solution of a peroxide bleach in the presence of a compound capable of inhibiting enzyme-induced decomposition of the bleach. United States Patent 3,606,990 30 discloses a wide variety of inhibitor compounds, including, for example, hydroxylamine salt, hydrazine and phenylhydrazine and their salts, substituted phenols and polyphenols and other compounds, as well as various detergent compositions containing a water-soluble inorganic peroxide bleach and contain an inhibitor compound. However, no mention is made of liquid detergent compositions containing the inhibitor compounds, nor is it stated that the inhibitor compounds would be effective in compositions containing, in addition to a peroxide bleach, a bleach activator. Furthermore, in said patent in column 7, lines 25-29, it is stated that in the case of hydroxylamine sulfate, the effective amount of inhibitor compound is 0.5-2 wt% of the total composition.

It has now been found that in the liquid detergent compositions of the invention containing a water-soluble inorganic peroxide bleach of the persalt type, the inclusion of very small amounts of less than about 0.5%, e.g. 0.01-0 * 45 %, 10 can effectively inhibit the enzyme-induced decomposition of the bleach. Furthermore, it was found that hydroxylamine sulfate in the composition is very stable and does not interfere at all with the activation of the bleaching system by conventional persalt bleach activators.

In a further aspect, the invention therefore relates to a heavy duty liquid laundry detergent composition containing a water-soluble inorganic peroxide bleach and an effective amount of a compound capable of inhibiting the enzyme-induced decomposition of the bleach, especially in a amount of less than about 0.5% by weight of the composition, as well as preferably an activator for bleach activation.

The nonionic synthetic organic detergents used for the practice of the invention may be selected from a wide variety of such compounds, which are well known and described, for example, in Schwartz, Perry and Berch, Surface Active Agents, Full. II, (1958), Interscience Publishers) and in McCutcheon's Detergents and Emulsifiers, 1969 Annual. Usually, the nonionic detergents are poly-layer alkoxy lipophils, in which the desired hydrophilic-lipophilic balance is obtained by addition of a hydrophilic poly-layer alkoxy group to a lipophilic molecule moiety. A preferred class of the nonionic detergents to be used is a poly-lower alkoxy higher alkanol containing 3-12 moles of alkylene oxide and wherein the alkanol contains 10-18 carbon atoms. Such materials are preferably used such that the higher alkanol is a higher fatty alcohol with 10-11 or 12-15 carbon atoms and contains 5-8 or 5-9 lower alkoxy groups per mole.

-10-

Preferably the lower alkoxy is ethoxy, but in some instances it may be desirable for the ethoxy to be mixed with propoxy, the latter group if present, usually, but not necessarily a minor amount (less than 50%). Examples of such compounds are those in which the alkanol contains 12-15 carbon atoms and which contain about 7 ethylene oxide groups per mole, for example Neodol 25-7 and Neodol 23-6.5, which products are marketed by Shell Chemical Company brought. . Neodol 25-7 is a condensation product of a mixture of fatty alcohols, containing on average 10 12-15 carbon atoms, with about 7 moles of ethylene oxide, and

Neodol 23-6.5 is a similar mixture in which the fatty alcohol contains 12-13 carbon atoms and the number of ethylene oxide groups present is on average about 6.5. The higher alcohols are primary alkanols. Other examples of such detergents are Tergitol 15 15-S-7 and Tergitol 15-S-9, both linear secondary alcohol ethoxylates, sold by Union Carbide Corporation. Tergitol 15-S-7 is a mixed ethoxylation product of a linear secondary alkanol with 11-15 carbon atoms and 7 moles of ethylene oxide, and Tergitol 15-S-9 is a similar product containing 9 moles of ethylene oxide.

As a component of the nonionic detergent in the present compositions, higher molecular weight nonionic materials may also be used, such as Neodol-45-11, a condensation product of a fatty alcohol having 14-15 carbon atoms and about 11 ethylene oxide groups per mole. Such products are also marketed by Shell Chemical Company. Other suitable nonionic materials belong to the commercially available Plurafac series and 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 with a terminal hydroxyl group. Examples are 30 Plurafac RA30 (a C ^ -C ^ fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide), Plurafac RA40 (a C13_C15 fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide), Plurafac D25 (a C ^ - Fatty alcohol, condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide), and Plurafac B26.

Generally, the condensation products of fatty alcohol with 7% vol. i? -11- a mixture of ethylene oxide and propylene oxide are represented by the general formula wherein R is a straight or branched chain primary or secondary aliphatic hydrocarbon group, preferably an alkyl or alkanyl group having 6-20 carbon atoms, preferably 10-18 carbon atoms and in the especially 14-18 carbon atoms, x represent a number with a value of 2-12, preferably 4-10, and y represent a number with a value of 2-7, preferably 3-6.

Another group of liquid non-ionic materials is marketed by the Shell Chemical Company under the trade name Dobanol. Dobanol 91-5 is an ethoxylated C ^ -C ^ fatty alcohol with an average of 5 moles of ethylene oxide and Dobanol 25-7 is an ethoxylated

Cj ^ C ^ fatty alcohol with an average of 7 moles of ethylene oxide, etc.

To achieve the best balance of hydrophilic and lipophilic molecular moieties in the preferred alkoxyalkanols, the number of alkoxy groups is usually 40-100%, preferably 40-60%, of the number of carbon atoms in the alcohol; the nonionic detergent preferably contains at least 50% of such alkoxyalkanol. Higher molecular alkanols and various other normally solid nonionic detergents and surfactants may contribute to gelation of the liquid detergent and are therefore preferably omitted from the present compositions or limited in these compositions, although minor amounts thereof can be used because of their cleaning properties and the like. Both in the preferred non-ionic detergents and in the less preferred non-ionic detergents, the alkyl groups present are generally linear, although branching is possible, for example, at a carbon atom adjacent or spaced of two carbon atoms away from the straight chain terminal carbon and away from the ethoxy-30 chain, when the branched alkyl group is not more than 3 carbon atoms in length. Normally, the number of carbon atoms in such a branched configuration is minor and rarely exceeds 20% of the total number of carbon atoms of the alkyl.

Although linear alkyl groups terminally attached to the ethylene oxide chain are highly preferred and are believed to provide the best combination of detergent, biodegradable. x, / -12- and non-gel-forming properties, medial or secondary adhesion to the ethylene oxide in the chain can also take place. This is usually only the case in a minor portion of the alkyl groups, generally less than 20%, but the portion 5 may also be larger, as is the case with said tergitols.

When propylene oxide is present in the alkylene oxide chain, it will usually, but not necessarily, be less than 20% thereof, and preferably less than 10% thereof.

When larger amounts of non-terminal alkoxylated alkanols, propylene oxide containing alkoxylated alkanols, and nonionic detergents with a less balanced distribution of hydrophilic and lipophilic molecular moieties than described above are used, and when nonionic detergents are used instead of those described herein, at Preferably non-ionic materials may be used that the resulting product may exhibit less good detergent, stability, viscosity and non-gelling properties than the preferred compositions, but use of the viscosity and gel control compounds of the invention may also improve the properties of detergents based on such nonionic materials. In some cases, for example, when a higher molecular alkoxylated alkanol is used, which is often because of its detergent, the amount thereof can be controlled or limited by the results of various tests to obtain a product of the desired detergent, which nevertheless does not form a gel and has the desired viscosity. It has also been found that it is only rarely necessary to use the higher molecular weight nonionic materials because of their detergent properties, as the preferred nonionic materials described herein are excellent detergents and additionally allow the desired viscosity in the liquid detergent without gel formation at low temperatures. Mixtures of two or more of these liquid non-ionic materials can also be used, and in some cases the use of such mixtures can be advantageous.

As already mentioned, the structure of the liquid nonionic surfactant can be optimized with respect to its carbon chain length and configuration (eg linear chains versus branched chains), and the content and distribution of alkylene oxide units. . Extensive research has shown that these structural properties have a large effect on various properties of the non-ionic material, such as the pour point, the cloud point, the viscosity, the tendency to gel and, of course, also on the detergent.

Most commercially available non-ionic materials exhibit a relatively wide distribution of ethylene oxide (EO) and propylene oxide (PO) units and of the lipophilic hydrocarbon chain length, with the stated EO and PO levels and hydrocarbon chain lengths averaging. This "polydispersity" of the hydrophilic chains and lipophilic chains can have a major influence on the product properties as can the specific values of those means.

The relationship between "polydispersity" and specific chain lengths with product properties can be shown for a well-defined nonionic material by the following data for the "Surfactant T8" series of nonionic materials sold by British Petroleum. These materials are obtained by ethoxylation of secondary fatty alcohols with a narrow EO distribution and have the following physical properties: 20 EO content Pour point ° C Cloud point

- (It's sol.) ° C

Surfactant T5 5 <"- 2 <25

Surfactant T7 7 -2 38

Surfactant T9 9 6 58 25 Surfactant T12 12 20 88

To determine the influence of EO distribution, a "Surfactant T8" was artificially prepared in two ways: a. 1: 1 mixture of T7 and T9 (T8a) b. 4: 3 mixture of T5 and T12 (T8b) 30 The following properties were found:

Average content Pour point Cloud point EO_ ° C (12 * 8 solution) ° C

Surfactant T8a 8 2 48

Surfactant T8b 8 15 <20 -14-

From these results, the following general conclusions can be drawn: 1. T8a matches well with an actual Surfactant T8 since its pour point and cloud point interpolate well between T7 and T9.

2. T8b is highly polydisperse and will generally be considered unsatisfactory because of its high pour point and low cloud point.

3. The properties of T8a are additive between T7 and T9, for T8b the pour point is close to that of the long EO chain (T12), while the cloud point is close to that of the short EO chain (T5).

The viscosities of Surfactant T5, T7, T7 / T9 (1: 1), T9 and T12 were measured at 25 ° C and 100 sec at concentrations of 20%, 30%, 40%, 50%, 60%, 80% and 100% (when a gel is formed the viscosity is the apparent viscosity): 15

Viscosity (mPa.s) non-ionic type T5 T7 T7 / T9 T9 T12% 100 36 63 61 149 20 80 65 104 112 165 60 750 78 188 239 32 200 50 4000 123 233 634 89 100 40 2050 96 149 211 187 30 630 58 38 27 25 20 170 78 28 100

From these results it can be concluded that Surfactant T7 is less gel sensitive than T5 and T9 is less gel sensitive than T12; 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 it is not intended to bind the invention to any particular theory, it is believed that these results may be explained as follows:

For T5: with only 5 EO groups, the hydrodynamic volume of the EO chain is almost equal to that of the fatty alcohol chain.

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As a result, the molecules can arrange into a laminar structure.

For T12: with 12 EO groups, the hydrodynamic volume of the FeO chain is greater than that of the fatty alcohol chain. When molecules try to arrange together, an interface curvature arises and bars are obtained. The superstructure is then hexagonal; with a longer EO chain or with higher hydration, the interface curvature may be such that actual spheres are obtained, and the lowest energy arrangement is a planar centered cubic lattice.

From T5 to T7 (and T8), the interface curvature increases, 10 and the energy of the lamellar structure increases. When the lamellar structure loses its stability, its melting temperature drops.

From T12 to T9 (and T8), the interfacial curvature decreases and the energy of the hexagonal structure increases (bars are increasing). When loss of stability occurs, the melting temperature of the structure is also lowered.

Surfactant T8 appears to be at the critical point where the lamellar structure is destabilized, i.e. the hexagonal structure is not yet stable enough and no gel is obtained during dilution. In fact, a 50% solution of T8 will eventually gel after 2 days, but superstructure formation is delayed enough to allow easy dispersibility in water.

The effects of molecular weight on the physical properties of the nonionic materials were also studied. Surfactant T8 25 (1: 1 mixture of T7 and T9) shows a good compromise between the lipophilic chain (G13) and the hydrophilic chain (E08 units), although the pour point and the maximum viscosity when diluted at 25 ° C are still high.

The equivalent EO compromise for and Cg lipophilic chains 30 was also determined using Shell's Dobanol 91-x series

Chemical Company, consisting of ethoxylated derivatives of C 1 -C 2 fatty alcohols (average C 2 q); and of the Alfonic 610-y series from Conoco, consisting of ethoxylated derivatives of Cg-C12 fatty alcohols (average Cg); x and y represent the weight percentage EO.

The table below shows the physical properties of the

Alfonic 610-y and Dobanol 91-x series stated: *%: -16- EO-a- Pour point Turbe- Max. ^ At dilution present% (%) at 25 ° G, (wt) point, C ( mPa.s)

Alfonic 610-50R 3 -15 gel (60%) 5 Alfonic 610-60 4.4 -4 41 36 (60%)

Dobanol 91-5 5 -3 33 gel (70%)

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; Dobanol 91-5 (T) topped is a lab scale product: it is Dobanol 91-5, from which the free alcohol has been removed. Since the components with the lowest ethoxylation have also been removed, the average number of EO units is equal to 6. Dobanol 91-5T gives the best results for the C 1 q lipophilic chain, since it does not gel at 25 ° C. The 1% cloud point (55 ° C) is higher than that of

Surfactant T8 (48 ° C). This is probably due to the lower molecular weight, where the entropy of the mixture is higher. Alfonic 610-60 delivers the best results from the Cg lipophilic chain.

The following table summarizes the best EO levels for each lipophilic chain length tested: C-Atoms EO Pour Point Turb- Max.η at Unit Thinning (%) at the point 25 ° C, mPa. s (1% yield) 25 _ ° _C_

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%)

The following conclusions were drawn from these data: Pouring points: as the molecular weight of the non-ionic material is lower, the pouring point also decreases. The relatively high pour point of Dobanol 91-5T can be explained by the high polydispersity. This was also observed with T8a and T8b, i.e., the pour point is increased by polydispersity chain.

Cloud points: as the number of molecules increases (if * \ -17- the molecular weight decreases), theoretically the mixing trophy increases, so that the cloud point will increase as the molecular weight decreases. This is actually the case for Surfactant T8 to Dobanol 91-5T, but has not been confirmed with Alfonic 610-60. Here it can be assumed that the polydispersity of the lipophilic hydrocarbon chain is the cause of the theoretically too low cloud point. The relatively large amount of C 1 -Q-EO present decreases solubility.

Maximum viscosity at dilution at 25 ° C: none of these 10 non-ionic materials gel at 25 ° G when diluted with water. The maximum viscosity drops sharply with the molecular weight. As the molecular weight of the non-ionic material is lower, the hydrogen bonds become less efficient. Unfortunately, non-low molecular weight non-ionic materials are not suitable for washing laundry: their critical micellar concentration (MCC) is too high, and under the practical conditions of washing a true solution with only limited detergent would be obtained .

With this information, research into the effects of the low molecular weight amphiphilic compounds on the rheological properties of liquid nonionic detergent compositions was continued.

This investigation showed that although it is possible to lower the pour point of the composition and obtain some degree of gel inhibition by using a short hydrocarbon chain, e.g. Cg, with a short ethylene oxide chain, e.g. about 4 moles, as an amphiphilic additive, such as Alfonic 610-60, these additives do not contribute significantly to the overall cleaning effect and do not exhibit an entirely satisfactory viscosity control under all normal conditions of use.

The invention is at least partly based on the discovery that the low molecular weight amphiphilic compounds, which in chemical structure can be considered analogous to the non-ionic surfactants based on ethoxylated and / or propoxylated fatty alcohols, but which have a short hydrocarbon chain (G ^ -C2) and low ethylene oxide and / or propylene oxide content (about 1-4 EO / PO units per molecule), function efficiently as viscosity controllers and gel inhibitors for the liquid nonionic surfactants.

1 * ». "n - - - -18-

The viscosity-regulating and gel-inhibiting amphiphilic compounds to be used according to the invention can be represented by the general formula 1 (see formula sheet) in which R is a C 1 -C 1 x 2 i preferably in particular and most preferably alkyl group, R 1 H or methyl, preferably H, and n represent a number with an average value of 1-4, preferably 2-4.

Examples of suitable preferred amphiphilic compounds are glycol monoethyl ether (H ^ -O-CHgC ^ OH) and diethylene glycol monobutyl ether (C ^ Hg-O-CCE ^ C ^ O ^ H). Diethylene glycol-10 monoethyl ether is particularly preferred and, as will be shown below, is uniquely effective in viscosity control.

Although the amphiphilic. compound, in particular diethylene glycol monobutyl ether, can be used in the compositions of the invention as the sole viscosity-controlling and gel-inhibiting additive, further improvements in the rheological properties of the anhydrous liquid nonionic surfactant compositions can be obtained by incorporation in the composition of a small amount of a non-ionic surfactant, which is modified by converting a free hydroxyl group thereof into a molecule portion with a free carboxyl group such as a partial ester of a non-ionic surfactant active substance and a polycarboxylic acid and / or an acidic organic phosphorus compound with an acidic POH group such as a partial ester of phosphoric acid and an alkanol.

As disclosed in U.S. Patent Application 597,948 filed April 9, 1984, the introduction of a free carboxyl group-modified nonionic surfactant, which can generally be characterized as polyether carboxylic acids, serves to lower the temperature at which the liquid does not ionic material forms a gel with water. The acidic polyether compound can also reduce the yield stress of such dispersions and thereby improve their dosability without a corresponding reduction in their settling stability. Suitable polyether carboxylic acids contain 2 a group with. formula 2, wherein R hydrogen or methyl, Y oxygen 35 or sulfur, Z an organic bond, p a positive number with a value of 3-50 and q zero or a positive number with a value of at most 10 8 I? M Ί

Av '> c *' * »4 y. * J

-19- proposals. Specific examples are the half-ester of Plurafac RA30 with succinic anhydride, the half-ester of Dobanol 25-7 with succinic anhydride, the half-ester of Dobanol 91-5 with succinic anhydride, etc. Instead of succinic anhydride, other poly-5 carboxylic acids or anhydrides thereof can also be used , for example, maleic acid, maleic anhydride, glutaric acid, malonic acid, succinic acid, phthalic acid, phthalic anhydride, citric acid, etc. Other bonds such as ether, thioether or urethane bonds obtained by conventional reactions can also be used. For example, 10 can form an ether bond. the nonionic surfactant may be reacted with a strong base (to convert the OH group to, for example, an ONa group) and then with a halocarboxylic acid such as chloroacetic acid or chloropropionic acid or the corresponding bromine compound. carboxylic acid 15 have the formula RY-ZCOOH, wherein R is the remainder of the nonionic surfactant (after removal of a terminal hydroxyl group), Y represents oxygen or sulfur, and Z represents an organic bond, such as a hydrocarbon group having, for example, 1 -10 carbon atoms, which may be attached to the oxygen (or sulfur), either directly or through an intermediate group such as an oxygen-containing bond, eg a carbonyl group or an amido group.

The polyether carboxylic acid can be prepared from a polyether which is not a nonionic surfactant, for example, by reaction with a polyalkoxy compound, such as polyethylene glycol, or a monoester or monoether thereof, which does not contain the long alkyl chain, which is characteristic of the non-ionic surfactants 2. For example, R may be of the formula 3 wherein R is hydrogen or methyl, R 1 alkylphenyl or alkyl or another chain-terminating group and n represents a number having a value of at least 3 such as 5-25. When a higher alkyl group R is a residue of a nonionic surfactant. As indicated above, R 1 may instead be hydrogen or a lower alkyl group (e.g. methyl, ethyl, propyl, butyl) or a lower acyl group (e.g. acetyl). If the acidic polyether compound is to be present in the detergent composition, it is preferably added dissolved in the nonionic surfactant.

^ · '. - '»I ...

. , j i i * * / -20-

Another suitable class of supplemental anti-gelling agents are the C8 -C18 alkyl or alkenyl dicarboxylic anhydrides, such as, for example, octenyl succinic anhydride, octenylmaleic anhydride, dodecyl succinic anhydride, etc. These compounds may be used in conjunction with 5 or instead of the polyether carboxylic acid anti-gelling agents or a part thereof are used.

As disclosed in U.S. Patent Application No. 597,793 filed April 6, 1984, the acidic organic phosphorus compound with an acidic POH group can improve the stability of a builder suspension, especially polyphosphate builders in the non-aqueous nonionic surfactant .

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

A specific example is a partial ester of phosphoric acid and a C 1 -C-C 2 g alkanol (Empiphos 5632 from Marchon); consisting of about 35% monoester and 65% diester.

The addition of very small amounts, for example of 0.05-0.3% by weight of the composition, of the acidic organic phosphorus compound makes the slurry significantly more stable against settling on standing, but the slurry remains pourable, likely as a result of increasing the flow value of the suspension, but the plastic viscosity decreases. It is believed that the addition of the acidic phosphorus compound can lead to the formation of high energy physical bonding between the -POH portion of the molecule and the surfaces of the inorganic polyphosphate builder, giving these surfaces an organic character and more compatibility with the non-ionic surfactant.

The acidic organic phosphorus compound can be selected from a wide variety of materials in addition to said partial esters of phosphoric acid and alkanols. For example, one can use a partial ester of phosphoric acid or phosphorous acid with a mono- or polyhydric alcohol, such as hexylene glycol, ethylene glycol, di- or triethylene glycol or higher polyethylene glycols, polypropylene glycol, glycerol, sorbitol, mono- or diglycerides of fatty acids, etc., wherein one, two or more of the alcoholic hydroxyl groups of the molecule with the phosphoric acid. ï ·.

-21- may have been esterified. The alcohol can be a nonionic surfactant such as an ethoxylated or ethoxylated and propoxylated higher alkanol, higher alkyl phenol or higher alkyl amide.

The POH group need not be bound to the organic part of the molecule via an ester bond; instead, the group may be directly attached to carbon (such as in phosphonic acid, for example, a polystyrene in which some of the aromatic rings carry phosphonic or phosphinic acid groups, or an alkyl phosphonic acid, such as propyl or lauryl phosphonic acid (or through other intermediates, for example, via oxygen , Sulfur or nitrogen atoms) are attached to the carbon, preferably the carbon: phosphorus atomic ratio in the organic phosphorus compound is at least 3: 1, for example 5: 1, 10: 1, 20: 1.30: 1 or 40: 1.

The detergent composition of the invention may and preferably will contain water-soluble builder salts. Examples of suitable builders are described in U.S. Pat. Nos. 4,316,812, 4,264,466 and 3,630,929. Water-soluble inorganic alkaline builder salts that can be used alone or in admixture with other builders with the detergent include alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates, and silicates (ammonium or substituted ammonium salts may also be used). Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate sodium bicarbonate, sodium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono- and diorthophosphate, and potassium. Sodium tripolyphosphate (TPP) is particularly preferred.

The alkali metal silicates are suitable builder salts, which also render the composition anti-corrosion for parts of the washing machine. Sodium silicates with Na 2 O / SiO 2 ratios of from 1.6 / 1 to 1 / 3.2, especially from 1/2 to 1 / 2.8, are preferred. Potassium silicates with the same proportions can also be used.

Another class of suitable builders are the water-insoluble aluminosilicates, both of the crystalline and amorphous type. Various crystalline zeolites (aluminosilicates) are described in British Patent 1,504,168, U.S. Patent 4,409,136 and Canadian Pat. Nos. 1,072,835 and 1,087,477. An example of suitable amorphous zeolites can be found in Belgian patent specification 835,351. The zeolites generally conform to the formula (M20) x. (Al 2 O 3) y. (SiO 2) z.WH 2 O where x = 1, y = 0.8-1.2 and preferably = 1, z = 1.5-3.5 or higher and 5 preferably = 2-3 , and w = 0-9, preferably = 2.5-6, wherein M is preferably sodium. A typical zeolite is type A or analogous structure, with type 4A being particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents per gram or more, for example 400 meq / g.

Other materials, such as clays, especially the water-insoluble types, may be useful adjuvants in the compositions of the invention. Bentonite is particularly useful. This material is mainly montmorillonite, a hydrated aluminum silicate, in which about 1/6 of the aluminum atoms can be replaced by magnesium atoms, and with which varying amounts of hydrogen, sodium, potassium, calcium and the like can be loosely bound. Bentonite in more purified form (i.e., free from fine grit, sand and the like), which is suitable for detergents, always contains at least 50% montmorillonite, so that the cation exchange capacity is at least 50-75 meq per 100 g bentonite. Particular preference is given to benthones from Wyoming or the western United States, supplied by Georgia Kaolin Co. are marketed as Thixo gels 1, 2, 3 and 4. These bentonites are known to soften textile products, as described in British Pat. Nos. 401,413 and 461,221.

Examples of organic alkaline sequestering builder salts, which can be used alone or in admixture with other organic and inorganic builders in detergents, are alkali metal, ammonium, or substituted ammonium aminopolycarboxylates, for example, sodium and potassium ethylenediaminotetraacetic acid (EDTA), sodium and potassium nitrilotriacetates (NTA) and triethanolammonium N- (2-hydroxyethyl) nitrilodiacetates. Mixed salts of these polycarboxylates can also be used.

Other suitable organic type builders are carboxy methyl succinates, tartronates and glycolates. The polyacetal carboxylates are of special value. The polyacetal carboxylates and their application »i -Λ '? Detergents in detergent compositions are described in U.S. Patent Nos. 4,144,226, 4,315,092, and 4,146,495. Similar builders are described in U.S. Patents 4,141,676, 4,169,934, 4,201,858, 4,204,852, 4,224,420, 4,225,685, 4,226,960, 4,233,422, 4,233,423, 4,302,564, and 4,303 .777. Also relevant are European patent applications 15024, 21491 and 63399.

Since the compositions of the invention are generally highly concentrated and can therefore be used in relatively small doses, it is desirable to add an auxiliary builder, such as a polymeric carboxylic acid with a high calcium binding capacity, to phosphate builders (such as sodium tripolyphosphate). to inhibit triggers, which may otherwise be caused by the formation of an insoluble calcium phosphate. Such help builders are generally known.

Other additives or auxiliary substances may also be present in the detergent, which give the detergent further desirable properties of a functional or aesthetic nature. For example, minor amounts of soil-suspending or anti-redeposition agents may be included in the composition, for example, polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose * hydroxypropylmethyl cellulose, optical brighteners, for example, cotton, amine and polyester brighteners, such as stilbene, triazole and benzidine sulfone compounds, in particular sulfonated substituted triazinyl stilbene, sulfonated naphtho-triazole stilbene, benzidene sulfone, and the like, with stilbene and triazole combinations being most preferred.

Examples of further additives are blue agents, such as ultramarine blue, enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papaxne, trypsin and peptin, as well as enzymes of the amylase type and / or lipase type, bactericides, eg tetrachlorosalicylanilide, hexachlorophene, fungicides dyes, pigments (water-dispersible), preservatives, UV absorbers, anti-yellowing agents, such as sodium carboxymethyl cellulose or a complex of a (^ t ^ -alkanol with C1-C6-alkyl sulfate) , pH modifying agents and pH buffers, color-safe bleaching agents, perfume and anti-foaming agents or suds suppressants, for example silicon compounds.

-24-

The bleaches can generally be divided into chlorine bleaches and oxygen bleaches. Examples of chlorine bleaching agents are sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% available chlorine) and trichloroisocyanuric acid (85% available chlorine). The oxygen bleaching agents are preferred and are represented by per compounds which liberate hydrogen peroxide in solution, i.e. compounds containing hydrogen peroxide or inorganic perhydrates which, upon dissolution, release the hydrogen peroxide contained in their crystal lattice. Preferred examples are sodium and potassium perborates, percarbonates and perphosphates, and potassium monopersulfate. The perborates, in particular without sodium perborate monohydrate, are particularly preferred.

Hydrogen peroxide and the precursors which release hydrogen peroxide in solution are good oxidizing agents for removing certain stains from clothes, especially stains caused by wine, tea, coffee, cocoa, fruits and the like.

Hydrogen peroxide and its precursors generally have a rapid bleaching action and are most effective at relatively high temperatures, for example between 80 and 100 ° C. However, such compounds 20 tend to decompose at lower temperatures and release gaseous oxygen. The release of gaseous oxygen, which is not involved in the oxidation of dyed goods, unnecessarily consumes a significant amount of hydrogen peroxide or precursors thereof, which are expensive products. Moreover, it has been found that various stains in fabrics and the like strongly accelerate the decomposition of hydrogen peroxide into gaseous oxygen during washing at ordinary temperature.

Generally, machine washing is done by hand, by cooking or in tubs by dissolving a bleach or detergent composition (containing, for example, perborate) in cold or lukewarm water, adding the soiled textiles (often some stains have already been removed by pre-soaking or prewashing) to the resulting solution, and heating, often to near boiling temperature.

However, it has been found that due to an analogous phenomenon such as already mentioned, the perborate decomposes in whole or in part during heating and in particular during the rise in temperature, that is to say that the perborate is completely or partially decomposed before the actually effective temperature has been reached.

It is believed that this rapid, low temperature decomposition of hydrogen peroxide, perborate or other hydrogen peroxide precursors to form gaseous oxygen is caused by the extremely strong catalytic action of certain enzymes, which are always present in stains, washable materials and in particular on dirty textiles, such as linen, which have enzymes from secretions or from bacterial origin. Hydroperoxidase is a group of enzymes which are particularly active in this regard, especially catalase, which is known as a very effective catalyst for the decomposition of hydrogen peroxide to gaseous oxygen. Such enzymes, referred to as "redox" or otherwise, have in common that they have a pronounced tendency to promote the decomposition of peroxide bleaches, the decomposition products formed having no effective bleaching action.

To take advantage of the low temperature effective detergents and the low wash temperatures currently widely used for temperature sensitive fabrics, the peroxygen compound is preferably used in conjunction with an activator therefor. Suitable activators, which can lower the effective operating temperature of the peroxide bleaching agent to about 40 ° C or less, are described, for example, in U.S. Patent 4,264,466 or in column 1 of U.S. Patent 4,430,244. Preferred activators to be used are polyacylated compounds; among these compounds, tetraacetylethylenediamine (TAED) and pentaacetyl glucose are particularly preferred; Examples of other suitable activators are acetylsalicylic acid and its salts, ethylidene benzoate acetate (EBA) and its salts, ethylidene carboxylate acetate and its salts, alkyl and alkenyl succinic anhydride, tetraacetyl glycouril (TAGU) and its derivatives. For other classes of useful activators, reference is made to U.S. Patents 4,111,826, 4,422,950 and 3,661,789.

The bleach activator usually interacts with the peroxygen compound to form a peroxyacid bleach in the wash water. Preferably also a sequestrant with a high. >

f B

-26- complexing ability incorporated to inhibit any undesired reactions that peroxyacid and hydrogen peroxide in the wash solution in the presence of metal ions. Preferred sequencing agents are capable of forming a complex with Cu ions, such that the stability constant (pK) of the complex formation is equal to or greater than 6 at 25 ° C in water at an ionic strength of 0.1 mol / liter, which pK is normally defined by the formula: pK = ~ log K, where K represents the equilibrium constant. For example, the pK values for the complexation of copper ions with NTA and EDTA under the conditions mentioned are 12.7 and 18.8, respectively. Examples of suitable sequestering agents other than those mentioned are diethylene triamine pentaacetic acid (DETPA), diethylene triamine pen tamethylene phosphonic acid (DTPMP) and ethylenediaminetetramethylene phosphonic acid (EDITEMPA).

Nevertheless, even in the presence of the bleach activator and even at temperatures as low as room temperature, decomposition of the persalt will occur in the presence of stained textiles, since the reaction rate of the bleach with the activator is less than the decomposition rate of hydrogen peroxide by catalase.

To prevent bleach losses due to enzyme-induced decomposition, the compositions of the invention preferably also contain an effective amount of a compound capable of inhibiting this decomposition. Suitable inhibitor compounds are described in U.S. Patent 3,606,990.

Particularly suitable inhibitor compounds are hydroxylamine sulfate and other water-soluble hydroxylamine salts, for example, the hydrochloride, hydrobromide, etc. It has been found that the hydroxylamine salts, especially the sulfate, effectively inhibit the deleterious effect of catalase, even in the presence of the composition. of very small amounts, for example less than 0.5%, such as 0.01-0.4%, preferably 0.04-0.2% and in particular about 0.1%, based on the weight of the total composition.

The hydroxylamine inhibitor is furthermore very stable in the composition: less than 20% loss after aging for 2 months at 43 ° C.

t »-27-

The hydroxylamine salts dissolve very quickly in water and can therefore react with catalase before the perborate or other peroxide bleach dissolves. Another advantage of the hydroxylamine salts is that they are quickly destroyed in the washing liquid, so that no nitrosamine derivatives are observed.

If the bleaching system is activated by one or more activators, for example by TAED, the activator is used more efficiently so that appropriate proportions of persalt, bleach / activator can be maintained at values much closer to the stoichiometric equivalent weights or with only a slight molar excess of the bleach.

The composition may also contain a very large surface inorganic insoluble thickener or dispersant, such as finely divided silica having an extremely fine particle size (for example, with a diameter of 5-100 millimicron, as marketed under the name Aerosil, or the other highly bulky inorganic support materials, described in U.S. Pat. No. 3,630,929, in amounts of 0.1-10%, eg, 1-5%. However, it is preferred that compositions that form peroxyacids in the wash liquor (eg, compositions, containing a peroxygen compound and an activator therefor) are substantially free of such compounds and of other silicates, for example, it has been found that silica and silicates promote undesirable decomposition of the peroxyacid.

In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solids is subjected to a particle size reduction in a friction type mill, in which the particle size of the solids is reduced to less than about 10 microns. for example, up to an average particle size of 2-10 microns or even less (eg 1 micron). Compositions in which the dispersed particles are of such small size have improved stability against separation or settling on storage.

During grinding, the amount of solids is preferably large (e.g., at least 40%, such as about 50%) that the solids are in contact with each other and are not shielded from each other by the nonionic surfactant.

»* **

<! * V

-28-

Mills in which grinding balls (ball mills) or similar mobile grinding elements are used have yielded very good results. For example, a laboratory mill with steatite grinding balls with a diameter of 8 mm can be used. For larger scale work, a continuously operating mill can be used, in which grinding balls with a diameter of 1mm or 1.5mm operate in a very small gap between a stator and a relatively high speed rotor (for example a CoBall mill) ; when such a mill is used, it is recommended that the mixture of non-ionic surfactant and solids is first passed through a mill that does not grind as finely (eg, a colloid mill), to reduce the particle size to less than 100 microns (e.g. up to about 40 microns) before milling to an average particle size of less than about 10 microns in the continuously operating ball mill.

In the preferred compositions of the invention, typical amounts (calculated on the total composition, unless otherwise stated) of the ingredients are as follows:

The suspended detergent builder is used in an amount of 10-60% such as 20-50%, for example 25-40%.

The amount of liquid phase, including the nonionic surfactant and dissolved amphiphilic viscosity regulating and gel inhibiting compound, is 30-70%, such as 40-60%; this phase may also contain minor amounts of a diluent such as a glycol, eg polyethylene glycol (such as "PEG 400") hexylene glycol and the like, up to 10%, preferably up to 5%, eg 0.5-2%. The weight ratio of the nonionic surfactant to the amphiphilic compound is between 100: 1 and 1: 1, preferably between 50: 1 and 2: 1, and especially between 25: 1, and 3: 1 .

The polyether carboxylic acid (gel inhibitory compound) is present in an amount sufficient to provide 0.5-10 parts (eg 1-6 parts, such as 2-5 parts) -C00H (molecular weight 45) per 100 parts mixture of the acidic compound and the nonionic surfactant.

The amount of polythercarboxylic acid compound is typically 0.01-1 dl, such as 0.05-0.6 dl, eg 0.2-0.5 dl, per dl nonionic surfactant.

-29-

The acidic organic phosphoric acid compound (anti-settling agent) is present in an amount up to 5%, e.g. 0.01-5%, such as 0.05-2%, e.g. 0.1-1%.

Suitable amounts of other optional detergent additives are: enzymes - 0-2%, in particular 0.7-1.3%; corrosion inhibitors <0-40%, and preferably 5-30%; anti-foaming agents and suds suppressants - 0-15%, preferably 0-5%, e.g. 0.1-3%; thickener and dispersants - 0-15%, for example 0.1-10%, preferably 1-5%; soil suspending or anti-redeposition agents and anti-yellowing agents - 0-10%, preferably 0.5-5%; colorants, perfumes, brighteners and bluing agents - 0-2% in total, preferably 0-1%; pH modifiers and pH buffers -0-5%, preferably 0-2%; bleach - 0-40%, preferably 0-25%, for example 2-20%; additive for inhibiting enzyme decomposition of the bleach - up to 0.5%, preferably 0.01-0.4 or 0.5%, especially 0.04-0.2%; bleach stabilizers and bleach activators 0-15%, preferably 0-10%, e.g. 0.1-8%; high complex forming ability sequestrant - up to 5%, preferably 1/4 - 3%, e.g. 1 / 2-2%. The adjuvants should be selected to be compatible with the main ingredients of the detergent composition.

All amounts and percentages are by weight unless otherwise stated.

It will be clear that the foregoing description is for illustrative purposes only, and that variations can be made without departing from the scope of the invention.

To demonstrate the effects of the viscosity-controlling and gel-inhibiting agents, compositions were prepared with the Surfactant T8 (C ^, EÖg) (50/50 mixture of Surfactant T7 and Surfactant 30 T9) described above as the non-aqueous liquid nonionic surfactant cleaner. Mixtures containing 5%, 10%, 15% or 20% amphiphilic additive were prepared and tested at 5eC, 10eC, 15 ° C 20 ° C and 25 ° C at various dilutions with water, typically 100%, 83%, 67 %, 50% and 33% concentrations of non-ionic Surfactant T8 35 plus additive, ie. after dilution in water. The tested additives * Λ 1 * -30- were Alfonic 610-60 (Cg-EO ^, ethylene glycol monoethyl ether ^ -EO ^), and diethylene glycol monobutyl ether (C ^ -E02). The results of viscosity behavior at dilution of each tested composition at any temperature shown in the graphs of fig. 1-3.

For Alfonic 610-60, a 5% addition was sufficient to inhibit gelation at 25 ° C; however, in the graph, in which the viscosity is plotted against the concentration of the non-ionic material, a sharp viscosity maximum is observed at a concentration of 67% and a shoulder at about 55-35% concentration. At 5 ° C, the addition of 15 % necessary to prevent gelation. The viscosity dropped to a minimum at a concentration of the nonionic material of about 83% at all additive concentrations at 5 ° C, while at higher temperatures viscosity minima were observed at the undiluted materials, ie at a concentration of the non- 100% ionic material At any temperature and 15 for any additive concentration tested (except at 20% additive at 25 ° C) until a relatively sharp peak is observed in the viscosity between 75 and 50% concentration of the nonionic material ( ie 25-50% dilution).

5% of the ethylene glycol monoethyl ether was able to inhibit gel formation even at 5 ° C. However, sharp peaks and / or viscosity maxima were observed at each temperature and additive concentration, although the effects were not as pronounced as with Alfonic 610-60, and for some applications the maximum viscosities, particularly at higher additive concentrations and / or higher temperatures are acceptable for commercial use.

On the other hand, no sharp viscosity peaks were observed for diethylene glycol monobutyl ether at all temperatures down to 5 ° C at the additive concentration of 20%.

Even at the lower additive concentrations, the viscosity peaks and viscosity values at virtually all dilutions (concentrations of the nonionic material) were lower than for the Co-E0. .or 0ο-Ε0Ί.

J 8 4.4 2 1

The following table is representative of the results obtained for the various additive concentrations, dilutions and temperatures, but the results are given for an o.

additive concentration of 20% and a temperature of 5 C.

Compositions Viscosity at Pour Point _ 5 ° C (Pa. Sec) / O ^

No water 50% water

Surfactant T8 only 1,140 1,240 5 80% Surfactant T8 + 20% A 0.086 0.401 -10 80% Surfactant T8-f-20% B 0.195 0.218 -2 80% Surfactant T8 + 20% C 0.690 0.936 3 * - * 10 A = * ethylene glycol monoethyl ether B * diethylene glycol monobutyl ether C - Alfonic 610-60 (Cg-E04 4> NB 1 Pa.sec * 10 poise (eg 0.218 Pa.sec * 218 tipoise)

Example I

A builder containing heavy duty non-aqueous nonionic cleaning composition was prepared having the following composition:

Wt%

Surfactant T 7 17.0 20 Surfactant T8 17.0

Dobanol 91-5 acid (1) 5.0

Diethylene glycol monobutyl ether 10.0

Dequest 2066 (2) 1.0 TPP Nw (sodium tripolyphosphate) 29.0925 25 Sokolan CP5 (3) (Calcium sequestrant) 4.0

Perborate H ^ O (sodium perborate monohydrate) 9.0 T.A.E.D. (tetraacetylethylenediamine) 4.5

Emphiphos * 5632 (4) 0.3

Stilbene 4 0.5 30 Esperase (proteolytic enzyme) 1.0

Duet 787 (5) 0.6

Relatin DM (6) (anti-redeposition agent) 1.0

Blue Foulan Sandolane (colorant) 0.0075 ύ * -32- 1) Dobanol 91-5 esterification product (a C 1 -C 2 fatty alcohol ethoxylated with 5 moles ethylene oxide) with succinic anhydride - the half ester.

2) Sodium salt of diethylene triamine pentamethylene phosphoric acid.

3) Copolymer of approximately equal molar amounts of methacrylic acid and maleic anhydride, completely neutralized to form the sodium salt.

4) Partial ester of phosphoric acid and a C 1 -g-C 1 -g alkanol (about 1/3 monoester and 2/3 diester).

5) 6) Mixture of sodium carboxymethyl cellulose and hydroxymethyl cellulose.

This composition is a stable, free-flowing, builder-containing non-gelling, liquid non-idnogenic detergent, wherein the polyphosphate builder is stably suspended in the liquid non-ionic surfactant phase.

Example II

In the same manner as in Example 1, the following builder containing non-aqueous liquid heavy duty nonionic cleaning composition 20 containing an enzyme inhibitor was prepared.

wt%

Plurafac RA 30 "37, 5

Diethylene glycol monobutyl ether 10.0

Octenyl succinic anhydride 2.0 25 TPP NW 28.4

Sokolan CP 5 4.0

Dequest 2066 1.0

Perborate. ^ O 9.0 TAED 4.5 30 Hydroxylamine sulfate 0.1

Emphiphos 5632 0.3 ATS-X 0.2

Esperase 1.0

Perfume 0.6 35 Relatin DM 4050 1.0

Ti02 0.4 * t -33-

This composition has the same advantageous properties as the composition of Example I and moreover had an improved bleaching effect.

Claims (5)

1. A liquid laundry detergent bleaching composition comprising a liquid nonionic surfactant, a water-soluble inorganic peroxide salt as a bleaching agent and an effective amount of a compound which inhibits the enzyme-induced decomposition of the peroxide salt bleaching agent. inhibits. The composition according to claim 1, characterized in that the bleaching agent is a perborate, percarbonate, perphosphate or persulphate and the inhibitor of the enzyme-induced bleaching decomposition is a hydroxyl amine salt. Composition according to claim 2, characterized in that the hydroxy1-amine salt is hydroxylamine sulfate, hydroxylamine hydrochloride or hydroxylamine hydrobromide. 3 fe -34- Composition according to claim 2, characterized in that the amount of hydroxylamine salt is 0.01-0.5% by weight of the composition. Composition according to claim 2, characterized in that the amount of the hydroxylamine salt is 0.01-0.4% by weight of the composition. The composition of claim 1, further comprising a bleach activator compound which reacts with the bleach in an aqueous washing liquid at a temperature of 40 ° C or less to form a peroxyacid bleach. Composition according to claim 6, characterized in that the bleach activator is N, N, N ', Ν'-tetraacetylethylene diamine. Composition according to claim 1, characterized in that the composition is substantially non-aqueous. 9. Non-aqueous liquid detergent composition, which can wash and bleach dirty fabrics at temperatures as low as 40 ° C or less, comprising a liquid nonionic surfactant, a mono or poly-C 2 -C alkylene glycol mono-C 1 -C 4 alkyl ether, a water-soluble inorganic peroxide bleach, a bleach activator for lowering the temperature, the bleach in aqueous solution releasing hydrogen peroxide, and 0.01-0.4 wt% based on the total composition, of a hydroxylamine salt, capable of inhibiting the enzyme-induced decomposition of the bleach, which enzyme is present in the soiled tissues. f * 5- -35- Composition according to claim 9, characterized in that the bleaching agent is sodium perborate monohydrate, the bleach activator Ν, Ν, Ν ', Ν'-tetraacetylethylene diamine and the hydroxylamine salt is hydroxylamine sulfate or hydroxylamine hydrochloride and is present in an amount of 0.02-0 , 2%. The composition of claim 9, further comprising a detergent builder salt suspended in the liquid nonionic surfactant. 12. Method for cleaning and bleaching dirty fabrics, characterized in that the dirty fabrics are brought into contact with the composition according to claim 1 in an aqueous washing bath. Method for cleaning and bleaching dirty fabrics, characterized in that the dirty fabrics are brought into contact with the composition according to claim 9 in an aqueous washing bath. A method according to claim 13, characterized in that the aqueous washing bath has a temperature of 40 ° C or less. 5 V R 'R0 (CHCH20) nH 2 <OCH2-CH2r> p <CH-CH2> -Y- Z-COOH CH3 3 R2 R1 (OCH-CH2) n- ’’'l