DK164120B - LIQUID BLENDING DETERGENTS - Google Patents

Description

in

DK 164120 B

The present invention relates to liquid laundry detergents.

More particularly, the invention relates to non-aqueous liquid laundry detergents which are easily pourable and which do not gel when added to water.

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Liquid, non-aqueous, powerful laundry detergents are well known. Funds of this type can e.g. comprising a liquid, nonionic surfactant containing dispersed particles of a builder, as shown e.g. in U.S. Patent Nos. 4,316,812, 3,630,929, 4,264,466, and British Patent Nos. 1,205,711, 1,270,040, and 1,600,981.

Liquid cleansers are often considered to be more convenient to use than dry, powdered or particulate products and have therefore been preferred by consumers. They can be easily measured, dissolved quickly in the wash water, easily applied in concentrated solutions or dispersions to soiled areas of clothing to be washed, and are non-dusty and usually take up less storage space. In addition, liquid detergents may have incorporated in their composition materials which could not withstand drying without destruction, which materials are often conveniently used for the manufacture of particulate products. Although they have many advantages over unit products or particulate solid products, liquid detergents often have some inherent disadvantages which must be overcome to produce acceptable industrial detergent products. Thus, some of these products separate upon storage, and others separate on cooling and are not readily dispersible. In some cases, the viscosity of the product changes and it becomes either too thick to pour or so thin that it looks watery. Some clear products become cloudy and others gel on standing.

The present inventors have extensively studied the rheology-35

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2, behavior of nonionic, liquid, surfactant systems, with and without particulate matter suspended therein, occurs. Of particular interest have been non-aqueous, builder-containing, liquid laundry detergents and the problems of gelling associated with nonionic surfactants, as well as the precipitation of the suspended builder and other additives. These considerations are important for e.g. the shelf life, dispersibility and stability of the product.

The rheological behavior of the non-aqueous builder-containing liquid laundry detergents can be 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 non-aqueous paint medium. . For simplification reasons, the suspended particles, e.g. builder, in the following discussion is sometimes referred to as "pigment".

It is known that one of the main problems with paints and builder-containing liquid laundry detergents is their physical stability. This problem is because the density of the solid pigment particles is higher than the density of the liquid matrix.

The particles are therefore prone to sediment in accordance with Stoke's law. There are two basic solutions to the sedimentation problem: the viscosity of the liquid matrix and the reduction of the solid particle size.

For example, it is known that suspensions can be stabilized against precipitation by adding inorganic or organic thickeners or dispersing agents such as e.g. inorganic materials with very high surface area, e.g. finely divided silica, clays, etc., organic thickening agents such as cellulose ethers, acrylic polymers 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 3

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low temperature. Furthermore, these additives do not contribute to the purity of the preparation.

Grinding to reduce particle size is more advantageous and has two main consequences: 1. The specific surface area of the pigment is increased and particle wetting with the non-aqueous carrier (liquid, nonionic) is proportionally improved.

2. The average distance between pigment particles is reduced by a proportional increase in the particle-particle reaction. Every 10 of these effects help to increase the residual gel strength and suspension tension, while significantly reducing the plastic viscosity.

The non-aqueous liquid suspensions of the detergent builder particles such as polyphosphate builders, especially sodium tripolyphosphate (TPP), in nonionic surfactant have been found to behave rheologically, substantially in accordance with the Casson equation: 1/2 _ 1/2, 1/2 1/2 σ "σο + γ where y is the shear rate, σ is the shear stress, 20 σβ is the yield stress (or float value), and is the" plastic viscosity "(apparent viscosity at infinite shear rate).

The yield stress is the minimum stress required to induce plastic deformation (flow) of the suspension.

Thus, by imagining the suspension as a loose network of pigment particles, the suspension, if the applied voltage is lower than the flow voltage, will behave as an electric

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4 gel, and no plastic flow will occur. Once the flow voltage is overcome, the network breaks at some · points and the sample begins to flow, but with a very high apparent viscosity. If the shear stress is much higher than the yield stress, the pigments are partially shear deflocculated and the apparent viscosity decreases.

Finally, if the shear stress is much higher than the yield stress, the pigment particles become completely shear deflocculated and the apparent viscosity is very low, as if there was no reaction between the particles at all.

Therefore, the higher the liquid tension of the suspension, the higher the apparent viscosity at low shear rate and the better the physical stability of the product.

In addition to the problem of precipitation or phase separation, the non-aqueous liquid laundry detergents, based on liquid, non-ionic, surfactants, suffer from the disadvantage that the non-ionic substances tend to gel when added to cold water. This is a particularly important problem with the usual use of European automatic household washing machines, where the user places the laundry detergent in a dispensing means (e.g. a drawer) in the machine. During operation of the machine, the detergent in the dispensing means is subjected to a stream of cold water to transfer it to the main body of the washing solution. Especially in the winter months, when the detergent and water supplied to the dispensing means are particularly cold, the viscosity of the detergent increases significantly and a gel is formed. As a result, some of the agent is completely flushed out of the dispensing member during machine operation and a deposition of the agent 30 is built up with repeated washing periods, which eventually requires the user to rinse the dispensing means with hot water.

The gelling phenomenon can also be a problem when one wants to

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5 perform washing using cold water, as recommended for certain synthetic and sensitive substances or substances which can crawl in hot water.

Partial solutions to the gelation problem in aqueous, essentially 5 builder-free agents have been proposed and include e.g.

diluting the liquid nonionic substance with certain viscosity regulating solvents and gel inhibitors such as lower alkanols, e.g. ethyl alcohol (see U.S. Patent No. 3,953,380), alkali metal formates and adipates (see U.S. Patent No. 4,368,147), hexylene glycol, polyethylene glycol, etc.

Furthermore, these two patents each describe the use of up to a maximum of approx. 2.5% of the lower alkyl (C ^-C ^) ether derivatives of the lower (C ^-C- ^ polyols, e.g. ethylene glycol) in these aqueous, liquid, builder-free cleansers instead of part of the 15 U.S. Patent Nos. 4,111,855 and 4,201,686 relate to a similar effect, but there is no description or suggestion in any of these patents that these compounds, of which some commercially available under the (R) 20 trade name Cellosolve, could function effectively as viscosity regulators and gel-preventing agents for non-aqueous, liquid, nonionic surfactants, especially those containing suspended builder salts such as the polyphosphate compounds, and especially such agents which do not depend on or require lower alkanols as solvents for viscosity control.

Further, British Patent No. 1,600,981 mentions that in non-aqueous, nonionic cleaners containing builders suspended therein by certain dispersants for the builder such as finely divided silica and / or polyether group containing compounds having a molecular weight of at least 500 , it may be advantageous to use mixtures of nonionic surfactants, one of which fulfills a surfactant function, and 6

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the second both fulfills a surfactant function and reduces the pour point of the agents. The former is exemplified by fatty alcohols having 5-15 moles of ethylene and / or propylene oxide per liter. moth. The second surfactant is exemplified by linear Cg-Cg or branched Cg-C3 fatty alcohols with 2-8 moles of ethylene and / or propylene oxide per liter. moth. Here, too, there is no description that these short carbon chain compounds could regulate viscosity and prevent gelling of the potent, non-aqueous, liquid, nonionic surfactants with builder suspended in the nonionic liquid. surfactant.

It is also known to modify the structure of nonionic surfactants to optimize their resistance to gelation upon contact with water, especially cold water. As an example 15 of modification of a nonionic surfactant, a particularly successful result has been obtained by acidifying the hydroxyl end group of the nonionic molecule. The advantages of introducing a carboxylic acid into the end of the nonionic substance include gel inhibition by dilution, lowering the pour point of the nonionic substance, and formation of an anionic surfactant when neutralized in the wash liquid. Optimization of the structure of the nonionic substance to minimize gelling is also known, e.g. controlling the boiling length of the hydrophobic-hydrophilic mole moiety and the number and composition of the alkylene oxide units (e.g.

(Ethylene oxide) in the hydrophilic moiety. For example, it has been found that a C- fed fatty alcohol ethoxylated with 8 moles of ethylene oxide exhibits only a limited tendency for gelling.

Nevertheless, further improvements in the stability, viscosity control and gel inhibition of non-aqueous liquid detergents are still desired.

It is therefore an object of the invention to provide non-aqueous liquid laundry detergents which do not gel when contacted or added to water, especially cold water.

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It is a further object of the invention to provide non-aqueous, liquid, builder-containing laundry detergents which are stable upon storage, can be easily poured and dispersed in cold, lukewarm or hot water.

Another object of the invention is to assemble builder-containing, powerful, non-aqueous, liquid, non-ionic surfactant detergents which can be poured at any temperature and which can be repeatedly dispersed from the dispensing means in European-type automatic laundry machines. clogging the dispensing body, even during the winter months.

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A particular object of the invention is to provide non-gelling, stable, low viscosity suspensions of powerful, tripolyphosphate, non-aqueous liquid non-ionic laundry detergents containing an amount of a low molecular weight amphiphilic compound which is sufficient to reduce the viscosity of the agent in the absence of water and after contact with cold water.

These and other objects of the invention, which will become apparent from the following detailed description of preferred embodiments, are generally achieved by adding to the liquid nonionic surfactant an amount of a low molecular weight amphiphilic compound ( lower (C 2 -C 3) alkylene) -glycol mono (lower (C 2 -C 5) alkyl} ether, which is effective in inhibiting the gelation of the nonionic surfactant in the presence of cold water.

According to the present invention, there is provided a non-aqueous liquid detergent capable of washing and bleaching dirty clothes at temperatures as low as ca. 40 ° C or 35 ° C

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8, comprising a suspension of a builder salt in a liquid, non-ionic surfactant, which detergent is characterized in that it comprises 30-70 wt.%, Preferably 40-60 wt.%, Of a liquid phase comprising liquid. , nonionic surfactant consisting of C1-C18 fatty carbon ethoxy clay with 3-12 moles of one C2-C3 alkylene oxide per mole of fatty alcohol, and an alkylene glycol monoalkyl ether of formula R 'i

R0 (CHCH2O) nH

wherein R is alkyl of 2 to 5 carbon atoms, R 1 is hydrogen or methyl, and n is an average of 2 to 4, preferably diethylene glycol monobutyl ether, the weight ratio of nonionic surfactant to the alkylene glycol monoalkyl ether

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is from 50: 1 to 2: 1, 20-50% by weight of a surfactant salt salt suspended in the liquid nonionic surfactant and a water-soluble inorganic peroxide bleach, preferably sodium perborate monohydrate, in an effective amount of up to 25% by weight , N, N, N ', N'-tetraacetylethylenediamine in an amount of 0.1-10% by weight as a bleach activator to lower the temperature at which the bleach will release hydrogen peroxide in aqueous solution, proteolytic enzyme in an amount of 0.7 -2 wt% and 0.01-0.4 wt%, preferably 0.02-0.2 wt%, based on the 25 P®1 total detergent, of hydroxy 1 amine 1 barrel, hydroxylamine hydrochloride or hydroxylamine hydrobromide to inhibit enzyme-induced cleavage of the bleach.

The liquid, nonionic laundry detergent can be dispersed in 30 and / or with cold water without the detergent undergoing gelation. Specifically, a container may be filled with the non-aqueous liquid laundry detergent in which detergents are composed, at least predominantly, of liquid, nonionic, surfactant, and for dispensing agents from the container to an aqueous wash bath, wherein Dispensers in the dispenser are effected by directing a stream of unheated water to the agent so that

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9 the agent is fed with the flow of water into the wash bath. The incorporation of a low molecular weight amphiphilic compound, i. the alkylene glycol monoalkyl ether, causes the detergent to be easily poured into the container even when it has a temperature below room temperature. Furthermore, the agent does not undergo gelling when contacted with the water stream and it is easily dispersed as it enters the wash bath.

As will be seen below, in addition to the active detergent component, the liquid detergents often contain one or more detergent additives. One of the more important of these, from the consumer's point of view and as far as beneficial purification is concerned, is the class of oxygen bleaches, of which sodium perborate monohydrate is a particularly preferred example. It is well known that in solution, peroxygen salts release hydrogen peroxide as the active oxidizing agent. However, hydrogen peroxide is decomposed by catalase, an enzyme that is always found in natural dirt and stains. This decomposition occurs even in the presence of 20 pale activators, since the rate of reaction between hydrogen peroxide and the activator is slower 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 catalase can be deactivated by increasing therapy in the wash bath.

One way to solve this problem has been to use an excess amount of perborate or other peroxide bleach, e.g. an amount which is generally 2 - 4 or more times that which would be required to effectively bleach dirty or stain in the absence of the peroxide-forming enzyme, and also 2-4 or more times molar excess relative to the number of moles of bleach activator.

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It has also been proposed to perform the bleaching with an aqueous solution of a peroxide bleach in the presence of a compound capable of inhibiting enzyme-induced decomposition of

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The bleach. Thus, U.S. Patent No. 3,606,990 discloses a relatively wide range of inhibitor compounds / including e.g. hydroxylamine salt, hydrazine and phenylhydrazine and their salts, substituted phenols and polyphenols and others, as well as various detergents containing the water-soluble inorganic peroxide bleach and the inhibitor compound. However, there is no description of liquid detergents containing the inhibitor compounds, nor is there any description that the inhibitor compounds could be effective in agents containing a bleach activator in addition to the peroxide bleach. Furthermore, in patent 7, lines 25-29, this patent states that in the case of hydroxylamine sulfate, the effective amount of inhibitor compound is from 0.5 to 2% of the total agent.

It has now been found that in the liquid detergents of the invention containing a water-soluble inorganic peroxide bleach of the persalt type, incorporation of very limited amounts of 0.01 -ca can be incorporated. The 0.4% inhibitor compound effectively prevents enzyme-induced decomposition of the bleach. Furthermore, it has been discovered that hydroxylamine sulfate is very stable in the agent and does not at all interfere with the activation of the bleaching system with the usual persalt bleach activators.

Those in the kitchen. In synthetic organic detergents used in the practice of the invention, poly lower alkoxylated lipophilic detergents are obtained in which the desired hydrophilic-lipophilic balance is obtained by adding a hydrophilic poly-lower α 1 -koxy group to a lipophilic molecular moiety. The nonionic detergent used is a poly-lower alkoxylated higher alkanol, wherein the alkanol has 10-18 carbon atoms and the number of moles of lower alkylene oxide (with 2 or 3 carbon atoms) is from 3 to 12. these materials are preferred to use those wherein the higher alkanol is a higher fatty alcohol having 10-11 or 12-15 carbon atoms and containing from 5 to 8 or 35 from 5 to 10 lower alkoxy groups per liter. moth. Preferably, it is lower alkoxy ethoxy, but in some cases it may conveniently be mixed with propoxy, the latter, if present, usually but not necessarily constituting a minor amount (less than 50%).

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Examples of such compounds are those compounds in which the alkanol has 12 to 15 carbon atoms which contain approx. 7 ethylene oxide groups per moles, e.g. "Neodol" 25-7 and "Neodol" 23-6.5, which are manufactured by Shell Chemical Company, Inc.

5 The former is a condensation product of a mixture of higher fatty alcohols having an average of approx. 12 to 15 carbon atoms with approx. 7 moles of ethylene oxide and the latter is a similar mixture in which the content of carbon atoms in the higher fatty alcohol is 12 or 13 and the number of ethylene oxide groups is about 6.5. The 10 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 Corporation. The former is a mixed ethoxylation product of a linear secondary alkanol having 11-15 carbon atoms with 7 moles of ethylene oxide, and the latter is a similar product but with 9 moles of ethylene oxide.

Also useful in the present compositions as a component of the nonionic detergent are high molecular weight, nonionic detergents such as "Neodol" 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, wherein the higher fatty alcohol has 14-15 carbon atoms. and the number of ethylene oxide groups per mole is approx. 11. These products are also manufactured by Shell Chemical Company. Other useful nonionic detergents are represented by the well-known, commercially available "Piurafac" series, which is the reaction product of a higher linear alcohol and a mixture of ethylene oxide and propylene oxide containing a mixed chain of ethylene oxide and propylene oxide a hydroxyl group. Examples include "Plurafac" RA30 (a C 1 -C 2 fatty alcohol condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide), "Plurafac" 30 RA 40 (a C 1 -C 2 fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide).

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In general, the mixed ethylene oxide / propylene oxide fatty alcohol condensation products may be represented by the general formula RO (C 2 H 4 O) x (C 3 10-18, especially 14-18 carbon atoms, x is a number from 2 to 12, preferably 4-10, and y is a number from 2-7, preferably 3-6.

Another group of liquid, non-in on detergents can be obtained from 10

Shell Chemical Company, Inc., under the trademark "Dobanol": "Dobanol" 25-7 is an ethoxylated C 1-6 fatty alcohol with an average of 7 moles of ethylene oxide, etc.

In order to obtain the best balance between lipophilic and hydrophilic molecular moieties in the preferred poly-lower alkoxylated higher alkanols, the number of lower alkoxy groups will be from 40 to 100% of the number of carbon atoms in the higher alcohol, preferably 40-60% thereof. the nonionic detergent will preferably contain at least 50% of such preferred poly lower alkoxy higher alkanol. Higher molecular weight alkanols and various other normally solid, nonionic detergents and surfactants can contribute to the gelation of the liquid detergent and will therefore preferably be omitted or limited in amount in the present agents, although smaller amounts thereof may be used. because of their purifying properties etc. As to both preferred and less preferred nonionic detergents, the alkyl groups therein are generally linear, although branching can be tolerated, such as at the carbon atom adjacent to or two carbon atoms removed from the terminated carbon atom of the straight chain and away from the ethoxy chain if such branched alkyl does not have a length over 3 carbon atoms. Usually, the amount of carbon atoms in such a branched configuration will be less and rarely exceed 20% of the total number of carbon atoms in alkyl. Although linear alkyls joined at the ends of the ethylene oxide chains are highly preferred and considered to result in the best combination of purity, biodegradability and non-biodegradability.

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gelling properties, similar or secondary bonding to ethyleneoxy may occur in the chain.

As a rule, only a minor amount of such intermediate pathways are one or two secondary alkyls, generally less than 20%, but as is the case with the said Tergitol® surfactants, it may be greater. When propylene oxide is found in the lower alkylene oxide chain, it will usually, but not necessarily, be less than 20% thereof and preferably less than 10% thereof.

When higher amounts of non-alkoxylated alkanols are used, propylene oxide-containing poly lower alkoxylated alkanols and less hydrophilic 11-1 ipofi 11 balanced nonionic detergents than mentioned above may not have the resulting product. so good cleaning, stability, viscous

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site and non-gelling properties as the preferred agents, but use of the viscosity regulating and regulating compounds of the invention may also improve the properties of the detergents based on such nonionic detergents. In 2q some cases, such as when If a more high molecular weight poly-lower alkoxylated higher alkanol is used, often because of its purity, the amount thereof will be controlled or limited, e.g. in accordance with the results of various experiments, to obtain the desired purity and still have a non-gelling product of the desired viscosity. It has also been found that it is only rarely necessary to utilize the more high molecular weight, nonionic detergents for their purity properties, the preferred nonionic detergents described in the present application all being excellent. detergents and additionally enables to obtain the desired viscosity in the liquid detergent without gelling at low temperatures. Mixtures of two or more of these liquid, nonionic detergents may also be used, and in some cases benefits may be obtained from the use of such mixtures.

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As mentioned above, the structure of the liquid, nonionic surfactant can be optimized with respect to the carbon chain length and configuration (e.g. linear versus branched chain etc.) and the content and distribution of alkylene oxide units. Extensive research has shown that these structural properties can have and indeed have a profound effect on such properties of the nonionic detergent zone pour point, cloud point, viscosity, gelation tendency and, of course, purity.

Typically, most industrially available, nonionic detergents have a relatively large distribution of ethylene oxide (EO) and propylene oxide (PO) units and of the lipophilic hydrocarbon chain length, indicating the EO and PO content and hydrocarbon chain lengths. are total averages. This "polydispersity" of the hydrophilic and lipophilic chains can have a great impact on the properties of the product, and so can the particular values for the average values.

The relationship between "polydispersity" and specific chain lengths and product characteristics of a well-defined, nonionic substance can be shown by the following data for the series of nonionic substances called "Surfactant" T, obtained from British Petroleum. The non-ionic "Surfactant" T substances are obtained by the ethoxylation of secondary C ^ g fatty alcohols with a narrow EO distribution and having the following physical properties: EO content Pour point Cloudiness point (average) (° C) (1% dissolution) (° C) "Surfactant" T 5 5 <-2 <25 "Surfactant" T 77-2 38 25 "Surfactant" T 9 9 6 '58 "Surfactant" T 12 12 20 88

To assess the significance of EO distribution, a "Surfactan F 8 was artificially prepared in two ways: a. 1: 1 mixture of T7 and T9 (T8a), 30 b. 4: 3 mixture of T5 and T12 (T8b).

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The following properties were found: E0 content Pour point Cloudiness point (average) (° c) (1% resolution) (° C) "Surfactant" T 8a 8 2 48 "Surfactant" T 8b 8 15 <20 5 These results can be made the following general observations: 1. T8a closely corresponds to an actual "surfactant" T 8, since it interpolates well between T7 and T9 with respect to both pour point and cloud point.

2. T8b, which is highly polydispersed, would generally be unsatisfactory due to its high slope and low cloud point.

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

The viscosity of the non-ionic surfactant T was measured at concentrations of non-ionic substance of 20%, 30%, 40%, 50%, 60%, 80% and 100% for T5, 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 viscosity) at 100 sec. 1 2 3 4 5 6

Non-ionic substance: Viscosity (mPa.s)% Type: T5 T7 T7 / T9 T9 T12 100 36 63 61 ~ 149 80 65 104 112 165 2 60 750 78 188 239 32200 3 50 4000 123 233 634 89100 4 40 2050 96 149 211 187 5 30 630 58 38 27 6 20 170 78 28 100 16

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From these results, it can be concluded that "Surfactant" T7 is less gel sensitive than T5 and that T9 is less gel sensitive than T12. Furthermore, 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.

The invention is not bound by any theory, but it is believed that these results can be explained by the following hypothesis:

For T5: With only 5 E0, the hydrodynamic volume of the E0 chain is almost the same as the hydrodynamic volume of the fatty chain. 10 Surfactant molecules can arrange to form a lamellar structure.

For T12: With 12 EO, the hydrodynamic volume of the EO chain is greater than that of the fat chain. When molecules try to arrange themselves, an interface curvature occurs and rods are obtained.

The superstructure is then hexagonal. With a longer EO chain or with a higher hydration, the interface curvature may be such that balls are actually obtained and the arrangement with the lowest energy is a flat-centered cubic grid.

From T5 to T7 (and T8), the interface curvature increases and the energy 20 of the lamellar structure grows. When the lamellar structure loses stability, its melting temperature is reduced.

From TI2 to T9 (and T8), the interface curvature decreases and the energy of the hexagonal structure grows (bars become larger and larger). When the loss in stability occurs, the melting temperature of the structure is also reduced.

"Surfactant" T 8 appears to be at the critical point where the lamellar structure is destabilized, i.e. that 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 30 after 2 days, but the superstructure formation is sufficiently delayed.

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17 long to allow easy dispersibility in water.

The effects of molecular weight on the physical properties of the nonionic detergents were also considered. "Surfactant" T 8 (1: 1 mixture of T7 and T9) exhibits a good compromise between the 5 lipophilic chain (C ^g) and the hydrophilic chain (EOg), although the pour point and maximum viscosity at dilution at 25 ° C are still high.

The equivalent EO compromise for C ^ g and Cg lipophilic chains was also determined using the "Dobanol" 91 x series of 10 Shell Chemical Company, which are ethoxylated derivatives of Cg-C · fatty alcohols (average: C and "Alfonic" 610 y series from Conoco, which are ethoxylated derivatives of C 6 -C 6 g fatty alcohols (average: C g), where x and y represent the E 0 weight percent.

The following table shows the physical properties of the "Alfonic" 610 y-15 and "Dobanol" 91 x series:

Max

EO Pour-Cloud Dilution (through point at 25 ° C

Non-ionic substance section) (° C) (° C) (mPa) "Alfonic" 610-50R 3 -15 Gel (60%) "Alfonic" 610-60 4.4 -4 41 36 (60%) "Dobanol "91-5 5 -3 33 Gel (70%) 20" 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" 91-5T is a laboratory-scale product: It is "Dobanol" 91-5, from which free alcohol has been removed. As the lowest ethoxylation representatives are also removed, the average EO number is 6. "Dobanol" 91-5T gives the best results with C ^ g-lipophilic chain as it does not gel at 25 ° C. The 1% cloud point (55 ° C) is higher than that of "Surfactant" T 8 (48 ° C).

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This is probably due to the lower molecular weight as the mixing entropy is larger. "Alfonic" 610-60 gives the best results in the series of C8-lipophilic chain.

A summary of the best EO content for each tested lipophilic 5 chain length is shown in the following table:

Blur Max * η at pour point dilution

point (1% solution) at 25 ° C

Non-ionic substance C EO (° C) (° C) (mPa.s) "Surfactant" T8 13 8 +2 48 223 (50%) "Dobanol" 91-5T 10 6 +2 55 126 (50%) " Alfonic "610-60 8 4.4. -4 41 36 (60%) 10 From these data the following conclusions can be drawn: Pour points: As the molecular weight of the non-ionic substance decreases, the pour points also fall. The relatively high pour point of "Dobanol" 91-5T can be explained by the higher polydispersity. This was also noted for T8a and T8b, i.e. the chain polydispersity increases the loading point.

Blur points: As the number of molecules increases (if the molecular weight decreases), the mixing entropy is theoretically higher, so that the cloud point would increase as the molecular weight decreases. This is actually the case from "Surfactant" T8 to "Dobanol" 91-5T, but 20 it has not been confirmed with "Alfonic" 610-60. Here, it is assumed that the polydispersity of the lipophilic hydrocarbon chain is responsible for the theoretically low cloud point. The relatively large amount of C10-EO present reduces the solubility.

Maximum viscosity on dilution at 25 ° C: None of these non-ionic detergents gels at 25 ° C when diluted with water. The maximum viscosity decreases sharply with the molecular weight. As the molecular weight of the nonionic detergent decreases, the hydrogen bridges become 19

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less effective. Unfortunately, non-low molecular weight non-ionic detergents are not suitable for laundry: their micellar critical concentration (MCC) is too high and a true solution with only limited purity under practical washing conditions would be obtained.

With this information, the present inventors continued their studies of the effects of the low molecular weight amphiphilic compounds on the rheological properties of liquid, nonionic detergents. These studies revealed that while it is possible to lower the pour point of the agent and achieve some degree of gel inhibition by using a short chain hydrocarbon, e.g. ca. Cg, provides these additives with a short chain ethylene oxide substitution, e.g. ca. 4 mols, as amphiphilic additive, such as "Alfonic" 610-60, make no significant contribution to the overall washability and still show no overall satisfactory viscosity control under all normal conditions of use.

Therefore, the present invention is based, at least in part, on the discovery that the low molecular weight amphiphilic compounds which may be considered to be analogous in chemical structure to the non-ionic surfactants which are ethoxylated and / or clay propoxylated fatty alcohols but having a shorter hydrocarbon chain length (C 2 -C 5 + 9) containing an alkylene oxide content, ie

ethylene oxide and / or propylene oxide (about 2 to 4 EO / PO units per molecule), effectively act as viscosity regulating and gel-inhibiting agents for the liquid, nonionic surfactant cleaners.

The viscosity-regulating and gel-inhibiting amphiphilic compounds used according to the invention are represented by the following general formula: R 'R0 (CHCHO) H 2 n where R is a C2-C5, preferably C2-C4, and especially C4-alkyl group, R' is H or CH 3, preferably H, and n is a number from 2-4 i

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20 averages in t.

A preferred example of suitable amphiphilic compounds include diethylene glycol monobutyl ether (C 4 H 9 -O- (CH 2 CH 2 O)) Diethylene glycol monoethyl ether is particularly preferred and, as shown below, is unique in controlling viscosity.

The amphiphilic compound, especially diethylene glycol monobutyl ether, may be the only viscosity-regulating and gel-inhibiting additive in the compositions of the invention, but further improvements in the rheological properties of the anhydrous, liquid, nonionic surfactants can be obtained by include a small amount of a nonionic surfactant which has been modified to convert 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.

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The nonionic surfactants modified with the free carboxyl group, which can be broadly characterized as polyethercarboxylic acids, have the function of decreasing the temperature at which the liquid, nonionic substance forms a gel 25 with water. The acidic polyether compound can also reduce the aircraft stress of such dispersions and contribute to their dispensability without a corresponding decrease in their stability to precipitation. Suitable polar yetherboxylic acids contain a group of the formula - (OCH2-CH2) p ~ (CH-CH2) qYZ-C00H wherein R3 is CH3 is hydrogen or methyl, Y is oxygen or sulfur, Z is an organic bond, p is a positive number from 3 to 50 and q is 0 or a positive number up to 10. Specific examples include the ester of "PIurafac" RA30 with succinic anhydride, 21

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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 polycarboxylic acids or anhydrides, e.g. maleic acid, maleic anhydride, glutaric acid, malonic acid, succinic acid, phthalic acid, phthalic anhydride, citric acid, etc. Further, other bonds such as ether, thioether or urethane bonds formed by usual reactions can be used. To form an ether bond, the nonionic surfactant may e.g. is treated with a strong base (to convert its OH group to, for example, an ONa group) and then reacted with a halogenated carboxylic acid such as chloroacetic acid or chloropropionic acid or the corresponding bromo 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. with e.g. 1-10 carbon atoms which may be bonded to the oxygen (or sulfur) of the formula directly or by an intermediate bond such as an oxygen-containing bond, e.g. O or 0 etc.

II II

-C- -C-NH- The polyether carboxylic acid may be made from a polyether which is not a nonionic surfactant; eg. can it produce; by reacting with a polyalkoxy compound such as polyethylene glycol, or a monoester or monoether thereof which does not have the long alkyl chain characteristic of the nonionic surfactants. Thus, R may have the formula R 1 (OCH-CH 2 J - wherein n 2 n 2 1 R R is hydrogen or methyl, R is alkylphenyl or alkyl or other chain terminating group, and n is at least 3 such as 5-25.

When the alkyl of R 1 is a higher alkyl, R is a residue of a non-ionic surfactant. As mentioned above, R 2 may instead of hydrogen be hydrogen or lower alkyl (e.g., methyl, ethyl, propyl, butyl) or lower acyl (e.g., acetyl, etc.). If the acidic polyether compound is present in the detergent, it is preferably added dissolved in the nonionic surfactant.

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22

Another useful class of supplemental anti-gelling agents are the Cg-C ^ ^ alkyl or the alkenyl dicarboxylic anhydrides, e.g.

5 octenyl succinic anhydride, octenyl maleic anhydride, dodecyl succinic anhydride, etc. These compounds can be used with or in place of some or all of the polyether carboxylic acid as anti-gelling agents.

Acidic organic phosphorus compounds with an acid -POH group can enhance the stability of the suspension of builder, especially polyphosphate builders, in the non-aqueous liquid nonionic surfactant.

15

The acidic / organic phosphorus compound may be e.g. a partial ester of phosphoric acid and an alcohol such as an alkanol having a lipophilic character and having e.g. more than 5 carbon atoms, e.g. 8-20 carbon atoms.

20

A concrete example is a partial ester of phosphoric acid and a C ^ g-C ^galkanol (Empiphos 5632 from Marchon). It is composed of approx. 35% monoester and 65% diester.

Inclusion of very small quantities, e.g. 0.05 to 0.3% by weight of the agent, of the acidic organic phosphorus compound, makes the suspension considerably more stable against precipitation upon standing, but it remains pourable, presumably due to increase of the liquid value of the suspension, but decreases its plastic viscosity. It is believed that the use of the acidic phosphorus compound moiety 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 have an organic character and become more compatible. with the nonionic surfactant.

35

The acidic organic phosphorus compound can be selected from many

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23 different materials in addition to the above partial esters of phosphoric acid and alkanols. One can, for example. use a partial ester of phosphoric acid or phosphoric acid with a mono- or polyhydric 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., wherein one, two or more of the alcoholic OH groups in the molecule may be esterified with the phosphoric acid. The alcohol may be a nonionic surfactant such as an ethoxylated or ethoxylated - propoxylated, higher alkanol, higher alkyl phenol or higher alkylamide. The -POH group need not be bound to the organic part of the molecule through an ester bond. Instead, it may be directly bonded to carbon (such as X 5 in a phosphonic acid / such as 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 may be attached to the carbon through an intermediate bond (such as bonds through O, S or N atoms). Preferably, the carbon: phosphorus atomic ratio of the organic phosphorus compound is at least 3: 1, e.g. 5: 1, 10: 1, 20: 1, 30: 1 or 40: 1.

The detergent according to the invention contains a builder in a variety of types. Typical suitable builders include e.g. those disclosed in U.S. Patent Nos. 4,316,812, 4,264,466, and 3,630,929. Water-soluble, inorganic, alkaline builder salts that can be used with the detergent compound or in admixture with other builders are α1ka1 in meta1carbonates, 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, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono- and diorthophosphate. Sodium tripolyphosphate (TPP) is particularly preferred.

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24

The alkali metal silicates are useful builder salts that also work; to make the agent anti-corrosive to washing machines. · in parts. Sodium silicates with Na2 / SiO2 * ratio from 1.6 / 1 to! 1 / 3.2, especially approx. 1/2 to 1/2 is preferred. Potassium silicates having the same ratio can also be used.

{

Another class of builders useful for the invention are water-insoluble aluminum silicates, both of the crystalline and the amorphous type. Various crystalline zeolites (i.e., aluminum silicates) are disclosed in British Patent No. 1,504,168, U.S. Patent No. 4,409,136, and Canadian Patent Nos. 1,072,835 and No. 1,087,477, all of which are incorporated herein by reference. An example of amorphous zeolites useful for the invention can be found in Belgian Patent No. 835,351. The zeolites generally have the formula 15 (M 2 O) x - (Al 2 O 3) y - (SiO 2) 2-WB 2 O where x is 1, y is from 0.8 to 1.2 and preferably 1, z is from 0.5 to 3, 5 or greater and preferably 2 to 3 and W is from 0 to 9, preferably 2.5 to 6, and M is preferably sodium. A typical zeolite is type A or a similar structure, with type 4A being particularly preferred. The preferred aluminum silicates have a calcium ion exchange capability of approx. 200 mill equivalent equivalents grams or more, e.g.

400 milliequivalents per gram.

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 ca. 1/6 of the aluminum atoms may be replaced by magnesium atoms, with which may be loosely bound varying amounts of hydrogen, sodium, potassium, calcium etc. The bentonite in its more 30 purified form (ie free of any gravel, sand, etc.) that is suitable for detergents, invariably contains at least 50% montmorillonite, and its cation exchange capacity is therefore at least 50 - 75 25

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milliequivalents per 100 g bentonite. Particularly preferred bentonites are Wyoming bentonite or Western U.S. bentonites which have been marketed as "Thixo gel" 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften fabrics as described in British Patent No. 401,413 and British Patent No. 461,221.

Examples of organic, alkaline, complex-binding builder salts that can be used alone with the detergent or in admixture with other organic and inorganic builders are alkali metal, ammonium or substituted ammonium aminopycarboxylates, e.g. sodium and potassium ethylenediaminetetraacetate (EDTA), sodium and potassium nitrilotriacetate (NTA) and triethanolammonium N- (2-hydroxyethyl) nitrilodiacetates. Mixed salts of these polycarboxylates are also suitable.

Other suitable organic type builders include carboxymethyl succinates, tartronates and glycolates. Of particular value are the polyacetal carboxylates. The polyacetal carboxylates and their use in detergents are described in U.S. Patent Nos. 4,144,226, 4,315,092, and 4,146,495. Other patents relating to similar builders include U.S. Pat. 4,141,676, 4,169,934, 4,201,858, 4,244,852, 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 Nos. 0015024, 0021491 and 0063399.

Since the agents of the invention are generally highly concentrated and can therefore be used in relatively small doses, it is convenient to supplement phosphate builder (such as sodium tripolyphosphate) with an auxiliary builder such as a high calcium binding polymeric carboxylic acid to prevent encrustation that could otherwise be caused by the formation of an insoluble calcium phosphate. Such auxiliary builders are also well known.

30 Various other detergent additives or additives can be found in the product to provide the additional desired properties, either functional or aesthetic.

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26 Thus, smaller amounts of soil suspending agents and agents for preventing re-deposition of dirt may be included in the composition, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose, optical brighteners, e.g. cleaning agents for cotton, amine and polyester, e.g.

stilbenes · triazole and benzidine sulfone materials, especially sulfonated, substituted triazinyl still life, sulfonated naphthotriazole still life, benzidine sulfone etc., and most preferably are stilben and triazole combinations.

Also, tins such as ultramarine blue, enzymes, preferably proteolytic enzymes such as subtilisin, bromelin, papain, trypsin and pepsin, as well as amylase-type enzymes, lipase-type enzymes and mixtures thereof, bactericides, e.g. tetrachlorosalicylanilide, hexachlorophen, fungicides, dyes, 15 pigments (water dispersible), preservatives, ultraviolet light absorbers, antigulants such as sodium carboxymethylcellulose, complex of CC-C ^ alkyl alcohol with C₂₂ and cushions, color-safe bleaches, perfumes and anti-foaming agents, e.g. silicone compounds.

The bleaching agents are broadly classified as chlorine bleaches and oxygen bleaches for convenience. Chlorine bleaches are typically sodium hypochloride (NaOCl), potassium dichloroisocyanurate (59% available chlorine) and trichloroisocyanuric acid (85% available chlorine). Oxygen bleaches are preferred and represented by per-compounds which release hydrogen peroxide in solution, i.e. compounds containing hydrogen peroxide or inorganic perhydrates which, when dissolved, release hydrogen peroxide contained in their crystal lattices. Preferred examples include sodium and potassium perborates, percarbonates and perphosphates and potassium monoperulfate. The perborates, especially sodium perborate monohydrate, are particularly preferred.

Hydrogen peroxide and the precursors which release it in solution are

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27 good oxidizing agents for removing certain stains from clothes, especially stains caused by wine, tea, coffee, cocoa, fruit etc.

Hydrogen peroxide and its precursors have generally been found to fade quickly and most effectively at relatively high temperatures, e.g. 80 - 100 ° C. However, these compounds tend to decompose and release gaseous oxygen at lower temperatures. The release of gaseous oxygen which does not participate in the oxidation of colored goods consumes uselessly a considerable amount of hydrogen peroxide or precursors which release it, both of which are costly products. Furthermore, it has been found that the various stains on clothing and the like greatly accelerate the decomposition of hydrogen peroxide to gaseous oxygen during washing at usual temperature.

In general, washing of clothes is carried out either in a machine, by hand or in a kettle or vessel by dissolving a bleaching or cleansing agent (containing, for example, perborate) in cold or lukewarm water and to the resulting solution of put the dirty clothes (from which some of the stains have often been removed already by soaking or pre-washing) and then heating, often just for cooking.

However, it has been found that in a phenomenon like the one mentioned above, part or all of the perborate was decomposed during heating and, more specifically, during the rise in temperature, i.e. that part or all 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 precursors of low temperature gaseous oxygen peroxide is due to the extremely potent catalytic effect of certain enzymes, which are always present in stains, 30 found on materials to be washed, and especially on soiled clothing such as linen, these enzymes being derived from secretions or of bacterial origin. Hydroperoxidases are a particularly active group of enzymes in this regard, especially catalase that is

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28 well known as a very effective catalyst for decomposing hydrogen peroxide into gaseous oxygen. However, such enzyme substances, whether called "redox" or otherwise, are all peculiar in showing a pronounced tendency to induce decomposition of peroxide bleaches, and the resulting compositional products comprise ineffective bleaching compounds.

In order to take advantage of the low temperature effective detergents and low temperature detergents now commonly used for temperature sensitive fabrics, the peroxygen compound is used in admixture with an activator which can reduce the effective operating temperature of the peroxide bleach to approx. 40 ° C

or lower and which is tetraacetylethylenediamine (TAEO).

15

The bleach activator usually reacts with the peroxygen compound to form a peroxyacid bleach in the wash water. It is preferred to include a complexing agent with high complexing ability to prevent any undesirable reaction between 2Q this peroxyacid and hydrogen peroxide in the wash solution in the presence of metal ions. Preferred complex binding agents are capable of forming a complex of Cu + + ions such that the stability constant (pK) of the complexation is equal to or greater than 6 at 25 ° C in water with an ionic strength of 0.1 mol / liter. 25, where pK is traditionally defined by the formula pK = logarithm K,.

where K represents the equilibrium constant. the pK values for e.g. the complex binding of copper ion with NTA and EDTA under the conditions indicated is e.g. 12.7 and 18.8, respectively. Suitable complexing agents include, for example, in addition to the above, diethylenetriamine pentaacetic acid (DETPA), diethylenetriamine pentomethylene phosphonic acid (DTPMP) and ethylenediaminetetramethylene phosphonic acid (EDITEMPA).

35 29

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However, even in the presence of the bleach activators and even at temperatures as low as room temperature, the persalt will be decomposed in the presence of the stained clothing, the rate of reaction between the bleach and the activator being slower than the rate of catalase hydrogen peroxide decomposition.

In order to avoid loss of bleach due to enzyme-induced decomposition, the compositions of the invention further contain an effective amount of a compound capable of preventing or inhibiting this enzyme-induced decomposition of bleach.

As the inhibitor compound in the detergents of the invention, hydroxyl amine sulphate, hydrochloride or hydrobromide is used.

15

It has now been found that hydroxy 1 aminase 1 tes, especially the sulfate, are effective in preventing the deleterious effect of catalase even when present in the agent in very limited amounts of 0.01-0.4%, preferably 0 , 02 - 0.2% and especially approx. 0.1%, based on the weight of the total agent.

Furthermore, the hydroxylamine inhibitor is very stable in the agent:

Less than 20% loss after aging for 2 months at 43 ° C. The hydroxyl amine salts are rapidly solubilized in water and can therefore react with 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 therefore no nitrosamine derivatives have been detected.

30 Where the bleaching system is activated by the bleach activator TAED, the activator is utilized more efficiently, and appropriate ratios of bleach and bleach activator may be maintained at levels much closer to the stoichiometric equivalent weights or with only small molar excesses of the bleach.

35

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30

The agent may also contain an inorganic, insoluble thickening agent or very high surface area dispersant, such as finely divided particle size silica (eg, with a diameter of 5 - 100 millimicrons, as it is sold under the name Aerosil®), or the other very bulky, inorganic carrier materials disclosed in U.S. Patent No. 3,630,929 in amounts of 0.1 to 10%, e.g. 1-5%. However, it is preferred that the agents which form peroxy acids in the wash bath and which contain the peroxygen compound and the activator therefor are substantially free of such compounds and of other silicates. It has e.g. It has been found that silica and silicates promote the undesirable decomposition of the peroxyacid.

In a preferred detergent according to the invention, the mixture of liquid, nonionic, active substance and solid components is subjected to treatment in a rubbing type mill in which the particle sizes of the solid components are reduced to less than ca. 10 mm, e.g. to an average particle size of 2-10 µm or even smaller (e.g. 1 mm). Agents whose dispersed particles are of such small size have improved stability to separation and precipitation upon storage.

In the grinding operation, it is preferred that the amount of solids is high enough (e.g., at least 40%, such as 50%) for the solid particles to be in contact with each other and not substantially shielded from each other by the nonionic, surfactant. Mills using grinding balls (ball mills) or similar moving grinding elements have produced very good results. Thus, a laboratory mill may be used which has steatite grinding balls with a diameter of 8 mm. On a larger scale 3 ° can be used a continuous working mill, in which there are grinding balls with a diameter of 1.5 mm or 1 mm, which operate at a very narrow space between a stator and a rotor running at relatively high speed. (for example, a CoBall mill). When such a mill is used, it is desirable to first conduct the mixture of nonionic surfactant

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31 through a mill which does not cause such fine milling (e.g., a colloid mill) to reduce the particle size to less than 100 µm (e.g. to about 40 µm) before the milling step to an average particle diameter below 10 yam in the continuous 5 ball mill.

In the powerful liquid detergents of the invention, typical amounts (based on the total agent, unless otherwise stated) of the components are as follows:

Suspended builder in the range of 20 - 50%, e.g.

25 - 40%.

Liquid phase comprising nonionic surfactant and dissolved amphiphilic viscosity regulating and gel inhibiting compound in the range of 30 to 70%, such as approx. 40 - 60%. This phase may also contain minor amounts of a diluent such as a glycol, e.g. polyethylene glycol (e.g., "PEG" 400), hexylene glycol, etc., e.g. up to 10%, preferably up to 20%, e.g. 0.5 - 2%. The weight ratio of nonionic surfactant to amphiphilic compound is in the range of 50: 1 to 2: 1, preferably 25: 1 to 3: 1.

Peroxide bleach up to 25%, preferably 2-20%, bleach activator 0.1-10%, preferably 0.1-8%, proteolytic enzyme 0.7-2%, preferably 0.7-1.3% and hydroxylamine salt to inhibit enzyme-induced cleavage of, inter alia, 0.01-0.4%, preferably 0.02-2%.

30

Preferably, the following components are also present:

Gel inhibiting compounds of polyether carboxylic acid in an amount sufficient to give 0.5-10 parts (eg 1-6, such as 2-5 parts) of -C00H (mol. Weight 45) per ml. 100 parts mixture of this acid compound and nonionic surfactant. Typically, the amount of the polyether carboxylic acid compound is in the range of 0.01 to 1 part nonionic surfactant, e.g.

0.05-0.6 parts, e.g. 0.2-0.5 parts.

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32

Acidic Organic Phosphoric Acid Compound as an Antidepressant: Up to 5%, e.g. in the range of 0.01 to 5%, such as 0.05-2%, e.g. 0.1-1%.

5

Suitable ranges for other optional additives are:

Corrosion on Wed in nhib i tors 0-40%, preferably 5-3 0%, anti-foaming agents 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 agents or agents for preventing re-deposition of dirt and anti-yellowing agents 0-10%, preferably 0.5-5%, coloring agents, perfumes, detergents and bleaching agents in a overall weight of 0-2% and preferably from 0 to 1%, pH modifiers and buffers 0-5%, preferably 0-2%, high complexing complexing agent in the range up to 5%, preferably \ -3% , such as% -2%. In selecting the additives, they are selected so as to be compatible with the main constituent of the detergent.

20

All quantities and percentages are by weight unless otherwise stated.

To demonstrate the effects of the viscosity regulating and gel inhibiting agents, various compositions were prepared using the "Surfactant" T8 (C (- EOg) described above (50/50 weight mixture of "Surfactant" T7 and "Surfactant"). "T9) as the non-aqueous, liquid, non-ionic, surfactant, cleanser. Compositions containing 5%, 10%, 15% or 3% 20% amphiphilic additive were prepared and tested at 5 ° C, 10 ° C, 15 ° C, 20 ° C and 25 ° C in various dilutions in water, i.e.

100%, 83%, 67%, 50% and 33% total amount of non-ionic "Surfactant" T8 plus additive concentrations, i.e. after dilution in water.

The additives tested were "Alfonic" 610-60 (Cg-EO 4), ethylene 33

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glycol monoethyl ether ("EO") and diethylene glycol monobutyl ether (C The results of the viscosity behavior by diluting each tested agent at each temperature are illustrated in the curves of FIG. 1 - 3.

5

For "Alfonic" 610-60, 5% addition was sufficient to prevent gelling at 25 ° C. However, in the curve of the viscosity dependence on the concentration of nonionic substance, a sharp viscosity maximum was observed at ca. 67% concentration and 10 a turning point were observed at ca. 55% - 35% non-ionic concentration. At 5 ° C, 15% addition was necessary to avoid gel formation. The viscosity decreased to a minimum at a concentration of non-ionic substance of approx. 83% at all levels of additive addition at 5 ° C, whereas at the higher temperatures viscosity minima were observed for the non-diluted compositions, i.e. concentrations of 100% non-ionic substance. At each temperature and for each tested concentration of additive (except at 20% additive at 25 ° C), a relatively sharp peak in the viscosity of between 75 and 50% concentration of non-ionic substance (i.e. 20% - 50% dilution) is seen.

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

30

On the other hand, no sharp peaks in diethylene glycol monobutyl ether viscosity were observed at any temperature down to 5 ° C and at the level of 20% additive. Even at the lower additive levels, the viscosity peaks and viscosity values of substantially all dilutions (concentrations of non-ionic substance) were lower than for both the Cg-E04 4 ~ and C2-E01 additive.

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34

The following table is representative of the results obtained for the different concentrations of additive, dilutions and temperatures, but is listed for 20% additive and a temperature of 5 ° C.

8 Viscosity at 5 ° C

(Pasek-): Pour point

Compositions No water 50% water '(° C) "Surfactant" T8 alone 1,140 1,240 5 80% "Surfactant" T8 + 20% A 0.086 0.401 -10 80% "Surfactant" T8 + 20% Β 0.195 0.218 - 2 80% " Surfactant "+8 + 20% C 0.690 0.936 3 in Ο A = ethylene glycol monoethyl ether.

Β = diethylene glycol monobutyl ether.

C = "Alionic" 610-60 (CQ-E0,,).

20 8 4'4 NOTE: 1 Pa sec. = 10 poise (eg 0.218 Pa sec = 218 centipoise).

25 30 35 35

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EXAMPLE 1. (Comparative Example).

A powerful, builder-containing, non-aqueous, 5 liquid, nonionic detergent is prepared having the following composition: Component Weight% 10 "Surfactant" T7 17.0 "Surfactant" Τδ 17.0 "Dobanol" 91-5 Acid ^ 5 0

Diethylene glycol monobutyl ether 10.0 "Dequest" 2066 ^ 1.0 TPP NW (sodium tripolyphosphate) 29.0925 3) "Sokolan" CP5 (complexing agent for calcium) 4.0 "Perborate" (sodium perborate monohydrate) 9.0 TAED (tetraacetylethylenediamine) 4, 5 "Emphiphos" 5632 4 ^ 0.3 20 "Stilbene" 4 (optical brightener) 0.5 "Esperase" (proteolytic enzyme) 1.0 "Duet" 787 5} 0.6 "Relatin" DM 4050 (anti- from bearing agent) 1.0 "Blue Fculan Sandolane (dye) 0.0075 25 -------------------------------- ---------------------------------- ^ The esterification product of "Dobanol" 91-5 (a C (fatty alcohol ethoxylated with 5 moles of ethylene oxide) with succinic anhydride - half ester.

2)

Diethylenetriamine pentamethylene phosphoric acid, sodium salt.

3)

A copolymer of approx. equal moles of methacrylic acid and maleic anhydride, completely neutralized to form the sodium salt.

4) 36

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Partial ester of phosphoric acid and a C 1/3 monoester and 2/3 diester.

6) Mixture of sodium carboxymethyl cellulose and hydroxymethyl cellulose.

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

EXAMPLE 2.

In the same manner as in Example 1, the following powerful, builder-containing, non-aqueous, liquid, nonionic detergent containing an enzyme inhibitor is prepared:

Ingredient 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 20 "Perborate" H20 9.0 TAED 4.5

Hydroxylamine Sulfate 0.1 "Emphiphos" 5632 0.3 ATS-X (Optical Clarifier) 0.2 "Esperase" 1.0

Perfume 0.6 "Relatin'1 DM 4050 1.0

TiO2 0.4

Claims (4)

1. Non-aqueous liquid detergent capable of washing and bleaching dirty clothes at temperatures as low as approx. 40 ° C or less, comprising a suspension of a builder salt in a liquid, nonionic detergent, characterized in that it comprises 30-70 wt.%, Preferably 40-60 wt.% Of a liquid phase comprising liquid , nonionic surfactant consisting of C Ciø-Cis fatty alcohol ethoxylated with 3-12 moles of one C₂-C3 alkylene oxide per mole of fatty alcohol and an alkylene glycol monoalkyl ether of the formula R the weight ratio of nonionic surfactant to alkylene glycol monoalkyl ether is from 50: 1 to 2: 1, 20-50% by weight of a detergent buildup suspended in the liquid, nonionic surfactant, and a water-soluble inorganic peroxy db idde1, preferably sodium perborate monohydrate, in an effective amount of up to 25% by weight, N, N, N ', N'-tetraacetylethyl than in am in an amount of 0.1-10% by weight as a bleach activator to lower the temperature. The bleaching agent will release hydrogen peroxide in aqueous solution, proteolytic enzyme in an amount of 0.7-2 wt% and 0.01-0.4 wt%, preferably 0.02-0.2 wt% based on the total detergent of hydroxylamine sulfate, hydroxylamine hydrochloride DK 164120 Bride or hydroxylamine hydrobromide to inhibit enzyme-induced digestion of bleach in diet. Detergent according to claim 1, characterized in that the bleach activator compound is present in an amount of 0.1-8% by weight of the detergent. Detergent according to claim 1 or 2, characterized in that the hydroxy 1 amine nsa 1 is hydroxyl amine nsul fat and is present in an amount of 0.04-0.2% by weight. Detergent according to any one of claims 1-3, characterized in that the detergent boiling salt comprises 25-40% by weight of an alkali metal tripolyphosphate. 15 20 25 30 35