NL8702062A - NON-AQUEOUS LIQUID, NON-IONIC LAUNDRY DETERGENT COMPOSITION, CONTAINING A PERZOUT BLEACH AND A LIQUID ORGANIC BLEACH ACTIVATOR AND METHOD FOR USING THE COMPOSITION. - Google Patents

Description

*> VO 9295

Title: Non-aqueous liquid non-ionic laundry detergent composition containing a persalt bleach and a liquid organic bleach activator, as well as a method of using the composition.

The invention relates to non-aqueous liquid compositions for the treatment of fabrics, in particular to liquid non-ionic laundry detergent compositions containing an inorganic persalt bleaching compound and a liquid organic bleach activator. The compositions are stable against phase separation and gel formation and are easy to pour. The invention also relates to the use of these compositions for cleaning dirty fabrics.

Liquid non-aqueous laundry detergent compositions are well known. Compositions of this type may contain a liquid non-ionic surfactant material in which particles of a builder material are dispersed, as described, for example, in U.S. Patents 4,316,812, 3,630,929, and 4,264,466 and British Patents 1,205,711 , 1,270,040 and 1,600,981.

Related pending U.S. Patent Applications 15 are No. 717,726, filed March 29, 1985, relating to a liquid nonionic laundry detergent composition containing a perborate bleach, a bleach activator and hydroxylamine sulfate as a bleach stabilizer and specifically as an inhibitor of catalase, an enzyme which is present in natural body dirt and rapidly decomposes hydrogen-20 peroxide, the active bleaching component of the perborate bleach; No. 597,793, filed April 6, 1984, relating to a non-aqueous liquid nonionic surfactant detergent composition comprising a suspension of a builder salt and containing a nonionic surfactant with terminal acid group (for example, the reaction product of a nonionic surfactant and succinic anhydride) to improve the dispersibility of the composition in an automatic washing machine; No. 687,815, filed December 31, 1984, relating to a non-aqueous liquid nonionic surfactant detergent composition comprising a suspension of builder salt and containing an alkylene glycol monoalkyl ether as viscosity and gelling control agent for B702062-2 improvement of the dispersibility of the composition in an automatic washing machine; and No. 597,948, filed April 9, 1984, relating to a non-aqueous liquid nonionic surfactant detergent composition comprising a suspension of polyphosphate builder salt 5 and containing an alkanol ester of phosphoric acid to improve the stability of the suspension against settling on storage.

The mentioned applications are directed to liquid non-aqueous non-ionic laundry detergent compositions.

Liquid detergents are often thought to be easier to use than dry powder or particulate products and are therefore markedly preferred by users. They are easy to measure, dissolve quickly in the wash water, can be easily applied in concentrated solutions or dispersions to dirty areas to be washed, do not dust and take up less storage space. Furthermore, liquid detergents may contain materials which cannot tolerate drying treatment without spoilage, which materials are often just desired in the preparation of particulate detergent products. While liquid detergents have many advantages over unitary or particulate solid products, they also have certain inherent drawbacks that must be overcome to obtain acceptable commercial detergent products. Some liquid products show separation on storage and others show separation on cooling and are not readily redispersed. In some cases, the viscosity of the product changes and the product becomes too thick to be poured or so thin that it appears watery. When standing, some clear products become cloudy and others form a gel.

An investigation was conducted into the behavior of non-ionic liquid surfactant systems containing particulate matter in suspension. Of particular interest were non-aqueous build-up liquid laundry detergent compositions and the problem of settling of the suspended builder and other additives, as well as the problem of gel formation associated with nonionic surfactants. These phenomena affect, for example, the stability, pourability and dispersibility of the product.

8702062> r

It is known that one of the major problems with built-up liquid laundry detergents is their physical stability. This problem arises from the fact that the density of the solid particles dispersed in the liquid nonionic surfactant is greater than the density of the liquid surfactant. As a result, the dispersed particles tend to settle. There are basically two solutions to the settling problem: increasing the viscosity of the nonionic liquid and reducing the particle size of the dispersed solid material.

It is known that settling suspensions can be stabilized by the addition of inorganic or organic thickeners or dispersants, such as inorganic materials with a very large surface area, for example finely divided silica, clay and the like, organic thickeners, such as the cellulose ethers, acrylic-15 and acrylamide polymers, polyelectrolytes, etc. Increasing the viscosity of the slurry is, of course, limited by the requirement that the liquid slurry must be easy to pour and flow even at low temperature. Furthermore, these additives do not contribute to the cleaning ability of the composition.

Grinding while reducing the particle size has the following advantages: 1. The specific surface area of the dispersed particles is increased, thereby proportionally improving wetting of the particles by the non-aqueous carrier (liquid non-ionic material).

2. The average distance between the dispersed particles is reduced with a proportional increase in the interaction between the particles.

Each of these effects contributes to increasing the residual gel strength and the yield stress of the slurry, while at the same time grinding significantly reduces the practical viscosity.

The yield stress is defined as the minimum stress required to induce a plastic deformation (flow) of the suspension. If the suspension is considered to be a loose network of dispersed particles, if the applied stress is lower than the yield stress 8702062-4, the suspensions will behave as an elastic gel and no plastic flow will occur. If the yield stress is exceeded, the network breaks at certain points and the sample starts to flow, but with a very high apparent viscosity. If the shear stress is much higher than the yield stress, the pigments are partially flocculated by shear and the apparent viscosity drops. Finally, if the shear stress is very much higher than the yield stress value, the dispersed particles are flocculated completely and the apparent viscosity is very low, as if there is no interaction between the particles.

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

In addition to the problem of settling or phase separation, the non-aqueous liquid laundry detergents based on liquid non-ionic surfactants also have the disadvantage that the non-ionic material has a tendency to gel when added to cold water. This is a particularly important problem in the ordinary use of European automatic washing machines for household use, where the user places the laundry detergent composition in a dispenser (eg a dispenser) of the machine. During machine operation, the detergent in the dispenser is exposed to a stream of cold water, which carries it to the main mass of the washing solution. Particularly during the winter months, when the detergent composition and the water fed to the dispenser are particularly cold, the detergent viscosity increases markedly and a gel is formed. As a result, part of the composition is not completely rinsed out of the dispenser during machine operation, so that upon repeated wash cycles, a deposit of the composition is built up, which must eventually be rinsed off by the user with hot water.

The phenomenon of gel formation can also be a problem when it is desirable to wash with cold water, as may be recommended for certain synthetic and delicate fabrics or fabrics that can shrink in warm or hot water.

8702062% * i - 5 -

The tendency of concentrated detergent compositions to form gel during storage is enhanced by storing the compositions in unheated storage areas or by transporting the compositions during the winter months in unheated transport vehicles.

There are proposals for partial solutions to the problem of gel formation in aqueous compositions that are substantially free of build-up salts, for example, dilution of the liquid nonionic material with certain viscosity-controlling solvents and gel inhibitors, such as low alkanols, for example ethanol (see U.S. Patent 3,953,380), alkali metal formates and adipates (see U.S. Patent 4,368,147), hexylene glycol, polyethylene glycol and the like, as well as modification and optimization of the nonionic structure. As an example of modification of the nonionic surfactant material, a particularly successful result can be mentioned which was achieved by acidifying the terminal hydroxyl group portion of the nonionic molecule. The advantages of introducing a carboxyl group at the end of the nonionic molecule are gel inhibition upon dilution, lowering the pour point of the nonionic material and formation of an anionic surfactant upon neutralization in the wash.

Optimization of the nonionic structure is directed to the chain length of the hydrophobic lipophilic molecular moiety and the number and arrangement of alkylene oxide (e.g. ethylene oxide) units of the hydrophilic molecular moiety. For example, it has been found that a fatty alcohol ethoxylated with 8 moles of ethylene oxide has only a limited tendency to gel.

There is a need to improve the bleaching properties and the stability and gel inhibition of non-aqueous liquid compositions for the treatment of fabrics containing a bleach and a bleach activator.

According to the invention, a highly concentrated stable non-aqueous liquid laundry detergent composition is prepared containing a persalt bleach and a liquid organic compound as a bleach activator. A preferred persalt bleaching compound 35 is sodium perborate monohydrate and a preferred liquid bleach activator is 8702082-6 bleaching agent ethylidene benzoate acetate. The liquid organic bleach activator is used in place of the conventionally used solid bleach activator, such as tetraacetylethylenediamine (TAED), to reduce the amount of solid in the concentrated detergent composition and to improve the pourability and dispersibility of the composition.

The persalt bleaching agent and an organic liquid bleach activator system of the invention can be used in phosphate-containing and only few phosphate-containing detergent build-up salt compositions.

To improve the viscosity properties of the composition, a nonionic surfactant with terminal acid group can be added. To further improve the viscosity properties of the composition and the storage properties of the composition, viscosity improving and anti-gelling agents, such as alkylene glycol monoalkyl ether, and an anti-settling agent, such as an alkanol ester of phosphoric acid, may be added. In a preferred embodiment of the invention, the detergent composition contains sodium perborate monohydrate as bleach, ethylidene benzoate acetate as bleach activator, a nonionic surfactant with terminal acid group, an alkylene glycol monoalkyl ether, and an alkanol ester of phosphoric acid stabilizing anti-settling agent.

The conventionally used peroxygen bleaching compounds, for example, sodium perborate, percarbonate, perphosphate and persulfate, can be used as a bleaching agent.

In one embodiment of the invention, the build-up components of the composition may be milled to a particle size of less than 100 µm, for example less than 40 µm, and preferably less than 10 µm, to further improve the stability of the build-up component slurry in the liquid nonionic surfactant detergent.

As further ingredients, anti-crusting agents, sequestering agents, anti-foaming agents, optical brighteners, enzymes, anti-redeposition agents, perfumes and dyes can be added to the composition.

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In one aspect, the invention provides a liquid laundry composition composed of a suspension of a peroxygen bleaching compound and a detergent build-up salt, for example, a phosphate build-up salt, in a liquid nonionic surfactant material, said bleach activator composition an effective amount of a liquid organic bleach activator compound, for example, ethylidene benzoate acetate.

In another aspect, the invention provides a concentrated liquid laundry detergent composition which has good bleaching properties at low temperature, is stable, does not settle on storage, and does not form gel on storage and in use. The liquid compositions of the invention are easy to pour, easy to measure, easy to place in the washing machine, and easy to disperse in water.

In another aspect, the invention relates to a method of dosing a liquid nonionic detergent composition in and / or with cold water without gel formation. In particular, a method is provided for filling a vessel with a non-aqueous liquid laundry detergent composition, which is at least predominantly composed of a liquid non-ionic surfactant, and for dosing the composition from the vessel into an aqueous washing bath. dosing by directing a stream of unheated water onto the composition such that the composition is fed through the stream into the wash bath.

The use of the liquid organic bleach activator in the composition in place of the solid bleach activator reduces the problem of dispersion of dispersed particles and improves the pourability of the composition.

The replacement of the known solid bleach activators, such as TAED, with a liquid organic activator reduces the total amount of solid material in the composition and provides the bleach activator in a disperse liquid form, in which the activator can more easily react with the persalt bleaching compound.

The concentrated non-aqueous liquid non-ionic surfactant laundry detergent composition of the invention have the advantages of being stable, not settling on storage and not forming a gel on storage. The liquid compositions are easily pourable, easily measured and can be placed in the washing machine and are easily dispersible in water.

The non-aqueous liquid nonionic laundry detergent detergent compositions of the invention contain a persalt bleaching compound and a liquid organic bleach activator as essential ingredients of the composition.

The persalt bleaching compounds are well known. They are dispersed in solid form in the nonionic surfactant 10 and are readily soluble upon addition of the detergent composition to the wash water. The persalts or oxygen bleaches are press compounds which form hydrogen peroxide in aqueous solution. Preferred examples are sodium and potassium perborates, percarbonates and perfosphates and potassium monopersulfate. The perborates, in particular sodium 15-perborate monohydrate, are particularly preferred.

Hydrogen peroxide and its precursors, which form hydrogen peroxide, are good oxidizing agents for removing stains from textiles, especially stains caused by wine, tea, coffee, cocoa, fruits and the like. Hydrogen peroxide and its precursors 20 generally appear to be fast and most effective at relatively high temperatures, for example, 80-100 ° C.

In order to take advantage of the low temperature effective detergents and the low temperature wash cycles, which are currently common for temperature sensitive fabrics, the persalt or peroxygen bleaching compound is used in conjunction with a bleach activator.

Heretofore, solid bleach activators have been used, such as tetracetylethylenediamine (TAED). The use of solid activators increased the amount of solid material dispersed in the nonionic surfactant detergent and required the bleach activators to dissolve in the aqueous bath liquid before being able to react with the persalt bleach.

According to the invention, clear liquid organic bleach activator compounds are used for activation of the persalt bleach compound. Since the organic bleach activators are liquid, they are quickly dispersed in the nonionic liquid surfactant detergent and can react more readily with the persalt bleaching compounds in the aqueous wash. The addition of the liquid organic bleach activator compounds can lower the effective operating temperature of the peroxide bleaches to 30 to 40 ° C.

The preferred organic liquid bleach activator compounds according to the invention have the general formula O-0-c-r 2

RrcH

O - C - R

3

O

wherein, R 2 and R 2 are hydrocarbon groups - R 2, R 2 and R 2 may independently represent alkyl, eg alkyl, such as alkyl, or aromatic groups, eg phenyl and lower alkyl aromatic groups, such as substituted phenyl or C 1 - Heterocyclic groups in which the heteroatom is oxygen, nitrogen or sulfur, such as furan, tetrahydrofuran, thiophene, tetrahydrothiophene, oxazine, pyridine, pyrrolidine, and pyrrolidone.

In the preferred embodiment, alkyl, preferably methyl, R 2 alkyl, preferably methyl, and R 1 phenyl and phenyl is substituted with 1-3 methyl groups, preferably phenyl, or heptanoyl, ethylidene heptanoate acetate, ethylidene octanoate acetate and ethylidene dodecanoate acetate. Each of these works well, but the heptanpate is the best, probably because the hydrophilic lipophilic balance is correct for tissue absorption and remains sufficiently hydrophilic for reaction with hydrogen peroxide.

The preferred organic liquid bleach-activator compound is ethylidene benzoate acetate, a clear flowing liquid that is readily available commercially.

Only small amounts of the liquid organic bleach activator compound, e.g., ethylidene benzoate acetate, are required for activation of the peroxygen bleaching compound. For example, suitable amounts of ethylidene benzoate acetate are 1 - 15%, preferably 1 - 8%, and most preferably 2 - 6%, based on the total weight of the non-.

8702062 - 10 - ionic liquid surfactant composition.

The bleach activator usually reacts with the peroxygen compound to form a peroxyacid bleach in the wash water.

Preferably, a high complexing power sequestrant is added per inhibition of any undesired reaction between the peroxyacid and hydrogen peroxide in the wash solution in the presence of metal ions.

Suitable sequestrants for this purpose are the sodium salts of nitrilotriacetic acid (NTA), ethylenediamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DETPA), diethylene triamine pentamethylene phosphonic acid (DTPMP) commercially available under the trade name Dequediametamethylphetamethylphetamethylpthiameter 2066.

The sequestrants can be used alone or as a mixture.

To prevent loss of peroxide bleach, for example sodium perborate, due to enzyme-induced decomposition, such as by catalase enzyme, the compositions may also contain an enzyme inhibitor compound, ie, a compound which is enzyme-induced decomposition of the peroxide bleach can inhibit. Suitable inhibitor compounds are described in US patent 3,606,990. Of particular interest as inhibitor compounds may be mentioned hydroxylamine sulfate and other water-soluble hydroxylamine salts. In an embodiment of the non-aqueous compositions of the invention, suitable amounts of the hydroxylamine salt inhibitors may be as low as 0.01-0.4%. Generally, however, suitable amounts of the enzyme inhibitors range up to about 15%, eg, 0.1-10%, based on the weight of the composition.

Stabilizers may also be included in the composition, for example, an acidic organic phosphorus compound with an acidic -POH group, such as a partial ester of phosphoric acid and an alkanol.

The nonionic surfactant detergents may be built up with polyphosphate builder salts or may have only a low polyphosphate content.

The nonionic synthetic organic detergents to be used according to the invention can be selected from a wide variety of known compounds.

8702062.-11-

As is known, the nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group. They are typically prepared by condensing an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (which is hydrophilic in nature).

Practically any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free oxygen atom bound to the nitrogen atom can be condensed with ethylene oxide or with its polyhydration product, polyethylene glycol, to form a nonionic detergent. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups. Typically suitable nonionic surfactants are described in U.S. Patent Nos. 4,316,812 and 3,630,929.

Usually, the nonionic detergents are poly-layer alkoxy lipophiles, in which the desired hydrophilic-lipophilic balance is obtained by addition of a hydrophilic poly-layer alkoxy group to a lipophilic molecular moiety. A preferred class of the nonionic detergent to be used is the poly-lower alkoxy higher alkanol, in which the alkanol contains from 20 to 18 carbon atoms and in which the number of moles of lower alkylene oxide (2 or 3 carbon atoms) is 3-12. Such materials are preferably used in which the alkanol contains 9-11 or 12-15 carbon atoms and which contains 5-8 or 5-9 lower alkoxy groups per mole. Preferably, the alkoxy group is ethoxy, but in some cases the ethoxy may be mixed with propoxy, which propoxy is then often present in a minor amount (less than 50%).

Examples of such compounds are those in which the alkanol has 12-15 carbon atoms and contains about 7 ethylene oxide groups per mole. For example, Neodol 25-7 and Neodol 23-6.5, which products are marketed by Shell Chemical Company. Neodol 25-7 is a condensation product of mixtures of fatty alcohols with an average of 12-15 carbon atoms and about 7 moles of ethylene oxide; Neodol 23-6.5 is a similar mixture in which the fatty alcohol contains 12-13 carbon atoms and the number of ethylene oxide groups averages about 6.5. The higher alcohols are primary alkanols.

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Other examples of such detergents are Tergitol 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates, sold by Union Carbide. Tergitol 15-S-7 is a mixed ethoxylation product of a linear secondary alkanol with 11-15 carbon 5 atoms and 7 moles ethylene oxide; Tergitol 15-S-9 is a similar product, but with 9 moles of ethylene oxide.

Also useful in the composition of the invention as a component of the nonionic detergent are higher molecular weight nonionic materials such as Neodol 45-11, a condensation product of fatty alcohol with 14-15 carbon atoms and about 11 moles of ethylene oxide. Such products are marketed by Shell Chemical Company.

Other suitable nonionic materials are commercially available under the brand name Plurafac. These materials are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxide. They contain a mixed chain of ethylene oxide and propylene oxide with a terminal hydroxyl group. Examples are (A) C-C fatty alcohol condensed with 6 moles ethylene oxide and 3 moles 13 propylene oxide, (B) C ^ C fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide, (C) C ^ C fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of ethylene oxide, and (D) a 1: 1 mixture of products (B) and (C).

Another group of liquid non-ionic materials is marketed by Shell Chemical Company under the brand name Dobanol: Dobanol 91-5 is an ethoxylated Cg-C 2 fatty alcohol with an average of 5 moles of ethylene oxide and Dobanol 25-7 is an ethoxylated C - fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

In order to have the best balance of hydrophilic and lipophilic molecular moieties in the poly-lower alkoxy higher alkanols, the number of lower alkoxy groups is usually 40 - 100% by number of carbon atoms in the higher alcohol and preferably 40 - 60% thereof; the nonionic detergent preferably contains at least 50% of such poly-lower alkoxy higher alkanol, which is preferred. Higher molecular alkanols and various other normally solid non-ionic detergents and surfactants may contribute to the gel formation of the liquid detergent and are therefore preferably omitted or limited in the compositions of the invention, although minor amounts thereof for their cleaning properties and the like can be used. In the preferred, as well as less preferred, nonionic detergents, the alkyl groups present are generally linear, although branching is permissible, such as on a carbon atom adjacent to or two carbon atoms away from the straight chain terminal carbon and on the other side of the ethoxy chain, provided that such branched alkyl has a length of no more than 3 carbon atoms. Normally, the number of carbon atoms in such a branched configuration is minor and rarely exceeds 20% of the total carbon atom content of the alkyl. Although linear alkyl groups terminally bonded to the ethylene oxide chains are particularly preferred and are believed to result in the best combination of detergent, biodegradability and non-gel-forming properties, medial or secondary bonding to the ethylene oxide chain may also occur. This is usually only in a minor amount of such alkyl groups, generally less than 20%, but may be larger, as in the case of the said Tergitols. If propylene oxide is present in the alkylene oxide chain, it will also usually be less than 20% thereof, and preferably less than 100%.

When using larger amounts of non-terminal alkoxylated alkanols, propylene oxide-containing poly-layer alkoxy alkanols, and nonionic detergent material with a less favorable hydrophilic-lipophilic balance than described above, or when using other nonionic detergents in place of the preferred materials described herein It may be that the resulting product does not have such good detergent, stability, viscosity and non-gelling properties as the preferred compositions, but the use of the viscosity control and gelling control additives of the invention may also reduce the properties of such non-ionic improve material-based detergents. In some cases, for example when a higher molecular poly-layer alkoxy higher alkanol is used, often for its detergent, the amount of 8702062-14-9 thereof can be controlled or limited by the results of routine tests to obtain the desired detergent, yet the product does not form a gel and has the desired viscosity. It has also been found that it is rarely necessary to use the higher molecular weight non-ionic materials to use their detergent properties, as the preferred nonionic materials described herein are excellent detergents and allow the desired viscosity in the liquid detergent without gel formation at low temperatures.

The nonionic surfactants can also be used which are marketed under the trade name Surfactant T by British Petroleum. These materials are obtained by ethoxylation of secondary fatty alcohols. Surfactant T5 contains an average of 5 moles of ethylene oxide; Surfactant T7 averaged 7 moles, Surfactant T9 averaged 9 moles and Surfactant Tl2 averaged 12 moles ethylene oxide per mole secondary c. fatty alcohol.

13

Preferably, the C 12 -C 5 secondary fatty alcohols ethoxylated with 7-9 moles of ethylene oxide and the C-C fatty alcohols ethoxylated with 5-6 moles of ethylene-9 11 oxide may be used in the compositions of the invention.

Mixtures of two or more liquid non-ionic surfactants can also be used and in some cases this offers advantages.

The viscosity and gelling properties of the liquid detergent compositions can be improved by including in the composition an effective amount of a liquid nonionic surfactant with terminal acid group. Such products consist of a nonionic surfactant compound which has been modified by converting a free hydroxyl group thereof into a molecular moiety with a free carboxyl group such as an ester or a partial ester of a nonionic surfactant and a polycarboxylic acid or anhydride.

As disclosed in U.S. Patent Application 597,948, filed April 9, 1984, the non-ionic surfactants modified by a free carboxyl group, which can be characterized as polyether carboxylic acids, can lower the temperature at which the liquid non-ionic compound with water forms a gel.

The addition of the nonionic surfactant with terminal acid group to the liquid nonionic surfactant promotes the dosability of the composition, especially the pourability, and reduces the temperature at which the liquid nonionic surfactant in water gel without compromising settling stability. The nonionic surfactant with terminal acid group reacts in the wash water with the alkalinity of the dispersed build-up salt phase of the detergent composition and acts as an active anionic surfactant.

Specific examples are the half esters of the nonionic surfactant (A) with succinic anhydride, the ester or half ester of Dobanol 25-7 with succinic anhydride and the ester or semester of Dobanol 91-5 with succinic anhydride. Instead of succinic anhydride, other polycarboxylic acids or anhydrides can also be used, for example, maleic acid, maleic anhydride, glutaric acid, malonic acid, phthalic acid, phthalic anhydride, citric acid and the like.

The nonionic acid-terminated compounds can be prepared as follows:

Product (A) with terminal acid group. 400 g of nonionic surfactant (A), an alkanol which is alkoxylated with the introduction of 6 ethylene oxide and 3 propylene oxide units per alkanol unit, is mixed with 32 g of succinic anhydride and heated at 100 ° C for 7 hours. The mixture is then cooled and filtered to remove unconverted succinic acid material. Infrared analysis shows that about half of the nonionic surfactant has been converted to its acidic half-ester.

Dobanol 25-7 with terminal acid group. 522 g of Dobanol 25-7, the ethoxylation product of an alkanol with about 7 ethylene oxide units per molecule of alkanol, are mixed with 100 g of succinic anhydride and 0.1 g of pyridine (which acts as an esterification catalyst) for 2 hours heated to 260 ° C and then cooled and filtered to remove unconverted succinic acid material. Infrared analysis shows that almost all free hydroxyl groups have reacted,

Dobanol 91-5 with terminal acid group. 1000 g Dobanol 91-5,5 the ethoxylation product of a C - C. alkanol with about 5 ethylene oxide units per molecule of alkanol, is mixed with 265 g of succinic anhydride and 0.1 g of pyridine catalyst and heated at 260 ° C for 2 hours, then cooled and filtered to remove unconverted succinic acid material. Infrared analysis shows that almost all free hydroxyl groups have reacted.

Instead of or in conjunction with pyridine, other esterification catalysts may also be used, such as an alkali metal alkoxide (e.g. sodium methoxide).

The acidic polyether compound, ie the nonionic surfactant with terminal acid group, is preferably added as a solution in the nonionic surfactant.

Fine particles of inorganic and / or inorganic detergent builder salts are dispersed and suspended in the liquid non-aqueous nonionic surfactant material used in the compositions of the invention.

The detergent compositions of the invention contain water-soluble and / or water-insoluble detergent build-up salts. The water-soluble inorganic alkaline builder salts, which can be used alone with the detergent compound or together with other builder salts, are alkali metal carbonates, bicarbonates, borates, phosphates, polyphosphates and silicates (ammonium or substituted ammonium salts may also be used) . Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexamethaphosphate, sodium sesquicarbonate, sodium mono and diorthophosphate and potassium. Sodium tripolyphosphate (TPP) is particularly preferred.

Since the compositions of the invention are generally highly concentrated and are therefore used in relatively small doses, it is desirable to supplement an optional phosphate builder salt (such as sodium tripolyphosphate) with an auxiliary builder such as a poly layer carboxylic acid or a polymeric carboxylic acid with a high calcium binding capacity to inhibit crusting, which could otherwise be caused by the formation of an insoluble calcium phosphate.

Suitable low polycarboxylic acids are alkali metal salts and low polycarboxylic acids, preferably the sodium and potassium salts. Suitable low polycarboxylic acids contain 2-4 carboxyl groups. Preferred sodium and potassium salts are the salts of citric acid and tartaric acid. Most preferred are the sodium salts of citric acid, especially trisodium citrate. The monosodium and disodium citrates can also be used, as can the monosodium and disodium tartrates. The alkali metal salts of low polycarboxylic acids are particularly good build-up salts; due to their high calcium binding capacity and magnesium, they inhibit crusting, which could otherwise be caused by the formation of insoluble calcium and magnesium salts.

To obtain a detergent composition without phosphate, the polyphosphates can be completely replaced by one or more of the auxiliary builder salts.

Other organic building materials are polymers and copolymers of polyacrylic acid and polymaleic anhydride and their alkali metal salts. Such builder salts may consist of a copolymer, which is the reaction product of approximately equal molar amounts of methacrylic acid and maleic anhydride, which is completely neutralized to form the sodium salt. This builder salt is commercially available under the brand name Sokalan CP5 and can inhibit crusting even when used in small amounts.

Examples of organic alkaline sequestering build-up salts, which can be used with the detergent build-up salts or mixed with other organic and inorganic builders, are alkali metal, ammonium, or substituted ammonium aminopolycarboxylates, for example, sodium and potassium ethylenediaminotetraaetate (EDTA), sodium and potassium nitrilotriacetate NTA), and triethanolammonium N- (2-hydroxyethyl) nitrile diacetates. Mixed salts of these aminopolycarboxylates 35 are also suitable.

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Other suitable organic or auxiliary builders of the organic type are carboxymethyl succinates, tartronates and glycolates.

The polyacetal carboxylates are of special value. The polyacetalcarboxylates and their use in detergent compositions are described in U.S. Patent Application 767,570 filed August 19, 1985, and in U.S. Patents 4,144,226, 4,315,092, and 4,146,495.

The alkali metal silicates are useful builder salts, which can also adjust or control the pH and make the composition anti-corrosion for washing machine parts. Sodium silicates with Na 2 O / SiC> 2 ratios of 1.6 / 1 to 1 / 3.2, especially 1/2 to 1 / 2.8, are particularly preferred. Potassium silicates with the same proportions can also be used.

Other suitable builders are described, for example, in U.S. Patents 4,316,812, 4,264,466 and 3,630,929. The inorganic builder salts can be used with the nonionic surfactant detergent material or together with other inorganic builder salts or organic builder salts.

Furthermore, the water-insoluble crystalline and amorphous aluminosilicate zeolites can be used. The zeolites generally have the formula (M + O) * (Al0O.J '(SiO)' wH-O 2x 2 3 y 2z 2 where x = 1, y = 0.8 - 1.2 and preferably 1, z = 1.5-3.5 or higher and preferably 2-3, w = 0-9, preferably 2.5-6, and M is preferably sodium A typical zeolite is type A or similar structure 25, with type 4A being particularly preferred The preferred aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents per gram or more, for example 400 meq per g.

Various crystalline zeolites (ie, aluminosilicates) that can be used are described in British Patent 1,504,168, U.S. Patent 4,409,136, and Canadian Pat. Nos. 1,072,835 and 1,087,477. An example of suitable amorphous zeolites can be found in Belgian patent 835,351.

8702062 - 19 -

Other materials, such as clay, especially of the water-insoluble type, may be useful adjuvants in the compositions of the invention. Bentonite is particularly suitable. This material is mainly montmorillonite, a hydrated aluminum silicate, in which about 1/6 of the aluminum atoms can be replaced by magnesium atoms, and which can combine loosely varying amounts of hydrogen, sodium, potassium, calcium, etc. Bentonite in its more purified form (free from grit, sand and the like), suitable for detergents, contains at least 50% montmorillonite and has a cation exchange capacity of at least 50-75 milliequivalents per 100 g bentonite. Particularly preferred bentonites are the Wyoming or Western U.S. bentonites, produced by Georgia Kaolin Co. when Thixo-jels 1, 2, 3 and 4 have been marketed. These bentonites are known to soften textiles, as described in U.K. patents 401,413 and 461,221.

The inclusion in the detergent composition of an effective amount of low molecular weight amphiphilic compounds, which act as viscosity regulators and gel inhibitors for the nonionic surfactant, leads to a marked improvement in the storage properties of the composition. The viscosity controlling and gel inhibiting agents lower the temperature at which the nonionic surfactant forms a gel upon addition to water. Such viscosity-controlling and gel-inhibiting agents can be, for example, low molecular weight amphiphilic alkylene oxide mono-layer alkyl ethers. The amphiphilic compounds may be considered analogous in chemical structure to the liquid nonionic surfactant ethoxylated and / or propoxylated fatty alcohols, but have relatively short hydrocarbon chain lengths (C-C) and a low content of ethylene oxide (about 2-6 ethylene oxide groups per 30 molecule).

Suitable amphiphilic compounds can be represented by the general formula 2

R

1 i R O (CHCH 2 O) H 2 n 1 2 where R is a "C 6 alkyl group and R represents hydrogen or methyl 35 and n is a number with an average value of 1 - 6.

8702062 - 20 -

Specific compounds are alkylene glycol mono alkyl ethers, in particular mono-, di- or trialkylene glycol mono alkyl ethers.

Examples of suitable amphiphilic compounds are ethylene-5-glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether and dipropylene glycol monomethyl ether. Diethylene glycol monobutyl ether is particularly preferred.

The inclusion in the composition of these low molecular weight alkylene glycol monoalkyl ethers reduces the viscosity of the composition such that it is easier to pour, improved stability against reflection, and improved dispersibility of the composition when added to hot or cold water.

The compositions of the invention have improved viscosity and stability properties and remain stable and pourable at temperatures of 5 ° C and below.

In an embodiment of the invention, a stabilizing agent, which is an alkanol ester of phosphoric acid, can be added to the composition. Improvements in the stability of the composition can be achieved by incorporating a small effective amount of an acidic organic phosphorus compound with an acid -POH group, such as a partial ester of phosphoric acid and an alkanol. As disclosed in US patent application 597,948, filed April 9, 1984, the acidic organic phosphorus compound having an acidic -POH group can increase the stability of the builder suspension in the non-aqueous liquid nonionic surfactant. The acidic organic phosphorus compound can be, for example, a partial ester of phosphoric acid and an alcohol, such as an alkanol with a lipophilic character, which contains, for example, more than 5 carbon atoms, for example 8-20 carbon atoms.

A specific example is a partial ester of phosphoric acid and a C - C alkanol (Empiphos 5632, Marchon); this product consists of 16 18 about 35% monoester and 65% diester.

The inclusion of relatively small amounts, for example 0.3% by weight, of the acidic organic phosphorus compound makes the suspension stable against settling on standing, while the suspension remains pourable and its plastic 8702062 ff - 21 - viscosity at the low concentration of the stabilizer, for example, less than about 1%, generally drops.

Other bleach activators may be added to the composition, if desired, such as tetraacetylethylenediamine (TAED) and pentaacetyl-5 glucose, acetylsalicylic acid derivatives, alkyl and alkenyl succinic anhydride, tetraacetylglycouril, and derivatives of these compounds.

In addition to the detergent builders, various other additives or adjuvants may be present in the detergent product to impart further desirable functional or aesthetic properties. For example, minor amounts of soil suspending or anti-redeposition agents may be included in the composition, for example, polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxypropyl methyl cellulose. A preferred anti-redeposition agent is sodium carboxymethyl cellulose with a CMC / MC ratio of 2: 1, 15 commercially available under the trade name Relatin DM 4050.

Small amounts of Duet 787, a laundry detergent perfume, marketed by International Flavors and Fragrances Inc., may also be included in the composition. Duet 787 can be added in amounts of 0-3%, preferably 0.2-2.0%, for example 0.5-2%, such as 0.3-1.0%, based on the weight of the composition.

In addition, optical brighteners for cotton, polyamide and polyester fabrics can be used. Suitable optical brighteners are stilbene, triazole, and benzidine sulfone compositions, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzidene sulfone, etc., with most preferred combinations of stilbene and triazole. A preferred brightener is Stilbene Brightener N4, a dianilino dimorpholinostilbene polysulfonate.

Enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papain, trypsin and pepsin, as well as amylase type enzymes, lipase type enzymes and mixtures thereof can be added. Preferred enzymes are protease suspension, esperase suspension and amylase. A preferred enzyme is Esperse SL8, a proteolytic enzyme.

8702062 * \ - 22 -

Furthermore, anti-foaming agents, for example silicon compounds, such as Silicane L 7604, a silicone, can be added in small effective amounts.

Other additives include bactericides, for example, tetrachloro-5-salicylanilide and hexachlorophene, fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet absorbers, anti-yellowing agents, such as sodium carboxymethyl cellulose, pH modifiers and pH buffers, color safe bleaches, perfume, and bluing agents, such as ultramarine blue.

In an embodiment of the invention, the stability of the build-up salts in the composition during storage and the dispersibility of the composition in water are improved by grinding the solid builders to particle sizes of less than 100 microns, preferably less than 40 microns, and preferably less than 10 micrometers. The solid builder salts, such as sodium tripolyphosphate (TPP), are generally supplied in particle sizes of about 100, 200 or 400 microns.

The nonionic liquid surfactant phase can be mixed with the build-up salts before or after grinding.

In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid ingredients is ground in a friction type mill, in which the particle size of the solid components is reduced to less than about 10 microns, for example to an average particle size of 2-10 micrometers or even less (e.g. 1 micrometer). Preferably, less than about 10%, especially less than about 5%, of all suspended particles have a particle size greater than 10 microns. Compositions in which the dispersed particles have such small dimensions have improved stability against separation or settling on storage. Addition of the nonionic 30-terminal acidic surfactant compound can decrease the yield stress of such dispersions and increase the dispersibility of the dispersions without correspondingly decreasing the stability of the dispersions against settling.

During grinding, the amount of solid ingredients is preferably so great (e.g., at least about 40%, such as about 50%), that the solid particles are in contact with each other and not substantially apart are shielded by the nonionic surfactant. After grinding, any remaining amount of liquid non-ionic surfactant can be added to the ground mixture. Mills in which grinding balls (ball mills) or similar mobile grinding elements are used give very good results. For example, a laboratory mill with steatite grinding balls with a diameter of 8 mm can be used. For larger-scale work, a continuously operating mill can be used, in which grinding balls with a diameter of 10 mm or 1.5 mm operate in a very small gap between a stator and a rotor rotating at a relatively high speed (e.g. a CoBall Mill) ; when using such a mill, it is desirable to first pass the mixture of nonionic surfactant and solid ingredients through a mill in which no such fine grinding is accomplished (eg, a colloid mill) while reducing the particle size to less than 100 µm (for example, up to about 40 µm), before the particle diameter is milled in the continuous ball mill to an average particle diameter of less than about 10 µm.

In the preferred liquid laundry detergent compositions of the invention, typical amounts (in percent, based on the total weight of the composition, unless otherwise stated) of the ingredients are as follows:

Liquid nonionic surfactant detergent: 10 - 60%, such as 20 - 50%, for example 30 - 40%.

Nonionic surfactant with terminal acid group as viscosity improving agent: 0 - 20%, such as 1 - 10%, for example 2-5%.

Detergent builder, such as sodium tripolyphosphate: 10 - 60%, 30 such as 15 - 50%, for example 25 - 35%.

Alkali metal salt of copolymer of acrylic acid and maleic anhydride, for example Sokalan CP5, as anti-encrusting agent: 0-10%, such as 1-8%, for example 2-4%.

Alkylene glycol monoalkyl ether as an anti-gelling agent: 5 - 30%, such as 5 - 20%, for example 5 - 15%.

8702062 * ft - 24 -

Phosphoric acid alkanol ester as a stabilizing agent: 0 - 2.0% or 0.1 - 1.0%, such as 0.2 - 0.5%.

Persalt bleach: 5 - 30%, such as 2 - 20%, for example, 5 - 15%.

Liquid organic bleach activator compound, for example 5 ethylidene benzoate acetate: 1 - 15%, such as 1-8%, for example 2-6%.

Bleach sequestrant, for example Dequest 2066: 0-3.0%, preferably 0.5-2.0%, e.g. 0.50-1.25%.

Anti-redeposition agent, for example Relatin DM 4050: 0 - 4.0%, preferably 0.5 - 3.0%, for example 0.5 - 1.5%.

Optical brightener: 0 - 2.0%, preferably 0.05 - 1.0%, for example 0.15 - 0.75%.

Enzymes: 0-3.0%, preferably 0.5-2.0%, e.g. 0.75-1.25%.

Perfume: 0-3.0%, preferably 0.10-1.25%, eg 0.25-1.0%.

Several of the aforementioned additives can be added if desired to achieve the desired function of the added materials.

The liquid organic bleach activator compound is preferably used in conjunction with one of the alkylene glycol monoether or nonionic surfactant terminal acid group viscosity controlling and anti-gelling agents. In some cases it may be advantageous to use both additives together.

The additives should be chosen to be compatible with the main components of the detergent composition.

As noted, all levels and percentages relate to the weight of the entire composition unless otherwise noted.

In an embodiment of the invention, the detergent composition is formulated as follows:

Wt% 30 Non-ionic surfactant detergent 20-45

Surfactant with terminal acid group, viscosity improving agent 0-20

Phosphate detergent build-up salt 10-60

Anti-crusting agent 0-10 8702062 £ - 25 -

Wt%

Alkylene glycol monoalkyl ether anti-gel-forming agent 5-15

Phosphoric acid alkanol ester, stabilizer 0-2.0

Anti-redeposition agent 0-4.0

Alkali metal perborate bleach 5-15 5 Liquid organic bleach activator, e.g. ethylidene benzoate acetate 1.0-8.0

Bleach sequestrant 0-3.0

Perfume (Duet 787) 0-3.0

Optical brightener 0.15-0.75 10 Enzymes 0.75-1.25

Perfume 0-3.0

The invention is further illustrated by the following examples.

EXAMPLE I

15 A concentrated non-aqueous liquid non-ionic surfactant detergent composition is formulated as follows:

Wt%

Non-ionic surfactant 37.0

Reaction product of Dobanol 91-5, with succinic anhydride 5.0 20 Sodium tripolyphosphate 31.4

Diethylene glycol monobutyl ether, anti-gelling agent 10.0

Phosphoric acid alkanol ester (Empiphos 5632) 0.3

Sodium perborate monohydrate 9.0

Ethylidene benzoate acetate bleach activator 4.5 25 Anti-redeposition agent (Relatin DM 4050) ^ 1.0

Optical brightener (Tinopal ATSX) 0.2

Perfume 0.6

Enzyme (Esperase) 1.0 100.0 (1) CMC / MC 2: 1 mixture of sodium carboxymethyl cellulose and hydroxymethyl cellulose 8702062 y Λ - 26 -

The mixture is ground for 1 hour, reducing the particle size of the suspended build-up salts to less than 40 microns. The composition thus obtained appears to be stable on storage and does not form a gel, is readily dispersible in water and has good bleaching properties.

EXAMPLE II

A concentrated non-aqueous liquid non-ionic surfactant detergent composition is formulated as follows:

Wt%

Product D 13.5 10 Surfactant T7 10.0

Surfactant T9 10.0

Reaction product of Dobanol 91-5 with succinic anhydride 5.0

Sodium tripolyphosphate 29.6 15 Anti-encrusting agent (Sokalan CP5) 4.0

Diethylene glycol monobutyl ether, anti-gelling agent 10.0

Phosphoric acid alkanol ester (Empiphos 5632) 0.3

Sodium perborate monohydrate, bleach 9.0

Ethylidene benzoate acetate, bleach activator 4.5 20 Bleach sequestrant (Dequest 2066) 1.0

Anti-redeposition agent (Relatin DM 4050) ^ 1.0

Optical brightener (Stilben) 0.5

Enzyme (Esperase suspension) 1.0

Duet 787 0.6 100.0 25 (1) CMC / MC 2: 1 mixture Of sodium carboxymethyl cellulose and hydroxymethyl cellulose.

The mixture is ground for 1 hour reducing the particle size of the suspended build-up salts to less than 40 microns. The composition thus obtained appears to be stable on storage and does not form a gel and is readily dispersible in water. The bleach is active at 40 ° C on both wine and immediate black stains.

8702062 f - 27 -

The compositions of Examples I and II can be prepared without grinding the build-up salts and suspended solids to a small particle size, but the best results are obtained by grinding the mixture while reducing the particle size of the suspended solids.

The build-up salts can be used in the form in which they are supplied, or the build-up salts and other suspended solids can be ground or partially ground before mixing with the nonionic surfactant. The grinding can be performed partially before mixing and the grinding can be completed after mixing, or the entire grinding operation can be performed nS. mixing with the liquid surfactant. The compositions containing suspended solid particles with dimensions less than 40 microns are preferred.

8702002

Claims (19)

A fabric detergent composition, characterized by a nonionic liquid surfactant detergent, an inorganic peroxygen compound as a bleaching agent and a liquid organic bleach activator compound. Composition according to claim 1, characterized by a viscosity regulating and anti-gel-forming agent. Detergent composition according to claim 2, characterized by at least one viscosity-controlling and anti-gel-forming agent selected from alkylene glycol monoalkyl ether and a nonionic surfactant compound having an acid terminal group. Composition according to claims 1-3, characterized by a suspension of insoluble inorganic detergent build-up salt. Composition according to claim 1, characterized in that the liquid organic bleach activator compound has the general formula 0 ° - ^ R2 6. Composition according to claim 4, characterized in that the insoluble inorganic build-up salt contains 10-60% of a polyphosphate detergent build-up salt. Detergent composition according to claims 1-6, characterized by one or more detergent auxiliaries selected from anti-encrustant, sequestrant, anti-redeposition agent, optical brightener, enzymes and perfume. Composition according to claims 1-7, characterized by 10 - 60% of a non-ionic liquid surfactant detergent. Composition according to claim 3, characterized by 5 - 30% of an alkylene glycol monoalkyl ether. 8702062 - 29 - 10 Phosphoric acid alkanol ester 0.2-0.5 Sodium perborate monohydrate 5-15 Ethylidene benzoate acetate 2-6.0 Sequestering agent 0.50-1.25 Anti-redeposition agent 0.5-1.5 Composition according to claim 4, characterized in that the inorganic build-up salt has a particle size of less than 40 micrometers. 11. A composition according to claims 1-10, characterized by 0.1-0.5 wt.%, Based on the total composition, of a phosphoric alkanol ester 5 as a stabilizing anti-settling agent. 12. Non-aqueous built-up laundry detergent composition, which is pourable at high and low temperature and does not form a gel when mixed with cold water, characterized by at least one liquid non-ionic surfactant in an amount of 10-60 wt%, at least one inorganic detergent build-up salt, suspended in the nonionic surfactant in an amount of 10-60 wt%, an inorganic peracid bleach in an amount of 5-15%, ethylidene benzoate acetate bleach activator in an amount of 1 - 8.0%, a nonionic surfactant with terminal acid group 15 as a gel-inhibiting additive in an amount of 0 - 20% and a compound of the formula R1 2 1 IR 0 (CHCH-O) H 8702062 2 waarin 2 wherein R is a C - C alkyl group, and R represents hydrogen or methyl 2 O and n is a number with an average value of 1-6, as a gel-20 inhibitory additive in an amount of 5-30% by weight. Composition according to claim 12, characterized by one or more detergent auxiliaries selected from anti-encrustant, sequestrant, anti-redeposition agent, optical brightener, enzymes and perfume. 14. Composition according to claim 12, characterized by the following composition: Wt% Nonionic surfactant 20-50 Sodium tripolyphosphate 15-50 Sodium salt of copolymer of acrylic acid and maleic anhydride 1-8 30 Diethylene glycol monoalkyl ether 5-20 Phosphoric acid alkanol ester 0.1-1.0 Sodium perborate monohydrate 2-20 Ethylidene benzoate acetate 1-8 * - 30 - Composition according to claim 12, characterized by the following composition: Wt. % Nonionic surfactant 30-40 Nonionic surfactant with terminal 5 acid group 1-10 Sodium tripolyphosphate 25-35 Sodium salt of copolymer of acrylic acid and maleic anhydride 2-4 Diethylene glycol monobutyl ether 5-15 R 1 -CHC 2 O-C-R 2 II 3 wherein R 4, R 4 and R 4 are hydrocarbon groups selected such that the organic compound is a liquid. A method for cleaning dirty fabrics, characterized in that the dirty fabrics are brought into contact with the detergent composition according to claim 1. Method according to claim 16, characterized in that the soiled fabrics are brought into contact with the composition according to claim 12. A method according to claim 16, characterized in that the soiled fabrics are brought into contact with the composition of claim 14. A method according to claim 16, characterized in that the soiled fabrics are brought into contact with the composition of claim 15. 8702062