CA1307182C - Nonaqueous liquid nonionic laundry detergent composition and method of use - Google Patents

Abstract

PATENT

NONAQUEOUS LIQUID NONIONIC LAUNDRY DETERGENT
COMPOSITION CONTAINING A PERSALT BLEACH AND
CALCIUM CYANAMIDE BLEACH ACTIVATOR AND METHOD OF USE

ABSTRACT OF THE DISCLOSURE
A liquid laundry detergent composition containing a perborate bleach and calcium cyanamide as a bleach activator. The preferred compositions are nonaqueous liquids based on liquid nonionic surfactants and include a detergent builder salt suspended in the liquid nonionic surfactant.

Description

~ 8~ 62301-1~35 NONAQUEOUS LI~UID NONIONIC LA~NDRY DETERGENT
COMPOSITION CONTAINING A PERSALT BLEACH

BACKGROUND OF THE INVENTION

(1) Field of Invention This invention relates to nonaqueous liquid fabric treating compositions. More particularly, this invention re-lates to liquid nonionic laundry detergent compositions which contain an inorganic persalt bleach compound and calcium cyan-amide as a bleach activator. The compositions are stable against phase separation and gelation and are easily pourable.
The compositions are used for cleaning soiled fabrics.

(2) Discussion of Prior Art Liquid nonaqueous heavy duty laundry detergent compo-sitions are well known in the art. For instancel compostions 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 sritish Patent Nos. 1,205,711, 1,270,040 and 1,600,981.
Related Canadian applications and U.S. patents as-signed to the common assignee are: 505,269 filed March 27, 1986 -describes a liquid nonionic laundry detergent composition con-~0 taining a perborate bleach, a bleach activator, and hydroxyl-amine sulfate as a bleach stabilizer and specifically as an inhibitor of catalase.
478,380 ~iled April 4, 1985 - describes a nonaqueous liquid nonionic surfactant detergent composition comprising a suspension of a builder salt and containing an acid terminated nonionic surfactant (e.g., the reaction product of a nonionic surfactant and succinic anhydride) to improve dispersibility of the composition in an automatic washing machine.

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~71~2 6~301-1~35 U.S. Patent ~,753,750 filed ~ecember 31, 1~4 - describes a nonaqueous liquid nonionic surfactant detergent cornposition comprising a suspension of builder salt and containing an al kylene glycol mono-alkyl ether as a viscosity and gel control agent to improve dispersibility of the composition in an auto-matic washing machine.
478,379 filed April 4, 1985 - describes a nonaqueous liquid nonionic surfactant detergent composition comprising a suspension of polyphosphate builder salt and containing an al-kanol ester of phosphoric acid to improve stability of the sus-pension against settling in storage.
These applications and U.S. Patent are directed to liquid nonaqueous nonionic laundry detergent compositions.
Liquid detergents are often considered to be more con-venient to employ than dry powdered or particulate products and, therefore, have found 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. Ad-ditionally, the liquid detergents may have incorporated in their formulations materials which could not stand drying operations without deterioration, which materials are often desirably em-ployed in the manufacture of particulate detergent products.
Although they are possessed of many advantages over unitary or particulate solld products, liquid detergents often have certain inherent disadvantages too, which have to be overcome to pro-duce acceptable commercial detergent products. Thus, some such products separate out on storage and other9 separate out on cooling and are not readily redi~persed. In some cases the product viscosity changes and it becomes either too thick to ,.~ ;2.

13~7~8Z ~23~ 35 pour or so thin as to appear watery. Some clear products be-come cloudy and others gel on standing.
The present inventors have been involved in studying the behavior of nonionic liquid surfactant systems with par-ticulate matter suspended therein. of particular interest has been nonaqueous built laundry liquid detergent co~positions and the problem of settling of the suspended builder and other -3a-j ~307~

laundry additives as ~ve]l ns the pro1~]~m of gellin~ Associatcd with noniorljc surfactants. These considerations have an impact on, for example, product stability, pourability and dispersibility.
It is kno~vn that one of the major problems with built licluid laundry detergents is their physical stability. This problem stems from the fact that the density of the solid partic]es dispersed in the nonionic liquid surfactant is higher than the density of the liquid surfactant.
Therefore, the dispersed particles tend to settle out. Two basic solutions exist to solve the settling out problem: increase nonionic liquid viscosity and reduce the dispersed solid particle size.
It is known that suspensions can be stabilized against settling by ndding inorganic or organic thickening agents or dispersants, such as, for example, very high suri`ace area inorganic materials, e.g. finely divided silica, clays, etc., organic thickeners, such as the cellulose ethers, acrylic and acrylamide polymers, polyelectrolytes, etc. However, such increases in suspension viscosity are naturally limited by the requirement that the liguid suspension be readily pourable and flowable, even at low temperature.
Furthermore, these additives do not contribute to the cleaning performance of the formulation.
Grinding to reduce the particle size provides the follo~ving advantages:
1. Specific surface area of the dispersed particles is increased, and, thercfore, particle wetting by the nonaqueous vehicle (liquid nonionic) is proportionately improved.
2, The average distance between dispersed particles is reduced with a proportionate increase in particle-to-particle interaction. Each of these effects contributes to increase the rest-gel stren~th and the suspension ~ield stress while at the same time, grinding significantly reduces plastic viscosity.
The yicld stress is defined as the minimum stress necessary to induce a plastic dcformation (f]ow) of the suspollsion. Thus, visuali7ing tlle ~ )7~L8~ 1 suspension as a loose ne~work of dispersed pa2 ticles, if the applied slress is lower than the y~eld stress, the suspension behaves like an elastic gel and no plastic flow will occur. Once the yield stress is overcome, the network brcal;s at some points and the samp]e ~,egins to flow, but with a very high apparent v~scosity. Jf the shear stress is much higher than the yield stress, the pigments are partially shear-deflocculated and the apparent viscosity decreases. Finally, if the shear stress is much higher than the yield stress value, the dispersed particles are completely shear-deflocculated and the apparent viscosity is very low, as if no particle interaction were present .
Therefore, the higher the yield stress of the suspension, the higher the apparen~ viscosity at low shear rate and the better is the physical stability against settling of the product.
` Tn addition to the problem of settling or phase separation, the nonaqueous liquid laundry detergents based on liquid nonionic surfactants suffer from the drawback that the nonionics 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 dispensin g drawer) of the machine. During the operation of the machine the detergent in the dispenser is subjected to a stream of cold water to transfer it to the main body of wash solution. Especially during the winter months when the detergent composition and water fed to the dispenser are particularly cold, the detergent viscosity increases markedly and a gel forms. As a result some of the composition is not flushed completely off the dispenser during operation of the machine, and a deposit of the composition builds up w ith repeated wash cycles, eventually requiring the user to ~lush the dispenser with hot water.
The gelling phenomenon can also be a problem whcnever it is desired to carry out washing using cold water as may be recommellded for certain l ~3L307~

synthetic and dc~icate fabrics or fabrics ~vhich can sh r ink in ~- arm or hot ~- ater .
The tendency of concentrated detergent compositions to gel during sto~age is aggravated by storinbr the compositions in unhcated storage areas, or by shipping the compositions during winter months in unheated kallsportation vehicles.
Partial solutions to the gelling problem in aqueous, substantially builder-free compositions have been proposed and include, for example, diluting the liquid nonionic with certain viscosity controlling solvents and gel-inhibiting agents, such as lower alkanols, e.g. ethyl alcohol (see U.S.P.

3,953,380), alkali met~ formates and adipates (see U.S.P. 4,368,147), he~Yylene ~Iycol, polyethylene glycol, etc. and nonionic structure modification nnd optimi zation . 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 carboxylic acid at the end OI the nonionic include gel inhibition upon dilution; decreasing the nonionic pour point; and formation of an anionic surfnctant uhen neutralized in the washing liquor. Nonionic structure optin7ization has ccntered 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 Cl3 fatty alcohol etho~;ylated with 8 moles of ethylene oxide presents only a limited tendency to gel formation.
Improvemcnts are desired in the bleach properties and the stability and gel inhibition of nonaqueous liquid fabric treating compositions containing a blench and bleach activator.
BRIE~F DESCRIPTION OF TI-IE INVEl`lTION
. _ .
In accordance with the prescnt invention a highly concentrated stable nonaqueous liquid Inundry detcrgent composition is prepnred containing a ~3~7182 ~2~0~-l435 persalt bleach compound and calcium cyanamide ble~ch actlvator.
A preferred persalt bleach compound is sodium perborate monohyclrate.
The calcium cyanamide bleach activator is used to replace the conven~ionally us~d organic bl~ach activators, such as tetraacetyl ethylene diamine (TAED), which release acid which is detrimental ~o de~ergency. The calcium cyanamide acts as an activator for ~he persalt bleach and increases the alkalinity of the aqueous wash liquor and improves detergency.
The persalt bleach and calcium cyanamide bleach activator system of the present invention can be used in phosphate and in low phosphate detergent builder salt compositions.
The invention there~ore provides a concentrated nonaqueous liquid heavy duty built laundry detergent composition which is pourable at high and low temperatures and which does not gel when added to cold water which comprises ~gh~.
At least one liquid nonionlc surfactant in an amount of about 10-50 At least one detergent builder suspended in the nonionic sur~actant in an amount of about 10-60 An inorganic peroxygen bleaching agent suspended in the nonionic sur~actant in an amount of about 5-30 Calcium cyanamide bleach activator in an amount of about 1-15 Alkylene glycol mono alkyl ether gel inhibitiny additive in an amount of about 5-30 In order to improve the viscosity characterlstics of the composition an acid terminated nonionic surfactant can be added. To further improve the viscosity characteristics of the C

~ 7~2 6~301-1~35 composition and the storage proper~ies of ~he compo~ltlon there can be added to the composi~ion viscosiky improving and anti gel agents such alkylene glycol mono alkyl ethers and an anti-settling agen~ such as an alkanol ester o~ phosphoric acid. In a preferred embodiment of the invention the dekergent composition contains sodium perborate monohydrate bleach, calcium cyanamide bleach activator, an acid termlnated nonionic surfactant, an alkylene glycol mono alkyl ether and an alkanol ester of phosphorlc acid anti-settllng stabilizing agent.
The conventionally used peroxygen bleach compounds, e.g., sodium perborate, percarbonate, perphosphate and persulfate can be used as the bleaching agent.
In an embodiment of the inventlon the builder components of the composition can be ground to a particle size of less than 100 microns, for example, less than 40 microns, and to preferably less than 10 microns to further improve the stability of the suspension of the bullder components in the liquid nonionlc surfactant detergent.

7a ~3()~

In addition other ingredients can be add~d to the composition such as anti-incrustation agents, sequestering agents, anti-foam agents, optica]
brighteners, enzymes, anti-redeposition agents, perfume and dyes.
Accordingly, in one aspect the present inven~ion provides a ]iquid heavy duty laundry composition composed of a suspension of a peroxygen bleach compound and a detergent builder salt, e. g. a phosphate builder salt, in a lic~uid nonionic surfactant wherein the composition includes as the bleach activator an effective amount of calcium cyanamide.
According to another aspect, the invention provjdes a concentrated liquid heavy duty laundry detergent composition which has good low temperature bleach properties, improved detergency, is stab]e, non-settling in storage and non-gelling in storage and in use. The liquid compositions of the present invention are easily pourable, easily measured and easily put into the washing machine and are readily dispersible in water.
1~ According to another aspect, the invention provides a method fordispensing a liquid nonionic laundry detergent composition into and/or with cold ~-ater without undergoing gelation. In particular, a method is provided for filling a container with a nonaqueous liquid laundry detergent composition in uhich the detergent is composed, at least predominantly, of a liquid ~0 nonionic surface active agent and for dispensing the composition from the container into an aqueous wash bath, wherein the dispensing is effectcd 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.
ADVANTAGES OVER THE PRIOR ART
The use of the calcium cyanamide bleach activator in the composition in plnce of the conventionally used organic bleach activators, e. g., TAED, provides good low tempcrature blcach propcrties while increasillg the alkalinity of the nqueous wash liquor and increases the detergency of the composition .

~3~7~8Z ~2301~1~35 The con~entr~ted nonayueou~ liquld no~loni~
surfactan~ laundry detergent compositions o~ the present invention have the a~vantages of being stable, non-settling in storage, and non-gelling in storage. The liquid compositlons are easily pourable, easily measured and easily pu~ into ~he laundry washing machines and are readily dispersible in water.
AIMS OF THE INVENTION
The present invention seeks to provide a stable liquid heavy duty nonaqueous nonionic detergent composition con~aining a persalt bleach compound and calcium cyanamide bleach activator, at least one viscosity control and anti-gel agent, an anti--settling stabilizing agent and an anionic ph~sphate detergent builder salt suspended in a nonionic surfactant.
The invention also seeks to provide llquid fabric treating compositions which have good low temperature hleach properties and improved detergency which are suspensions of insoluble inorganic particles in a nonaqueous liquid and which are storage stable, easily pourable and dispersible in cold, warm or hot water.
This inventlon also seeks to formulate highly built heavy duty nonaqueous liquld nonionic surfactant laundry detergent compositions whiah can be poured at all temperatures and which can be repeatedly dispersed from the dispensing unit of ~uropean style automatic laundry washing machlnes without fouling or plugging of the dispenser even during the win~er months.
;~ This invention further seeXs to provide non-~elling, ~ stable suspenslons of heavy duty bullt nonaqueous liquid ~ 30 nonionic laundry detergent composition which contain a persalt bleaah compound and include an ef~eatlve amount of a calcium C

130718~ 62301-1~35 cyanamide bleach activator.
The invention will become more apparent from ~he following detailed description of preferred embodiments which are generally provided for by prepariny a detergent composition comprising a nonaqueous liquid nonionic suriactant, a persalt bleach compound and calcium 9a ~ ~307~8Z ~

cyanamide bleach activator, ~ herein said composition inc]udes inorganic or organic fabric treating addi~ives, e. g. viscosity improving agents, and one or more anti-gel agents, anti-incrustation agents, pH control agents, anti-foam agents, optical bri~hteners, enzymes, anti-redeposition agents, perfume and dyes.
DETAILED DESCRIPTION OF THE INVENTION
Persalt Bleach Compounds The nonaqueous liquid nonionic laundry detergent compositions of the present invention contain a persalt bleach compound and calcium cyanamide bleach activator as essential ingredients of the composition.
The persalt bleach compounds are well known in the art, are dispersed as solids in the nonionic surfactant and are readily soluble on the addition of the dctergent composition to the aqueous wash water. The persalt compounds, or oxygen bleaches are percompounds which liberate hydrogen peroxide in aqueous solution. Preferred examples include sodium and potassium perborates, percarbonates, perphosphates, and potassium monopersulfate. The perborates, particularly sodium monohydrate, are especially preferred.
Hydrogen peroxide and the precursors which liberate hydrogen peroxide are good oxidizing agents for removing stains from cloth, especially stains caused by l-~ine, tea, coffee, cocoa, fruits, etc. Hydrogen peroxide and its precursors have been found in general to bleach quickly and most effectively at a relativcly high temperature, e.g., about 80 to 100C.
In order to take advantage of the low temperature effective detergents and low temperature washing cycles now commonly used for temperature sensitive fabrics, the persalt or peroxygen bleach compound is used in admixture ~-~ith a blcnch activator, Hcretofol e organic bleach activfltors have been used, such as tetraacetyl cthylene dianline tTAED). The use of such organic bleach ~3~ 82-acti~ ators increascs the acidity of the aqucous tvash liquor and accorc3inglY
adversely effected the detergency of the composition.
The ca]cium cyanamide bleach activator is used as an activator for the persalt bleach compounds. The calcium cyanamid reacts in ~he aqueous ~<~sh liquor with the hydrogen peroxide produced by the persalt b]each compound to produce a low temperature b]eaching moiety.
The calcium of the calcium cyanamide in the aqueous wash liquor increases lhe alkalinity of the wash liquor and improves the detergency of the detergent composition. The addition of calcium cyanamide as the bleach activator to the detergent composition can lower the effectiYe operating temperature of the peroxide bleaching agents to temperatures as low es about 60C. In detergent compositions where lower operating temperatures are desired sma]l amounts of the conventionally used bleach activators, such as TAED can be added. In the preferred embodiment of the invention calcium c~,anamid is the only bleach activator, or the major constituent, i.e., more than 50%, of the bleach activator used in the detergent composition.
Only small amounts of calcium cyanamide bleach activator are required to activate the peroxygen bleach compound. For example, based on the total u~eight of the nonionic liquid surfactant composition, suitable amounts of calcium cyanamide are ln the range of from about 1~ to about 15%, preferably from about 1~ to about 8~ and more preferably about 2% to 6~6.
The blcach activator usually interacts with the peroxygen compound to form a peroxyacid bleaching agent in the wash water, It is preferred to include a sequestcring agent of high complexing power to inhibit any undesired reaction bet~een such peroxyacid and hydrogen peroxide in the ~vash solution in tl-e presence of metal ions.
Sal~s _ Suitable sequcstering agents for this purpo.se include the sodium of nitrilotriacetic acid (NTA), ethylene diamine tetraacetic acid (EDTA), dicthylclle triamine pcntaacetic acicl (DETPA), diethylene triamine ~ en 4,~
pcntametllylclle phosl)1lollic ncid (DTPI~iP) sokl under the ~Dcquest ~ ~3~ 132 6Z3()1 -] ~35 OG6; and eth~lcne dinmine Ictrllmc~hylcnc phosphoIlic nci~] (f DI I I ~IPA).
Tl1c scqucslelin~ ngents cnn be used n~one or in ndmixluJe.
]n order to avoid loss Or peroxide bleaching ngent e. g. sodium pcrbora~e resul~ing ~rom enzyme-illc~uced decomposition such as by Cr3~ LlSe cnzyme the composi~ions mny nddilionn~ly 3nclude nn cnzyme inhibitor compound i.e. a compound cnpable of inhibiting enzyme-induced docomposition of the peroxide b]eachin~ n~ent. Suitnble inhibilor compounds nre disclosed in U S P. 3 606 990.

Of special interest tiS the inhibitor compound mention can be m3de of h~droxylnmine su]fnte nnd other wnter-so~uble hydroxylnmine snlts. In nn embod;men~ of the nonnqueous compositions of this invention suilablc nmoun~s of the hydroxylnmine salt inhibitors can be as low as about 0.01 to 0.4~. Generrlly ho~Yever suitablc amounts of enzyme inhibitors are up to nbout 15~ for exnmple 0.1 to 10~ by weight of the composition.
There cnn nlso be added to the formulation stabilizcrs such as for cxamp]e an ricidic orgallic phosphorus compound having an ncidic - POH
gI`OUp such as a parliul estcr of phosphorous ncid and an aiknnol.
The nonionic surftlctant detergents can be built with only polyphosphate builder stlits or can be lo~v in polyphosphates.
Nonionic Surfflctant Deter~ent I`hc l~onic nic synthclic orgnnlc delergcnts cmploycd in the praclice of lI~c in~ eIltion may be any of a \vide variety of known compollnds.
/~s is ~cll kno\~n tlle nonJonic synthetic .ol gnnic detergents nrc e))nl nctcrized by thc prcscnce of sn orgnnic ]lydrophobic gl`OUp nnd nn orgnnic hydrol)hjlic group nlld are typicn~ly produced by lhe condensation of tln Ol'gnlliC nlipl1rltic or nllcyl nlomnlic hydrophobic compound \Yith ethylene o~;idc (hydroplli)ic in nutule). Prncticn]ly nny hydrop)lobic compound hnving n cnrbn~;y hy(llo~;y nmiclo or nmino glOUp ~it)l n rrcc hydloGon ~Illnchc(l lo ~hc nitrogen cnl1 bc condcnscd \~ith ctl~ylcne o:~idc or ~ilh the poly)lydl n~ion ! , ~L3()7:1~32 product th~rcof, pol~cthylcne ~Iycol, to form a rlonionic detergent. rhe length of the hydrophilic or polyoxy eth~lene chain can be readi]y adjusted to achieve the desired ba~ance bet~een the hydrophobic and hydrophilic groups. T~-pic~ql suitab]e nonionic surfflctants are those disclosed in U S.
patents 4,316,812 and 3,630,929.
Usually, the nonionic detergents are poly-lower alkoxylated lipophi]es wherein the desired hydrophile-lipophile balance is obtained from addition of a hydrophilic poly-lower alkoxy group ~o 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 mois 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 alknnol 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 mol.
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 15 carbon atoms and which contain about 7 ethylene oxide groups per mol, ~0 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 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 avcrages about 6. 5, The higher alcohols are primary alkanols.
Other examples of such detergcnts include Tergitol 15-S-7 and Tergitol~ /
15-S-9, both of which are lincar secondary alcohol etlloxylates made by Union Carbide Corp. The former is mixcd ethoxylation product of 11 to 15 carbon atoms linear sccolldary a]knllol ~Yith scvcn mols of cthylcllc oxidc and ~, 1~o~

~ ~ 307~

the latter is a simi]ar product but with nine mols of ethy]ene oxide being reacted .
A]so useful in the present composition as a component of the nonionic dctergent are higher molecu]ar ~veight nonionics, such as l~'eodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14 to 15 carbon atoms and the number of 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 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 oxidç and propylene oxide, terminated by a hydroxyl group. Examples include products which are (A) C13-C15 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide, (B) C13-C1S fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide, (C) C13-C15 fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide, and (D) which is a 1:1 mixture of products (B) and (C).
Another group of liquid nonionics are commercially available from Shell Chemical Company, Inc. under the Dobanol trademark: Dobanol 91-5 is an ethoxylated C9-C11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12-C15 fatty alcohol with an average of 7 moles ethy~ene oxide per mole of fatty alcohol.
In the preferred poly-lower alkoxylated higher alkanols, to obtain the best balance of hydrophilic and lipophilic moieties the number of lower alkoxies will usually be from 40% to 100% of the number of carbon atoms in the higher alcohol, preferably 40 to 60~ thercof and the nonionic detergent will preferably contain at least 50~ of such preferred poly-lower alkoxy higher alkanol. Higher molecular wcight alkanols and various other normally solid nonionic dctcrgcnts alld surfnce active ag,ents may be contributory to - ~3~ L8~ ~

gelation of t}le liquid dc~ergent and cons~queJ1tly, ~vil~ preferably be omittedor limited in quantity in the present compositions, although minor proportions thereof may be employed for their cleaning properties, etc ~'ith respect to both prefel u ed and less prcferred nonionic detergents the alXyl groups present therein are generally linear a]though branching may be tolerated, such as at a car~on next to or two carbons removed from the terminal carbon of the straight chain and away from the ethoxy 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 rarely exceeding 20% of the total carbon alom content of the alkyl.
Similarly, 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 detergcncy, biodegradability and non-gelling characteristics, medial or secondary joinder to the ethy]ene oxide in the chain may occur. It i~ ~ is usually in only a minor proportion of such alkyls, generally less than 20%
rerg~fa/s but, as is in the cases of the mentioned T~i~l~ may be greater. A]so, ~hen propylene oxide is present in the lower alkylene oxide chain, it will usually be less than 20~ thereof and preferably less than 10% thereof.
~'hen greater proportions of non-terminally alkoxylated alkanols, propylene oxide-containing poly-lo~ver alkoxylated alkanols and less hydrophile-lipophile ba]anced nonionic detergent than mentioned above are employed and when other nonionic detergents are used instead of the prcferred nonionics recited herein, the product resulting may not have as good detergency, stabi]ity, viscosity and non-gelling properties as the ~5 preferred compositions but use of the ~iscosity and gel controlling compounds of the invelltion can also improve the properties of the detergents based on such IlOIliOlliCS. In some cases, as when a higher molecular weight })olylo~ver alkoxylated higher alkanol is cmployed, often for its detergency, the proportion thereof will be rcgulated or limited in accordance with the results of r outine c~peI iments, to obtain the dcsired d~tcrgency and still ~3~71~2 6~301-1~35 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 de-sired viscosity in the liquid detergent without gelation at low temperatures.
Another useful group of nonionic surfactants are the "Surfactant T" series of nonionics available from British Petro-leum. The Surfactant T nonlonics are obtained by the ethoxy-lation of secondary C13 fatty alcohols having a narrow ethyleneoxide 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 Tl2 and average of 12 moles of ethylene oxide per mole of secondary C fatty alcohol.
In the compositions of this invention, preferred non-ionic surfactants include the C12-Cl5 secondary fatty alcohols with relatively narrow contents of ethylene oxide in the range of from about 7 to 9 moles, and the C9 to Cll fatty alcohols ethoxylated with about 5-6 moles ethylene oxide.
Mixtures of two or more of the liquid nonionic sur-factants can be used and in some cases advantages can be ob-tained by the use of such mixtures.
Acid Terminated Nonionic Surfactant The viscosity and gel properties of the liquid deter-gent compoRitions can be improved by including in the eompo-sition an effective amount of an acid terminated liquid nonionic surfactant. The acid terminated nonionic surfactants consist of a nonionic surfactant which ha~ been modified to convert a free hydroxyl group thereof to a moiety having a free earboxyl group, s -16-~3~7~8X ~3~1-1435 such as an ester or a partial ester of a nonionic surfactant and a polycarboxylic acid or anhydride.
As disclosed in the commonly assigned Canadian appli-cation No. 478,379 filed April 4, 1985 -16a-~' ~307~B2 6Z301.-1~35 the free carboxyl group modified nonionic surfact~nts, which may be bro~dly cllnrùc~cri~ed ns polye~ller cnTboxylic nci(ls rollc~ion ~o ]O~el (hc~en pcr~ure nl \vhich the liquid nonionic forms n gel ~vilh ~vnler l`he u(ltlilion Or the ncid termin~!e~l nonionic ;urrnctllrlls lo l~lc lillui nOIliOniC surrnclont nicis in the clispensibili~y Or tl)e cornposi/ion i c pournbility nnd lowers the tempel nlure ut ~vhic)l lhc li(~llicl noni()liiC
surrnclnnls rorm n E~el in ~vnter ~vilhout n dccrensc in thcir s~nl)ili~y n~nitl~sl set~ g The ucid terminuted nonionic surfac~unt rcoc~s in lllc ~shing mllchine ~vn~er ~vilh Lhe alknlini~y Or tl1e ~lispersed l~uilder sult phnsc Or tl~e detergent coml~osilion nnd ~cts ug nn er~cctlve nniollic surroclnnt spcciric exnrnplcs include the hnlf-esters Or nonionic sur~ncl~nl producl ~A) wi~h succinic nnhydri~e lhe es~er or hnlf eslcr of Dobnnol 25-7 ~vilh SUCCilliC nnhy(lride and the ester or hnlf es~er of Dobnnol 91-5 wilh succinic nnhydride lnslend of succinie unhydride other polycarboxylic acids or nnh~cll ides cnn be used e g. molele neid mnleie ncid nnhydriclc ~]UIrll IC
neid mn~onie neid phthnlle neid phthuiie nnhydricie eilric aeid oncl tl)c li)ce l he neid terminnted nonionie surfnetnnts cun be prepored ns follo~vs Acid Terminn(ed produet (A) ~IOOg of nonionic surrnclnnt produc~ (A) ncnionie ~surrlctnnt ~ hich is u C13 to C15 ~knnol ~vl~i~h hns bc~n nJl~oxylnlc~l îo inllo(l~lce G etllylelle o:~ide nnd 3 propylene oxide UllitS per nlknllol unil is mixcd ~vil)) 32g Or sueeinie anhydlide nnd heuted for 7 hours ut 100C T1-e mixlure is cooled nnd riitered to remove unrencted succinic mu~erinl Infrnl ed nnnlysis indieuled t}lnt ubout one hnlf of the nonionic surrnclùnt hns been eonvertetl to tl-e ncidie l-nlf-ester thereof.
Aeid Tern~innted DobDnol 25-7. 522g of Dobnnol 25-7 noniooic su~ ~neînnt ~vhic}l is the produet of ethoxylutlon of n C12 to C15 ~Iknnol nrl ~h;ns ubout 7 ctl~ylene oxide units per molecule of nllcnnol is mixccl ~vith 1 OO(r Or ~SUCCil)iC nl)lly(lride und 0 1~ Or ~)yridille (~vhicll nct s ns nn cStcriricnli()ll cn~;~ly~st) ;ulcl heuted nî 2G0C for 2 hours cooled nncl rillered lo l'CIIlovC
.
. .
, ~31~)7~8Z

UllreaCted SUCCilliC m~terial. Infl ared fln~lJysis indicatcs that substf~nti~lly all the free hydroxyls of the surfactant have reacted.
et~ nQ~ed Acid ~ Dobanol 91-5 1000 of DGbanol 91-5 nonionic surfactant which is the product of ethox~ tion of a Cg to Cll alkanol and has about S
ethylcne oxide units per molecule of alkanol is mixed with 265g of succinic anhydride and 0. lg of pyridine catalyst and heated at 260C 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) may be used in place of, or in admixture with, the py ridine .
The acidic polyether compound, i . e . the acid terminated nonionic surfactant is preferably added dissolved in the nonionic surfactant.
BUILDER SALTS
The liquid nonaqueous nonionic surfactant used in the compositions of the present invention has dispersed and suspended therein fine particles of org ~ Sc V ~norgani~and/or inorganic detergent builder salts.
The invention detergent compositions include water soluble and/or ~vater inso]ub]e detergent builder salts. Water soluble inorganic alkaline builder salts ~hich can be used alone with the detergent compound or in admixture ~Yith other builders are alkali metal carbonates, bicarbonates, borates, phosphates, polyphosphates, and silicates. (Ammonium or substituted ammonium salts can also be used. ) Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexarnetaphosphate, sodium sesquicarbonate, sodium mono and diorthophosphate, ar.d potassium bicarbonate. Sodium tripolyphosphate (TPI') is especinlly preferrod.

- ~L3~7~L~Z
, ~

Since the compositions of t~,is invention are genera]ly highly concentrnted, and, therefore, may be used ~t relatively low dosages, it is desirable to supp]emcnt any phosphate bui]der (such as sodium tripo]yphosphate) w ith an auxiliary bui]der such as a poly ]ower carboxy]ic scid or a po]ymeric carboxy]ic acid having high ca]cium binding capacity to inhibit incrustation which cou]d otherwise be caused by formation of an insoluble calcium phosphate.
A suitable lower poly carboxylic acid comprises alkali metal salts of lower polycarboxylic acids, preferably the sodium and potassium salts.
Suitable lower polycarboxylic acids have two to four carboxylic acid groups.
The preferred sodium and potassium lower polycarboxylic acids salts are the citric and tartaric acid salts. The sodium citric acid salts are the most preferred, especially the trisodium citrate. The monosodium and disodium citrates can also be used. The monosodium and disodium tartaric acid salts can also be used. The alkali metal lower polycarboxylic acid salts are partic~`nrly ~ood builder salts; because of their high calcium and magnesium bind;ng capacity they inhibit incrustation which could otherwise be caused by formation of insoluble calcium and magnesium salts.
In order to obtain a nonphosphate detergent composition the pol~phosphates can be replaced entirely by one or more of the auxiliary builder salts.
Other organic builders are polymers and copolymers of polyacrylic acid and polymflleic anhydride and the alkali metal salts thereof. I\~ore specifically 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 neutrali~ed to form the sodium salt thereof. The builder is r~
~- commcrcinlly avnilable under the ~e of Solcalan CP5. This builder serves whe3l used evcn in small nmounts to inhibit incrustation.
~:nmples of organic alka]ine sequcstrallt builder salts which can be uscd ~ith t]le detcrgent buikler ~;rllts or in admi~;ture with other or~nnic nnd 62301-1~35 13~)7~3Z
inorganic builders are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, e.gO sodium and potassium ethylene diaminetetraacetate (EDTA), sodiu~ and potassium nitrilotriacetates (NTA), and triethanolammonium N-(2-hydroxy-ethyl)nitrilodiacetates. Mixed salts of these aminopolycarbo-xylates are also suitable.
Other suitable builders or auxiliary builders of the orqanic type include carboxymethylsuccinates, tartronates and glycollates. Of special value are the polyacetal carboxylates.
The polyacetal carboxylates and their use in detergent compo-sitions are described in Canadian application No. 516,256 filed August 19, 1986 assigned to applicants' assignee and in a U.S.P~
Nos. 4,144,226, 4,315,092 and 4,146,495.
` The alkali metal silicates are useful builder salts which also function to adjust or control the pH and to make the composition anticorrosive to washing machine parts. Sodium silicates of Na2O/SiO2 ratios of from 1.6/1 to 1/3.2, espe-cially about 1/2 to 1/2.8 are preferred. Potassium silicates of the same raiios can also be used.
Other typical suitable builders include, for example, those disclosed in U.S. Patents 4,316,812, 4,264,466 and 3,630,929. The inorganic builder salts can be used with the nonionic surfactant detergent compound or in admixture with other inorganic builder salts or with organic builder salts.
The water insoluble crystalline and amorphous alum-inosilicate zeolites can be used. The zeolites generally have the formula (M2O)X (A12O3)y (SiO2)z wH2O

wherein x is 1, y i9 from 0.8 to 1.2 and preferably 1, z i9 - from 1.5 to 3.5 or higher and preferably 2 to 3 and w i9 from ~s -20-.~ `', .

~ 307~2 ~2301-1435 0 to 9, preferably 2.5 to 6 and M is preferably sodium. A
typical zeolite is type ~ or similar structure, with type 4A
particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of about 200 millequivalents per gram or greater, e.gu 400 meq lg.

-20a-~307182 ~3al-l4~s Various crystalllne zeoli~es (i.e. alumino-sillcates~
that can be used are descrlbed in British Patent 1,504,168, U.S.P. 4,409,136 and Canadian Patents 1,072,835 and 1,087,477.
An e~ample of amorphous zeolites u~eful herein c~n be found in selgium Patent 835,351.
O~her 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 a~oms and with which varylng 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% montmorillonite and thus i~s cation exchange capaclty is at least about 50 to 75 meq per lOOg of bentonite. Particularly preferred bentonites are the Wyoming or Western U.S. bentonites which have been sold a~ Thixo-jels*, 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.
Viscositv Control and Anti Gel Aaents The inclusion in the detergent composition of an effective amount of low molecular weight amphiphillic compounds which function as viscosity control and gel inhibiting agents for the nonionic surfactant substantially improves the storage properties of the composition. The viscosity control and gel inhibiting agents act to lower the temperature at which the nonionic surfactant will form a gel when added to water. Such viscosity control and gel inhibiting agent~ can be, for *Trade-mark C

` 1307~ 6~301-1435 example, low molecular welght alkylene oxide lower mono-alkyl ether amphilic compoun~s. The amphiphilic compounds can be considered to be analogous in chemical structure to the ethoxylated and~or propoxylated fatty al~ohol liquid nonlonic surfactants but 21a have rclatively short hydrocal1bon chain ]en~ths (C2 to C8) and a low ¦ content of ethylene ox~de (about 2 to 6 ethylene oxide groups per mo]ecule).
l Suilable amphiphilic compounds are represented by the following general ¦ formula ¦ R2 R10~/~HCH20)nH
where R1 is a C2-C8 alkyl group, R2 is hydrogen ar methyl and n is a number of from about 1 to 6, on average.
l Specifically the compounds are lower (C2 to C3) alkylene glycol mono ¦lower (C2 to C5) alkyl ethers.
l More specifically the compounds are mono-, di- or tri- lower (C2 to C3) ¦alkylene glycol mono lower (C1 to C5) alkyl ethers.
Specific examples of suitable amphiphilic compounds include l ethylene glycol monoethyl ether C2H5-O-CH2CH2OH, l diethylene glycol monobutyl ether C4Hg-O-(CH2CH2O)2H, tetraethylene glycol monobutyl ether C4H7-O-(CH2CH2O)4H and dipropylene glycol monomethyl ether CH3-O-(CHCH2O)2H. Diethylene glycol l 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 ¦~vater or cold water.
2 5 ¦ The compositions of the present invention have improved viscosity and stability characteristics and remain stable and pourable at temperatures as ow as about 5C and lower.
In an embodiment of this invention a stabilizing agent which is an - lkanol ester of phosphoric acid can be added to the formulntion, mprovemellts in stnbility of the composition may be achieved by ncorporation of a small effective amount of an acidic organic phosphorus 62301-1~35 compound having an acidic - POH group, such as a partial ester of phosphorous acid and an alkanol. As disclosed in the com-monly assigned Canadian application No. 478,379 filed April 4, 1985 the acidic organic phosphorous 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 al-kanol 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 35% monoester and 65% diester.
The inclusion of quite small amounts, e.g. 0.3% by weight, of the acidic organic phosphorus compound makes the suspension stable against settling on standing but remains pourable, while, for the low concentration of stabilizer, e.g.
below about 1%, its plastic viscosity will generally decrease.
Other bleach activators can optionally be added to the composition: among these are bleach activator compounds such as tetraacetyl ethylene diamine (TAED) and pentaacetyl glucose, acetylsalicylic acid derivatives, ethylidene benzoate acetate and its salts, ethylidene carboxylate acetate and its salts, al~yl and alkenyl succinic anhydride, tetraacetylgly-couril t"TAGU"), and the derivatives of these. Other useful classes of activators are disclosed, for example, in U.S.P.

4,111,826, 4,422,950 and 3,661,789.
The second or auxiliary bleach activator can be added to supplement the calcium cyanamide bleach activator and to further lower the temperature, e.g. below about 60 C, at which the peroxygen bleach becomes effective.

*Trade-Mark -23-1~)7~1~3Z
62301-1~35 In addition to the detergent builders, variou~ other detergent additives or adjuvants may be present in the detergent product to give it additional -23a-- ~307~

desired properties, cither of functional or aesthetic nature. Thus, there may be included in the formulation, minor amounts of soil suspending or anti-redeposition agcnts, e. g. polyvinyl a]cohol, f~tty amides, sodium carboxymethyl cellulose, hydroxy-propyl methyl cellulose A prcfcrrcd anti-redeposition agent is sodium carboxymethyl cellulose having a 2 :1 ratio rQde~n-Qr`~
of CMC/MC which is sold under the~ Relatin DM 4050.
There may also be included in the composition small amounts of Duet 787 which is a perfume , i. e ., fragrance and which is supplied by International Flavors and Fragrances, Inc., Union Beach, N.J. 07735. The Duet 787 can be added in amounts such as 0 . 3 to 1. 0 percent, preferably 0 . 2 to 2 . 0 percent e . g. 0 . 5 to 2 percent, such as 0 . 3 to 1. 0 percent by weight of the composition .
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. A preferred brightener is Stilbene Brightener~N4 which is a dianilinodimorpholino stilbene polysulfonate.
Enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papain, trypsin and pepsin, as well as amylase type enzymes, lipase type en~ymes, and mi~;tures thereof can be added. Preferred enzymes include protease slurry, esperase slurry and amylase. A preferred enzyme is Esperse~SL8 which is a proteolytic enzyme. Anti-foam agents, e. g. silicon compound, such as Silicane L 7604, which is polysiloxane can also be added in small effective amounts.
Bactericides, e.g. tetrachlorosalicylanilide and hexachlorophene, fungicides, dyes, pigments (water dispersible), prcservatives, ultraviolet absorbers, anti-yellowing agent9, such as sodium carboxymethyl cellulose, pH modifiers and pH buffers, color safe bleaches, perfume, and dyes and bluiJlg agents such as ultramarille blue can be uscd ~ 24 ~f~ ,no~

~ ~ ~3~7~

In an embodimcnt of the invention the ~t~bility of t~le builder 5a~'~5 ir.
the composition during storage and the dispersibility of the composition in ~vater is improved by grinding and reducing the parti~ le size of the solid builders to iess than 100 microns, preferably less than 4û microns and mo~ e preferably to less than 10 microns. The solid builders, e.g. sodium tripolyphosphate (TPP), are generally supplied in particle sizes of about 100, 200 or 400 microns. The nonionic liquid surf~3ctant phase can be mixed with the solid builders prior to or after carrying out the grinding operntion.
In a preferred embodiment of the invention, the mixture of liquid nonionic surfactant and solid ingredients is subjected to an attrition type of mill in which the particle sizes of the solid ingredients are reduced to less than about 10 microns, e.g. to an average particle size of 2 to 10 microns or even lower (e.g. 1 micron). Preferably less than about 10%, especially less tharl about 5~ of all the suspended particles have particle sizes greater than 10 microns. Compositions whose dispersed particles are of such small size have improved stability against separation or settling on storage. Addition of the acid terminated nonionic surfactant compound can decrease the yield stress of such dispersions and aid in the dispersibility of the dispersions without a corresponding decrease in the dispersions stability ngainst;
2 0 set tlin g .
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~O) that the solid particles are in contact with each other and are not substantially shielded rom one another by the nonionic surfactant liquid. After the ~5 ~ grinding step any remaining liquid nonionic surfactant can be added to tne ground formulation. Mills ~vhich 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 g~rinding balls. For lal ger scale work a continuously opcrating ,mill in which thcre are 1 mm or 1 5 mm diametcr grindillg ba]ls working in a very small g~p bctween a stator b~ ~3~8~ -and a l~otor operating at a l~elltively high spcecl (e. g. a CoBall rnill) may be emp]oyed; when using such a mill~ it is desirable to pass the b]end of nonionic surfactant and solids first through a mill which does not effect such fine grinding (e g. a col]oid mill) to reduce the particle size to less thsn 100microns (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 ingredients are as follows:
Liquid nonionic surfactant detergent in the range of about 10 to 60, such as 20 to 50 percent, e. g. about 30 to 40 percent.
Acid terminated nonionic surfactant viscosity improving agent in an amount in the range of about 0 to 20, such as 3 to 15 percent, e. g. about 4 to 10.
Detergent builder, such as sodium tripolyphosphate (TPP), in the range of about 10 to 60, such as 15 to 50 percent, e.g. about 25 to 35 percent.
Copolymer of polyacrylate and polymaleic anhydride alkali metal salt, e.g. Sokalan CP5, anti-incrustation agent in the range of about 0 to 10, such as 2 to 8 percent, e. g. about 3 to 5 percent.
Alky]ene glycol monoalkylether anti-gel agent in an amount in the range of about 5 to 30, such as 5 to 20 percent, e.g. about 5 to 15 percent.
Phosphoric acid alkanol ester stabilizing agent in the range of 0 to 2 . 0 or 0,1 to 1 0, such as 0.2 to 0.5 percent.
Bleaching agent in the range of about 5 to 30, such as 2 to 20, e. g.
about 5 to 15 percent.
Calcium cyanamide bleach activator in the range of about 1 to 15, such as 1 to 8, e.g. about 2 to 6 percent.
Sequesterin~ agent for bleach, e.g. Dcquest 20G6, in the range of about 0 to 3.0, prcferably 0.5 to 2.0 percent, e.g. about 0.75 to 1.25 percent .

~ ~L3~ 32 Anti-rcdeposition agent, e.g. Rc~atin ~M 9050, in the range of about 0 to 4 . 0, preferably 0 . 5 to 3 . 0 percent, e . g. 0 . 5 to 1. 5 percent .
Optical brightener in the range of about 0 to 2.0, preferably 0.05 to 1 0 percent, e. g. 0.15 to 0. 75 percent.
Enzymes in the range of about 0 to 3.0, preferrably 0.5 to 2.0 percent, e. g. 0 . 75 to 1. 25 percent .
Perfume in the range of about 0 to 3.0, preferably 0.10 to 1.25 percent, e. g. 0 . 25 to 1. 0 percent .
Various OI the previously mentioned additives can optionally be added to achieve the desired function of the added materials.
The calcium cyanamide bleach activator is preferably use with at least one of the alkylene glycol mono-ether or the acid terminated nonionic surfactant viscosity control and anti-gel agents. In some cases advantages can be obtained by using both the alkylene glycol mono-ethers and the acid terminated nonionic surfactants.
In the selection of the additives, they will be chosen to be compatible with the main constituents of the detergent composition. ln 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.

1 130'Y~82 In an embodiment of the invention the detergent composition of a typical formulation is formulated using the below named ingredients:
~'eight %
Nonionic surfactant detergent. 30-40 Acid terminated surfactant viscosity improving agent. 0-20 Phosphate detergent builder sa]t. 10-60 Anti-incrustation agent. 0-10 Alkylene glycol monoalkylether anti-gel agent.5-15 Phosphoric acid alkanol ester stabilizing agent 0-2.0 Anti-redeposition agent. 0-4 ~
Alkali metal perborate persalt bleaching agent. 5-15 Calcium cyanamide bleach activator. 1.0-8.0 Sequestering agent for bleach. 0-3,0 Duet 787 . 0-3 ~
Optical brightener . 0 . lS-0 . 75 Enzymes . 0 . 75-1. 25 Perfume . 0-3 . 0 ' ~3(17~

The present invention is further il~ustrated by the fol~o~ing examp~es.
X AM PLE
A concentrated nonaqueous liquid nonionic surfactant detergent composition is formu]ated from the follo~ing ingredients in the amounts specified .
Weight %
Nonionic surfactant . 38 . 8 Acid terminated Dobanol 91-5 reaction product with succinic anhydride . 5 Sodium tri polyphosphate (TPP). 29.6 Diethylene glycol~ monobutylether anti-gèl agent. 10 Phosphoric acid al~anol ester (Emphiphos 5632). 0.3 Sodium perborate monohydrate bleaching agent. 9.0 Calcium cyanamide bleach activator . 4 . 5 Anti-redeposition agent (Relatin DM 4050)(1~ 1.0 Optical brightener. 0.2 Perfume (Duet 787). 0.6 Enzyme~(which is Esperase). 1.0 100.~
(1) CMC/~C 2:1 mixture of sodium carboxymethyl cellulose and hydroxymethylcellulose .
The formulation is ground for about 1.0 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 readily dispersible in water and to have good bleach properties and improved detcrgency .

~ 3~

EX Al~ PLE 2 A concentrated non~queous liquid nonionic surfact~nt delergent composition is formu]ated from the fol~owing ingredients in the amounts spccified .
Wei ~ht Nonionic surfactant Product D . 13 . 5 Surfactant T7. 10 Surîactant T9. 10 Acid terminated Dobanol 91-5 reaction product with succinic anhydride. 5 Sodium tri-polyphosphate (TPP) . 29 . 6 Anti-incrustation agent (Sokalan CP5)~ 4.0 Diethylene glycol monobutylether anti-gel agent. 10 Phosphoric acid alkanol ester (Empiphos 5632) . 0 . 3 Sodium perborate monohydriate bleaching agent. 9 Calcium cyanamide bleach activator . 4 . 5 Sequestering agent for bleach (Dequest 206B~. 1.0 Anti-redeposition agent (Relatin DM 4050)(1). 1.0 Optical brighteners (Stilbene). 0.5 Enz~ me (Esperase slurry) . 1.0 Duet 787 ( ) 0 . 6 ' 100.0 (1) Cl\~C/MC 2:1 mixture of sodium carboxymethyl cellulose and hydroxymethylcellulose .
(2) Duet 787 which is a fragrance from IFF Inc.
The formulation is ground for about 1 hour to reduce the particle size of the suspended builder salts to less than 90 microns. The formulated . detergent composition is found to be stable and non-gelling in storage andreadily dispersible in water. The bleach is active at 60C on immedial black.
The calcium cyanamide 9.5~6 concentration gave a ~Rd=5 3 a9 compared with a ~Rd of 0. 8 witllout an activator. The pH o~ the aqucous wash water without ~0~

a bleach activtitor is pH 9 . 6, ~vith 4 . S~i c~cium cyan~3rnide activ~lor is pl~ 9 . 9 and with 4 . 5~ TAED activator is pH 9 . 0 .
The formu]ations of E~amp]es 1 and 2 can ~e prepared without grinding the builder snlts and suspended solid p~rticles to a sma]l particle size, but best results are obtained by grinding the formulation lo reduce the p~rticle 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 nonionie surfactant. The grinding can be earried out in part prior to mixing and grinding eompleted after mixing or the entire grinding operation can be earried out after mixing with the liquid surfaetant. The formulations containing suspended builder and solid particles less than 40 microns in size are preferred.
The persalt bleach eompound and the ealeium eyanamide bleach activator system of the present invention ean also be used in nonionie surfactant detergent dishwashing eompositions, eream seourers, and other compositions in which bleaching is required sueh as dry powder and dry granular detergent eompositions.
It is understood that the foregoing detailed description is given merely by way of illustration and that variations may be made therein without departing from the spirit of the invention.

Claims (17)

1. A concentrated nonaqueous liquid heavy duty built laundry detergent composition which is pourable at high and low temperatures and which does not gel when added to cold water which comprises Weight %
At least one liquid nonionic surfactant in an amount of about 10-60 At least one detergent builder suspended in the nonionic surfactant in an amount of about 10-60 An inorganic peroxygen bleaching agent suspended in the nonionic surfactant in an amount of about 5-30 Calcium cyanamide bleach activator in an amount of about 1-15 Alkylene glycol mono alkyl ether gel inhibiting additive in an amount of about 5-30

2. The detergent composition of claim 1 additionally comprising 3 to 15% of a carboxylic acid terminated nonionic surfactant viscosity control agent.

3. The detergent composition of claim 1 which comprises a suspension of insoluble organic builder salt in an amount of 1 to 50%.

4. The detergent composition of claim 1 comprising an alkali metal polyphosphate builder salt in an amount of 15 to 50%.

5. The detergent composition of claim 1 additionally comprising about 0.1 to 1.0% of a phosphoric acid alkanol ester anti-settling stabilizing agent.

6. A concentrated stable non-settling nonaqueous liquid heavy duty built laundry detergent composition which is pourable at high and low temperatures and which does not gel when added to cold water which comprises Weight %
At least one liquid nonionic surfactant in an amount of about 20-50 At least one detergent builder suspended in the nonionic surfactant in an amount of about 15-50 An inorganic peroxygen bleaching agent suspended in the nonionic surfactant in an amount of about 2-20 Calcium cyanamide bleach activator in an amount of about 1-8 Alkylene glycol mono alkyl ether gel inhibiting additive in an amount of about 5-20

7. The composition of claim 6 comprising a carboxylic acid terminated nonionic surfactant in an amount of about 3 to 15%.

8. The composition of claim 6 wherein the detergent builder comprises polyphosphate detergent builder.

9. The detergent composition of claim 6 which additionally comprises about 0.1 to 1.0% of an anti-settling stabilizing agent.

10. The composition of claim 6 wherein the inorganic builder salt has particle size of less than 40 microns.

11. The detergent composition of claim 6 additionally comprising one or more detergent adjuvants selected from the group consisting of anti-incrustation agent, sequestering agent, anti-redeposition agent, optical brightener, enzymes and perfume.

12. A detergent composition which comprises Weight %
Nonionic surfactant in an amount of about 30-40 Sodium tripolyphosphate in an amount of about 25-35 Alkylene glycol monoalkyl ether in an amount of about 5-15 Phosphoric acid alkanol ester anti-settling stabilizing agent in an amount of about 0.2-0.5 Sodium perborate monohydrate bleaching agent in an amount of about 5-15 Calcium cyanamide bleach activator in an amount of about 2-6,0

13. A concentrated stable non-settling nonaqueous liquid heavy duty built laundry detergent composition which is pourable at high and low temperatures and does not gel when mixed with cold water, wherein the essential ingredients consist of Weight %
At least one poly lower alkylene oxide fatty alcohol liquid nonionic surfactant in an amount of about 20-50 At least one alkali metal polyphosphate detergent builder suspended in the nonionic surfactant in an amount of about 15-50 An alkali metal perborate monohydrate bleaching agent suspended in the nonionic surfactant in an amount of about 2-20 Calcium cyanamide bleach activator in an amount of about 1-8 A C2-C3 alkylene glycol mono C2-C5 alkyl ether gel inhibiting additive in an amount of about 5-20

14. The detergent composition of claim 13 additionally comprising a carboxylic acid terminated nonionic surfactant in an amount of about 3 to 15%.

15. The detergent composition of claim 13 additionally comprising about 0.1 to 1.0% of a phosphoric acid alkanol ester anti-settling stabilizing agent.

16. The detergent composition of claim 13 which additionally contains one or more detergent adjuvants selected from the group consisting of anti-incrustation agent, sequestering agent, anti-redeposition agent, optical brightener, enzyme and perfume.

17. A method for cleaning soiled fabrics which comprises contacting the soiled fabrics with the laundry detergent composition of any one of claims 1 to 16.