AU597029B2 - Built non-aqueous liquid laundry detergent compositions - Google Patents

Description

COMMONWEALTH OF AUSTRALIA Patent Act 1952 5 7029

COMPLETE

S P E C IF I C A T IO N

(ORIGINAL)

Class Int. Class Application Number p 57/ 7 Lodged Complete Specification Lodged Accepted Published This document contains the amendments made under Section 49 and is correct for printing.

Priority 21 February 1986 Related Art Name of Applicant Address of Applicant Actual Invento-r/s Address for Service :COLGATE-PALMOLIVE COMPANY S300 Park Avenue, New York, New York, 10022, United States of America :Trazollah Ouhadi, Louis Dehan F.B. RICE CO., Patent Attorneys, 28A Montague Street, BALMAIN 2041.

Complete Specification for the invention entitled: BUILT NON AQUEOUS LIQUID LAUNDRY DETERGENT COMPOSITIONS The following statement is a full description of this invention including the best method of performing it known to us/Wi- 0" 44 44 44nn 44 44o 444 44 44 n 44 Cs 44 r 444 4 4 44 444 44440 44 4444 447 444 444 44B 44 44 4 BACKGROUND OF THE INVENTION Field of Invention This invention relates to nonaqueous liquid fabric treating compositions.

More particularly, this invention relates to nonaqueous liquid laundry detergent compositions containing a suspension of a linear condensed.

polyphosphate builder salt in nonionic surfactants which compositions are stable against phase separation and gelation and are easily pourabic and to the use. of these compositions for cleaning soiled fabrics.

Discussion of Prior Art 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 related pending applications assigned to the common assignee are: SN 687,816, filed December 31, 1984 describes a nonaqueous liquid nonionic surfactant detergent composition comprising a suspension of a builder salt and containing an acid terminated nonionic surfactant the reaction product of a nonionic surfactant and succinic anhydride) to improve dispersibility of the composition in an automatic washing machine.

SN 687,815, filed December 31, 1984 describes a nonaqueous liquid nonionic surfactant detergent composition comprising a suspension of builder salt and containing an alkylene glycol mono-alkyl ether as a viscosity and gel control agent to improve dispersibility of the composition in an automatic washing machine.

1c\ j: i I_ _I_ SN 597,793, filed April 6, 1984 describes a nonaqueous liquid nonionic surfactant detergent composition comprising a suspension of polyphosphate j builder salt and containing an alkanol ester of phosphoric acid to improve stability of the suspension against settling in storage.

SN 725,455, filed April 22, 1985 describes a nonaqueous liquid nonionic surfactant detergent composition comprising a suspension of builder salt and containing an aluminum stearate to improve stability of the suspension against settling and to improve the yield stress of the composition while at the same time improving or lowering the plastic viscosity of the composition.

The washing power of synthetic nonionic surfactant detergents in laundry detergent compositions can be increased by the addition of builders. Sodium tripolyphosphate is one of the conventionally used builders. However, the use i sodium polyphosphate in dry powder detergents does involve several disadvantages such as, for example, the tendency of the polyphosphates to hydrolyse into pyro- and ortho-phosphates which represent less valuable builders.

In addition the sodium tripolyphosphate tends to cake when added to water ii: and has a relatively low water solubility and relatively low sequestering capacity for calcium.

Liquid detergents are often considered to be more convenient to employ than dry powdered or particulate products and, therefore, have found I substantial favor 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-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 2 with other builders are alkali metal carbonates, bicarbonates, borates, phosphates, polyphosphates, and silicates. (Ammonium or substituted ammonium salts can also be used.) Examples of conventionally used builder acnltq are sodium triDolvphosphate, sodium carbonate, sodium tetaborate, particulate 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 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 standing.

The conventionally used sodium tripolyphosphate builder salt has the disadvantage of tending to degrade in concentrated nonaqueous liquid nonionic surfactant detpegent compositions.

Though hexametaphosphates have been suggested for use in liquid Sdetergent compositions as builder salts they have not been used because they are not current raw material and they are expensive. In addition to the problem of settling or phase separation the nonaqueous liquid laundry ,i5 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 t automatic washing machines where the user places the laundry detergent Scomposition in a dispensing unit a dispensing drawer) of the machine.

°20 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 wash cycles, eventually 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 or 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 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. 3,953,380), alkali metal formates and adipates (see U.S.P. 4,368,147), hexylene glycol, polyethylene 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 moiety end group of the nonionic molecule. The advantages of introducing a on carboxylic acid at the end of the nonionic include gel inhibition upon dilution; 5 decreasing the nonionic pour point; and formation of an anionic surfactant when neutralized in the washing liquor. Nonionic structure optimization has centered on the chain length of the hydrophobic-lipophilic moiety and the number and o, make-up of alkylene oxide (eg. ethylene oxide) units of the hydrophilic moiety.

O%,o For example, it has been found that a C 13 fatty alcohol ethoxylated with 8 moles of ethylene oxide presents only a limited tendency to gel formation.

Nevertheless, improvements are desired in the dispersibility, pourability, solubility, stability and gel inhibition of polyphosphate builder salt nonaqueous liquid nonionic surfactant fabric treating compositions.

BRIEF DESCRIPTION OF THE INVENTION In accordance with the present invention a highly concentrated nonaqueous liquid laundry detergent composition is prepared by dispersing a long linear chain condensed polyphosphate builder salt in a liquid nonionic surfactant detergent.

The long linear chain condensed polyphosphate builder salts used in accordance with the present invention are known compounds. The alkali 4 L metal and ammonium salts of linear condensed polyphosphate builder salts are readily water soluble.

The linear condensed polyphosphates used in the present invention have the general formula O MO-(P-O) -M I n

OM

wherein M is hydrogen, an alkali metal, such as sodium and potassium, or ammonium cation, and n=20 to 30, preferably about It is preferred that all of the M's are alkali metal. A preferred linear condensed polyphosphate is hexametaphosphate in which In accordance with the present invention it was found that hexametaphosphate built concentrated nonaqueous liquid nonionic surfactant detergents have improved pourability and dispersibility as compared to sodium tripolyphosphate detergent compositions. The detergent compositions containing hexametaphosphates as the principle builder salt do not cake when added to water and the hexametaphosphates have a higher water solubility than sodium tripolyphosphate. It was further found that the hexametaphosphate in the concentrated nonaqueous liquid nonionic surfactant detergent compositions did not tend to degrade while in storage.

The hexametaphosphates were also found to be good anti-scaling an anti-encrustation agents and to prevent calcium crystal growth. The hexametaphosphates were formed to act in the nonaqueous liquid nonionic surfactant detergent compositions as superior sequestering agents for calcium. On gram of hexametaphosphate can sequester up to 163 mg. of calcium as compared to 1 gram of sodium tripolyphosphate which can sequester up to 111 mg. of calcium.

In the preferred embodiment of the invention the conventionally used sodium tripolyphosphate builder salt is replaced with the long linear change condensed polyphosphate of the present invention, alkali metal hexametaphosphate. In the detergent compositions of the present invention mono di- or tri lower

(C

2 to C3) More specifically the compounds are mono alkylene Vlycl mono lower

(C

1 to C5) alkyl ethers.

S ifc examples of suitable amphiphilic compounds include 00 0 0 00 0 00 000 0 0~ 200 0 0 0 OrO SOr 00 0 0 the phosphate builder consists essentially of the long linear chain condensed polyphosphate, alkali metal hexametaphosphate.

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 the storage properties of the composition there can be added to the compos*tion viscosity improving and anti gel agents such alkylene glycol mono alkyl ethers and anti settling agents such as phosphoric acid esters and aluminum stearate. In preferred embodiment of the invention the detergent composition contains an acid terminated nonionic surfactant and/or an alkylene glycol mono alkyl ether, and an anti settling agent.

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 composition are ground to a particle size of less than 100 microns preferably less than 40 microns and more preferably less than 10 microns to further improve the stability of the suspension of the builder components in the liquid nonionic surfactant 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 up to 100°C. Up to 18.5 gallons (70 liters) of water are used during the wash and rinse cycles.

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

In accordance with the present invention where the highly concentrated liquid detergent is used normally only about 100 gms (77 ml) or less of the liquid detergent composition is required to wash a full load of dirty laundry.

a..

Accordingly, in one aspect the present invention there is provided a liquid heavy duty laundry composition composed of a suspension of an alkali metal linear condensed polyphosphate builder salt in liquid nonionic surfactant.

According to another aspect, the invention provides a concentrated liquid heavy duty laundry detergent composition whirc- s 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 liquid nonionic laundry detergent composition into and/or with cold water without undergoing gelation. In particular, a method is provided S" Ifor filling a container with a nonaqueous liquid laundry detergent composition in which the detergent is composed, at least predominantly, of a suspension of a long linear chain condensed polyphosphate in a liquid nonionic surface active agent and for dispensing the composition from the container into an aqueous wash bath, wherein the dispensing is effected by directing a stream Sof unheated water onto the composition such that the composition is carried I: by the stream of water into the wash bath, ADVANTAGES OVER THE PRIOR ART The concentrated nonaqueous liquid nonionic surfactant detergent compositions containing a long linear chain condensed polyphosphate builder o o' salt have the advantages over sodiuo tripolyphosphate built detergent ,composition of having improved pourability and dispersibility of the builder salt, the builder salt does not tend to cake on the addition to water and the builder salt has a higher water solubility. The compositions of the present invention containing, alk&li metal hexametaphosphate builder salt do not tend to degrade in the liquid nonionic surfactant and exhibit good anti-scaling and anti-encrustation properties and have a high sequestering capacity for calcium.

The concentrated nonaqueous liquid nonionic surfactant laundry detergent compositions of the 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.

OBJECTS OF THE INVENTION It is an object of the present invention to provide a liquid heavy duty nonaqueous nonionic detergent composition containing an alkali metal hexametaphosphate builder salt suspended in a nonionic surfactant.

It is another object of the invention to provide liquid fabric treating compositions which are suspensions of an alkali hexametaphosphate builder salt in a nonaqueous liquid and which are storage stable, easily pourable and 0 0 .o dispersible in cold, warm or hot water.

o 0 Another object of this invention is to formulate a highly built heavy 0 o S005 duty nonaqueous liquid nonionic surfactant laundry detergent compositions Soo which can be poured at all temperatures and which can be repeatedly OOo 0 dispersed from the dispensing unit of European style automatic laundry %o washing machines without fouling or plugging of the dispenser even during 0o0, the winter months.

0 Another object of this invention is to provide a non-gelling, stable suspensions of heavy duty built nonaqueous liquid nonionic laundry detergent composition which include an effective amount of an alkali metal S°o hexametaphosphate builder salt.

A further object of this invention is to provide non-gelling, stable suspensions of heavy duty built nonaqueous liquid nonionic laundry detergent composition which include an amount of phosphoric acid alkanol ester and/or aluminum faity acid salt anti-settling agent which is sufficient to increase the stability of the composition, ie, prevent settling of builder particles, etc., preferably while reducing or at least without increasing the plastic viscosity of the composition.

8 t I0 4. 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 detergent composition by adding to a nonaqueous liquid nonionic surfactant an effective amount of an alkali metal hexametaphosphate builder salt and inorganic or organic fabric treating additives, e.g. viscosity improving and anti-gel agents, anti-settling agents, anti-incrustation agents, bleaching agents, bleach activators, anti-foam agents, optical brighteners, enzymes, anti-redeposition agents, perfume and dyes.

Nonionic Surfactant Detergent The nonionic synthetic organic detergents employed in the practice of the invention may be any of a wide variety of such compounds, which are well known.

As is well known, the nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically 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, 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 between 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 hydrophile-lipophile 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 9 200i and ethylene diamine tetramethylene phosphonic acid (EDITEMPA).

The sequestering agents can be used alone or in admixture.

tn nrdelr to avoid lose of neroxide bleachin agent, e g. sodium 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 5 to 8 or 5 to 9 lower alkoxy groups per mole.

Preferably, the 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 carbon atoms and which contain about 7 ethylene oxide groups per mole, 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 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 averages about 6.5. The higher alcohols are primary alkanols.

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

Also useful in the present composition as a component of the nonionic detergent are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation produus of higher fatty alcohols, with the higher fatty alcohol being of 14 to 15 carbon atoms and the number of ethylene oxide groups per mole 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 under the trademark Plurafac. The Plurafacs are the 0 Enzymes, preferably proteolytie enzymes, such as subtilisin, bromelin, papail, trypsin and pepsin, as well as amylase type anzymes, lipase type A hn,,nr t si hp tse.d. Preferred enzymes include I eaction 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

1 3

-C

1 5 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide), Product B (a C 1 3

-C

1 5 fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide), and Product C (a C 1 3

-C

1 fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide).

Another group of liquid nonionics are commercially available from Shell Chemical Company, Inc. under the Dobanol trademark: Dobane! 91-5 is an ethoxylated C 9

-C

1 1 fatty alcohol with an average of 5 moles ethylene oxide Sand Dobanol 25-7 is an ethoxylated C 1 2

-C

1 5 fatty alcohol with an average of 7 moles ethylene oxide per mole of fatty alcohol.

0 In the preferred poly-lower alkoxylated higher alkanols, to obtain the best balance of hydrophilic and lipophilic moieties the number of lower Salxoxies will usually be from 40% to 100% of the number of carbon atoms in the higher alcohol, preferably 40 to 60% thereof and the nonionic detergent S..o will preferably contain at least 50% of such preferred poly-lower alkoxy higher alkanol. Higher molecular weight alkanols and various other normally o 20 solid nonionic detergents and surface active agents may be contributory to gelation of the liquid detergent and consequently, will preferably be omitted So or limited in quantity in the present compositions, although minor proportions thereof may be employed for their cleaning properties, etc. With respect to both preferred and less preferred nonionic detergents the alkyl groups present therein are generally linear 'although branching may be tolerated, such as at a carbon next to or two carbons removed from the terminal carbon of the straight chain ,isd away from the ethoxy chain, if su.h branched alkyl is not more than thi e arb*~n i3 Normally, the proportion of carbon atoms sin ie branched configuration will be minor erarey exceeding "P '-bon atom content of the alkyl Similariy, although linear alkyls which are terminally joined to the ethylene oxide chains are highly preferred and are considered to result in the best combination of detergency, biodegradability and non-gelling characteristics, medial or secondary joinder to the ethylene oxide in the chain may occur. It is usually in only a minor proportion of such alkyls, generally less than but, as is in the cases of the mentioned Terigtols, may be greater. Also, when propylene oxide is present in the lower alkylene oxide chain, it will usually be less than 20% thereof and preferably less than 10% thereof.

When greater proportions of non-terminally alkoxylated alkanols, propylene oxide-ccntaining poly-lower alkoxylaied 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, 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 I wer alkoxylated higher alkanol is employed, often for its detergency, the proportion thereof will be regulated or limited in accordance with thf results of routine experiments, to obtain the desired detergency and still I 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 Snonionics 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.

Another useful group of nonionic surfactants are the "Surfactant T" serieis 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 an 12 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 C 1 3 fatty alcohol.

In the compositions of this invention, preferred 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 C9 to Cl1 fatty alcohols ethoxylated with about 5-6 moles ethylene oxide.

Mixtures of two or more of the liquid nonionic surfactants can be used and in some cases advantages can be obtained by the use of such mixtures.

Acid Terminated Nonionic Surfactant The viscosity and gel properties of the liquid detergent compositions can be improved by including in the composition an effective amount an acid terminated liquil nonionic surfactant. The acid te." inated nonionic o S surfactants consist of a nonionic surfactant which has been modified to .o coniert 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.

o s o As disclosed in the commonly assigned copending application Serial No.

597,940 filed April 9, 1984, the disclosure of which is incorporated herein by o o refer;ence, the free carboxyl group modified nonionic surfactants, which may O 0 0 be broadly characterized as polyether carboxylic acids, function to lower the temperature at which the liquid nonionic forms a gel with water.

The addition of the acid terminated nonionic $urfactants to the liquid e ,25 2 nonionic surfactant aids in the dispensibility of the composition, i.e.

pourability, and lowers the temperature at which the liquid nonionic surfactants form a gel in water without a decrease in their stability ag.'nst 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.

13 i y 0 1 0a 0~i Specific examples include the half-esters of Plurafac RA30 with succinic anhydride, the ester or half ester of Dobanol 25-7 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 g of Product A nonionic surfactant which is a C 1 3 to C 1 5 alkanol which has been alkoxylated to introduce 6 ethyleneoxide and 3 propylene oxide units per alkanol unit is mixed with 32g of succinic anhydride and heated for 7 hours at 100 0 C. The mixture is cooled and filtered 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 g of Dobanol 25-7 nonionic surfactant which is the product of ethoxylation of a C 1 2 to C 1 5 alkanol and has about 7 ethyleneoxide units per molecule of alkanol is mixed with 100g of succinic anhydride and b.lg of pyridine (which acts as an esterification catalyst) and heated at 2600C for 2 hours, cooled and filtered to remove unreacted succinic material. Infrared analysis indicates that substantially all the free hydroxyls of the iurfactant have reacted.

Acid Terminate Dobanol 91-5. 1000 g of Dobanol 91-5 nonionic surfactant which is the product of ethoxylation of a C 9 to C 1 1 alkanol and has about 5 ethylene oxide units per molecule of alkanol is mixed with 2 of succinic anhydride and O.lg of pyridine 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 surfactant have reacted.

Other esterification catalysts, such as an alkali metal alkoxide (e.g.

sodium methoxide) miy be used in place of, or in admixture with, the pyridine.

14 tAif-l« f i$ s W *jtZ r"4,-tS., a ,0 '2 I- -r r_ I-n Anti-redeposition agent (Relatine DM 4050) Alkali metal perborate bleaching agent Bleach activator (TAED) 0-3.0 8-15 2-6 15 00 0 a aa ar a aaa a a aoo 2 0* 25a~ a C, a, a aaaD aQ u ao a oaa The acidic polyether compound, i.e. the acid terminated nonionic surfactant is preferably added dissolved in the nonionic surfactant.

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

The present invention includes as an essential part of the composition long linear chain condensed polyphosphate builder salts.

The long linear chain condensed polyphosphate builder salts used in the detergent compositions of the present invention have the following general formula 0

II

MO-(P-O) -M

OM

wherein M is a member selected from the group consisting of hydrogen, alkali metal and ammonium cation, and n=20 to 30, preferrably about 25. All the M's are preferrably alkali metals or ammonium, sodium and potassium, with sodium being the more preferred. A preferred builder salt is the alkali metal or ammonium hexametaphosphate.

A specific example of a linear condensed polyphosphate builder salt that can be used is 0

II

NaO-(P-0) -Na 0

I

The detergent compositions containing alkali metal hexametaphosphates provide improved cleaning performance. For example, a 100 gm (77 cc) of 29.6% concentration of sodium hexametaphosphate provides cleaning performance equivalent to 100 gm (77 cc) of 30% sodium tripolyphosphate built detergent.

The invention detergent compositions include water soluble and/or water insoluble detergent builder salts. Water soluble inorganic alkaline builder salts which can be used alone with the detergent compound or in admixture II U -1~LL t A a i The formulation is ground for about 1 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 in storage and to have a high detergent capacity.

with other builders are alkali metal carbonates, bicarbonates, borates, phosphates, polyphosphates, and silicates. (Ammonium or substituted ammonium salts can also be used.) Examples of conventionally used builder salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium and potassium bicarbonate. Sodium tripolyphosphate (TPP) is a commonly used builder salt.

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 Na2O/SiO 2 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. A preferred alkali metal silicate is sodium disilicate.

Since the compositions of this invention are generally highly concentrated, and, therefore, may be used at relatively low dosages, it can be desirable to supplement the long linear chain condensed polyphosphate a builder with an auxiliary builder such as an alkali metal lower polycarboxylic Sacid having high calcium and magnesium binding capacity to inhibit incrustation which could otherwise be caused by formation of insoluble O 20 calcium and magnesium salts. Suitable alkali metal polycarboxylic acids are o 00 o* alkali metal salts of citric and tartaric acid, monosodium citrate (anhydrous), trisodium citrate, glutaric acid salt, glutonic acid salt and diacid salt with a longer chain.

Other organic builders are polymers and copolymers of polyacrylic acid 0o 25 and polymaleic anhydride and the alkali metal salts thereof. More specifically S o o such builder salts can 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 of inhibit incrustation, 16 i "r, 4 4 4 4 4 44 4 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 diaminetetraaceatate (EDTA), sodium and potassium nitrilotriacetates (NTA), and triethanolammonium N-(2-hydroethyl)nitrilodiacetates. Mixed salts of these aminopolycarboxylates are also suitable.

Other organic builders include the polyacetal carboxylates. The polyacetal carboxylates and their use in detergent compositions are described in application Serial No. 767,579 filed August 19, 1985, assigned to applicants' assignee and in a U.S.P. Nos. 4,144,226 4,315,092 and 4,146,495.

Other typical suitable builders include, for example, those disclosed irn 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 ccmpound or in admixture with other organic or inorganic builder salts The water insoluble crystalline and amorphous aluminosilicate zeolites can be used. The zeolites generally have the formula

(M

2 0)x (A203 y' (SiO 2 wherein x is 1, y is 2 rom 0.8 to 1.2 and preferably 1, z is from 1.5 to or higher and 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 aluminsilicates have calcium ion exchange capacities of about 200 milliequivalents per gram or greater, e.g. 400meq Ig.

Various crystalline zeolites alumino-silicates) 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 useful herein can be found in Belgium Patent 835,351 and this patent too is incorporated herein by reference.

17 2 2~i 4 .4'uYAn.

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 aluminum silicate in which about 1/6th of the aluminum atoms may be replaced by magnesium atoms and with which varying amounts of hydrogen, sodium, potassium, calcium, etc., may be loosely combined. The bevatonite in its more purified form free from any grit, sand, etc.) suitable for detergents contains at least 50% montmorillonite and thus its cation exchange capacity is at least about 50 to 75 meq per 100g of bentonits. 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 Guan.

Viscosity Control and Anti Gel Agents S""~ib The inclusion in the detergent composition of an effective amount of low O molecular weight amphiphilic compounds which function as viscosity control oQ and gel-inhibiting agents for the nonionic surfactant substantially improves o athe storage properties of the composition. The amphiphilic compounds can be considered to be analagous in chemical structure to the ethoxylated o 20 and/or propoxylated fatty alcohol liquid nonionic surfactants but have o, relatively short hydrocarbon chain lengths (C 2 to C 8 and a low content of 0 00 ethylene oxide (about 2 to 6 ethylene oxide groups per molecule).

o r Suitable amphiphilic compounds can be represented by the following general formula o 5 RO(CH 2

CH

2 O) H where R is a C 2

-C

8 alkyl group, and n is a number of from about 1 to 6, on average.

Specifically the compounds are lower (C 2 to C3) alkylene glycol mono lower (C2 to Cg) alkyl ethers.

18 r r r~r~l~ r~~ilr, .ua* l~r* d .L "Ctl it rrt~cC~ ~O CCT~U:I~E C ~;II V «tt l W r^ T. 009 0 0 ove 00 0 0 V 4 00 0 4 aa *0 2 0o 0 0 00 4s 0 044 40 O More specifically the compounds are mono di- or tri lower (C 2 to C 3 alkylene glycol mono lower (C 1 to C5) alkyl ethers.

Specific examples of suitable amphiphilic compounds include ethylene glycol monoethyl ether (C 2

H

5

-O-CH

2

CH

2

OH),

diethylene glycol monobutyl ether (C4Hg-O-(CH 2

CH

2 0) 2

H),

tetraethylene glycol monobutyl ether (C 4 H -O-(CH 2 CH20)4H) and dipropylene glycol monomethyl ether (CH 3

-O-(CH

2

CHO)

2

H.

CH

3 Diethylene glycol monobutyl ether is especially preferred.

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 and remain stable and pourable at temperatures as low as about 50C and lower, Stabilizing Agents 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 aluminum salt of a higher fatty acid.

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 the disclosure of which is incorporated herein by reference, the acidic organic phosphorus compound having an acidic POH 19

I

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, more than 5 carbon atoms, e.g. 8 to 20 carbon atoms.

A specific example is a partial ester of phosphoric acid and a C16 to C18 alkanol (Empiphos 5632 from Marchon); it is made up of about 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 the low concentration of stabilizer, e.g. below about 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 aluminum salt of a higher fatty acid to the composition.

The aluminum salt stabilizing agents are the subject matter of the commonly assigned copending application Serial No. 725,455, filed April 22, 1985, 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 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 mray 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 aluminum salt stabilizers can be formed include, decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicosanoic acid, tallow fatty acid, coco fatty acid, mixtures of these acids, etc. The aluminum salts of these acids are L

L

generally commercially available, and are preferably used in the triacid form, e.g. aluminum stearate as aluminum tristearate Al(C 1 7

H

3 5

COO)

3 The monoacid salts, e.g. aluminum monostearate, Al(OH) 2

(C

1 7

H

3 5 COO) and diacid salts, e.g. aluminum distearate, Al(OH)(C 1 7

H

3 5

COO)

2 and mixtures of two or three of the mono-, di- and triacid aluminum salts can also be used. It is most preferred, however, that the triacid aluminum salt comprises at least 30%, preferably at least 50%, especially preferably at least of the total amount of aluminum fatty acid salt.

The aluminum salts, as mentioned above, are commercially available and can be easily produced by, for example, saponifying a fatty acid, e.g.

animal fat, stearic acid, etc., followed by 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 aluminum salt functions to prevent settling of I 15 the suspended particles, it is presumed that the aluminum salt increases the Swettability of the solid surfaces by the nonionic surfactant. This increase in wettability, therefore, allows the suspended particles to more easily remain in suspension.

Only very small amounts of the aluminum salt stabilizing agent is 20 required to obtain the significant improvements in physical stability.

In addition to its action as a physical stabilizing agent, the aluminum salt has the additional advantages over other physical stabilizing agents that it is non-ionic in character and is compatible 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.

Bleaching Agents The bleaching agents are classified broadly, for convenience, as chlorine bleaches and oxygen bleaches. Chlorine bleaches are typified by sodium hypochlorite (NaOCI), potassium dichloroisocyanurate (59% available chlorine), and trichloroisocyanuric acid (95% available chl'orine). 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 monopersulfate. The perborates, particularly sodium perborate monohydrate, are especially preferred.

The peroxygen compound is preferably used ii 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.F. 4,430,244, the relevant disclosures of which are incorporated herein by reference.

Polyacylated compounds are preferred activators; among these, compounds such as tetraaietyl ethylene diamine ("TAED") 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, tetraacetylglycouril and the derivatives of these, Other useful 20 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 perrxyacid 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), ethylene diamine tetraacetic acid (EDTA), diethylene t amine pentaacetic acid (DETPA), diethylene triamine pentamethylene phosphonic acid (DTPMP) sold under the tradename Dequest II .il- YI I( I I 20 44 r44 4 4n 4 4 44 44 4 2066; and ethylene diamine tetramethylene phosphonic acid (EDITEMPA).

The sequestering agents can be used alone or in admixtpre.

In order to avoid loss of peroxide bleaching agent, e.g. sodium perborate, resulting from 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 incorpora'ed herein by reference.

Of special interest as the inhibitor compound, mention can be made of hydroxylamine sulfate and other water-soluble hydroxylamine salts. In the preferred nonaqueous compositions of this invention, suitable amounts of the hydroxylamine SLIt 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 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 amountz of soil suspending or anti-redeposition agents, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxy-propyl methyl cellulose. A preferred aiti-redeposition agent is sodium carboxymethyl cellulose having a 2:1 ratio of CM/MC which is sold under the tradename Relatin DM 4050.

Optical brighteners for cotton, polyamide and polyester fabrics can be used. Suitable optical brighteners include stilbene, triazole and benzidine sulfone compositions, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzidene sulfone, etc., most preferred are stilbene and triazole combinations. Preferred brighteners are Stilbene Brightener N4 which is a dimorpholino dianilino stilbene sulfonate and Tinopal ATS-X which is well known in the art.

S23 I Enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papain, trypsin and pepsin, as well as amylase type anzymes, lipase type enzymes, and mixtures thereof can be used. Preferred enzymes include protease slurry, esperase slurry and amylase. A preferred enzyme is Esperse SL8 which is a 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 buffers, color safe bleaches, perfume, and dyes and bluing agents such as ultramarine blue can be used.

The composition may also contain an inorganic insoluble thickening agent or dispersant of very high surface area such as finely divided silica of extremely fine particle size of 5-100 millimicrons diameters such as sold 0o oQ. under the name Aerosil) or the other highly voluminous inorganic carrier oooo materials disclosed in U.S.P. 3,630,929, in proportions of 0,1-10%, eg. 1 to O° It is preferable, however, that compositions which form peroxyacids in oa a the wash bath compositions containing peroxygen compound and activator therefor) be substantially free of such compounds and of other Isilicates it has been found, for instance, that silica and silicates promote o the undesired decomposition of the peroxyacid.

In an embodiment of the invention the stability of the builder salts in the composition during 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 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 grinding operation.

24 Lli IYI~--LLLLL- i L. illd Lif-ji-LL-- _It Z I~f r I _i i

:Y

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 40 microns, preferrably to less than about 10 microns, e.g. to an average particle size of 2 to 10 microns or even lower 1 micron).

Preferably less than about 10%, especially less than about 5% of all the suspended particles have particle sizes greater than 10 microns.

Compositions whose dispersed particles are of such nmall size have improved stability against separation 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.

In the grinding operation, it is preferred that the proportion of solid ingredients be high enough at least about 40% such as about 50%) that the solid particles are in contact wi', each other and are not substantially shielded from one another by the noniic surfactant liquid. After the grinding step any remaining liquid nonionic surfactant can be added to the ground formulation. 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 mm diameter grinding balls working in a very small gap between a 4 ator and a rotor operating at .a relatively high speed 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 does not effect such fine grinding a colloid mill) to reduce the particle size to less than 100 microns 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 ingredients are as follows: k Liquid nonionic surfactant detergent in the range of about 10 to such as 20 to 50 and 30 to 40 percent.

Acid te minated 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 percent.

Long linear chain condensed polyphosphate builder salts in the range of abut 10 to 60, such as 20 to 50 and 25 to 35 percent.

Copolymer of polyacrylate and polymaleic anhydride alkali metal salt anti encrustation agent in 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 or 0.1 to 2,0, such as 0.10 to 1.0 percent.

Aluminum salt of fatty acid stabilizing agent in the range of about 0 to 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 aluminum 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 percent.

Bleach activator in the range of about 0 to 20, such as 1 to 15 and 2 to 6 percent.

Sequestering agent for bleach in the range of about 0 to pro. .'ably 0.5 to 2.0 and 0.5 to 1.5 percent.

Anti-redeposition agent in the range of about 0 to 3.0, suh as 0.5 to and 0,5 to 1.5 percent.

Optical brightener in the range of about 0 to 2.0, such as 0.05 to 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 percent.

26

'I

CrC-* .s.r r rl ii*nr*iWir~cHI .u, I;ii. 1' L_ Il -I Perfume in the range of about 0 to 2.0, such as 0.10 to 1.25 and 0.5 to percent.

Dye in the range of about 0 to 1.0, such as 0.0025 to 0.050 and 0.0025 to 0.0100 percent.

Various of the previously mentioned additives can optionally be added to achieve the desired 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, e.g. phosphoric acid alkanol ester.

In the selection of the additives, they will be chosen to be compatible with the main constituents of the detergent composition. In tIhis 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 machines normally use 250 gn,s of powder deterrent to wash a full load of laundry. In accordance with the present invention only about 77 ml or about 100 gms of the concentrated liquid nonionic detergent composition is needed.

In a preferred embodiment of the invention the detergent composition of a typica. formulation is formulated using the below named ingredients: Weight Nonionic surfact~it detergent 30-40 Acid terminated nonionic surfactant 5-15 Alkali metal hexametaphosphate 25-35 Anti-encrustation agent (Sokalan CP-5) 0-10 Alkylene glycol monoalkl ether 8-12 Alkanol phosphori, acid ester (Empiphos 5632) 0.1-1.0 S 4 St. r 20 ii 0 4 4 lr 12 4t bl*.a ft Anti-redeposition agent (Relatine DM 4050) 0-3.0 Alkali metal perborate bleaching agent 8-15 Bleach activator (TAED) 2-6 Sequestering agent (Dequest 2066) 0-3.0 Optical brightener (ATS-X) 0.05-1.0 Enzymes (Protease-Esperase SL8) 0.5-1.5 Perfume 0.5-1.0 The present invention is further illustrated by the following example.

EXAMPLE 1 A concentrated nonaqueous liquid nonionic surfactant detergent composition is formulated from the following ingredients in the amounts specified.

A mixture of C 1 3

-C

1 5 fatty alcohol condensed with 7 moles of propylene oxide and moles ethylene oxide and C -C1 fatty alcohol condensed with 5 moles propylene oxide ana 10 moles ethylene oxide Surfactant T 7 Surfactant T 9 Acid terminated Dobanol 91-5 reaction product with succinic anhy d]ride Sodium hexametaphosphate Diethylene glycol monobutyl ether Alkanol phosphoric acid ester (Empephos 5632) Anti-encrustation agent (Sokalan CP-5) Sodium perborate monohydrate bleaching agent Tetraacetylethylene diamine (TAED) bleach activator Sequestering agent (Dequest 2066) Optical brightener (Tinopal ATS-X) Anti-redeposition agent (Relatin DM 4050) Esperase slurry (Esperase SL8) Perfume Dye Weight 15.5 29.6 0.3 10.0 0.5925 0.0075 ioo.o0 i -i L ii 11 i'- The formulation is ground for about 1 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 in storage and to have a high detergent capacity.

The formulations 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 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 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.

EXAMPLE 2 In order to demonstrate the effect on cleaning and anti-encrustation or anti-scaling performance of the substitution of sodium tripolyphosphate by sodium hexametaphosphate detergent builder salt of the present invention, th(, detergent composition formulation of Example 1 containing 29.6% by weight of sodium hexametaphosphate is compared in repeated laundry washing machine cycles with the same composition in which the hexametaphosphate is replaced with 30% by weight of sodium tripolyphosphate.

The repeated wash cycles are carried out at laundry wash water concentrations of each of the detergent compositions of 5 gm/liter of the /I respective detergent compositiors.

After each detergent composition is used in twelve wash cycles in a washing machine the amount of encrustation or scaling that results, the percent ash deposit is measured. The percent ash deposit measurement is determined by calcination of washed swatches.

29 -l .r i.',r The results that are obtained are that the sodium hexametaphosphate detergent composition's cleaning performance is equivalent or better than the sodium tripolyphosphate and the sodium hexametaphosphate detergent composition provides improved anti-encrustation or anti-scaling performance to that of the sodium tripolyphosphaie.

As far as the encrustation buildup is concerned, no buildup is observed with the hexametaphosphate, whereas a small buildup is observed with the sodium tripolyphosphate detergent builder LIlt.

The hexametaphosphate detergent builder salts can also be used to replace the polyphosphate builder salts in concentrated aqueous detergent compositions. At concentrations of 50 to 60%, due to the hexametaphosphate's polymeric structure, a viscous solution is obtained.

Because of the viscous nature of the concentrated aqueous solution the physical stability and rheological behavior of the aqueous concentrated composition is improved.

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 (14)

1. A heavy duty detergent composition which comprises at least one liquid nonionic surfactant detergent and a long linear chain condensed polyphosphate of the formula 0 MO-(P-O)n-M OM wherein M is a member from the group consisting of hydrogen, alkali metal and ammonium cation, and n=20 to dispersed therein as the principle detergent builder salt.

2. The detergent composition of claim 1 comprising at least one of the members of the groups consisting of an acid terminated nonionic surfactant anti-gel agent, an alkylene glycol mono ether and an alkanol phosphoric acid ester stabilizing agent.

3. The detergent composition of claim 1 comprising one or more detergent adjuvants selected from the group consisting of bleaching agent, bleach activator, optical brightener, enzymes and perfume.

4. The detergent composition of claim 1 comprising 10 to percent of a long linear chain detergent builder salt. The detergent composition of claim 1 comprising 5 to percent of an acid terminated surfactant.

6. The detergent composition of claim 1 comprising 0.10 to 2.0 percent of an alkanol phosphoric acid ester.

7. The detergent composition of claim 1 comprising about to 15 percent of an alkylene glycol mono-ether.

8. The detergent composition of claim 1 wherein the nonionic surfactant has dispersed therein detergent builder particles having a particle size of less than about 40 microns.

9. The detergent composition of claim 1 which comprises at least one liquid nonionic surfactant rn an amount of to an acid-terminated nonionic surfactant in an amount of 5 to an alkali metal hexametaphosphate (n=25) builder salt in an amount of 20 to an alkalene glycol mono-ether in an amount of 5 to and an alkanol phosphoric acid ester in an amount of 0.1 to The detergent composition of claim 9 comprising an alkali metal perborate monohydrate bleaching agent in an amount of 5 to tetraacetylethylene diamine bleach activator in an amount of 1 to 15%, 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.

11. The detergent composition of claim 9 where the detergent builder comprises the sodium salt of hexametaphosphate

12. The detergent composition of ;laim 9 wherein the ~sodium salt of hexametaphosphate has the formula: I o d NaO) (P-O)n Na ONa wherein I A- 32 4'

13. The detergent composition of claim 9 where the alkanol phosphoric acid ester comprises a C 16 to C 18 alkanol ester of phosphoric acid.

14. The detergent composition of claim 9 which is pourable at high and low temperatures, is stable in storage and does not gel when mixed with cold water. The detergent composition of claim 9 which comprises sodium hexametaphosphate (n=25) builder salt in an amount of 25 to 35 percent.

16. A concentrated nonaqueous liquid nonionic surfactant heavy duty laundry detergent composition which comprises Nonionic surfactant in an amount of Acid Terminated surfactant in an amount of Sodium salt of hexametaphosphate (n=25) in an amount of Alkylene glycol monobutyl ether in an amount of C 1 6 to C 1 8 alkanol ester of phosphoric acid in an amount of Sodium perborate monohydrate bleaching agent in an amount of Tetraacetylethylene diamine (TAED) bleach activator in an amount of

30-40% 5-15% 25-35% 8-12% 0,1-1.0% 8-15% 2-6% 17. The detergent composition of claim 16 wherein the composition comprises an anti.redeposition agent and anti-encrustation agent, and a sequestering agent for the bleach. 18. A method for cleaning soiled fabrics which comprises contacting the soiled fabrics with the detergent composition of claim 1. 19. The method of claim 18 for cleaning soiled fabrics which comprises contacting the soiled fabrics with the detergent composition of claim 9. 33 1 The method of claim 18 for cleaning soiled fabrics which comprises contacting the soiled fabrics with the laundry detergent composition of claim 16. DATED this 22nd day of February 1990 COLGATE-PALMOLIVE COMPANY Patent Attorneys for the Applicant: F.B. RICE CO. 4 4 i 1 d 5i51 fl I 4 S S S