SE467623B - Aqueous-free liquid detergent bleach composition - Google Patents

Description

467 623 10 15 20 25 30 others separate on cooling and cannot be readily redispersed. In some cases the viscosity of the product changes and it becomes either too thick J; to pour or so thin 'that it seems watery.

Some clear products become cloudy and other gels at rest.

The inventors have thoroughly studied the rheological behavior of nonionic liquid surfactant systems - with and without particulate matter suspended therein. Of particular interest have been anhydrous reinforced liquid detergent compositions and the gelling problems associated with nonionic surfactants as well as deposition of the suspended builder and other detergent additives. These considerations are important for, for example, the product's pourability, dispersibility and stability.

The rheological behavior of the anhydrous reinforced liquid detergents is analogous to the rheological behavior of paints in which the suspended builder particles correspond to the inorganic pigment and the nonionic liquid surfactant corresponds to the anhydrous paint vehicle. In the following discussion, for the sake of simplicity, the suspended particles, e.g. detergent enhancers, sometimes referred to as the "pigment".

It is known that one of the main problems with paints and reinforced liquid detergents is their physical stability. This problem enamers from g the fact that the density of the solid pigment particles is higher than the density of the liquid matrix. Therefore, the particles tend to settle according to Stokes 10 l5 20 25 -Ph O '\ \ J O \ ß) OJ law. There are two basic solutions to solve the sedimentation problem: liquid matrix viscosity and reduction of solid particle size.

For example, it is known that such suspensions can be stabilized against precipitation or deposition by the addition of inorganic or organic thickeners or dispersants, such as e.g. inorganic materials with a very high surface area, e.g. finely divided silica, clays, etc., organic thickeners such as the cellulose ethers, acrylic acid and acrylamide polymers, polyelectrolytes, etc. However, such increases in the viscosity of the suspension are naturally limited by the requirement that the liquid suspension be easily pourable and flowable, even at low temperature.

Furthermore, these additives do not contribute to the cleaning ability of the preparation.

Grinding to reduce the particle size is more advantageous and has two main consequences: 1. The specific surface area of the pigment is increased and therefore particle wetting of the anhydrous vehicle (liquid nonionic agent) is improved proportionally. 2. The average distance between pigment particles is reduced by a proportional increase in particle-to-particle interaction. Each of these effects contributes to increasing the quiescent gel strength and the yield strength of the suspension, while at the same time significantly reducing its plastic viscosity.

The anhydrous liquid suspensions of detergent builder particles, such as the polyphosphate builders, especially sodium tripolyphosphate (TPP) in nonionic surfactant, have been found to behave rheologically substantially according to Casson's equation: where W is the shear rate, C is shear rate, C is shear rate C: is the yield stress (or yield strength), and rm is the "plastic viscosity" (apparent viscosity at infinite shear rate).

The yield stress is the minimum force required to induce a plastic deformation (flow) of the suspension. Thus, considering the suspension as a loose network of pigment particles, if the applied force is lower than the yield stress, the suspension acts as an elastic gel and no plastic flow will occur. As soon as the yield stress is overcome, the network breaks at certain points and the sample begins to flow, but with a very high apparent viscosity. If the shear force significantly exceeds the yield stress, the pigment particles are partially shear-deflocculated and the apparent viscosity decreases.

Finally, if the shear force is much higher than the yield strength, the pigment particles are completely shear-flocculated and the apparent viscosity is very low, as if there was no particle interaction.

Therefore, the higher the yield strength of the suspension, the higher the apparent viscosity at low shear rates and the better the physical stability of the product. 10 15 20 25 30 467 623 In addition to the problem of precipitation or phase separation, the anhydrous liquid detergent based on liquid nonionic surfactants suffer from the disadvantage that the nonionic agents tend to gel when added to cold water. This is a particularly important problem in the ordinary use of European household automatic washing machines, where the user places the detergent composition in a dispensing unit (eg a drawer) on the machine.

During operation of the machine, the detergent in the dispenser is exposed to a stream of cold water for transferring the detergent to the washing solution.

Especially during the winter months, when the detergent composition and the water fed to the delivery device are particularly cold, the detergent viscosity increases markedly and a gel is formed. As a result, the composition is not completely flushed from the dispenser during operation of the machine and a deposit of the composition builds up during repeated wash cycles, possibly requiring the user to flush the dispenser with hot water.

The gelation phenomenon can also become a problem as soon as it is desirable to carry out washing with cold water, which is recommended for certain synthetic and sensitive textiles or textiles that can shrink in water or hot water.

Sub-solutions to the gelling problem in aqueous, substantially builder-free compositions have been proposed and include, for example, dilution of the liquid nonionic agent with certain viscosity-regulating solvents and gel-inhibiting agents, such as lower alkanols, e.g. ethyl alcohol (compare U.S. Patent 467,623, No. 3,953,380), alkali metal formats and adipates (compare U.S. Patent No. 4,368,147), hexylene glycol, polyethylene glycol, etc.

In addition, each of these two patents describes the use of up to at most about 2.5% of the lower alkyl (C1-C4) ethereal derivatives of the lower (C2-C3) polyols, e.g. ethylene glycol, in these aqueous liquid builder-free detergents instead of a portion of the lower alkanol, e.g. ethanol, as a viscosity regulating solvent.

The same applies to U.S. Pat. Nos. 4,115,855 and 4,201,686.

However, there is no description herein or any of these patents suggest that these compounds, some of which are commercially available under the trademark Cellosolve, could act effectively as viscosity regulating and gelling agents for anhydrous liquid nonionic surfactant compositions, especially such compositions. - containing suspended builder salts, such as the polyphosphate compounds, and in particular those compositions which are not dependent on or require lower alkanol solvents as viscosity control agents.

Furthermore, British Patent Specification 1 600 981 mentions that in anhydrous nonionic detergent compositions containing builders suspended therein by means of certain dispersant dispersants, such as atomized silica and / or polyester groups containing compounds having molecular weights of at least 500, it may be advantageous to use mixtures nonionic surfactants, one of which fulfills the surfactant function and the other both fulfills a surfactant function and reduces the pour point of the compositions. The former is exemplified by C12-C15 fatty alcohols with 5 to 15 moles of ethylene and / or propylene oxide per mole. The second surfactant is exemplified by linear C6-C8 or branched C8-C11 fatty alcohols with 2 to 8 moles of ethylene and / or propylene oxide per mole. Again, it is not taught that these lower carbon chains containing compounds could control the viscosity and prevent gelation of high performance anhydrous liquid nonionic surfactant compositions with enhancers suspended in the nonionic liquid surfactant.

It is also known to modify the structure of nonionic surfactants to optimize their resistance to gelation on contact with water, especially cold water. As an example of modification of nonionic surfactant, a particularly successful result has been obtained by converting the hydroxyl moiety end group of the nonionic molecule to acid. The benefits of introducing a carboxylic acid at the end of the nonionic molecule include gel inhibition upon dilution, reduction of the pour point of the nonionic agent, and formation of an anionic surfactant upon neutralization in the wash liquor. Optimization of the nonionic structure to minimize gel formation is also known, for example by controlling the chain length of the hydrophobic-lipophilic moiety and by controlling the number of alkylene oxide moieties (eg ethylene oxide) in the hydrophilic moiety.

For example, it has been found that a C13 fatty alcohol ethoxylated with 8 moles of ethylene oxide has only a limited tendency to gel. 467 623 10 15 20 25 30 35 Nevertheless, further improvements in stability, viscosity control and gel inhibition for anhydrous liquid detergent compositions are sought.

Thus, an object of the invention is to provide anhydrous liquid laundry detergents which do not gel on contact with or upon addition to water, particularly cold water.

Another object of the invention is to provide anhydrous liquid reinforced laundry detergent compositions which are storage stable, easy to pour and dispersible in cold, hot or hot water.

Another object of the present invention is to formulate highly reinforced high performance anhydrous liquid nonionic surfactant detergent compositions which can be maintained at all temperatures and which can be repeatedly dispensed from the dispenser of European type automatic washing machines without depositing or plugging the dispenser even during the winter months. .

A specific object of the present invention is to provide non-gelling stable low viscosity suspensions of high performance tripolyphosphate enhanced anhydrous liquid nonionic detergent detergent composition comprising an amount of a low molecular weight amphiphilic compound sufficient to reduce the viscosity of the composition and the absence of viscosity of the composition. in contact with cold water.

Its object of the invention is achieved by a detergent composition of the initially indicated species, which comprises a liquid phase comprising a liquid 4-67,623 nonionic surfactant and a mono- or poly- (Cf 4 L) alkylene glycol mono (Cf 30-70%, a water-soluble inorganic peroxide bleach in an effective amount of up to 25%, a bleach activator for lowering the temperature at which the bleach releases hydrogen peroxide in aqueous solution in an effective amount of up to 10%, proteolytic enzyme in a amount of about 0.7 to 2% by weight, and about 0.01 - 0.4% by weight, based on the total composition, of a hydroxylamine salt which inhibits the enzyme-induced decomposition of bleach, which enzyme is present in the soiled the textiles.

Thus, in one aspect, the present invention relates to a liquid high performance detergent composition composed of a suspension of a builder salt in a liquid nonionic surfactant, the composition comprising an amount of a lower (C; (lower) (C) viscosity in the absence of water and when the composition is brought into contact with water.

In a more specific embodiment, the present invention relates to an anhydrous liquid cleaning composition which remains pourable at temperatures below about 5 ° C and which does not gel when contacted with or added to water at temperatures below about 20 ° C, which composition is composed of a liquid nonionic surfactant and C 1 -C 4 alkylene glycol mono (C 1 -C 3) alkyl ether and which is substantially free of water.

According to the invention there is further provided a method of filling a container with an anhydrous liquid detergent composition in which the detergent is at least predominantly composed of a liquid nonionic surfactant and for dispensing the composition from the container into a liquid detergent composition. aqueous wash bath, the discharge or release being effected by directing a stream of unheated water towards the composition so that the composition of the water stream is transported into the wash bath. the incorporation of a low molecular weight amphiphilic compound, i.e. a lower C 2 -C 3 alkylene glycol mono (lower) (C 1 -C 5) alkyl ether, the composition can be easily poured into the container, even when the composition has a temperature below room temperature. Furthermore, the composition does not gel when it is brought into contact with the stream of water and it is easily dispersed at the entrance to the washing bath. As will be seen below, in addition to the detergent active ingredient, the liquid detergent compositions often comprise one or more detergent additives or excipients. One of the more important of these in terms of consumer preferences and in terms of cleaning benefits is the class of bleaches, especially oxygen bleaches, of which sodium perborate monohydrate is a particularly preferred example.

It is well known in the art that in solution the oxygen bleach persalt releases hydrogen peroxide as the active oxidizing agent. However, hydrogen peroxide is decomposed by catalase, an enzyme that is always present in natural dirt and stains. This decomposition also occurs in the presence of bleach activators, since the reaction rate of the reaction between hydrogen peroxide and the activator is lower than the decomposition of hydrogen peroxide of catalase. The activity of the catalase is very high, even at room temperature, and a significant proportion of the active oxygen is lost before the catalase is deactivated by increasing the temperature of the washing bath.

One approach to solving this problem has been to use an excess amount of perborate or other peroxide bleach, e.g. an amount which usually amounts to 2 to 4 times more than would be needed to effectively bleach the dirt or stain in the absence of peroxide decomposing enzyme and also 2 to 4 or more times molar excess relative to the number of moles of bleach activator.

It has also been proposed to carry out the bleaching with an aqueous solution of peroxide bleach in the presence of a compound capable of inhibiting enzyme-induced decomposition of bleaches; Thus, U.S. Patent No. 3,606,990 discloses a relatively wide range of inhibitor compounds, including, for example, hydroxylamine salt, hydrazine and phenylhydrazine and their salts, substituted phenols and polyphenols, and other as well as various detergent compositions comprising the water-soluble inorganic peroxide bleach and inhibitor bitorföreningen. However, it is not taught that liquid detergent compositions comprising the inhibitor compounds nor is it taught that the inhibitor compounds would be effective in compositions containing a bleach activator in addition to the peroxide bleach. It is further claimed in this patent in column 7, lines 25-29, that in the case of hydroxylamine sulphate the effective amount of inhibitor compound amounts to about 0.5-2% by weight of the total composition.

It has now been found that in liquid detergent compositions according to the invention containing a water-soluble inorganic peroxide bleach of persalt type the incorporation in very limited amounts of less than about 0.5%, for example 0.01 to about 0.45% can effectively inhibit enzyme-induced decomposition of the bleach. It has further been found that hydroxylamine sulphate is very stable in the composition and does not interfere at all with the activation of the bleaching system by conventional persalt bleach activators.

Thus, in accordance with a further embodiment of the present invention, there is provided a liquid high performance laundry detergent composition comprising a water soluble inorganic peroxide bleach and an effective amount of a compound capable of inhibiting enzyme-induced decomposition of the bleach, especially in an amount of less than about 0.5% by weight of the composition, and preferably with an activator for activating the bleach.

Other features and specific embodiments of the invention will become apparent from the following detailed description, and the invention will also be more readily understood by reference thereto.

The nonionic synthetic organic detergents used in the practice of the invention may be any of a wide variety of such compounds, which are well known and are described, for example, in the text Surface Active Agents, Volume II, by Schwartz, Perry and Berch. , published in 1959 by Interscience Publishers, and in McCutcheon's Detergents and Emulsifiers, 1969 Annual, and the relevant portions of which are incorporated herein by reference. Typically, the nonionic detergents are poly-lower alkoxylated lipophilic files, wherein the desired hydrophilic-lipophilic balance is achieved by adding a hydrophilic poly-lower alkoxy group to a lipophilic moiety. A preferred class of the nonionic detergent used is the poly-lower alkoxylated-higher alkanol, in which the alkanol has 10 to 18 carbon atoms and in which the number of moles of lower alkylene oxide (having 2 or 3 carbon atoms) amounts to 3 to 12. Of these materials, those in which the higher alkanol is a higher fatty alcohol having 10 to 11 or 12 to 15 carbon atoms and which contains from 5 to 8 or 5 to 9 lower alkoxy groups per mole are preferably used. Preferably the lower alkoxy group is ethoxy, but in some cases it may suitably be mixed with propoxy, the latter being usually but not necessarily present being a minor part (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, e.g.

Neodol 25-7 and Neodol 23-6.5, which products are manufactured by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols with an average of about 12 - 15 carbon atoms with about 7 moles of ethylene oxide and the latter is a corresponding mixture, in which the carbon atom content of the higher fatty alcohol is 12-13 and the number of ethylene oxide groups present averages 6.5. The higher alcohols are primary alkanols. Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates manufactured by Union Carbide Corp. The former is a mixed ethoxylation product of linear secondary alkanol having 11 to 15 carbon atoms with 7 moles of ethylene oxide and the latter is a similar product but in which 9 moles of ethylene oxide have been reacted. In the present compositions, as a component of the nonionic detergent, also useful are the higher molecular weight nonionic member, such as Neodol 45-111, which are similar to ethylene oxide condensation products of higher fatty alcohols, where the higher fatty acid the alcohol has 14 - 15 carbon atoms and the number of ethylene oxide groups per mole amounts to about 11. Such products are also manufactured by Shell Chemical Company.

Other useful nonionic agents are represented by the well-known commercially available Plurafac series, which are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include Plurafac RA30 (a C13-C15 fatty alcohol condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide), Plurafac RA40 (a C13-C15 fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide), Plurafac D25 (a C13-C15 fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide), and Plurafac B26.

In general, the mixed ethylene oxide-propylene oxide-fatty alcohol condensation products can be represented by the general formula RO (C 2 H 4 O) x (C 3 H 6 O) y H, where R is a straight or branched primary or secondary aliphatic hydrocarbon, preferably alkyl or alkenyl of 6 - 20 and preferably - 18, and especially preferably 14 - 18 carbon atoms, x is a number of 2 - 12, preferably 4 - 10, and y is a number of from 2 - 7, preferably 3 - 6.

Another group of liquid nonionic agents can be obtained from Shell Chemical Company, Inc. under the trademark 10 15 20 25 30 467 623 15 Dobanol: Dobanol 91.5 is an ethoxylated C 9 -C 15 fatty alcohol having an average of 5 moles of ethylene oxide, 12 -C15 fatty alcohol with an average of 7 moles of ethylene oxide, etc.

Dobanol 25-7 is an ethoxylated CI the preferred poly-lower alkoxylated-higher alkanols, to obtain the best balance between hydrophilic and lipophilic units, the number of lower alkoxy groups normally amounts to 40 - 10% of the number of carbon atoms in the higher the alcohol, preferably 40-60% thereof and the nonionic detergent preferably contains at least 50% of said preferred poly-lower alkoxy-higher alkanol. Higher molecular weight alkanols and various other normally solid nonionic detergents and surfactants may contribute to the gelling of the liquid detergent and thus these are preferably released or limited in amount in the present compositions, although minor proportions thereof may be used for their cleaning properties. etc.

With respect to both preferred and less preferred nonionic detergents, the alkyl groups present therein are generally linear although branching may be tolerated, such as with a carbon adjacent or two carbon atoms i- from the straight chain end carbon and from the ethoxy chain, if said branched alkyl is not is longer than three carbon atoms. Normally the proportion of carbon atoms in such a branched configuration is smaller, and rarely exceeds 20% of the total carbon atom content of the alkylene. Similarly, although linear alkyls terminally attached to the ethylene oxide chain are highly preferred and are considered to result in the best combination of cleaning ability, biodegradability and non-gelling properties, medial or secondary bonding to ethylene oxide in the chain may occur. This is usually the case only in a smaller proportion of said alkyls, usually less than 20% but as in the case of said Tergitols the proportion may be greater. Even when propylene oxide is present in the lower alkylene oxide chain, it usually but not necessarily amounts to less than 20% thereof and preferably less than 10% thereof.

When larger proportions of non-terminally alkoxylated alkanols, propylene oxide-containing poly-lower alkoxylated alkanols and less hydrophilic-lipophilically balanced nonionic detergents than above are used, and when other nonionic detergents are used in place of the preferred nonionic member listed herein, the resulting product has possibly not as good cleaning ability, stability, viscosity and non-gelling properties as the preferred compositions, but use of the viscosity and gel controlling compounds of the invention can also improve the properties of the detergents based on such nonionic agents. In some cases, such as when a poly-lower alkoxylated-higher alkanol of higher molecular weight is used, often for its cleaning ability, the proportion thereof is regulated or limited according to the results of various experiments to achieve the desired cleaning ability and still maintain the product non-gelling and with the desired viscosity.

It has also been found that it is only rarely necessary to use the higher molecular weight nonionic agents for their detergent properties, since the preferred nonionic agents described herein are excellent detergents and also allow the desired viscosity of the liquid detergent to be achieved without gel formation at low temperatures. Mixtures of two or more of these liquid nonionic agents may also be used and in some cases advantages may be obtained by the use of such mixtures.

As mentioned above, the structure of the liquid nonionic surfactant can be optimized with respect to their carbon chain length and configuration (eg, linear to branched chains, etc.) and their content and distribution of alkylene oxide units. Extensive research has shown that these structural properties can and do have a decisive effect on such properties of the nonionic member as pour point, cloud point, viscosity, gel-forming tendency, as well as of course on cleaning ability.

Typically, most commercially available nonionic agents have a relatively large distribution of ethylene oxide (EO) and propylene oxide (PO) units and of the lipophilic hydrocarbon chain length, and the stated EO and PO contents and hydrocarbon chain lengths are total averages. This "polydispersity" of the hydrophilic and lipophilic chains can be of great importance for the product properties as well as the specific values of the average values. The relationship between "polydispersity" and specific chain lengths with product properties of a well-defined nonionic agent can be shown by the following data for the "surfactant T" series of nonionic agents available from British Petroleum. Surfactant T-nonionic agents are obtained by ethoxylation of secondary C13 fatty alcohols with a narrow EO distribution and have the following physical properties: 467 623 10 15 20 25 18 EO pour point cloud point (1% solution) hold ( ° c) (° c) surfactant T5 5 <-2 <25 surfactant T7 7 -2 38 surfactant T9 9 6 58 surfactant Tl2 12 20_ 88 To investigate the significance of EO distribution, a "surfactant T8" was artificially produced on two methods: a. 1: 1 mixture of T7 and T9 (T8a) b. 4: 3 mixture of T5 and T12 (T8b).

The following properties were obtained: E0 content cloud point hold point (1% solution) (average) (° c) (° c) surfactant T8a 8 2 48 surfactant T8b 8 15 <20 From these results, the following general observations can be made: tions are made: l. T8a corresponds closely to a real surfactant T8 as it interpolates well between_T7 and T9 both in terms of pour point and cloud point. 2. T8b, is highly polydisperse and would be generally unsatisfactory due to its high pour point and low cloud point temperature. The properties of T8a are generally additive between T7 and T9, while T8b is close to the long EO chain (Tl2) with respect to the pour point, while the cloud point is close to the short one. EO chain (T5).

The viscosities of the surfactant T nonionic agents were measured at 20%, 30%, 40%, 50%, 60%, 80% and 100% nonionic concentrations for TS, T7, T7 / T9 (1 = 1). T9 and T12 at 25 ° C with the following results (when a gel is obtained the viscosity is the apparent wickness) at 100 sec = nonionic viscosity (mPa.s) average tYP% T5 T7 T7 T7 / T9 T9 Tl2 100 36 63 61 149 80 65 104 ll2 165 60 750 78_ 188 239 32200 50 4000 123 233 634 89100 40 2050 96 149 211 187 30 630 58 38 27 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, and further, the mixture of T7 and T9 (T8) does not gel and its viscosity exceeds 225'mPa.s. T5 and T12 do not form the same gel structure. Although the intention is not to establish any particular theory, it is assumed that these results can be explained by the following hypothesis: 467 625 10 15 20 25 30 20 For T5: with only 5 E0, the hydrodynamic volume of the EO chain is essentially the same as the hydrodynamic volume of the fat chain. The surfactant molecules can thus arrange themselves to form a lamella structure.

For T12: with 12 EO, the hydrodynamic volume of the EO chain is greater than that of the fat chain. When the molecules strive to arrange themselves together, an interfacial curvature is formed and rods are obtained. The superstructure is then hexagonal, with a longer E0 chain or with a higher hydration, the interfacial curvature can be such that real spheres are achieved, and the arrangement with the lowest energy is a surface-centered cubic lattice.

From T5 to T7 (and T8) the interfacial curvature increases and the energy of the lamella structure increases. As the lamellar structure loses 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). When the loss of stability occurs, the melting temperature of the structure is also reduced.

Surfactant T8 appears to be at the critical point at which the lamellar structure is destabilized, i.e. the hexagonal structure is not yet sufficiently stable and no gel is obtained upon dilution. In fact, a 50% solution of T8 finally gels after 2 days, but the superstructure formation is delayed long enough to allow easy dispersibility in water. l0 l5 20 25 30 467 623 21 The effects of molecular weight on the physical properties of the nonionic agents were also taken into account. Surfactant T8 (1: 1 mixture of T7 and T9) shows a good compromise between the lipophilic chain (C13) and the hydrophilic chain (E08), although the pour point and maximum viscosity when diluted at 250 ° C are still high. .

The corresponding EO compromise for C10 and C8 lipophilic chains was also determined using the Dobanol 91-x series from Shell Chemical Co., which are ethoxylated derivatives of C9-C11 fatty alcohols (average: C10), and Alfonic 61 the γ series from Conoco, 6-C10 fatty alcohols (average C8), where x and y represent which are ethoxylated derivatives of the C weight percent EO.

The following table shows the physical properties of the Alfonic 610-y series and Dobanol 9l-x series: nonionic number of EO pour-grum- max. viscosity medium (penetration point at dilution section) (° c) point 2s ° 'c (mPa. s) (° c) Alfonic 610-SOR 3 -15 C gel (60%) Alfonic 610-60 4.4 -4 4l 36 (60%) Dobanol 91-5 5 -3 33 gel (70%) Dobanol 9l-ST 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 91-1-topped (T) is a laboratory scale product in the form of Dobanol 91-5 from which 467 623 10 15 20 25 30 22 free alcohol has been removed. When the lowest ethoxylation products have also been removed, the average EQ number is 6. Dobanol 91-51 gives the best results for C10 lipophilic chain as it does not gel at 250 ° C. Cloud point at 1% concentration (550 ° C) is higher than for surfactant T8 (480 C). This is probably due to the lower molecular weight, as the entropy of the mixture is higher. Alfonic 610-60 gives the best results for the lipophilic C8 chain series.

A summary of the best EO contents for each tested lipophilic chain length is shown in the following table: nonionic number of pouring grum- max. viscosity agent C EO point lings- at dilution (° c) point (%) at 25 ° c (1% (mPa.s) solution.) <° c> surfactant T8 13 8 +2 48 223 (50%) Dobanol 91 -ST 10 6 +2 55 126 (50%) Alfonic 610-60 8 4.4 -4 41 36 (60%) From these data the following conclusions are drawn: Pour points: when the molecular weight of the nonionic agent is reduced, its pour points are also reduced. The relatively high pour point for Dobanol 91-ST can be explained by the higher polydispersity. This was also noted for T8a and T8b, i.e. the chain polydispersity increases the pour point. 10 15 20 25 30 467 623 23 Clouding points: theoretically, when the number of molecules increases (if the molecular weight decreases) the mixing entropy is higher, so the cloud point would increase when the molecular weight decreases. This is the case for surfactant T8 for Dobanol 91-ST, but has not been confirmed with Alfonic 610-60. In this case, it is assumed that the lipophilic hydrocarbon chain polydispersity is responsible for the theoretically too low cloud point. The relatively large amount of C10-EO present reduces the solubility.

Maximum viscosity when diluted at 250 DEG C.: none of these nonionic agents gels at 25 DEG C. when diluted with water. The maximum viscosity decreases markedly with the molecular weight. As the molecular weight of the nonionic agent decreases, the hydrogen bridges become less effective. Unfortunately, non-ionic agents with too low a molecular weight are suitable for washing, as their critical micelle concentration (MCC) is too high and a true solution with only limited cleaning ability would be obtained under practical washing conditions.

With this information, the studies of the effects of the low molecular weight of the amphiphilic compounds on the rheological properties of liquid nonionic detergent cleaning compositions were continued. These studies showed that while it is possible to lower the pour point of the composition and obtain some degree of gel inhibition through the use of a short chain hydrocarbon. for example about C8, with a short chain ethylene oxide substitution, e.g. about 4 moles, as an amphiphilic additive, such as Alfonic 610-60, these additives do not contribute significantly to the total washability 467 623 10 15 20 25 24 and still do not exhibit overall satisfactory viscosity control over 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 in chemical structure to the ethoxylated and / or propoxylated fatty alcohol nonionic surfactants, but which have short hydrocarbon chain lengths (Cl C5) and a low content of alkylene oxide, ie ethylene oxide and / or propylene oxide (approximately 1 to 4 EO / PO units per molecule), act effectively as viscosity regulating and gel inhibiting agents for the liquid nonionic surfactants.

The viscosity regulating and gel inhibiting amphiphilic compounds used in the present invention can be represented by the following general formula: R 1 I Ro (cHcH 2 O) n H where R is a C 1 -C 5, preferably C 2 -C 5, particularly preferably C 2 -C 4 and especially C 4 alkyl group, R 'is H or CH 3, preferably H, and n is a number between about 1 and 4, preferably 2-4 on average.

Preferred examples of suitable amphiphilic compounds are (2CH 2 OH), 9-O- (CH 2 CH 2 O) 2 H).

Diethylene glycol monoethyl ether is particularly preferred, including ethylene glycol monoethyl ether (C 2 H 5 -O-CH and diethylene glycol monobutyl ether (C 4 H and as will be shown below) is uniquely effective in controlling viscosity. may be the only viscosity regulating and gel inhibiting additive in the compositions of the invention, further improvements in the rheological properties of the anhydrous liquid nonionic surfactant compositions can be achieved by incorporating into the composition a minor amount of a nonionic surfactant, which modified by converting a free hydroxyl group therein to a moiety having a free carboxyl group, such as a partial ester 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 phosphoric acid and an alkanol.

It is further known that the modified non-ionic surfactants with the free carboxyl group, which can generally be characterized as polyether carboxylic acids, have the function of lowering the temperature at which the liquid nonionic agent forms a gel with water.

The acidic polyether compound can also lower the yield stress of such dispersions, which helps their dischargeability without a corresponding decrease in its precipitation stability. Suitable polyethercarboxylic acids contain a grouping of the formula R 2 - (αCH 2 -CH 2 -p-EFH-CH 2 -CY 2 -COOH where R * is hydrogen CH 2 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 a positive number up to 10. Specific examples include the half ester of 467 625 10 15 20 25 30 26 Plurafac RA3O with succinic anhydride, the half ester of Dobanol 25-7 with succinic anhydride, the half ester of Dobanol9l With succinic anhydride, etc. In place of an succinic anhydride, other polycarboxylic acids or anhydrides may be used, eg maleic acid, maleic anhydride, glutaric acid, malonic acid, succinic acid, phthalic acid, phthalic anhydride, citric acid, etc. other bonds are used, 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 convert its OH group t in a ONa group, for example) and then reacted with a halocarboxylic acid such as chloroacetic acid or chloropropionic acid or the corresponding bromine compound.

Thus, the resulting carboxylic acid may have the formula RY-ZCOOH, where R is the residue of a nonionic surfactant (after removal of a terminal OH), Y is oxygen or sulfur and Z represents an organic bond such as a hydrocarbon group of for example one to ten carbon atoms, which may be attached to the oxygen (or sulfur) in the formula directly or through an intermediate bond such as an oxygen-containing bond, e.g.

O O n u a -C- or -C-NH- etc.

The polyether carboxylic acid may be prepared from a polyether which is not a nonionic surfactant, e.g. it can be prepared by reaction with a polyalkoxy compound such as a polyethylene glycol or monoester or monoether thereof, which does not contain the long alkyl chain as the nonionic surfactants. Thus, R may have the formula R: R * ((| 3CH-CH 2) 2 -, wherein R * is hydrogen or methyl, R * is alkylphenyl or alkyl or other chain terminating group and "n" is at least 3 such as 5 to 25. When the alkyl of R * is a higher alkyl, R is a residue of a nonionic surfactant. As indicated above, R * may instead be hydrogen or lower alkyl (e.g. methyl, ethyl, propyl, butyl) or lower acyl (eg acetyl, etc.) The acidic polyether compound, if present in the detergent composition, is preferably added dissolved in the nonionic surfactant.

Another useful class of complementary anti-gelling agents is C 1 -C 6 alkyl or alkenyldicarboxylic acid anhydride, such as e.g. octenyl succinic anhydride, octenylmaleic anhydride, dodecyl succinic anhydride, etc. These compounds may be used in conjunction with or in place of some or all of the polyether carboxylic acid anti-gelling agent.

It is known that the acidic organic phosphorus compound having an acidic POH group increases the stability of the builder suspension, especially polyphosphate builder, in the anhydrous liquid nonionic surfactant.

The acidic organic phosphorus compound may be, for example, a partial ester of phosphoric acid and an alcohol such as an alkanol having a lipophilic character having, for example, more than 5 carbon atoms, e.g. 8 - 20 carbon atoms. 467 625 »l0 15 20 25 30 28 A specific example is a partial ester of phosphoric acid and a C16-C18 alkanol (Empiphos 5632 from Marchon), which consists of about 35% monoester and 65% diester.

The incorporation of very small amounts of, for example, about 0.05 - 0.3% by weight of the composition of the acidic organic phosphorus compound makes the suspension significantly more stable to precipitation at rest but remains pourable, probably as a result of increasing yield strength of the suspension, but lowers its plastic viscosity. It is believed that the use of the acidic phosphorus compound may result in the formation of a high energy physical bond between the POH moiety of the molecule and the surfaces of the inorganic polyphosphate builder so that these surfaces assume an organic character and become more compatible with the nonionic surfactant. medlet.

The acidic organic phosphorus compound can be selected from a large number of different materials, in addition to the partial esters of phosphoric acid and alkanols mentioned above.

Thus, one can use a partial ester of phosphoric acid or phosphoric acid with a mono- or polyvalent alcohol such as hexylene glycol, ethylene glycol, di- or triethylene glycol or higher polyethylene glycol, polypropylene glycol, glycerol, sorbitol, mono- or diglycerides of fatty acids, etc. in which one, two or more of the alcoholic OH groups in the molecule may be esterified with the phosphoric acid or the phosphoric acid. The alcohol may be a nonionic surfactant such as an ethoxylated or ethoxylated-propoxylated higher alkanol, higher alkylphenol, or higher alkylamide. The POH group need not be attached to the organic portion of the molecule through an ester bond but may instead be directly attached to carbon (such as in phosphonic acid, such as a polystyrene in which some of the aromatic rings carries phosphonic acid or phosphinic acid groups, or an alkylphosphonic acid such as propyl or laurylphosphonic acid) or it may be attached to the carbon by an intermediate bond (such as bonds through O, S or N atoms).

Preferably, the carbon: phosphorus atomic ratio of the organic phosphorus-containing compound is at least about 3: 1, such as 5: 1, 10: 1, 20: 1, 30: 1 or 40: 1.

The detergent composition of the invention may also preferably comprise water-soluble detergent builder salts. Typical suitable builders include, for example, those described in U.S. Patent Nos. 4,316,812, 4,264,466 and 3,630,929. Water-soluble inorganic alkaline builder salts which can be used alone with the detergent compound or in admixture with other builders are alkali metal carbonate. -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, potassium tripolyphosphate and sodium phosphate, sodium phosphate. Sodium tripolyphosphate (TPP) is especially preferred. The alkali metal silicates are useful builder salts, which also work to make the composition anti-corrosive to washing machine parts. Sodium silicates with a Na 2 O / SiO 2 ratio of 1.6 / l - 1 / 3.2, especially about 1/2 - 1 / 2.8 are preferred. Potassium silicates with the same conditions can also be used. Another class of builders useful herein are the water-insoluble aluminosilicates, both of the crystalline and the amorphous type. Various crystalline zeolites (i.e., aluminosilicates) are described in British Patent Specification 1,504,168, U.S. Patent No. 4,409,136 and Canadian Patents 1,072,835 and 1,087,477, all of which are incorporated herein by reference for the description of said zeolites. An example of amorphous zeolites useful herein is found in Belgian Patent Specification 835,351 and this patent specification is also incorporated herein by reference. The zeolites generally have the formula (Mzmx- (Al2 O3) y- (S102) z-wnzo where x is 1, y is 0.8 - 1.2 and preferably 1, z is 1.5 - 3.5 or higher and preferably 2 3 and W are 0-9, preferably 2.5-6 and M is preferably sodium, a typical zeolite is type A or similar structure, with type 4A being particularly preferred.The preferred aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents per gram or higher, eg 400 meq / g.

Other materials such as clays, especially of the water-insoluble types may be useful additives in the compositions of the invention. Particularly useful is bentonite. This material is primarily montmorillonite, which is 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, etc. may be loosely bound. The bentonite in its purified form (ie free from all gravel, sand, etc.) suitable for detergents invariably contains at least 50% montmorillonite and thus its cation exchange capacity is at least about 50-75 meq. per 100 grams of bentonite.

Particularly preferred bentonite is Wyoming or.

Estern US bentonites, which have been sold as Thixojels 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften textiles as described in British Pat. Nos. 401,413 and 461,221.

Examples of organic alkaline sequestering builder salts which can be used alone with detergents or in admixture with other organic and organic builders are alkali metal, ammonium or substituted ammonium aminopolycarboxylates, e.g. sodium and potassium ethylenediaminetetraacetate (EDTA), sodium and potassium nitrilotriacetates (NTA) and triethanolammonium N- (2-hydroxyethyl) nitrilodiacetates.

Mixed salts of these polycarboxylates are also suitable.

Other suitable builders of the organic type include carboxymethyl succinates, tartronates and glycolates. The polyacetate carboxylates are particularly valuable. The polyacetal carboxylates and their use in detergent compositions are described in U.S. Patent Nos. 4,144,266, 4,315,092 and 4,146,495. Other patents relating to similar builders include U.S. Patent Nos. 4,141,676, 4,669,934, 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. European patent applications Nos. 0 015 024, 0 021 491 and 0 063 399 are also relevant. Since the compositions of the present invention are generally highly concentrated and therefore can be used at relatively low dosages, it is desirable to supplement any phosphate builder (such as sodium tripolyphosphate) with an additional builder such as a polymer. carboxylic acid with high calcium binding capacity to prevent incubation, which could otherwise be caused by the formation of an insoluble calcium sulphate. Such complementary amplifiers are also well known in the art.

Various other detergent additives or excipients may be present in the detergent product to impart to it additional desirable properties, either of a functional or aesthetic nature. Thus, smaller amounts of soil suspending or anti-redeposition agent can be incorporated into the preparation, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethylcellulose, hydroxypropylmethylcellulose, optical brighteners, e.g. cotton, amine and polyester brightness enhancers, e.g. stilbene, triazole and benzidine sulfone compositions, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzene sulfone, etc., with stilbene and triazole combinations being most preferred.

Blending agents such as ultramarine blue, enzymes, preferably proteolytic enzymes such as subtilisin, bromelain, papain, trypsin and pepsin as well as amylase type, lipase type enzymes and mixtures thereof, bactericides, e.g. tetrachlorosalicylanilide, hexachlorophene, fungicides, dye, pigments (water-dispersible), preservatives, ultraviolet absorbers, anti-yellowing agents such as sodium carboxymethylcellulose, complexes of C12-C22-alkyl alcohol with Cl2-C18-alkyl-C -modifiers and pH buffers, color-safe bleaches, perfumes and antifoams or suds suppressors, e.g. silicone compounds, can also be used.

The bleaches are generally classified as chlorine bleaches and oxygen bleaches. The chlorine bleaches can typically be exemplified by sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% available chlorine) and trichloroisocyanuric acid (85% available chlorine). The oxygen bleaches are preferred and represented by percompounds which release hydrogen peroxide in solution, i.e. compounds containing hydrogen peroxide or inorganic perhydrates which on dissolution release hydrogen peroxide enclosed in their crystal lattice. Preferred examples include sodium and potassium perborates, percarbonates and perphosphates, and potassium monopersulfate. The perborates, and especially sodium perborate monohydrate, are especially preferred.

Hydrogen peroxide and precursors that release hydrogen peroxide in solution are good oxidizing agents for removing certain stains from tY9, especially stains caused by wine, tea, coffee, chocolate, fruit, etc.

Hydrogen peroxide and its precursors have been found to generally bleach rapidly and most effectively at a relatively high temperature, e.g. about 80 - l00o C.

However, such compounds have a tendency to decompose and release gaseous oxygen at lower temperatures. The release of gaseous oxygen, which is not involved in the oxidation of colored goods, unnecessarily consumes a considerable amount of hydrogen peroxide or precursors which release it, both of which are expensive products. Furthermore, it has been found that the various stains in fabric and the like greatly accelerate the decomposition of hydrogen peroxide to gaseous oxygen during washing at ordinary temperature.

In general, washing of fabric is achieved: either by machine, by hand or in a boiler or vessel by dissolving a bleaching or detergent composition (containing, for example, perborate) in cold or lukewarm water, adding to the solution thus formed of the soiled laundry (from which a certain part of the stains has often already been removed by soaking or previous washing) and heating, often just before boiling.

However, it has been found that by a phenomenon similar to that described above, all or part of the perborate decomposes during heating and more specifically during temperature rise, i.e. all or part of the perborate was decomposed before the truly effective temperature was reached.

It is believed that this rapid decomposition of hydrogen peroxide, perborate or other starting compounds for hydrogen peroxide to gaseous oxygen at low temperature is due to the extremely strong catalytic action of certain enzymes, which are always present in stains, which occur on materials to be washed, and especially on soiled fabrics such as linen, which enzymes come from secretions or have bacterial origin.

Hydrogen peroxidase is a particularly active group of enzymes in this respect, especially catalase, which is well known as a very effective catalyst for the decomposition of hydrogen peroxide to gaseous oxygen. Such enzyme substances, whether called "redox" or otherwise, are all characterized by the fact that they have a pronounced tendency to induce decomposition of peroxide bleaches, and the decomposition products released thereby comprise ineffective bleaching agents.

To take advantage of the low temperature effective detergents and low temperature wash cycles now in widespread use for temperature sensitive fabrics, the peracid compound is preferably used in admixture with an activator therefor. Suitable activators which can lower the effective operating temperature of the peroxide agent to about 400 ° C or below are described, for example, in U.S. Patent No. 4,264,466 or in column 1 of U.S. Patent No. 4,430,244, the disclosures of which are incorporated herein by reference. Polyacylated compounds are preferred activators, and among these, compounds such as tetraacetylethylenediamine ("TAED") and pentaacetyl glucose are particularly preferred. Other useful activators include, for example, acetylsalicylic acid and its salts, ethylidene benzoate acetate (EBA) and its salts, ethylidene carboxylate acetate and its salts, alkyl and alkenyl succinic anhydride, tetraacetylglycouril (TAGU) and their derivatives.

See also U.S. Patent Nos. 4,118,826, 4,422,950 and 3,661,789 to other classes of activators useful herein.

The bleach activator usually cooperates with the peracid compound to form a peroxyacid bleach in the washing water. Preferably, a sequestering agent with high complexing power is incorporated to inhibit undesired reaction between said peroxyacid and hydrogen peroxide in the washing solution in the presence of metal ions. Preferred sequestrants can form a complex with Cu "ions, such that its stability constant (pK) for complex formation is equal to or greater than 6 at 25 ° C in water with an ionic strength of 0.1 mol. / liter, where pK is conventionally defined by the formula pK = -log K, where K represents the equilibrium constant.

Thus, e.g. The pK values for complex binding of copper ion with NTA and EDTA under specified conditions are 12.7 and 18.8, respectively. Suitable sequestrants include e.g. in addition to the above-mentioned diethylenetriaminepentaacetic acid (DETPA), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and ethylenediaminetetramethylenephosphonic acid (EDITEMPA).

However, even in the presence of the bleach activators and even at temperatures as low as room temperature, decomposition of the persalt will occur in the presence of the stained fabric, since the rate of reaction between the bleach and the activator is lower than the rate of decomposition of hydrogen peroxide of catalase.

To avoid loss of the bleach due to enzyme-induced decomposition, the compositions of the present invention preferably also comprise an effective amount of a compound capable of inhibiting this enzyme-induced decomposition of bleach. Suitable inhibitor compounds are described in U.S. Patent No. 3,606,990, and the relevant disclosure thereof is incorporated herein by reference.

Of particular interest and importance as an inhibitor compound are hydroxylamine sulfate and other water-soluble hydroxylamine salts, including, for example, hydrochloride, hydrophobic bromide, etc. It has now been found that the hydroxylamine salts, especially the sulfate, are effective. inhibits the deleterious effect of the catalase, even when present in the composition in very limited amounts of, for example, less than 0.5%, such as 0.01 - 0.4%, preferably 0.04 - 0.2%, and particularly preferably about 0.1%, based on the weight of the total composition.

Furthermore, the hydroxylamine inhibitor is very stable in composition: less than 20% loss after aging for 2 months at 430 ° C. The hydroxylamine salts are solubilized in water very quickly and can thus react with the catalase before dissolving the perborate or other peroxide bleach. Another advantage of the hydroxylamine salts is that they are rapidly destroyed in the washing liquid and thus no nitrosamine derivatives have been detected.

When the bleach system is activated by one of the bleach activators, e.g. TAED, the activator is used more efficiently and thus suitable conditions of persalt bleach / bleach activator can be maintained at levels much closer to the stoichiometrically equivalent weights or with only a small molar excess relative to the bleach.

The composition may also contain an inorganic insoluble thickener or dispersant having a very high surface area such as atomized silica with extremely fine particle size (eg 5 to 100 milli-fl diameter, such as that sold under the name Aerosil) or the other high volume inorganic carriers. len described in U.S. Pat. No. 3,630,929, in proportions of 0.1 to 10%, e.g. l - 5%. However, it is preferred that compositions which form peroxyacids in the wash bath (e.g., compositions containing peracid compound and activator therefor) be substantially free of such compounds and other silicates, as it has been found that, for example, silica and silicates promote the undesired decomposition of the peroxyacid.

According to a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid ingredients is subjected to a friction type mill in which the particle sizes of the solid ingredients are reduced to less than about 10 μm e.g. to an average particle size of 2 - 10 / nn or even lower (eg l fmü.

Compositions whose dispersed particles are of such a small size have improved stability against separation or precipitation during storage.

In the grinding operation, it is preferred that the proportion of solid ingredients be high enough (eg at least about 40% such as about 50%) for the solid particles to come into contact with each other and not be substantially protected from each other by the nonionic the surfactant liquid. Grinders that use grinding balls (ball grinders) or similar moving grinding elements have given very good results. Thus, one can use a batch of laboratory attritors with 8 mm diameter steatite bullets. For work on a larger scale, a continuously operating grinder, in which 1 mm or 1.5 mm diameter grinding balls operate in a very small gap between a stator and a rotor, which operates at a relatively high speed (t .ex. and CoBall mill). When using such a grinder, it is desirable to pass the mixture of nonionic surfactant and solid particles first through a grinder which does not effect such grinding (e.g. a colloid grinder) to re-grind. reduce the particle size to less than 100 microns (eg to about 40 / HH) before the grinding step to an average particle diameter below about 10 / nn in the continuous ball mill.

In the preferred high performance liquid detergent compositions of the invention, typical proportions (based on the total composition unless otherwise indicated) of the ingredients are as follows: Suspended detergent builder in the range of about 10 - 60% such as about 20 - 50%, e.g. about 25 - 40%.

Liquid phase containing nonionic surfactant and dissolved amphiphilic viscosity regulating and gel inhibiting compound in the range of about 30-70%, such as about 40-60%. This phase may also contain minor amounts of a diluent such as a glycol, e.g. polyethylene glycol (eg "PEG 400"), hexylene glycol, etc., such as up to 10%, preferably up to 5%, for example 0.5 - 2%. The weight ratio of nonionic surfactant to amphiphilic compound is in the range of about 100: 1 - 1: 1, preferably about 50: 1 - 2: 1, and most preferably about 25: 1 - 3: 1.

Polyethercarboxylic acid gel inhibiting compound in an amount to add about 0.5 - 10 parts (eg about 1-6 parts, such as about 2 - 5 parts) of -COOH (molecular weight 45) per 100 parts mixture of said acid compound and nonionic surfactant. Typically the amount of the polyethercarboxylic acid compound is in the range of about 0.01 to 1 part per part of nonionic surfactant, such as about 0.05 to 0.6 parts, e.g. about 0.2 - 0.5 parts.

Acidic organic phosphoric acid compound as an anti-precipitating agent of up to 5%, for example in the range 0.01 - 5%, such as about 0.05 - 2%, e.g. about 0.1 - 1%.

Suitable ranges for other optional detergent additives are: enzymes - 0 - 2%, especially 0.7 - 1.3%; corrosion inhibitors - about 0 - 40%, and preferably 5 - 30%; anti-foaming agents and suds suppressors - 0 - 15%, preferably 0 - 5%, e.g. 0.1 - 3%; thickeners and dispersants - 0 - 15%, e.g. 0.1 - 10%, preferably 1 - 5%; dirt suspending or anti-redeposition agents and anti-yellowing agents - 0 - 10%, preferably 0.5 - 5%; dyes, perfumes, brighteners and bleaches - total weight 0 - about 2% and preferably 0 - about 1%; pH modifiers and pH buffers - 0 - 5%, preferably 0 - 2%, bleach - 0 - about 40% and preferably 0 - about 25%, e.g. 2 - 20%; inhibitor compound for inhibiting enzyme-induced decomposition of bleach - up to about 0.5%, preferably 0.01 - 0.4 or 0.5%, more preferably 0.04 - 0.2%; bleach stabilizers and bleach activators 0 - about 15%, preferably 0 - 10%, e.g. 0.1 - 8%; sequestrants with high complexing power in the range up to about 5%, preferably about 0.25 - 3%, such as about 0.5 - 2%. In the selection of the various additives, these are selected so that they are compatible with the main constituents of the detergent composition.

L! l0 15 20 25 30 467 625 4l All shares and percentages refer to weight unless otherwise stated.

The above detailed description has been given to illustrate the invention and, of course, variations may be made therein without departing from the scope of the invention.

To demonstrate the effects of the viscosity regulating and gel inhibiting agents, various compositions were prepared using the above-described surfactant T8 (C13, E08) (50/50% by weight mixture of surfactant T7 and surfactant T9) as the anhydrous fly. nonionic surfactant detergent. Formulations containing 5%, 10%, 15% or 20% of the amphiphilic additive were prepared and tested at 50 ° C, 100 ° C, 15 ° C, 20 ° C and 25 ° C for various dilutions with water, i.e. 100%, 83%, 67%, 50% and 33% total concentration of nonionic surfactant T8 plus additive, i.e. after dilution in water. The additives tested were Alfonic 610-60 (C8-EO4.4), ethylene glycol monoethyl ether (C2-E01), and diethylene glycol monobutyl ether (C4-EO2). The results showing viscosity behavior at dilution for each of the tested compositions at each temperature are illustrated in the curves of Figures 1 - 3 attached.

For Alfonic 610-60, a 5% additive was sufficient to inhibit gelation at 250 ° C, but on the viscosity versus concentration curve of the nonionic agent, a sharp viscosity maximum was observed at about 67% concentration and one batch was observed. at about 55 - 35% nonionic concentration. At 50 DEG C., a 15% addition was necessary to avoid gel formation. The viscosity decreased to a minimum at a nonionic concentration of about 83% at all levels of additives at 50 ° C, while at the higher temperatures viscosity minima were observed for the undiluted formulations, i.e. l00% nonionic concentrations.

At each temperature and for each additive concentration tested (except at 20% additive at 250 ° C) a relatively sharp peak can be observed for the viscosity between 75 - 50% concentration of nonionic agent (i.e. 25 - 50% dilution).

For ethylene glycol monoethyl ether, gel formation was prevented even at 5 ° C at a 5% addition. However, sharp peaks and / or maximums of viscosity are again observed at each temperature and additive concentration, although the effects are not as pronounced as for Alfonic 610-60, and for some applications the maximum viscosities, especially at higher additive concentrations and / or higher temperatures, may be accepted. for commercial use. On the other hand, no sharp peaks in viscosity of diethylene glycol monobutyl ether were observed at any temperature down to 59 ° C at the addition level of 20%. Even at the lower additive levels, the viscosity peaks and viscosity values at substantially all dilution levels (concentrations of nonionic agents) were lower than for the C8-EO4.4 and C2-E01 additive. The following table shows the results obtained for the different additive concentrations. - the temperatures and temperatures, but are given for 20% additive and 50 C temperature: In 10 l5 43 compositions viscosity at 50 C (Pa.sec) no 50% water water surfactant T8 only 1.40 1,240 80% surfactant T8 + 20% A 0.086 0.401 80% surfactant T8 + 20% B 0.195 0.218 80% surfactant T8 + 20% C 0.690 0.936 A = ethylene glycol monoethyl ether B = diethylene glycol monobutyl ether C = Alfonic 610-60 (C8-4.4EO) Note: 1 Pa.sec = 10 poise (eg 0.218 Pa.sec centipoise) Example gel l 467 623 pour point (° c) 218 II A high-performance enhanced anhydrous liquid nonionic cleaning composition of the following formula was prepared: 4657 10 15 20 25 6223 44 Ingredient weight -% surfactant T7 17.0 surfactant T8 17.0 Dobanol 91-5 acid 5.0 diethylene glycol monobutyl ether 10.0 Dequest 20662 1.0 TPP NW (sodium tripolyphosphate) 29.0925 Sokolan CP53 (calcium sequestrant) 4.0 perborate ~ H2O (sodium perborate monohydrate) 9.0 T.A.E.D. (tetraacetylethylenediamine) 4.5 Emphiphos 56324 o .3 stilben 4 (optical brightener) 0.5 Esperase (proteolytic enzyme) 1.0 Duet 7875 0.6 Relatin DM 40506 (anti-redeposition flour> 1.0 Blue Foulan Sandolane (dye ) 0.0075 l) The esterification product of Dobanol 91-5 (a C9-C fatty alcohol ethoxylated with 5 moles of ethylene oxide) with the succinic anhydride half ester. 2) Diethylenetriaminepentamethylene phosphoric acid, sodium salt. 3) A copolymer of approximately equal moles of methacrylic acid and maleic anhydride, completely neutralized to form its sodium salt. 4) Partial ester of phosphoric acid and a C 16 -C 18 alkanol (about 1/3 monoester and 2/3 diester). 5) Fragrances. 6) Mixture of sodium carboxymethylcellulose and hydroxymethylcellulose. 11 '-fx, ¿: l0 15 20 25 467 625 45 This composition is a stable free-flowing reinforced non-gelling liquid nonionic cleaning composition in which the polyphosphate builder is stably suspended in the liquid nonionic surfactant phase.

Example 2 In the same manner as in Example 1, the following high performance enhanced anhydrous liquid nonionic cleaning composition containing an enzyme inhibitor is prepared: Ingredient '% by weight Plurafac RA 30 37.5 diethylene glycol monobutyl ether 10.0 octenyl succinic anhydride 2.0 TPP NW 28.4 Sokolan CP5 4.0 Dequest 2066 1.0 perborate-H 2 O 9.0 TAED 4.5 hydroxylamine sulphate 0.1 Emphiphos 5632 0.3 ATS-X (optical brightener) 0.2 Esperase 1.0 perfume 6 0.6 Relatin DM 4050 1.0 TiO2 0.4 This composition has the same advantageous properties as the composition according to Example 1 and also provides improved bleaching ability.

Claims (3)

Anhydrous liquid detergent composition for washing and bleaching soiled fabrics at temperatures down to about 40 DEG C. or lower, characterized in that it comprises a liquid phase comprising a liquid nonionic surfactant and a mono- or poly- ( C2-C3) alkylene glycol mono (C1-C5) alkyl ether in an amount of 30-70%, a water-soluble inorganic peroxide bleach in an effective amount of up to 25%, a bleach activator for lowering the temperature at which the bleach releases hydrogen peroxide. oxide in aqueous solution in an effective amount of up to 10%, proteolytic enzyme in an amount of approx. 0.7 to 2% by weight, and about 0.01 - 0.4% by weight, based on the total composition, of a hydroxylamine salt which inhibits the enzyme-induced decomposition of bleach, which enzyme is present in the soiled the textiles. Composition according to Claim 1, characterized in that the bleaching agent is sodium perborate monohydrate in an effective amount of up to 25%, in that the bleaching agent activator is N, N, N ', N'-tetraacetylethylenediamine in an effective amount of up to 10% and that the hydroxylamine salt is hydroxylalamine sulfate or hydroxylalmin hydrochloride and is present in an amount of about 0.02 - 0.2%. A composition according to claim 1 or 2, characterized in that it further comprises about 20 to 50% of a detergent builder salt suspended in the liquid nonionic surfactant.