PT90771B - PROCESS FOR THE PREPARATION OF LIQUID DETERGENT COMPOSITIONS OF HIGH ALKALINITY, FOR AUTOMATIC MACHINE OF LAVAR CRAZY, CONTAINING A TIXOTROPIC AGENT BASED ON CLAY - Google Patents

Abstract

The physical stability of liquid gel-like compositions based on montmorillonite, attapulgite, hectorite or other inorganic colloid-forming clay or other thixotropic thickener, and small amounts, such as 0.1 to 0.2 weight percent, of calcium, magnesium, aluminium or zinc stearate or other polyvalent metal salt of long chain fatty acid is greatly improved by increasing the alkalinity level to such an extent that when the composition is added to an aqueous wash bath at a concentration of about 10 grams per liter the pH of the wash bath becomes at least 11.2. The aqueous compositions preferably also includes chlorine bleach, and the chlorine-bleach loss with time is also reduced in the high alkalinity formulations. Use as liquid gel-like automatic dishwasher compositions are described.

Description

DESCRIPTIVE MEMORY

Summary The present invention relates to a process for the preparation of structured aqueous liquid detergent compositions for automatic dishwashing machines with better cleaning performance and physical stability More specifically the invention concerns the use of higher levels of alkalinity for meCOLGATE-PALMOLIVE COMPANY

PROCESS FOR THE PREPARATION OF LIQUID DETERGENT COMPOSITIONS OF HIGH ALKALINITY. FOR AUTOMATIC DISHWASHING MACHINE. CONTAINING A CLAY-BASED THIXOTROPIC AGENT

-2better cleaning performance and rheological properties of thickened and stabilized liquid detergent compositions of long chain fatty acids (and their metal salts) for automatic dishwashing machines.

the present invention specifically concerns a process for the preparation of detergent compositions for automatic dishwashing having thixotropic properties. better chemical and physical stability and with a higher apparent viscosity and which are easily dispersible in the washing medium to provide a better cleaning performance for porcelain cups and the like. The process is characterized by including a thixotropic agent based on clay ' ^: an amount of an alkali metal salt of at least one long-chain fatty acid effective to increase the physical stability of the composition, a chlorine-based bleaching agent, a detergent builder and. still alkaline and alkaline earth metal components in an amount such that the pH of an aqueous solution with about 10 g / l of said composition, is. at least 11.2

The present invention relates to a process for preparing structured liquid aqueous detergent compositions for automatic dishwashing machines, with better cleaning performance and physical stability More specifically. the invention relates to the use of higher levels of alkalinity to improve the cleaning performance and the rheological properties of thickened and stabilized liquid detergent compositions of long chain fatty acids (and their metal salts) for automatic dishwashers in the present invention. specifically with respect to a process for the preparation of detergent compositions for automatic dishwashing, having thixotropic properties with better chemical and physical stability and with greater apparent viscosity and which are easily dispersible in the washing medium to form a better cleaning performance for plates, glasses , porcelain and the like.

Detergents for domestic dishwashing machines sold in powder form have several disadvantages, e.g. non-uniform composition of the expensive operations necessary for its manufacture; tendency to agglutination in the warehouse with high humidity resulting in the formation of torons that are difficult to disperse; dust ^1. ' a source of particular irritation for users suffering from allergies; and tendency to agglutinate in the dishwasher device.

However, the liquid forms of those compositions cannot generally be used in automatic dishwashers.

The recent research and development activity has focused on the form of tropic gel or tix of such compositions for ex cleaning products

-4 degreasing and automatic dishwasher products characterized as thixotropic pastes. The dishwasher products thus presented are mainly subject to objections as they are insufficiently viscous and to remain anchored in the dishwasher's dispensing cup. Ideally, thixotropic cleaning compositions should be highly viscous in a resting state, of the plastic nature of Binham and have relatively high yield values. However, when subjected to shear stresses, such as when they are agitated in a container or squeezed through an orifice, they must fluidize quickly and. after cessation of the applied shear stress, quickly revert to Bingham's state of high viscosity / plastic nature. Stability is also of primary importance. this and there should be no significant evidence of phase separation or lack of tightness after a long rest, the condition that the compositions for automatic dishwasher in the form of gel must have the previous properties has thus proved to be problematic, especially that respects the compositions for use in domestic dishwashers For effective use, it is generally recommended that detergents for automatic dishwashing, from now also called DLA, contain (1) sodium tripolyphosphate (TPFNa) to soften or bind hard water minerals and to emulsify and / or peptize dirt; (2) sodium silicate to provide the necessary alkalinity for an effective detergent and to provide protection to the enamel and fine porcelain contour; (3) sodium carbonate generally considered to be optional for increasing alkalinity; (4) a chlorine release agent to contribute to the elimination of dirt stains that lead to water staining; and (5) foam suppressor / surfactant to reduce foam thereby increasing the efficiency of the machine and providing the necessary detergency. for example.

-5 & SDA DETERGENTS IN DEPTH Formulation Aspects of Machine Dishwashing. Thomas Oberle (1974) Cleaning products that approximate the previously described compositions are mainly liquids or powders. It has been found difficult to combine such ingredients in an effective gel form for use in domestic machines. In general, such compositions omit the bleaching agent hypochlorite base as it has a tendency to react with other chemically active ingredients in particular surfactant. Thus the U.S. Patent. 4,115,308 discloses thixotropic pastes for automatic dishwashers containing a suspending agent eg CMC. synthetic or similar clays; inorganic salts including silicates. phosphates and polyphosphates; a small amount of surfactant and a foam suppressant.

No disclosure is made of a bleaching agent. U.S. Patent 4,147,650 and the like, optionally including a Cl- based bleaching agent (hypochlorite) but without organic surfactant or foam suppressant.

In addition, the product is described as a detergent paste with no apparent thixotropic properties.

US Patent 3,985,668 describes gel-type abrasive degreasing cleaning products containing (1) suspending agent, preferably smectite clay and atapulgite (2) abrasive types, eg sand. and silica or perlite; and

-6 (3) filler consisting of powdered polymers of low density expanded perlite and the like, which has a buoyant power and thus a stabilizing effect on the composition in addition to serving as a swelling agent thereby replacing the unwanted layer of supernatant by water, the formation of which is due to the lack of tightness and destabilization of phases.

The above ingredients are the essential ingredients. Optional ingredients include hypochlorite-based bleaching agent, stable surfactant in the presence of bleaching agent and buffer solution, eg silicates. carbonates and monophosphates.

structurers. namely TPFNa. can be included as other optional ingredients. for providing or completing the structuring function. not ensured by the buffer solution. not exceeding the amount of that structurer 5% of the total composition, according to the patent.

The maintenance of the desired pH levels of 10 to / or higher is achieved by the buffer solution / structuring components at a high pH and considered to reduce to a minimum the decomposition of chlorine-based bleaching agent and the undesired interaction between the surfactant -active and the whitening agent. When present, TPFNa is limited to 5%. as stated. A foam suppressor is not revealed.

-Ί Νο English Patent application

GB 2,116 199A and GB 2,140450A. both attributed to Colgate-Palmolive, liquid DLA compositions are revealed, which have desirably thixotropic characterization properties. gek-type structuring machines that include each of the various ingredients necessary for an effective detergent inside an automatic dishwasher.

The aqueous detergent composition, usually of the gel type. for automatic dishwasher, having thixotropic properties. includes the following ingredients, on a weight basis:

(a) 5 to 35% alkali metal tripolyphosphate.

(b) 2.5 to 20% sodium silicate;

(c) 0 to 9% alkali metal carbonate;

(d) 0.1 to 5% of water-dispersible active organic material, stable in the presence of chlorine-based bleaching agent;

(e) 0 to 5% suppressor and stable foam in the presence of the chlorine bleaching agent;

(f) chlorine-based bleaching compound, in an amount sufficient to provide about 0.2 to 4% of available chlorine (g) thixotropic thickener in an amount sufficient to give the composition a thixotropy index of about

2.5 to 10;

-8 (h) sodium hydroxide. when necessary, by adjusting the pH; and (i) water to be made up.

The DLA compositions thus formulated are of low foam formation; they are quickly soluble in the washing medium and highly effective at pH values that better lead to a better cleaning performance viz. pH 10.5-14. The compositions usually have the consistency of the gel. this is. a highly viscous, opaque and gelled type material. having a plastic nature of Bingham e. therefore, relatively high yield values. Accordingly, a defined cutting force is required to initiate or increase the flow. Under such conditions the imposition is quickly fluidized and easily dispersed. When the cutting force is interrupted, the fluid composition quickly reverts to high viscosity, Bingham's plastic nature very close to its previous consistency

U.S. Patent 4,511,487 of April 16, 1985 describes a low-foaming detergent paste for dishwashers. The thixotropic cleaning agent of the patent has a viscosity of at least 30 Pa.s at 20 ° C as determined by a rotary viscometer at a spindle speed of 5 revolutions per minute. The composition is based on a mixture of hydrated sodium metasilicate finely divided into an active chlorine compound and a thickening agent which is a shale silica of the hectorite type. A small amount of nonionic surfactant derivatives and alkali metal carbonates and / or hydroxides can be used.

Although these liquid DLA formulations previously disclosed are not subject, or are subject to a lesser degree, to one or more of the deficiencies referred to above, it has been found that in actual practice further improvements in physical stability are necessary to increase the product's life span thereby increasing their acceptance by the consumer.

In the application for a common and equally applicable assignment. series no.903.924 deposited on September 5, 1986. the disclosure of which is incorporated by reference to some of the present inventors indicated the binding of smaller amounts of metal salts of fatty acids, namely aluminum stearate, as additives, anti-sedimentation to improve the physical stability and rheological properties of thixotropic aqueous liquid DLA compositions based on clay

Although this previous application reveals sufficient alkalinity levels to provide DLAL compositions with values of at least 9 5 of preference at least 12 5 in actual practice these pH levels of the compositions correspond to pH levels in the aqueous wash bath, which are substantially lower, normally with a pH below 11 For example, the compositions exemplified in the examples of the series no.903.924. include 22% by weight, or 3.1%. by weight of a caustic soda solution (50% NaOH) to give the composition a pH of approximately 13. However, when added to the aqueous wash bath at a typical concentration level of about 10 grams per liter, the wash bath has a pH below 11. namely 10.9

-10Although these previous compositions showed an improved physical stability and an acceptable cleaning performance. it was desirable to obtain an even better cleaning performance for this purpose. the present inventors have decided to increase the alkalinity level of the liquid DLA compositions containing clay / fatty acid salt, as disclosed in the aforementioned application Serial No. 903,924.

It has been surprisingly discovered that an increasing alkalinity not only provides the desired improvement in cleaning performance, but also unexpectedly, it also provides news and a remarkable improvement in stability against changes over time, of the logical properties. It was also discovered and also quite surprisingly. that at superlot levels of alkalinity the reduction of available chlorine in compositions containing chlorine-based bleaching agent is greatly enhanced.

Accordingly, it is an object of the invention to present liquid DLA compositions having a better cleaning performance as well as better physical stability and rheological properties.

It is yet another object of the invention to present liquid DLA compositions containing a chlorine-based bleaching agent, in which the loss of estrus available over time is reduced

-11More specifically. it is an objective of this invention to improve the cleaning performance and the physical stability of aqueous liquid detergent pastes or gels for automatic dishwashing machines containing suspended particles (eg bleaching agent structuring salts, etc.), thickener based on clay and fatty acid metal salt stabilizer.

These and other objects of the invention. which will become more easily understood from the following specification of the invention and its preferred embodiments are achieved by a structured, liquid, liquid composition. thickened, clay-based, highly alkaline, for automatic machine. dishwasher, containing a physical stabilizer, which is a long chain fatty acid metal salt, and containing with alkaline stations so that. when the composition is added to an aqueous wash bath, at a concentration of 10 grams per liter the wash bath has a pH of at least 11.2. In a preferred embodiment the composition further includes a chlorine-based bleaching compound, being assi ^m nieveis due to high alkalinity less subject to loss of available chlorine during storage.

According to an especially preferred embodiment, the present invention features a thickened aqueous detergent composition for automatic dishwashers that includes, on a weight basis:

(a) 5 to 35% alkali metal tripolyphosphate;

(b) 2.5 to 30% alkali metal silicate;

(c) / 0 to 9% alkali metal carbonate;

-12 (d) 2 to 10% alkali metal hydroxide;

(e) 0.1 to 5% of active water-dispersible organic detergent material, stable in the presence of chlorine-based bleaching agent;

(f) Ô to 5% of stable foam suppressant in the presence of chlorine-based bleaching agent;

(g) chlorine bleaching compound, in an amount sufficient to provide about 0.2 to 4% of available chlorine;

(h) 0.1 to 10% inorganic clay that forms colloids;

(i) a metal salt of a long chain fatty acid in an amount effective to increase physical stability of the composition; and (j) water to be made up;

providing the total amount of:

(b) sodium silicate (c) alkali metal carbonate and (d) alkali metal hydroxide at a pH sufficiently high that. when the composition is diluted in an aqueous wash bath to provide a concentration of 10 grams per liter, the pH of the aqueous wash bath is at least 11.2.

The invention also features a method for cleaning dishes in an automatic dishwasher, with an aqueous washing bath containing an effective amount of liquid detergent composition for automatic dishwashers (DLAL) as previously described.

In accordance with this aspect of the invention, the DLAL composition can be easily poured into

-13 an automatic dishwasher dispensing cup and will be viscous enough to remain safe inside the dispensing cup until cutting forces are applied again, such as those caused by the water jet coming from the dishwasher.

It is known that the effectiveness of DLAL is directly related to (a) available chlorine levels; (b) alkalinity; (c) solubility in the washing medium; and (d) foam inhibition. It has therefore been suggested that the PH of the DLAL composition is at least about 9.5, more preferably at least about 12.5. In the previous order no. 903,924, quantities of about 0.5 to 6% by weight of NaOH and cecca of 2 to 9% by weight of sodium carbonate in the DLAL composition were proposed.

According to the present invention the types and amounts of alkaline compounds are chosen so that when the composition is added to an aqueous wash bath to form a concentration of 10 grams of composition per liter of wash bath the pH of the bath washing time is at least 11.2, preferably at least 11.5, namely from 11.5 to 13.5, preferably 11.5 to 12.5. Operating at these levels of alkalinity higher than normal, the cleaning performance is better and, at the same time, the rheological properties and especially the physical stability are better. Furthermore, in the preferred embodiment of the invention, in which the chlorine bleaching compound is included in the DLAL composition, the additional advantage of reducing the loss of active chlorine is also obtained.

-14To obtain these high pH levels, it is necessary to increase the toatl concentration of the alkaline components, compared to the levels actually used in the previous known DLAL compositions

Such a composition is presented as Example 4 in our previous application Serie No.903.924, namely:

Ingredient Amount (A.I)% by weight

Sodium silicate (47.5% solution Na ₂ 0 = Si0 ₂ = 1/2, 4) 7.48

0.16 Mono-steari-phosphate

Dowfax 3B-2 0.36

Thermphos NW 12.0

Thermphos N Hexa 12.0

Aluminum tri-stearate 0.1

Sodium carbonate, anhydrous 5.0 caustic soda solution (50% NaOH) 3.1

Pharmagel Euroclay (Mg / Al silicate clay), 25

-15 (CONT) sodium hypochlorite solution (11%)

, 0

Water to make pH 13 to 13.4

In this Example 4, the amount of sodium hydroxide was increased from 2.2 wt% (1.1 wt% ia) to 6.2 wt% (3.1% wt ia) with a corresponding decrease in the added water content, leaving the levels of sodium carbonate and qosium mestassicate unchanged (5.0% and 15.74% (7.48%) ia) respectively.

Tests for cleaning performance and rheological properties of the high alkalinity composition of Example 4 demonstrated that these compositions were superior to the control composition / caustic soda solution β 2.2% by weight). However, when testing for available chlorine content, the control composition was slightly superior to the composition of Example 4. In contrast, when a high alkalinity formulation was prepared according to the invention, increasing the concentration of soda caustic at the expense of sodium carbonate, not only increased cleaning performance and rheological properties, but also substantially reduced the loss of available chlorine compared to that of control. Similarly, when replacing NazCO ^ with additional alkali metal silicate the loss of available chlorine is also reduced while improving cleaning performance and stabilizing rheological properties.

Accordingly, according to an especially preferred embodiment of this invention, high alkalinity is obtained in a liquid dishwashing composition for automatic dishwashers, containing chlorine-based bleaching agent stabilized with fatty acid salt, thickened with clay , wherein the alkaline compounds include, on a dective basis, based on the total composition, from about 3 to 20% by weight of alkali metal silicate, from about 1.0 to 4.5% by weight, of alkali metal hydroxide and from 0 to about 4% by weight of alkali metal carbonate, with the proviso that the total amount of alkali metal hydroxide and alkali metal carbonate is not more than about 6.5 % by weight, and the total amount of alkali metal silicate and alkali metal carbonate is not more than about 20% by weight, the pH of the composition being at least 12.8 and the pH of 1 liter of washing bath aqueous, containing 10 grams of composition, at least the 11.5,

Although the alkali metal of the alkaline compounds: silicate, carbonate and hydroxide is preferably sodium, the corresponding poiassium compounds, or mixtures of sodium and potassium compounds, can also be used.

sodium silicate, which provides alkalinity and hard surface protection, such as fine porcelain contour and enamel, is used in an amount ranging from about 2.5 to 20%, by weight, preferably about 5 to 15% by weight in the composition. The sodium bicarbonate is generally added in the form of an aqueous solution, preferably having a Na20: Si02 ratio of about 1: 1.3 to 1: 2.8 and most preferably 1: 2.0 to 1 : 2.6. At this point, it should be noted that most of the

-17other components of this composition, in particular NaOH and sodium hypochlorite, are also frequently added in the form of a dispersion or aqueous solution previously prepared.

The liquid dishwashing detergent compositions of this invention generally also include an alkali metal phosphate-based detergent builder, namely sodium triphosphate (TPFNa), and this will also contribute to the pH of the composition.

Preferred TPFNb is used in the DLAL composition in a form of about Θ to 35%, by weight, preferably about 20 to 30%, by weight and should preferably be carbide istanbul, which tends to decompose or inactivate sodium hypochlorite preferred and others with chlorine-based bleaching components. TPFNa can be hydrated or hydrated, including hexahydrate established with a hydration degree of 6 corresponding to about 10% by weight of water or more. Especially preferred DLAL compositions are obtained, for example, when a weight ratio of 0.5; 1 to 2: 1 is carried out from anhydrous TPFNa to hexahydrate, with values of about 1: 1 being particularly preferred.

In addition, or in replacement of part or all of the structuring agent, for detergent based on TPFNa, other salts can be used in the composition, for detergents, porous or non-phosphorous, inorganic or organic.

Examples of suitable drying builders for detergents include, for example,

-18 trisodium sodium nitrilotriacetate, ethylenediamine tetra-sodium tetraacetate, sodium citrate and the corresponding potassium salts. One can also use tetrapota sodium or tetrasodium pyrophosphate. However, sodium tripolyphosphate is highly preferred, where detergents containing phosphorus are allowed.

Foam inhibition is important to increase the efficiency of the dishwasher and to minimize the destabilizing effects that could occur inside the dishwasher, during its use, due to the presence of excess foam.

The foam must be sufficiently reduced by the appropriate selection of the type and / or amount of active detergent material, the main foam-producing component. The degree of foam is also somewhat dependent on the hardness of the washing water inside the machine, and an appropriate adjustment of the proportions of the TPFNa, which has an eagle softening effect, can contribute to providing the desired degree of foam inhibition.

However, it is generally preferable to include a stable foam suppressant or inhibitor in the presence of the chlorine-based bleaching agent. Particularly effective are phosphonic acid alkyls of the formula

HO o

THE

-P-R

OR

-19 and in particular the acidic phosphate esters of formula 1 to

HO - P ^0R

OR

In the above formulas, one or both R groups in each type of ester may represent independently an alkyl group ^C 12 ^-C 2O ^{'may be} used od ethoxylated derivatives of each type of ester, for example the condensation products of one mole of ester with 1 to 10 mol, preferably 2 to 6 mol, more preferably 3 or 4, mol, of ethylene oxide. Some examples of the above are commercialized, such as Hooker's SAP products and Knapsack's LPKn-158. Mixtures of the two types, or any other types stable in the presence of chlorine-based bleaching agents, or mixtures of mono- and di-esters of the same type, may be used. Especially preferred is a mixture of mono and dialkyl esters ^C 16 ^C 18 acid phosphate, such as 1,2 / 1 mono stearyl / distearyl acid phosphates, and their 3 to 4 mol ethylene oxide condensates. When foam suppressor is used in the composition, a proportion of 0.1 to 5% by weight, preferably 0.1 to 5% by weight, preferably 0.1 to 0.5% by weight, typically varying generally the weight ratio of active detergent component (d) to foam suppressor (e) of about 10: 1 to 1: 1 and preferably about 5: 1 to 1: 1 Other foam suppressors that can be used and to be used include, for example, the known silicones, such as those sold by Dow Chemicals. Furthermore, it is a

It is an advantageous aspect of this invention that many of the stabilized salts, namely the stearate salts, for example aluminum stearate, are also effective foam suppressors.

Although any chlorine-based bleaching compound can be used in the compositions of this Invention, namely dichloro-isocyanurate, dichloro-dimethyl-handantoin or chlorinated FTS, alkali metal or alkaline earth metal, lithium, for example, potassium hypochlorite, is preferred. , magnesium and especially sodium. The composition must contain enough chlorine-based bleaching compound to provide about 0.2 to 4.0%, by weight of available chlorine, as for example, by acidifying 100 parts of the composition with excess hydrochloric acid.

A solution containing about 0.2 to 4.0% by weight of sodium hypochlorite contains or provides practically the same percentage of available chlorine. Especially preferred is an amount of about 0.8 to 1.6%, by weight, of available chlorine. For example, a sodium hypochlorite (NaOCl) solution of about 11 to about 13% of available chlorine in amounts of about 3 to 20%, preferably about 7 to 12%, can be used advantageously.

detergent active material used for this purpose must be stable in the presence of chlorine-based bleaching agent, in particular hypochlorite-based bleaching agent and those of the types of anionic organic water-dispersible surfactants, amine, phosphine oxide, sulfoxide

-21 or betaine, with the anions mentioned above being most preferred. They are used in amounts ranging from about 0.1 to 5%, preferably about 0.3 to 2.0%. Particularly preferred surfactants for this purpose are the mono- and / or di- (Cg-C4) alkyl or branched-diphenyl-oxido-mono- and / or alkali metal disulfates, sold, for example, with DowFax (registered trademark) 3B-2 and DOWFAX 2A-1. In addition, the surfactant must be compatible with the other ingredients in the composition.

Other suitable surfactants include primary alkyl sulfates, alkyl-sulfonates to alkyl-sulfonates and alkyl-sulfates. Examples include C1 -C4 alkyl sodium sulfates such as sodium dodecyl sulfate and sodium and tallow alcohol sulfate; sodium alkane [10] ^C 18 ^sulfonates such as sodium hexadeci1-1-sulfonate and sodium ^C 12 ^_C 18 alkyl benzene sulfonate, namely sodium dodeci1-benzene sulfonates.

The corresponding potassium salts can also be used. Like other suitable detergents'surfactants','amine oxide surfactants typically have the structure R ₂ R ¹ N - * - 0, where each R represents a lower alkyl group, for example methyl and R ¹ represents a long chain alkyl group having 8 to 22 carbon atoms, for example, a lauryl, myristyl, palmlyl or cetyl group. Instead of an amine oxide, a corresponding phosphine oxide R ₂ R ¹ P0 surfactant or RR ¹ SO sulfoxide can be used.

Betaine surfactants typically have the structure R ₂ R ¹ NR ¹ COO-, where each

-22R represents a lower alkylene group having from 1 to 5 carbon atoms. Specific examples of these surfactants include lauryl-dimethyl-amine oxide, myristyl-dimethyl-amine oxide, the corresponding phosphine and sulfoxide oxides and the corresponding betaines, including dodeci1-dimethyl-ammonium acetate, tetradeci-pentanoate1- diethyl ammonium, hexadeci1-dimethyl ammonium hexanoate and the like.

Due to biodegradation, the alkyl groups in these surfactants should be linear, with three compounds being preferred.

Surfactants of the foregoing type, all well known in the art are described, for example, in U.S. Patent Nos. 3,985,668 and 4,271,030.

Thixotropic thickeners, ie thickeners for suspending agents that provide an aqueous medium with thixotropic properties, are known in the art and can be organic or inorganic water-soluble, water-dipping or colloid-forming, and monomeric or polymeric and should, of course, they are stable in these compositions, e.g., stable in high alkalinity and chlorine bleaching compounds, such as sodium hypochlorite. Especially preferred are in general types of inorganic smectite and / or atapulgite clays that form colloids.

These materials are generally used in amounts of about 0.1 to 10, preferably 1 to 5%, by weight, to impart the desired thixotropic properties and plastic nature of Bingham. However, in the presence of the metal salt fatty acid stabilizers, the desired thixotropic and plastic properties of Bingham can be obtained with lesser amounts of thixotropic thickeners. For example, amounts of smectite and / or atapulgite colloidal inorganic clays, in the range of 0.1 to 3%, preferably 0.1 to 2.5%, especially 0.1 to 2%, they are generally sufficient to obtain the desired thixotropic properties and Bingham's plastic nature when used in combination with the physical stabilizer.

Smectite clays include mont morylonite (bentonite), hectorite, smectite, saponite and the like Montmorillonite clays are preferred and are sold under the trade names of Thixogel (registered trademark) no.1 and GelWhite (registered trademark) GP, H, etc., by Georgia Kaolin, Company; and ECCAGUM (registered trademark) GP, H, etc. by Luthen Cl ay'Products. Atapulgite clays include materials sold under the trade name of Attagel (registered trademark), that is, Attagel 40, Attagel 50, and Attagel 150 by Engelhard Minerais and Chemicals Corporation

Mixtures of the smectite and atapulgite types, in weight ratios, from 4: 1 to 1: 5 are also useful for this purpose. Abrasives or polishing agents should be avoided in DLAL compositions, as they can damage the surface of fine china, crystals and ends.

Preferred long-chain fatty acids are higher aliphatic fatty acids having about 8 to 22 carbon atoms, more preferably about 10 to 20 carbon atoms, and most preferably about 12 to 18 carbon atoms including the carbon atom of the fatty acid carboxyl group. The aliphatic radical can be saturated or unsaturated and can be linear or branched.

Straight chain saturated g-ordos are preferred. Mixtures of fatty acids can be used, such as those derived from natural sources, namely tallow fatty acid, fatty acid from a cup, or soybean fatty acid, etc., or from synthetic sources sold by industrial manufacturing processes.

Thus, examples of fatty acids, from which polyvalent metal salts can be formed or stabilized, include for example, decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicosanoic acid, grodo acid tallow, coconut fatty acid, soy fatty acid, mixtures of these acids, etc., Stearic acid and mixed fatty acids are preferred.

The preferred metals are the polyvalent metals of groups IIA, IIB and IIIB, namely magnesic calcium, aluminum, and zinc, although other polyvalent metals can also be used, including Groups IIIA, IVA VA, IB, IVB, VB, VIB, VIIB , and VIII of the Periodic Table of the Elements.

-25The specific Examples of those other polyvalent metals include T1, Zr, V, Nb, MN, Be, Co Ni, Cd, Sn, Sb, Bi, etc., In general, the metals may be present in the bivalent to pentavalent state. Preferably, the metal salts are used in their higher oxidation states. Naturally for DLAL compositions, as well as any other applications in which the composition of the invention is or may come into contact with articles used for the handling, storage or service of food products, or which may otherwise be in contact or can be consumed by people or animals the metal salt should be selected taking into account the toxicity of the metal. For this purpose, calcium and magnesium salts are especially preferred, as they are generally reliable food additives.

Many of these metal salts are marketed. For example, aluminum salts are sold in the form of a tracid, e.g., aluminum stearate in the form of aluminum triesterate, Al ( ^c - | 7-H35COO) g. Mono-acid salts, eg aluminum mono-stearate and di-acid salts, eg, aluminum distearate, and mixtures of two or three of the mono-, di- and tri-acid salts, can be used for those metals eg, Al, with +3 valences, and mixtures of the mono and di-acid salts can be used for those metals, eg, Zn, with +2 valences. It is highly preferable that the dl-acids of metals with a valence of +2 and the triacids of metals with a valence of +3, the tetra-acids of metals with a valence of +4 and the penta-acids of metals with a valence of +5 are used in predominant quantities.

-26Metal salts, as mentioned above, are generally commercialized, although they can be easily produced, for example by saponification of a fatty acid, eg animal fat, followed by treatment with a polyvalent metal oxide hydroxide, for example in the case of the aluminum salt with alum, alumina, etc., or by reacting a soluble metal salt with a soluble fatty acid salt.

calcium stearate, that is, calcium distearate, magnesium stearate, that is, magnesium distearate, aluminum stearate, that is, aluminum tristereate and zinc stearate, that is, zinc stearate are the stabilizers of preferred addition salts and polyvalent fatty acids. Metal salts of mixed fatty acids, as well as acids of natural origin, eg coconut acid, as well as the many fatty acids resulting from the commercial manufacturing process, are also used to advantage, as an economical but effective source of long chain fatty acid.

The amount of the fatty acid salt stabilizer needed to achieve the desired improvement in physical stability will depend on factors such as the nature of the fatty acid salt, the nature and quantity of the thixotropic agent, active detergent compound, inorganic substances, especially TPFNa, others DLAL ingredients, as well as advance storage and shipping conditions.

In general, however, amounts of the stabilizing agents based on polyvalent metal fatty acid salts in the range of about 0.002 to 1%, preferably from about 0.06 to 0.8%, most preferably from about 0.08 to 0.4%, provide long-term stability and no phase separation at rest or during transport, both at low and high temperatures as required for a commercially acceptable product.

Depending on the quantities, proportions and types of physical stabilizers and thixotropic agents, the addition of fatty acid type salts not only increases physical stability, but also provides a simultaneous increase in apparent viscosity. Ratio of fatty acid salt to thixotropic agent in the range of about 0.08-0.4% by weight of fatty acid salt and about 1-2.5% by weight of thixotropic agent are usually sufficient to that these simultaneous advantages are obtained, and therefore, the use of these ingredients in these relationships is highly preferred.

The amount of water contained in these compositions must, of course, neither be so high as to produce unduly low viscosity and fluidity nor so low as to produce unduly high viscosity and low fluidity, in both cases the thixotropic properties being reduced or destroyed. such an amount is easily determined by routine experimentation in any specific case, generally ranging from about 30 to 75% by weight, preferably about 35 to 65% by weight. The water should also preferably be deionized or soft.

According to a preferred method for preparing these compositions, all inorganic salts, i.e., corbonate (when used), silicate and tripolyphosphate, must be dissolved or dispersed in the aqueous medium first. The thickening agent is added last. The foam suppressant (when used) is previously prepared in the form of an aqueous dispersion, such as the thickening agent. The dispersion of foam suppressant, caustic soda (when used) and inorganic salts are first mixed and elevated temperatures in aqueous solution (deionized water), and then cooled, using deep and uniform stirring. The bleaching agent, the surfactant, the fatty acid metal salt stabilizer and the thickener dispersion at room temperature are then added to the cooled solution (25-35 ° C). Excluding chlorine-based bleaching compound, the total salt concentration (TPFNe) (and sodium carbonate) is generally about 20 to 50% by weight. Preferably about 30 to 40% by weight. , in the composition.

another highly preferred method for mixing the ingredients of DLAL formulations is to first form a mixture with water, foam suppressant, detergent, physical stabilizer (fatty acid salt) and thixotropic agent, eg, clay.

These ingredients are mixed with each other under cutting conditions, preferably starting at room temperature, until they form a uniform dispersion. The remaining ingredients are added to this pre-mixed portion under low shear mixing conditions. For example, the amount of pre-mix needed

-29 is introduced in a low-cut mixing machine and then the remaining ingredients are added, with mixing, either in sequence or simultaneously.

Preferably the ingredients are added in sequence, although it is not necessary to complete the addition of an entire ingredient before starting the addition of the next ingredient. In addition, one or more of the ingredients can be divided into portions and added at different times. Good results have been obtained with the addition of the remaining ingredients in the following sequence: sodium hydroxide, alkali metal carbonate, sodium silicate, alkali metal tripolyphosphate (hydrated), alkali metal tripolyphosphate (anhydrous or up to 5% water) bleaching agent (preferably sodium hypochlorite) and sodium hydroxide.

Other conventional ingredients can be included in these compositions in small amounts in general, less than about 3% by weight, namely perfume, hydrotropic agents such as benzene, toluene, xylenp and sodium cumene sulfonates, preservatives, dyes and pigments and the like , evidently all being stable in the presence of the chlorine bleaching compound and high alkalinity (properties of all components). Chlorinated phthalocyanines, as well as aluminum aluminosiicate polysulfates which provide pleasant shades of green and blue respectively, are especially preferred as dyes.

One can use TiO ₂ for whitening or neutralizing descoloraç ^T oes.

The liquid ADD compositions of this invention are readily employed in known manner for washing dishes, utensils, cooking and the like in an m £ ^r quin automatic dishwasher, equipped with a detergent distributing device suitable, in an aqueous wash bath containing an effective amount of the composition is generally sufficient to fill or partially fill the dispensing cup of the machine to be used.

The invention can be put into practice in several ways and a series of specific forms of carrying out the invention will be described to illustrate it with reference to the examples that accompany it.

All quantities of the proportions referred to herein are by weight, based on composition, unless otherwise specified.

Example 1

In order to demonstrate the effect of the alkalinity of liquid DLA formulations thickened with clay, stabilized with a metal salt of fatty acids, compositions are prepared as indicated in Table I, with various amounts of alkaline compounds.

-32 «*>

The w &

AND

d)

0)

T3

Π3

Ό o

'S · ra

Μ <X>

Z

Ό ^{1/1 will} 'υιό μ o

z o

'&

ra μ

O 1 1 1 tn O O O tO O CM CM 1 1 1 CM O O O · - ( 00 • • 1 1 | • • • ♦ • « CM 1 1 1 00 CM CM OO O O ro 1 1 1 CM r-H rd

o in rH CM

O r-t o o CM

CM m τ o i o C- r ~ | o • · I · in oo i cm · —I I f — 1

CM

tn O O -Μ ¹ 1 1 O O r * CM O r— 1 1st O • • • • 1 1 · • tn 00 tn tra i 1 CM CM co <-1 i 1 r-1 r — 1

the o

O tn O O • 'T i 1st z r * CM O r- ~ i 1st 2 p '' ¹ • • • 1 1 · s Γ- GRANDFATHER tra go there 1 CM frog ΓΟ M 1 1 r — t μ

O o

CM σι σ \ «o o · - (00 • · o o o in r-t CM

O r-t (0 o i-t 00 o in r-l CM

The r-l

G0 o r-t 00 o tn r-t CM

R-l ο

or α

<

ç

Cr o

ire in Ut ra υιό ~ Ut o

0)

4->

c (D • rd 'S &

c l-t

O CM 1 1 τ i Γ- 1 1st 1st O O O O see you 00 O i — 1 tn CM O O • 1 • 1 1 • • • · • r- 1 in i 1 CM CM GO the o O r-l O 1 Γ — 1 1 1 i — 1 rH O

tn O O ’Τ i 1st O O grandfather O O r- CM O r ~ 1 i o O O i — 1 00 - * - * - J 1 1 • • • • i — 1 uo CM m i 1 CM ~ CM G0 O O O M > —T l 1 "-( r-1

CM

tn O O V 1 1 O O O grandfather O r- CM O Γ- 1 1st O O rH 00 • * · • -I 1 · • • • r- | CM uo in i i or CM cn O O r-l 1 1 «—1 "-1

the m

The r-l CM X Ό κ.

fO r-l

X

Ό

GO o

ro c

Ό X ra o n ra en -η υ ~ c -η ra o + J

-rl (fl X (fl 2 Q ra -ro ro Ό υ z ra ra · co

CM (8 (8 ^

CM

O

Ή ω

O

CM ra z

CM - • · CM CM i — 1 «· • · II f — 1 "-1 CM II II O CM CM-rH O O W ♦ i-l ♦ · tn O • « CM d O fS CM (MZ ní «J - z Z » » OO X * uo uo OU * uo r— r- OU rtj fO co 1 • « 1—1 rH rH O O 0 (fl (fl

a <p 2 s2 £ • rl - c. 0 -H o

4-1 ira Ή ra ira -ri _

M-t υ * o ra (page 3 a>

—Ι Ό (D 1) (μ 0 -d Ό Ό ra cp. „_ _ Ra ¹ ra ra 7Í rt -μ 4-ι xrj μ cm · μ ra ro ro ro ju c μ <-uj ο ώ oo ra 4) the 4i m ra μ ra (fl Ο Η -U *

4) x c 3 m e i ra o (fl fl) o M-t e ra i ra c 3 -H -h, c £ &% · ί & ϊ ss s

CP s

0)

Ό m

Ot liter

-33 In the preparation of these formulations, the mono-stearyl phosphate-based foam suppressant and the active detergent compound Dowfax 3B-2 are added to the mixture just before the Pharmagel H clay thickener all NaOH is added after the clay.

The remaining liquid DLA formulations shown in Table I are evaluated for cleaning performance (QUARTER II); and as for density and physical stability (phase separation), at rest and in an expedition test. Results are shown in Table III

-34 TABLE II

CLEANING PERFORMANCE

Composition of operation no.

Average rating for mixed dirt

Average rating for soiling in starch baee ² )

CONTROL

Powder ¹ )

5.71

5.85

5.12

6.11

3.80.00

3.50

4.61

1) DLA powder, pH = 12.2 commercially available

2) Rice dishes and cutlery with rice and flour porridge

3510 ro magnet

Ε

Φ

CO tO · &

<3

Ό

Ή

TABLE III

Ό f0

4->

•H

CP ro

The iro

Ç

O

Ό

0 trO O •H Ό 0 Φ iro α O X ro Φ Ju ίΠ Φ & Ό Λ Φ + J ο to σ £

all rO

ÉM-fO HJ ro-H

04- »ro ro 'V

ιη ιη <ώ H « Η ο ο α + 1 + 1 • Η rH

m e- <

Cí

Τ3 Φ 4-> Ό <—Ι Ο tro Ο «0 Μ-) ίΒ 99 co Η 13 Π) α & U α (11 s υ Λ ο

Φ

Ό <3 • H (0 c

m £

o σ

5 · §.

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The in o

n m

o .53

Έί φ

Ό to <3

L-i í3

5d

CP

AND

Φ to o

Ui • H

Φ

CP í3 (0 r3

CL

Φ

TJ <3 a

4- »r3 • H>

<0

CN

The r * cs

CN

V <N

V r *

CN v

the m

v.

GO

CN

-36Example 2

The composition of control and the composition of operations nos. 3 and 5 were aged at 4 ° C, at room temperature (RT) at 35 ° C or 43 ° C and the viscosity of each sample was measured after storage in a plastic bottle for 1, 4, 6 and 12 weeks with a Brookfield LVT viscometer using a No. 54 spindle at 3 rpm. The results are shown in Table IV.

TABLE IV

Or and

ω

Ei an ε ε d) ο 4-1 ο 'S · ° ·' «'8 · ζ Ο nj α ρ Ε Φ

O&

Ο lH

4->

C <3 ro ιη

Example 3

The composition of control and the composition of operations nos. 3 and 5 and a reference example in which the alkaline stearate was omitted from the control composition and the amount of clay was increased to 2%, were subjected to a test to measure the rheological properties after standing at room temperature for 10 days, 6 weeks and 3 months.

The results are revealed in the

Table V.

a f0

d)

Ό fO

Ό • rd u

V) • H>

<0

Ή a

the u

4- »

X m tn CD · tn <o rd 0 «i tn cn · in 0 <CN

I tn tn to ro m (X>

tn \

(0 o <

m ox Π rd l ^r loo cn

CN <N I <O I o cn cn * to ox

I · * * x · *

I HO rd

m un cn m cn o o

OX with CN CN • -.I

O I O

CN 10 OX O cd oo r »| ♦ - · - rs.

I Η Η Η H io co cn i0 un

one io 10 CN The CN rd CN OX N ·  · - · - r * "-s ·. rd un CN | CN cn rd co «Η OX 10 CN rd <N | CN CN CN rd Ο) Η H

10 OX m i 1st rd color- un 00 in 10 10 10 1 I in Γ- cn ox 10 cn rd Γ ~ CN X0 OX ox cn <0 un CN rd r-1 rd rd rd rd rd rd

TABLE ε

0 The u Ό f0 ΦΟ > dn Φ Li

Φ Li ΰ 8 <9

O

X

Ή <2 cn tn rd * O £

tn cr <o

0.

Οζ?

D <0 04

O

4->

-H & 8 ε r:

0) rH ÇZ Q)>

ç

Φ o

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O • H tn a

ε «* T P * rd O

O O

I o o o o · »« I OX l cn rd o o o o - I · O | o cn cn r * cn co o o o o o o r * · * r i cn cn i cn

P * CN CN cd ox un cn cn cn un · άο «> Η vΓ ** Ή cn m m

ox "-1 r-1 X0 ox O co co r- ·, f · - - · · - · *. · »· - CD rd un i cn rd P * co Ο Η H CN CN cn 1 cn m CN m cn cn

cn cn ox X0 1 X0 tn «0 00 10 10 Γ * m rd cn ♦. * _ «- p * · r-xo • X0 10 cn tn tn tn <0 ro <0 fO ç tn ç tn c tn ç tn r9 φ tn ro φ tn ro φ tn g φ ro ε tn ro g <n ro and tn ro £ tn 'and φ tn φ ε • d Ό w £ Ή τ) φ φ cn e • Η φ • tj tn £ O 10 cn O 10 cn ο io cn Ο X0 cn rd rd rd rd

ro • H ϋ

c <φ k

Φ

Ud £

OC un o

iro

O <0

-40Example 4

Using the control composition and the compositions of operations Nos. 1, 3 and 5, the available chlorine levels were measured after storage at room temperature, 35 ° C and 43 ° C, for 2, 4 , 6 or 12 weeks. The results are shown in Table VI.

i

CM

CO

CM

CM cn cn

L *>

CJ o

m tn cn

LO

The cn

OL tn

CM

CM tn rin tn

LO

LO

LO

LO

LO

OL n * · tn

LO

Γ *

LD tn

CO

LO

CM TN

LO

TABLE VI

4) «c z

M

O

H

Hi

The <

s

M

W gj g!

w

Q cn

LD

U o

LT) m

CM tn rCM

OL

CM

Γ * o

OL c

with

co

CM

OL

CM

OL cm r * oo fhI r- co r * co lo, o tn ol cn

I OL OL 00 OL «<· lo cm m

I OL OL OL OL

CM LO 00 «H 00

I OL OL OL OL w

flj £

0) tn

O

M

-P

C, 8U ro ·

O iro cn O iro tn O O ro • ro • u O O z z

Claims (16)

1 ^a .- Process for the preparation of an aqueous thixotropic liquid composition, characterized in that water, a clay-based thixotropic agent, includes an amount of a metal salt of at least one long chain fatty acid effective to increase the physical stability of the composition of organic detergent, chlorine-based bleaching agent and detergent builder and because it also includes components of alkali metal and metal at 1 Ca 1 -Cine in an amount sufficient to provide a pH at least 11.2 when about 10g of composition is added to a liter of water. 2 ^fl .- Process according to claim 1, characterized in that the metal salt is a polyvalent metal salt of a metal of Group Ιί, III or IV of the Periodic Table of the elements and a long chain fatty acid of about 8 to 22 carbon atoms or a mixture of two or more of such fatty acids. 3. ^A process according to claim 1, characterized in that the polyvalent metal is aluminum, zinc, calcium or magnesium. 4. The process of claim 1 wherein the fatty acid metal salt is calcium stearate or magnesium stearate. 5 ^fi .- Process for the preparation of an aqueous thixotropic composition for an automatic dishwasher, characterized in that it includes, by weight, and in approximate values: (a) 5 to 35% alkali metal tripolyphosphate; (b) 2.5 to 30% alkali metal silicate; (c) 0 to 9% alkali metal carbonate; (d) 2 to 10% alkali metal hydroxide; (e) 0.1 to 5 active water-dispersive organic detergent-1 material, stable in the presence of chlorine-based bleaching agent; (f) 0 to 5% stable foam suppressant in the presence of the chlorine-based bleaching agent; (g) chlorine-based bleaching compound in an amount sufficient to provide about 0.2 to 4% of chlorine available; (h) 0.1 to 10% inorganic clay that forms colloids; (i) a metal salt of a long chain fatty acid as a physical stabilizer in an amount effective to increase the physical stability of the composition; and -44 (j) water; by providing the total amount of component (b), (c) and (d) a pH to the composition so that when it is diluted to give a concentrate of 10 g per liter, the pH of the water becomes at least 11.2. 6 * .- Process according to claim 5, characterized in that the physical stabilizer (i) is a polyvalent metal salt of an aliphatic grod acid having from about 12 to 18 carbon atoms. 7. A process according to claim 6, characterized in that the polyvalent metal is selected from the group formed by Mg, Ca, Ti, Zr, V, Sb, Mn, Fe, Co, Ni, Cd, Sn, Sb, Bi , Al and Zn. 8. The method of claim 5, wherein the physical stabilizer (i) is the aluminum, zinc, magnesium, or calcium stearic acid salt. 9 ⁴ .- A method according to claim 5, wherein the physical stabilizer (i) is present in an amount of about 0.02 to 1%. 45. ^A process according to claim 5, characterized in that the clay (h) is an atapulgite clay or a smectite clay. 11. ^A process according to claim 10, characterized in that the amount of clay (S) is in the range of about 0.1 to 3%. 12. ^A process according to claim 10, characterized in that said composition includes about 0.1 to 0.5% of the physical stabilizer (i) and about 0.1 to 2%, by weight, of agent of colloid formation (h). 13. ^A process according to claim 5, characterized in that the chlorine-based bleaching compound (f) is sodium hypochlorite. 14. ^A process according to claim 5, characterized in that at least about 0.1% by weight of foam suppressor (e) is included in said composition. 15th. - Process according to claim 14, characterized in that the foam suppressant is a phosphate acid alkyl ester, an alkyl phosphonic acid ester containing one or two alkyl groups ^is i2-20 a 'its ethoxylated product , or a mixture thereof. 16th. Process according to claim 5, characterized in that the amount of components (b), (c) and (d) is such that, when the composition is diluted to 10 g / l, the pH of the diluted composition is about from 11.5 to 13.5. 17th. Method for washing dirty dishes in an automatic dishwasher by contacting said dirty dishes with an aqueous washing bath, characterized in that said bath has dispersed in it an effective amount of composition prepared according to claim 5, in a sufficient amount to provide the wash bath with a pH of at least 11.2. 18th. - Method to improve the stability against phase separation of a composition containing an aqueous gel-like dispersion of at least one structuring material, for finely divided detergent, insoluble in water, characterized in that about 1 to 2 are incorporated into the dispersion, 5% by weight, from 1 to 2.5% by weight, smectite clay-based thickening agent and about 0.08 to 0.4% by weight of a C-fatty acid metal salt C long chain of a polyvalent metal selected from Groups IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB, and VIII of the Periodic Table of the Elements, in which said composition has a viscosity, in low-cut conditions, which is about 2 to 3 times higher than viscosity, in -47 low cut, of the composition without the long-chain fatty acid metal salt and where the viscosity of the composition, in high shear conditions, is about 1/2 to 1/10 of the viscosity in low shear conditions, including there is sufficient sodium hydroxide, sodium carbonate and sodium silicate in said composition so that when about 10 g of the composition is added to 1 liter of water, the pH of the water reaches at least 11.2. Lisbon, 7 June 1989 RUA VICTOR CORDON, 10 - A 3 · * 1200 LISBON A process according to claim 14, characterized in that the foam suppressor is an alkyl ester of acid phosphate, an alkyl ester of phosphonic acid containing one or more ^C 12-20 alkyl groups and ^an ethoxylated product or a mixture thereof. 16. A process according to claim 5, characterized in that the quantity of components (b), (c) and (d) is such that, when the composition is diluted to 10 g / l, the pH of the diluted composition is about 11.5 to 13.5. 17 · .- Method for cleaning dirty dishes in an automatic dishwasher, which consists of putting dirty dishes in an automatic dishwasher, in contact with an aqueous washing bath that has an effective amount of prepared composition dispersed in it. according to claim 5, in an amount sufficient to provide the wash bath with a pH of at least 11.2. 18 · .- Method to improve the stability against phase separation of a composition containing an aqueous dispersion gel type of at least one structuring material, for finely divided detergents, insoluble in water, the said method consisting of incorporate in the dispersion about 1 to 2.5% by weight, from 1 to 2.5% by weight, thickening agent based on smectite clay and about 0.08 to 0.4% by weight, of a long chain fatty acid metal salt of a polyvalent metal selected from Groups IIA, ΠΙΑ, IVA, VA, -ΜΙΒ, ΙΙΒ; ΙΙΙΒ, IVB, VB, VIB, VIIB, and VIII of the Periodic Table of the Elements, in which said composition has a viscosity, in low shear conditions, which is about 2 to 3 times higher than the viscosity ',' in conditions of low shear, of the composition without the long chain fatty acid metal salt and where the viscosity of the composition, in high shear conditions, is about 1/2 to 1/10 of the viscosity in low shear conditions, including- if there is sufficient sodium hydroxide, sodium carbonate and sodium silicate in said composition so that when about 10g of the composition is added to 1 liter of water, the pH of the water reaches at least 11.2. Lisbon, 7 June 1989