DK168398B1 - Non-aqueous, liquid, powerful, builder-containing laundry detergent - Google Patents

Description

DK 168398 B1

The present invention relates to non-aqueous, liquid, high-performance, builder-containing fabric treatment agents which are stable to phase separation and gelling and are easily pourable. These agents are used for the purification of soiled 5 substances.

Liquid non-aqueous powerful laundry detergents are well known. Funds of this type can e.g. comprise a liquid nonionic surfactant in which particles of a builder are dispersed, as shown e.g. in U.S. Patents Nos. 4,316,812, 3,630,929 and 4,264,466, and U.S. 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 are easy to measure, dissolve quickly in the wash water, can easily be used in concentrated solutions or dispersions on dirty areas of clothing to be washed, and are not dusty and usually take up less storage space. Furthermore, the liquid detergents may have incorporated in their composition materials which could not withstand drying without destruction, which materials are often desirable in the manufacture of particulate detergent products. Although they have many advantages over unit products or particulate solid products, liquid detergents often have certain inherent disadvantages that must be overcome to produce acceptable industrial detergent products. Thus, some products separate on storage and others on cooling and do not readily disperse. In some cases, the viscosity of the product changes and it becomes either too thick to pour or so thin that it seems watery.

30 Some clear products become fuzzy and some gels on standing.

The present inventors have therefore investigated the behavior of nonionic liquid surfactant systems with particulate matter suspended therein. Of particular interest have been 2 DK 168398 B1 non-aqueous builder-containing liquid laundry detergents and the problem of precipitation of the suspended builder and other detergent additives as well as the problem of gelling associated with non-ionic surfactants. These 5 considerations have a bearing on e.g. the stability, pourability and dispersibility of the product.

It is known that one of the main problems with builder-containing liquid laundry detergents is their physical stability. This problem is because the density of the solid particles dispersed in the nonionic liquid surfactant is higher than the density of the liquid surfactant.

Therefore, the dispersed particles tend to precipitate. There are two basic solutions to solve the precipitation problem: increasing the viscosity of the nonionic liquid and reducing the particle size of the dispersed solid.

It is known that suspensions can be stabilized against precipitation by adding inorganic or organic thickeners or dispersants, such as e.g. inorganic materials 20 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. These increases in suspension viscosity are naturally limited by the requirement that liquid suspension 25 be easily pourable and flowable. even at low temperature. Furthermore, these additives do not contribute to the purity of the preparation.

Grinding to reduce particle size provides the following advantages: 1. The specific surface area of the dispersed particles increases and the particle wetting with the non-aqueous carrier (liquid non-ionic substance) improves proportionally.

3 DK 168398 B1 2. The average distance between dispersed particles is reduced by a proportional increase in the particle-particle reaction. Each of these effects contributes to increasing the residual gel strength and the liquid yield stress of the suspension while significantly reducing the plastic viscosity.

The yield stress is defined as the minimum stress required to induce a plastic deformation (flow) of the suspension. Thus, when the suspension is conceived as a loose network of dispersed particles, the suspension will behave as an elastic gel and no plastic flow will occur if the applied voltage is less than the yield stress. 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 greater 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 flow stress, the dispersed particles become completely shear-deflocculated and the apparent viscosity is very low, as if there was no reaction between the particles.

Therefore, the higher the flow stress of the suspension, the higher the apparent viscosity at low shear rate and the better the physical stability against precipitation 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 are prone to gelling when exposed to cold water. This is a particularly important problem in the usual use of European automatic household washing machines, where the user places the laundry detergent in a dispensing unit (eg a drawer) in the machine. During operation of the machine, the detergent in the dispensing unit 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 unit are particularly cold, the viscosity of the detergent increases markedly and a gel is formed. As a result, some of the agent is not completely rinsed by the dispensing unit during machine operation, and a deposition of the agent is built up in repeated washing periods and finally requires the user to rinse the dispenser 10 with hot water.

The gelling phenomenon can also be a problem when one wants to. perform washing using cold water, as recommended for certain synthetic and delicate substances or substances that can crawl in hot water.

The tendency of concentrated cleaners to gel during storage is exacerbated by the storage of the agents in unheated storage areas or by shipping the agents in the winter months in unheated transport means.

Partial solutions to the gelation problem have been proposed, e.g. by 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., and by structural modification and optimization of the nonionic substance. As an example of modification of nonionic surfactant, a particularly good result has been obtained by acidifying the hydroxyl molecule end 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 washing liquid. Structural optimization of the nonionic substance has been centered on the chain length of the hydrophobic-lipophilic molecular moiety and the number and structure of alkylene oxide (e.g., ethylene oxide) units in the hydrophilic moiety. For example, it has been found that a c13 fatty alcohol ethoxylated with 8 moles of ethylene oxide shows only a limited tendency for gelling.

Nevertheless, improvements in both stability and gel inhibition of non-aqueous liquid drug treatment agents are desired.

According to the present invention, a highly concentrated, stable, non-aqueous liquid laundry detergent is prepared by adding to the agent small effective amounts of a quaternary surfactant ammonium agent as anti-precipitating and stabilizing additive.

According to the invention, there is thus provided a non-aqueous, liquid, vigorous, builder-containing laundry detergent, characterized in that it comprises: 1 to 70% by weight of at least one liquid, non-ionic, surfactant wherein ionic surfactant consists of a poly lower alkoxylated higher alkanol wherein the alkanol contains 9-18 carbon atoms and the number of 20 moles of the lower alkylene oxide is from 3-12 per mole of the alkanol, 10-60 wt% of at least a particulate detergent builder salt suspended in the liquid, nonionic surfactant, 0.1-5% by weight of a cationic quaternary ammonium salt as surfactant anti-precipitant selected from the group consisting of (I) mono-higher alkyl tri-lower -alkyl quaternary ammonium salt, (II) di-higher-alkyl-di-lower-alkyl quaternary ammonium salt, (III) mono-high ore-alkyl-mono-lower-alkyl-di-ethoxylated, quaternary ammonium salt, and (IV) di -Higher-alkyl-diethoxyler a quaternary ammonium salt, 5 to 30% by weight of a viscosity regulating and gel-inhibiting agent selected from the group consisting of alkylene glycols and alkylene glycol monoalkyl ethers, 0-2.0% by weight of a phosphoric acid alkanol ester stabilizer, 0-5.0% by weight of an aluminum salt of a fatty acid as a stabilizing agent, 0-30% by weight of a bleaching agent, 0-15% by weight of a bleach activator, 0-3.0% by weight of a metal ion sequestrant, 0-5.0% by weight of an antigen deposition agent, 10.0 - 2.0% of an optical brightener, 0 - 3.0% enzymes, 0 - 3.0% perfume, and 0 - 0.10% dye.

The anti-precipitating stabilizing additives of quaternary ammonium compound are cationic surfactants. The quaternary cationic surfactant ammonium compounds useful for the invention are the surfactants which contain a long hydrophobic hydrocarbon group in the molecular structure and a hydrophilic group, i.e. a water-soluble salt-forming anion group. The cationic quaternary ammonium compounds as surfactant anti-precipitators and stabilizers of the invention are well known and commercially available. The quaternary ammonium compounds have been used as fabric softeners and have been used as surfactant detergents.

The quaternary ammonium compounds used in the compositions of the invention are mono- and di-higher alkyl, lower-alkyl, quaternary ammonium salts, and mono- and di-higher alkyl di-ethoxylated quaternary ammonium salts.

The quaternary ammonium salts are thought to react with anionic phosphate builder salts to coat the anionic phosphate with a lipophilic skin. The lipophilic coating makes the anionic phosphate builder salts more compatible with the nonionic surfactant and enhances the contact between the phosphate and nonionic surfactant. The improvement in contact between the phosphate and nonionic surfactant increases the stability of the phosphate suspension in the nonionic surfactant.

The preferred surfactant anti-precipitating and stabilizing cationic quaternary ammonium compounds used in the compositions of the invention are representatives of the group consisting of: In mono-higher alkyl, tri-lower alkyl quaternary ammonium salts.

II di-higher alkyl, di-lower alkyl quaternary ammonium salts.

III mono-higher alkyl, mono-lower alkyl diethoxylated quaternary ammonium salts, and 15 IV di-higher alkyl diethoxylated quaternary ammonium salts.

The anti-precipitating and stabilizing cationic quaternary ammonium compounds of the invention are briefly described as follows: Compounds of formula I are mono-higher alkyl, tri-lower alkyl quaternary ammonium salts represented by formula R2 + R1-N-R2 X "(I), R2 R1 is a long chain aliphatic radical of from 10 to 22

ISLAND

carbon atoms, the Rs, independently of each other, are lower-alkyl or hydroxyalkyl having from 1 to 4 carbon atoms, and X is a water-soluble salt-forming anion.

8 DK 168398 B1

Compounds of formula II are di-higher alkyl, di-lower alkyl quaternary ammonium salts represented by the formula R · + · + R1-N-R2 X ((II), 5 l R _ wherein the R1s, independently of each other, are long chain aliphatic radicals having from 10 to 22 carbon atoms, R2, eme, independently of each other, are lower-alkyl or hydroxyalkyl having from 1 to 4 carbon atoms, and X is a water-soluble salt-forming anion.

The compounds of formula III are mono-higher alkyl, mono-lower alkyl diethoxy quaternary ammonium compounds represented by formula R2 +

Rx-N- (C ^C ^O) ^X "(III),

(CH 2 CH 2 O) yH

wherein R1 is a long chain aliphatic radical having from 10 to 22 carbon atoms, R2 is lower-alkyl or hydroxyalkyl having from 1 to 4 carbon atoms, x and y are each positive numbers of at least 1 and the sum of x + y is from 2 to 15, and X is a water-soluble salt-forming anion.

The compounds of formula IV are di-higher alkyl diethoxylated quaternary ammonium salts represented by formula R1 + R1-N- (CH2 CH2 O) x H X- (IV),

(CH2 CH2 O) yH

wherein the R17s, independently of each other, are long chain aliphatic radicals having from 10 to 22 carbon atoms, x and y are each positive numbers of at least 1 and the sum of x + y is from 2 to 15 and X is a water-soluble salt-forming anion.

9 DK 168398 B1

To improve the viscosity properties of the agent and the storage properties of the agent, viscosity enhancers and anti-gelling agents such as alkylene glycols, polyalkylene glycols and alkylene glycol monoalkyl ethers may be added, and additional anti-precipitating agents such as phosphoric acid ester and / or aluminum stearate.

Hygiene agents or bleaches and activators can therefore be added to improve the bleaching and cleansing properties of the agent.

In one embodiment of the invention, the builder components of the agent are ground to a particle size less than 100 μπι and preferably less than 10 μπι to further improve the stability of the suspension of the builder components in the liquid nonionic surfactant cleaner.

In addition, other constituents may be added to the agent such as optical brighteners, enzymes, agents for preventing re-deposition of dirt, perfumes and dyes.

The currently manufactured household washing machines usually operate at washing temperatures up to 95 ° C. Ca. 20 liters of water are used during the wash and rinse period.

Usually approx. 200 - 250 g powdered detergent per wash.

According to the present invention, where highly concentrated liquid detergent is used, only 100 25 g (78 cm 3) of the liquid detergent is usually required to wash a full load of soiled clothing.

Therefore, one aspect of the invention discloses a liquid powerful laundry detergent composed of a suspension of a builder salt or of an anionic builder salt, e.g. a phosphate builder salt, in a liquid nonionic surfactant, wherein the agent includes an effective amount of a surfactant quaternary ammonium agent to enhance the stability of the suspension against precipitation.

In another embodiment, the invention discloses a concentrated liquid powerful laundry detergent which is stable, non-precipitating upon storage and non-gelling upon storage and use. The liquid agents according to the invention are easily pourable, can be easily measured and easily loaded into the washing machine.

Another aspect of the invention relates to a liquid non-ionic laundry detergent which can be dispensed, optionally with cold water, without undergoing gelation. In particular, a non-aqueous liquid laundry detergent in which the detergent is composed, at least predominantly, of a liquid nonionic surfactant for filling a container and for dispensing the agent from the container into the aqueous wash bath, wherein the dispensing is effected by direct a stream of unheated water towards the agent so that the agent is carried by the flow of water into the wash bath.

The addition of the surfactant quaternary ammonium compounds to the cleaners reduces the problem of dispersed particles and phase separation.

The concentrated non-aqueous liquid nonionic surfactant laundry detergents of the invention have the advantage of being stable, non-precipitating upon storage and non-gelling upon storage. The liquid agents are easily pourable, can be easily measured and easily put into washing machines.

It is an object of the invention to provide a stable, liquid, powerful, non-aqueous, nonionic detergent containing at least one anti-precipitating and stabilizing quaternary ammonium compound and at least one anionic phosphate builder salt suspended in a nonionic surfactant.

i r- ^ i - 11 DK 168398 B1

It is another object of the invention to provide liquid fabric treating agents which are suspensions of insoluble inorganic particles in a non-aqueous liquid and which are storage stable, readily pourable and dispersible in cold or hot water.

Another object of the invention is to assemble powerfully constructed, powerfully acting non-aqueous liquid nonionic surfactant detergents which can be poured at any temperature and which can be repeatedly dispersed from the dispenser 10 in automatic washing machines of European type without to soothe or clog the dispensing unit even during the winter months.

A particular object of the invention is to provide non-gelling, stable suspensions of strongly acting builder-containing non-aqueous liquid, nonionic laundry detergents which contain an effective amount of a surfactant quaternary ammonium compound sufficient to increase the yield stress of the agent thereby to increase its stability, i.e. prevent buildup of builder particles, etc., preferably at the same time as reducing or at least not increasing the plastic viscosity (viscosity under shear conditions).

These and other objects of the invention, which will become more apparent from the following detailed description of preferred embodiments, are generally set forth for the preparation of a detergent by adding to the non-aqueous liquid nonionic surfactant an effective amount of a surfactant quaternary. ammonium compound as anti-precipitating and stabilizing agent sufficient to prevent precipitation of the suspended particles, wherein the agent includes inorganic or organic substance treatment additives, e.g. viscosity enhancing agents and one or more anti-gelling agents, anti-incrustation agents, pH regulating agents, bleaching agents, bleach activators, anti-foaming agents, optical brighteners, enzymes, agents in DK 168398 B1 12 for preventing re-deposition of dirt, perfumes and dyes.

According to the present invention, the physical stability of the suspension of the anionic phosphate builder compound or the anionic builder compound or compounds and any other suspended additives, such as bleach, etc., in the liquid nonionic surfactant carrier is substantially enhanced by the addition of an anti-precipitant and stabilizer which is a surfactant quaternary 10 ammonium compound.

The addition of very small amounts of the surfactant quaternary ammonium compound as anti-precipitating and stabilizing agent is sufficient to substantially improve the physical stability of the detergents.

Thus, the agents of the invention contain as a substantial component a surfactant anti-precipitating, stabilizing quaternary ammonium compound. The anti-precipitating and stabilizing additive may comprise one or more quaternary surfactant ammonium compounds.

The anionic surfactants useful in the invention are the cationic surfactants which contain a long hydrophobic hydrocarbon group in the molecular structure and a hydrophilic group, i.e. a water-soluble salt-forming anion group.

The preferred anti-precipitating and stabilizing cationic quaternary surfactant ammonium compounds of the invention are representatives of the group consisting of: In mono-higher alkyl, tri-lower alkyl, quaternary ammonium salts.

30 II di-higher alkyl, di-lower alkyl, quaternary ammonium salts.

III mono-higher alkyl, mono-lower alkyl, diethoxylated quaternary ammonium salts, and IV di-higher alkyl, diethoxylated quaternary ammonium salts.

The cationic anti-precipitating and stabilizing agents of formula I used according to the invention are mono-higher alkyl, tri-lower alkyl, quaternary ammonium compounds represented by the formula "- R2 + R1-N-R2 X" (I),

I T

Wherein R 1 is a long chain aliphatic radical having from 10 to 22 carbon atoms and the R 2's are independently lower alkyl or hydroxyalkyl radicals and X is a water-soluble salt-forming anion such as halide, i.e. chloride, bromide, iodine, sulfate, nitrate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate or a similar inorganic or organically soluble radical. The R 1 carbon chain of the aliphatic radical containing 10 to 22 carbon atoms, especially 12 to 20, and preferably 12 to 18, and especially 16 to 18 carbon atoms, may be

, Oh

20 straight or branched, and saturated or unsaturated. The lower alkyl radicals have from 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl and butyl, preferably I or 2 carbon atoms, and especially preferably methyl, and may contain a hydroxyl radical.

The preferred ammonium salt is a mono-higher alkyl trimethyl ammonium chloride in which the alkyl group is derived from tallow, hydrogenated tallow or stearic acid. Particular examples of quaternary ammonium compounds which are antiudfældende-stabilizer, of the formula I which are suitable for use in the composition of the invention include the following: 30 talgtrimethylammoniumchlorid hydrogenated talgtrimethylammoniumchlorid stearyltrimethylammonium 14 DK 168398 B1 stearyltriethylairanoniumchlorid cetyltrimethylammonium chloride SO j atrimethylammoniumchlorid stearyldimethylethylammoniumchlorid 5 tallow diisopropylme thylammoniumchlorid

The corresponding sulfate, methosulfate, ethosulfate, bromide and hydroxide may also be used.

The cationic anti-precipitating and stabilizing agents of formula II used according to the invention are the higher alkyl, di-lower alkyl quaternary ammonium compounds represented by the formula: ~ - R1 + R ^ N-R2 X "(I), * Wherein the R 1s are independently long chain aliphatic radicals having from 10 to 22 carbon atoms and the R 2s are independently lower alkyl or hydroxyalkyl radicals and X is a water-soluble salt-forming anion such as halide, i. chloride, bromide, iodide, sulphate, nitrate, citrate, 20 acetate, hydroxide, methosulphate, ethosulphate, phosphate or similar inorganic or organically soluble radicals. The R1 carbon chains of the aliphatic radicals containing 10 to 22 carbon atoms, especially 12 to 20, and preferably 12 to 18, and especially preferably 16 to 18 carbon atoms, may be straight or branched chain and saturated or unsaturated. The R 2 lower alkyl radicals have from 1 to 4 carbon atoms, for example, methyl, ethyl, propyl and butyl, preferably 1 or 2 carbon atoms, especially preferably methyl, and may contain a hydroxyl radical.

Typical cationics of formula II include the sequence-30: 15 DK 168398 B1 distearyl dimethyl ammonium chloride ditallow dimethyl ammonium chloride ditallow dimethyl ammonium chloride dihexadecyl 5 distearyl dimethyl ammonium bromide di (hydrogenated tallow) -dimethyl-ammonium bromide ditalgisop s OPY LME t hy 1 atnmoniumchl o distearyldi chloride (isopropyl) ammonium chloride distearyldimethylammoniummethosulfat.

A preferred class of cationic substances are of Formula II wherein two of the R 1 groups are C 14 -C 18, an R 2 is methyl or ethyl and an R 2 is methyl, ethyl, ispropyl, n-propyl, hydroxyethyl or hydroxypropyl.

The cationic anti-precipitating and stabilizing agents of formula III used according to the invention are the mono-higher alkyl, mono-lower alkyl diethoxylated quaternary ammonium compounds represented by the formula: R2 + in R-L-N- (CH 2 CH 2 O) x H X (III),

20 (CH 2 CH 2 O) H

L y wherein is a long chain aliphatic radical having from 10 to 22 ot carbon atoms and R is lower-alkyl or hydroxyalkyl radicals, x and y each are positive numbers of at least 1 and the sum of x + y is from 2 to 15 and X is a water-soluble salt-forming anion, such as halide, i.e. chloride, bromide, iodide, sulfate, nitrate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate or similar inorganic or organically soluble radiolabelling agents.

ISLAND

cabbage. The R-carbon chain of the aliphatic radical containing 10 to 22 carbon atoms, especially 12 to 20, and preferably 12 to 18, and especially 30 to 18 to 18 carbon atoms, may be straight or branched, and saturated or unsaturated. The R 2 lower alkyl radicals have from 1 to 4 carbon atoms, e.g. methyl, ethyl, propyl and butyl, preferably 1 or 2 carbon atoms, especially preferably methyl, and DK 168398 B1 16 may contain a hydroxyl radical.

Typical examples of anti-precipitating stabilizing cationic quaternary ammonium compounds of formula III suitable for use in the composition of the invention include the following: 5 coconut methyl diethoxylated (x + y = 2) ammonium chloride coconut methyl diethylated (x + y = 15) ammonium chloride 2) ammonium chloride oleinmethyl diethoxylated (x + y = 15) ammonium chloride stearylmethyl diethoxylated (x + y = 2) ammonium chloride 10 stearylmethyl diethoxylated (x + y = 15) ammonium chloride tallowmethyl diethoxylated (x + y = 10).

The anti-precipitating stabilizing cationic agents of formula IV used in the invention are di-higher alkyl di-ethoxylated quaternary ammonium compounds represented by the following formula: * R1 + R1 - (CH2CH2O) xH X "(IV),

(CH2CH20) y H

wherein the R1s, independently of each other, are a long chain aliphatic radical having from 10 to 22 carbon atoms, x and y each being positive numbers of at least 1 and the sum of x + y being from 2 to 15 and X being a water-soluble salt-forming anion such as halide, i.e. chloride, bromide, iodide, sulfate, nitrate, citrate, acetate, hydroxide, methosulfate, ethosulfate, phosphate or the like inorganic or organically soluble radical. The R1 carbon chains of the aliphatic radicals containing 10 to 22 carbon atoms, especially 12 to 20, and preferably 12 to 18, and especially 16 to 18 carbon atoms, may be straight or branched, and saturated or unsaturated.

A particular example of an anti-precipitating and stabilizing quaternary cationic ammonium agent of formula IV suitable for use in the composition of the invention is ditalgal diethoxylated (x + y = 4) ammonium chloride ("Ethoquat 2T / 14 ").

The mono- and di-higher alkyl diethoxylated compounds are stable in both acidic and alkaline solutions and have greater water solubility and compatibility than other related compounds.

In the compounds of formulas I to IV, the long carbon chains of long chain fatty acids, such as those derived from sebum and soybean oil, are obtained. The terms "soy" and "tallow", etc., as used in the present disclosure, refer to the source from which the long chain fatty alkyl chains are derived. Mixtures of quaternary ammonium compounds as anti-precipitators and stabilizers can be used.

The linear higher alkyl quaternary ammonium salts are readily biodegradable and preferred.

Although the invention is not tied to any particular theory of the way in which the quaternary surfactant ammonium compounds function to prevent the precipitation of the suspended anionic phosphate builder salts, it is believed that the quaternary 20 ammonium salts react with the anionic phosphate builder salts to coat the phosphate anion salts. a cationic lipophilic skin, which makes the phosphate more compatible with the nonionic surfactant, improves contact between the phosphate and the nonionic surfactant and increases the wettability of the dispersed solid phosphate particles surface with the nonionic surfactant. The improvement in the contact between the phosphate and nonionic surfactant and the improved wettability of the dispersed phosphate particles with the nonionic surfactant increases the stability of the phosphate suspension and allows the suspended phosphate to remain in suspension more easily.

in 18 DK 168398 B1

The increased physical stability is manifested by an increase in the yield stress of the agent e.g. from 65 dynes / cm2 to 260 dynes / cm2 and increase in apparent viscosity, e.g. from 2350 to 3250 (LVT, spindle 4, 60 rpm) compared to the same agent without the stabilizing quaternary ammonium salt. Thus, as described above, the higher the flow voltage, the higher the apparent viscosity at low shear rate and the better the physical stability.

In addition to their action as a physical stabilizer, the higher alkyl quaternary ammonium salts have the additional advantage over other physical stabilizers that they are cationic and compatible with the nonionic surfactant component.

Only very small amounts of the stabilizing quaternary ammonium salt are required to achieve the significant improvements in physical stability. Calculated on the total weight of the nonionic liquid surfactant, suitable amounts of the quaternary ammonium salt are e.g. in the range of from 0.1% to 5%, preferably from 0.3% to 2.0%, and more preferably 0.5 to 1.5%.

The quaternary ammonium salts are effective in their physical stabilizing effect, but other known physical stabilizers such as e.g. an acidic organic phosphorus compound having an acidic POH group such as 25 partial ester of phosphoric acid and an alkanol and / or aluminum salt of a fatty acid.

Nonionic surfactant detergent.

The nonionic synthetic organic detergents used in the invention may be any of a variety of known compounds.

19 DK 168398 B1

As is well known, the nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically prepared by condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic character). Practically any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen bonded to the nitrogen can be condensed with ethylene oxide or with its polyhydration product polyethylene glycol to form a nonionic detergent. The length of the hydrophilic chain or polyoxyethylene chain can be easily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups. Typical suitable nonionic surfactants are those disclosed in U.S. Patents Nos. 4,316,812 and 15,630,929.

As a rule, the nonionic detergents are poly-lower alkoxylated lipophiles in which the desired hydrophilic-lipophilic balance is obtained by adding a hydrophilic poly-lower alkoxy group to a lipophilic moiety. A preferred class of the nonionic detergent used is the poly lower alkoxylated higher alkanol wherein the alkanol has 9-18 carbon atoms and the number of moles of lower alkylene oxide (2-3 carbon atoms) is from 3 to 12. Of these materials, it is preferred to use those wherein the higher alkanol is a higher fatty alcohol having 9 to 11 or 12 to 15 carbon atoms and containing from 5 to 8 or 5 to 9 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, often being a minor amount (less than 50%).

Examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and contains about 7 ethylene oxide groups per moles, e.g. "Neodol 25-7" and "Neodol 23-6.5" which are manufactured by Shell Chemical Company, Inc. The former is a condensation product of a mixture of higher 35 fatty alcohols with 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 carbon atom content of the higher fatty alcohol is 12-13 and the number of ethylene oxide groups is on average approx.

6.5. The higher alcohols are primary alkanols.

Other examples of such detergents include Tergitol® 15-S-7 and Tergitol® 15-S-9, both of which are linear secondary alcohol ethoxylates manufactured by Union Carbide Corp. The former is a mixed ethoxylation product of a linear secondary alkanol having 11 to 15 carbon atoms with 7 moles of ethylene oxide and 10 the latter is a similar product but reacted with 9 moles of ethylene oxide.

Also useful in the present invention as a component of the nonionic detergent are high molecular weight nonionic substances 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 non-ionic substances are represented by the industrially well-known non-ionic substances traded under the trademark Plurafac®. Plurafac® is the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated with a hydroxyl group. Examples include products which are (A) C 13 -C 15 fatty alcohol condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide, (B) C 1-6 C - fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide, ( C) C13-C15 fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide, and (D) a product which is a 1: 1 - 30 mixture of products (B) and (C).

Another group of liquid non-ionic substances is available commercially from Shell Chemical Company, Inc. under the trade mark Dobanol®: Dobanol®91-5 "is an ethoxylated C9" C11 fatty alcohol having, in general, 5 moles of ethylene oxide and Dobanol®25-7 is an ethoxylated O2 - - fatty alcohol having an average of 7 moles of ethylene oxide. per. moles of fatty alcohol.

In order to achieve the best balance between hydrophilic and lipophilic 5 moieties in the preferred poly-lower alkoxylated higher alkanols, the number of lower alkoxy groups will generally be from 40% to 100% of the number of carbon atoms in the higher alcohol, preferably 40 - 60%. thereof, and the nonionic detergent will preferably contain at least 50% of such preferred poly lower alkoxy higher alkanol. More high molecular weight alkanols and various other normally solid nonionic detergents and surfactants may contribute to the gelation of the liquid detergent and will therefore preferably be omitted or limited in amount in the present agents, although 15 smaller amounts thereof may be used due to their purification. properties, etc. With respect to both preferred and less preferred nonionic detergents, the alkyl groups contained therein are generally linear although branching can be tolerated, such as by a carbon atom adjacent to or two carbon atom-20 being removed from the terminal carbon atom of the straight chain and away from the ethoxy chain if such branched alkyl does not have a length of more than 3 carbon atoms. Usually, the amount of carbon atoms in such a branched configuration will be less and rarely exceed 20% of the total carbon atom content of the alkyl. Although linear alkyls terminally linked to the ethylene oxide chains are highly preferred and considered to result in the best combination of purity, biodegradability and non-gelling properties, intermediate or secondary linkage to the ethylene oxide in the chain may occur. It is usually only in a minor amount of such alkyls, generally less than 20%, but as in the case of said Tergitol®s, it may be greater. When propylene oxide is found in the lower alkylene oxide chain, it will also generally be less than 20% thereof and preferably less than 10% thereof.

l 22 DK 168398 B1 When larger quantities of non-alkoxylated alkanols are used, propylene oxide-containing poly lower alkoxylated alkanols and less hydrophilic-lipophilic balanced nonionic detergent than mentioned above and other nonionic detergents instead of the preferred nonionic agents herein, the resulting product may not have as good purity, stability, viscosity and non-gelling properties as the preferred agents, but the use of the viscosity-regulating and gel-regulating compounds. The invention can also improve the properties of detergents based on such non-ionic substances. In some cases, when using a high molecular weight poly-lower alkoxylated higher alkanol, often due to its purification effect, the amount thereof will be controlled or limited in accordance with the results of routine experiments to obtain the desired purity and still have a gelling product of desired viscosity. It has also been found that the high molecular weight non-ionic substances are rarely used due to their cleaning properties, the preferred non-ionic substances disclosed in the present application being excellent detergents and additionally enabling the desired viscosity to be achieved. in the liquid detergent without gelling at low temperatures.

Another useful group of non-ionic surfactants is the 25 "Surfactant T" series of non-ionic substances available from British Petroleum. "Surfactant T" non-ionic substances are obtained by the ethoxylation of secondary C13 - fatty alcohol has a narrow ethylene oxide distribution. "Surfactant T5" has on average 5 moles of ethylene oxide; "Surfactant T7" averages 7 moles of ethylene oxide; "Surfactant T9" averages 9 moles of ethylene oxide and "Surfactant T12" averages 12 moles of ethylene oxide per moles of secondary C13 fatty alcohol.

In the compositions of the invention, preferred nonionic surfactants include the C2 - 2 secondary fatty alcohol hollow with relatively narrow content of ethylene oxide in the range of from 7 to 9 moles, and Cg-C C fatty alcohols are ethoxylated with approx. 5 - 6 moles of ethylene oxide.

Mixtures of two or more of the liquid nonionic surfactants can be used and in some cases benefits can be obtained from using such mixtures.

Builder.

The liquid non-aqueous non-ionic surfactant used in the compositions of the invention has dispersed and suspended therein fine particles of inorganic and / or inorganic detergent builder salts.

The detergents of the invention include water-soluble and / or water-insoluble detergent builder salts. Water-soluble inorganic alkaline builder salts that can be used alone with the detergent compound or in admixture with other builders are alkali metal carbonates, bicarbonates, borates, phosphates, polyphosphates and silicates. (Ammonium salts or substituted ammonium salts may also be used). Particular examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexame-taphosphate, sodium sesquicarbonate, sodium mono-bicarbonate and sodium di-bicarbonate. Sodium tripolyphosphate (TPP) is particularly preferred.

Since the agents of the invention are generally highly concentrated and therefore can be used in relatively low doses, it is desirable to supplement any phosphate builder (such as sodium tripolyphosphate) with an auxiliary builder such as a poly lower carboxylic acid or a polymeric carboxylic acid having high calcium binding capacity. , to prevent encrustation which might otherwise occur due to formation of an insoluble calcium phosphate.

in 24 DK 168398 B1

A suitable lower polycarboxylic acid comprises the alkali metal salts of lower polycarboxylic acids, preferably the sodium and potassium salts. Suitable lower polycarboxylic acids have two to four carboxylic acid groups. The preferred sodium and potassium lower polycarboxylic acid salts are the citric and tartaric acid salts.

The sodium citric acid salts are the most preferred, especially the trisodium citrate. The monosodium and disodium citrate can also be used. The monosodium and disodium tartaric acid salts can also be used. Alkali metal lower polycarboxylic acid salts are particularly good builder's teas. Because of their high calcium and magnesium binding capacity, they inhibit encrustation which could otherwise be caused by the formation of insoluble calcium and magnesium salts.

Other organic builders are polymers and copolymers of polyacrylic acid and polymaleic anhydride and the alkali metal salts thereof. More particularly, such builder salts may consist of a copolymer, which is the reaction product of ca. equal moles of methacrylic acid and maleic anhydride, which have been completely neutralized to form the sodium salt thereof. The builder is available in the trade under the trade name "Sokalan CP5". This builder 20 serves to prevent encrustation even when used in small quantities.

Examples of organic alkaline complex-binding builder salts that can be used with the scavenger builder salts or in admixture with other organic and inorganic builders are alkali metal, ammonium or substituted ammonium aminopoly-carboxylates, e.g. sodium and potassium ethylenediaminetetraacetate (EDTA), sodium and potassium nitrilotriacetates (NTA) and triethhanolammonium N- (2-hydroxyethyl) nitrilodiacetate. Mixed salts of these aminopolycarboxylates are also suitable.

Other suitable organic type builders include carboxymethylsuccinates, tartronates and glycolates. Of particular value are the polyacetal carboxylates. The polyacetal carboxylates and their use in detergents are disclosed in U.S. Patent Nos. 4,144,226, 4,315,092 and 4,146,495.

The alkali metal silicates are useful builder salts which also act to adjust or adjust the pH and to make the agent anticorrosive to the parts of the washing machine. Sodium silicates with Na 2 O / SiO 2 ratios from 1.6 / 1 to 1 / 3.2, in particular approx. 1/2 to 1 / 2.8 is preferred. Potassium silicates with the same ratio can also be used.

Other typical suitable builders include e.g. those described in U.S. Patents Nos. 4,316,812, 4,264,466, and 3,630,929. The inorganic builder salts may be used in conjunction with the nonionic surfactant cleanser or in admixture with other inorganic builder salts or with organic builder salts.

The water-insoluble crystalline and amorphous aluminum ilikat zeolites can be used. The zeolites generally have the formula (M20) χ. (Α1202) y. (SiO2) z.wH2O, where x is 1, y is from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3. , 5 or higher and preferably 2-3, and w is from 0 to 9, preferably 2.5 - 6, and M is preferably sodium. A typical zeolite is type A or a similar structure, with type 4Ά being particularly preferred. The preferred aluminum silicates have calcium ion exchange capabilities of approx. 200 mill equivalent equivalents grams or greater, e.g. 400 milliequivalents per gram.

Various crystalline zeolites (i.e., aluminum silicates) which can be used are described in British Patent No. 1,504,168, U.S. Patent No. 4,409,136, and Canadian Patents Nos. 1,072,835 and 1,087,477, all of which are incorporated herein by reference. this reference. An example of amorphous zeolites useful for the invention can be found in Belgian Patent No. 835,351 26 DK 168398 B1 and this patent is also incorporated herein by this reference.

Other materials, such as clays, especially of the water-insoluble types, may be useful additions to the compositions of the invention. Especially useful is bentonite. This material is primarily montmorillonite, which is a hydrated aluminum silicate in which ca. 1/6 of the aluminum atoms may have been replaced by magnesium atoms and with which may be loosely linked varying amounts of hydrogen, sodium, potassium, calcium, etc. The ben-10 tonite in its more purified form (ie free of mineral grains, sand, etc.) suitable for cleansers contains at least 50% montmorillonite and its cation exchange capacity is thus at least approx. 50 -70 milliequivalents per 100 g bentonite. Particularly preferred bentonites are Wyoming or Western U.S. bentonites that have been sold as "Thixo jels" 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften fabrics as disclosed in British Patent No. 401,413 and British Patent No. 4,017,137.

461,221.

Viscosity regulating and anti-curing agents.

Addition to the detergent of an effective amount of viscosity regulating and gel inhibiting agents for the nonionic surfactant improves the storage properties of the agent. The viscosity regulating and gel inhibiting agents act to reduce the temperature at which the nonionic surfactant will form a gel when added to water. These viscosity regulating and gel inhibiting agents can e.g. be lower alkanol, e.g. ethyl alcohol (see U.S. Patent No. 3,953,380), hexylene glycol, polyethylene glycol, e.g. polyethylene glycol having a molecular weight of approx. 400 (PEG 400) and low molecular weight alkylene oxide lower monoalkyl ether amphiphilic compounds.

Preferred viscosity regulating and gel inhibiting compounds are the low molecular weight amphibious compounds. The amphiphilic compounds act as viscosity regulating and gel inhibiting agents for the non-ionic surfactant and significantly improve bearing properties. The amphiphilic compounds may be considered to be analogous in chemical structure to the ethoxylated and / or propoxylated fatty alcohol liquid nonionic surfactants, but have relatively short hydrocarbon chain length (C2-Cg) and a low content of ethylene oxide (ca. 2 - 6 ethylene oxide groups per molecule).

Suitable amphiphilic compounds are represented by the following general formula 10 R 30 (CH 2 CH 2 O) n H, where R 3 is a C 2 -C 8 alkyl group and n is a number from ca. 1 to 6 on average.

Specifically, the compounds are lower (C2-C3) alkylene glycol monolavers (C2-Cg) alkyl ethers.

More particularly, the compounds are mono-, di- or tri-lower (C 2 -C 3) alkylene glycol mono-lower (C 1 -C 6) alkyl ethers.

Particular examples of suitable amphiphilic compounds include ethylene glycol monoethyl ether (C 2 H 9 -O-CH 2 CH 2 OH), diethyl englycol monobutyl ether (C 3 H 8 -O- (CH 2 CH 2 O) 2 H), tetraethylene glycol monobutyl ether (C 4 H 7 O -O- (CHCH 2 O) 2H).

CH3

Diethylene glycol monobutyl ether is particularly preferred.

The content of the low molecular weight lower alkylene glycol monoalkyl ether agent lowers the viscosity of the agent so that it is more easily pourable, improves the precipitation stability, and improves the dispersibility of the agent when added to hot or cold water.

The compositions of the invention have improved viscosity and stability and remain stable and pourable at temperatures as low as approx. 5 ° C and lower.

In one embodiment of the invention, a supplemental stabilizing agent, which is an alkanol ester of phosphoric acid or an aluminum salt of a higher fatty acid, can be added to the composition.

Improvements in stability of the agent can be achieved by incorporating a small effective amount of an acidic organic phosphorus compound having an acidic POH group such as a partial ester of phosphoric acid and an alkanol.

The acidic organic phosphorus compound having an acidic POH group can enhance the stability of the suspension of builders in the non-aqueous liquid nonionic surfactant.

The acidic organic phosphorus compound can e.g. may be 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.

A particular example is a partial ester of phosphoric acid and a Cig-C18 alkanol (Empiphos® 5632 from Marchon). It consists of approx. 35% monoester and 65% diester.

Adding very small amounts of the acidic organic phosphorus compound makes the suspension stable against precipitation upon standing, but it remains pourable while its plastic viscosity generally decreases at a low concentration of stabilizer, e.g. below approx. 1%.

29 DK 168398 B1

Improvements in the stability and anti-precipitation properties of the agent can also be achieved by the addition of a small effective amount of an aluminum salt of a higher fatty acid.

The preferred higher aliphatic fatty acid will have from about 8 to about 5. 22 carbon atoms, more preferably from about 10 to 20 carbon atoms, and more preferably from ca. 12 to 18 carbon atoms. The aliphatic radical may be saturated or unsaturated and may be chained or branched. As in the case of the nonionic surfactants, mixtures of 10 fatty acids, such as those derived from natural sources such as tallow fatty acid, coconut fatty acid, can also be used.

Examples of fatty acids from which the stabilizing aluminum salt can be formed include decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicosanoic acid, tallow fatty acid, coconut fatty acid, mixtures of these acids, etc. The aluminum salts of these acids are generally found in and is preferably used in the triacid form, e.g. aluminum stearate as aluminum ri tearate Al (C17H35C00) 3. The mono acid salts, e.g. aluminum monostearate Al (OH) 2 (C17H35COO) and diacid salts, e.g. aluminum distearate Al (OH) (C17H35COO) 2 / and mixtures of two or three of the mono-, di- and trisal aluminum salts may also be used. However, it is most preferred that the trisyreal aluminum salt constitutes at least 30%, preferably at least 50%, and especially at least 80% of the total amount of aluminum fatty acid salt.

The aluminum salts, as mentioned above, are industrially available and can be readily prepared, e.g. by saponifying fatty acid, e.g. animal fat, stearic acid, etc., and then treat the emerging soap with alum, alumina, etc.

Only very small amounts of the stabilizing aluminum salt are required to achieve an improvement in physical stability.

30 DK 168398 B1

Bleaching agents.

The bleaches are broadly classified for convenience, such as chlorine bleaches and oxygen bleaches. Chlorine bleaches can be exemplified by type of sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% available chlorine) and trichloroisocyanuric acid (95% available chlorine). Oxygen bleaches are preferred and represented by per-compounds which release hydrogen peroxide in solution. Preferred examples include sodium and potassium perborate, percarbonate and perphosphate and potassium monopersulfate. The perborates, especially sodium perborate monohydrate, are particularly preferred.

The peroxygen compound is preferably used in admixture with an activator therefor. Suitable activators which can reduce the effective operating temperature of the peroxide bleach are described, e.g. in U.S. Patent No. 4,264,466 or in column 1 of U.S. Patent No. 4,430,244. Polyacetylated compounds are preferred activators and among these, compounds such as tetraacetylethylenediamine ("TAED") and pentaacetyl glucose are particularly preferred.

Other useful activators include e.g. acetylsalicylic acid derivatives, ethylidene benzoate acetate and its salts, ethylidene carboxylate acetate and its salts, alkyl and alkenyl succinic anhydride, tetraacetylglycouril ("TAGU") and derivatives thereof. Other useful classes of activators are described e.g. in U.S. Patent Nos. 4,111,826, 4,422,950 and 3,661,789.

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 this peroxy acid and hydrogen peroxide in the wash solution in the presence of metal ions.

31 DK 168398 B1

Suitable complexing agents for this purpose include the sodium salts of nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriamine pentacetic acid (DETPA), diethylenetriamine pentamethylene phosphonic acid (DTPMP), negotiated under the trade name "Deitene ether 20 The complex binding agents can be used alone or in admixture.

To avoid loss of peroxide bleach, e.g. In addition, sodium perborate due to enzyme-induced decomposition, such as with catalase enzyme, the agents may contain an enzyme inhibitor compound, i. a compound capable of inhibiting enzyme-induced decomposition of the peroxide bleach. Suitable inhibitor compounds are described in U.S. Patent No. 3,606,990.

Of particular interest as an inhibitor compound may be mentioned hydroxylamine sulfate and other water-soluble hydroxylamine salts. In the preferred non-aqueous agents of the invention, suitable amounts of the hydroxylamine salt inhibitors may be as low as about 0.01 to 0.4%. However, in general, suitable amounts of enzyme inhibitors are up to about 15%, e.g. 0.1 to 10% by weight of the medium.

In addition to the detergent builders, various other detergent additives or additives can be found in the detergent product to provide the additional desired properties, either functional or aesthetic. Thus, the composition may include 25 minor amounts of dirt suspending agents or agents for preventing re-deposition of dirt, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose and hydroxypropyl methyl cellulose. A preferred agent for preventing re-deposition of dirt is sodium carboxymethyl cellulose having a 2: 1-30 ratio CM / MC, which is negotiated under the trade name "Relatin DM 4050".

Small quantities of "Alcosperse D107", which is sodium polyacrylate, may also be included in the quaternary ammonium-containing agent in 32 DK 168398 B1 and acting as an anti-scalding agent. "Alcosperse D107" may be included in amounts such as 0.5-8%, preferably 2-6%, and more preferably 3-5% by weight of the agent.

Optical clarifiers for cotton, polyamide and polyester fabrics can be used. Suitable optical clarifiers include stilbene, triazole, and benzidine sulfone compounds, especially sulfonated substituted triazinyl still life, sulfonated naphtho triazole still life, benzidene sulfone, etc., and most preferably are stilbene and triazole combinations. A preferred clarifier 10 is "Stilbene Brightener N4", which is a dianilinodimorphalino stilbene polysulfonate.

Enzymes, preferably proteolytic enzymes such as subtilisin, bromelin, papain, trypsin and pepsin, as well as amylase-type, lipase-type and mixtures thereof, can be added. Preferred enzymes include protease slurry, esperase slurry and amylase. A preferred enzyme is Esperase® SL8, which is a proteolytic enzyme. Anti-foaming agents, e.g. silicon compounds such as "Silicane L 7604" which is a polysiloxane can be added in small effective amounts.

Bactericides, e.g. tetrachlorosalicylanilide and hexachlorophen, fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet light absorption agents, anti-yellowing agents such as sodium carboxymethyl cellulose, pH modifiers and pH buffers, dye bleaches and color bleaches, color-proof bleaches, color-proof bleaches, color-proof bleaches, can be used.

The agent may also contain small amounts of paint pigments to give color, such as TiO 2, white pigment. TiCl 3 may be added in amounts such as 0.1-4%, preferably 0.1-2%, and more preferably 0.1-1%.

The agent may also contain small amounts of Bentone® 27, which is an organic derivative of aqueous magnesium aluminum in the leachate. Bone tone 27 may be used in amounts such as 0.2 - 3%, preferably 0.5 - 2%, and more preferably approx. 1% by weight.

The agent may also contain an inorganic insoluble thickener or dispersant having a very high surface area, such as finely divided particle size silica (e.g., 5 to 100 millimicron diameter as negotiated under the name Aerosil®) or the other very voluminous 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 peroxyacid in the wash bath (e.g. agents containing peroxygen compound and activator therefor) are substantially free of such compounds and other silicates. It has e.g. It has been found that silica and silicates promote the undesirable decomposition of the peroxyacid.

In one embodiment of the invention, the stability of the builder salts in the agent during storage and the dispersibility of the agent in water is improved by grinding and reducing the particle size of the solid builders to less than 100 μτα, preferably less than 40 μτα and more preferably to less than 10 μτα. The fixed 20 builders, e.g. sodium tripolyphosphate (TPP), is generally supplied in particle sizes of approx. 100, 200 or 400 μτα.

The nonionic liquid surfactant phase can be mixed with the solid builders before or after the grinding operation is performed.

In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solids is subjected to an abrasion-type mill in which the particle sizes of the solids are reduced to less than ca. 10 μτα, e.g. to an average particle size of 2 30 - 10 μνα or even lower (eg 1 μτα). Preferably, less has approx. 10%, especially less than 5% of all the suspended particles, particle sizes greater than 10 μιη. Agents whose dispersed particles have such a small size have improved stability against separation or precipitation by storage. Addition of the acid-terminated nonionic surfactant can reduce the flow stress of such dispersions and aid in the dispersibility of the dispersions without a corresponding decrease in dispersion stability against precipitation.

In the grinding operation, it is preferred that the amount of solids is sufficiently high (e.g., at least about 40%, such as about 50%) for the solid particles to be in contact with each other and not substantially shielded from each other by the nonionic 10 surfactant. After the grinding step, any residual liquid nonionic surfactant may be added to the ground preparation. Mills using grinding balls (ball mills) or similar moving grinding elements have produced very good results. Thus, one can use a laboratory grinder having steamer grinding balls 8 mm in diameter. For large-scale work, a continuously operating mill may be used in which there are grinding balls 1 mm or 1.5 mm in diameter and operating at a very small space between a stator and a rotor running at high speed (eg a CoBall mill). When such a mill is used, it is convenient to first pass the mixture of nonionic surfactant and solids through a mill which does not produce such a fine coating (e.g., a colloid mill), to reduce the particle size. to less than 100 μιη (e.g., to about 40 μτη) before milling to an average particle diameter below ca. 10 μτη in the continuous ball mill.

In the preferred heavy duty liquid laundry detergents of the invention, typical amounts (percent based on the total weight of the agent, unless otherwise stated) of the ingredients are as follows:

Liquid nonionic surfactant detergent in the range of 10 to 70, such as 20 - 50 or 60%, e.g. 30 - 40 or 50%.

DK 168398 B1

Detergent builder, such as sodium tripolyphosphate (TPP), in the range of 10 to 60, such as 15 - 50%, e.g. 15 or 25 - 35.

The anti-gelling alkylene glycol monoalkyl ether may be used in an amount in the range of 5 to 30, such as 5 to 20%, e.g. 5 5 - 15%.

Alkylene glycol as a viscosity regulating and gel inhibiting agent can be used together with the quaternary ammonium additive in an amount in the range of 5 to 30, such as 5 to 25%, e.g. 15 -25%. The preferred viscosity regulating and gel inhibiting agents are the alkylene glycol monoalkyl ethers.

The anti-precipitating and stabilizing quaternary ammonium salt ranges from 0.1 to 5, preferably 0.2 - 2.0 and more preferably 0.5 - 1.5%.

Phosphoric acid alkanol ester stabilizer in the range of 0 to 2.0 or 0.1 to 2.0, such as 0.10 - 1.0%.

Stabilizing aluminum salt of fatty acid in the range of 0 to 5.0, such as 0.5 - 2.0%, e.g. 0.1 - 1.0%.

Bleach in the range of 0 to 30, such as 2-20, e.g. 5 - 15%.

20 B1 activator in the range of 0 to 15, such as 1-8 or 10, e.g. 1-8 or 2-6%.

Bleach complexing agent, e.g. "Dequest 2066", in the range of 0 to 3.0, preferably 0.5 - 2.0%, e.g. 0.75 - 1.25%.

Means for preventing re-deposition of dirt, e.g. "Relatin DM 4050", in the range of 0 to 4.0 or 5.0, preferably 0.5 - 3.0 or 4.0%, e.g. 1.0 - 3.0 or 0.5 - 1.5%.

DK 168398 Pg 36

Optical brightening agents in the range of 0 to 2.0, preferably 0.05 or 0.25 - 1.0%, e.g. 0.15 or 0.25 - 0.75%.

Enzymes range from 0 to 3.0, preferably 0.10 or 0.25 - 1.25%, e.g. 0.25 or 0.75 - 1.0%.

Perfume in the range of 0 to 3.0, preferably 0.10 or 0.25 - 1.25%, e.g. 0.25 or 0.75 - 1.0%.

Staining pigments in the range of 0.1 to 4.0, preferably 0.1 to 2.0 and more preferably 0.1 to 1.0%.

Dye in the range of 0 to 0.10, preferably 0.0025 to 10.50, e.g. 0.0025 - 0.0100%.

Various of the aforementioned additives may optionally be added to achieve the desired function of the added materials.

The anti-precipitating agent is preferably used with at least one of the alkylene glycol monoether or the acid-terminated nonionic surfactant as viscosity regulating and anti-gelling agents. In some cases, benefits can be obtained by using both the alkylene glycol monoethers and the acid-terminated nonionic surfactants.

Mixtures of the acid-terminated nonionic surfactant and viscosity regulating and gelling agents, e.g. alkylene glycol alkyl ether as anti-gelling agent can be used and in some cases benefits can be obtained by using such mixtures alone, or together with the addition of the anti-precipitating stabilizer mixture.

In selecting the additives, they will be selected to be compatible with the main constituents of the detergent. In the present application, as mentioned above, all quantities and samples are by weight of the entire composition or composition, unless otherwise stated.

The concentrated non-aqueous non-ionic liquid detergent of the invention is readily dispensed into the water of the washing machine.

The liquid nonionic detergents of the invention are preferably non-aqueous, e.g. they are essentially anhydrous. Although smaller amounts of water can be tolerated, it is preferred that the agents contain less than 3%, preferably less than 2% 10, and more preferably less than 1% water.

The currently used household washing machines usually use 200 - 250 g of powder detergent to wash a full load of laundry. According to the present invention, only 100 cc or 78 g of the concentrated liquid nonionic detergent is needed.

In one embodiment of the invention, a typical cleanser is composed using the following ingredients: Watt%.

Nonionic surfactant detergent 20 or mixtures thereof 30 - 50

Phosphate Detergent Builder Salt 15-35

Copolymer of polyacrylate and polymaleic acid anhydride alkali metal salt anti-crustacean ("Sokalan CP-5) 0-10 25 Alkylene glycol viscosity regulating and gel inhibiting agent 0.2 - 2.0

Antigen Deposition Agent 0-5.0

Alkali metal perborate bleach 3-15

Bleach Activator (TAED) 1.0 - 6.0 38 DK 168398 B1

Complex Binding Agent 0-3.0

Optical Clarifier ("Stilbene Brightener N4") 0 - 2.0

Enzymes (protease-Esperase® SL8) 0-3.0

Perfume 0-3.0 5 The invention is further illustrated by the following example.

Example.

Concentrated non-aqueous liquid nonionic surfactants were composed of the following ingredients in the amounts indicated.

10 A_B

Plurafac® RA50 35 35

Plurafac® B26 9.0 9.0

Sodium Tripolyphosphate (TPP) 18 18

Polyethylene Glycol (Molecular Weight 400) Antigellant 20 20

Quaternary ammonium salt ^ 1.0

Sodium perborate monohydrate bleach 3.6 4.1

Tetraacetylethylenediamine (TEAD) bleach activator 4.5 5.0 20 "Relatin DM4096" (CMC / MC) (2) antigen depositor 3.0 3.0 EDTA complex binding agent 0.9 0.9

Bentone® 27 (4) 1.0 1.0 "Alcosperse D107" ^ 4.0 4.0 25 100.0 100.0 1. "Ethoquat 2T14", which is di-tallow diethoxy (x + y = 4) quaternary ammonium chloride.

2. A 2: 1 mixture of sodium carboxymethyl cellulose and hydroxymethyl cellulose.

3. Ethylenediaminetetraacetic acid.

39 DK 168398 B1 4. Organic derivative of aqueous magnesium aluminum ilate, which acts as an anti-precipitant.

5. "Alcosperse D107", which is sodium polyacrylate and acts as an agent to prevent dandruff deposition.

The composition was ground for approx. 15 minutes to reduce the particle size of the suspended builder salts to less than 10 μτα. The composite cleaning agent A according to the invention is found to be stable and non-gelling upon storage and to have a high cleaning performance.

A comparison of agent A of the invention with anti-precipitating and stabilizing quaternary ammonium salt with agent B without the quaternary ammonium salt gave the following results.

A_B

Apparent Viscosity (LVT, Column 4, 60 rpm) (m Pa) 3250 2350

Stability after 48 hours: phase separation% 1% 7%

Flow voltage (Pa) 26 6.5

Plastic Viscosity (m Pa) 400 510 20 The data show that the addition to the composition of as little as 1% quaternary ammonium salt as anti-precipitating and stabilizing agent according to the invention substantially increases the stability of the composition, increases the apparent viscosity, increases the flow tension and decreases the plastic viscosity. -25 site.

The composition of the example can be prepared without grinding the builder salts or suspended solid particles to a smaller particle size, but best results are obtained by grinding the preparation to reduce the particle size of the 30 suspended solid particles.

Claims (8)

1. Non-aqueous, liquid, powerful, builder-containing laundry detergent, characterized in that it comprises: 10 - 70% by weight of at least one liquid, non-ionic, surfactant wherein the liquid, non-ionic, surfactant consists of a poly-1 avere-alkoxylated, higher alkanol, wherein the alkanol contains 9-18 carbon atoms and the number of moles of the lower alkylene oxide is from 3-12 per mole of the alkanol, 10 - 60 weight percent of at least one particulate detergent builder-20 salt suspended in the liquid, nonionic surfactant, 0.1-5% by weight of a cationic quaternary ammonium salt as surfactant anti-precipitant selected from the group consisting of (I) mono-higher-alkyl tri-lower -alkyl quaternary ammonium salt, (II) di-higher-alkyl-di-lower-alkyl quaternary ammonium salt, (III) mono-higher-alkyl-mono-lower-alkyl-di-ethoxylated, quaternary ammonium salt, and (IV) di-higher-alkyl-diethoxylated quaternary ammonium salt, 5-30 walls t% of a viscosity regulating and gel inhibiting agent selected from the group consisting of alkylene glycols and alkylene glycol monoalkyl ethers, 0-2.0% by weight of a phosphoric acid alkanol ester stabilizer, 0-5.0% by weight of an aluminum salt of a fatty acid as stable 0-30 wt% of a bleaching agent, 0-15 wt% of a bleach activator, 0-3.0 wt% of a metal ions sequestering agent, 0-5.0 wt% of an antigen scavenger, 0 - 2.0% of an optical brightener, 0 - 3.0% enzymes, 0 - 3.0% perfume, and 0 - 0.10% dye. An agent according to claim 1, characterized in that the cationic quaternary ammonium salt has the formula:, 1] ♦ R1-N-R2 X '(II), * 2 wherein R1 is independently long chain aliphatic radicals having from 10 to 22 carbon atoms, R 2 is independently lower alkyl radicals and X is a water-soluble salt-forming anion. Agent according to claim 1, characterized in that the cationic quaternary ammonium salt has the formula: Wherein R1 is independently long chain aliphatic radicals having from 10 to 22 carbon atoms, x and y each being positive numbers of at least 20 1 and the sum of x + y is from 2 to 15 and X is a water-soluble salt-forming anion. An agent according to claim 1, characterized in that the 2 particulate detergent builder salt has a particle size 3 distribution such that no more than 10% by weight of the particles 430 has a particle size of more than 10 µπι. DK 168398 B1 An agent according to claim 1, characterized in that the cationic quaternary ammonium salt as a surfactant anti-precipitating agent is present in an amount of 0.2 to 2.0% by weight. Composition according to claim 2, characterized in that the cationic quaternary ammonium salt is distearyl-dimethylammonium chloride. An agent according to claim 3, characterized in that the cationic quaternary ammonium salt of formula (IV) 10 R1 + R1-N- (CH2CH2O) xH X "(IV), (CH2CH2O) yH is diethyl diethoxylated ammonium chloride where x + y is equal to 4 An agent according to claim 1, characterized in that the viscosity-regulating and gel-inhibiting agent is polyethylene glycol. An agent according to claim 1, characterized in that the viscosity-regulating and gel-inhibiting agent is diethylene gly-20 monobutyl ether.