FI84279C - Anhydrous liquid detergent composition - Google Patents

Description

1 84279

This invention relates to anhydrous liquid laundry detergent compositions. More specifically, this invention relates to anhydrous, liquid laundry detergent compositions which can be easily poured and which do not gel when added to water, and the use of these compositions for washing soiled clothes.

Liquid, anhydrous high performance laundry detergent compositions are well known in the art. Compositions of this type may, for example, contain a liquid nonionic surfactant dispersed with enhancer particles, as disclosed, for example, in U.S. Patents 4,316,812, 3,630,929, 4,264,466 and GB Patents 1,205,711; 270,040 and 1,600,981.

Liquid detergents are often considered to be more comfortable to use than products in dry powder or particulate form and have therefore become very popular with consumers. They are easy to dispense, dissolve quickly in wash water, can be easily applied as concentrated solutions or dispersions to stained areas of garments to be washed and do not dust, and usually require less storage space. In addition to liquid detergents, substances may be added to their formulations which would not withstand drying operations without decomposition, which substances would often be desired in the manufacture of particulate detergent products. Although they have several advantages over solid or particulate solid products, liquid detergents often also have some inherent drawbacks that must be overcome in order to obtain suitable commercial detergent products. In some such products, for example, 84279 separates during storage or cooling and does not readily redisperse. In some cases, the viscosity of the product changes and becomes either too thick to pour or so thin that it looks watery. Some bright products become cloudy and some geliy when standing.

The rheological behavior of nonionic liquid surfactant systems, with or without particulate matter suspended in them, has now been extensively studied. Of particular interest have been the anhydrous enhanced liquid laundry detergent compositions and gelling problems associated with nonionic surfactants, as well as the settling of suspended builder and other laundry additives. These studies focus, for example, on the pourability, dispersion and stability of the product.

The Theological behavior of anhydrous enhanced liquid laundry detergents is analogous to the Theological behavior of paints, and the suspended builder particles correspond to an inorganic pigment and the nonionic liquid surfactant corresponds to a water-free paint solvent. For simplicity, in the following presentation, suspended particles, for example a detergent builder, are sometimes referred to as a "pigment".

It is known that one of the main problems in paints and liquid enhanced laundry detergents is their physical stability. This problem is due to the fact that the density of the solid pigment particles is higher than the density of the liquid matrix. The particles therefore tend to sediment according to Stoke's law. To solve the sedimentation problem, there are two possibilities: the viscosity of the liquid matrix and the reduction of the size of the solid particles.

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It is known, for example, that such suspensions can be stabilized against precipitation by the addition of inorganic or organic thickeners or dispersants such as very large surface area inorganic substances, for example finely divided silica, clay, etc., organic thickeners such as cellulose ethers, acrylic - and acrylamide polymers, polyelectrolytes, etc. But the increase in the viscosity of the suspension is naturally limited by the requirement that the liquid suspension must be easy to pour and flow, even at low temperatures. In addition, these additives do not enhance the washing performance of the formulation.

Reducing the particle size by grinding is more advantageous and provides two important results: 1. The specific surface area of the pigment is increased and therefore the wetting of the particles as an anhydrous solvent (liquid nonionic substance) is relatively improved.

2. The average distance of the pigment particles decreases and at the same time the interaction between the particles increases proportionally. Both of these effects, in turn, help to increase the strength of the residual gel and raise the stretch limit of the suspension while g significantly reduces the plastic viscosity.

Detergent builder particles such as polyphosphate builders, especially sodium tripolyphosphate (TPP), in anhydrous liquid suspensions in nonionic surfactants have been found to behave rheologically mainly according to the Casson equation where γ = σ „i + 842 , σ is the shear stress, σ, is the elongation limit (i.e., yield strength) and n is the "plastic viscosity" (apparent viscosity at infinite shear rate).

The elongation limit is the minimum stress required to induce plastic deformation (runoff) of the suspension. Thus, if the suspension is perceptibly understood as a loose network of pigment particles, then if the stress applied to it is lower than the tensile limit, the suspension behaves like an elastic gel and no plastic flow occurs. When the elongation limit is exceeded, the mesh breaks at some points and the sample begins to drain, but at a very high apparent viscosity.

If the shear stress is very much higher than the stretch limit, the pigments are partially deflocculated by shear and the apparent viscosity is reduced. Finally, if the shear stress is much higher than the tensile limit, the pigment particles deflocculate completely by shear and the apparent viscosity is very low as if no particle interaction existed.

Thus, the higher the yield point in 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 settling, i.e. phase separation, non-aqueous liquid laundry detergents based on liquid nonionic detergents suffer from the downside that nonionic detergents tend to gel when added to cold water. This is a particularly important problem in the normal use of automatic washing machines in European households, where the user puts the laundry detergent composition in a dispensing unit (e.g. a machine dispenser). While the machine is running, the 84279 detergent in the tank is subjected to a stream of cold water which transfers it to the main part of the washing solution. Especially during the winter months, when the detergent composition and the water fed to the tank are particularly cold, the viscosity of the detergent increases considerably and a gel is formed. As a result, some of the composition is not completely flushed out of the tank during machine operation, and repeated washing cycles form a precipitate of the composition, possibly requiring the user to rinse the tank with hot water.

The gelation phenomenon can also be a problem whenever it is desired to perform washing with cold water, as may be recommended for some synthetic and sensitive textiles or textiles that may shrink in warm or hot water.

Partial solutions to the gelation problem in aqueous, virtually non-enhancing compositions have been proposed and include, for example, dilution of a liquid nonionic agent with certain viscosity controlling solvents and anti-gelling agents such as lower alkanols and lower alcohols, e.g. ethyl alcohol (see U.S. Pat. (see U.S. Patent 4,368,147), hexylene glycol, polyethylene glycol, etc.

The two patents further disclose that lower alkyl (C 1 -C 4) ether derivatives of up to about 2.5% lower (C 2 -C 3) polyols, for example ethylene glycols, can be used in these aqueous liquid non-active detergents. instead of a lower alkanol, for example ethanol, as a viscosity controlling solvent. U.S. Patents 4,111,855 and 4,201,686 have the same meaning. However, none of these patents discloses or suggests that these compounds, some of which are commercially available under the trademark Cellosolve under the trademark Cellosolve, could effectively act as viscosity controlling and anti-gelling agents in anhydrous liquid nonionic surfactant compositions, especially in compositions containing suspended builder salts such as polyphosphate compounds and especially especially in compositions that are not dependent on or require lower alkanol solvents as viscosity controllers.

GB Patent Specification 1,600,981 further mentions that in non-aqueous non-ionic detergent compositions containing excipients suspended in some excipient dispersants 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 non- mixtures of ionic surfactants, one of which fulfills the function of a surfactant and the other of which fulfills both the function of a surfactant and lowers the flow temperature of the compositions.

An example of the above is 2-C 1-4 fatty alcohols with 5-15 moles of ethylene and / or propylene oxide per mole. An example of another surfactant is straight chain C8-C8 or branched C8-C18 fatty alcohols with 2-8 moles of ethylene and / or propylene oxide per mole. Again, it is not advised that these short chain compounds could control viscosity and prevent gelation in high potency non-aqueous nonionic surfactant compositions in which the enhancer is suspended in a nonionic liquid surfactant.

It is also known to modify the structure of nonionic surfactants in order to maximize their resistance to gelation with water, especially cold water, upon contact with 7 84279. An example of the conversion of a nonionic surfactant is a particularly successful result achieved by acidifying the hydroxyl end group of a nonionic molecule. The advantages of introducing a carboxylic acid at the end of a nonionic substance are inhibition of gelation upon dilution; lowering the pour point of the nonionic substance; and the formation of an anionic surfactant when neutralized with a washing liquid. It is also known to make the structure of a nonionic substance optimal to minimize gelation, for example, hydrophobic-lipophilic control of the chain length of the moieties and control of the number of alkylene oxide units (e.g., ethylene oxide) in the hydrophilic moiety. For example, it has been found that a C 1-4 fatty alcohol ethoxylated with 8 moles of ethylene oxide has only a limited tendency to form a gel.

However, further improvements are needed in the stability, viscosity control, and gelation inhibition of non-aqueous liquid detergent compositions.

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

It is a further object of the invention to provide anhydrous, liquid enhanced laundry detergent compositions which are stable on storage, easy to pour and disperse in cold, warm or hot water.

It is a further object of the invention to formulate high performance laundry detergent compositions which are active ingredients, anhydrous liquid non-ionic surfactants which can be poured at all temperatures and which can be repeatedly dispersed from European type 8 84279 automatic washing machine tankers even in the winter months.

It is a particular object of this invention to provide non-gelling, stable, low viscosity suspensions of a high performance, tripolyphosphate-enhanced anhydrous liquid nonionic laundry detergent composition which contain a sufficient amount of water to reduce the molecular weight of the amphiphilic compound.

The invention therefore relates to an anhydrous liquid detergent composition capable of washing and bleaching soiled garments at temperatures as low as about 40 ° C or lower, which composition is characterized in that it contains 30-70% by weight of a liquid phase with a non- ionic surfactant and mono- or poly- (C2-C3) -alkylene glycol mono- (C1-C8) -alkyl ether, about 2-25% by weight of water-soluble inorganic peroxide bleach, about 0.1-10% by weight of % bleach activator to lower the temperature at which the bleach releases hydrogen peroxide in aqueous solution, about 0.7-2% by weight of a proteolytic enzyme, and about 0.01-0.4% by weight of a hydroxylamine salt capable of inhibiting enzyme-induced bleach degradation by the enzyme. in dirty clothes. According to the invention, an amount of a low molecular weight amphiphilic compound, in particular a mono-, di- or tri- (C2-C3) -alkylene glycol mono- (C1-C5) -alkyl ether, is added to the liquid non-ionic surfactant composition which: inhibits the gelation of the nonionic surfactant in cold water.

Thus, in accordance with one aspect of the present invention, there is provided a liquid high performance laundry detergent composition comprising a suspension of a builder salt in a liquid nonionic surfactant, the composition comprising an amount of (Ca-CaJ-alkylene glycol mono-fCx-C5) -alkyl , which lowers the viscosity of the composition without water and when the composition comes into contact with water.

In an even more specific embodiment, the present invention provides an anhydrous, liquid detergent composition that remains pourable at temperatures below about 5 ° C and does not gel upon contact or when added to water at temperatures below about 20 ° C, and the composition contains a liquid nonionic surfactant and (C2-C3) -alkylene glycol mono- (C1-C5) -alkyl ether and is almost completely anhydrous.

As will be seen below, liquid detergent compositions often contain, in addition to the active detergent ingredient, one or more detergent additives or excipients. One of the most important of these, from the point of view of the consumer and the washing effect itself, is the category of bleaches, in particular oxygen bleaches, of which sodium perborate monohydrate is a particularly well-liked example. It is well known in the art that in solution, an oxygen bleach, which is a per salt, releases hydrogen peroxide as the active oxidizing agent. However, hydrogen peroxide is easily degraded by catalase, an enzyme that is always present in natural stains and dirt. This degradation occurs in the presence of up to 10,84279 bleach activators because the reaction of hydrogen peroxide with the activating agent is slower than the degradation of hydrogen peroxide by catalase. The effect of catalase is very strong, even at room temperature, and a considerable part of the active oxygen is lost before the catalase can be deactivated by raising the temperature of the washing solution.

One attempt to solve this problem has been to use an excess of perborate or other peroxide bleach, for example usually 2-4 or more times what would be needed to effectively whiten dirt or stain without the presence of a peroxide degrading enzyme and also 2-4 or more molar excess relative to the bleach activating agent. the number of moles of the substance.

It has also been proposed to perform bleaching in an aqueous solution of a peroxide bleach containing a compound capable of inhibiting enzyme-induced degradation of the bleach. U.S. Patent No. 3,606,990 to Colgate-Palmolive Company Gobert and Mouret discloses a relatively wide range of inhibitory agents, such as hydroxylamine salt, hydrazine and phenylhydrazine and their salts, substituted phenols and polyphenols, and the like, as well as various detergent compositions. containing a water-soluble inorganic peroxide bleach and an inhibitor. But no information is provided on liquid detergent compositions containing inhibitory compounds, nor is it stated that inhibitory compounds could be effective in compositions containing a bleach activating agent in combination with a peroxide bleaching agent. In addition, this patent states, column 7, lines 25-29, that in the case of hydroxylamine sulfate, an effective amount of the inhibiting compound is from about 0.5% to about 2% by weight of the total composition.

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It has now been found that in the liquid detergent compositions of this invention containing a water-soluble inorganic peroxide bleach of the persalt type, the addition of a small amount of hydroxylamine salt of about 0.01 to about 0.4% can effectively inhibit enzyme-induced bleach degradation. In addition, it has been found that hydroxylamine sulfate is very stable in the composition and does not interfere at all with the activation of the bleaching system by conventional persalt bleach activators.

Other features and specific embodiments of the invention will become apparent and the invention may be more readily understood from the following detailed description.

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 described, for example, for a very long time in Surface Active Agents, Part II, Schwartz, Perry and Berch, v.

1958, Interscience Publishers, and in the text Detergents and Emulsifiers, McCutcheon, 1969 yearbook, and related commentaries are attached as a source. Nonionic detergents are usually poly-lower alkoxylated lipophiles in which the desired hydrophilic-lipophilic balance is achieved by adding a hydrophilic 12,84279 poly-lower alkoxy group to the lipophilic moiety. The preferred class of nonionic detergents used is poly-lower alkoxylated-higher alkanol having from 10 to 18 carbon atoms in the alkanol and having from 3 to 12 moles of lower alkylene oxide (2 or 3 carbon atoms). wherein the higher alkanol is a higher fatty alcohol having 10 to 11 or 12 to 15 carbon atoms and containing 5 to 8 or 5 to 9 lower alkoxy groups per mole. The lower alkoxy is predominantly ethoxy, but in some cases it may be necessary to mix it with propoxy and the latter, if present, usually has a lower proportion but not necessarily, (less than 50%). Examples of such compounds are those in which the alkanol contains 12 to 15 carbon atoms and contains about 7 ethylene oxide groups per mole, such as Neodol 25-7 and Neodol 23-6.5, manufactured by Shell Chemical Company, Inc. The foregoing is a condensation product. consisting of a mixture of higher fatty alcohols having an average of about 12 to 15 carbon atoms with about 7 moles of ethylene oxide, and the latter is a corresponding mixture having an average number of carbon atoms of 12 to 13 in the higher fatty alcohol and an average number of ethylene oxide groups of about 6.5 . Higher alcohols are primary alkanols. Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15-S-9, both of which are straight chain secondary alcohol ethoxylates manufactured by Union Carbide Corp. The former is a mixed ethoxylation product of a straight-chain secondary alkanol containing 11 to 15 carbon atoms with seven moles of ethylene oxide, and the latter is a similar product, but there have been nine moles of ethylene oxide in the reaction.

Also useful in the present compositions as a nonionic detergent component are higher molecular weight nonionic compounds such as Neodol 45-11, 13 84279 which are similar ethylene oxide condensation products of higher fatty alcohols, and the higher fatty alcohol contains 14-15 carbon atoms and the number of ethylene oxide groups per mole is about 11. These products are also manufactured by Shell Chemical Company. Other useful nonionic compounds are represented by the well-known, commercially available Plurafac series, which are reaction products of a higher straight chain alcohol and a mixture of ethylene oxide and propylene oxide containing mixed mixtures of ethylene oxide and propylene oxide ending in a hydroxyl group. Examples are Plurafac RA30 (C 1-4 fatty alcohol condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide), Plurafac RA40 (C 1-4 fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of propylene oxide). with ethylene oxide), Plurafac D25 (a C 3-3-C 1-4 fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide) and Plurafac B26.

The mixed condensation products of ethylene oxide-propylene oxide with a fatty alcohol can usually be represented by the general formula Η0 ^ 2Η ^ 0) χ (^ Η £ 0) ^ Η, where R is a straight-chain or branched primary or secondary aliphatic hydrocarbon, mainly alkyl or alkenyl, having 6 to 20, predominantly 10 to 18 carbon atoms and very particularly preferably 14 to 18 carbon atoms, x is a number from 2 to 12, predominantly from 4 to 10, and y is a number from 2 to 7, predominantly from 3 to 6.

Another class of liquid nonionic compounds is available from Shell Chemical Company, Inc. under the trademark Dobanol: Dobanol 91-5 is an ethoxylated C 1 -C 4 fatty alcohol with an average of 5 moles of ethylene oxide; Dobanol 25-7 is an ethoxylated C 2 -C 12 fatty alcohol with an average of 7 moles of ethylene oxide; etc.

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In order to obtain the best balance of hydrophilic-lipophilic moieties in the preferred poly-lower alkoxylated higher alkanols, the number of lower alkoxy groups should usually be 40-100% of the number of higher alcohol carbon atoms, preferably 40-60% thereof, and the nonionic detergent preferably contains at least 50% preferred poly-lower-alkoxy-higher alkanol. Higher molecular weight alkanols and several other normally solid nonionic detergents and surfactants may promote gelation of the liquid detergent and are therefore preferably avoided or limited in such compositions. Although in smaller amounts they can be used due to their washing properties and the like. Alkyl groups in both preferred and less preferred nonionic detergents are usually straight chain, although branching may be acceptable as at the one following or two carbons from the terminal carbon, away from the ethoxy group, provided that such branched alkyl is not more than three carbons in length. Normally, the proportion of carbon atoms in such a branched configuration is lower, rarely more than 20% of the total concentration of carbon atoms in the alkyl group. Similarly, although straight chain alkyls terminally linked to ethylene oxide chains are highly regarded and are considered to result in the best combination of detergency, naturally degradable, and non-gelling properties, intermediate or secondary linkages to the ethylene oxide chain may occur. They are usually present only in a smaller proportion of such alkyls, usually less than 20%, but, as in the case of the Tergitols mentioned, may be higher. Similarly, when propylene oxide is present in the lower alkylene oxide chain, it is usually, but not necessarily, less than 20% thereof, and preferably less than 10% thereof.

When higher amounts of alkanols other than terminally alkoxylated propylene oxide-containing poly-lower alkoxylated alkanols and less hydrophilic lipophilic balanced nonionic detergent are used than those mentioned above, and when other nonionic detergents are used in addition to the above preferred non-ionic detergents. instead of ionic compounds, the resulting product may not have as good detergency, stability, viscosity and non-gelling as the preferred compositions, but the use of the viscosity and gel control agents of the invention may also improve the properties of detergents based on such nonionic compounds. In some cases, such as when a higher molecular weight poly-lower alkoxylated higher alkanol is used, often due to its detergency, its proportion is regulated or limited based on the results of several experiments to obtain the desired washing power and yet non-gelling product and viscosity. It has also been found that it is seldom necessary to use higher molecular weight nonionic compounds due to their detergent properties, as the preferred nonionic compounds described herein are excellent detergents and can also achieve the desired viscosity of a liquid detergent without gel melt at low temperatures. . Mixtures of two or more of these liquid nonionic detergents may also be used, and in some cases the use of such mixtures may be advantageous.

As mentioned above, the liquid structure of the nonionic surfactant can be optimized in terms of their carbon chain length and configuration (e.g., straight-chain branched chains, etc.) and the number and distribution of their alkylene oxide units. Extensive studies have shown that these structural properties have a major effect on the properties of a non-ionic compound such as pour point, cloud point, viscosity, tendency to gel as well as, of course, washability.

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Most commercially available nonionic compounds typically have a relatively wide distribution of ethylene oxide (EO) and propylene oxide (PO) and lipophilic hydrocarbon chain lengths, and reported EO and PO concentrations and hydrocarbon chain lengths are generally average. This "polydispersion" of hydrophilic chains and lipophilic chains can play a major role in the properties of the product, as can the specific values of the average values.

The relationship between the "polydispersion" and the specific lengths of the chain and the properties of the product with a well-defined nonionic compound can be demonstrated by the following data in the "surfactant T" series of nonionic compounds from British Petroleum. Nonionic surfactants T are obtained by ethoxylation of secondary 2-fatty alcohols with a narrow EO distribution and having the following physical properties: EO content- Drainage- Dewiness temperature point (1% <° C) solution) (oc)

Surfactant T5 5 <-2 <25

Surfactant T7 7 -2 38

Surfactant T9 9 6 58

Surfactant T12 12 20 88 For the study of EO distribution, "surfactant T8" was artificially prepared in two ways: a) a 1: 1 mixture of T7 and T9 (T8a) b) a mixture of T5 and T12 (T8b) 4: 3 ratio.

The following properties were observed: 17 84279 EO concentration- Drainage- Melting temperature point (average (° C) (1% solution)) (OC)

Surfactant T8a 82 48

Surfactant T8b 8 15 <20 The following general observations can be made from these results: 1. T8a corresponds very closely to the actual surfactant T8, as it interpolates well between T7 and T9 in terms of both flow temperature and cloud point.

2. T8b is highly polydispersed and would generally be disadvantageous due to its high pour point and low cloud point temperature.

3. The properties of T8a are generally additive between T7 and T9, while the flow temperature of Tb is close to the long EO chain (T12), while the cloud point is close to the short EO chain (T5).

The viscosities T of nonionic surfactants were measured at nonionic compound concentrations of 20%, 30%, 40%, 50%, 60%, 80%, and 100% T5, T7, T7 / T9 (1 : 1), for T9 and T12 at 25 ° C with the following results (when a gel is obtained, the viscosity is the apparent viscosity), 100 ~ s:

Non-ionic Viscosity (mPa * s) type% _T5 T7_T7 / T9_T9_T12 100 36 63 61 149 80 65 104 112 165 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 18 84279 From these results, it can be concluded that surfactant T7 is less gel-sensitive than T5, and T9 is less gel-sensitive than T12; in contrast, 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.

While not wishing to be bound by any particular theory, it is assumed that these results can be explained by the following hypothesis: T5: since it has only 5 EO, the hydrodynamic volume of the EO chain is almost the same as the hydrodynamic volume of the fat chain. Thus, the surfactant molecules may be organized to form a lamellar structure.

T12: because it has 12 EO, the hydrodynamic volume of the EO chain is larger than that of the fat chain. As the molecules try to organize with each other, interfacial arcs are created and rods are obtained. The superstructure is then hexagonal; with a longer EO chain or higher hydration, the inter-surface curvature may be such that true spheres are obtained and the lowest energy order is a surface-centered cubic lattice.

As you go from T5 to T7 (and T8), the interfacial curvature increases and the energy of the lamellar structure increases. When a lamellar structure loses its stability, its melting point decreases. As you go from T12 to T9 (and T8), the inter-surface curvature decreases and the energy of the hexagonal structure increases (the bars get bigger and bigger). When the loss of stability occurs, the melting point of the structure also decreases.

Surfactant T8 appears to be at the critical point at which the lamellar structure is destabilized, i. the hexagonal structure is not yet stable enough and no gel is obtained during dilution. However, a 50% solution of T8 finally gels after two days, but the formation of the superstructure is delayed long enough to allow easy dispersion in water.

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The effects of molecular weight on the physical properties of nonionic compounds have also been studied. Surfactant T8 (a 1: 1 mixture of T7 and T9) shows a good compromise between the lipophilic chain (C. ^) and the hydrophilic chain (E08), although the flow temperature and maximum viscosity when diluted at 25 ° C are still high .

An equivalent EO compromise was also determined for C8-lipophilic chains using the Dobanol 91-x series from Shell Chemical Co., which are ethoxylated derivatives of C8-C4 fatty alcohols (average: c- | q)? and the Alfonic 610-γ series from Conoco, which are ethoxylated derivatives of Cg-C10 fatty alcohols (average Cg); x and y represent EO weight percentages.

The following table shows the physical properties of the Alfonic 610-y and Dobanol 92-x series:

Non-ionic § EO Drain- Smear- Maximum n mean temperature (° C) on dilution

degree of space (° C) at 25 ° C

(MPa • s)

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

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

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

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

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

Dobanol 91-5 and Dobanol 91-8 are commercially available products; Dobanol 91-5 with the addition of T is a product made on a laboratory scale: it is Dobanol 91-5 from which free alcohol has been removed. Since the lowest ethoxylation products have also been removed, the average EO number is 6. Dobanol 91-5T gives the best results of the C ^ g lipophilic chain, as it does not gel at 25 ° C. The cloud point of the 1% concentration (55 ° C) is higher than the surfactant T8 (48 ° C). This is presumably due to the lower molecular weight because the entropy of the 20,84279 mixture is higher. Alfonic 610-60 gives the best results from the CQ lipophilic chain series.

O

The best EO concentrations for each lipophilic chain length tested are summarized in the following table:

Non-ionic # C # EO Drain- Smear- Maximum η temperature when diluted

state (1% (%) at 25 ° C

(° C) solution) (° 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%) The following conclusions can be drawn from these data:

Runoff temperatures: As the molecular weight of a nonionic compound decreases, its runoff temperatures also decrease. The relatively high flow temperature of Dobanol 91-5T can be explained by the higher polydispersion. This was also observed for T8a and T8b, i.e. the polydispersion of the chain raises the flow temperature.

Turbidity points: theoretically, as the number of molecules increases (if the molecular weight decreases), the mixing entropy is higher, so that the turbidity point would decrease as the molecular weight decreases. This is indeed the case for the surfactant from T8 to Dobanol 91-5T, but has not been validated for Alfonic 610-60. Here, it is assumed that the polydispersion of the lipophilic hydrocarbon chain is the reason for the theoretically too low cloud point.

The relatively large amount of C 1 -C 3 -OO present reduces the solubility.

Maximum viscosity on dilution at 25 ° C: none of these non-ionic compounds gelled at 25 ° C when diluted with water. The maximum viscosity decreases sharply with molecular weight. As the molecular weight of the nonionic compound decreases to 21,84279, hydrogen bridges become less effective. Unfortunately, non-ionic compounds with too low a molecular weight are not suitable for laundry: their micellar critical concentration (MCC) is too high and a true solution with only limited washing capacity would be obtained under practical laundry conditions.

Based on this information, studies have continued on the effects of low molecular weight amphiphilic compounds on the rheological properties of liquid nonionic laundry detergent compositions. These studies have shown that while it is possible to lower the pour point of the composition and obtain some degree of inhibition of gelation by using a short chain hydrocarbon, e.g. Cg, substituted with short chain ethylene oxide, e.g. about 4 moles, as an amphiphilic additive, e.g. Alfonic 610 60, these additives do not significantly contribute to the overall cleaning performance of the laundry, but do not provide satisfactory overall viscosity control under normal conditions of use.

The present invention is therefore based, at least in part, on the finding that low molecular weight amphiphilic compounds which can be considered analogous in chemical structure to ethoxylated and / or propoxylated fatty alcohol non-ionic surfactants, but which: has a short hydrocarbon chain length (C 1 -C 6) and a low alkylene oxide content, i.e. ethylene oxide and / or propylene oxide content (about 1-4 EO / PO units per molecule) effectively act as viscosity controlling and gelling inhibitors for liquid nonionic surfactants.

The viscosity-controlling and gelation-inhibiting amphiphilic compounds used in the present invention can be represented by the following general formula 22 84279 R * R0 (CHCH_O) H2n wherein R is C1-C5, especially C2-C5, particularly preferably C2-C4, and most especially C the alkyl group, R 'is H or CH 2, especially H, and n is a number from about 1 to 4, preferably on average 2 to 4.

Preferred examples of suitable amphiphilic compounds are, for example, ethylene glycol monoethyl ether (C 2 H 2 -O-CH 2 CH 2 OH) and diethylene glycol monobutyl ether (C 4 H 8 -O- (CH 2 CH 2 O) 2 H). Diethylene glycol monoethyl ether is considered to be particularly preferred and, as will be shown below, a uniquely effective viscosity control.

Although the amphiphilic compound, especially diethylene glycol monobutyl ether, may be the only viscosity controlling and gelling inhibitor additive in the compositions of the invention, further improvements in the rheological properties of anhydrous liquid nonionic surfactant compositions can be obtained by adding a small amount of nonionic surfactant to the composition. a substance modified to transfer its free hydroxyl group to the part having a free carboxyl group, such as a partial ester of a nonionic surfactant and a polycarboxylic acid and / or an acidic phosphorus compound having an acidic POH group, such as a partial phosphoric acid and an alkanol ester.

Non-ionic surfactants modified with respect to the free carboxyl group, which can be generally characterized as polyether carboxylic acids, act to lower the temperature at which the liquid nonionic compound forms a gel with water. The acid 23 84279 polyether compound can also lower the elongation limit of such dispersions, which aids in their distribution, without a corresponding decrease in their stability with respect to settling. Suitable polyether carboxylic acids include a group of the formula -fOCl 2 -CH 2 p-fCH-Cl 2 -CH 2 ZYZ-COOH, wherein R 1 is hydrogen or 3 H 3 methyl, Y is oxygen or sulfur, Z is an organic bond, p is positive a number of about 3 to about 50 g and q is zero or a positive number of up to 10. Specific examples are the half ester of Plu-rafac RA30 and succinic anhydride. Half ester of Doba-nol 25-7 and succinic anhydride. Half ester of Dobanol 91-5 and succinic anhydride, etc. Instead of succinic anhydride, other polycarboxylic acids or anhydrides can be used, for example, maleic acid, maleic anhydride, succinic acid, glutaric acid, malonic acid, succinic acid, phthalic acid, phthalic acid, phthalic acid, -, 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 to an ONa group, for example) and then reacted with a halocarboxylic acid such as chloroacetic acid or chloropropionic acid or a similar bromine compound. The resulting carboxylic acid may thus have the formula RY-ZCOOH, wherein R is a residue of a nonionic surfactant (with the terminal OH removed), Y is oxygen or sulfur, and Z represents an organic bond such as a hydrocarbon group having, for example, 1 to 10 carbon atoms which may be attached to the oxygen (or sulfur) in the formula either directly or by a mediating bond such as an oxygen-containing bond, for example O or O, etc.

n il -C- -C-NH- 24 84279

The polyether carboxylic acid can be prepared from a polyether which is not a nonionic surfactant, for example, by reaction with a polyalkoxy compound such as polyethylene glycol or a monoester or monoether thereof which does not have the long alkyl chain properties of nonionic surfactants. active substances. Thus, R 2 may have the formula ^ 2, wherein R is hydrogen or methyl, R 1 (OCH-CH 0) -1 n R is alkylphenyl or alkyl or another chain end group, and "n" is at least 3, such as 5-25. When the alkyl of R 1 is higher alkyl, R is a residue of a nonionic surfactant. As stated above, R 1 may also be hydrogen or lower alkyl (e.g. methyl, ethyl, propyl, butyl) or lower acyl (e.g. acetyl, etc.). The acidic polyether compound, if present in the detergent composition, is preferably added dissolved in a nonionic surfactant.

Another class of anti-gelling additives are C 8 -C 4 alkyl or alkenyl dicarboxylic acid anhydrides such as octenyl succinic anhydride, octenyl malic anhydride, dodecyl succinic anhydride with some or all of these polyoxides.

An acidic organophosphorus compound having an acidic POH group can increase the stability of a builder suspension, especially polyphosphate builders, in an anhydrous liquid nonionic surfactant.

The acidic phosphorus compound may be, for example, a partial ester of a phosphoric acid and an alcohol such as an alkanol having a lipophilic nature and, for example, more than 5 carbon atoms, for example 8 to 20 carbon atoms.

84279 25

A specific example is a partial ester of phosphoric acid and a C 1 -C 6 alkanol (Empiphos 5632, from Marchon); it consists of about 35% monoester and 65% diester.

The addition of very small amounts, for example about 0.05 to 0.3% by weight of the composition, of an acidic organophosphorus compound makes the suspension considerably more stable with respect to settling, but it remains pourable presumably due to the increased elongation limit of the suspension, but its plastic viscosity decreases. It is believed that the use of an acidic phosphorus compound results in a high energy physical bond between the -POH moiety of the molecule and the surfaces of the inorganic polyphosphate enhancer, so that these surfaces assume an organic nature and become more compatible with the non-ionic surfactant.

The acidic phosphorus compound can be selected from a wide variety of substances in addition to the aforementioned partial esters of phosphoric acid and alkanols. Thus, a partial ester of phosphoric acid or phosphoric acid with monohydric or polyhydric alcohols such as hexylene glycol, ethylene glycol, di- or triethylene glycol or higher polyethylene glycol, polypropylene glycol, glycerol, monoacid, sorbitol may be used. , two or more of the alcoholic OH groups in the molecule may now be esterified with phosphoric acid. The alcohol may be a nonionic surfactant such as ethoxylated or ethoxylated-propoxylated higher alkanol, higher alkylphenol or higher alkylamide, it is not necessary to link the -POH group to the organic moiety of the molecule with an ester bond; instead, it may be attached directly to carbon (such as in a phosphonic acid, for example polystyrene, where some of the aromatic rings contain phosphonic acid or phosphinic acid groups; or an alkylphosphonic acid such as propyl or laurylphosphonic acid) or may be attached to the carbon via another bond ( such as bonds through O, S or N atoms). The carbon: phosphorus atomic ratio in the organophosphorus compound is preferably about 3: 1, such as 5: 1, 10: 1, 20: 1, 30: 1 or 40: 1.

The detergent composition of the invention may also contain, and preferably contains, water-soluble detergent builder salts. Typical such enhancers are, for example, those disclosed in U.S. Patents 4,316,812, 4,264,466 and 3,630,929. Water-soluble inorganic time-enhancing salts that can be used alone with a detergent compound or in admixture with other enhancers include alkali metal carbonates. borates, phosphates, polyphosphates, bicarbonates and silicates. (Ammonium and substituted ammonium salts can also be used). Specific examples of such salts include sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium disodium carbonate, sodium sesquicarbone. Sodium tripolyphosphate (TPP) has been particularly preferred. Alkali metal silicates are suitable builder salts which also act to make the composition anti-corrosive to parts of the washing machine. Sodium silicates with Na 2 O / SiO 2 ratios of 1.6 / 1 to 1 / 3.2, especially about 1/2 to 1 / 2.8, are preferred. Potassium silicates with the same ratios can also be used.

Another useful class of enhancers are water-insoluble aluminum silicates, both crystalline and amorphous.

27 84279

Several crystalline zeolites (i.e., aluminosilicates) are described in GB Pantent 1,504,168, U.S. Patent 4,409,136, and CA Patents 1,072,835 and 1,087,477, all of which are incorporated herein by reference. An example of suitable amorphous zeolites in this connection can be found in BE patent 835 351 and this patent is also incorporated herein by reference. The formula of zeolites is usually {M2 °> x- (A12 ° 3) y. <SiO2) z.WH2 ° where x is 1, y is 0.8 to 1.2 and predominantly 1, z is 1.5 to 3, 5 or higher and predominantly 2-3 and W is 0-9, predominantly 2.5 -6 and M is predominantly sodium. One typical zeolite is of type A or similar structure and type 4A is particularly preferred. The best aluminosilicates have a calcium exchange capacity of about 200 milliequivalents per gram or greater, for example 400 meq / g.

Other substances such as clays, especially water-insoluble types, may be useful excipients in the compositions of this invention. Bentonite is particularly suitable.

This substance is mainly montmorillonite, which is a hydrogenated aluminosilicate in which about 1/6 of the aluminum atoms can be replaced by magnesium atoms and which may be associated with varying amounts of hydrogen, sodium, potassium, calcium, etc. very loosely. Bentonite in a more purified form (i.e., free of coarse gravel, sand, etc.) suitable for detergents always contains at least 50% montmorillonite and thus has a cation exchange capacity of at least about 50-70 meq / 100 g bentonite. Particularly preferred bentonites are Wyoming or Western US bentonites sold under the name Thixo-jel 1, 2, 3 and 4 from Georgia Kaolin Co.

These bentonites are known to soften textiles, as described in GB Patent 401,413 and GB Patent 461,221.

0 ft 84279

Examples of organic temporal sequestering enhancer salts that can be used either alone with the detergent or in admixture with some other organic and inorganic enhancers include alkali metal, ammonium or substituted ammonium aminopolycarboxylates, for example sodium and potassium methylene diaminotetra acetates. , sodium and potassium nitrilotriacetates (NTA) and triethanolammonium N- (2-hydroxyethyl) nitrilodiacetates. Mixed salts of these polycarboxylates are also suitable.

Other suitable organic type enhancers include carboxymethyl succinates, tartronates and glycollates. Of particular value are polyacetal carboxylates. Polyacetal carboxylates and their use in detergent compositions are described in patents 4,144,226, 4,315,092 and 4,146,495. Other patents for similar effects include 4,141,676, 4,169,934, 4,201,858, 4,204,852, 4,224,420, 4,225,685, 4,226,960, 4,233,422, 4,233,423, 4,302,564 and 4,303,777.

EP patent applications Nos. 0 015 024, 0 021 491 and 0 063 399 also apply to the same subject.

Because the compositions of this invention are usually well concentrated and can therefore be used in relatively small doses, it is preferable to supplement any phosphate enhancer (such as sodium tripolyphosphate) with an adjuvant such as a polymeric carboxylic acid having strong calcium-binding ability to inhibit calcium birth. Such excipients are also well known in the art.

Several other detergent additives or excipients may be present in the detergent product to give it additional desired properties, either functional or aesthetic in nature. Smaller amounts of dirt suspending or anti-redeposition agents may be added to Formulation 29 84279, for example, polyvinyl alcohol, fatty amides, sodium carboxymethylcellulose, hydroxypropylmethylcellulose; optical brighteners, e.g., cotton, amine, and polyester brighteners, e.g., stilbene, triazole, and benzidine sulfone compositions, in particular, sulfonated substituted triazinyltilbene, sulfonated naphthotriazolistilbene, benzidine sulfone, etc., are most preferred, etc.,

Sealants such as ultramarine blue may also be used; enzymes, primarily proteolytic enzymes such as subtilisin and bromelain, papain, trypsin and pepsin, as well as amylase-type enzymes, lipase-type enzymes and mixtures thereof; bactericides, for example tetrachlorosalicylanilide, hexachlorophene; fungicides; coloring agents; pigments (water dispersible); preservatives; ultraviolet absorbers; anti-yellowing agents such as sodium carboxymethylcellulose, a C 1 -C 22 alkyl alcohol complex with g-alkyl sulfate; pH regulators and pH buffers; bleaching agents which do not damage dyes, perfumes and antifoams or anti-foaming agents, for example silicone compounds.

Bleaching agents can be generally classified into chlorine bleaches and oxygen bleaches for convenience. Chlorine bleaches are of the type sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% available chlorine) and trichloroisocyanuric acid (85% available chlorine). Oxygen bleaches are preferred and are represented by basic compounds which release hydrogen peroxide into solution, i. compounds containing hydrogen peroxide or inorganic perhydrates which, when dissolved, liberate hydrogen peroxide enclosed in their crystal lattice. Preferred examples are sodium and potassium perborates, percarbonates and perphosphates, and potassium monopersulfate. Perborates, especially sodium perborate monohydrate, are considered to be particularly preferred.

Hydrogen peroxide and the precursors that release it into solution are good oxidizing agents that remove certain stains from clothing, especially wine, tea, coffee, cocoa, fruit stains and the like.

Hydrogen peroxide and its precursors have generally been found to bleach rapidly and most efficiently at relatively high temperatures, for example at about 80 to 100 ° C. However, these compounds tend to decompose and release gaseous oxygen at lower temperatures. The release of gaseous oxygen, which is not involved in the oxidation of colored goods, unnecessarily consumes a considerable amount of hydrogen peroxide or the precursors that release it, and both are expensive products. In addition, it has been found that several stains on clothing and others greatly accelerate the release of hydrogen peroxide into gaseous oxygen during washing at ordinary temperatures.

Washing of clothes, either in a machine, by hand, in a cooking pot or in a washing spoon, is usually done by dissolving a bleach or detergent composition (containing perborate, for example) in cold or lukewarm water, adding a soiled garment to the resulting solution (often stained or previously washed). and often heated just to the boiling point.

However, it has been found that due to a phenomenon similar to the above-mentioned phenomenon, all or part of the perborate decomposes during heating and especially especially as the temperature rises, i. that all or part of the perborate decomposes before the effective temperature is reached.

31 84279

It is believed that the rapid decomposition of hydrogen peroxide, perborate or other hydrogen peroxide precursors to gaseous oxygen at low temperature is due to the infinitely strong catalytic effect and they are of bacterial origin. Hydroperoxidases are a particularly active group of enzymes in this respect, especially catalase, which is well known as a highly efficient catalyst that decomposes hydrogen peroxide into gaseous oxygen. However, such enzymes, referred to as "redox" or by any other name, are well known to have a clear tendency to induce peroxide bleach degradation, and the degradation products that result are ineffective bleaches.

In order to take advantage of the low temperature effective detergents and low temperature washing cycles commonly used in the washing of sensitive textiles today, the peroxygen compound is preferably used in combination with an activating agent. Suitable activating agents capable of lowering the effective working temperature in peroxide bleaching to about 40 ° C or lower are described in U.S. Patent 4,264,466 or Column 1 of U.S. Patent 4,430,244, which are incorporated herein by reference. Preferred activating agents are polyacylated compounds; of these, compounds such as tetraacetyl-ethylenediamine (TAED) and pentaacetyl-glucose are particularly preferred. Other useful activating agents 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, tetraacetyl glycuryl and tetraacetyl glucuryl. See. see also U.S. Patents 4,111,826, 4,422,950 and 3,661,789, which contain other classes of activating compounds suitable herein.

32 84279

The bleach activating agent and the peroxygen compound usually interact to form a bleaching peroxyacid in the wash water. It is preferred to add a sequestering agent having a strong complexing power to prevent all other undesired reactions between this peroxyacid and hydrogen peroxide in a washing solution containing metal ions. The preferred sequestering agents are capable of complexing with Cu ions such that the complexation stability constant (pK) is equal to or greater than 6 at 25 ° C in water with an ionic strength of 0.1 mol / liter, and the pK is conveniently determined by the formula according to: pK = -log K, where K represents the equilibrium constant. Thus, for example, the pK values for the formation of a copper ion complex with NTA and EDTA under the conditions shown are 12.7 and 18.8, respectively. Examples of suitable sequestering agents include, in addition to the above, diethylene-triaminepentaacetic acid (DETPA); diethylene-triamine-nipentamethylenephosphonic acid (DTPMP); and ethylenediamine-tetramethylenephosphonic acid (EDITEMPA).

But even in the presence of bleach activators and even at temperatures as low as room temperature, decomposition of persalt occurs during washing of soiled clothing because the reaction between the bleach and the activator is slower than the rate of decomposition of hydrogen peroxide due to catalase.

In order to avoid the loss of bleach caused by enzyme-induced degradation, the compositions of this invention further contain an effective amount of a compound capable of inhibiting enzyme-induced degradation of this bleach. Suitable inhibitory compounds are described in U.S. Patent 3,606,990, which is incorporated herein by reference.

33 84279

A particularly interesting and important inhibitory compound is hydroxylamine sulfate and other water-soluble hydroxylamine salts such as hydrochloride, hydrobromide, etc. It has now been found that hydroxylamine salts, especially sulfate, are effective in preventing the detrimental effect of catalase, even when only well present. a limited amount of 0.01 to 0.4%, preferably 0.04 to 0.2% and particularly preferably about 0.1% by weight of the total composition.

In addition, hydroxylamine is a very stable inhibitory agent in the composition: less than 20% loss on aging for 2 months at 43 ° C. Hydroxylamine salts are very soluble in water and thus can react with catalase before dissolving perborate or other peroxide bleach. Another advantage of hydroxylamine salts is that they degrade rapidly in the wash liquor and therefore no nitrosamine derivatives have been identified.

When the bleaching system is activated with a bleach activating agent, for example TAED, the activating agent is used more efficiently and therefore appropriate ratios of persalt-bleach / bleach activator can be maintained, much closer to stoichiometric equivalent weights levels or with a very small molar excess of bleach.

The composition may also contain an inorganic insoluble thickener or dispersant having a very large surface area such as finely divided silica having an infinitesimal particle size (e.g., 5 to 100 millimicrons in diameter, as sold under the name Aerosil) or other very bulky inorganic carriers. substances disclosed in U.S. Patent 3,630,929 in an amount of 0.1 to 10%, for example 1 to 5%. However, it is preferred that compositions that form peroxyacids in the wash solution (e.g., compositions containing the peroxygen compound 34,84279 and an activating agent therein) be substantially free of such compounds and other silicates; for example, silica and silicates have been found to promote harmful degradation of peroxyacid.

In a preferred form of the invention, a mixture of a liquid nonionic surfactant and solids is placed in an abrasion mill in which the particle sizes of the solids are reduced to less than about 10 microns, e.g., an average particle size of 2-10 microns or even smaller (e.g., 1 microns). Compositions with such small dispersed particle sizes have improved stability to separation or settling during storage.

In the grinding step, it is preferred that the proportion of solid ingredients be high enough (e.g., at least about 40%, or about 50%), that the solid particles be in contact with each other, and that they be not protected from each other by a nonionic surfactant liquid. Mills using grinding balls (ball mills) or similar mobile grinding elements have given very good results. Thus, a laboratory batch-grinding mill with 8 mm diameter grinding balls can be used. When working on a larger scale, a continuously operating mill with 1 mm or 1.5 mm diameter grinding balls operating in a very small space between the stator and a rotor at a relatively high speed (e.g. a CoBall mill) can be used; when using such a mill, it is preferable to allow the mixture of nonionic surfactant and solids to first pass through a mill that does not perform such fine grinding (e.g., a colloid mill), thereby reducing the particle size to less than 100 microns (e.g., about 40 microns); to an average particle size of less than about 10 microns in a continuous ball mill.

35 84279

In the preferred high performance liquid detergent compositions of the invention, typical proportions of ingredients (based on the total composition, unless otherwise specified) are as follows: suspended detergent builder about 10-60%, such as about 20-50%, for example about 25-40%; a liquid phase containing a non-ionic surfactant and a dissolved amphiphilic viscosity regulating and anti-gelling compound, about 30-70%, such as about 40-60%; this phase may also contain smaller amounts of diluent such as glycol, for example polyethylene glycol (for example "PEG 400"), hexylene glycol, etc., up to 10%, in particular up to 5%, for example 0.5-2%. The weight ratio of nonionic surfactant to amphiphilic compound is from about 100: 1 to 1: 1, preferably from about 50: 1 to about 2: 1, particularly preferably from about 25: 1 to about 3: 1 polyethercarboxylic acid, a gelling inhibitor, in an amount such that about 0.5 to 10 parts (for example 1 to 6 parts, for example about 2 to 5 parts) of -COOH groups (molecular weight 45) per 100 parts of a mixture of such an acid compound and a nonionic surfactant. The amount of polyether carboxylic acid is typically in the range of about 0.01 to 1 part per part of nonionic surfactant, such as about 0.05 to 0.6 parts, for example about 0.2 to 0.5 parts; acidic phosphoric acid compound as anti-settling agent: up to 5%, for example between 0.01-5%, such as about 0.05-2%, for example about 0.1-1%.

Suitable amounts of other detergent additives are: proteolytic enzymes about 0.7-2%; corrosion inhibitors of about 0-40%, preferably 5-30%; antifoaming and anti-foaming agents 0-15%, preferably 0-5%, for example 0.1-3%; thickener and dispersants 0-15%, for example 0.1-10%, preferably 1-5%; stain suspending or anti-redeposition agents 36 8 4 2 7 9 and anti-yellowing agents 0-10%, mainly 0.5-5%; colorants, perfumes, brighteners and sealants in a total weight of 0% to about 2% and preferably 0% to about 1%; pH modifiers and pH buffers 0-5%, preferably 0-2%; a bleaching agent of about 2-25%, for example 2-20%, a hydroxylamine salt which inhibits enzyme-induced degradation of the bleaching agent by about 0.01-0.4%, preferably 0.04-0.2%; a bleach stabilizer and a bleach activator of about 0.1-10%, for example 0.1-8%; a sequestering agent having a strong complexing ability of up to about 5%, preferably about 1/4 to 3%, such as about 1/2 to 2%. When excipients are selected, they are selected to be compatible with the main ingredients of the detergent composition.

All parts and percentages are by weight unless otherwise indicated.

It is to be understood that the foregoing detailed description is provided for illustrative purposes only and that modifications may be made without departing from the spirit of the invention.

To demonstrate the effects of viscosity regulating and gelling inhibiting agents, several compositions were prepared using the above-described surfactant T8 (C13, E08) (a 50/50 weight ratio mixture of surfactant T7 and surfactant T9) as an anhydrous liquid nonionic surface. as an active detergent. Formulations were prepared containing 5%, 10%, 15% or 20% amphiphilic additive and tested at 5 ° C, 10 ° C, 20 ° C and 25 ° C at various dilutions in water, i. At 100%, 83%, 67%, 50% and 33% total concentrations of nonionic 37,84279 surfactants T8 plus additives, i.e. diluted in water. The additives tested were Alfonic 610-60 (C8-E04.4), ethylene glycol monoethyl ether (C2-E01) and diethylene glycol monobutyl ether (C4-E02). The results of the viscosity behavior of each tested composition diluted at each temperature are shown in the curves attached to Figures 1-3.

For Alfonic 610-60, a 5% increase was sufficient to inhibit gelation at 25 ° C; however, in the viscosity / concentration curve of the nonionic substance, a sharp viscosity maximum was observed at a concentration of about 67% and a protrusion was observed at a concentration of about 55% to 35% nonionic substance. At 5 ° C, a 15% increase was required to prevent gel formation. Viscosity was reduced to a minimum at a nonionic concentration of about 83% at all levels of the additive at 5 ° C, while at higher temperatures viscosity minima were observed with the undiluted formulation, i. at non-ionic substance concentrations of 100%. At each temperature and at each tested concentration of the additive (except at a concentration of 20% additive at 25 ° C), a relatively sharp peak is seen in the viscosity of the nonionic substance at concentrations of 75-50% (i.e., 25-50% dilution).

With respect to ethylene glycol monoethyl ether, the addition of 5% was able to inhibit gel formation even at 5 ° C. But again, sharp peaks and / or maximum viscosity values were observed at each temperature and additive concentration, although the effects were not as clear as with Alfonic 610-60, and in some applications maximum viscosities could occur, especially at higher additive concentrations and / or higher temperatures. .

On the other hand, no sharp peaks were observed in the viscosity of diethylene glycol monobutyl ether at a temperature of 3884279 going down to 5 ° C with an additive concentration of 20%. Even at lower additive concentrations, viscosity peaks and viscosity values at almost all dilutions (nonionic substance concentrations) were lower than with both C8-E04.4 or C2-E01 additives.

The following table shows typical results obtained with different concentrations, dilutions and temperatures of the additives, but is given at an additive concentration of 20% and a temperature of 5 ° C.

Compositions Viscosity Pouring temperature at 5 ° C (Pa.s.)

Iina water 50% water

Surfactant only T8 1,140 1,240 5 80% surfactant T8 + 20% A 0,086 0,401 -10 80% surfactant T8 + 20% B 0,195 0,218 -2 80% surfactant substance T8 + 20% C 0,690 0,936 3 A = ethylene glycol clone monoethyl ether B = diethylene glycol clone monoethyl ether C = Alfonic 610-60 (C8-4,4EO)

Note: 1 Pa.s. = 10 Poise (e.g. 0.218 Pa.s. = 218 centipoise)

Example 1

A high performance anhydrous liquid nonionic detergent composition having the following formula is prepared: 39 84279

Ingredient Weight%

Surfactant T7 17.0

Surfactant T8 17.0

Dobanol 91-5 acid 1 5.0

Diethylene glycol monobutyl ether 10.0

Dequest 2066 ^ 1.0 TPP NW (sodium tripolyphosphate) 29.0925 3

Sokolan CP5 (calcium sequestrant) 4.0

Perborate H_0 (sodium perborate monohydrate) 9.0 T.A.E.D. (tetraacetyl-ethylenediamine) 4.5

Emphiphos 5632 ^ 0.3

Stilbene 4 (optical brightener) 0.5

Esperase (proteolytic enzyme) 1.0

Duet 7875 0.6 g

Relatin DM 4050 (anti-fouling agent) 1, 0

Blue Foulan Sandolane (dye) 0.0075 1) Esterification product of Dobanol 91-5 (C 1 -C 4 fatty alcohol ethoxylated with 5 moles of ethylene oxide) with succinic anhydride - half ester.

2) Sodium salt of diethylenetriamine-pentamethylene-phosphoric acid.

3) A copolymer with almost equal molar amounts of methacrylic acid and maleic anhydride, completely neutralized to form its sodium salt.

4) Partial ester of phosphoric acid and C 1 -C 6 alkanol, about 1/3 monoester and 2/3 diester.

5) Fragrance.

6) A mixture of sodium carboxymethylcellulose and hydroxymethylcellulose.

This composition is a stable, free-flowing, enhanced, non-gelling, liquid nonionic detergent composition in which the polyphosphate enhancer is stably suspended in the liquid nonionic surfactant phase.

40 84279

Example 2

In the same manner as in Example 1, the following high-performance anhydrous liquid nonionic detergent composition 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

Perborate I ^ O 9.0 TAED 4.5

Hydroxylamine sulphate 0,1

Emphiphos 5632 0.3 ATS-X (optical brightener) 0.2

Esperase 1.0

Perfume 0.6

Relatin DM 4050 1.0

TiO 2 0.4 This composition has the same advantageous properties as the composition of Example 1 and, in addition, has better bleaching performance.

Claims (7)

Anhydrous liquid detergent composition with which one can wash and bleach dirty clothes at temperatures as low as about 40 ° C or less, characterized in that it contains 30-70% by weight of a liquid phase containing a nonionic surfactant and a mono or poly (C 2 -C 3) alkylene glycol mono (C 1 -C 3) alkyl ether, about 2-25% by weight of a water-soluble inorganic peroxide bleaching agent, about 0.1-10% by weight of a bleach activator to lowering the temperature at which the bleaching agent releases hydrogen peroxide in aqueous solution, about 0.7-2% by weight of a proteolytic enzyme and about 0.01-0.4% by weight of a hydroxylamine salt capable of inhibiting the enzyme-induced degradation of the bleaching agent, which enzyme is present in the dirt. Composition according to claim 1, characterized in that it further contains about 20-50% by weight of a builder salt for the detergent suspended in the liquid nonionic surfactant. Composition according to claim 2, characterized in that it contains as a builder salt for the detergent about 25-40% by weight of an alkali metal tripolyphosphate. 4. A composition according to any one of claims 1-3, characterized in that the bleaching agent is a perborate, percarbonate, perfosphate or persulfate present in an amount of about 2-20% by weight. Composition according to claim 4, characterized in that the bleaching agent is sodium perborate monohydrate. 84279 Composition according to any one of claims 1-5, characterized in that the bleaching activator is Ν, Ν, Ν ', Ν'-tetra-acetylethylenediamine present in an amount of about 0.1-10% by weight. , preferably about 0.1-8% by weight. 7. A composition according to any one of claims 1-6, characterized in that the hydroxylamine salt is hydroxylamine sulfate or hydroxylamine hydrochloride present in an amount of about 0.02-0.2% by weight.