WO1994004655A1

WO1994004655A1 - Automatic dishwashing detergent

Info

Publication number: WO1994004655A1
Application number: PCT/US1993/007611
Authority: WO
Inventors: Andrea Motyka; Guy Broze
Original assignee: Colgate-Palmolive Company
Priority date: 1992-08-19
Filing date: 1993-08-17
Publication date: 1994-03-03
Also published as: EP0656053A1; MY111592A; AU5009093A; TR27483A

Abstract

A shear thickening composition having a complex viscosity at room temperature at 2 sec-1 of 12 to 80 pascal seconds which comprises by weight of 10 to 45 % of an alkali metal silicate; 0.1 to 30 % of an organic compound having at least one hydroxyl group; 0 to 5.0 % of at least one organic detergent active material and the balance being water. The composition is especially useful as an automatic dishwasher detergent.

Description

AUTOMATIC DISHWASHING DETERGENT

Field of invention

The invention relates to a shear thickening aqueous liquid composition which is especially useful as an automatic dishwasher detergent composition. If the water content is low enough, shear thickening is exhibited.

This invention also relates to liquid, aqueous, stable, effective, safe, detergent cleaning compositions which have shear thickening properties and are commonly referred to as detergents for cleaning of fabrics. The compositions are physically stable, do not separate, whereby the user is assured of the optimum performance to be expected from the various components and their amounts and ratios with respect to one another.

Background of the Invention

Liquid automatic dishwasher detergent compositions, both aqueous and nonaqueous, have recently received much attention, and the aqueous products have achieved commercial popularity. The acceptance and popularity of the liquid formulations as compared to the more conventional powder products stems from the convenience and performance of the liquid products. However, even the best of the currently available liquid formulations still suffer from two major problems, product phase instability and bottle residue, and to some extent cup leakage from the dispenser cup of the automatic dishwashing machine.

Representative patent art in this area includes Rek, U.S. Patent 4,556,504;

Bush, et al., U.S. Patent 4,226,736; Ulrich, U.S. Patent 4,431 ,559; Sabatelii. U.S.

Patent 4,147,650; Paucot, U.S. Patent 4,079,015; Leikhem, U.S. Patent 4,116,849;

Milora, U.S. Patent 4,521 ,332; Jones, U.S. Patent 4,597,889; Heile, U.S. Patent 4,521 ,332; Laitem, U.S. Patent 4,753,748; Sabatelli, U.S. Patent 3,579,455; Hynam, U.S. Patent 3,684,772. Other patents relating to thickened aqueous detergent compositions include U.S. Patent 3,985,668; U.K. Patent Applications GB 2,116,199A and GB 240.450A; U.S. Patent 4,511 ,487; U.S. Patent 4,752,409 (Drapier, et al.); U.S. Patent 4,836,946 (Dixit); U.S. Patent 4,889,653 (Ahmed, et al.). Commonly assigned co-pending patents include, for example, Serial No. 427,912 filed October 24, 1989; Serial No. 924,385, filed October 29, 1986; Serial No. 323,138, filed March 13, 1989; Serial No. 328,716, filed March 27, 1989; Serial No. 323,137, filed March 13, 1989; Serial No. 323,134, filed March 13, 1989.

The solubilizing effect of potassium salts on sodium tripolyphosphate in aqueous detergent compositions is described in U.S. Patent 3,720,621 (Smeets). This patent describes homogeneous liquid compositions containing 14 to 35 percent sodium tripolyphosphate, 0.1 to 50 percent of potassium and/or ammonium salt of an inorganic or organic acid, water, and optional surfactants, solubilizing agent, organic sequestering agent, per-compound, and other adjutants. Potassium pyrophosphate (TKPP) is disclosed as the preferred potassium salt for its sequestering and solubilizing activity and also because "it effectively stabilizes the tripolyphosphate agent Rydrolysis in aqueous solution into sodium pyrophosphate and sodium orthophosphate." The patent also states that, "[t]he content [of TKPP] should not...be too great so as to undergo a double-decomposition reaction with TPP to form sodium pyrophosphate, which is well known, has a very low solubility in water and, therefore, tends to separate out as precipitate. The applicants investigations have shown that the optimum proportion of potassium pyrophosphate incorporated in the liquid detergent compositions...is between 5 and 25 percent based on the TPP present in the compositions."

U.S. Patent 4,836,948 discloses a viscoelastic gel detergent composition characterized by its viscosity under low and high shear conditions, pH, and steady state viscoelastic deformation compliance. The composition requires the presence of a polycarboxylate polymeric thickener, preferably a cross-linked polyacrylic acid. The compositions of this patent also, however, require a trivalent metal containing material, especially an aluminum containing material such as alumina. The compositions may further include a structuring chelant which may be a salt of carbonate, pyrophosphate or mixture thereof, and preferably the potassium salts.

The recently issued U.S. Patent 4,859,358 discloses the incorporation of metal salts of long chain hydroxy fatty acids, as anti-tamishing agents, in thickened aqueous automatic dishwashing detergent compositions. The thickeners for these compositions may be a high molecular weight polycarboxylate polymer, such as those sold under the Carbopol trade name, and specific 600 to 900 series resins are mentioned, it is also disclosed that the compositions may include entrained gas, e.g. air bubbles to further ensure stability. Amounts of air in the range of from 1% to 20%, preferably from 5 to 15% by volume will lower the specific gravity of the overall composition to within from 5% more than to 10% less than, preferably from 1% more than to 5% less than, the specific gravity of the aqueous phase. In Example III of this patent, the specific gravity of the composition was stated as 1.32g/cm3. The compositions are not described as being linear viscoelastic and exemplified do not include any potassium salts. While the compositions disclosed in the prior art provide satisfactory solutions to the problems of phase instability and bottle residue, as well as cup leakage, it has not been found that under some storage/handling conditions and/or processing conditions, additional improvements would be desirable. Specifically, if the viscoelastic composition is subjected to repeated heating and cooling cycles, growth of crystals and product thinning and/or precipitate formation has been observed. Chemical analysis of the precipitated crystals has shown that these crystals are comprised predominantly of sodium pyrophosphate. In addition, it appears that the crystals tend to become entangled with the polymeric thickener which tendency is presumed to account for the thinning out or aqueous phase separation which has been observed in conjunction and crystal formation and precipitation.

The prior art of liquid automatic dishwashing compositions teach compositions that exhibit thixotropic properties. These prior art compositions exhibit shear thinning or a decrease in viscosity as the shear rate is increased. The compositions of the instant invention do not shear thin as the shear rate increases but the instant compositions shear thicken (viscosity increases) as shear rate increases.

All of the compositions disclosed in the prior art do not possess shear thickening properties. These compositions of the prior art are shear thinning as the rate of shear is increased. In other words, as the shear rate is increased as in the process of scrubbing, the viscosity of the composition will decrease. The compositions of the instant invention exhibit shear thickening properties which means that as the shear rate is increased the compositions will shear thicken. This increase is independent of the time scale of the experiment. In a scrubbing process which causes an increase in the shear rate, the viscosity of the composition will increase and the composition will exhibit gel-like properties. This shear thickening property of the compositions of the instant invention make them especially useful in a hand cleaning operation of fabrics.

United States patent 4,575,530 (March 11 , 1986) describes hydrocarbon solution additives which are polyampholytes which incorporates cationic and anionic moieties on the same polymeric backbone. These hydrocarbon solutions have shear thickening properties.

U.S. patent 4,536,539 (August 20, 1985) claims include increasing the viscosity of water under increasing shear rates (22.0 - approaching 100 sec"¹ ). This shear thickening behavior is primarily attributed to the increase in apparent molecular weight of the interpolymer complex through formation of intermolecular ionic linkages.

Our patent teaches that these thickened silicates show shear thickening, an increase in viscosity as shear rate is increased. Furthermore, the viscosity values at each shear rate are independent of the timescale of the experiment. Once the shear rate is applied, the viscosity reaches a steady value after a few seconds up to sevaral minutes. Shear thickening occurs when the applied shear forces predominate the interparticle forces. The shear forces change the dispersion from a certain degree of order to clusters of particles. Shear thickening behavior is dependent on particle shape, size and size distribution; particle volume fraction; type and strength of inter-particle interaction; continuous phase viscosity; and the experimental parameters characterizing the shear thickening. These parameters include the type, rate, and duration of the applied shear deformation.

Summary of the Invention Physically stable, detergent cleaning compositions having shear thickening properties are provided and include an alkali metal silicate, an organic compound containing at least one hydroxyl group and water and, a surfactant, and optionally at least one electrolyte.

Accordingly, it is an object of the present invention to provide liquid, aqueous, stable, detergent cleaning composition which is shear thickening upon increasing shear rate.

According to the present invention there is provided an improved aqueous liquid automatic dishwasher detergent composition that has shear thickening properties which means that the composition will show an increase in viscosity as the shear rate increases. Viscosity value at a given shear rate is independent of the time scale of the experiment. The composition exhibits substantially indefinite stability against phase separation or settling of dissolved particles under high and low temperature conditions, low levels of bottle residue, relatively high bulk density, but also by its overall product consistency from batch to batch and run to run and over a wide range of storage and aging conditions, including superior aesthetics, freedom from fish-eyes, absence of crystal formation and growth, and resistance to cup leakage of less than 10%.

The present invention can be accomplished, for example, by the use of an alkali metal silicate such as potassium silicate and an organic compound containing at least one hydroxyl group in a weight ratio of 1000/1 to 1/1 and the elimination of inorganic clay, polymeric or fatty acid thixotropic thickeners.

Accordingly, in one aspect the present invention provides an improved automatic dishwasher detergent composition comprising water from 0.0 to 5% by weight of low foaming water dispersible automatic dishwasher organic detergent, from .01 to 40% by weight of an organic compound containing at least one hydroxyl group and 20 to 60 weight percent of alkali metal silicate.

The weight ratio of the alkali metal silicate to the organic compound containing at least one hydroxyl group is 1000/1 to 1/1 , more preferably 500/1 to 1/1. In a preferred embodiment, the aqueous liquid automatic detergent comprises approximately, by weight percent:

(a) .01 to 40% of an organic compound containing at least one hydroxyl group;

(b) 10 to 60% alkali metal silicate; (c) 0 to 5%, water dispersible organic detergent active material;

(d) optionally, 0 to 1.5% foam depressant;

(e) optionally, an inorganic or organic compound containing an alkali metal cation such as a detergency builder salt; and

(f) water. wherein the entire composition, which exhibits shear thickening properties, has cup leakage of less than 10 wt. %, more preferably less than 8 wt. 90 and most preferably less than 6 wt. %.

Detailed Description and Preferred Embodiments The compositions of this invention are shear thickening aqueous liquids containing various cleansing active ingredients, detergent builder salts and other detergent adjutants, structuring and thickening agents and stabilizing components, although some ingredients may serve more than one of these functions.

One of the objects of this invention are obtained in accordance with the following description wherein the liquid, shear thickening aqueous, detergent composition comprises an aqueous aikali metal silicate, an inorganic or organic compound containing an at least one hydroxyl group and water and, non-soap anionic surfactant, nonionic surfactant, at least one electrolyte, and an alkali metal hydroxide compound and, optionally, at a fabric softner. In a preferred embodiment of the instant detergent composition comprises approximately by weight

(a) 1 to 45% of at least one detergent builder salt if used in fabric cleaning composition; (b) 10 to 45% of an alkali metal silicate;

(c) 0 to 8% of an alkali metal hydroxide;

(d) 0 to 5% of a fabric softner;

(e) 0 to 15% of a water dispersible organic detergent active material;

(f) 0.01 to 30% of at least one organic compound containing at least one hydroxyl group;

(g) optionally, 0 to 1.5% of a foam depressant; (h) 0 to 5% of an antistatic agent; and

(i) balance being water.

The advantageous characteristics of the automatic dishwashing compositions of this invention, include physical stability, as manifested by little or no phase separation, low spotting and filming, dirt residue removal, and consistency in product characteristics and performance, and superior aesthetics. These characteristics are believed to be attributed to several interrelated factors such as low solids, that is undissolved particulate content, product density and shear thickening rheology. These facts are, in turn, dependent on several critical compositional components and processing conditions of the formulations, namely, (1) a mixture of an alkali metal silicate and an organic compound containing at least one hydroxyl group in a weight ratio of 1000/1 to 1/1 ; (2) a product bulk density of at least 1.26 g/cc, especially at least 1.32 g/cc, and (3) maintaining the pH of the detergent composition at least at 11 preferably at least at 11.5.

The compositions of this invention are characterized by their low bottle residue and cup leakage of less than 10 wt. %, more preferable less than 8 wt. % and most preferably less than 6 wt. %. The shear thickening characteristics of the aqueous automatic dishwashing detergent are formed by the incorporation into the aqueous liquid automatic dishwashing detergent of the mixture of an alkali metal silicate and an organic compound containing at least one hydroxyl group and having the formula C_nH_2n+2-x(OH)_x wherein x = 1 , 2 or 3 and n=1 to 20, more preferably 1 to 12 in the critical weight ratio of 1000/1 to 1/1 , more preferably 500/1 to 1/1.

The alkali metal silicate employed in the instant invention is selected from the group consisting of lithium silicate, sodium silicate and potassium silicate, wherein the alkali metal silicate has a concentration in the composition of 10 to 60 wt.%, more preferably 20 to 50 wt.%.

The alkali metal silicate is used in ;ne form of an aqueous solution, wherein the concentration of the alkali metal silicate is 30 to 60 wt. %.

The organic compound, having at least one hydroxyl group which is employed in the instant compositions has the formula

C_nH2n₊2-x(OH)_x wherein x= 1 , 2 or 3 and n is 1 to 20, preferably 1 to 12. Typical examples of organic compounds having at least one hydroxyl group are selected from the group consisting of methanol, ethanol, n-propanol, esopropanol, n-butanol, isobutanol, propylene glycol, 1 ;6-hexane-diol,sec-butanol, n-pentanol, esopentanol, neopentanol, n-hexanol, isohexanol, n-heptanol, isoheptanol, n-octanol, eso-octanol, glycerol, butanidol, pentanediol, hexanetriol, heptanetriol, nonyl alcohol, decanol, heptadecanol, hexanedecanol and pentadecanol.

Foam inhibition is important to increase dishwasher machine efficiency and minimize destabilizing effects which might occur due to the presence of excess foam within the washer during use. Foam may be reduced by suitable selection of the type and/or amount of detergent active material, the main foam producing component. The degree of foam is also somewhat dependent on the hardness of the wash water in the machine whereby suitable adjustment of the proportions of the builder salts, such as NaTPP which has a water softening effect, may aid in providing a degree of foam inhibition. Optionally, a foam depressant or inhibitor can be included. Particularly effective are the alkyl phosphoric acid esters of the formula

O II

HO-P--R

I OR and especially the alkyl acid phosphate esters of the formula

O

II

HO--P--OR I

OR

In the above formulas, one or both R groups in each type of ester may represent independently a C12-C20 ^a,ky' ^or ethoxylated alkyl group. The ethoxylated derivatives of each type of ester, for example, the condensation products of one mole of ester with from 1 to 10 moles, preferably 2 to 6 moles, more preferably 3 or 4 moles, ethylene oxide can also be used. Some examples of the foregoing are commercially available such as the products SAP from Hooker and LPKN-158 from Knapsack. Mixtures of the two types, or any other chlorine bleach stable types, or mixtures of mono- and di-esters of the same type, may be employed. Especially preferred is a mixture of mono- and di- Cι β-C-i 8 alkyl acid phosphate esters such as monostearyl/distearyl/acid phosphates

1.2/1 , and the 3 to 4 mole ethylene oxide condensates thereof. When employed, proportions of 0.05 to 1.5 weight percent, preferably 0.1 to 0.5 weight percent, of foam depressant in the composition is typical the weight ratio of detergent active component (d) to foam depressant (e) generally ranging from 10:1 to 1 :1 and preferable 5:1 to 1 :1. Other defoamers which may be used include, for example, the known silicones, such as available from Dow Chemicals.

The detergent builder salts of the instant invention which can be optionally used are selected from the group consisting of sodium carbonate, lithium carbonate and potassium bicarbonate, lithium, sodium and potassium citrate, lithium, sodium and potassium phosphinates, lithium, sodium and potassium bicarbonate, lithium, sodium and potassium sesquicarbonate, lithium, sodium and potassium orthophosphates, lithium, sodium and potassium tripolyphosphates, lithium sodium and potassium pyrophosphate or hexametaphosphate, lithium, sodium or potassium tetraborate, anhydrous pentahydrate, decahydrate, as illustrative of the inorganics and ethyline diamine tetraacetic acid and tetrasodium or potassium salt, trisodium or tripotassium nitrilotriacetate, sodium polymaleate, and the like as illustrative of the organics.

The electrolyte used herein is typically an alkaline, builder-type inorganic or organic salt. The usuε' salts comprise the alkali metal bicarbonates, borates, carbonates, phosphates, phosphinates and polyphosphates among the inorganics and the polycarboxylates, such as polyacetates, tartrates, citrates, maleates, oxydiacetates, alkenyl succinates, carboxymethyloxy succinates, oxydisucci nates and the like, among the organics. Polymeric builder salts, such as the water-soluble salts of polymers of maleic acid, itaconic acid and the like, may be used as well as copolymers and interpolymers thereof with polymerizable ,β-ethylenically unsaturated compounds, such as vinyl ethers, esters, alkyl alcohol, acrylic and methacrylic acid and esters thereof, etc.

The electrolyte may vary over a considerable range from as little as 5% to 50% or more. A preferred range is from 10% to 50%; typically a mixture of carbonate and phosphate may total 10 to 40%.

Specific electrolytes include sodium and potassium carbonate, sodium and potassium bicarbonate, sodium and potassium sesquicarbonate, sodium and potassium orthophosphates, pyrophosphates, tripolyphosphate and hexametaphosphates, sodium and potassium tetraborate anhydrous, pentahydrate, decahydrate, as illustrative of the inorganics and ethylenediamine tetraacetic acid tetrasodium or potassium salt, trisodium nitrilotriacetate, disodium polymaleate, and the like, as merely illustrative of the organics. The liquid nonionic surfactants that can be, optionally, used in the present nonaqueous liquid automatic dishwasher detergent compositions are well known. A wide variety of these surfactants can be used.

The non-soap anionic may be chosen from any of the conventional anionics, such as the alkyl benzene sulfonates, the alkyl sulfates, alcohol sulfates, the alcohol ether sulfates, olefin sulfonates, paraffin sulfonates, fatty acid monoglyceride sulfates, sarcosides, taurides and the like and their salts, such as alkali, alkaline, earth and ammonium salts. Of these, the sulfates and sulfonates are preferred.

The preferred non-soap anionic surfactants are the paraffin sulfonates (C rj- C20); the linear alkyl benzene sulfonates, the alcohol and the alcohol ether sulfates. The most preferred anionics (non-soap) are the C12-C18 paraffin sulfonates inthe form of their alkali metal or ammonium salts; C8-C20 alkyl benzene sulfonates with C12-C16 being most highly preferred; the alkyl (i.e. alcohol) sulfates of C12-C18 and the corresponding ether sulfates with 3 to 50 (e.g. 3, 5, 10, 20, 30 or 50) moles of condensed ethylene oxide. The most preferred salt forming cation is sodium. The amount of the non-soap anionic may range from 0.1 to 15% by weight, preferably 0.1 to 10% and more preferably 0.1 to 5% by weight.

Some specific examples of suitable anionics are sodium lauryl sulfate, sodium paraffin (C14-C17) sulfonate, sodium decyl sulfate, sodium tridecyl sulfonate, sodium tallow alkyl sulfate, sodium coconut alkyl sulfate, sodium oxotridecyl- (triethoxyl) [sulfate (sulfated - 3 E.O. condensate with oxotridecyl alcohol], sodium dodecyl benzene sulfonate, sodium tridecyl benzene sulfonate, sodium tetradecyl benzene sulfonate and sodium (C15) olefin sulfonate.

The nonionic synthetic organic detergents are generally described as ethoxylated propoxylated fatty alcohols which are low-foaming surfactants and are possibly capped, characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide and/or propylene oxide. Practically any hydrophobic compound having a carboxyl, hydroxy and amido or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a nonionic detergent. The length of the hydrophilic or polyoxy ethylene propylene chain can be readily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups. Typical suitable nonionic surfactants are those disclosed in U.S. Patent Nos. 4,316,812 and 3,630,929.

Preferably, the nonionic detergents that are used are the low foaming poly-lower alkoxylated lipophiles, wherein the desired hydrophile-lipophile balance is obtained from addition of a hydrophilic poly-lower alkoxy group to a lipophilic moiety. A preferred class of the nonionic detergent employed is the poly-lower alkoxylated higher alkanol wherein the alkanol is of 9 to 18 carbon atoms and wherein the number of moles of lower alkylene oxide (of 2 or 3 carbon atoms) is from 3 to 15. Of such materials it is preferred to employ those wherein the higher alkanol is a high fatty alcohol of 9 to 11 or 12 to 15 carbon atoms and which contain from 5 to 8 or 5 to 9 lower alkoxy groups per mole. Preferably, the lower alkoxy is ethoxy but in some instances, it may be desirably mixed with propoxy, the latter, if present, usually being minor (no more than 50%) portion. Exemplary of such compounds are those wherein the alkanol is of 12 to 15 carbon atoms and which contain 7 ethylene oxide groups per mole.

Useful nonionics are represented by the low foaming Plurafac series from BASF Chemical Company which are the reaction product of a higher linear alcohol and a mixture of ethylene and propylene oxides, containing a mixed chain of ethylene oxide and propylene oxide, terminated by a hydroxyl group. Examples include Product A (a C-|3-C-|5 fatty alcohol condensed with 6 moles ethylene oxide and 3 moles propylene oxide), Product B (a C-J3-C-J5 fatty alcohol condensed with 7 mole propylene oxide and 4 mole ethylene oxide), and Product C (a C13-C-15 fatty alcohol condensed with 5 moles propylene oxide and 10 moles ethyiene oxide). A particularly good surfactant is plurafac 132 which is a capped nonionic surfactant. Another group of low foam liquid nonionics are 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 ethylene oxide.

Another liquid nonionic surfactant that can be used is sold under tradename Lutensol SC 9713. Synperonic nonionic surfactant such as Synperonic LF D25 or LF RA 30 are especially preferred nonionic surfactants that can be used in the nonaqueous liquid automatic dishwasher detergent compositions of the instant invention. Other useful nonionic surfactants are Synperonic RA 30, Synperonic RA 40 and Synperonic RA 340. The Synperonic surfactants are especially preferred because they are biodegradable and low foaming.

Other useful surfactants are 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 12 to 13 carbon atoms and the number of ethylene oxide groups present averages 6.5. The higher alcohols are primary alkanols. Other examples of such detergents include Tergitol 15-S-7 and Tergitol 15-S-9

(registered trademarks), both of which are linear secondary alcohol ethoxy lates made by Union Carbide Corp. The former is mixed ethoxylation product of 11 to 15 carbon atoms linear secondary alkanol with seven moles of ethylene oxide and the latter is a similar product but with nine moles of ethylene oxide being reacted. Another useful surfactant is Tergitol MDS-42 a mixed ethoxylation product of 13-15 cations and alcohols with 10 moles of EO and 5 moles of PO.

Also useful in the present compositions as a component of the nonionic detergent are higher molecular weight nonionics, such as Neodol 45-11 , which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14 to 15 carbon atoms and the number of ethylene oxide groups per mole being 11. Such products are also made by Shell Chemical Company. 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% thereof and the nonionic detergent will preferably contain at least 50% of such preferred poly-lower alkoxy higher alkanol.

The alkylpolysaccharides surfactants, which are used alone in conjunction with the aforementioned surfactant and have a hydrophobic group containing from 8 to 20 carbon atoms, preferably from 10 to 16 carbon atoms, most preferably from 12 to 14 carbon atoms, and polysaccharide hydrophilic group containing from 1.5 to 10, preferably from 1.5 to 4, more preferably from 1.6 to 2.7 saccharide units (e.g., galactoside, glucoside, fructoside, glucosyl, fructosyl; and/or galactosyl units). Mixtures of saccharide moieties may be used in alkyl polysaccharide surfactants. The number x indicates the number of saccharide units in a particular alkylpolysaccharide surfactant. For a particular alkylpolysaccharide molecule x can only assume integral values. In any physical sample of alkylpolysaccharide surfactants there will be in general molecules having different x values. The physical sample can be characterized by the average value of x and this average value can assume non-integral values. In this specification the values of x are to be understood to be average values. The hydrophobic group (R) can be attached at the 2-, 3-, or 4-positions rather than at the 1 -position, (thus giving e.g. a glucosyl or galactosyl as opposed to a glucoside or galactoside). However, attachment through the 1 -position, i.e., glucosides, galactoside, fructosides, etc., is preferred. In the preferred product the additional saccharide units are predominately attached to the previous saccharide unit's 2-position. Attachment through the 3-, 4-, and 6-positions can also occur. Optionally and less desirably there can be a polyalkoxide chain joining the hydrophobic moiety (R) and the polysaccharide chain. The preferred alkoxide moiety is ethoxide.

Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from 8 to 20, preferably from 10 to 18 carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group can contain up to 3 hydroxy groups and/or the polyalkoxide chain can contain up to 30, preferably less than 10, alkoxide moieties. Suitable alkylpolysaccharides are decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, and octadecyl, di-, tri-, tetra-, penta- and hexaglucosides, galactosides, lactosides, fructosides, fructosyls, lactosyls, glucosyls and/or galactosyls and mixtures thereof. The alkylmonosaccharides are relatively less soluble in water than the higher alkylpolysaccharides. When used in admixture with alkylpolysaccharides, the alkylmonosaccharides are solubilized to some extent. The use of alkylmonosaccharides in admixture with alkylpolysaccharides is a preferred mode of carrying out the invention. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.

The preferred alkyl polysaccharides are alkyl polyglucosides having the formula

R2θ(C_nH_2nO)r(Z)_x wherein Z is derived from glucose, R is a hydrophobic group selected from the group consisting of alkyl, alkylphenyl, hydroxyalkylphenyl, and mixtures thereof in which said alkyl groups contain from 10 to18, preferably from 12 to 14 carbon atoms; n is 2 or 3 preferably 2, r is from 0 to 10, preferably 0; and x is from 1.5 to 8, preferably from 1.5 to 4, most preferably from 1.6 to 2.7. To prepare these compounds a long chain alcohol (R2OH) can be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside. Alternatively the alkylpolyglucosides can be prepared by a two step procedure in which a short chain alcohol (R-|OH) can be reacted with glucose, in the presence of an acid catalyst to form the desired glucoside. Alternatively the alkylpolyglucosides can be prepared by a two step procedure in which a short chain alcohol (C-|_6) is reacted with glucose or a polyglucoside (x=2 to 4) to yield a short chain alkyl glucoside (x=1 to 4) which can in turn be reacted with a longer chain alcohol (R OH) to displace the short chain alcohol and obtain the desired alkylpolyglucoside. If this two step procedure is used, the short chain alkylglucoside content of the final alkylpolyglucoside material should be less than 50%, preferably less than 10%, more preferably less than 5%, most preferably 0% of the alkylpolyglucoside. The amount of unreacted alcohol (the free fatty alcohol content) in the desired alkylpolysaccharide surfactant is preferably less than 2%, more preferably less than 0.5% by weight of the total of the alkylpolysaccharide. For some uses it is desirable to have the alkylmonosaccharide content less than 10%. The used herein, "alkylpolysaccharide surfactant" is intended to represent both the preferred glucose and galactose derived surfactants and the less preferred alkylpolysaccharide surfactants. Throughout this specification, "alkylpolyglucoside" is used to include alkylpolyglycosides because the stereochemistry of the saccharide moiety is changed during the preparation reaction. An especially preferred APG glycoside surfactant is APG 625 glycoside manufactured by the Henkel Corporation of Ambler, PA. APG 25 is a nonionic alkyl polyglycoside characterized by the formula:

C_nH2n₊lO(C₆H₁₀θ5)_xH wherein n=10 (2%); n=12 (65%); n=14 (21-28%); n=16 (4-8%) and n=18 (0.5%) and x (degree of polymerization) = 1.6. APG 625 has: a Ph of 6-8 (10% of APG 625 in distilled water); a specific gravity at 25°C of 1.1 g/ml; a density at 25°C of 9.1 lbs/gallon; a calculated HLB of 12.1 and a Brookfield viscosity at 35°C, 21 spindle, 5-10 RPM of 3,000 to 7,000 cps.

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

Detergent active material useful herein should be stable in the presence of chlorine bleach, especially hypochlorite bleach, and for this purpose those of the organic anionic, amine oxide, phosphine oxide, sulphoxide or betaine water dispersible surfactant types are preferred, the first mentioned anionics being most preferred. Particularly preferred surfactants herein are the linear or branched alkali metal mono- and/or di-(C8-C-|4) alkyl diphenyl oxide mono- and/or di-sulphates, commercially available for example as DOWFAX (registered trademark) 3B-2 and DOWFAX 2A-1. In addition, the surfactant should be compatible with the other ingredients of the composition. Other suitable organic anionic, non-soap surfactants include the primary alkylsulphates, alkylsulphonates, alkylarylsulphonates and sec.-alkylsulphates. Examples include sodium C-JQ-CI 8 alkylsulphates such as sodium dodecylsulphate and sodium tallow alcoholsulphate; sodium C-]o-C-|8 alkanesulphonates such as sodium hexadecyl-1-sulphonate and sodium C12-C-18 alkylbenzenesulphonates such as sodium dodecylbenzenesulphonates. The corresponding potassium salts may also be employed.

As other suitable surfactants or detergents, the amine oxide surfactants are typically of the structure R2R1 NO, in which each R represents a lower alkyl group, for instance, methyl, and R-| represents a long chain alkyl group having from 8 to 22 carbon atoms, for instance a lauryl, myristyl, palmityl or cetyl group. Instead of an amine oxide, a corresponding surfactant phosphine oxide R2R1 PO or sulphoxide RR-I SO can be employed. Betaine surfactants are typically of the structure R2R-| N⁺R"COO-, in which each R represents a lower alkylene group having from 1 to 5 carbon atoms. Specific examples of these surfactants include lauryl-dimethylamine oxide, myristyl-dimethylamine oxide, the corresponding phosphine oxides and sulphoxides, and the corresponding betaines, including dodecyldimethylammonium acetate, tetradecyldiethylammonium pentanoate, hexadecyldimethylammonium hexanoate and the like. For biodegradability, the alkyl groups in these surfactants should be linear, and such compounds are preferred. Surfactants of the foregoing type, all well known in the art, are described, for example, in U.S. Patents 3,985,668 and 4,271 ,030. If chlorine bleach is not used then any of the well known low-foaming nonionic surfactants such as alkoxylated fatty alcohols, e.g. mixed ethylene oxide-propylene oxide condensates of C8-C22 fatty alcohols can also be used. The water dispersible organic detergent-active material (surfactant) will normally be present in the composition in minor amounts, generally 1% by weight of the composition, although smaller or larger amounts, such as up to 5%, such as from 0.1 to 5%, preferably from 0.3 or 0.4 to 2% by weight of the composition, may be used. The nonaqueous liquid nonionic or anionic surfactant has dispersed therein fine particles or organic and/or inorganic detergent builders. A preferred solid builder salt is an alkali metal polyphosphate such as sodium tripolyphosphate ("TPP"). In place of all or part of the alkali metal polyphosphate one or more other detergent builder salts can be used. Suitable other builder salts are alkali metal carbonates, borates, phosphates, bicarbonates, silicates, lower polycarboxylic acid salts, and polyacrylates, polymaleic anhydrides and copolymers of polyacrylates and polymaleic anhydrides and poiyacetal carboxylates.

Specific examples of detergent builder salts include the polyphosphates, such as alkali metal pyrophosphate, alkali metal tripolyphosphate, alkali metal metaphosphate, and the like, for example, sodium or potassium tripolyphosphate (hydrated or anhydrous), tetrasodium or tetrapotassium pyrophosphate, sodium or potassium hexa- metaphosphate, trisodium ortripotassium orthophosphate and the like, sodium or potassium carbonate, sodium or potassium citrate, sodium or potassium nitrilotriacetate, sodium or potassium phosphonate, and the like. The phosphate builders, where not precluded due to local regulations, are preferred and mixtures of tetrapotassium pyrophosphate (TKPP) and sodium tripolyphosphate (NaTPP) (especially the hexahydrate) are especially preferred. Typical builders also include those disclosed in U.S. Patent Nos. 4,316,812, 4,264,466 and 3,630,929 and those disclosed in U.S. Patent Nos. 4,144,226, 4,135,092 and 4,146,495, all of which are herein incorporated by reference.

The alkali metal silicates are useful builder salts which also function to make the composition shear thickening. Sodium or potassium silicates of Na2θ/Siθ2 ratios of from 1 :1 to 1 :4 especially 1 :2 to 1 :4 are preferred. Potassium silicates of the same ratios can also be used. The preferred alkali metal silicates are sodium disilicate and sodium metasiiicate.

A preferred builder salt is sodium tripolyphosphate (TPP). The TPP is a blend of anhydrous TPP and a small amount of TPP hexahydrate such that the chemically bound water content is 1%, which corresponds to one H2O per pentasodium tripolyphosphate molecule. Such TPP may be produced by treating anhydrous TPP with a limited amount of water. The presence of the hexahydrate slows down the rapid rate of solution of the TPP in the wash bath and inhibits caking. One suitable TPP is sold under the name Thermphos NW. The particles size of the Thermphos NW TPP, as supplied, is usually averages 200 microns with the largest particles being 400 microns. In conjunction with the builder salts are optionally used a low molecular weight polyacrylates which have a molecular weight of 1 ,000 to 100,000 more preferably 2,000 to 80,000. A preferred low molecular weight polyacrylate is Sokalan^tm CP45 manufactured by BASF and having a molecular weight of 4,500. Another preferred low molecular weight polyacrylate is Acryso|t^m 45ND manufactured by Rohm and Haas and having a molecular weight of 45,000. A suitable suspending and anti-redepositing agent consists of a copolymer of a polyacid and an acid anhydride. Such a material should have a water absorption at 38°C and 78 percent relative humidity of less than 40 percent and preferably less than 30 percent. The builder is commercially available under the tradename of Sokalan CP45. This is a partially neutralized copolymer of acrylic acid and maleic acid sodium salt. This suspending and antideposition agent also serves to inhibit encrustation, i.e. inhibits the formulation and precipitation of dicalcium phosphate. This suspending agent has a low hygroscopicity as a result of a decreased hydroxyl group content. An objective is to use suspending and anti- redeposition agents that have a low hygroscopicity. Copolymerized polyacids have this property, and particularly when partially neutralized. Acusol^tm 640ND provided by Rohm & Haas is another useful suspending agent, other builder salts which can be mixed with the sodium carbonate are gluconates and nitriloacetic acid salts.

In addition to the detergent active surfactant, optionally, a foam inhibitor, alkali metal silicate corrosion inhibitor, and detergent builder salts, which all contribute to the cleaning performance, it is also known that the effectiveness of the liquid automatic dishwasher detergent compositions is related to the alkalinity, and particularly to moderate to high alkalinity levels. Accordingly, the compositions of this invention will have pH values of at least 9.5, preferably at least 11 to as high as 14, generally up to 13 or more, and, when added to the aqueous wash bath at a typical concentration level of 10 grams per liter, will provide pH in the wash bath of at least 9, preferably at least 10, such as 10.5, 11 , 11.5 or 12 or more.

The alkalinity may be achieved, in part, by the alkali metal ions contributed by the alkali metal detergent builder salts, e.g. potassium tripolyphosphate; however, it is usually necessary to include alkali metal hydroxide, e.g. NaOH or KOH, to achieve the desired high alkalinity. Amounts of alkali metal hydroxide in the range of from 0 to 8%, preferably from 1 to 6%, more preferably from 1.2 to 4%, by weight of the composition will be sufficient to ensure the desired pH level. Other conventional ingredients may be included in these compositions in small amounts, generally less than 3 weight percent, such as enzymes, perfumes, preservatives, dyestuffs and pigments and the like, all of course being stable to chlorine bleach compound and high alkalinity. Especially preferred for coloring are the chlorinated phthalocyanines and polysulphides of aluminosilicate which provide, respectively, pleasing green and blue tints. To achieve stale yellow colored products, the bleach stable mixed dyes Cl. Direct Yellow 28 (Cl. 19555) or Cl. Direct Yellow 29 (Cl. 19556) can be added to the compositions. Tiθ2 may be employed for whitening or neutralizing off-shades.

The amount of water contained in these compositions should, of course, be neither so high as to produce unduly low viscosity and fluidity, nor so low as to produce unduly high viscosity and low flowability. Such amount is readily determined by routine experimentation in any particular instance, and generally will range from 30 to 80 weight percent, preferably 35 to 75 weight percent. Preferably, the water should also be deionized or softened. The manner of formulating the invention compositions is critical. The order of mixing the ingredients as well as the manner in which the mixing is performed will generally have a significant effect on the shear thickening properties of the composition, and in particular on product density, (by incorporation of more or less air), viscosity and physical stability (e.g. phase separation). Thus, according to the preferred practice of this invention the compositions are prepared by mixing the alkali metal silicate with the organic compound containing at least one hydroxyl group with stirring at a temperature of 15 to 30°C, more preferably 20 to 25°C for 1 to 5 minutes. The alkali metal silicate is selected from the group consisting of lithium silicate, sodium silicate and potassium silicate, wherein the alkali metal silicate is in an aqueous solution at a concentration of 30 wt.% to 60 wt.%. Subsequently, after homogenous mixing of the aqueous alkali metal silicate, and the organic compound containing at least one hydroxyl group has been achieved, and remaining detergent additives, including any alkali metal hydroxide and the surface-active components are added with stirring. All of the additional ingredients can be added simultaneously or sequentially. Preferably, the ingredients are added sequentially, with mixing continued for from 2 to 10 minutes for each ingredient, although it is not necessary to complete the addition of one ingredient before beginning to add the next ingredient. Furthermore, one or more of these ingredients can be divided into portions and added at different times. These mixing steps should also be performed under moderate to medium shear rates to achieve complete and uniform mixing water is added as the last ingredient to control viscosity. These additional ingredients mixing steps may be carried out at room temperature. The composition may be allowed to age for a few hours, if necessary, to cause dissolved or dispersed air to dissipate out of the composition. In accordance with an especially preferred embodiment, the shear thickening aqueous automatic dishwasher detergent composition of this invention includes, on a weight basis:

(a) 0 to 40% of a detergent builder salt;

(b) 10 to 60%, preferably 20 to 40%, alkali metal silicate; (c) 0 to 8%, preferably 1 to 6% alkali metal hydroxide;

(d) 0 to 5%, preferably 0.1 to 3, more preferably 0.5 to 2%, water-dispersible, low-foaming organic detergent active material, preferably non-soap anionic detergent;

(e) optionally, 0 to 1.5%, preferably 0.5 to 1.5%, foam depressant;

(f).1 to 30% of an organic compound having at least one hydroxyl group; and (g) water, wherein the composition has a viscosity at 2 sec¹ at room temperature of 12 -80 pascal seconds, more preferably 15-75 pascal seconds and a viscosity at 5 sec¹ at room temperature of 15 to 90 pascal seconds, more preferably 18 to 85 pascal seconds. The compositions will be supplied to the consumer in suitable dispenser containers preferably formed of molded plastic, especially polyolefin plastic, and most preferably polyethylene, for which the invention compositions appear to have particularly favorable slip characteristics. The shear thickening compositions can be readily poured from their containers without any shaking or squeezing, i.e. have a sufficiently low yield stress value to flow under their own weight (gravity), although squeezable containers are often convenient and accepted by the consumer for the shear thickening products.

The liquid aqueous dilatant automatic dishwasher compositions of this invention are readily employed in known manner for washing dishes, other kitchen utensils and the like in an automatic dishwasher, provided with a suitable detergent dispenser, in an aqueous wash bath containing an effective amount of the composition, generally sufficient to fill or partially fill the automatic dispenser cup of the particular machine being used.

The invention also provides a method for cleaning dishware in an automatic dishwashing machine with an aqueous wash bath containing an effective amount of the liquid shear thickening automatic dishwasher detergent composition as described above. The composition can be readily poured from the polyethylene container with little or no squeezing or shaking into the dispensing cup of the automatic dishwashing machine and will be sufficiently viscous and cohesive to remain securely within the dispensing cup until shear forces are again applied thereto, such as by the water spray from the dishwashing machine.

The weight ratio of the alkali metal silicate to the organic compound containing at least one hydroxyl group is 1000/1 to 1/1 , more preferably 500/1 to 1/1. The resultant composition of the alkali metal silicate, water and the compound containing at least one hydroxyl group exhibits shear thickening characteristics. The viscosity of the resultant compositions at 2 sec¹ at a room temperature 12 to 80 pascal seconds, more preferably 15 to 75 Pascal seconds and the viscosity at 5 sec¹ at room temperature is 15 to 90 pascal seconds, more preferably 1&to 85 pascal seconds. When the viscosity is plotted against the shear rate for the compositions of the instant invention a positive slope is obtained thereby indicating that the instant compositions are shear thickening. Upon the application of increasing shear rate to an aqueous solution of the composition the aqueous solution will shear thicken and an increase in viscosity will occur. The compositions of the prior art exhibit a negative slope thereby showing these compositions are non shear thinning - decrease in viscosity. To the shear thickening composition of the alkali metal silicate and the organic compound containing at least one hydroxyl group can be added various ingredients in any order, wherein the order of addition is not critical and the addition of these ingredients does not destroy the shear thickening property of the composition. The various ingredients are added at a temperature of 15°C to 30°C, more preferably 20°C to 25°C The various ingredients are the anionic or the nonionic surfactant, detergent builder salt, bleach compound and foam depressant and the aforementioned optional ingredients. The addition of these ingredients to the solution of the alkali metal silicate and the organic compound containing at least one hydroxyl group will not destroy the dilatant characteristics and the final composition will exhibit a viscosity of 12 to 80 pascal seconds at 2 sec¹ at room temperature. Water can be added last to control the viscosity of the composition. The organic compound containing at least one hydroxyol group is present in the composition at a concentration level of 0.1 to 30 weight %, more preferably 0.5 to 30 weight percent. The resultant composition of the alkali metal silicate, water and the organic compound containing at least one hydroxyl group exhibits shear thickening characteristics. The viscosity of the resultant compositions for a shear rate of 22 sec¹ at room temperature is 12 to 80 pascal seconds, more preferably 15 to 75 pascal seconds and the viscosity at a shear rate of 52 sec¹ at room temperature of 15 to 90 pascal seconds, more preferably 18 to 85 pascal seconds. When the viscosity is plotted against the shear rate for the compositions of the instant invention a positive slope is obtained thereby indicating that the instant compositions are shear thickening. Upon the application of increasing shear rate to an aqueous solution of the composition, the aqueous solution will shear thicken and an increase in viscosity will occur. Viscosity value at a given shear rate is independent of the time scale of the experiment. The compositions of the prior art exhibit a negative slope thereby showing these compositions are non shear thinning - decrease in viscosity. To the shear thickening composition of the aqueous alkali metal silicate and the organic compound having at least one hydroxyl group can be added various ingredients in any order, wherein the order of addition is not critical and the addition of these ingredients does not destroy the shear thickening property of the composition. The various ingredients are added at a temperature of 15°C to 30°C and at a moderate mixing speed. The various ingredients are the alkali metal hydroxide, fabric softner the non- soap anionic surfactant, the nonionic surfactant, any previously non added electrolyte containing an alkali metal cation, and the other optional ingredients. The addition of these ingredients to the solution of the alkali metal silicate, water and the inorganic or organic compound containing the alkali metal cation will not destroy the shear thickening characteristics and the final composition will exhibit a viscosity of 12 to 80 pascal seconds at a shear rate of 22 sec¹ at room temperature and, a viscosity of 15 to 90 pascal seconds at a shear rate of 5 sec¹ at room temperature.

In addition to the detergent builders, various other detergent additives or adjuvants may be present in the detergent product to give it additional desired properties, either of functional or aesthetic nature. Thus, there may be included in the formulation, minor amounts of soil suspending or anti-redeposition agents, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxy-propyl methyl cellulose. A preferred anti-redeposition agent is sodium carboxymethyl cellulose having a 2:1 ratio of CM/MC which is sold under the tradename Relatin DM 4050. The antistatic agent of choice in the instant compositions of the present invention is N-cocoisostearamide. Such antistatic agent is an amide which is chemically derivable from isostearic acid and cocoamine by the condensation reaction shown below: o o

RCOH + R'NH2 >RCNHR' + H2θ

Isostearic acid, o RC - OH is a saturated fatty acid of the formula C17H35COOH, which is a complex mixture of isomers, primarily of the methyl-branched series, that are mutually soluble and virtually inseparable. While such acid normally has uses similar to those of stearic or oleic acids, it is considered that it is far superior to such materials in manufacturing effective antistatic agents, which are most suitable for incorporation in applicant's synthetic organic anionic liquid detergent compositions. Cocoamine is an aliphatic amine in which the aliphatic group is derived from coconut oil. Other primary aliphatic amines, preferably higher alkylamines of 7 to 18 carbon atoms in the alkyl, such a RΗH2, wherein R' is such a higher alkyl, may also be used, but cocoamine produces N-alkyl isostearamide of the best properties for incorporation in detergent compositions. Such amine is named CISA.

While CISA is the most highly preferred antistatic agent (such may be referred to as antistats) it is within the broader aspects of this invention to employ other N-aliphatic isostearamides, such as those derives from primary aliphatic amines containing up to 20 carbon atoms, preferably 7-18 carbon atoms, the aliphatic parts of which may or may not be hydrogenated, provided that the amides made have sufficient antistatic effect in the described use. Some examples thereof are the N-alkylisostearamides of 7 to 18 carbon atoms, such as N-decylamine, N-octylamine and those derived from N- tallow-amine. However, it is considered that CISA is the best of the N- alkylisostearamides in antistatic activity and therefore when the other isostearamides are used, such use will preferably be with CISA, and the proportion of other isostearamide (s) will preferably be minor, with respect to the CISA. In some cases the hydrogen atom on the amide nitrogen may be replaced by suitable radicals, such as lower alkyl, e.g., methyl, providing that a desired antistatic effect is still obtained, but it has been found that the tertiary isostearamides usually are of little antistatic activity. The concentration of the antistatic agent in the composition is 0 to 5 wt.%, more preferably 0.1 to 4.5 wt.% and most preferably 0.2 to 4 wt.%.

A typical fabric softening agent used in the instant composition id di-stearyl di¬ methyl ammonium chloride, but any other conventional fabric softener can be used. The fabric softening agent is used in the composition at a concentration level of 0 to 5 wt. %, more preferably 0.1 to 4 wt.%, and most preferably 0.2 to 4 wt.%

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

Enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papain, trypsin adn pepsin, as well as amylase type anzymes, lipase type enzymes, and mixtures thereof can be used. Preferred enzymes include protease slurry, esperase slurry and amylase. A preferred enzyme is Esperse SL8 which is a protease. Anti- foam agents, e.g. silicon compounds, such as Silicane L 7604 can also be added in small effective amounts. Bactericides, e.g. tetrachlorosalicylanilide and hexachlorophene, fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet absorbers, anti-yellowing agents, such as sodium carboxymethyl cellulose, pH modifiers and pH buffers, color safe bleaches, perfume, and dyes and bluing agent such as ultramarine blue can be used. The following examples will serve to illustrate the present invention without being deemed limitative thereof. Parts and percents are by weight unless otherwise indicated. Example 1 - Formulation of the following ingredients are prepared:

Example 1 (Continued^ - Formulation of the following ingredients are prepared:

To the solution of the aqueous potassium silicate is added with stirring at room temperature for 1-5 minutes the methanol, n-hexanol, 1 -propanol, 2-propanol, 1-hetanol, propylene glycol and 1 ,6 hexanediol. Example

The following automatic dishwashing formula was made according to the following procedure.

A solution of potassium silicate, water and propylene glycol was made according to the procedue of Example I. The Dowfax 3B2 was then added with mixing to form the composition.

Claims

WHAT IS CLAIMED IS;

1. A shear thickening composition having a viscosity at room temperature at a 2 sec^"1 of 12 to 80 pascal seconds which comprises by weight of:

(a) 10% to 60% of an alkali metal silicate; (b) .1% to 30% of an organic compound having at least one hydroxyl group; and

(c) 0 to 5.0 of at least one organic detergent active material; and

(d) balance being water.

2. The composition of claim 1 , wherein said alkali metal silicate is selected from the group consisting of lithium silicate, sodium silicate and potassium silicate.

3. The composition of claim 2, wherein said organic compound has the formula ^cn^H2n+2-x(^OH)x wherein x=1 , 2 or 3 and n ^■= 1 to 20.

4. The composition of claim 2, wherein said organic compound is selected from the group consisting of methanol, ethanol, glycerol, hexanol and decanol.

5. The composition of claim 1 further including at least inorganic or organic builder salt containing an alkali metal cation.

6. The composition of claim 5 further including a foam depressant.

7. A composition having a complex viscosity at room temperature at a shear rate of 22 sec¹ of 12 to 80 pascal seconds and a viscosity at room temperature at a shear rate at 5 sec^"1 of 15 to 85 pascal seconds which comprises by weight percent of: (a) 10 to 45% of an alkali metal silicate;

(b) 0.1 to 30% of an organic compound having an at least one hydroxyl group;

(c) 0.1 to 15 of at least one surfactant; and

(d) water.

8. The composition of claim 7, wherein said alkali metal silicate is selected from the group consisting of lithium silicate, sodium silicate and potassium silicate.

9. The composition of claim 8, wherein said organic compound containing at least hydroxyl group has the formula

C_nH2n₊2-x(OH)_x wherein x = 1 , 2 or 3 and n = 1 to 20.

10. The composition of claim 8, wherein said organic compound is selected from the group consisting of methanol, ethanol, propanol, hexanol, glycerol, 1 ,6 hexaneciol and propylene glycol.

11. The composition oτ c. aim 8, wherein said x = 1 and n = 1 to 12.

12. The composition of claim 7, further including at least inorganic or organic builder salt containing an alkali metal cation.

13. The composition of claim 7, where, said surfactant is a nonionic surfactant an anionic surfactant.

14. The composition of Claim 7, wherein said surfacant is a nonionic surfactant.

15. The composition of Claim 7, wherein said surfactant is an anionic surfactant.

16. The composition of Claim 7 further including a fabric softner.