CA1283016C - Liquid laundry detergent composition and method of use - Google Patents

Abstract

LIQUID LAUNDRY DETERGENT
COMPOSITION AND METHOD OF USE

ABSTRACT OF THE DISCLOSURE

A liquid heavy duty laundry detergent composition comprising a suspension of builder salt in liquid nonionic surfactant. To improve dispensibility in automatic washing machines, the composition contains as a viscosity and gel controlling agent an alkylene glycol monoalkyl ether, especially diethyleneglycol monobutyl ether.

Description

62301-135~.
~283~6 LI~UID LAUNDRY DETERGENT

COMPOSITION AND MET~IO~ OF USE
BACKGROUND OF THE INVENTION
(1) Field o~ Invention This invention relates to liquid laundry detergent compositions. More particularly, this invention relates to non-aqueous liquid laundry detergent compositions which are easily pourable and which do not gel when added to water and to the use of these compositions for cleaning soiled fabrics.

(2) Discussion of Prior Art Liquid non-aqueous heavy duty laundry detergent compositions are well known in the art. For instance, compositions of that type may comprise a li~uid nonionic surfactant in which are dispersed particles of a builder, as shown for instance in the U. S. Patents Nos. 4,316,812;

3,630,929; 4,264,466, and British Patents Nos. 1,205,711, 1,270,040 and 1,600,9~1.
Liquid detersents are often considered to be more convenient 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. Additionally, the liquid detergents may have incorporated in their formulations materials which could not stand drying operations without deterioration, which materials are often desirably employed in the manufacture of particulate detergent products. Although they are possessed of many advantages over unitary or particulate solid products, liquid detergents often have certain inherent disadvantages too, which i- 62301-1352 ~283~6 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 yel on standins.
The present inventors have been extensively involved in studyiny the rheoloyical behavior of nonionic liquid surfactant systems with and without particulate matter suspended therein. Of particular interest has been non-aqueous built laundry liquid deteryent compositions and the problems of gelling associated with nonionic surfactants as well as settling of the suspended builder and other laundry additives.
These considerations have an impact on, for example, product pourability, dispersibility and stability.
The rheological behavior of the non-aqueous built liquid laundry detergents can be analogized to the rheological behavior of paints in which the suspended builder particles correspond to the inorganic pigment and the nonionic liquid surfactant corresponds to the non-aqueous paint vehicle. For simplicity, in the following discussion, the suspended particles, e.g. detergent builder, will sometimes be referred to as the "pigment". ~-~
It is known that one of the major problems with paints and built liquid laundry detergents is their physical stability. This problem stems from the fact that the density of the soIid pigment particles is higher than the density of the liquid matrix. Therefore, the particles tend to sediment according to Stoke's law. Two basic solutions exist to solve the sedimentation problem: liquid matrix viscosity and .::

6~301-1352 ~33~

reducing solid particle size.
For instance, it is known that such suspensions can be stabilized against settling by adding inorganic or organic thickening agents or dispersants, such as, for example, very high surface 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 liquid 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 is more advantageous and provides two major consequences:
1. The pigment specific surface area is increased, and, therefore, particle wetting by the non-aqueous vehicle (liquid nonionic) is proportionally improvedO
2. The average distance between pigment particles is reduced with a proportionate increase in particle-to-particle interaction. Each of these effects contributes toincrease the rest-gel strength and the suspension yield stress while at the same time, grinding significantly reduces plastic viscosity.
The non-aqueous liquid suspensions of the detergent builders, such as the polyphosphate builders, especially sodium tripolyphosphate (TPP) in nonionic surfactant are found to behave, rheologically, substantially according to the Casson equation:

~`~ L2~33~)~LS
~ = aD~ + n,3~ ~
where y is the shear rate, a is the shear stress, ~O is the yield stress (or yield value), and n~ is the "plastic viscosity" (apparent viscosity at infinite shear rate).
The yield stress is the mini~um stress necessary to induce a plastic deformation (flow) of the suspension. Thus, visualizin the suspension as a loose network of pigment particles, if the applied stress is lower than the yield stress, the suspension behaves like an elastic gel and no plastic flow will occur.
Once the yield stress is overcome, the network breaks at some points and the sample begins to flow, but with a very high apparent viscosity. If the shear stress is much higher than the yield stress, the pigments are partially shear-defloccul te and the apparent viscosity decreases. Finally, if the shear stress is much higher than the yield stress value, the pigment particles are completely shear-deflocculated and the apparent viscosity is very low, as if no particle interaction were present.
Therefore, the higher the yield stress of the suspension, the higher the apparent viscosity at low shear ra~e and the better is the physical stability of the product.
In addition to the problem of settling or phase separation the non-aqueous liquid laundry detergents based on liquid nonionic surfactants suffer from the drawback that the nonionics te,nd to gel ~hen added to cold water. This is a particularly important problem in the ordinary use of European household automatic washing machines where ~he user places the laundry detergent composition in a dispensing unit ~e.g. a dispensing drawer) of the machine. During the operation of the machine . _ . , ,. ~

~ 331)~;
., 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 compositio 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 syn~hetic and delicate fabrics or fabrics which can shrink in warm or hot water.
Partial solutions to the gelling problem in aqueous, substantially builder-free compositions have been proposed and include, for example, diluting the liquid nonlonic with certain viscosity controlling solvents and gel-inhibiting agents, such as lower alkanols, e.g. ethyl alcohol (see U.S.
Patent 3,953,380), alkali metal forma~es and adipates (see U.S. Patent 4,368,147), hexylene glycol, polyethylene glycol, etc.
In addition, these two patents each disclose the use of up to at most about 2.5% of the lower alkyl (Cl-C4) etheric derivatives of the lower (C2-C3) polyols, e.g. ethylene glycol, in these aqueous liquid builder-free detergents in place of a portion of the lower alkanol, e.g. ethanol, as a viscosity control solvent. To similar efect are U.S. Patents 4,111,855 and 4,201,686. However, there is no disclosure or suggestion in any of these patents that these compounds, some of which are commercially available under the tradename Cellosolve~, . ~Z~33~
could function effectively as viscosity control and gel-preventin agents for non-aqueous liquid nonionic surfactant compositions, especially such compositions containing suspended builder salts, such as the polyphosphate compounds, and especially particularly such compositions which do not depend on or require the lower alkanol solvents as viscosity control agents.
Furthermore, British Patent Specification 1,600,981 mentions that in non-aqueous nonionic detergent compositions containing builders suspended therein with the aid of certain dispersants for the builder, such as finely divided silica and/or polyether group containing compounds having molecular weights of at least 500, it may be advantageous to use mixtures of nonionic surfactants, one of which fulfills a surfactant function and the other of which both fulfills a surfactant function and reduces the pour point of the compositions.
The former is exemplified by C12-Cls fatty alcohols with 5 to 15 moles of e~hylene and/or propylene oxide per mole.
The other surfactant is exemplified by linear C~-Cg or branched Cg-Cll fatty alcohols with 2 to 8 moles ethylene and/or propylene oxide per mole. Again, there is no teaching that these low carbon chain compounds could control the viscosity and prevent gelation of the heavy duty non-aqueous liquid nonionic surfactant compositions with builder suspended in the non;onic liquid surfactant.
It is also known to modify the structure of nonionic surfactants to optimize their resistance to gelling upon contact with water, particularly cold water. 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 introducin a carboxylic acid at the end of the nonionic include gel ~L2~

inhibition upon dilution; decreasing the nonionic pour point;
and formation of an anionic surfactant when neutrali~ed in the washing liquor. Nonionic structure optimization for minimizing gelation is also known, for example, controlling 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 C13 fatty alcohol ethoxylated with 8 moles of ethylene oxide presents only a limited tendency to gel forma-tion.
Nevertheless, still further improvements are desiredin the stability, viscosity control and gel inhibition of non-aqueous liquid detergent compositions.
Accordingly, it is an object of the invention to provide non-aqueous liquid laundry detergents which do not gel when contacted with or when added to water, especially cold water.
It is a Eurther object of the invention to provide non-aqueous liquid built laundry detergent compositions which are storage stable, easily pourable and dispersible in cold, warm or hot water.
Another object of this invention is to formula-te highly built heavy duty non-aqueous liquid nonionic surfactant laundry detergent compositions which can be poured at all temperatures and which can be repeatedly dispersed from the dispensing unit of European style automatic laundry washing machines without fouling or plugging of the dispenser even during the winter months.
A specific object of this invention is to provide non-gelling, stable, low viscosity suspensions of heavy duty tripolyphosphate built non-aqueous liquid nonionic laundry detergent composition which include an amount of a low molecu~r ~, - 7 -12~3~ 62301-1352 weight amphiphilic compound sufficient to decrease the viscosity of the composition in the absence of water and upon contact with cold water.
These and other objects of the invention which will become more appaxent from the following detailed description of preferred embodlments are generally provided by a~ding to the liquid nonionic surfactant composition an amount of a low molecular weight amphiphilic compound, particularly, mono-, di-or tri(lower (C2 to C3) alkylene)glycol mono(lower (C1 to C5) alkyl) ether, effective to inhibit gelation of the nonionic surfactant in the presence of cold water.
Accordingly, in one aspect the present invention provides a nonaqueous heavy duty laundry composition comprising a suspension of a detergent builder salt in a liquid nonionic surfactant, an amount of mono- or poly- (C2 to C3 alkylene)glycol mono-(C1 to C5 alkyl)ether su~ficient to decrease the viscosity of the composition both in the absence of water and upon con~actlng of the composition with water, an~
an acid-terminated nonionic surfactant which is obtained by converting a free hydroxyl group of a nonionic surfactant to a moiety having a free carboxyl group, the amount of said acid-terminated nonionic surfactant being sufficient to further lower the temperature at which the liquid nonionic surfactant forms a gel with water, said composition comprising from about 30 to about 70% o~ the liquid nonionic surfactant and the alkylene glycol monoalkyl ether at a weight ratio of nonionic surfactant to glycol ether in the range of from about 100:1 to 3:1, and from about 10 to about 60% of the suspended detergent builder.
The invention further relates to a nonaqueous liquid heavy duty laundry composition consisting essentially of ~ J

~2~30~ 62301-1352 (A) from about 30 to 70% by weight of a llquid phase compo~ed o~ a liquid nonionic surfactant and a viscosity-controlling and gel-inhibiting compound of the formula RO(CHCH20)nH
where R is alkyl of 2 to 5 carbon atoms, R' is hydrogen or methyl, and n is a number of from 2 to 4 on average, the welght ratio of surfactant to said compound being from 100:1 to ~tl, (B) from about 10% to about 60% of detergent builder salt suspended in the liquid phase;
(C) a polyether carboxylic acid gel-inhibiting compound in an amount from about 0.5 to 10 parts of -COOH group per 100 parts of the polyether carboxylic acid and liquid nonionic surfactant;
(D) 0.01 to 5% by weight of an acidic organic phosphorus compound as an anti-settling agent, and (E) one or more detergent additives elected from the group consisting of (a) enzymes, O to 2 % by weight, (b) corrosion inhibitors, O to 40% by weight, Ic) anti-~oam agents and suds-suppressors, O to 15% by weight ~d) inorganic thickening agents and dispersants, O to 15% by weight, le) soil-suspending anti-redeposition and anti-yellowing agents, O to 10% by weight, (f) colorants, perfumes, optical brighteners and bluing agents, O
to 2% by weight, (g) pH modifisrs and pH buffers, O to 5% by wsight, (h) bleaching agent, O to 40% by weight, (i) bleach stablizers and bleach activators, O to 15% by weight, and (j) sequestering agents, O to 5% by weight.
8a t33~

In a more specific embodiment, the presen~ inventlon provides a nonaqueous liquid eleaning composition which remains pourable at temperatures below about 5C and which does not gel when contacted with or added to water at temperatures below about 20C, the composition being connposed of a liquid nonionic surfactant and C2 to C3 alkylene glycol mono(C1 to C5)alkyl ether and being substantially free oi. water.
Accordiny to another aspect:, the invention provides a method ior dispensing a liquid nonionic laundr~ detergent composition into and~or with cold water without underyoing gelation. In particular, a method is provided for filling a container with a nonaqueous liquid laundry detergent composition in which the det;ergent is composed, at least predominantly, 8b i 1 ' ~,.i`

~ 2301-1352 of 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 of unheated water onto the composition such that the composition is carried by the stream of water into the wash bath. By including a low molecular weight amphiphilic compound, i.e. a lower C2 to C3 alkylene glycol mono(lower) (Cl to Cs)alkyl ether, -the composition can be easily poured into the container even when the composition is at a temperature below room temperature. Furthermore, the composition does not undergo gelation when it is contacted by the stream of water and it readily disperses upon entry into the wash bath.
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 and, for example, are described at length in the text Surface Active Agents Vol. II, by ~chwartz, Perry and Berch, published in 1958 by Interscience Publishers, and in McCutcheon's Detergents and Emulsifiers, 1969 Annual. 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 allsanol is of 10 to 18 carbon atoms and wherein the number of mols of lower alkylene oxide (of 2 or 3 carbon atoms) is from 3 to 12. Of such materials it is preferred to employ those wherein the higher alkanol is a higher fatty alcohol of 10 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, _ g _ ~LZ~3~

the lot~er al~oxy is ethoxy but in some instances, it may be desir2bly mixed with propoxy, the latter, if present, usually being a rninor (less than 50~/O) proportion. Exemplary of such compounds are those wherein the alkanol is of 12 to 15 carbon atoms and which contain abou~ 7 ethylene oxide groups per mol, e.g. Neodol~ 5-7 and Neodol~ 3-6.5, 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 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 15 carbon atoms linear secondary alkanol with seven mols of ethylene oxide and the latter is a similar product but with nine mols of ethylene oxide being reacted.
Also useful in the present compositions as a componerlt of the nonionic detergent are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensati n 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 aré represented by the Plurafac~series from BASF Chemical Company which are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containin a mixed chain of ethylene oxide and propylene oxide, terminated ~ral~ U~k -10-: ILZ~3301~6 by a hydroxyl~group. Examples include Plurafac RA30 (a C13-Cls fatty alcohol condensed ~ith 6 moles ethylene oxide and 3 moles propylene oxide), Plurafac RA40 (a C13-Cls fatty alcohol condensed with 7 moles propylene oxide and 4 moles ethylene oxide), Plurafac D25 (a C13-Cls fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethylene oxide`), ~nd Plurafac B26. Another group of liquid nonionics are available from Shell Chemical Company, Inc. under the Dobanol trademark:
Dobanol 91-5 is an ethoxylated Cg-Cll fatty alcohol with an average of 5 moles ethylene oxide; Dobanol 25-7 is an ethoxylated Cl2-Cls fatty alcohol with an average of 7 moles ethylene oxide; etc.
In the preferred poly-lower alkoxylated higher alkanols, to obtain the best balance of hydrophilic and l;pophilic 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% thereof and the nonionic detergent will preferably contain at least 50% of such preferred poly-lower alkoxy higher alkanol. Higher molecular weight alkanols and various other normally solid nonionic detergents and surface active agents may be contributory to gelation of the liquid detergent and consequently, will preferably be omitted 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 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 : ~L2~0~6 a branched configuration will be minor rarely exceeding 20%
of the to~al carbon atom content of the alkyl. Similarly, although linear alkyls which are terminally joined to the eThylene oxide chains are hi~hly 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 20% but, as is in the cases of the mentioned Terigtols, ~ay 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-containing poly-lower alkoxylated alkanols and less hydrophile-lipophile balanced nonionic deter~ent 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 i~prove the properties of the detergents based on such nonionics.
In some cases, as when a higher molecular weight polylower alkoxylated higher alkanol is employed, often for its detergency, the proportion thereof will be regulated or limited as in accordance with the results of various experiments, to obtain the desired detergency and still have the product non-gelling and of desired viscosity. Also, it has been found that it is only rarely necessary to utilize the higher molecular weight nonionics for their detergent properties since the preferred nonionics described herein are excellent detergents - . -`: ~ ~ 3 ~
and additionally, permit the attainment of the desired viscosityin the liquid detergent withou~ gelation at low temperatures.
Mixtures of two or more of these liquid nonionics can also be used and in some cases advantages can be obtained by the use of such mixtures.
As mentioned above, the structure of the liquid nonionic surfactant may be optimized with regard to their carbon chain length and configuration (e.g. linear versus branched chains, etc.) and their content and distribution of alkylene oxide units. Extensive research has shown that these structural characteristics can and do have a profound effect on such properties of the nonionic as pour point, cloud point, viscosity, gelling tendency, as well, of course, as on detergency.
Typically most com~7ercially available nonionics have a relatively large distribution of ethylene oxide (E0~
and propylene oxide (P0) units and of the lipophilic hydrocarbon chain length, the reported E0 and P0 contents and hydrocarbon chain lengths being overall averages. Thi~ "polydispersity"
of the hydrophilic chai~s and lipophilic chains can have great importance on the product properties as can the specific values of the average values. The relationship between "poly-dispersity" and specific chain lengths with product properties for a well-defined nonionic can be shown by the followi~g L~ data for the "Surfactan~ T' series of nonionics available from British Petroleum. The Surfactant T nonionics are obtained by ethoxylation of secondary C13 fatty alcohols having a narrow E0 distribution and have the following physical char-acteristics:

Cloud Point (1% sol) E0 Content Pour Point (~C) (C) Surfactant T5 5 <-2 <25 Surfactant T7 7 -2 38 Surfactant T9 9 6 58 Surfactant T12 12 20 88 .
~ ~rQ~
-l3-:; - I ~Z~33~6 I ..
. .
To assess the impact of EO distribution, a "Surfactant T8" was artificially prepared in two ways:
a. 1:1 mixture of T7 and T9 (T8a) b. 4:3 mixture of T5 and T12 (T8b).
The following properties were found:

EO Content Pour Point Cloud Point (lV/~ sol'n) (av~) (C) _(C) Surfactant T8a 8 2 48 Surfactant T8b 8 15 <20 From these results, the following general observations can be made:
. 1. T8a corresponds closely to an actual surfactant T8 as it interpolates well between T7 and T9 for both pour point and cloud point.
2. T8b which is highly polydisperse and would be generally unsatisfactory in view of its high pour point and low cloud point temperatures.
3. The properties of T8a are basically additive between T7 and T9 whereas for T8b the pour point is close to the long EO chain (T12) while the cloud point is close to the short EO chain (T5~.
The viscosities of the Surfactant T nonionics were measured at 20%, 30%, 40%, 50%, 60%, 80% and 100% nonionic concentrations for T5, T7, T7/T9 (1:1), T9 and T12 at 25C
with the following results (when a gel is obtained, the viscosity is~the Bingham viscosity):

~ ~301~

Nonionic Viscosity (mPa s) - T5 T7 ¦ T7/T9 T9 ¦ rl z lO0 ~ ~36 63 61 - 149 750 78 188 239 3~200 -From these results, it may be concluded that Surfactant T7 is less gel-sensitive than T5, and T9 is less gel-sensitive than T12; moreover, the mixture of T7 and T9 (T8) does not gel, and its viscosity does not exceed 225 m Pa s. T5 and T12 do not form the same gel structure.
Although not wishing to be bound by any particular theory, it is presumed that these results may De accounted for by the following hypothesis:
For T5: with only 5 E0, the hydrodynamic volume of the E0 chain is almost the same as the hydrodynamic volume of the fatty chain. Surfactant molecules can accordingly arrange themselves to form a lamellar structure.
For T12: with 12 E0, the hydrodynamic volume of .. . . . ~
the E0 chain is greater than that of the fatty chain. When molecules try to arrange themselves together 9 an interface curvature occurs and rods are obtained. The superstructure is then hexagonal; with a longer E0 chain, or with a higher hydratation, the interface curvature can be such that actual spheres are obtained, and the arrangement of the lowest energy is a face-centered cubic latice.
From T5 to T7 (and T8), the interface curvature increases, and the energy of the lamellar structure increases.
As the lamellar structure looses stability, its meltin~ temperatu e is reduced.

~8~ 6 .
From T12 to T9 (and T8), the interface curvature decreases, and ~he energy of the hexa~onal structure increases (rods beco~e bigger and bigger). As the loss in stability occurs, the structure melting temperature is also reduced.
Surfactant T8 appears to be at the critical point at which the lamellar structure is destabilized, i.e. the hexagonal structure is not yet stable enough and no gel is obtained during dilution. In fact, a 50% solution of T8 will finally gel after two days, but the superstructure formation is delayed long enough to allow easy water dispersability.
The effects of the molecular weight on physical properties of the nonionics were also considered. Surfactant T8 tl:l mixture of T7 and T9) exhibits a good compromise between the lipophilic chain (C13) and the hydrophilic chain (E08), although the pour point and maximum viscosity on dilution at 25C are still high.
The equivalent E0 compromise or C~0 and C8 lipophilic chains was also determined using the Dobanol 91-~ series from Shell Chemical Co., which are ethoxylated derivatives of C9-Cll fatty alcohols (average: C10); and Alfonic 610-y X
series from Conoco which are ethoxylated derivatives of C6-Clo fatty alcohols (average Cg); x and y represent the E0 weight percentage.
The next table reports the physioal characteristics of the Alfonic 610-y and Dobanol 91-x series-Nonionic # E0 Pour Point Cloud Pt. Max. on dilution " ~av~.) (C) (C)at 25C ~mPa- 5) Alfonic 610-50R 3 -15 Gel (60%~
Alfonic 610-60 4.4 -4 41 36 (60%) Dobanol 91-5 5 03 33 Gel (70%~
Dobanol 91-5T 6 +2 55 126 (50%) Dobanol 91-8 8 +6 81 Gel (50%~

~ rr ~ 16 __ ~;2 B3~

Dobanol 91-5-and Dobanol 91-8 are co~mercially available products; Dobanol 91-5 topped (T) is a lab scale product:
it is Dobanol 91-5 from which free alcohol has been removed.
As the lowest ethoxylation members are also removed, the average E0 number is 6. Dobanol 91-5T provides the best results of C10 lipophile chain ac: it does not gel at 25C.
The 1% cloud point (55C) is higher than for surfactant T8 (48C). This is presumably due to the lower molecular weight since the mixture entropy is higher. Alfonic 610-60 provides the best results of the C8 lipophile chain series.
A summary of the best E0 contents for each tested lipophilic chain length is provided in the following table:

Cloud Pt.
Nonionic # C # E0 Pour Pt. (1% soln~ Max n on dil.~%) (C) (~) at 25C (mPa s) Surfactant T8 13 8 +~ 48 223 (50%) Dobanol 91-5T 10 6 ~2 55 126 (50%) Alfonic 610-60 8 4.4 -4 41 36 (60%) From this data, the following conclusions were reached:
Pour points: as the nonionic molecular weight decreases, its pour points decrease too. The relatively high pour point of Dobanol 91-5T can be accounted for by the higher polydispersit .
This was also noticed for T8a and T8b, i.e. the chain polydispers ty increases the pour point.
Cloud points: theoretically, as the number of molecules increases (if the molecular weigh~ decreases~, the mixing ent~opy is higher, so the cloud point would increase as the molecular weight decreases. It is actually the case from Surfactant T8 to Dobanol 91-5T but it has not been confirmed with Alfonic 610-60. Here it is presumed that the lipophilic hydrocarbon chain polydispersi~cy is responsible for the theoretic l]y - ~ 83~L~
too low cloud~point. The relatively large amount of C10-E0 present reduces the solubility.
Maximum viscosity on dilution at 25C: none of these nonionics gel at 25C when they are diluted with water.
The maximum viscosity decreases sharply with the molecular weight. As the nonionic molecular weight decreases, the less efficient becomes the hydrogen bridges. Unfortunately, too low molecular weight nonionics are not suitable for laundry washing: their micellar critical concentration (MCC) is too high, and a true solution, with only a limited detergency would be obtained under practical laundry conditions.
With this information, the present inventors continued their studies on the effects of the low molecular weight amphiphilic compounds on the rheological properties of liquid nonionic detergent cleaning compositions. These studies revealed that while it is possible to lower the pour point of the composition and obtain some deg~ee of gel inhibition by using a short chain hydrocarbon~ e.g. about Cg, with a short chain ethylene oxide substi~ution, e.g. about 4 moles, as amphiphilic additive, such as Alfonic 610-60, these additives do not significantly contribute to the overall laundry cleaning performance and still do not exhibit overall satisfactory viscosity control over all normal usage conditions.
The present invention is, therefore, based, at least in part, on the discovery that the low molecular weight amphiphil c compounds which can be considered to be analogous in chemical structure to the ethoxylated and/or propoxylated fatty alcohol nonionic surfactants but which have short hydrocarbon chain lengths (Cl-C5) and a low content of alkylene oxide, i.e.
ethylene oxide and/or propylene oxide (about 1 to 4 E0/P0 units per molecule) function effectively as viscosity control ~ a 3 ~ ~ 62301-1352 and gel-inhibiting agents for the liquid nonionic surface active cleaning agents.
The viscosity-controlling and gel-inhibiting amphi-philic compounds used in the present invention can be represented by the following general -formula R' RO(CHCH20)r~H
where R is a Cl-Cs, preEerably C2 to Cs, especially preferably C2 to C4, and particularly C4 alkyl group, R' is H or CH3, preferably H, and n is a number of from about 1 to 4, preferably 2 to 4 on average.
Preferred examples of suitable amphiphilic compounds include ethylene glycol monoethyl ether (C2Hs-O-CH2CH20H), and diethyl-ene glycol monobutyl ether (C4Hg-O-(CH2CH20)2H).
Diethylene glycol monoethyl ether is especially preferred and, as will be shown below, is uniquely effective to control viscosity.
While the amphiphilic compound, particularly diethylene glycol monobutyl ether, can be the only viscosity control and gel inhibiting additive in the invention composi-20 tions 20 further improvements in the rheological proper-ties oE
the anhydrous liquid nonionic surfactant compositions can be obtained by including in the composition a small amount of a nonionic surfactant which has been modified to convert a free hydroxyl group thereof to a moiety having a free carboxyl group, such as a partial ester of a nonionic surfactant and a polycarboxylic acid and/or an acidic organic phosphorus compound having an acidic - POH group, such as a partial ester of phosphorus acid and an alkanol.
As disclosed in the commonly assigned copending Canadian Application No. 478,379 filed on April 4th, 1985 the -free carboxyl ~, - 19 -~ 33'~
group modified nonionic surfactants, which may be broadly characterized as polyether carboxylic acids, function to lower the temperature at which the liquid nonionic forms a gel with water. The acidic polyether compound can also decrease the yield stress of such dispersions, aiding in their dispensibility, without a corresponding decrease in their stability against settling. Suitable polyether carb~xylic cids contain a grouping of the Eormula ~OCH2-CH2~p~CH-CH2~-Y-Z-COOH where R2 is hydrogen or methyl, Y is oxygen or sulfur, Z is an organic linkage, p is a positive number of from about 3 to about 50 and q is zero or a posit;ve number of up to 10. Specific examples include the half-ester of Plurafac RA30 with succinic anhydride, the half ester of Dobanol 25-7 with succinic anhydride, the half ester of Dobanol 91-5 with succinic anhydride, etc. Instead of a succinic acid anhydride, other polycarboxylic acids or anhydrides may be used, e.g.
maleic acid, maleic anhydride, glutaric acid, malonic acid, succinic acid, phthalic acid, phthalic anhydride, citric acid, etc. Furthermore, other linkages may be used, such as ether, thioether or urethane linkages~ formed by conventional reactions. For instance, to form an ether linkage, the nonionic surfactant may be treated with a strong base (to convert its OH group to an ONa group for instance) and then reac~ed with a halocarboxylic acid such as chloroacetic acid or chloropro pionic acid or the corresponding bromo compound. Thus, the resulting carboxylic acid may have the formula R-Y-ZCOOH
where R is the residue of a nonionic surfactant (on removal of a terminal OH), Y is oxygen or sulfur and Z represents an organic linkage such as a hydrocarbon group of, say, one to ten carbon atoms which may be attached to the oxy~en ~or sulfur) of the formula directly or by means of an intervening ~283[3~6 o linkage such as an oxygencontaining linkage, e.g. a ~C-or O , etc.
-C-NH-The polyether carboxylic acid may be produced from apolyether which is not a nonionic surfactant, e.g. it may be made by reaction with a polyalkoxy compound such as poly ethylene glycol or a monoester or monoether thereof which does not have the long alkyl chain characteristic of the nonionic surfactants. Thus, R may have the formula Rl(OCH-CH2)n-where R2 is hydrogen or methyl, Rl is alkylphenyl or alkyl or other chain terminating group and "n" is at least 3 such as 5 to 25. When the alkyl of Rl is a bigger alkyl, R is a residue of a nonionic surfactant. As indicated above Rl may instead by hydrogen or lower alkyl (e.g. methyl, ethyl, propyl, butyl) or lower acyl (e.g. acetyl, etc.). The acidic polyether compound if present in the detergent composition, is preferably added dissolved in the nonionic surfactant.
As disclosed in the commonly assigned copending Canadian patent application no. 478,379 filed on April 4th, 1985, the acidic organic phosphorus compound having an acidic -POH group can increase the stability of the suspension of builder, especially polyphosphate builders, in the nonaqueous liquid nonionic suractant.
The acidic organic phosphorus compound may be, for instance, a partial ester of phosphoric acid and an alcohol ~z~3~ 62301-1352 such as an alkanol which has a lipophilic character, having, for instance, more than 5 carbon atoms, e.g. 8 to 20 carbon atoms.
~ speciEic example is a pa:rtial ester of phosphoric acid and a C16 to Clg alkanol (Empiphos* 5632 from Marchon);

*Trade Mark - 21a -` -~ z~33 13~G
it is made up-of about 35% monoester and 65% diester.
The inclusion of quite small amounts of the acidic organic phosphorus compound makes the suspension significantly more stable against settling on standing but remains pourable, presu~ably, as a result of increasing the yield value of the suspension, but decreases it~s plastic viscosity. It is believed that the use of the acidic phosphorus compound may result in the formation of a high energy physical bond between the -POH portion of the molecule and the surfaces of the inorganic polyphosphate builder so that these surfaces take on an organic character and become more compatible with the nonionic surfactant.
The acidic organic phosphorus compound may be selected from a wide variety of materials, in addition to the partial esters of phosphoric acid snd alkanols mentioned above.
Thus, one may employ a partial ester of phosphoric or phosphorous acid with a mono or polyhydric alcohol such as hexylene glycol, ethylene glycol, di- or tri-ethylene glycol or higher polyethylen glycol, polypropylene glycol, glycerol, sorbitol, mono or diglycerides of fatty acids, etc. in which one, two or more of the alcoholic OH groups of the molecule may be esterified with the phosphorus acid. The alcohol may be a nonionic surfactant such as an ethoxylated or ethoxylated-propoxylated higher alkanol, higher alkyl phenol, or higher alkyl amide.
The -POH group need not be bonded to the organic portion of the molecule through an ester linkage; instead it may be directly bonded to carbon (as in a phosphonic acid, such as~a polystyrene in which some of;the aromatic rings carry _ phosphonic acid or phosphinic acid groups; or an alkylphosphonic acid, such as propyl or laurylphosphonic acid) or may be connected to the carbon through other intervening linkage ~2~3~6 62301-1352 (such as linkages through 0, S or N atoms). Preferably, the carbon:phosphorus atomic ratio in the organic phosphorus compound is at least about 3:1, such as 5:1, 10:1, 20:1, 30:1 or 40:1.
The invention detergent composition may also and preferably does include water soluble detergent builder salts.
Typical suitable builders include, for example, those disclosed in U.S. Patents 4,316,812, 4,264,466, and 3,630,929. Water-soluble inorganic alkaline builder salts which can be used alone with the detergent compound or in admixture with other builders are alkali metal carbonate, borates, phosphates, poly-phosphates, bicarbonates, and silicates. (Ammonium or substi-tuted ammonium salts can also be used.) 5pecific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyro-phosphate, sodiun~ bicarbonate, potassium tripolyphosphate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono and diorthophosphate, and potassium bicarbonate. Sodium tri-polyphosphate (TPP) is especially preferred. The alkali metal silicates are useful builder salts which also function to make the composition anticorrosive to washing machine parts. Sodium silicates of Na20/SiO2 ratios of from 1.6/1 to 1/3.2 especially about 1/2 to 1/2.8 are preferred. Potassium silicates of the same ratios can also be used.
Another class of builders useful herein are the water-insoluble aluminosilicates, both of the crystalline and amorphous type. Various crystalline zeolites (i.e. alumino-silicate are described in British Patent 1,504,168, U.S.
Patent 4,409,136 and Canadian Patents 1,072,835 and 1,087,477.
An example of amorphous zeolites useful herein can be found ~, I . ~ Y3'~
¦ in Belgium Patent 835,351 and this patent too is incorporated ¦ herein by reference. The zeolites generally have the formula l (M20)X- (A1203)y- (SiO2)z-WH20 ¦ wherein x is 1, y is from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3.5 or higher and 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 sluminosilicates have calcium ion exchange capacities of about 200 milliequivalent per gram or greater, e.g. 400 meq/~.
Other materials such as clays, particularly of the waterinsoluble 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 bentonite in its more purified form (i.e. free from any grit, sand, etc.) suitable or detergent invariably contains at least 50% montmorillonite and thus its cation exchange capacity is at least about 50 to 75 meq.-per 100 ~ of bentonite. Particularly preferred bentonite 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'tex'tiles as described in British Patent 401,413 to Marriott and British Patent 461,221 to Marriott and Dugan.
- Examples of organic alkaline sequestrant builder salts which can be used alone with the detergent or in admixture with other organic and inorganic builders are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, ~Z ~ 3~L~ -e.g. sodi~lm and potassium ethylene dia~inetetraacetate (EDTA), sodium and potassium nitrilotriacetates ~NTA) and triethanolammon um N-(2-hydroxy~thyl)nitrilodiacetates. Mixed salts of these polycarboxylates are also suitable.
Other suitable builders of the organic type include carboxymethylsuccinates, tartronates and glycollates. Of special value are the polyacetal carboxylates. The polyacetal carboxylates and their use in detergent compositions are described in 4,144,226; 4,315,092 and 4,146,495. Other patents on similar builders include 4,141,676; 4,169,934; 4,201,858;

4,204,852; 4,224,420; 4,225,685; 4,226,960; ~,233,422; 4,233,423;
4,302,564 and 4,303,777. Also relevant are European Patent Application Nos. 0015024; 0021491 and 0063399.
Since the compositions of this invention are generally highly concentrated, and, therefore, may be used at relatively low dosages, it is desirable to supplement any phosphate builder (such as sodium tripolyphosphate) with an auxiliary builder such as a polymeric carboxylic acid having high calcium binding capacity to inhibit incrustation which could otherwise be caused by formation of an insoluble calcium phosphate.
Such auxiliary builders are also well known in the art. _ 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 amounts of soil suspending or anti-redeposition agents, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxy-pr P) methyl cellulose; optical brighteners, e.g. cotton, amine and polyester brighteners, for example, stilbene, triazole and benzidine sulfone compositions, especially sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzidene sulfone, etc., mos~ preferred are stilbene ~ 6 ¦ and triazole~combinations.
Bluing agents such as ultramarine blue; enzymes, pre~erably proteolytic enzymes, such as subtilisin, bromelin, papain, trypsin and pepsin, as well as amylase type enzymes, lipase type enzymes, and mixtures thereof; bactericides, e.~. tetrachlorosalicylanilide, hexachlorophene; fungicides;
dyes; pigments (water dispersible); preservatives; ultraviolet absorbers; anti-yellowing agents~ such as sodium carboxymethyl cellulose, complex of C12 to C22 alkyl alcohol with C12 to Clg alkylsulfate; pH modifiers and pH buffers; color safe bleaches, perfume, and anti-foam agents or suds-suppressors, e.g. silicon compounds can also be used.
The bleaching agents are classified broadly, for convenience, as chlorine bleaches and oxygen bleaches. Chlorine bleaches are typified by sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% available chlorine), and trichloroiso-cyanuric acid (85% available chlorine). Oxygen bleaches are represented by sodium and potassium perbora~es, percarbonates and perphosphates, and potassium monopersulfate. The oxygen bleaches are preferred and the perborates, particularly sodium perborate monohydrate is especially preferred.
The peroxygen compound is preferably used in admixture with an activator therefor. Suitable acti~ators are those disclosed in U.S. patent 4,264,466 or in column 1 of U.S.
Patent 4,430,~44. Polyacylated compounds are preferred activator ;~
among these, compounds such as tetraacetyl ethylene diamine ("TAED"~ and pentaacetyl glucose are particularly preferred.
- The activiator usually interacts with the peroxygen compound to form a peroxyacid bleaching agent in the wash water. It is preferred to include a sequestering agent of hi~h complexing power to inhibit any undesired reaction between lZ83016 such peroxyacid and hydrogen peroxide in the wash solution in the presence of metal ions. Preferred sequestering agents are able to form a complex with Cu2~ ions, such that the stability constant (pK) of the co~plexation is equal to or greater than 6, at 25C, in water, of an ionic strength of 0.1 mole/liter, pK being conventionally defined by the formula:
pK=-log K where K represents the equilibrium constant. Thus, for example, the pK values for complexation of copper ion with NTA and EDTA at the stated conditions are 12.7 and 18.8, respectively. Suitable sequestering agents include for example, in add;tion to those mentioned above, diethylene triamine pentaacetic acid (DETPA); diethylene tria~ine pentamethylene phosphonic acid (DTPMP); and ethylene diamine tetramethylene phosphonic acid (EDITEMPA).
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 (e.g. of 5-100 millimicrons diameters such as sold under the name Aerosil) or the other highly voluminous inorganic carrier materials disclosed in U.S. Patent 3,630,929, in proportions of 0.1-10%, e.g; 1 to 5%. It is preferable, however, that compositions which form peroxyacids in the wash bath (e.g. compositions containing peroxygen compound and activator therefor) be substantially free of such compounds and of other silicates; it has been found, for instance, that silica and silicates promote the undesired decomposition of the peroxyacid.
, ................. . .. . . . ...... .. _ . . . ..
In a preferred form of the invention, the mixture of liquid nonionic surfactant and solid ingredients ;s subjected to an attrition type of mill in ~hich the particle sizes of the solid ingredients are reduced to less than about 10 micron .

-~ 3~
e.g. to an average particle size of 2 to 10 microns or even lower (e.g. 1 micron). Compositions whose dispersed particles are of s~lch s~all size have impro~ed stability against separation or settling on storage. .
In the grinding operation, it is preferred that the proportion of solid ingredients be high enough (e.g. at least about 40% such as about 50%) that the solid particles are in contact with each o~her and are not substantially shielded from one another by the nonionic surfactant liquid. Mills which employ grinding balls (ball mills) or similar mobile grinding elements have given very good results. Thus, one may use a laboratory batch attritor having 8 mm diameter steatite grinding balls. For larger scale work a continuously operating mill in which there are 1 mm or 1.5 mm diameter grinding balls working in a very small gap between a stator and a rotor operating at a relatively high speed (e.g. a CoBall mill) may be employed; when using such a mill, it is desirable to pass the blend of nonionic surfactant and solids first through a mill which does not effect such fine grinding (e.g. a colloid mill) to reduce the particle size to less than 100 microns (e.g., to about 40 microns) prior to the step of grinding to an average particle diameter below about 10 microns in the continuous ball mill.
In the preferred heavy duty liquid detergent compositions of the invention, typical proportions (based on the total composition, unless otherwise specified) of the ingredients are as follows:
,' Suspended detergent builder, within the range of about 10 to 60% such as about 20 to 50%, e.g. about 25 to:
40%;
Liquid phase comprising-nonionic surfactant and dissolved amphiph~lic viscosity-controlline and gel-inhibiting compound, Il .

8 3~1 ~
within the range of about 30 to 70/0, such as abou~ 40 to 60%; this phase ~ay also include minor amounts of a diluent such as a glycol, e.g. polyethylene glycol (e.g., "PEG 400"), hexylene ~lycol, etc. such as up to 10%, preferably up to 5%, for example, 0.5 to 2%~ The weight ratio of nonionic surfactant to amphiphilic compound is in the range of from about lOO:l to l:l, preferably from about 50:1 to about 2:1, especially preferably, from about 25:1 to about 3:1.
Polyether carboxylic acid gel-inhibiting compound, in an amount to supply in the r~lnge of about 0.5 to lO parts (e.g. about 1 to 6 parts, such as about 2 to 5 parts) of -COOH (M.W. 45) per 100 parts of blend of such acid compound and nonionic surfactant. Typically, the amount of the polyether carboxylic acid compound is in the range of about 0.01 to 1 part per part of nonionic surfactant, such as about 0.05 to 0.6 part, e.g. about 0.2 to 0.5 part;
Acidic organic phosphoric acid compound, as anti-settling agent: up to 5%, for example, in the range of 0.01 to 5%, such as about 0.05 to 2%~ e.g. about 0.1 to 1%.
Suitable ranges of other optional detergent additives are: enzymes - O to 2%, especially 0.7 to 1~3%; corrosion inhibitors - about O to 40/0; and preferably 5 to 30%; anti-foam agents and suds-suppressors - O to 15%, preferably O to 5%, for example 0.1 to 3%; thickening agent and dispersants -O to 15%, for example 0.1 to 10%, preferably 1 to 5%; soil suspending or anti-redeposition agents and anti-yellowing agents - O to 10%, preferably 0.5 to 5%; colorants, perfumes, brighteners and bluing agents total weight 0% to about 2%
and preferably 0% to about 1%; pH modifiers and pH buffers - O to 5%, preferably O to 2%; bleaching agen~ - 0% to about 40% and ,referably 0% to about 25%, for ~xample 2 to 20%

~2~

bleach stabilizers and bleach activators 0 to about 15%, preferably 0 to 10~/ol for example, 0.1 to 8%; sequestering agent of high co~plexing power, in the range of up to about 5%, preferably about 1/4 to 3%, such as about 1/2 to 2%.
In the selections of the adjuvants, they will be chosen to be compatible with the main constituents of the detergent compo 5 ition.
A11 proportions and percentages are by weight unless otherwise indicated.
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.
In order to demonstrate the effects of the viscosity control and gel-inhibiting agents, various compositions were prepared using the above described Surfactant T8 (C13, E08) (50/50 weight mixture of Surfactant T7 and Surfactant T9) as the non-aqueous liquid nonionic surface active cleaning agent. Formulationscontaining 5%, 10%, 15~/D~ or 20% of amphiphili additive were prepared and were tested a~ ~C, 10C, 15C, 20C and 25C for differen~ dilutions with water, i.e. 100%, 83%~ 67%, 50% and 33% total nonionic Surfactant T8 plus additive concentrations, i.e. after dilution in water. The additives tested were Alfonic 610-60 (C8-E04.4), ethylene glycol monoethyl ether (C2 E01~, and diethylene glycol monobutyl ether (C4-E02).
The results of viscosity behavior on dilution of each tested composition at each temperature is illustrated in the graphs attached as Figures 1-3.
For Alfonic 610-60, 5% addition was sufficient to inhibit gelation at 25~C; however, in the plot of viscosity vs. concentrat:ion of nonionic a sharp viscosity maximum ~ L283~
was observed~at about 67% concentration and a shoulder was observed at about 55% to 35% nonionic concentration. At 5C, 15~/~ addition was necessary to avoid gel formation.
The viscosity decreased to a minimum at a nonionic concentration of about 83% at all levels of additive addition at 5C whereas at the higher temperatures, viscosity minimums were observed for the non-diluted formulations, i.e. 100% nonionic concentratio 8 .
At each temperature and for each tested concentration of additive (except at 20% additive at 25~C) a relatively sharp peak is seen in the viscosity existing between 75 to 50%
concentration of nonionic (i.e. 25 to 50% dilution).
For ethylene glycol monoethyl ether 5% additive was capable of inhibiting gel formation even at 5C. However, sharp peaks and/or maxima of viscosity were again observed at each temperature and additive concentration, although the effects were not as pronounced as for Alfonic 610-60, and for some applications the maximum viscosities, especially at higher additive concentrations and/or higher temperatures could be acceptable for commercial use.
On the other hand, there were no sharp peaks in viscosity observed for diethylene glycol monobutyl ether at any temperature down to 5C at the 20% additive level. Even at the lower additive levels the viscosity peaks and the viscosity values at substantially all dilutions (concentrations of nonionics) were lower than for either the C8-E04.4 or C2-E01 additive.
The following table is representative of the results which were obtained for the different additive concentrations, dilutions, and temperatures, but are given for 20% sdditîve and 5C temperature:

~Z;133~
Compositions Viscosity Pour Point at 5C (Pa sec) (C) No Water 50V/o Water Surfactant T8 only 1.140 1.240 5 80% Sur~actant T8+20V/oA 0.086 0.401 -10 80% Surfactant T8+20%B 0.195 0.218 -2 80% S~lrfactant T8+20%C 0.~90 0.936 3 A = ethylene glycol monoethyl ether B = diethylene glycol monobutyl ether C = Alfonic 610-60 (C8-4.4EO) Note:' 1 Pa-sec = 10 poises (e.g. 0.218 Pa-sec - 218 centipoises) Example , ,, A heavy duty built nonaqueous liquid nonionic cleaning composition having the following formula is prepared:
In~redient Weight%
Surfactant T7 17.0 Surfactant T8 ' .' 17.0 Dobanol 91-5 Acid 1 . 5.0 Diethylene gl~col monobutyl ether 10.0 Dequest 2066 ~ 1.0 TPP NW (sodium tripolyphosphate) 29.0925 Sokolan CP5 3 (Calcium sequestering agent) 4.0 Perborate H2O tsodium perborate monohydrate) 9.0 T.A.E.D. (tetraacetylethylene diamine) 4.5 Emphiphos 5632 4 0-3 ¦ Stilbene 4 ~optical brightener) ., 0.5 ¦ Esperase ~proteolytic enzyme) 1.0 Duet 787 ~ 0.6 Relatin DM 4050 6 (anti-redeposition agent) 1.0 ¦ Blue Foulan Sandolane ~dye) - 0.0075 I . _ l 1) The esterification product~of'D'ob'anol'91-5 (a ~g-Cll'~'~
¦ fatty alcohol ethoxylated with 5 moles ethylene oxide) with succi ic ¦ anhydride - the half-ester.
I 2) I ~ ..

¦ 3) A copolymer of about equal moles of methacrylic acid ¦ and maleic anhydride, completely neutralized to form the sodium I . . _ . _-- . . . . . _ . . _-- .-- _ . . .
salt thereof.
4) Part;al ester of phosphoric acid and a C16toC18 alkano :
about 1/3 monoester and 2/3 d;ester).

,,:. ' ,...... ,, :

.
,.
. ,_._ _ ~ 83~

6) Mixture of sodium carboxymethyl cellulose and hydroxy-methylcellulose.- .
This composition is a stable, free-flowing, built, non-gelling, liquid nonionic cleaning compositions in which the polyphosphate builder is stably suspended in the liquid nonionic surfactant phase.

. . . . ..

Claims (12)

1. A nonaqueous heavy duty laundry composition comprising a suspension of a detergent builder salt in a liquid nonionic surfactant, an amount of mono- or poly- (C2 to C3 alkylene)glycol mono-(C1 to C5 alkyl)ether sufficient to decrease the viscosity of the composition both in the absence of water and upon contacting of the composition with water, and an acid-terminated nonionic surfactant which is obtained by converting a free hydroxyl group of a nonionic surfactant to a moiety having a free carboxyl group, the amount of said acid-terminated nonionic surfactant being sufficient to further lower the temperature at which the liquid nonionic surfactant forms a gel with water, said composition comprising from about 30 to about 70% of the liquid nonionic surfactant and the alkylene glycol monoalkyl ether at a weight ratio of nonionic surfactant to glycol ether in the range of from about 100:1 to 3:1, and from about 10 to about 60% of the suspended detergent builder.

2. The composition of claim 1 wherein the alkylene glycol monoalkyl ether is diethylene glycol monobutyl ether.

3. The composition of claim 2 wherein the liquid nonionic surfactant is a Cd10 to C18 fatty alcohol alkoxylated with from 3 to 12 moles of a C2 to C3 alkylene oxide per mole of fatty alcohol.

4. The composition of claim 1 wherein the liquid nonionic surfactant is a C10 to C18 fatty alcohol alkoxylated with from 3 to 12 moles of a C2 to C3 alkylene oxide per mole of fatty alcohol.

5. The composition of claim 1 which further comprises an acidic organic phosphorus compound having an acidic - POH group in an amount to increase the stability of the suspension of the detergent builder in the liquid nonionic surfactant.

6. The composition of claim 1 wherein the acid-terminated nonionic surfactant is present in an amount of from about 0.5 to 10 parts of -COOH group thereof per 100 parts of the acid-terminated nonionic surfactant and the liquid nonionic surfactant; said composition further comprising an acidic organic phosphoric acid compound, as an anti-settling agent, in an amount in the range of from about 0.1 to 5%, and one or more detergent additives selected from enzymes, corrosion inhibitors, anti-foam agents, suds suppressors, thickening agents, dispersants, soil suspending agents, anti-redeposition agents, anti-yellowing agents, colorants, perfumes, optical brighteners, pH modifiers, pH buffers, bleaching agents, bleach stabilizers, bleach activators, and sequestering agents.

7. The composition of claim 1 wherein the detergent builder comprises an alkali metal polyphosphate, the alkylene glycol ether is diethylene glycol monobutyl ether, and the liquid nonionic surfactant comprises a secondary C13 fatty alcohol ethoxylated with about 8 moles ethylene oxide per mole of fatty alcohol.

8. The composition of claim 7 wherein the acid-terminated nonionic surfactant comprises the partial ester of C9 to C11 fatty alcohol ethoxylated with about 5 moles ethylene oxide with succinic acid or succinic acid anhydride, and the acidic organic phosphoric acid compound comprises a partial ester of phosphoric acid and a C16 to C18 alkanol.

9. The composition of claim 1 wherein the nonionic surfactant and the glycol ether are present in the composition at a weight ratio of 25:1 to 3:1.

10. A nonaqueous liquid heavy duty laundry composition consisting essentially of (A) from about 30 to 70% by weight of a liquid phase composed of a liquid nonionic surfactant and a viscosity-controlling and gel-inhibiting compound of the formula where R is alkyl of 2 to 5 carbon atoms, R' is hydrogen or methyl, and n is a number of from 2 to 4 on average, the weight ratio of surfactant to said compound being from 100:1 to 3:1, (B) from about 10% to about 60% of detergent builder salt suspended in the liquid phase;
(C) a polyether carboxylic acid gel-inhibiting compound in an amount from about 0.5 to 10 parts of -COOH group per 100 parts of the polyether carboxylic acid and liquid nonionic surfactant;
(D) 0.01 to 5% by weight of an acidic organic phosphorus compound as an anti-settling agent; and (E) one or more detergent additives selected from the group consisting of (a) enzymes, 0 to 2 % by weight, (b) corrosion inhibitors, 0 to 40% by weight, (c) anti-foam agents and suds-suppressors, 0 to 15% by weight (d) inorganic thickening agents and dispersants, 0 to 15% by weight, (e) soil-suspending anti-redeposition and anti-yellowing agents, 0 to 10% by weight, (f) colorants, perfumes, optical brighteners and bluing agents, 0 to 2% by weight, (g) pH modiflers and pH buffers, 0 to 5% by weight, (h) bleaching agent, 0 to 40% by weight, (i) bleach stablizers and bleach activators, 0 to 15% by weight, and (j) sequestering agents, 0 to 5% by weight.

11. The composition of claim 10 wherein (A) the liquid nonionic surfactant is comprised of C10 to C18 fatty alcohol ethoxylated with from 3 to 12 moles of a C2 to C3 alkylene oxide per mole of fatty alcohol and the compound of the formula is diethylene glycol monobutylether;
(B) the detergent builder is comprised of an alkali metal polyphosphate;
(C) the polyether carboxylic acid is comprised of a partial ester of a C9 to C11 fatty alcohol ethoxylated with about 5 moles ethylene oxide with succinic acid or succinic acid anhydride; and (D) the acidic organic phosphorus compound is comprised of a partial ester of phosphoric acid and an alkanol having from 8 to 20 carbon atoms.

12. The composition of claim 11 wherein (A) the liquid nonionic surfactant is comprised of a secondary C13 fatty alcohol ethoxylated with about 8 moles ethylene oxide per mole of fatty alcohol or a 1:1 mixture of a secondary C13 fatty alcohol ethoxylated with about 9 moles ethylene oxide per mole of fatty alcohol, the total amount of the surfactant and the compound of the formula is from about 40 to 60% by weight, and the ratio of surfactant to said compound is from 25, to 3:1;
(B) the detergent builder salt is present in an amount of from about 20 to 50% by weight;
(C) the gel-inhibiting compound is present in an amount of from about 0.05 to 0.6 part per part of the liquid nonionic surfactant;
(D) the acidic organic phosphorus compound is a partial ester of phosphoric acid with a C16 to C18 alkanol and is present in an amount of from about 0.05 to 2% by weight.