GB2194536A - Polyether surfactants used in nonaqueous liquid nonionic laundry detergent compositions - Google Patents

Description

1 GB2194536A 1

SPECIFICATION

Nonaqueous liquid nonionic laundry detergent composition and method of use This invention relates to nonaqueous liquid fabric treating compositions. This invention particu- 5 larly relates to nonaqueous liquid laundry detergent compositions containing a suspension of builder salt in nonionic surfactants which compositions are stable against phase separation and gelation and are easily pourable and to the use of these compositions for cleaning soiled fabrics.

More particularly this invention relates to nonionic surfactant detergent compositions in which the nonionic surfactant is highly biodegradable. 10 Liquid nonaqueous heavy duty laundry detergent compositions are well known in the art. For instance, compositions of that type may comprise a liquid nonionic surfactant in which are 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.

The washing power of synthetic nonionic surfactant detergents in laundry detergent compo- 15 sitions can be increased by the addition of builders.

Liquid detergens 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 concentrated solutions or dispersions to soiled areas on garments to be laundered and are non- 20 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 solid particles, liquid detergents often have certain inherent disadvantages too, which have to be 25 overcome to produce acceptable commercial detergent products. Thus, some such products exhibit a low degree of biodegradability, separate out on storage, have a high pour point temperature, foam excessively in use, 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 30 standing.

The conventionally produced and commercially available synthetic nonionic surfactant deter- gents generally contain only polyethoxy groups. Though some of the conventionally used no nionic surfactants contain both polyethoxy and polypropoxy groups. The propoxy groups, how ever, are usually present in only minor amounts. The ethoxy and propoxy groups are generally 35 randomly disiributed in the ethoxy propoxy chain attached to the fatty alcohol and the ethoxy group is genE!rally attached to the alkyl group of the fatty alcohol.

The biodegradability of the conventionally used'nonionic surfactants vary to a wide degree depending on the presence of the propoxy group and the location of the propoxy group, and the location and distribution in the polyalkoxy chain of the propoxy and ethoxy group constituents of 40 the chain.

Applicants found, for example, that a nonionic surfactant of the formula R-(OC,H4)y(OC2H,),OH, 45 that is where the polyethoxy group was attached to the alkyl group of the fatty alcohol and the polypropoxy group was attached to the hydroxy group that the surfactant was only about 20 percent or less biodegradable.

Applicants on the other hand unexpectedly found that when the nonionic surfactant had the formula 50 R-(OC3H6)x(OC2H4)YOH that is, when the polypropoxy group was attached to the alkyl group of the fatty alcohol and the polyethoxy group was attached to the hydroxy group that the surfactant was at least 60 percent 55 and usually at least 80 percent biodegradable. Some specific nonionic surfactants of the present invention were found to be 90 to 100 percent biodegradable.

The biodegradability of the nonionic surfactants of the present invention. is determined by OECD screening method.

In addition to the problems of low biodegradability, and settling or phase separation the 60 nonaqueous liquid laundry detergents based on liquid nonionic surfactants suffer from the drawback that the nonionics 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 65 2 G132 194536A 2 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 wash cycles, eventually requiring the user to 5 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 or fabrics which can shrink in warm or hot water.

The tendency of concentrated detergent compositions to gel during storage is aggravated by 10 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 builder-free compositions have been proposed, for example, by 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. 15 3,953,380), alkali metal formates and adipates (see U.S.P. 4,368,147), hexyiene glycol, poly ethylene glycol, etc. and nonionic structure modification and optimization. As an example of nonionic surfactant modification one particularly successful result has been achieved by acidifying the hydroxyl moeity end group of the nonionic molecule. The advantages of introducing a carboxylic acid at the end of the nonionic include gel inhibition upon dilution; decreasing the 20 nonionic pour point; and formation of an anionic surfactant when neutralized in the washing liquor. Nonionic structure optimization has centred on the chain length of the hydrophobic lipophilic moiety and the number and make-up of alkylene oxide (e.g. ethylene oxide) units of the hydrophilic, moiety. For example, it has been found that a CM fatty alcohol ethoxylated with 8 moles of ethylene oxide presents only a limited tendency to gel formation. 25 Nevertheless, improvements are desired in the biodegradability, stability and gel inhibition of non-aqueous liquid fabric treating compositions.

In accordance with the present invention a concentrated highly biodegradable, nonaqueous liquid laundry detergent composition is prepared'by using as a principle surfactant a propoxylated ethoxylate fatty alcohol in which the propylene oxide groups are adjacent to the alkyl and the 30 ethylene oxide groups are adjacent to the hydroxy group.

Applicants unexpectedly found that when the propylene oxide groups were adjacent to the alkyl R group and the ethylene oxide groups were at the end of the molecule adjacent to the OH group that the nonionic surfactant was highly biodegradable, e.g. more than 80 percent biode gradable. On the other hand, applicants found that when the ethylene oxide groups were 35 adjacent to the alkyl R group and the propylene oxide groups were at the end of the molecule adjacent to the OH group that the nonionic surfactant exhibited a low degree of biodegradability, e.g. less than 20 percent biodegradable.

The highly biodegradable propoxylated ethoxylated fatty alkyl alcohol nonionic surfactants of the present invention have the general formula 40 R-PC31-16),(OC,H4)y0H wherein R represents a C, to C,, alkyl, preferably C, to C, alkyl, x+y equals 20 to 100 percent, preferably 40 to 80 percent of the number of carbon atoms of the alky], x is at least one, 45 preferably at least 2, and y is at least one, preferably at least 2.

The propoxylate ethoxylate fatty alcohol nonionic surfactants of the present invention are at least 60 percent, preferably at least 80 percent biodegradable. The propoxylated ethoxylated fatty alcohol nonionic surfactants of the present invention can be used as the only nonionic surfactant detergent or it can be used in mixtures with the conventional commercially available 50 nonionic surfactants. It is preferred that the propoxylated ethoxylated fatty alcohol nonionic surfactant comprise at least 50 percent and more preferably at least 70 percent of the nonionic surfactants used in the detergent composition.

In order to improve the viscosity characteristics of the composition an acid terminated nonionic surfactant can be added. To further improve the viscosity characteristics of the composition and 55 the storage properties of the compositions there can be added to the composition viscosity improving and anti-gel agents such as alkylene glycol mono alkyl ethers and anti-settling agents such as phosphoric acid esters and aluminium stearate. In preferred embodiments of the inven tion the detergent composition contains an acid terminated nonionic surfactant and/or an alky lene glycol mono alkyl ether, and an anti-settling agent. 60 Sanitizing or bleaching agents and activators therefore can be added to improve the bleaching and cleansing characteristics of the composition.

In an embodiment of the invention the builder components of the composition are ground to a particle size of less than100 microns and to preferably less than 10 microns to further improve the stability oythe suspension of the builder components in the liquid nonionic surfactant 65 3 GB2194536A 3 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.

The presently manufactured washing machines for home use normally operate at washing temperatures of up to 1000C. Up to 18.5 gallons (70 litres) of water are used during the wash 5 and rinse cycles.

About 175 gms of powder detergent per wash is normally used.

In accordance with the present invention there is provided a liquid heavy duty laundry deter- gent composition comprising a highly biodegradable nonionic surfactant which surfactant consists of propoxylated ethoxylated fatty alkyl alcohol in which the propylene oxide groups are attached 10 to the alkyl and the ethylene oxide groups are attached at one end to the terminal propylene oxide group and at the other end to the hydroxy group.

Accordingly, in one aspect of the present invention there is provided a liquid heavy duty detergent composition composed of a suspension of a builder salt in the liquid nonionic surfac tant. 15 According to another aspect, the invention provides a liquid heavy duty laundry detergent composition in which the nonionic surfaGtant is highly biodegradable, the composition 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.

According to another aspect, the invention provides a method for dispensing a highly biode- 20 gradable liquid nonionic laundry detergent composition into and/or with cold water without undergoing gelation. In particular, a method is provided for filling a container with a nonaqueous liquid laundry detergent composition in which the detergent is composed, at least predominantly, of a highly biodegradable liquid nonionic surface active agent of the present invention and for - dispensing the composition from the container into an aqueous wash bath, wherein the dispens- 25 ing is effected by directing a stream of unheated water onto the composition such that the composition is carried by the stream of water into the wash bath.

The liquid heavy duty laundry detergent compositions of the present invention have substan- tially improved biodegradability because they comprise as a principle essential constituent of the compositions a propoxylated ethoxylated fatty alcohol in which the propylene oxide groups are 30 attached to the alkyl and the ethylene oxide groups are attached to the hydroxy group.

The compositions of the present invention have the advantages of having a low pouring temperature, being nongelling in contact with water, being nonfoaming and having good deter gency performance.

The propoxylated ethoxylated fatty alcohol nonionic surfactants of the present invention exhibit 35 a high degree of biodegradability, e.g. they are more than 80 percent biodegradable, they are low foaming in use, they exhibit a low pour point, e.g. -2'C and they are nongelling in contact with water at 5'C. The nonionic surfactant of the present invention also exhibit good detergency performance.

The concentrated nonaqueous liquid nonionic surfactant laundry detergent compositions of the 40 present invention have the added 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 laundry washing machines.

The present invention aims to provide a highly biodegradable propoxylated ethoxylated fatty alcohol nonionic surfactant detergent in which the propylene oxide groups are attached to the 45 alkyl group and the ethylene oxide groups are attached to the hydroxy group.

The invention also aims to provide liquid fabric treating compositions which are suspensions of builder salt in the propoxylated ethoxylated fatty alcohol surfactant which are storage stable, easily pourable and dispersible in cold, warm or hot water.

This invention also aims to formulate built heavy duty nonaqueous liquid nonionic surfactant 50 laundry detergent compositions which contain the propoxylated ethoxylated fatty alcohol nonioniG as the principle nonionic surfactant and 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 foul or plug the dispenser even during the winter months. 55 This invention also aims to provide low foaming, nongelling, stable suspensions of heavy duty built nonaqueous liquid nonionic laundry detergent compositions which include as the principle surfactant the propoxylated ethoxylated fatty alcohol surfactants of the present invention.

The non-gelling, stable suspensions of heavy duty built nonaqueous liquid nonionic laundry detergent compositions of the present invention may include an amount of phosphoric acid 60 alkanol ester and/or aluminium fatty acid salt anti-settling agent which is sufficient to increase the stability of the composition, i.e. prevent settling of builder particles, etc., preferably while reducing or at least without increasing the plastic viscosity of the composition.

These and other objects of the invention which will become more apparent from the following detailed description of preferred embodiments are generally provided for by preparing a deter-

4 GB2194536A 4 gent composition by adding to the nonaqueous liquid nonionic surfactant of the present invention an effective amount of a builder salt and inorganic or organic fabric treating additives, e.g.

viscosity improving and anti-gel agents, anti-settling agents, antiincrustation agents, bleaching agents, bleach activators, anti-foam agents, optical brighteners, enzymes, anti-redeposition agents, perfume and dyes. 5 The highly biodegradable propoxylated ethoxylated fatty alkyl alcohol nonionic surfactants of the present invention have the general formula R-(OC3H6MOC2HJy0H 10 wherein R represents C. to C2, alkyl, preferably C, to C, alkyl, and more preferably Q, to C, and C12 to C, alky]. The value of the integers x+y equal 20 to 100 percent, preferably 40 to percent and more preferably 45 to 60 percent of the number of carbon atoms of the R alkyl.

The value of x is at least 1 and preferably at least 2 and more preferably x is 3 or more.

The propoxylated ethoxylated fatty alcohol nonionic surfactants of the present invention are at 15 least 60 percent, preferably at least 80 percent and more preferably at least 90 percent biodegradable.

The highly biodegradable nonionic synthetic organic detergents of the present invention are produced by (1) the condensation of a fatty aliphatic alcohol with propylene oxide or polypropyl ene glycol followed by (2) further reaction of the first condensation product obtained with 20 ethylene oxide or polyethylene glycol.

The fatty alkyl alcohol reacts with the propylene oxide or polypropylene glycol to attach a linear low molecular weight, e.g. x=2 to 15, preferably 2 to 8, and more preferably 3 to 6, chain of propylene oxide polymer. The propylene oxide chain normally attaches to the alkyl group at a primary or secondary carbon of the fatty alcohol. The fatty alcohol propylene oxide 25 condensate is then reacted with ethylene oxide or polyethylene glycol to add the desired number of ethylene oxide groups. The ethylene oxide groups normally join or attach to the terminal propylene oxide group and condense to form a low molecular weight, e.g. y=2 to 15, prefera bly 2 to 8, and more preferably 3 to 6, chain of ethylene oxide polymer terminated by the hydroxy group. 30 By carrying out separate propylene oxide and ethylene oxide condensation reactions a low molecular weight linear propylene oxide polymer attaches to the primary or secondary carbon atom of the fatty alcohol and a low molecular weight linear ethylene oxide polymer attaches to the terminal propylene oxide molecule. The end of the ethylene oxide polymer chain has a hydroxy group. 35 The highly biodegradable nonionic surfactant detergents of the present invention are polypro- poxylate ethoxylated lipophiles wherein the desired hydrophile lipophile balance is obtained from the addition of the hydrophilic polypropoxy polyethoxy groups to the lipophilic aliphatic moiety.

A preferred class of the nonionic detergents are the C, to C, fatty alkyl alcohols which contain 4 to 16 propylene oxide and ethylene oxide groups, i.e. x+y=4 to 16. Other classes of 40 the nonionic detergents are the C, to C, fatty alkyl alcohols in which x+ y=5 to 10, and the C12 to C, fatty alkyl alcohols in which x+y=5 to 15.

The higher molecular weight C11-C16 fatty alkyl alcohol propylene oxide ethylene oxide conden- sates, exhibit a high degree of biodegradability but tend to more easily form gels in the detergent concentrate and in some instances may be solids at room temperature. Though the 45 Cl,_C26 surfactants may contribute to gelation of the liquid detergent they can, if desired, be added to the detergent composition in small amounts, this is particularly true where low gel forming concentrates are not needed.

In the preferred polylower alkoxylated higher alkanols, to obtain the best balance of hydrophilic and lipophHic moieties the number of lower alkoxies, i.e. the sum of x+y, will usually be from 50 to 100 percent of the number of carbon atoms in the higher alcohol, preferably 40 to 80 percent and more preferably 45 to 60 percent thereof. The nonionic surfactant detergent compo ent of the composition will preferably contain at least 50 percent, preferably at least 70 percent of the highly biodegradable nonionic surfactant of the present invention.

Suitable highly biodegradable propoxylated ethoxylated fatty alkyl alcohols of the present 55 invention are as follows:

GB2194536A 5 R-(C03H,)x(OC2H4),OH R X y 1 - ci-C,5 3 5 2. C127C11 5 4 3. C,-C,, 3 5 4. Cg-C 11 2 4 5. C,-C,, 3 6 10 6. C,-C,, 2 4 With respect to both the preferred C,-C,, and less preferred CE,_C2r, nonionic detergents the alkyl groups present therein are generally linear although a small amount of branching may be tolerated, such as at a carbon next to or two carbons removed from the terminal carbon of the 15 straight chain and away from the propoxy chain, if such branched alkyl is not more than three carbons in length. Normally the proportion of carbon atoms in such a branched configuration will be minor, e.g. less than 20 percent of the total carbon atom content of the alkyl. Similarly although linear alkyls which are terminally joined to the propoxy chains are highly preferred and are considered to result in the best combination of detergency, biodegradability and nongelling 20 characteristics, media] or secondary joinder of the alkoxy, i.e. propoxy chains to the alkyl may occur. It is usually present, i.e. the branch chain alky], in only a minor proportion of such alkyls, e.g. generally less than 20 percent thereof and preferably less than 10 percent thereof.

The propoxylated ethoxylated fatty alkyl alcohol nonionic surfactants of the present invention can be used as the only nonionic surfactant detergent or it can be used in mixtures with the 25 conventional commercially available nonionic surfactant detegents. The propoxylated ethoxylated fatty alcohol nonionic surfactant of the present invention can comprise 40 to 100 percent, preferably 50 to 100 percent and more preferably 70 to 100 percent of the nonionic surfactant component of the detergent composition.

The conventional nonionic synthetic organic detergents that can be used with the highly 30 biodegradable propoxylated ethoxylated fatty alcohol surfactants of the present invention may be any of a wide variety of such compounds, which are well known. Typical suitable nonionic surfactants are those disclosed in U.S. Patent 4,316,812 and 3,630,929.

Usually, the nonionic detergents are poly-lower alkoxylated lipophiles wherein the desired hydrophile-lipophile balance is obtained from addition of a hydrophilic poly-lower alkoxy group to 35 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 mols 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 5 to 8 or 5 to 9 lower alkoxy groups 40 per mol. Preferably, the lower alkoxy is ethoxy but in some instances, it may be desirably mixed with propoxy.

Exemplary of such compounds are those wherein the alkanol is of 12 to 15 carbon atoms and 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 Chemical Company, Inc. The former is a condensation product 45 of a mixture of higher fatty alcohols averaging about 12 to 15 carbon atoms, with about 7 mols 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 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 50 which are linear secondary alcohol ethoxylates made by Union Carbide Corp. The former is mixed ethoxylation product of 11 to 15 carbon atoms linear secondary alkanol with seven mols of ethylene oxide and the latter is a similar product but with nine mols of ethylene oxide being reacted.

Also useful in the present composition as a component of the nonionic detergent are higher 55 molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensa tion products of higher fatty alcohols, with the higher fatty alcohol being of 14 to 15 carbon atoms and the number of ethylene oxide groups per mol being about 11. Such products are also made by Shell Chemical Company.

Other useful nonionics are represented by the commercially well known class of nonionics sold 60 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 of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include Product A (a C,,-C,, fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide), Product B (a C,,-C,, fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide), 65 6 GB2194536A 6 Product C (a C13-Cl. fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide, Plurafac B26), and Product D (a mixture of equal parts Product C and Product B).

Another group of liquid nonionics are commercially available from Shell Chemical Company, Inc. under the Dobanol trademark: Dobanol 91-5 is a ethoxylated C,,-C,, fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C,,- C,. fatty alcohol 5 with an average of 7 moles ethylene oxide per mole of fatty alcohol.

When greater proportions of non-terminally alkoxylated alkanols, propylene oxide-containing poly-lower alkoxylated alkanols and less hydrophile-lipophile balanced nonionic detergent than mentioned above are employed and when other nonionic detergents are used instead of the preferred nonionics recited herein, the product resulting may not have as good detergency, 10 stability, viscosity and non-gelling properties as the preferred compositions but use of the viscosity and gel controlling compounds of the invention can also improve the properties of the detergents based on such nonionics. In some cases, as when a higher molecular weight poly lower alkoxylated higher alkanol is employed, often for its detergency, the proportion thereof will be regulated or limited in accordance with the results of routine experiments, to obtain the 15 desired detergency. and still have the product non-gelling and of desired viscosity. Also, it has been found that it is only rarely necessary to utilize the higher molecular weight nonionics for their detergent properties since the preferred nonionics described herein are excellent detergents and additionally, permit the attainment of the desired viscosity in the liquid detergent without gelation at low temperatures. 20 Another useful group of nonionic surfactants are the -Surfactant T- series of nonionics -available from British Petroleum. The Surfactant T nonionics are obtained by the ethoxylation of secondary C,, fatty alcohols having a narrow ethylene oxide distribution. The Surfactant T5 has 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 25 12 moles of ethylene oxide per mole of secondary C13 fatty alcohol.

In the compositions of this invention, preferred conventional nonionic surfactants include the C13-C15 secondary fatty alcohols with relatively narrow contents of ethylene oxide in the range of from about 7 to 9 moles, and the C. to C,, fatty alcohols ethoxylated with about 56 moles ethylene oxide. 30 Mixtures of two or more of the conventional liquid nonionic surfactants can be used with the highly biodegradable propoxylated ethoxylate fatty alcohol surfactant of the present invention and in some cases advantages can be obtained by the use of such mixtures.

The viscosity and gel properties of the liquid detegent compositions canbe improved by including in the composition an effective amount of an acid terminated liquid nonionic surfactant. 35 The acid terminated nonionic surfactants consist of a nonionic surfactant which has been modi fied to convert a free hydroxyl group thereof to a moiety having a free carboxyl group, such as an ester or a partial ester of a nonionic surfactant and a polycarboxylic acid or anhydride.

As disclosed in the commonly assigned copening application Serial No. 597,948 filed April 9, 1984, corresponding to GB Application No. 8509084 Serial No. 2158454, the disclosure of 40 which is incorporated herein by reference, the free carboxyl group modified nonionic surfactants, which may be broadly characterised as polyether carboxylic acids, function to lower the tempera ture at which the liquid nonionic forms a gel with water.

The addition of the acid terminated nonionic surfactants to the liquid nonionic surfactant aids in the dispensibility of the composition, i.e. pour-ability, and lowers the temperature at which the 45 liquid nonionic surfactants form a gel in water without a decrease in their stability against settling. The acid terminated nonionic surfactant reacts in the washing machine water with the alkalinity of the dispersed builder salt phase of the detergent composition and acts as an effective anionic surfactant.

Specific examples include the half-esters of Product A with succinic anhydride, the ester or 50 half ester of DobanoV25-7 with succinic anhydride, and the ester or half ester of Dobanol 91-5 with succinic anhydride. Instead of succinic anhydride, other polycarboxylic acids or anhydrides can be used, e.g. maleic acid, maleic acid anhydride, citric acid and the like.

The acid terminated nonionic surfactants can be prepared as follows:

Acid Terminated Product A. 400 9 of Product A nonionic surfactant which is a C13 to C15 55 alkanol which has been alkoxylated to introduce 6 ethylene oxide and 3 propylene oxide units per alkanol unit is mixed with 32 9 of succinic anhydride and heated for 7 hours at 100'C. The mixture is cooled andfiltered to remove unreacted succinic material. Infrared analysis indicated - that about one half of the nonionic surfactant has been converted to the acidic half-ester thereof.

Acid Terminated Dobanol 25-7. 522 9 of Dobanol 25-7 nonionic surfactant which is the 60 product of ethoxylation of a C12 to C,, alkanol and has about 7 ethylene oxide units per molecule of alkanol is mixed with 100 9 of succinic anhydride and 0. 1 9 of pyridine (which acts as an esterification catalyst) and heated at 260'C for 2 hours, cooled and filtered to remove unreacted succinic material. Infrared analysis indicates that substantially all the free hydroxyls of the surfac tant have reacted. 65 7 GB2194536A 7 Acid Terminated Dobanol 91-5. 1000 g of Dobanol 91-5 nonionic surfactant which is the product of ethoxylation of a C9 to C11 alkanol and has about 5 ethylene oxide units per molecule of alkanol is mixed with 265 g of succinic anhydride and 0.1 g of pyridine catalyst and heated at 260'C for 2 hours, cooled and filtered to remove unreacted succinic material. Infra-red analysis indicates that substantially all the free hydroxyls of the surfactant have reacted. 5 Other esterification catalysts, such as an alkali metal alkoxide (e.g. sodium methoxide) may be used in place of, or in admixture with, the pyridine.

The acidic polyether compound, i.e. the acid terminated nonionic surfactant is preferably added dissolved in the nonionic surfactant.

The liquid nonaqueous nonionic surfactant used in the compositions of the present invention 10 has dispersed and suspended therein fine particles of organic and/or inorganic detergent builder salts.

The preferred organic builder salts comprises alkali metal salts of polyacetal carboxylic acid and alkali metal alphahydroxy acrylic acid polymer as disclosed in US Serial Nos. 767,570 and 767635 corresponding to GB Application No. 8619793, Serial No. 2179365, alkali metal salts 15 of lower polycarboxylic acids as disclosed in US Serial No. 762,165, corresponding to GB Application No. 8618858, Serial No. 2180551 and alkali metal salts of nitilotriacetic acid (NTA) as disclosed in US Serial No. 762,164, corresponding to GB Application No. 8618887, Serial No.2178754.

In certain detergent compositions the aforementioned organic builder salts can be used as the 20 principle builder salt and can be used without the addition of an inorganic builder salt, such as polyphosphate builder salt, or with only a small amount of a polyphosphate builder salt, or the polyphosphate can be the principle builder salt.

Other organic builders that can be used are polymers and copolymers of polyacrylic acid and polymaleic anhydride and the alkali metal salts thereof. More specifically such builder salts can 25 consist of a copolymer which is the reaction product of about equal moles of methacrylic acid and maleic anhydride which has been completely neutralized to form the sodium salt thereof.

The builder is commercially available under the tradename of Sokalan CP5. This builder serves when used even in small amounts to inhibit encrustation, i e. as an anti- encrustation agent.

Since the compositions of this invention are generally highly concentrated, and, therefore, may- 30 be used at relatively low dosages, it is desirable to supplement the builder with an auxiliary builder such as an alkali metal lower polycarboxylic acid having high calcium and magnesium binding capacity to inhibit encrustation which could otherwise be caused by formation of insol uble calcium and magnesium salts. Suitable alkali metal polycarboxylic acids are alkali metal salts of citric and tartaric acid, e.g. monosodium citrate (anhydrous), trisodium citrate, glutaric acid 35 salt, gluconic acid salt and diacid salt with longer chain.

Examples of organic alkaline sequestrant builder salts which can be used or which can be used in admixture with other organic and inorganic builders are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, e.g. sodium and potassium ethylene diaminetetraacetate (EDTA), sodium and potassium nitriloacetates (NTA) and triethanolammonium N-(2-hydroxyethyl)- 40 nitrilodiacetates. Mixed salts of these aminopolycarboxylates are also suitable.

Other suitable builders of the organic type include carboxymethylsuccinates, tartronates and glycollates.

The detergent composition s of the present invention can also include inorganic water soluble and/or water insoluble detergent builder salts. Suitable inorganic alkaline builder salts that can be 45 used are alkali metal carbonates, borates, bicarbonates, and silicates. (Ammonium or substituted ammonium salts can also be used.) Specific examples of such salts are sodium carbonate, sodium tetraborate, sodium bicarbonate, sodium sesquicarbonate and potassium bicarbonate.

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. Sodium silicates of 50 Na20/SiO2 ratios of from 1.6/1 to 1/3.2, especially about 1/2 to 1/2.8 are preferred. Potassium silicates of the same ratios can also be used. The preferred alkali metal silicate is sodium disilicate.

Though the detergent composition can be phosphate or polyphosphate free or substantially polyphosphate free, small amounts of the conventional polyphosphate builder salts can be added 55 where the local legislation permits such use. Specific examples of such builder salts are sodium tripolyphosphate (TPP), sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphos phate and sodium hexametaphosphate. The sodium tripolyphosphate (TPP) is a preferred poly phosphate. In the formulations where the polyphosphate is added it is added in an amount of 0 to 50%, such as 0 to 30% and 5 to 15. As mentioned previously, however, the formulations 60 can be polyphosphate free or substantially polyphosphate free.

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 alkaline builder salts can be used with the nonionic surfactant detergent compound or in admixture with other organic or inorganic builder salts, The water insoluble crystalline and amorphous aluminosilicate zeolites can be used. The zeol- 65 8 GB2194536A 8 ites generally have the formula (M20)x I (AI203)y - (SiOl. wH20 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 5 preferably 2 to 3 and w 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/g.

10, Various crystalline zeolites (i.e. aluminosilicates) that can be used are described in British 10 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 useful 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 15 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 form (i.e. free from any grit, sand, etc.) suitable for detergents contains at least 50% montmoril- 20 lonite and thus its cation exchange capacity is at least about 50 to 75 meq per 100 g 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 to Marriott and Duggan. 25 The inclusion in the detergent composition of an effective amount of low molecular weight amphiphilic compounds which function as viscosity control and gel- inhibiting agents for the nonionic surfactant substantially improves the storage properties of the composition. The amphi philic 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 hydrocar- 30 bon chain lengths (C, to C,) and a low content of ethylene oxide (about 2 to 6 ethylene oxide groups per molecule).

Suitable amphiphilic compounds can be represented by the following general formula RO(CH2CH2O)nH, 35 where R is a C2_C, alkyl 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 (C, to CJ alkyl ethers.

More specifically the compounds are mono di- or tri-lower (C2 to CI) alkylene glycol mono 40 lower (C, to C,) alkyl ethers.

Specific examples of suitable amphiphilic compounds include ethylene glycol monoethyl ether (C,H,-O-CH2CH2OH), diethylene glycol monobutyl ether (C,H,-O-(CH2CH2O)2H), tetraethylene glycol monobutyl ether 45 (C4H,-O-(CH2CH2O)4H) and dipropylene glycol monomethyl ether 50 CH,-O-:-(CH2CHO)2H.

CH3 Diethylene glycol moqobutyl ether is especially preferred. 55 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 improved viscosity and stability characteristics 60 and remain stable and pourable at temperatures as low as about 5"C and lower.

In an embodiment of this invention the physical stability of the suspension of the detergent builder compound or compounds and any other suspended additive, such as bleaching agent, etc., in the liquid vehicle is improved by the presence of a stabilizing agent which is an alkanol ester of phosphoric acid or an aluminium salt of a higher fatty acid. 65 9 GB2194536A 9 Improvements in stability of the composition may be achieved in certain formulations by incorporation of a small effective amount of an acidic organic phosphorus compound having an acidic -POH group, such as a partial ester of phosphorous acid and an alkanol.

As disclosed in the commonly assigned copending application Serial No. 597,948 filed April 9, 1984 corresponding to GB Application No. 8509084, Serial No. 2158454, the disclosure of 5 which is incorporated herein by reference, the acidic organic phosphorus compound having an acidic -POH group can increase the stability of the suspension of builders in the nonaqueous liquid nonionic surfactant.

The acidic organic phosphorus 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, 10 more than 5 carbon atoms, e.g. 8 to 20 carbon atoms.

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

The inclusion of quite small amounts of the acidic organic phosphorus compound makes the suspension significantly more stable against settling on standing but remains pourable, while, for 15 the low concentration of stabilizer, e.g. below about 1%, its plastic viscosity will generally decrease.

Further improvements in the stability and anti-settling properties of the composition may be achieved by the addition of a small effective amount of an aluminium salt of a higher fatty acid to the composition. 20 The aluminium salt stabilizing agents are the subject matter of the commonly assigned copend- ing application Serial No. 725,455 filed April 22, 1985, corresponding to GB Application No.

8604969, Serial No. 2172897, the disclosure of which is incorporated herein by reference.

The preferred higher aliphatic fatty acids will have from about 8 to about 22 carbon atoms, more preferably from about 10 to 20 carbon atoms, and especially preferably from about 12 to 25 18 carbon atoms. The aliphatic radical may be saturated or unsaturated and may be straight or branched. As in the case of the nonionic surfactants, mixtures of fatty acids may also be used, such as those derived from natural sources, such as tallow fatty acid, coco fatty acid, etc.

Examples of the fatty acids from which the aluminium salt stabilizers can be formed include, decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicosanoic 30 acid, tallow fatty acid, coco fatty acid, mixtures of these acids, etc. The aluminium salts of these acids are generally commercially available, and are preferably used in the triacid form, e.g.

aluminium stearate as aluminium tristearate (AI(C17H35C00)3. The monoacid salts, e.g. aluminium monostearate, (AI(OH)2(C17H35C00) and diacid salts, e.g. aluminium distearate, AI(O1-1)(CH35COO6 and mixtures of two or three of the mono-, di- and triacid aluminium salts 35 can also be used. It is most preferred, however, that the triacid aluminium salt comprises at least 30%, preferably at least 50%, especially preferably at least 80% of the total amount of aluminium fatty acid salt.

The aluminium salts, as mentioned above, are commercially available and can be easily pro- duced by, for example, saponifying a fatty acid, e.g. animal fat, stearic acid, etc., followed by 40 treatment of the resulting soap with alum, alumina, etc.

Although applicants. do not wish to be bound by any particular theory of the manner by which the aluminium salt fupctions to prevent settling of the suspended particles, it is presumed that the aluminium salt increases the wettability of the solid surfaces by the nonionic surfactant. This increase in wettability. therefore, allows the suspended particles to more easily remain in sus- 45 pension.

Only very small amounts of the aluminium salt stabilizing agent is required to obtain the significant improvements in physical stability.

In addition to its action as a physical stabilizing agent, the aluminium salt has the additional advantages over other physical stabilizing agents that it is nonionic in character and is compat- 50 ible with the nonionic surfactant component and does not interfere with the overall detergency of the composition; it exhibits some anti-foaming effect; it can function to boost the activity of fabric softeners, and it confers a longer relaxation time to the suspensions.

The bleaching agents are classified broadly, for convenience, as chlorine bleaches and oxygen bleaches. Chlorine bleaches are typified by sodium hypochlorite (NaOCi), potassium dichloroisocy- 55 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. 60 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---) 65 GB2194536A 10 and pentaacetyl glucoe 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, tetraacetylglycouril ("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. 5 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 sodium salts of nitrilotriacetic acid (NTA), 10 ethylene diamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DETPA); 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 15 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 20 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.

In addition to the detergent builders, various other detergent additives or adjuvants may be 25 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 anti-redeposition agents, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxy-propyl methyl cellulose. A preferred anti-redeposition agent is sodium carboxymethyl cellulose having a 30 2:1 ratio of CM/MC which is sold under the tradename Relatin DIVI 4050.

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 naphthotriazole stilbene, benzidene sulphone, etc., most preferred are stilbene and triazole combinations. Preferred brighteners are Stilbene Brightener N4 35 which is a dimorpholino dianilino stilbene sulphonate and Tinopal ATS-X which is well known in the art.

Enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papin, trypsin and pep- sin, as well as amylase type enzymes, lipase type enzymes, and mixtures thereof can be used.

Preferred enzymes include protease slurry, esperase slurry and amylase. A preferred enzyme is 40 Esperse SL8 which is protease. Anti-foam agents, e.g. silicon compounds, such as Silicane L 7604 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 buffersl colour safe bleaches, perfume, and dyes 45 and bluing agents such as ultramarine blue can be used.

The composition may also contain an inorganic insoluble thickening agent or dispersant of very 4 high surface area such as finely divided silica of extremely fine particle size (e.g. of 5-100 millimicrons diameters such as sold under the name Aerosil) or the other highly voluminous inorganic carrier materials disclosed in U.S.P. 3,630,929, in proportions of 0.1-10%, e.g. 1 to 50 5%. It is preferable, however, that compositions which form peroxyacids in the wash bath (e.g.

compositions containing peroxygen compound and activator therefor) be substantially free of such compounds and of other silicates; it has been found, for instance, that silica and silicates promote the undesired decomposition of the peroxyacid.

In an embodiment of the invention the stability of the builder salts in the composition during 55 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. alkali metal polyphos phates, 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 60 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. I micron). Preferably less than about 10%, especially less than 65 GB2194536A 11 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 aids in the dispersibility of the dispersions without a corresponding decrease in the dispersions stability against settling. 5 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 10 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 15 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 20 ingredients are as follows:

Highly biodegradable propoxylated ethoxylated fatty alkyl alcohol liquid nonionic surfactant detergent in the range of about 10 to 60, such as 20 to 50 and 30 to 40 percent; Acid terminated nonionic surfactant may be omitted, it is preferred however that it be added to the composition in an amount in the range of about 0 to 30, such as 5 to 25 and 5 to 15 25 percent; Organic builder salt in the range of about 0 to 50, such as 10 to 40 and 25 to 35 percent; Polyphosphate detergent builder salt in the range of about 0 to 50 percent, such as 0 to 30 and 5 to 15 percent; Copolymer of polyacrylate and polymaleic anhydride alkali metal salt antiencrustation agent in 30 the range of about 0 to 10, such as 2 to 8 and 2 to 6 percent; Alkylene glycol monoalkylether anti-gel agent in an amount in the range of about 0 to 20, such as 5 to 15 and 8 to 12 percent; Phosphoric acid alkanol ester stabilizing agent in the range of 0 to 2.0 or 0.1 to 1.0, such as 0. 10 to 0.5 percent; 35 Aluminium salt of fatty acid stabilizing agent in the range of about 0 to 3.0, such as 0. 1 to 2.0 and 0.5 to 1.5 percent; (it is preferred that at least one of phosphoric acid ester or aluminium salt stabilizing agents be included in the composition.) Bleaching agent in the range of about 0 to 35, such as 5 to 30 and 8 to 15 percent; 40 Bleach activator in the range of about 0 to 25, such as 3 to 20 and 4 to 8 percent; Sequestering agent for bleach in the range of about 0 to 3.0, preferably 0.5 to 2.0 and 0.5 to 1.5 percent; Anti-redeposition agent in the range of about 0 to 3.0, such as 0.5 to 2. 0 and 0.5 to 1.5 percent; 45 Optical brightener in the range of about 0 to 2.0, such as 0. 1 to 1.5 and 0.3 to 1.0 percent; Enzymes in the range of about 0 to 3.0, such as 0.5 to 2,0 and 0.5 to 1.5 percent; Perfume in the range of about 0 to 2.0, such as 0.10 to 1.0 and 0.5 to 1. 0 percent; Dye in the range of about 0 to 1.0, such as 0.0025 to 0.050 and 0.25 to 0. 0100 percent.

Various of the previously mentioned additives can optionally be added to achieve the desired 50 function of the added materials.

Mixtures of the acid terminated nonionic surfactant and the alkylene glycol alkyl ether anti-gel agents can be used and in some cases advantages can be obtained by the use of such mixtures alone, or with the addition to the mixture of a stabilizing and anti- settling agent, eg. phosphoric.

acid alkanol ester. 55 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 dispenses readily in the water in the washing machine. The presently used home washing 60 machines normally use 175 gms of powder detergent to wash a full load of laundry. In accordance with the present invention only about 77 m] or about 100 gms of the concentrated liquid nonionic detergent composition is needed.

In order to compare the physical properties of the propoxylatedethoxylated fatty alcohol nonionic surfactants of the present invention with the conventional commercially available no- 65 12 GB2194536A 12 nionic surfactants the below described comparative tests were carried out.

1. A nonionic surfactant of the formula R-(OC3H6MOC2H4),0H wherein R is C12-CI5, x equals 3 and y equals 5 is compared to Product D, with regard to the biodegradability of the respective surfactants. The Product D as described above is a mixture of equal parts of product B (a C13-C15 fatty alcohol condensed with 7 moles of propylene oxide and 4 moles of ethylene oxide) 5 and Product C (a C13-Cl. fatty alcohol condensed with 5 moles propylene oxide and 10 moles of ethylene oxide.

In the Product B surfactant the propylene oxide molecules are not attached to the alkyl portion of the surfactant structure.

In the Product C surfactant the propylene oxide molecules are not attached to the alkyl portion 10 of the surfactant structure.

The comparative biodegradability tests are carried out using the OECD screening method mentioned above. The tests show that the surfactant of the present invention is at least 90 percent biodegradable and that the Product D is less than 40 percent biodegradable. The biodegradable characteristics of the surfactant of the present invention are thus superior to those 15 of Product D.

2. The nonionic surfactants of the present invention exhibit low foaming characteristics in use. In order to demonstrate the low foaming characteristics the nonionic surfactant of the present invention of the above comparative test 1, was compared with the conventionally used Surfactant T 7/9. The Surfactant T 7/9 which was used was obtained by ethoxylating a 20 secondary C,3 fatty alcohol with an average of 7-9 ethylene oxide groups per mole of fatty alcohol. Conventional foaming tests are carried out.

The test results thus show that the nonionic surfactant of the present invention is low foaming as compared to the conventionally used Surfactant T 7/9 nonionic surfactant.

3. The nonionic surfactant of the present invention used in the above comparative test 1 is 25 compared to Surfactant T 7/9 to determine the pour point characteristics of each surfactant.

The pour point temperature in each case was determined by increasing slowly the temperature 2'C/minute. The pour point temperature is the temperature at which the nonionic begins to flow.

The comparative tests results show that the surfactant of the present invention exhibits a lower pouring temperature of -2'C as compared to the Surfactant T 7/9 which exhibits a 30 pouring temperature of +3'C.

4. In order to determine the gelling characteristics of the nonionic surfactant of the present invention of the above test 1, it was compared to Product D and Surfactant T 7/9. The test is carried out by contacting the respective surfactants with water at 5'C and measuring the viscosity concentration relationship. 35 The comparative tests show that the nonionic surfactant of the present invention does not gel in contact with water at 5'C (though an increase in viscosity of the surfactant is noted) whereas the Product D and the Surfactant T 719 on contact with water -at 5,C do gel.

In a preferred embodiment of the invention the detergent composition of a typical formulation is formulated using the below named ingredients: 40 Weight % Highly biodegradable propoxylated ethoxy- 30-40 lated fatty alkyl alcohol nonionic 45 surfactant detergent.

Acid terminated surfaOtant. 5-15 Sodium tripolyphosphte builder salt. 25-35 Anti-encrustation agent (Sokalan CP-5). 0-10 Organic builder salt. 0-30 50 Alkylene glycol monoalkyl ether. 8-12 Alkanol phosphoric acid ester (Empiphos 0.1_0.5 5632).

Anti-redeposition agent (Relatin DM 4050). 0-3.0 Alkali metal perborate bleaching agent. 8-15 55 Bleach activator (TAED). 4-8 Sequestering agent (Dequest 2066). 0-3.0 Optical brightener (ATS-X). 0.3-1.0 Enzymes. 0.5-1.5 Perfume. 0.5-1.0 60 The present invention is further illustrated by the following example.

EXA MPLE - A concentrated nonaqueous liquid nonionic surfactant detergent composition is formulated - 13 GB2194536A 13 from the following ingredients in the amounts specified.

Weight % Highly biodegradable nonionic surfactant of 38.7 5 the formula R-(OC,Hjx(OC,HJy(l) Acid terminated Dobanol 91-5 reaction product 5.0 with succinic anhydride.

Sodium tripolyphosphate. 36.0 Diethylene glycol monobutyl ether. 6.0 10 Alkanol phosphoric acid ester (Empiphos 5632). 0.3 Anti-encrustation agent (Sokalan CP-5). 4.0 Sodium perborate monohydrate bleaching agent. 12.0 Tetraacetylethylene diamine (TAED) bleach 4.0 activator. 15 Sequestering agent (Dequest 2066). 1.0 Optical brightener (Tinopal ATS-X). 0.5 Anti-redeposition agent (Relatin DIV! 4050). 1.0 Protease (Esperase SL8). 1.0 Perfume. 0.5 20 100.0 (1) R=Cl,-C,., x=3, and y=5.

The formulation is ground for about 1 hour to reduce the particle size of the suspended 25 builder salts to less than 40 microns. The nonionic surfactant component of the formulation is found to be 90 percent biodegradable. The formulated detergent composition is found to be stable and non-gelling in storage and to have a high detergent capacity and to be non-foaming in use.

The formulations can be prepared without grinding the builder salts and suspended solid 30 particles to a small particle size, but best results are obtained by grinding the formulation to reduce the particle size of the suspended solid particles.

The builder salts can be used as provided, or the builder salts and suspended solid 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 35 grinding operation can be carried out after mixing with the liquid surfactant. The formulations containing suspended builder and solid particles less than 100 microns in size are preferred.

The highly biodegradable propoxylated ethoxylated fatty alcohol nonionic surfactant detergents of the present invention can be used to formulate polyphosphate builder salt, low polyphosphate builder salt and no polyphosphate builder salt detergent compositions and can be used as the 40 only or as the principle nonionic surfactant in aqueous built or nonbuilt heavy detergent compo sitions.

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.

45

Claims (27)

1. A compound of the formula R-(OC3H6),(OC2H4),OH 50 wherein R represents C8 to C26 aliphatic group, the value of x+y equals 20 to 100 percent of the number of carbon atoms of the R group, and x is at least one and y is at least one.

2. A compound as claimed in Claim 1 in which R represents C, to C, alky], and x is at least 2 and y is at least 2.

3. A compound as claimed in Claim 1 in which R represents C, to C, alkyl and x is at least 55 3 and y is at least 3.

4. A compound as claimed in Claim 1 in which R represents C12 to C, alkyl and x is at least 3 and y is at least 3.

5. A compound as claimed in Claim 1 in which R represents C, to C, alkyl, x is at least 2 and Y is at least 2 and x+y=4 to 16. 60

6. A compound as claimed in any one of Claims 1 to 5 in which x=2,to 8 and y=2 to 8.

7. A compound as claimed in Claim 1 in which R represents C, to C, alkyl, x is at least 2 and y is at least 2 and x+y=5 to 10.

8. A compound as claimed in Claim 1 in which R represents C12 to C, alkyl, x is at least 2 and Y is at least 2 and x+y=5 to 15. 65 14 GB2194536A 14

9. A compound as claimed in any one of Claims 1 to 7 in which x and y are different.

10. A compound as claimed in Claim 8 in which x and y differ by 1 or 2.

11. A heavy duty laundry detergent composition which comprises a highly biodegradable nonionic surfactant of the formula 5 R(OC3H6(x(OC2H4)YOH wherein R represents C1 to C26 aliphatic group, and x is 2 to 15 and y is 2 to 15.

12. A detergent composition as claimed in Claim 11 comprising at least one of the members of the group organic builder salt and inorganic builder salt. 10

13. A detergent composition as claimed in Claim 11 or Claim 12 comprising at least one of the members of the group consisting of acid terminated nonionic surfactant anti-gel agent, an alkylene glycol monoalkyl ether, and an alkanol phosphoric acid ester stabilizing agent. 15

14. A detergent composition as claimed in Claim 111 12 or 13 comprising one or more detergent adjuvants selected from the group consisting of bleaching agent, bleach activator, optical brightener, enzymes and perfume.

15. A detergent composition as claimed in any one of Claims 11 to 14 in which R repre- sents C, to C1. alkyl, x is at least 2 and y is at least 2 and x+y=4 to

16. 20 16. A detergent composition as claimed in any one of Claims 11 to 14 in which R repre- sents C, to C11 alkyl, x is at least 2 and y is at least 2 and x+y=5 to 10.

17. A detergent composition as claimed in any one of Claims 11 to 14 in which R repre- sents C12 to C,., alkyl, x is at least 2 and y is at least 2 and x+y=5 to 15.

18. A detergent composition as claimed in any one of Claims 11 to 17 in which x and y are 25 different.

19. A detergent composition as claimed in Claim 18 in which x and y differ by 1 or 2.

20. A detergent composition as claimed in any one of Claims 11 to 19 comprising a nonionic suffactant of the formula 30 R(OC3H,)x(OC2H4)YOH, wherein R represents C, to C18 alkyll x is 2 to 8 and y is 2 to 8, in an amount of about 20 to percent, a detergent builder salt in an amount of about 10 to 40 percent, 35 an acid terminated surfactant in an amount of about 5 to 25 percent, an alkylene glycol mono-alkyl ether in an amount of about 5 to 15 percent, and an alkanol phosphoric acid ester in an amount of about 0.1 to 1.0 percent.

21. A detergent composition as claimed in any one of Claims 11 to 20, comprising an alkali metal perborate bleaching agent in an amount of about 5 to 30 percent, tetraacetylethylene 40 diamine (TAED) bleach activator in an amount of about 3 to 20 percent, and optionally one or more detergent adjuvants selected from the group consisting of anti- encrustation agent, anti redeposition agent, sequestering agent for the bleach, optical brighteners, enzymes and perfume.

22. A detergent composition as claimed in any one of Claims 11 to 21 which is nonaqueous and in which the surfpctant is liquid and the builder salt comprises sodium tripolyphosphate. 45

23. A detergent composition as claimed in any one of Claims 11 to 22 which is nonaqueous comprising a highly b'lodegradable liquid nonionic surfactant of the formula R-(OC3H,)x(OC2H4)YOH, 50 wherein R represents C, to C,, alkyl, x+y equals 4 to 16, x is at least 2 and y is at least 2, in an amount of 20 to 50 percent, acid terminated surfactant in an amount of about 5 to 25 percent, sodium tripolyphosphate builder salt in an amount of about 10 to 40 percent, alkylene glycol monoalkylether in an amount of about 5 to 15 percent, 55 alkanol ester of phosphoric acid in an amount of about 0.1 to 1 percent, sodium perborate monohydrate bleaching agent in an amount of about 8 to 15 percent, and tetraacetylethylene diamine (TAED) bleach activator in an amount of about 4 to 8 percent.

24. A detergent composition as claimed in Claim 23 which is pourable at high and low temperatures, is stab[ IS storage and does not gel when mixed with cold water. 60 70mpositio-n as claimed in Claim 23 in which the nonionic surfactant is at

25. A detergent least 80 percent biodegradable.

26. A detergent composition as claimed in Claim 11 substantially as specifically described herein with reference to the accompanying example.

27. A method for cleaning soiled fabrics which comprises contacting the soiled fabrics with a 65 GB2194536A 15 laundry detergent composition as claimed in any one of Claims 11 to 26.

Published 1988 at The Patent Office, State House, 66/71 High Holborn, London WC1R4TP. Further copies maybe obtained from The Patent Office, Sales Branch, St Mary Cray, Orpington, Kent BR5 3RD. Printed by Burgess & Son (Abingdon) Ltd. Con. 1/87.