NL8702112A - Highly foaming non-aqueous liquid non-ionic laundry detergent composition and process for its use. - Google Patents

Description

$ VO 9286

Highly foaming non-aqueous liquid non-ionic laundry detergent composition and method for its use.

The invention relates to non-aqueous liquid compositions for the treatment of fabrics. More particularly, the invention relates to high foaming non-aqueous liquid laundry detergent compositions which are stable to phase separation and gel formation and are easily pourable, as well as 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 nonionic surfactant compound in which particles of a build-up salt 10 are dispersed, as described, for example, in U.S. Patent Nos. 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 pertaining to liquid non-aqueous nonionic laundry detergent compositions are Nos. 687,815 filed December 31, 1984, 597,793 filed April 6, 1984, and 597,948 filed April 9, 1984.

Liquid detergents are often thought to be easier to use than dry powder or particulate products and are therefore appreciated by consumers. They are easy to measure, quickly dissolve in the wash water, can be easily applied in concentrated solutions or dispersions on dirty parts of garments to be washed, do not dust and usually take up less storage space. Furthermore, the liquid detergents may contain materials which are not resistant to drying without spoilage, which materials are often highly desirable for use in the preparation of particulate detergent products. Although they have many advantages over unitary or particulate solid products, liquid detergents often also have certain drawbacks which must be overcome for the preparation of acceptable commercial detergent products. Some of such products do not foam easily and form partitions on storage and other form partitions on cooling and are not readily redispersed. In some cases, the viscosity of the product changes and becomes either too thick to be poured or so thin that it appears watery. When standing, some clear products become cloudy and others form a gel.

° 7 (* -2-

An investigation was conducted into the behavior of non-ionic liquid surfactant systems in which particulate matter is suspended. Of particular interest were non-aqueous liquid build up 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. Such phenomena affect, for example, product stability, pourability and dispersibility.

It is known that one of the major problems with built up laundry detergents is their physical stability. This problem is caused by the density of the solid particles dispersed in the nonionic liquid surfactant being greater than the density of the liquid surfactant.

The dispersed particles therefore tend to settle. There are basically two solutions to the settling problem: increasing the viscosity of the nonionic liquid and decreasing the particle size of the dispersed solid material.

It is known that settling suspensions can be stabilized by adding inorganic or organic thickeners or dispersants, such as, for example, very large surface inorganic materials, for example finely divided silica, clay and the like, organic thickeners, such as the cellulose ethers , acrylic and acrylamide polymers, polyelectrolytes, etc. Such increases in the viscosity of the slurry are, of course, limited by the requirement that the liquid slurry be easily pourable and liquid even at low temperature. In addition, these additives do not contribute to the cleaning behavior of the mixture.

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

2. The average distance between dispersed particles is reduced with a proportional increase in the interaction between the 35 particles.

Each of these effects helps to increase the residual gel 1702112 * f

a

-3- strength and the yield stress of the slurry, while at the same time grinding significantly reduces the plastic viscosity.

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

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 have the drawback that the non-ionic material does not readily form a stable foam and, when added to cold water, tends to gel . This is a particularly important problem in the normal use of European household automatic washing machines, where the user places the detergent detergent composition in a dispenser (eg a dispenser drawer) of the machine. During the operation of the machine, the detergent in the doser is exposed to a stream of cold water, which transfers it to the main mass of the washing solution. Especially during the winter months, when the detergent composition and the water supplied to the dispenser are particularly cold, the viscosity of the detergent increases markedly and a gel is formed. As a result, during operation of the machine, a portion of the composition is not completely rinsed out of the dispenser and, after repeated use of the machine, a deposit of the composition may build up, which ultimately results in the user needing 8702112 "* Ί * - 4- causes rinsing of the dosing device with hot water.

Gel formation can also be a problem when it is desired to perform the wash with cold water, such as for certain synthetic and delicate fabrics or for fabrics that can shrink in warm or hot water.

The tendency of concentrated detergent compositions to gel during storage is enhanced by storage of the compositions in unheated spaces or by transportation of the compositions during the winter months in unheated transport vehicles.

Partial solutions have already been proposed for the gel formation problem in aqueous compositions, which are substantially free of build-up salts. Such solutions include, 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 the U.S. Patent 4,368,147), hexylene glycol, polyethylene glycol, etc., as well as modification and optimization of the nonionic structure.

There is a need for improvements in the formation of a stable foam and in the stability and gel inhibition of non-aqueous liquid compositions for the treatment of fabrics.

In accordance with the invention, a high foaming, highly concentrated stable non-aqueous liquid laundry detergent composition is prepared by adding to the composition as the principal nonionic surfactant of a C 1 -C 3 fatty alcohol ethoxylated by 5 moles ethylene oxide per mole alcohol .

The compositions of the invention contain, as an essential ingredient and as the major constituent of the liquid nonionic surfactant component of the composition, a C 2 -C 6 fatty alcohol ethoxylated by 5 moles ethylene oxide per mole alcohol. The C 8 -C 16 alkyl (C 1 H O) OH nonionic surfactant of the invention constitutes about 50-100% of the nonionic surfactant component of the composition, e.g. 50-90%, such as 50-75% of the non-ionic component. To improve the viscosity and storage properties of the composition, viscosity enhancing and anti-gel-forming agents can be added to the composition, such as alkylene glycol monoalkyl ethers and anti-settling agents, such as phosphoric acid alkanol ester. In a preferred embodiment of the invention, the detergent composition contains an alkylene glycol monoalkyl ether and a phosphoric alkanol ester as a stabilizing anti-settling agent. To the composition, no nonionic surfactant acid terminated gelling agents such as described in U.S. Patent Application 597,793, filed April 6, 1984, are added because they are believed to be present in the wash liquor. calcium ions form a calcium salt, which is a foam inhibitor.

To improve the bleaching and cleaning properties of the composition, bleaches and activators therefor can be added.

In one embodiment of the invention, the build-up salt components of the composition are milled to a particle size of less than 100 µm, preferably less than 40 µm, to further improve the stability of the suspension of the build-up components in the liquid non- ionic surfactant detergent.

Furthermore, other ingredients can be added to the composition, such as anti-crusting agents, anti-foaming agents, optical brighteners, enzymes, anti-redeposition agents, perfume and dyes.

In one aspect, therefore, the invention relates to a liquid washing composition composed of a suspension of a detergent build-up salt, for example, a phosphate build-up salt, in a liquid nonionic surfactant material, the composition being the major nonionic component contains a foam-producing c9 "c11 fatty alcohol, ethoxylated by 5 moles of ethylene oxide per mole of alcohol, which composition foams strongly, is stable to settling and is easily dispersible in water.

In another aspect, the invention relates to a concentrated liquid laundry detergent composition which is stable, does not settle on storage and does not form a gel on storage and during use. The liquid compositions of the invention are easy to pour, easy to measure and easy to put in the washing machine, and are easily dispersible in water.

In another aspect, the invention relates to a work

way of dosing a strongly foaming C - C. alkyl (C 10 H 10) OH

8702112 -6- liquid non-ionic laundry detergent composition in and / or with cold water without forming a gel.

The use of the strong foaming C-CL. alkyl (C 10 H O) OH non-7 11 2 2 5 ionic surfactant as the major component of the non-ionic surfactant in the compositions provides a high foaming detergent composition without the need for specific foaming agents added.

The concentrated non-aqueous liquid nonionic surfactant laundry detergent compositions of the invention have the advantage that they are stable, do not settle on storage, and do not form a gel on storage. The liquid compositions are easy to pour, easy to measure, easy to place in the washing machine and are easily dispersible in water.

According to the invention, the foaming properties of the non-aqueous liquid non-ionic laundry detergent composition are remarkably improved by adding C 1 -C 6 alkyl (CH.CH.O) -OH nonionic 7 XX 22b surfactant to the composition.

The addition of C 1 -C alkyl (CH 2 CH 4 O) OH as the major 7 XX 22b component of the nonionic surfactant component of the composition significantly improves the foaming properties of the composition. The compositions of the invention contain as

Substantial ingredient is the C 1 -C 2 -alkyl (CHCH 2 O) -OH as the major constituent part of the nonionic surfactant component of the composition.

The C8 -C18 alkyl (CH2CH2O) ^ nonionic surfactant compound is commercially available under the trade name Dobanol 91-5 (Shell Chemical Company).

Nonionic synthetic organic detergents, which can be used in small amounts according to the invention, can be selected from a wide variety of known compounds.

The nonionic synthetic organic detergents, as known, 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 (which is hydrophilic nature).

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 nitrogen ionic detergent. The length of the hydrophilic or polyoxyethylene chain can be easily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups. Typical suitable nonionic surfactants are described in U.S. Pat. Nos. 4,316,812 and 3,630,929.

The nonionic detergents are usually poly-layer alkoxylated 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-layer alkoxylated higher alkanols, in which the alkanol contains 9-18 carbon atoms and in which the number of moles of lower alkylene oxide (2 or 3 carbon atoms) is 3-12.

Preferably, such materials are used where the high alkanol is a fatty alcohol of 9-11 or 12-15 carbon atoms and contains 6-8 or 5-9 lower alkoxy groups per mole. Preferably, the lower alkoxy group is an ethoxy group, but in some cases it may be desirable for the ethoxy to be mixed with propoxy, which is then present in minor amount (less than 50%).

Examples of such compounds are those in which the alkanol contains 12-15 carbon atoms and which contain 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 a mixture of fatty alcohols having an average of 12-15 carbon atoms with about 7 moles of ethylene oxide. Neodol 23-6.5 is a similar mixture, in which the carbon content of the alcohol is 12-13 and the number of ethylene oxide averages about 6.5. The alcohols are primary alkanols.

Other examples of such detergents are Tergitol 15-S-7 and

Tergitol 15-S-9, both linear secondary alcohol ethoxylates, sold by Union Carbide. Tergitol 15-S-7 is a mixed ethoxylation product of a linear secondary alkanol of 11-15 carbon atoms with 7 moles of ethylene oxide. Tergitol 15-S-9 is a similar product, but with 35 9 moles of ethylene oxide.

8702112 «* k -8-

As components of the nonionic detergent in the composition according to the invention, higher molecular weight nonionic materials can also be used, such as Neodol 45-11, a condensation product of ethylene oxide with higher fatty alcohols, in which the higher fatty alcohol contains 14-15 carbon atoms and in which the number of ethylene oxide groups per mole is about 11. Such products are also marketed by Shell Chemical Company.

Other suitable nonionic materials are represented by the products marketed under the brand name Plurafac. The Plurafacs are reaction products of a higher linear alcohol and a mixture of ethylene and propylene oxides containing a mixed chain of ethylene oxide and propylene oxide ending in a hydroxyl group.

Examples are products such as (A) c13 "c15 fatty alcohol, condensed with 6 moles of ethylene oxide and 3 moles of propylene oxide, (B) C 1 -C 3 g of fatty alcohol, condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide, (C) C-C . fatty alcohol condensed with 5 moles of propylene oxide and 10 moles of 13 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 trade name 20 Dobanol, for example Dobanol 25-7, an ethoxylated C 12 - 15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.

Another useful group of non-ionic surfactants is the "Surfactant T" series, sold by British Petroleum. The Surfactant T nonionic materials are obtained by ethoxylation of secondary C 2 fatty alcohols with a narrow ethylene oxide distribution. Surfactant T5 contains an average of 5 moles of ethylene oxide, Surfactant T7 has an average of 7 moles of ethylene oxide, Surfactant T9 has an average of 9 moles of ethylene oxide and Surfactant T12 contains an average of 12 moles of ethylene oxide per mole of secondary C 1 fatty alcohol.

Suitable nonionic surfactants for use in the compositions of the invention include the <RTI ID = 0.0> 22-C15 </RTI> secondary fatty alcohols having relatively narrow ethylene oxide contents between 7-9 moles, and the Cq-C3 fatty alcohols ethoxylated with 5- 6 moles of ethylene-y xi oxide.

Mixtures of two or more of the liquid non-ionic surfactants can also be used with the high foaming 8702112 * -9-

C 8 -C 12 alkyl (CH 2 CH 2 O) 50 H surfactant of the invention and in some cases the use of such mixtures may even be advantageous.

Fine particles of inorganic and / or organic detergent builders are dispersed and suspended in the liquid non-aqueous nonionic surfactant material used in the compositions of the invention. The compositions of the invention contain water-soluble and / or water-insoluble detergent build-up salts. Water-soluble inorganic alkaline build-up salts, which can be used alone with the detergent compound or mixed with other build-up salts, are alkali metal carbonates, bicarbonates, borates, phosphates, polyphosphates, and silicates. (Ammonium or substituted ammonium salts can also be used). Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium bicarbonate and potassium phosphate. Sodium tri-polyphosphate (TPP) is particularly preferred.

Since the compositions of the invention are generally highly concentrated and can therefore be 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 polycarboxylic acid or a polymeric carboxylic acid with a high calcium-binding capacity. ability to inhibit crusting, which might otherwise be caused by the formation of an insoluble calcium phosphate.

Suitable polycarboxylic acids are alkali metal salts of low polycarboxylic acids, preferably the sodium and potassium salts. Suitable low polycarboxylic acids have 2-4 carboxyl groups. Preferred sodium and potassium polycarboxylates 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. The monosodium and disodium salts of tartaric acid can also be used. The alkali metal salts of low polycarboxylic acids are particularly good build-up salts; due to their high calcium and magnesium binding capacity, they inhibit crusting, 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 their alkali metal salts. More specifically, 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 has been completely neutralized to form the sodium salt. Such a builder is commercially available under the brand name Sokalan CP5. This builder 10, even when used in small amounts, can inhibit crusting.

Examples of organic alkaline sequestering builder salts, which can be used with the detergent builder salts or mixed with other organic and inorganic builder substances, are alkali metal, ammonium or substituted ammonium aminopolycarboxylates, for example sodium and potassium ethylenediaminotetraacetate (EDTA), sodium and potassium nitrilotriacetates (NTA) and triethanolammonium N- (2-hydroxyethyl) nitrilo-diacetates. Mixed salts of these aminopolycarboxylates are also suitable.

Other suitable organic-type builders include carboxymethyl succinates, tartronates and glycolates. The polyacetal carboxylates are of special value. The polyacetal carboxylates and their use in detergent compositions are described in U.S. Patent Application 767,570, filed August 19, 1985, and 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 serve to adjust or control the pH and render the composition anti-corrosive to washing machine parts. Sodium silicates with

Na O / SiO ratios from 1.6 / 1 to 1 / 3.2, especially about 2 2 | 30 1/2 to 1 / 2.8 are preferred. Potassium silicates with the same proportions can also be used.

Other suitable builders are described 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 compound or mixed with other inorganic builder salts or with organic builder salts.

8702112 -11-

The water-insoluble crystalline and amorphous aluminosilicate zeolite are also useful. The zeolites generally have the formula (M_0). (Al 0) - (SiO) .wH 0 2x23y2z2 where x = 1, y = 0.8-1.2 and preferably 1.2 = 1.5- 3.5 or more and preferably 2-3, and w = 0-9, preferably 2.5-6, and M preferably represents sodium. A typical zeolite is type A or similar structure, with type 4A being particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of about 10 200 milliequivalents per gram or more, for example 400 meg / g.

Various useful crystalline zeolites (aluminosilicates) 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 useful amorphous zeolites can be found in Belgian Patent 835,351.

Other materials, such as clays, 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. Detergent bentonite in its more purified form (i.e., free from grit, sand, etc.) contains at least 50% montmorillonite and has a cation exchange capacity of at least 50-75 meq / 100 g bentonite. Particularly preferred bentonites are the Wyoming or Western U.S. bentonites, produced by Georgia Kaolin Co. are marketed as Thixojels 1, 2, 3 and 4. These bentonites are known to soften textiles, as described in British Pat. Nos. 401,413 and 30,461,221.

The inclusion in the detergent composition of an effective amount of low molecular weight amphiphilic compounds, which serve as viscosity regulators and gel inhibitors for the nonionic surfactant, significantly improves the storage properties of the composition. The viscosity controlling and gel inhibiting agents lower the temperature at which the nonionic surfactant 8702112-12 forms a gel when added to water. Such viscosity controlling and gel inhibiting agents can be, for example, amphiphilic low molecular weight alkylene oxide (low monoalkyl) ethers. The amphiphilic compounds may be considered analogous in chemical structure to the ethoxylated and / or propoxylated fatty alcohol liquid nonionic surfactants, but have relatively short hydrocarbon chain lengths (c2, cg) and a low ethylene oxide content (2-6 ethylene oxide groups). per molecule).

Suitable amphiphilic compounds are represented by the following general formula R 2 1 'RO (CHCH O) H 2 n 1 2 wherein R represents a C 1 -C 4 alkyl group and R represents hydrogen or methyl and 2 is a number with an average value from 1-6.

Specific compounds are C 1 -C 4 alkylene glycol mono C 2 -C 5 allyl ethers, more specifically mono-, di or tri-C 2 -C 3 alkylene glycol mono C 1 -C 5 alkyl ethers.

Specific examples of suitable amphiphilic compounds are ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetra-ethylene glycol monobutyl ether and dipropylene glycol monomethyl ether.

Diethylene glycol monobutyl ether is particularly preferred and is manufactured by Dow Chemical Co. marketed under the brand name Dowanol DB.

s

Another suitable viscosity controlling and 1-inhibiting agent is Dowanol PIB-T, which is a mixture of mono-, di- and tripropylene glycol monomethyl ether.

Incorporation into the composition of the low molecular weight alkylene glycol monoalkyl ether lowers the viscosity of the composition so that it is easier to pour, improves settling stability, and improves dispersibility of the composition when added to hot water or cold water.

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

In one embodiment of the invention, a small amount of a stabilizing agent, which is 87021 12-13 an alkanol ester of phosphoric acid, may be added to the mixture. Improvements in the stability of the composition can be achieved by incorporating a small effective amount of an acidic organic phosphorus compound with an acidic POH group, such as a partial ester of phosphoric acid and an alkanol. As disclosed in U.S. Patent Application 597,948 filed April 9, 1984, the acidic organic phosphorus compound having an acidic - POH group increases the stability of the builder suspension in the non-aqueous liquid nonionic surfactant material. 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, for example with more than 5 carbon atoms, such as 8-20 carbon atoms.

A specific example is a partial ester of phosphoric acid and a C 1 -C-C 2 g alkanol (Empiphos 5632 from Marchon); the product consists of about 35% monoester and 65% diester.

The inclusion of relatively small amounts, for example 0.3 wt%, of the acidic organic phosphorus compound makes the slurry stable upon standing, the slurry remaining pourable, while its plastic viscosity will generally decrease at the low stabilizer concentration. The addition of more than about 0.3%, for example, 1.0% or more, should be avoided since the organic phosphorus ester at such higher concentrations can inhibit foaming.

The bleaches are generally conveniently classified as chlorine bleaches and oxygen bleaches. Chlorine bleaches are typified by sodium hypochlorite (NaOCl), potassium dichloro-25 isocyanurate (59% available chlorine) and trichloroisocyanuric acid (95% available chlorine). Oxygen bleaches are preferred and are represented by per compounds which form hydrogen peroxide in solution. Preferred examples are sodium and potassium perborates, percarbonates and perphosphates, and potassium monopersulfate. The perborates, in particular sodium perborate monohydrate, are particularly preferred.

Peroxygen compounds are preferably used in admixture with an activator. Suitable activators, which can lower the effective operating temperature of the peroxide bleach, are described, for example, in U.S. Patent 4,264,466 or in column 35 of U.S. Patent 4,430,244. Polyacylated compounds are preferred activators; among these, compounds, such as tetraacethylethylenediamine (TAED) and pentaacetyl glucose, are particularly preferred.

Other suitable activators are, for example, acetylsalicylic acid derivatives, ethylidene benzoate acetate and its salts, ethylidene carboxylate acetate and its salts, alkyl and alkenyl succinic anhydride, tetraacetylglycouril (TAGU), and the derivatives of these compounds.

Other suitable classes of activators are described, for example, in U.S. Patents 4,111,826, 4,422,950, and 3,661,789.

The activator usually acts on the peroxygen compound to form a peroxyacid bleach in the wash water. Preferably, a high complexing ability sequestrant is added to inhibit any undesired reactions between such 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), sold under the trade name Dequestiamethylphetamethylphthamethylphetamethylphenethylphenethyl. The sequencing agents can be used alone or mixed.

To prevent loss of peroxide bleach, for example sodium perborate, due to enzyme-induced decomposition, such as * by catalase enzyme, the compositions may further contain an enzyme inhibitor compound, ie, a enzyme-induced compound decomposition of the peroxide bleach can inhibit. Suitable inhibitor compounds are described in U.S. Patent 3,606,990.

Of particular interest as inhibitor compounds may be mentioned hydroxy1-amine sulfate and other water-soluble hydroxylamine salts. In the preferred non-aqueous compositions of the invention, suitable amounts of the hydroxylamine salt inhibitors may be as low as about 0.01-0.4%. Generally, however, suitable amounts of enzyme inhibitors range up to about 15%, for example 0.1-10%, based on the weight of the composition.

In addition to the detergent builders, various other detergent additives or adjuvants may be present in the detergent product to impart further desirable properties, whether of a functional or aesthetic nature. For example, minor amounts of soil suspending or anti-redeposition agents, for example, polyvinyl alcohol, fatty amides, sodium carboxymethyl-5 cellulose, hydroxypropylmethyl cellulose, may be included in the mixture. A preferred anti-redeposition agent is 2: 1 CMC / MC sodium carboxymethyl cellulose, which is commercially available under the trade name Relatin DM 4050.

Small amounts of Duet 787, a perfume marketed by International Flavors and Fragrances, may also be included in the composition. Duet 787 can be added in amounts of 0-3%, preferably 0.2-3%, e.g. 0.5-2%, such as 0.3-1.5%, 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, benzidenesulfone, etc., with most preferred combinations of stilbene and triazole. A preferred brightener 20 is Stilbene Brightener N4, a dianilino dimorphalino stilbene polysulfonate.

Furthermore, enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papaine, trypsin and pepsin, as well as enzymes of the amylase, enzymes of the lipase type, and mixtures thereof can be added. Preferred enzymes are, for example, protease suspension, esperase suspension and amylase. A preferred enzyme is Esperase SL8, a proteolytic enzyme. Anti-foaming agents, for example silicon compounds, such as Silicane L 7604, a silicone, can also be added in small effective amounts.

Also, bactericides, for example, tetrachlorosalicylanilide and hexachlorophene, fungicides, dyes, pigments {water dispersible), preservatives, ultraviolet absorbers, anti-yellowing agents such as sodium carboxymethyl cellulose, pH modifiers and pH buffers. safe bleaches, perfumes and dyes and bluing agents such as ultramarine blue are used.

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 and reducing the particle size of the solid builders to less than 100 µm, preferably less than 40 µm and most preferably up to less than 10 µm. The solid builders, for example sodium tripolyphosphate, are generally supplied in particle sizes of about 100, 200 or 400 µm. The nonionic liquid surfactant phase can be mixed with the solid builders before or after the grinding operation.

In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid components is ground in a mill, in which the particle sizes of the solid components are reduced to less than about 10 µm, for example to an average particle size from 2-10 ym or even less (eg 1 ym). Preferably less than about 10%, especially less than about 5% of all suspended particles have particle sizes greater than 10 µm. Compositions whose dispersed particles are of such small size have improved stability against separation and settling on storage. Addition of a nonionic surfactant with terminal acid group can decrease the yield stress of such dispersions and promote the dispersibility of the dispersions without correspondingly reducing the stability of the dispersions against settling.

During grinding, the amount of solid components is preferably so large (eg, at least about 40%, such as about 50%) that the solid particles are in contact with each other and are not significantly shielded from each other by the nonionic capillary active liquid. After grinding, any remaining liquid nonionic 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 1 mm or 1.5 mm operate in a very small gap between a stator and a relatively high speed rotating rotor (e.g. a CoBall mill); when such a mill is used, it is desirable to first pass the mixture of nonionic surfactant and solids through a mill, 8702112-17 in which no such fine grinding takes place (eg, a colloid mill) while reducing the particle size to less than 100 µm (eg, to about 40 µm), before the material is milled in the continuous ball mill to an average particle size of less than 10 µm.

The preferred liquid laundry detergent compositions according to the invention may contain the following ingredients in the percentages mentioned (calculated on the total weight of the composition, unless otherwise stated):

Liquid C -C. alkyl (CHCHO) OH non-ionic capillary-XX 2 2 5 10 active detergent: 10-60%, such as 20-60%, for example 30-45%.

Detergent builder, such as sodium tripolyphosphate: 10-60%, such as 15-50%, e.g. 25-35%.

Alkali metal silicate: 0-30%, such as 5-25%, for example 10-20%. Copolymer of polyacrylate and polymalinic anhydride alkali-15 metal salt, for example Sokalan CP5 (anti-encrusting agent): 0-10%, such as 2-8%, for example 3-5%.

Alkylene glycol monoalkyl ether (anti-gelling agent): 0-30%, preferably 5-30%, such as 5-20%, for example 5-15%.

Phosphoric acid alkanol ester (stabilizing agent): 0-0.75% or 0.1-0.5%, such as 0.20-0.5%.

Bleach: 0-30%, such as 2-20%, for example 5-15%.

Bleach activator: 0-15%, such as 1-8%, e.g. 2-6%.

Bleach sequestrant, for example, Dequest 2066: 0-3.0%, preferably 0.5-2.0%, for example, 0.75-1.25%.

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%, for example 0.75-1.25%.

Perfume: 0-3.0%, preferably 0.10-1.25%, e.g. 0.25-1.0%. Several of the aforementioned additives can be added if desired to fulfill the desired function of the added materials.

35 The C -C. alkyl (CHCHO) OH nonionic surfactant Y XX 2 2 5 compound is preferably used with the alkylene glycol monoether-870 21 1 2 * -18 viscosity-controlling and anti-gelling agents. In some cases it may be advantageous to use both the alkylene glycol monoethers and the phosphoric acid alkanol ester stabilizers.

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

As mentioned, all ratios and percentages are by weight, based on the total mixture or composition, unless otherwise stated.

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

Wt. % C. -C. Alkyl (CHCHLO) - OH 30 - 45 9 11 Z Z 5

Phosphate detergent build-up salt 10-60

Anti-crusting agent 0-10 15 Alkylene glycol monoalkyl ether anti-gelling agent 5-15

Phosphoric acid alkanol ester 0.2-0.5

Anti-redeposition agent 0-4.0

Alkali metal perborate bleach 5-15

Bleach Activator (TAED) 2.0-6.0 Bleach Sequestrant 0-3.0

Duet 787 0-3.0

Optical brightener 0.15-0.75

Enzymes 0.75-1.25

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

EXAMPLE I

A high foaming concentrated non-aqueous liquid nonionic surfactant detergent composition is formulated as follows.

1702112 u

Wt. % -19- C9 "C11 alkyl (CH2CH2O) 50h (1) 39.7

Sodium tripolyphosphate (TPP) 30.0 (2)

Diethylene glycol monobutyl ether 13.7 5 Phosphoric acid alkanol ester (Empephos 5632) 0.3

Sodium perborate monohydrate bleach 1 9.0

Tetraacetylethylenediamine (TAED) bleach activator 4.5

Anti-redeposition agent (Relatin DM 4050) ^ 1.0

Optical brightener 0.2 10 Perfume 0.6

Enzyme (Esperase) 1.0 100.0 (1) Nonionic Surfactant, by Shell Chemical Co. marketed under the brand name Dobanol 91-5.

15 (2) Anti-gelling agent, by Dow Chemical Co. marketed under the brand name Dowanol DB.

(3) CMC / MC 2: 1 mixture of sodium carboxymethyl cellulose and hydroxymethyl cellulose,

The mixture is ground for about 1 hour, reducing the particle size of the suspended builder salts to less than 40 µm.

The composition appears to be stable on storage and not to form a gel, to be readily dispersible in water and to form a very stable foam in an aqueous washing liquid.

EXAMPLE II

A high foaming concentrated non-aqueous liquid non-ionic surfactant detergent composition is formulated as follows.

8702112 λ

Wt. % -20-

C 1 -C 11 alkyl (C 1 C 4 O) 5OH (1) 36.7

Sodium tripolyphosphate (TPP) 34.0 (2)

Dowanol PIB-TV '12.7 5 Poshic acid alkanol ester (Empiphos 5632) 0.3

Sodium perborate monohydrate bleach 9.0

Tetraacetylethylenediamine (TAED) bleach activator 4.5 (3)

Anti-redeposition agent (Relatin DM 4050) J 1.0

Optical brightener 0.2 10 Perfume 0.6

Enzyme (Esperase) 1.0 100.0 (1) Nonionic Surfactants, by Shell Chemical Co. marketed under the trade name Dobanol 91-5.

(2) Anti-gel-forming agent, a mixture of mono-, di- and tripropylene glycol monomethyl ether (Dow chemical Co.).

(3) CMC / MC 2: 1 mixture of sodium carboxymethyl cellulose and hydroxymethyl cellulose.

The mixture is ground for about 1 hour, reducing the particle size of the suspended builder salts to less than 40 µm. The composition appears to be stable on storage and does not form a gel, is readily dispersible in water and forms a very stable foam in an aqueous washing liquid.

EXAMPLE III

A high foaming concentrated non-aqueous liquid nonionic surfactant detergent composition was formulated as follows.

! 170 21 1 2

Wt. % ft -21- C9 -C13L alkyl (GH2 <2T20) 50H (1) 36.4

Sodium tripolyphosphate (TPP Thermos NW) 29.6

Anti-encrusting agent (Sokalan CP5) 4.0 12) 5 Diethylene glycol monobutyl ether 12.1

Phosphoric acid alkanol ester (Empiphos 5632) 0.3

Sodium perborate monohydrate bleach 9.0

Tetraacetylethylenediamine (TAED) bleach activator 4.5

Bleach sequestrant (Dequest 2066) 1.0 (3) 10 Anti-redeposition agent (Relatin DM 4050) 1.0

Optical brighteners (Stilbene 4) 0.5

Enzyme (Esperase 8.0's suspension) 1.0 (4)

Duet 787K 1 0.6 100.0 15 (1) Nonionic surfactant compound, pass

Shell Chemical Co. marketed under the brand name Dobanol 91-5.

(2) Anti-gelling agent, by Dow Chemical Co. marketed under the brand name Dowanol DB.

(3) CMC / MC 2: 1 mixture of sodium carboxymethyl cellulose and hydroxymethyl cellulose.

(4) Duet 787 is a fragrance marketed by IFF.

The yield stress of the composition is 9 Pa, the plastic viscosity is 0.135 Pa.s at 25 ° C and the composition does not form a gel when diluted in water at 5 ° C.

The mixture is ground for about 1 hour, reducing the particle size of the suspended builder salts to less than 40 µm. The composition appears to be stable on storage and does not form a gel, is readily dispersible in water and forms a very stable foam in an aqueous washing liquid. During a wash cycle in a mini-washer at a temperature of up to 60 ° C, the foam rose to the dispenser even in the presence of dirt.

The mixtures of Examples I, II and III 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.

8702112 -22- t

The build-up salts can be used in the form in which they are supplied, or can be ground or partially ground with the suspended solids before mixing with the nonionic surfactant.

870 2 1 1 2

Claims (19)

Highly foaming nonionic liquid surfactant detergent composition, characterized by alkyl (CH 2 CH 2 O) 50H as the major nonionic surfactant detergent ingredient. Composition according to claim 1, characterized by a viscosity-5 regulating and anti-gel-forming agent. Composition according to claim 2, characterized in that the composition contains an alkylene glycol monoalkyl ether as a viscosity regulating and anti-gel-forming agent. Composition according to claims 1-3, characterized by a suspension 10 of insoluble inorganic detergent build-up salt. Composition according to claim 4, characterized in that the insoluble inorganic build-up salt comprises an alkali metal phosphate. 6. A composition according to claims 1-5, characterized in that the inorganic build-up salt comprises 10-60% of an alkali metal polyphosphate detergent build-up salt. Detergent composition according to claims 1-6, characterized by one or more detergent auxiliaries selected from anti-encrusting agent, bleaching agent, bleach activator, 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. Composition according to claim 3, characterized by 5-30% of an alkylene glycol monoalkyl ether. 10. A composition according to claim 4, characterized in that the inorganic build-up salt has a particle size of less than 40 µm. Composition according to claims 1-10, characterized by 0.1-0.5% by weight, based on the total composition, of a phosphoric acid alkanol ester as a stabilizing anti-settling agent. 12. Non-aqueous build-up laundry detergent composition, which is pourable at high and low temperatures and does not form a gel when mixed with cold water, characterized by a C 1 -C 2 alkyl (CH 2 CH 2 O) 50H liquid non-ionic surfactant in a amount of 10-60% by weight, at least one inorganic detergent build-up salt, suspended in the nonionic surfactant in an amount of 10-60% by weight, 6702112 4 * -24- and a compound of the formula R2 1 R 0 (CHCH 0) H 2 n 1 2 wherein R is a C 1 -C alkyl group and R is hydrogen or methyl and 2 is a number having an average value of 1-6 as a gel inhibiting additive in an amount of 5-30 wt%. Composition according to claim 12, characterized by one or more detergent auxiliaries selected from anti-encrusting agent, bleaching agent, bleach activator, sequestrant, anti-redeposition agent, optical brightener, enzyme and perfume. Composition according to claim 12, characterized by Wt. % C -C Λ alkyl (CH CH 0) OH nonionic capillary 11 2 2 y active compound 20-50 Sodium tripolyphosphate 15-50 Composition according to claim 12, characterized by C 8 -C 4 alkyl (CH 2 CH 2 O) 5QH nonionic surfactant 30-40 Sodium tripolyphosphate 25-35 25 Copolymer of polyacrylate and polymaleic anhydride sodium salt 3-5 Diethylene glycol monobutyl ether 5-15 Phosphoric alkanol ester 0.2-0.5 Sodium perborate monohydrate bleach 5-15 30 Tetraacetylethylenediamine (TAED) bleach activator 2-6.0 Bleach sequestrant 0.75-1.25 Anti-redeposition agent 0.5-1.5 15 Copolymer of polyacrylate and polymaleic anhydride sodium salt 2-8 Diethylene glycol monoalkyl ether 5-20 Phosphoric acid alkanol ester 0-0.75 Sodium perborate monohydrate bleach 2-20 Tetraacetylethylenediamine (TEAD) 1-10 16. Method for cleaning dirty fabrics, characterized in that the dirty fabrics are brought into contact with the detergent composition according to claim 1. 870 21 12 t -25- Method according to claim 16, characterized in that the soiled fabrics are brought into contact with the composition according to claim 12. 18. Method according to claim 16, characterized in that the soiled fabrics are brought into contact with the composition according to claim 14. Method according to claim 16, characterized in that the soiled fabrics are brought into contact with the composition according to claim 15. 10 (i 8702112