GB2194955A - High foam nonaqueous liquid nonionic laundry detergent composition - Google Patents

Description

1 GB2194955A 1

SPECIFICATION

High foam nonaqueous liquid nonionic laundry detergent composition and method of use _j The present invention relates to nonaqueous I! ' quid fabric treating compositions. More particularly, 5 this invention relates to high foam nonaqueoUs liquid laundry detergent compositions which are stable against phase separation and gelation and are easily pourable and to the use of these compositions for cleaning soiled fabrics.

Liquid nonaqueous heavy duty laundry detergent compositions are well known in the art. For instance, compositions of that type may comprise a liquid nonionic surfactani in which are 10 dispersed particles of a builder, as shown for instance in the U.S.P. Nos. 4,316,812, 3,630,929 and 4,264,466 and British Patent Nos. 1,205,711, 1,270,040 and 1,600,981.

Liquid detergents are often considered to be more convenient to employ than dry powdered or particulate products and, therefore, have found substantial favour with consumers. They are readily measurable, speedily dissolved in the wash water, capable of being easily applied in 15 concentrated solutions or dispersions to soiled areas on garments to be laundered and are non dusting, and they usually occupy less storage space. Additionally, the liquid detergents may have incorporated in their formulations materials which could not stand drying operations without deterioration, which materials are often desirably employed in the manufacture of particulate detergent products. Although they are possessed of many advantages over unitary or particulate 20 solid products, liquid detergents often have certain inherent disadvantages too, which have to be overcome to produce acceptable commercial detergent products. Thus, some such products do not readily foam, separate out on storage and others separate out on cooling and are not readily redispersed. In some cases the product viscosity changes and it becomes either too thick to pour or so thin as to appear watery. Some clear products become cloudy and others gel on 25 standing.

The present inventors have been involved in studying the behaviour of nonionic liquid surfac tant systems with particulate matter suspended therein. Of particular interest has been nonaque ous built laundry liquid detergent compositions and the problem of settling of the suspended builder and other laundry additives as well as the problem of gelling associated with nonionic 30 surfactants. These considerations have an impact on, for example, product stability, pourability and dispersibility.

It is known that one of the major problems with built liquid laundry detergents is their physical stability. This problem stems from the fact that the density of the solid particles dispersed in the nonionic liquid surfactant is higher than the density of the liquid surfactant.

Therefore, the dispersed particles tend to settle out. Two basic solutions exist to solve the settling out problem: increase nonioniC liquid viscosity and reduce the dispersed solid particle size.

It is known that suspensions can be stabilized against settling by adding inorganic or organic thickening agents or dispersants, such as, for example, very high surface area inorganic ma- 40 terials, e.g. finely divided silica, clays, etc., organic thickeners, such as the cellulose ethers, acrylic and acrylamide polymers, polyelectrolytes, etc. However, such increases in suspension viscosity are naturally limited by the requirement that the liquid suspension be readily pourable and flowableve, even at low temperature. Furthermore, these additives do not contribute to the cleaning performance of the formulation.

Grinding to reduce the particle size provides the following advantages:

1. Specific surface area of the dispersed particles is increased, and, therefore, particle wetting by the nonaqueous vehicle (liquid nonionic) is proportionately improved.

2. The average distance between dispersed particles is reduced with a proportionate increase in particle-to-particle interaction. Each of these effects contributes to increase thq rest-gel 50 strength and the suspension yield stress while at the same time, grinding significantly reduces plastic viscosity.

The yield stress is defined as the minimum stress necessary to induce a plastic deformation (flow) of the suspension. Thus, visualizing the suspension as a loose network of dispersed particles, if the applied stress if lower than the yield stress, the suspension behaves like an 55 elastic gel and no plastic flow will occur. Once the yield stress is overcome, the network breaks at some points and the sample begins to flow, but with a very high apparent viscosity. If the shear stress is much higher than the yield stress, the particles are partially shear-deflocculated and the apparent viscosity decreases. Finally, if the shear stress is much higher than the yield stress value, the dispersed particles are completely shear-deflocculated and the apparent viscosity is very low, as if no particle interaction were present.

Therefore, the higher the yield stress of the suspension, the higher the apparent viscosity at low shear rate and, the better is the physical stability against settling of the product.

In addition to the problem of settling or phase separation, the nonaqueous liquid laundry detergents based on liquid nonionic surfactants suffer from the drawback that the nonionics do 65 2 GB2194955A not readily produce a stable foam and they tend to gel when added to cold water. This is a particularly important problem in the ordinary use of European household automatic washing machines where the user places the laundry detergent composition in a dispensing unit (e.g. a dispensing drawer) of the machine. During the operation of the machine the detergent in the dispenser is subjected to a stream of cold water to transfer it to the main body of wash solution. Especially during the winter months when the detergent composition and water fed to the dispenser are particularly cold, the detergent viscosity increases markedly and a gel forms. As a result some of the composition is not flushed completely off the dispenser during operation of the machine, and a deposit of the composition builds up with repeated w0sh cycles, eventu- ally requiring the user to flush the dispenser with hot water.

The gelling phenomenon can also be a problem whenever it is desired to carry out washing using cold water as may be recommended for certain synthetic and delicate fabrics which can shrink in warm or hot water.

The tendency of concentrated detergent compositions to gel during storage is aggravated by storing the compositions in unheated storage areas, or by shipping the compositions during winter months in unheated transportation vehicles.

Partial solutions to the gelling problem in aqueous substantially builderfree compositions have been proposed and include, for example, diluting the liquid nonionic with certain viscosity controlling solvents and gel-inhibiting agents, such as lower alkanols, e. g. ethyl alcohol (see U.S.P. 3,953,380), alkali metal formates and adipates (see U.S.P. 4,368, 147), hexylene glycol, 20 polyethylene glycol, etc. and nonionic structure modification and optimization.

Improvement are desired in the production of a stable foam, and in the stability and gel inhibition of nonaqueous liquid fabric treating compositions.

In accordance with the present invention a high foam, highly concentrated stable nonaqueous liquid laundry detergent composition is prepared by adding to the composition as the main 25 nonionic surfactant component a C9-C,1 fatty alcohol ethoxylated by 5 moles of ethylene oxide per mole of alcohol.

The compositions of the present invention contain as an essential ingredient and as the major constituent of the liquid nonionic surfactant component of the composition a C,-C,, fatty alcohol ethoxylated by 5 moles of ethylene oxide per mole of alcohol. The Cg-C,, alkyl (C2H2-0),OH nonionic surfactant of the present invention will comprise about 50 to 100% of the nonionic surfactant component of the composition, e.g. 50 to 90%, such as 50 to 75% of the nonionic component. In order to improve the viscosity characteristics of the composition and the storage properties of the composition there can be added to the composition viscosity improving and anti-gel agents such alkylene glycol mono alkyl ethers and anti-settling agents such as phos phoric acid alkanol ester. In preferred embodiments of the invention the detergent composition contains an alkylene glycol mono alkyl ether and a phosphoric acid alkanol ester anti-settling stabilizing agent. Acid terminated nonionic surfactant anti-gel agents, e. g. those disclosed in the commonly assigned application U.S. Ser. No. 597,793, filed April 6, 1984, corresponding to G.B. Application No. Serial No. are not added to the composition because they 40 are believed to form with the calcium ions present in the wash liquor a calcium salt which is a foam inhibitor.

Sanitizing or bleaching agents and activators therefor can be added to improve the bleaching and cleansing characteristics of the composition.

In an embodiment of the invention the builder components of the compositions are ground to a particle size of less tahn 100 microns and to preferably less than 40 microns io further improve the stability of the suspension of the.builder components in the liquid nonionic surfac tant detergent.

In addition other ingredients can be added to the composition such as anti-incrustation agents, anti-foam agents, optical brighteners, enzymes, anti-redeposition agents, perfume and dyes.

Accordingly, in one aspect the present invention provides a liquid heavy duty laundry compo sition composed of a suspension of a detergent builder salt, e.g. a phosphate builder salt, in a liquid nonionic surfactant wherein the composition includes as the main nonionic component a high foam producing C,-Cl, fatty alcohol ethoxylated by 5 moles of ethylene oxide per mole of alcohol, which composition produces high foam, is stable against settling and is readily dispersi- 55 ble in water.

According to another aspect, the invention provides a concentrated liquid heavy duty laundry detergent composition which is stable, non-settling in storage and non- gelling in storage and in use. The liquid compositions of the present invention are easily pourable, easily measured and easily put into the washing machine and are readily dispersible in water.

According to another aspect, the invention provides a method for dispensing a high foam Cg-C,, alkyl (C2H20),OH liquid nonionic laundry detergent composition into and/or with cold water without undergoing gelation.

The use of the high foam C,-C,, alkyl (C2H20)50H nonionic surfactant as the main component of the nonionic surfactant in the compositions produces a high foaming detergent composition 65 h 11 z 11 Q..

3 GB2194955A 3 1 without the need to add specific foaming agents.

The concentrated nonaqueous liquid nonionic surfactant laundry detergent compositions of the present invention have the advantages of being stable, non-settling in storage, and non-gelling in storage. The liquid compositions are easily pourable, easily measured and easily put into the 5 laundry washing machines and are readily dispersible in water.

The present invention aims to provide a high foaming, stable liquid heavy duty nonaqueous nonioniG detergent composition containing an antisettling stabilizing agent and an anionic phosphate detergent builder salt suspension in a nonionic surfactant.

The invention also aims to provide high foam liquid fabric treating composilions which are suspensions of insoluble inorganic particles in a nonaqueous liquid and which are storage stable, 10 easily pourable and dispersible in cold, warm or hot water.

This invention also aims to formulate high foam built heavy duty nonaqueous liquid nonionic surfactant laundry detergent compositions which can be poured at a wide range of temperatures and which can be repeatedly dispersed from the dispensing unit of European style automatic laundry washing machines with less tendency to fouling or plugging of the dispenser even during 15 the winter months.

This invention also aims to provide a high foam, non-gelling, stable suspension heavy duty built nonaqueous liquid nonionic laundry detergent composition which includes as the main nonionic surfactant component constituent a C.-C11 alkyl (CH2CH2O),OH nonionic surfactant.

A detergent composition in accordance with the invention may be prepared by adding to the 20 nonaqueous liquid nonionic surfactant a high foam C9 to C,1 alkyl (CH2CH20)50H nonionic surfac tant, and the said composition may include inorganic or organic fabric treating additives, e.g.

viscosity improving agents and one or more anti-gel agents, antiincrustation agents, pH control agents, bleaching agents, bleach activators, anti-foam agents, optical brighteners, enzymes, antiredeposition agents, perfume and dyes.

In accordance with the present invention the foaming properties of a nonaqueous liquid nonionic laundry detergent composition is substantially improved by the addition of C,-C, alkyl (CH2CH20)r,OH nonionic surfactant to the composition.

The addition of C,-C1, alkyl (CH2CH20),OH as the major constituent of the nonionic surfactant component of the composition substantially improves the foaming properties of the composition. 30 The compositions of the present invention contain as an essential ingredient the C,-C,, alkyl (CH2CHA5OH as the main constituent of the nonionic surfactant component of the composition The C9-C11 alkyl (CH2CH20)rOH nonionic surfactant is available from Shell Chemical Company, Inc. under the Dobanol 91-5 trademark.

Nonionic synthetic organic detergents that can be employed in small amounts in the practice 35 of the invention may be any of a wide variety of known compounds.

As is well known, the nonionic synthetic organic detergents are characterised by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature). Practically any hydrophobic compound having a carboxy, hydroxy, 40 amido or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a nonionic detergent. The length of the hydrophilic or polyoxy ethylene chain can be readily adjusted to achieve the desired balance betwen the hydrophobic and hydrophilic groups. Typical suitable nonionic surfactants are those disclosed in U.S. Patents 4,316,812 and 3, 630,929.

Usually, the nonionic detergents are poly-lower alkoxylated lipophiles wherein the desired hydrophilelipophile balance is obtained from addition of a hydrophilic poly-lower alkoxy group to a lipophilic moiety. A preferred class of the nonionic detergent employed is the poly-lower alkoxylated higher alkanol wherein the alkanol is of 9 to 18 carbon atoms and wherein the number of moles of lower alkylene oxide (of 2 or 3 carbon atoms) is from 3 to 12. Of such materials it is preferred to employ those wherein the higher alkanol is a higher fatty alcohol of 9 to 11 or 12 to 15 carbon atoms and which contain from 6 to 8 or 5 to 9 lower alkoxy groups per mol. Preferably, Jhe lower alkoxy is ethoxy but in some instances, it may be desirably mixed with propoxy, the latter, if present, often being a minor (less than 50%) proportion., Exemplary of such compounds are those wherein the alkanol is of 12 to 15 carbon atoms and 55 which contain about 7 ethylene oxide groups per mol, e.g. Neodol 25-7 and Neodol 23-6.5, which products are made by Shell Chernial Company, Inc. The former is a condensation product of a mixture of higher fatty alcohols averaging about 12 to 15 carbon atoms, with about 7 moles of ethylene oxide and the latter is a corresponding mixture wherein the carbon atom content of the higher fatty alcohol is 12 to 13 and the number of ethylene oxide groups present 60 averages about 6.5. The higher alcohols are primary alkanols.

Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15S-9, both of which are linear secondary alcohol ethoxylates made by Union Carbide Corp. The former is mixed ethoxylation product of 11 to 15 carbon atomp linear secondary alkanol with seven mols of ethylene oxide and the latter is a similar product but with nine mols of ethylene oxide being 4 GB2194955A 4 reacted.

Also useful in the compositions of the present invention as a component of the nonionic detergent are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14 to 15 carbon atoms and the number of the ethylene oxide groups per mol being about 5 11. Such products are also made by Shell Chemical Company.

Other useful nonionics are represented by the commercially well known class of nonionics sold under the trademark Plurafac. The Plurafacs are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain ofethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include products which are (A) 10 C13-C15 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide, (B) (C,,-C,. fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide, (C) C13 C,., fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide, and (D) which is a 1: 1 mixture of products (B) and (C).

Another group of liquid nonionics are commercially available from Shell Chemical Company, Inc. under the Dobanol trademark, e.g. Dobanol 25-7 which is an ethoxylated C12-Cl. fatty alcohol with an average of 7 moles ethylene oxide per mole of fatty alcohol.

Another useful group of nonionic surfactants are the---SurfactantT- series of nonionics available-from British Petroleum. The surfactant T nonionics are obtained by the ethoxylation of secondary C13 fatty alcohols having a narrow ethylene oxide distribution. The surfactant T5 has 20 an average of 5 moles of ethylene oxide; Surfactant T7 an average of 7 moles of ethylene oxide; Surfactant T9 an average of 9 moles of ethylene oxide and Surfactant T12 an average of 12 moles of ethylene oxide per mole of secondary C13 fatty alcohol.

In the compositions of the present invention, useful nonionic surfactants include the C,,-C,, secondary fatty alcohols with relatively narrow contents of ethylene oxide in the range of from 25 about 7 to 9 moles, and the C9 to C,, fatty alcphols ethoxylated with about 5-6 moles ethylene oxide.

Mixtures of two or more of-the liquid nonionic surfactants can be used with the high foam C,C,, alkyl (CH2CH20),OH surfactant of the present invention and in some cases advantageous can be obtained by the use of such mixtures.

The liquid nonaqueous nonionic surfactant used in the compositions of the present invention preferably has dispersed and suspended therein fine particles of inorganic andlor organic deter gent builder salts.

The detergent compositions of the present invention include water soluble and/or water insoluble detergent builder salts. Water soluble inorganic alkaline builder salts which can be used along with the detergent compound or in admixture with other builders are alkali metal carbo nates, bicarbonates borates, phosphates, polyphosphates, and silicates. (Ammonium or substi tuted ammonium salts can also be used.) Specific examples of such salts are sodium tripoly phosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophos phate, sodium bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium ses- 40 quicarbonate, sodium mono- and diorthophosphate, and potassium bicarbonate. Sodium tripoly phosphate (TPP) is especially preferred.

Since the compositions of the present invention are generally highly concentrated, and, there fore, may be used at relatively low dosages, it is desirable to supplement any pilosphate builder (such as sodium tripolyphosphate) with an auxiliary builder such as a poly lower carboxylic acid or a polymeric carbqxylic acid having high calcium binding capacity to inhibit incrustation which could otherwise be caused by formation of an insoluble calcium phosphate.

A suitable lower poly carboxylic acid comprises alkali metal salts of lower polycarboxylic acids, preferably the sodium and potassium salts. Suitable lower polycarboxylic acids have two to four carboxylic acid groups. The preferred sodium and potassium lower polycarboxylic acids salts are 50 the citric and tartaric acid salts.

The sodium citric acid salts are the most preferred, especially the trisodium citrate. The monosodium and disodium citrates can also be used. The monosodium and disodium tartaric acid salts can also be used. the alkali metal lower polycarboxylic acid salts are particularly good builder salts; because of their high calcium and magnesium binding capacity they inhibit incrusta tion which could otherwise be caused by formation of insoluble calcium and magnesium salts.

Other organic builders are polymers and copolymers of polyacrylic acid and polymaleic anhy dride and the alkali metal salts thereof. More specifically such builder salts can consist of a copolymer which is the reaction product of about equal moles of methacrylic acid arid maleic anhydride which has been completely neutralized to form the sodium salt thereof. The builder is 60 commercially available under the tradename of Sokalan CP5. This builder serves when used even in small amounts to inhibit incrustation.

Examples of organic alkaline sequestrant builder salts which can be used with the detergent builder salts or in admixture with other organic and inorganic builders are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, e.g. sodium and potassium ethylene diaminet- 65 't 15;e I 1 1 GB2194955A etraacetate (EDTA), sodium and potassium nitrilotriacetates (NTA), and triethanol-ammoniurn N(2-hydroxyethyl)nitrilodiacetates. Mixed salts of these aminopolycarboxylates are also suitable.

Other suitable builders of the organic type include carboxymethylsuccinates, tartronates and glycollates. Of special value are the polyacetal carboxylates. The polacetal carboxylates and their use in detergent compositions are described in application U.S. Serial No. 767,570, filed August 19, 1985, corresponding to G.B. Application No. 8619793 Serial No. 2179365 assigned to applicants' assignee and in a U.S. P. Nos. 4,144,226, 4,315,092 and 4,146,495.

The alkali metal silicates are useful builder salts which also function to adjust or control the pH and to make the composition anticorrosive to washing machine parts. Sodiurp silicates of Na20/SiO2 ratios of from 1.6/1 to 1/3.2, especially about 1/2 to 1/2.8 are preferred. Potassium 10 silicates of the same ratios can also be used.

Other typical suitable builders include, for example, those disclosed 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 in admixture with other inroganic builder salts or with organic builder salts.

The water insoluble crystalline and amorphous aluminosilicate zeolites can be used. The zeolites generally have the formula (M20)xl(A1203)y(SiO2)zlsH20 20 wherein x is 1, y is from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3. 5 or higher and preferably 2 to 3 and 2 is from 0 to 9, preferably 2.5 to 6 and M is preferably sodium. A typical zeolite is type A or similar structure, with type 4A particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents per gram or greater, e.g. 400 meg/9.

Various crystalline zeolites (i.e. aluminosilicates) that can be used are described in British Patent 1,504,168, U.S.P. 4,409,136 and Canadian Patents 1,072,835 and 1, 087,477, all of which are hereby incorporated by reference for such descriptions. An example of amorphous zeolites usetful herein can be found in Belgium Patent 835,351 and this patent too is incorpor ated herein by reference.

Other materials such as clays, particularly of the water-insoluble types, may be useful adjuncts in compositions of this invention. Particularly useful is bentonite. This material is primarily montmorillonite which is a hydrated aluminium silicate in which about 1/6th of the aluminium atoms may be replaced by magnesium atoms and with which varying amounts of hydrogen, sodium, potassium, calcium, etc., may be loosely combined. The bentonite in its more purified 35 form (i.e. free from any grit, sand, etc.) suitable for detergents contains at least 50% montmoril lonite and thus its cation exchange capacity is at least about 50 to 75 meq per 100g of bentonite. Particularly preferred bentonites are the Wyoming or Western U. S. bentonites which have been sold as Thixo-jels 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften textiles as described in British Patent 401,413 to Marriott and British Patent 461,221 40 to Marriott and Duggan.

The inclusion in the detergent composition of an effective amount of low molecular weight amphilic compounds which function as viscosity control and gel inhibiting agents for the nonionic surfactant substantially improves the storage properties of the composition. The viscosity controland gel inhibiting agents act to lower the temperature at which the nonionic surfactant will form 45 a gel when added to water. Such viscosity control and gel inhibiting agents can be, for example, low molecular weight alkylene oxide lower mono-alkyl ether amphilic compounds. . The amphiphilic compounds can be considered to be analogous in chemical structure to the ethoxylated and/or propoxylated fatty alcohol liquid nonionic surfactants but have relatively short hydrocarbon chain lengths (C2 to C8) and a low content of ethylene oxide (about 2 to 6 ethylene oxide grups per 50 molecule).

Suitable amphiphilic compounds are represented by the following general formula R 2 1 RIO(CHCH20),H where R' represents a C2-Ca alkyl group, R 2 represents a hydrogen atom or a methyl group and n is a number of from about 1 to 6, on average.

Specifically the compounds are lower (C2 to C3) alkylene glycol mono lower (Cl to C.) alkyl 60 ethers.

More specifically the compounds are mono-, di- or tri- lower (C2 to C3) alkylene glycol mono lower (C. to C5) alkyl ethers.

Specific examples of suitable amphiphilic compounds include ethylene glycol monoethyl ether C2H5-O-CH2CH2OH, 6 GB2194955A 6 diethylene glycol monobutyl ether C41-19-0-(CH2CH20)2H, tetraethylene glycol monobutyl ether C4H9-0-(CH2CH20)4H and dipropylene glycol monomethyl ether CH,-O-(CHCH20)21-1. 1 CH3 Diethylene glycol monobutyl ether is especially preferred and is supplied by, Dow Chemical Co.

under the trademark Dowanol DB.

Another suitable viscosity control and gel inhibiting agent supplied by Dow Chemical Co. that can be used is Dowanol PIB-T, which is a mixture of mono-, di- and tripropylene glycol monomethyl ether.

The inclusion in the composition of the low molecular weight lower alkylene glycol mono alkyl ether decreases the viscosity of the composition, such that it is more easily pourable, improves the stability against settling and improves the dispersibility of the composition on the addition to warm water or cold water.

The compositions of the present invention have high foam properties, improved viscosity and stability characteristics and remain stable and pourable at temperatures as low as about 5'C.

In an embodiment of this invention a small amount of a stabilizing agent which is an alkanol 20 ester of phosphoric acid can be added to the formulation. Improvements in stability of the composition may be achieved by incorporation of a small effective amount of an acidic organic phorphorous compound having an acidic -POH group, such as a partial esterof phosphorous acid and an alkanol. As disclosed in the commonly assigned copending application U.S. Serial No.

597,948 filed April 9, 1984 corresponding to G.B. Application No. 8509084 Serial No.

2158454 the disclosure of which is incorporated herein by reference, the acidic organic phos phorus compound having an acidic -POH group can increase the stability of the suspension of builders in the nonaqueous liquid nonionic surfactant. The acidic organic phosphorous compound may be, for instance, a partial ester of phosphoric acid and an alcohol such as an alkanol which has a lipophilic character, having, for instance, more than 5 carbon atoms, e.g. 8 to 20 carbon 30 atoms.

A specific example is a partial ester of phosphoric acid and a C1. to C1, alkanol (Empiphos 5632 from Marchon); it is made up of about 35% monoester and 65% diester.

The inclusion of quite small amounts, e.g. 0.3% by weight of the acidic organic phosphorous compound makes the suspension stable against settling on standing but remains pourable, while, 35 for the low concentration of stabilizer its plastic viscosity will generally decrease. The addition of more than about 0.3%, e.g. about 1.0% or more is avoided since the higher concentration of organic phosphorous ester would be expected to inhibit foam.

The bleaching agents are classified broadly, for convenience, as chlorine bleaches and oxygen bleaches. Chlorine bleaches are typified by sodium hypochlorite (NaOCQ, potassium dichloroisocy- 40 anurate (59% available chlorine), and trichloroisocyanuric acid (95% available chlorine). Oxygen bleaches are preferred and are represented by percompounds which liberate hydrogen peroxide in solution. Preferred examples include sodium and potassium perborates, percarbonates, and perphosphates, and potassium monopersulphate. The perborates, particularly sodium perborate monohydrate, are especially preferred.

The peroxygen compound is preferably used in admixture with an activator therefor. Suitable activators which can lower the effective operating temperature of the peroxide bleaching agent are disclosed, for example, in U.S.P. 4,264,466 or in column 1 of U.S.P. 4,430,244, the relevant disclosures of which are incorporated herein by reference. Polyacylated compounds are preferred activators; among these, compounds such as tetraacetyl ethylene diamine ("TAED") 50 and pentaacetyl glucose are particularly preferred.

Other useful activators include, for example, acetylsalicylic acid derivatives, ethylidene benzoate acetate and its salts, ethylidene carboxylate acetate and its salts, alkyl and alkenyl succinic anhydride, tetraacethylglycouril ("TAGU"), and the derivatives of these. Other useful classes of activators are disclosed, for example, in U.S.P. 4,111,826, 4,422,950 and 3,661,789.

The bleach activator usually interacts with the peroxygen compound to form a peroxyacid bleaching agent in the wash water. It is preferred to include a sequestering agent of high complexing power to inhibit any undesired reaction between such peroxyacid and hydrogen peroxide in the wash solution in the presence of metal ions.

Suitable sequestering agents for this purpose include the sodium salts of nitrilotriacetic acid 60 (NTA), ethylene diamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DETPA)I diethylene triamine pentamethylene phosphonic acid (DTPMP) sold under the tradename Dequest 2066; and ethylene diamine tetramethylene phosphonic acid (EDITEMPA). The sequestering agents can be used alone or in admixture.

In order to avoid loss of peroxide bleaching agent, e.g. sodium perborate, resulting from 65 1 7 GB2194955A 7 enzyme-induced decomposition, such as by catalase enzyme, the compositions may additionally include an enzyme inhibitor compound, i.e. a compound capable of inhibiting enzyme-induced decomposition of the peroxide bleaching agent. Suitable inhibitor compounds are disclosed in U.S.P. 3,606,990, the relevant disclosure of which is incorporated herein by reference.

Of special interest as the inhibitor compound, mention can be made of hydroxylamine sulphate 5 and other water-soluble hydroxylamine salts. In the preferred nonaqueous compositions of this invention, suitable amounts of the hydroxylamine salt inhibitors can be as low as about 0.01 to 0.4%. Generally, however, suitable amounts of enzyme inhibitors are up to about 15%, for example, 0.1 to 10%, by weight of the composition. I In addition to the detergent builders, various other detergent additives or adjuvants may be 10 present in the detergent product to give it additional desired properties, either of functional or aesthetic nature. Thus, there may be included in the formulation, minor amounts of soil suspend ing or anti-redeposition agents, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellu lose, hydroxy-propyl methyl cellulose. A preferred anti-redeposition agent is sodium carboxyme thyl cellulose having a 2:1 ratios of CMC/MC which is sold under the tradename Relatin DM 4050.

There may also be included in the composition small amounts of Duet 787 which is a fragrance, i.e. perfume, and which is supplied by International. Flavours and Fragrances, Inc., Union Beach, NJ 07735. The Duet 787 can be added in amounts such as 0 to 3, preferably 0.2 to 3 percent, e.g. 0.5 to 2 percent, such as 0.3 to 1.5 percent by weight of the composition. 20 Optical brighteners for cotton, polyamide and polyester fabrics can be used. Suitable optical brighteners include stilbene, triazole and benzidine sulphone compositions, especially sulphonated substituted triazinyl stilbene, sulphonated napthotriaolze stilbene, benzidene sulphone, etc., most preferred are stilbene and triazole combinations. A preferred brightener is Stilbene Brightener N4 which is a dianilinodimorphalino stilbene polysulphonate.

Enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, trypsin and pepsin, as well as amylase type enzymes, lipase type enzymes, and mixtures thereof can be added. A preferred enzyme is Esperase SL8 which is a proteolytic enzyme. Anti-foam agents, e.g. silicon compound, such as Silicane L 7604, which is a polysiloxane, can also be added in small effective amounts.

Bactericides, e.g. tetrachlorosalicylanilide and hexachlorophene, fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet absorbers, anti-yellowing agents, such as sodium carboxymethyl cellulose, pH modifiers and pH ' buffers, colour safe bleaches, perfume, and dyes and bluing agents such as ultramarine blue can be used.

In an embodiment of the invention the stability of the builder salts in the composition during 35 storage and the dispersibility of the composition in water is improved by grinding and reducing the particle size of the solid builders to less than 100 microns, preferably less than 40 microns and more preferably to less than 10 microns. The solid builders, e.g. 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 solid builders prior to or after carrying out the 40 grinding operation.

In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid ingredients is subjected to an attrition type of mill in which the particle sizes of the solid ingredients are reduced to less than about 10 microns, e.g. to an average particle size of 2 to 10 microns or even lower (e.g. 1 micron). Preferably less than about 10%, especially less than 45 about 5% of all the suspended particles have particle sizes greater than 10 microns. Compo sitions whose dispersed particles are of such small size have improved stability against separa tion or settling on storage. Addition of the acid terminated nonionic surfactant compound can decrease the yield stress of such dispersions and aid in the dispersibility of the dispersions without a corresponding decrease in the dispersions stability against settling.

In the grinding operation, it is preferred that the proportion of solid ingredients be high enough (e.g. at least about 40% such as about 50%) that the solid particles are in contact with each other and are not substantially shielded from one another by the nonionic surfactant liquid. After the grinding step any remaining liquid nonionic surfactant can be added to the ground formula tion. Mills which employ grinding balls (ball mills) or similar mobile grinding elements have given very good results. Thus, one may use a laboratory batch attritor having 8 mm diameter steatite grinding balls. For larger scale work a continuously operating mill in which there are 1 mm or 1.5 mm diameter grinding balls working in a very small gap between a stator and a rotor operating at a relatively high speed (e.g. a CoBall. mill) may be employed; when using such a mill, it is desirable to pass the blend of nonionic surfactant and solids first through a mill which 60 does not effect such fine grinding (e.g. a colloid mill) to reduce the particle size to less than 100 microns (e.g. to about 40 microns) prior to the step of grinding to an average particle diameter below about 10 microns in the continuous ball mill.

In the preferred heavy duty liquid laundry detergent compositions of the invention, typical proportions (percent based on the total weight of composition, unless otherwise specified) of the 65 8 GB2194955A 8 ingredients are as follows:

Liquid C,-C,l alkyl (CH2CH.O),OH nonionic surfactant detergent in the range of about 10 to 60, such as 20 to 60 percent, e.g. about 30 to 45 percent; Detergent builder, such as sodium tripolyphosphate (TPP), in the range of about 10 to 60, 5 such as 15 to 50 percent, e.g. about 25 to 35 percent; Alkali metal silicate in the range of about 0 to 30, such as 5 to 25 percent, e.g about 10 to 20 percent; Copolymer of polyacrylate and polymaleic anhydride alkali metal salt, e.g. Sokalan CP5, antiincrustation agent in the range of about 0 to 10, such as 2 to 8 percent, e.g. about 3 to 5 percent; Alkylene glycol monoalkylether anti-gel agent in an amount in the range of 0 to 30, preferably about 5 to 30, such as 5 to 20 percent, e.g. about 5 to 15 percent; Phosphoric acid alkanol ester stabilizing agent in the range of 0 to 0.75 or 0.1 to 0.5, such as 0.20 to 0.5 percent; Bleaching agent in the range of about 0 to 30, such as 2 to 20, e.g. about 5 to 15 percent; Bleach activator in the range of about 0 to 15, such as 1 to 8, e.g. about 2 to 6 percent; Sequestering agent for bleach, e.g. Dequest 2066, in the range of about 0 to 3.0, preferably 0.5 to 2.0 percent, e.g. about 0.75 to 1.25 percent; Anti-redeposition agent, e.g. Relatin DM 4050, in the range of about 0 to 4.0, preferably 0.5 to 3.0 percent, e.g. 0.5 to 1.5 percent; Optical brightener in the range of about 0 to 2.0, preferably 0.05 to 1.0 percent, e.g. 0.15 to 0.75 percent; Enzymes in the range of about 0 to 3.0, preferably 0.5 to 2.0 percent, e. g. 0.75 to 1.25 percent; and Perfume in the range of about 0 to 3.0, preferably 0. 10 to 1.25 percent, e.g. 0.25 to 1.0 25 percent.

Various of the previously mentioned additives can optionally be added to achieve the desired function of the added materials.

The C,-C,l alkyl (CH2CH2O)5OH nonionic surfactant is preferably used with the alkylene glycol mono-ether viscosity control and anti-gel agents. In some cases advantages can be obtained by 30 using both the alkylene glycol mono-ethers and the phosphoric acid alkanol ester stabilizers.

In the selection of the additives, they will be chosen to be compatible with the main constitu ents of the detergent composition. In this application, as mentioned above, all proportions and percentages are by weight of the entire formulation or composition unless otherwise indicated.

The concentrated nonaqueous nonionic liquid detergent composition of the present invention 35 dispenses readily in the water in the washing machine. The presently used home washing machines normally use 200 to 250 gms of powder detergent to wash a full load of laundry. In accordance with the present invention only 78 cc or 100 gms of the concentrated liquid high foam nonionic detergent composition is neede.

In an embodiment of the invention the detergent composition of a typical formulation is 40 formulated using the below named ingredients:

_Z Weight % C,-C,, alkyl (CH2CH20)50H. 3045 Phosphate detergent builder salt. 10-60 45 Anti-incrustation agOnt. 0-10 Alkylene glycol monoalkylether anti-gel agent. 5-15 Phosphoric Acid Alkanol Ester. 0.2-0.5 Anti-redeposition agent. 0-4.0 50 Alkali metal perborate bleaching agent. 5-15 Bleach activator (TAED). 2.0-6.0 Sequestering agent for bleach. 0-3.0 Duet 787. 0-3 0 Optical brightener. 0.15-0.75 55 Enzymes. 0.75-1.25 Perfume. 0 to 3.0 The invention may be put into practice in various ways and a number of specific embodiments will be described to illustrate the invention with reference to the accompanying examples. 60 EXAMPLE 1

A high foam concentrated nonaqueous liquid nonionic surfactant detergent composition is formulated from the following ingredients in the amounts specified as set out in Table 1 below.

9 GB2194955A 9 TABLE 1

Ingredients Weight % C9-C, alkyl (CH2CH20),OH(I). 39.7 Sodium tripolyphosphate (TPP). 30.0 5 Diethylene glycol monobutylether anti gel agent(2). 13.7 Phosphoric acid alkanol ester (Empiphos 5632). 0.3 Sodium perborate monohydrate bleaching 10 agent. 9.0 Tetraacetylethylene diamine (TAED) bleach activator. 4.5 Anti-redeposition agent (Relatin DM 4050)(3). 1.0 15 Optical brightener. 0.2 Perfume. 0.6 Enzyme (which is Esperase). 1.0 100.0 20 Notes on Table 1 (1) The nonionic surfactant is available from Shell Chemical Co. under the trademark Dobanol 91-5. (2) The anti-gel agent is available from Dow Chemical Co. under the trademark Dowanol D13. (3) CMC/MC 2:1 mixture of sodium carboxymethyl cellulose and hydroxymethylcellulose.

The formulation is ground for about one hour to reduce the particle size of the suspended builder salts to less than 40 microns. The formulation detergent composition is found to be stable and non-gelling in storage and readily dispersiblp in water and to form a high stable foam 30 in an aqueous wash.

EXAMPLE 2

A high foam concentrated nonaqueous liquid nonionic surfactant detergent composition is formulated from the following ingredients in the amounts specified as set out in Table 2 below.35 TABLE 2

Ingredients Weight % C9C1, alkyl (CH2CH20),OH(I). 36.7 40 Sodium tripolyphosphate (TPP). 34.0 Dowanol PIB-T anti-oel agent(2). 12.7 Phosphoric Acid Alkanot Ester (Empiphos 5632). 0.3 Sodium perborate rnonohydrate bleaching 45 agent. 9.0 Tetraacetylethylene diamine (TAED) bleach activator. 4.5 Anti-redeposition agent (Relatin DM 4050)(3). 1.0 50 Optical brightener. 0,2 Perfume. 0.6 Enzyme (which is Esperase). tb 100.0 55 Notes on Table 2 (1) See note 1 Table 1.

(2) The anti-gel agent is a mixture of mono-, di- and tripropylene glycol monomethyl ether and is 60 available from Dow Chemical Co.

(2) See note 3 Table 1.

The formulation is ground for about one hour to reduce the particle size of the suspended builder salts to less than 40 microns. The formulated detergent composition is found to be stable and non-gelling storage and readily dispersible in water to form a high stable foam in an 65 GB2194955A 10 aqueous wash.

EXAMPLE 3

A high foam concentrated nonaqueous liquid nonionic surfactant detergent composition was formulated from the following ingredients in the amounts specified as set out in Table 3 below. 5 TABLE 3

Ingredients Weight % C,-C,, alkyl (CHCH20),OH(l). 36.4 10 Sodium tripolyphosphate (TPP Thermos NW). 29.0 Anti-incrustation agent (Sokalan CP5) 4.0 Diethylene glycol monobutylether anti-gel agent(2). 12.1 15 Phosphoric Acid Alkanol Ester (Empiphos 5632). 0.3 Sodium perborate monohydrate bleaching agent. 9.0 Tetraacetylethylene diamine (TAED) 20 bleaching agent. 4.5 Sequestering agent for bleach (Dequest 2066). 1.0 Anti-redeposition agent (Relatin DM 4050).(3). 1.0 25 Optical brighteners (Stilbene 4). 0.5 Enzyme (Esperase 8.0 slurry). 1.0 Duet 787(4). 0.6 100.0 30 Notes on Table 3 (1) See note 1 Table 1.

(2) See note 2 Table 1.

(3) See note 3 Table 1.

(4) Duet 787 is a fragrance and is available from IFF, Inc.

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 gel on dilution in water at 50C.

The formulation is ground for about 1 hour to reduce the particle size of the suspended 40 builder salts to less than 40 mirons. The formulated detergent composition is found to be stable and non-gelling in storage and readily. dispersible in water and to form a high stable foam in an aqueous wash. During a miniwascator at a temperature of up to 60C washing cycle the foam raised up to the dispenser, even in the presence of soil.

The formulations of Examples 1, 2 and 3 can be prepared without grinding the builder salts and suspended solid particles to a small particle size, but best results are obtained by grinding the formulation to re duce the particle size of the suspended solid particles.

The builder salts can be used as provided or the builder salts and suspended soli particles can be ground or partially ground prior to mixing them with the nonionic surfactant. The grinding can be carried out in part prior to mixing and grinding completed after mixing or the entire grinding 59 operation can be carried out after mixing with the liquid surfactant. The formulations containing suspended builder and solid particles less than 40 microns in size are preferred.

It is understood that the foregoing detailed description is given merely by way of illustration and that variations may be made therein without departing from the spirit of the invention.

Claims (17)

1. A high foam nonionic liquid surfactant detergent composition which comprises C,-C,, alkyl (CH,CH,O),OH as the main nonionic surfactant detergent constituent.

2. A composition as claimed in Claim 1 in which the composition comprises a viscosity control and anti-gel agent.

3. A detergent composition as claimed in Claim 1 in which the composition comprises an alkylene glycol monalkyl ether viscosity control and anti-gel agent.

4. A composition as claimed in any one of Claims 1 to 3 in which the composition corn prises a suspension of insoluble inorganic detergent builder salt.

5. A composition as claimed in Claim 4 in which the insoluble inorganic builder salt corn- 65 11 GB2194955A 11 prises an alkali metal phosphate.

6. A composition as claimed in Claim 5 in which the inorganic builder salt comprises 10 to percent of an alkali metal polyphosphate detergent builder salt.

7. A detergent composition as claimed in any one of Claims 1 to 6 comprising one or more detergent adjuvants selected from the group consisting of anti- incrustation agent, bleaching 5 agent, bleach activator, sequestering agent, anti-redeposition agent, optical brightener, enzymes and perfume.

8. A composition as claimed in any one of Claims 1 to 7 in which the composition corn prises 10 to 60 percent of a nonionic liquid surfactant detergent.

9. A detergent composition as claimed in any one of Claims 1 to 8 comprising 5 to 30 10 percent of an alkylene glycol mono-alkyl ether.

10. A composition as claimed in Claim 4 or any one of Claims 5 to 9 when dependant on Claim 4 in which the inorganic builder salt has a particle size of less than 40 microns.

11. A composition as claimed in any one of Claims 1 to 10 which contains from about 0. 1 to about 0.5 percent by weight, based on the total composition, of a phosphoric acid alkanol 15 ester anti-settling stabilizing agent.

12. A nonaqueous heavy duty, built laundry detergent composition which is pourable at high and low temperatures and does not gel when mixed with cold water, the said composition comprising Cg-Cl, alkyl (CH2CH20)50H liquid nonionic surfactant in an amount of from about 10 to about 20 percent by weight; at least one inorganic detergent builder salt suspended in the nonionic surfactant in an amount of from about 10 to about 60 percent by weight; and a compound of the formula 11 R2 1 R1O(CHCH20W where RI represents a C2_CI alkyl group, R2 represents a hydrogen atom or a methyl group and 30 n is a number having an average value in the range of from about 1 to 6, as a gel inhibiting additive in an amount up to about 5 to 30 percent by weight.

13. A detergent composition as claimed in Claim 12 which optionally contains one or more detergent adjuvants selected from the group consisting of anti- incrustation agent, bleaching agent, bleach activator, sequestering agent, anti-redeposition agent, optical brightener, enzyme 35 and perfume.

14. A nonaqueous liquid heavy duty laundry detergent composition as claimed in Claim 12 or Claim 13 which comprises in weight percent:

C,-C,l (CH2CH20),OH nonionic surfactant in an amount of about 20-50; Sodium tripolyphosphate (TPP) in an amount of about 15-50; Copolymer of polyacrylate and polymaleic anhydride sodium salt in an amount of about 2-8; Diethylene glycol monoalkylether in an amount of about 5-20; Phosphoric acid alkanol ester in an amount of about 0-0.75; Sodium perborate monohydrate bleaching agent in an amount of about 2-20; ond Tetraacethylethylene diamine (TEAD) in an amount of about 1-10.

15. A nonaqueous liquid heavy duty laundry detergent composition as claimed in Claim 12 which comprises in weight percent:

C9-C1, alkyl (CH2CH20),OH nonionic surfactant in an amount of about 30-40; Sodium tripolyphopphate in an amount of about 25-35; Copolymer of polyacrylate and polymaleic anhydride sodium salt in an amount of about 3-5; 50 Diethylene glycol monobutylether in an amount of about 5-15; Phosphoric acid alkanol ester in an amount of about 0.2-0.5; Sodium perborate monohydrate bleaching agent in an amount of about 5-15; Tetraacetylethylene diamine (TEAD) bleach activator in an amount of about 2-6.0; Sequestering agent for bleach in an amount of about 0.75-1.25; and Anti-redeposition agent in an amount of about 0.5-1.5.

16. A composition as claimed in Claim 1 substantially as specifically described herein with reference to the accompanying examples.

17. A method for cleaning soiled fabrics which comprises contacting the soiled fabrics with a detergent composition as claimed in any one of Claims 1 to 16.

Published 1988 at The Patent Office, State House, 66/71 High Holborn, London WC 1 R 4TP. Further copies may be obtained from The Patent Office, Sales Branch, St Mary Cray, Orpington, Kent BR5 3RD. Printed by Burgess & Son (Abingdon) Ltd. Con. 1/87.