CH675252A5 - - Google Patents

Description

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description

The invention relates to an aqueous suspension of thixotropic clay with improved physical stability. It contains potassium polyphosphate and at least one long-chain fatty acid or a metal salt thereof.

The suspension according to the invention is characterized in that it contains a thixotropic clay, potassium polyphosphate and at least one long-chain fatty acid or a metal salt of a long-chain fatty acid, the potassium polyphosphate and the fatty acid or the fatty acid metal salt being present in an effective amount for physical stability and stability increasing the changes in rheological properties with time of composition, containing water and at least one additional component from the group of organic detergents, pH-changing agents, chlorine bleach detergent builder, gelling agents, foam inhibitors, abrasive particles and mixtures thereof.

The suspension according to the invention is preferably in the form of an aqueous thixotropic composition for dishwashers.

The invention also relates to a commercial process for cleaning dirty dishes in dishwashers using the suspension according to the invention.

The addition of small effective amounts of potassium polyphosphates and small effective amounts of polyvalent metal salts of long chain fatty acids significantly improves the physical stability and the changes in the rheological properties over time of composition from aqueous suspensions of thixotropic clay and detergent. Compared to the absence of potassium phosphate as a stabilizer, the thixotropic properties can be improved by using smaller amounts, e.g. 0.25 to 0.50% of the thixotropic clay thickener, maintained or improved.

The invention relates in particular to detergent compositions for dishwashers which have thixotropic properties, improved chemical and physical stability, improved stability against changes in rheological properties over time and increased apparent viscosity and are easily dispersible in the washing medium in order to effectively clean dishes , Glassware, porcelain and the like.

Commercial powder detergents for household dishwashers have several disadvantages, e.g. inconsistent composition, expensive processes necessary for their production, tendency to cake when stored under high humidity, which leads to the formation of chunks that are difficult to disperse, dustiness, which is a particular source of irritation for allergenic users, and the tendency in the dispenser of the dishwasher cake.

Recent research and development activities have focused on the gel or thixotropic form of such compositions, e.g. Abrasive cleaners and dishwasher products in the form of thixotropic pastes.

Dishwasher products of this type are particularly objectionable to the extent that they are insufficiently viscous to remain anchored in the dispenser bowl of the dishwasher. Ideally, the thixotropic cleaning compositions should be highly viscous, naturally Bingham-plastic in a motionless state and have relatively high flow values. Nevertheless, when exposed to shear loads such as Shaking in a container or squeezing out through an opening should quickly become fluid and return to the highly viscous, Bingham-plastic state after the applied shear stress has ceased. Stability is also of paramount importance, i.e. there should be no significant phase separation or leakage after long periods of standing.

DE-OS 3 619 460 detergent compositions for dishwashers with aqueous suspensions of thixotropic clay are known which contain aluminum stearate as a physical stabilizing agent. The compositions show improvement in the physical stability of the detergent composition and improvement over phase separation compared to those clay-containing compositions which do not contain aluminum stearate. However, in some cases the formulations are difficult to achieve stability against changes in rheological properties over time and with large changes in temperature and generally require a relatively high clay content, e.g. 0.25 to 2.0%.

Compositions for dishwashers in gel form, which have the properties described above, which are other than for the improvements described in the above-mentioned DE-OS 3 619 460, have particularly been concerned with compositions for use in household dishwashers until now proved problematic. For effective use, it is generally recommended that the dishwasher detergent, hereinafter referred to as ADD, (1) sodium tripolyphosphate (NaTPP) to soften or bind hard water minerals and to emulsify and / or peptize dirt, (2) Sodium silicate to provide the alkalinity necessary for effective detergent action and to protect the glaze and patterns of fine porcelain, (3) sodium carbonate, generally considered to be optional to increase the alkalinity, (4) a chlorine donor to to aid in the removal of stains that lead to water stains and (5) contains defoamer / surfactant to reduce foam, thereby reducing the Ma2

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Efficiency shine increased and the required detergent effect is made available. For an example, see SDA Detergents in Depth, “Formulations Aspects of Machine Dishwashing”, Thomas Oberle (1974). Cleaners that come close to the compositions described above are mostly liquids or powders. The combination of such ingredients in gel form, which is effective in household dishwashers, has proven difficult. In general, such compositions do not have hypochlorite bleaching because they tend to react with other chemically active ingredients, especially the surfactant. From U.S. Patent 4,115,308 thixotropic pastes for dishwashers are known which contain a suspending agent, e.g. Carboxymethyl cellulose, synthetic clays or the like, inorganic salts including silicates, phosphates and polyphosphates, a small amount of surfactant and a foam inhibitor, but do not contain bleach. Similar products are described in US Pat. No. 4,147,650 which may contain Ci-hypochlorite bleach, but no organic surfactant or foam inhibitor. Furthermore, the product is described as a detergent slurry with no discernible thixotropic properties.

U.S. Patent 3,985,668 describes abrasive abrasive cleaners having a gel-like consistency which include (1) suspending agents, preferably clays of the smectite and atapulgite types, (2) abrasives, e.g. Contains quartz sand or pearlite and (3) filler, which comprises powdered low density polymers, inflated pearlite and the like, which has a buoyancy and thus stabilizing effect on the composition in addition to its function as a filler, thereby replacing water which is otherwise responsible for undesired formation a protruding layer would be available due to leakage and phase destabilization. The aforementioned components are the essential components.

Any ingredients present include hypochlorite bleach, bleach stable surfactant and buffer, e.g. Silicates, carbonates and monophosphates. Builders, e.g. NaTPP, may be included as additional components, if any, in order to provide or supplement the framework function not provided by the buffer, the amount of such framework substances not exceeding 5% of the total composition. Maintaining the desired pH values of greater than 10 is achieved by means of buffer / framework components. High pH values are said to minimize the decomposition of the chlorine bleach and undesirable reactions between the surfactant and bleach. If available, NaTPP is limited to 5%. Foam inhibitors are not available.

GB 2 116 199 A and GB 2 140 450 A describe liquid ADD compositions which have properties which are desirably characterized by a thixotropic gel-like structure and which contain all the constituents which are required for an effective washing action with a dishwasher. The normally gel-like aqueous detergent composition for dishwashers, which has thixotropic properties, contains 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% chlorine bleach, stable, water-dispersible, organic detergent-active material,

(e) 0 to 5% chlorine bleach stable foam inhibitor,

(f) chlorine bleach compound in an amount to provide about 0.2 to 4% available chlorine,

(g) thixotropic thickener in an amount sufficient to provide the composition with a thixotropy index of about 2.5 to 10,

(h) sodium hydroxide if necessary to adjust the pH and

(i) on 100% water.

ADD compositions formulated in this way foam little, are readily soluble in the washing medium and are most effective at pH values that are most useful for improved cleaning performance, namely a pH of 10.5 to 14.0. The compositions normally have a gel-like consistency, i.e. they are a highly viscous, opaque, jelly-like material with a Bing-ham plastic character and thus relatively high flow values. Under such conditions, the composition quickly becomes fluid and easily dispersed. When the shear force is interrupted, the flowing composition quickly returns to a highly viscous Bingham plastic state that approximates the original consistency.

US Pat. No. 4,511,487 describes a low-foaming detergent paste for dishwashers. The thixotropic detergent has a viscosity of at least 30 Pa.s at 20 ° C, this with a rotary viscometer at a spindle speed of 5 U / min. was determined. The composition is based on a mixture of finely divided hydrated sodium metasilicate, an active chlorine compound and a thickener, which is a leaf silicate of the Hekorite type. Small amounts of non-ionic surfactants and alkali metal carbonates and / or hydroxides can be used.

The formation of organoclay by reaction of clays, e.g. Bentonite and hectorite, with organic

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Connections, e.g. quaternary ammonium salts have also been described (W.S. Madis, JAOCS, Vol. 61, No. 2, page 382 (1984)).

Although the aforementioned liquid ADD formulations have none, or to a lesser extent, one or more of the shortcomings described above, it has been found that further improvements in physical stability and stability against changes in rheological properties over time are desired to increase the shelf life of the product and thereby increase consumer acceptance.

It is also highly desirable to increase the physical stability and stability against changes in rheological properties over time of other clay-based thixotropic liquid formulations, such as e.g. Abrasive cleaners, toothpastes, liquid soaps and the like.

The invention is therefore based on the object of providing sedimentation inhibitors for aqueous thixotropic clay suspensions and also of providing liquid ADD compositions which have thixotropic properties together with improved physical stability and improved stability against changes in the rheological properties over time.

This object is achieved by the aqueous suspension of thixotropic clay as defined above and in claim 1.

A preferred suspension according to the invention which has thixotropic properties and is in the form of an aqueous composition for dishwashers contains on a weight basis:

(a) 5 to 35% sodium tripolyphosphate,

(b) 2.5 to 20% sodium silicate,

(c) 0 to 9% alkali metal carbonate,

(d) 0.1 to 5% chlorine bleach-stable, water-dispersible, organic, detergent-active material,

(e) 0 to 5% chlorine bleach-stable foam inhibitor,

(f) chlorine bleach compound in an amount to provide 0.2 to 4% available chlorine,

(g) thixotropic clay thickener in an amount sufficient to provide the composition with a thixotropic index of 2.0 to 10,

(h) 0 to 8% sodium hydroxide,

(i) Potassium polyphosphates and a polyvalent metal salt of a long chain fatty acid in amounts effective to increase the physical stability of the composition and the physical stability of the composition against changes in rheological properties over time and

(j) on 100% water.

In addition, the invention provides a commercial process for cleaning dishes in a dishwasher with an aqueous wash bath which contains an effective amount of the liquid suspension for dishwashers (LADD) as described above. According to this aspect of the invention, the LADD composition can be easily poured into a dispenser bowl of an automatic dishwasher and will thicken to its normal gel-like or pasty state within a few seconds.

In general, the LADD activity is directly related to (a) the available chlorine levels, (b) the alkalinity, (c) the solubility in the washing medium and (d) the foam inhibition. It is preferred that the pH of the LADD composition be at least about 9.5, preferably about 10.5 to 14.0, and most preferably at least about 11.5. The presence of carbonai is often necessary as well, since it acts as a buffer to help maintain the desired pH. However, excess carbonate should be avoided, as it can cause the formation of needle-like crystals of carbonate, which increases the stability, thixotropy and / or detergent effect of the LADD product as well as the possibility of dispensing the product, e.g. Wash bottles to be deteriorated. Sodium hydroxide has the additional function, if present, of neutralizing phosphorus or phosphonic ester foam inhibitors. About 0.5 to 6 wt% NaOH and about 2 to 9 wt% sodium carbonate in the LADD composition are typical, although it should be noted that sufficient alkalinity can be provided by NaTPP and sodium silicate. NaTPP is used in the LADD composition in the range of about 8 to 35% by weight, preferably 20 to 30% by weight, and should preferably be free of heavy metals that tend to decompose the preferred sodium hypochlorite and other chlorine bleach compounds or to inactivate. The NaTPP can be anhydrous or water-containing, including the stable hexahydrate with a degree of hydration of 6, which corresponds to approximately 18% by weight of water or more. Particularly preferred LADD compositions are e.g. obtained when a 0.5: 1 to 2: 1 weight ratio of anhydrous to hexahydrated NaTPP, particularly preferably a ratio of about 1: 1, is used.

Foam inhibition is important to increasing the effectiveness of the dishwasher and reducing destabilizing effects that can occur due to the presence of excess foam within the washer during use. Foam can be reduced sufficiently by a suitable choice of the type and / or the detergent active material which is the primary foam-forming component. The amount of foam also depends on the hardness

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of the washing water in the machine, which is why a suitable adjustment of the proportions of NaTPP, which has a water softening effect, can have a supportive effect in order to achieve the desired degree of foam inhibition. Nevertheless, it is generally preferred to include a chlorine bleach stable foam reducer or inhibitor. Alkylphosphonic acid esters of the formula are particularly effective

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Ho-P - R

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e.g. are available from BASF-Wyandotte (PCUK-PAE) and especially the alkyl acid phosphate esters of the formula

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HO-P -OR

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e.g. are available from Hooker (SAP) and Knapsack (LPKn-158), in which one or both R groups in both ester types can independently represent a C12-C20 alkyl group. Mixtures of both types or any other chlorine bleach-stable types or mixtures of mono- and di-esters of the same type can be used. A mixture of mono and di-Ci6 to cis-alkyl acid phosphate esters, such as e.g. Monostearyl / distearyl acid phosphates 1,2 / 1 (Knapsack) or (Ugine KOLHPLAN). If used, fractions of 0.1 to 5% by weight, preferably 0.1 to 0.5% by weight, of foam-reducing agent in the suspension are typical. The weight ratio of detergent-active ingredient (d) to foam-reducing agent (e) is generally in the range from 10: 1 to 1: 1 and preferably 5: 1 and 1: 1. Other defoamers that can also be used, e.g. the known silicones. In addition, it is an advantageous feature of the invention that many of the stabilizing salts, e.g. the stearate salts, e.g. Aluminum stearate are also effective as foam inhibitors.

Although any chlorine bleaching compound can be used in the suspensions according to the invention, e.g. Dichloroisocyanurate, dichlorodimethylhydantoin or chlorinated TSP, alkali metal hypochlorite, e.g. Potassium, lithium, magnesium and especially sodium hypochlorite are preferred. The suspension should also contain enough chlorine bleach to provide 0.2 to 4.0% by weight of available chlorine, e.g. is determined by acidifying 100 parts of the suspension with excess hydrochloric acid. A solution containing about 0.2 to 4% by weight sodium hypochlorite contains or provides approximately the same amount of available chlorine; 0.8 to 1.6% by weight of available chlorine is particularly preferred.

For example, sodium hypochlorite solution (NaOCl) with 11 to 13% available chlorine can advantageously be used in amounts of 3 to 20%, preferably 7 to 12%.

The sodium silicate, which provides alkalinity and protects hard surfaces such as fine porcelain glaze and patterns, is used in an amount in the range of 2.5 to 20% by weight, preferably 5 to 15% by weight used. The sodium silicate is generally added in the form of an aqueous solution, preferably with a Na20: Si02 ratio of 1: 2 to 1: 2.8.

Detergent-active material which can also be used in the suspensions according to the invention must be stable in the presence of chlorine bleach, especially hypochlorite bleach, preference being given to the organically anionic, amine oxide, phosphine oxide, sulfoxide or betaine water-soluble surfactant types, in particular the first-mentioned anionic surfactants. They are used in amounts in the range from 0.1 to 5%, preferably 0.3 to 2.0%. Particularly preferred surfactants are the linear or branched alkali metal mono- and / or di-Cis to Cw-alkyldiphenyloxide mono and / or disulfates or disulfonates, which are commercially available, for example as Dow Fax 3B-2 and Dow Fax 2A-1. In addition, the surfactant should be compatible with the other components of the suspension. Other suitable surfactants include the primary alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates and secondary alkyl sulfates. Examples include sodium Cio to Ci8 alkyl sulfates such as Sodium dodecyl sulfate and sodium tallow alcohol sulfate, sodium cio to cia alkane sulfonates, e.g. Sodium hexadecyl-1-sulphonate and sodium Ci2 to cis-alkylbenzenesulfonates, e.g. Sodium dodecylbenzenesulfonate. The corresponding potassium salts can also be used.

Other also suitable surfactants or detergents are diamine oxide surfactants with the structure R2R1N-0, in which each R has a lower alkyl group, e.g. Represents methyl and R1 is a long chain alkyl

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group with 8 to 22 carbon atoms, e.g. represents a Lautyl, Myristyl, Palmityl or Cetyl group. Instead of an amine oxide, a corresponding phosphine oxide RsR1PO or sulfoxide RR1SO surfactant can be used. Betaine surfactants typically have the structure R2R1N-R'COO ~, in which each R represents a lower alkylene group having 1 to 5 carbon atoms. Specific examples of these surfactants are lauryldimethylamine oxide, myristyldimethylamine oxide, the corresponding phosphine oxides and sulfoxides and the corresponding betaines, including dodecyldimethylammonium acetate, tetradecyldimethylammonium pentanoate, hexadecyldimethylammonium hexanoate and the like. For biodegradability, the alkyl groups of these surfactants should be linear and such compounds are preferred.

Surfactants of the aforementioned type are well known to those skilled in the art and are e.g. in U.S. Patents 3,985,668 and 4,271,030.

In the aqueous suspension according to the invention, the thixotropic clay imparts thixotropic properties to the suspension mentioned. The thixotropic clay behaves to a high level of alkalinity and also to chlorine bleaching compounds, stable. A chlorine bleach compound is e.g. Sodium hypochlorite. The particularly preferred thixotropic clays include the inorganic, colloid-forming clays of the smectite and / or attapulgite types. These materials are generally used in amounts of 1.5 to 10, preferably 2 to 5% by weight to give the aforementioned LADD formulations according to GB 2 116 199A and 2 140 450A the desired thixotropic properties and the Bingham plastic properties To give character. One of the advantages of the LADD suspension according to the invention is that the desired thixotropic properties and the Bingham plastic character can be obtained in the presence of the potassium polyphosphates and fatty acid metal salt stabilizers with smaller amounts of thixotropic thickeners. In general, e.g. Amounts of the inorganic colloid-forming clays of the smectite and / or attapulgite types in the range from 0.1 to 0.5%, preferably 0.2 to 0.4%, particularly preferably 0.25 to 0.3%, are sufficient to to achieve the desired thixotropic properties and Bingham plastic character when used in conjunction with the potassium polyphosphates and fatty acid metal salts as physical stabilizers.

Smectite clays include montmorillonite (bentonite), hectorite, attapulgite, smectite, saponite and the like. Montmorillonite clays are preferred and are available under the trademarks, e.g. Thixogel No. 1 and Gelwhite GP, H etc., available from Georgia Kaolin Company and ECCAGUM GP, H, etc., available from Luthern Clay Products. Attapulgittone close those under the trademark Attagel, e.g. Attagel 40, Attagel 50 and Attagel 150 from Engelhard Mineral and Chemicals Corporation, commercially available materials. Mixtures of smectite and attapulgite types in weight ratios of 4: 1 to 1: 5 can also be used. Thickening or suspending agents of the aforementioned types are well known in the art and are e.g. in U.S. Patent 3,985,668.

Abrasives or polishes should be avoided in the LADD suspensions, as they can damage the surface of fine dishes, crystals and the like.

The amount of water contained in the suspensions according to the invention should neither be so high that inappropriately low viscosity and high fluidity result, nor so low that inappropriately high viscosity and low fluidity result. The thixotropic properties are reduced or destroyed in both cases. The appropriate amount of water is easily determined by routine experimentation in each particular case and is generally in the range of 30 to 75% by weight, preferably 30 to 65% by weight. The water should also be deionized or softened.

So far, unless stated otherwise, the description of the LADD product according to the invention has been consistent with the compositions according to GB 2 116 199A and GB 2 140 450A mentioned above.

The LAD D products of GB 2 116 199A and GB 2 140 450A show improved rheological properties, as determined by checking the product viscosity as a function of the shear rate. The compositions have higher viscosity at a low shear rate and lower viscosity at a high shear rate, the data indicating effective liquefaction and gelling within the shear rate range of standard dishwashers. This means improved filling and processing features as well as less leakage from the machine's dispenser cup compared to previous liquid or gel-like ADD products. At shear speeds corresponding to 3 to 30 rpm, the corresponding viscosities (Brookfield) were from about 10,000 to 30,000 / s to about 2000 to 6000 / s, as was the measurement at room temperature after 3 minutes using an LVT Brookfield viscometer Using a # 4 spindle revealed one day after manufacture. A shear rate of 7.4 / s corresponds to a spindle rotation speed of approximately 3 rpm. An approximately 10-fold increase in shear rate results in an approximately 3 to 9-fold decrease in viscosity. With previous ADD gels, the corresponding reduction in viscosity was only about 2-fold. In addition, with such compositions the viscosity recorded at about 3 rpm was only about 2500 to 2700 / s. The compositions according to GB 2 116 199A and GB 2 140 450A thus begin to liquefy at lower shear rates and to a much greater extent in the form of increases in shear rate compared to reduced viscosity. This property of the LADD products is summarized in the form of a thixotropy index (Tl), which results from the ratio of the apparent viscosity at 3 rpm and at 39 rpm. The earlier meetings

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Settings have a TI of 2 to 10. The LADD compositions tested showed substantial and rapid return to the previous still state when the shear force was interrupted.

The present invention is based on the fact that physical stability, i.e. the resistance to phase separation, settling etc. of the liquid aqueous ADD compositions according to GB 2 116 199A, GB 2 140 450A and DE-OS 3 619 460 by adding a small but effective amount of potassium polyphosphates and small effective amounts of a metal salt of a long-chain fatty acid can be significantly improved or at least not adversely affected, while at the same time the stability to changes in the rheological properties with time and temperature are significantly improved.

As an example of the improvement in rheological properties, it was found that the viscosities at low shear rates, e.g. at a spindle speed of about 3 rpm, by incorporating 1 to 2% or less of the potassium polyphosphates and 0.25 to 0.5% of the fatty acid metal salt stabilizer can often be increased 2 to 3 times. At the same time, the physical stability can be improved to such an extent that even after 12 weeks or longer at temperatures in the range from freezing to 40 ° C. and more, the suspensions containing the potassium polyphosphate and the metal salt stabilizers against changes in the rheological properties with the Time and temperature are stable and there is no visible phase separation.

The potassium polyphosphates contained in the suspension are generally commercially available. Specific examples of potassium polyphosphates are potassium tripolyphosphate (TPP), potassium pyrophosphate and potassium hexametaphosphate. Potassium tripolyphosphate (TPP) is preferred.

The amount of potassium polyphosphates needed to achieve the desired increase in physical stability will depend on factors such as the nature of the fatty acid salt, the nature and amount of the thixotropic agent, detergent active compound, inorganic salts, sodium TPP and other LADD components as well as depend on the expected storage and shipping conditions.

The amounts of the potassium polyphosphate stabilizing agents (50%) which can be used are in the range from 0.5 to 3.0%, preferably 0.80 to 2.0%, particularly preferably 1.0 to 1.8%.

The preferred long chain fatty acids are the higher aliphatic fatty acids having 8 to 22 carbon atoms, preferably 10 to 20 carbon atoms and particularly preferably 12 to 18 carbon atoms, including the carbon atom of the carboxyl group of the fatty acid. The aliphatic radical can be saturated or unsaturated and linear or branched. Straight chain, saturated fatty acids are preferred. Mixtures of fatty acids can be used, e.g. those derived from natural sources, such as Tallow fatty acid, coconut fatty acid, soy fatty acid etc. or from synthetic sources obtainable by industrial production processes.

Thus, the examples of fatty acids from which the polyvalent metal salt stabilizers can be formed, e.g. Decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, oleic acid, eicosanoic acid, tallow fatty acid, coconut fatty acid, soy fatty acid etc. and mixtures of these acids. Stearic acid and mixed fatty acids are preferred.

The preferred metals are the polyvalent metals of groups IIA, IIB and HIB, e.g. Magnesium, calcium, aluminum and zinc, although other polyvalent metals including those of Groups IIIA, IVA, VA, VIA, VIIA, IB, IVB, VB, VIB, VIIB and VIII of the Periodic Table of the Elements can also be used. Specific examples of such other polyvalent metals include Ti, Zr, V, Nb, Mn, Fe, Co, Ni, Cd, Sn, Sb, Bi, etc. In general, the metals can be in the divalent or pentavalent state. The metal salts are preferably used in their higher oxidation states. Of course, for LADD compositions, as well as for any other application in which the composition of the invention can come into contact with articles used in the treatment, storage or serving of food, or otherwise come into contact with humans or animals or consumed by them, the toxicity of the metal is taken into account when choosing the metal salt. For these purposes, calcium and magnesium salts are particularly preferred as generally safe food additives.

Many of these metal salts are commercially available. For example, the aluminum salts are available in their three acid form, e.g. Aluminum stearate as aluminum tristearate AI (Ci7H3sCOO) 3. The monoacid salts, e.g. Aluminum monostearate Al (OH) 2 (Ci7H3sCOO), and the diacid salts, e.g. Aluminum distearate Al (OH) (Ci7H3sCOO) 2, and mixtures of two or three of the mono-, di- and tri-acid salts can be used for metals with the oxidation state +3, e.g. AI, can be used and mixtures of the mono- and di-acid salts can be used for metals with the oxidation state +2, e.g. Zn, can be used. It is particularly preferred that the diacidic salts of the metals with the oxidation level +2 and the triacidic salts of the metals with the oxidation level +3, the four-acidic salts of the metals with the oxidation level +4 and the pentacidic salts of the metals with the oxidation level +5 in predominant amounts are used. For example, at least 30%, preferably at least 50%, particularly preferably 80 to 100% of the total metal salt should be in the highest possible oxidation state, i.e. each of the possible valences is replaced by a fatty acid residue.

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As mentioned above, the metal salts are generally commercially available, although they are also readily available, e.g. Esterification of a fatty acid, e.g. animal fat, stearic acid etc., or the corresponding fatty acid ester followed by treatment with a hydroxide or oxide of the polyvalent metal, e.g. in the case of aluminum salt with alum, aluminum oxide, etc. can be produced.

Calcium stearate, e.g. Calcium distearate, magnesium stearate, e.g. Magnesium distearate, aluminum stearate, e.g. Aluminum tristearate and zinc stearate, e.g. Zinc distearate are the preferred polyvalent fatty acid salt stabilizers. Mixed fatty acid metal salts such as e.g. that of naturally occurring acids, e.g. Coconut acid, as well as that of mixed fatty acids derived from industrial manufacturing processes, are also advantageously used as a cheap but effective source of long chain fatty acid.

The amount of potassium polyphosphate and fatty acid salt stabilizers with which the desired increase in physical stability is achieved also depends on factors such as the nature of the fatty acid salt, the nature and amount of the thixotropic agent, the detergent active compound, the inorganic salts, and the NaTPP and other LADD components, as well as depending on expected storage and shipping conditions.

Nevertheless, the amounts of the polyvalent metal fatty acid salt stabilizer are in the range of 0.10 to 0.5%, preferably 0.2 to 0.4%, particularly preferably 0.25 to 0.30%. The use of the potassium polyphosphates together with the polyvalent metal fatty acid salt stabilizers ensures long-term physical stability, stability against changes in rheological properties with time and temperature, and absence of phase separation when standing or during transport at both low and elevated temperatures as for an acceptable commercial product is required.

In another embodiment of the invention, the fatty acids themselves can be used as stabilizers instead of the fatty acid metal salts described above.

. Long chain fatty acids that can be used, for example, are the higher aliphatic fatty acids having 8 to 22 carbon atoms, preferably 10 to 20 carbon atoms and particularly preferably 12 to 18 carbon atoms, including the carbon atom of the carboxyl group of the fatty acid. The aliphatic residue can be saturated or unsaturated and linear or branched. Straight chain saturated fatty acids are preferred. Mixtures of fatty acids, e.g. those derived from natural sources, such as Tallow fatty acid, coconut fatty acid, soybean fatty acid, etc., or the sources available from synthetic, industrial manufacturing processes can be used.

Thus, the examples of the fatty acids that can be used as stabilizers, e.g. Decanoic acid, dodecanoic acid, palmitic acid, myristic acid, stearic acid, behenic acid, oleic acid, eicosanoic acid, tallow fatty acid, coconut fatty acid, soy fatty acid, etc. and mixtures of these acids.

Many of these fatty acids are commercially available. Stearic and behenic acids are e.g. easily available. Mixed fatty acids, e.g. the naturally occurring acids, e.g. Coconut acid, as well as mixed fatty acids derived from industrial manufacturing processes, are also advantageously used as a cheap but effective source of long chain fatty acids. The sodium and potassium salts of the fatty acids can also be used as stabilizers.

The amount of the fatty acid stabilizers and / or the sodium or potassium salts thereof which can be used are in the same range as the amounts of the above-mentioned fatty acid metal salts.

From the examples given below it can be seen that, depending on the amounts, the proportions and types of the physical stabilizers and thixotropic agents, the addition of the potassium polyphosphates and the fatty acid salt not only increases the physical stability, but also in some cases a simultaneous increase in the apparent viscosity and provides stability to changes in rheological properties with time and / or temperature.

The physically stabilizing agents are added just before the clay thickener is added. With the exception of the chlorine bleach compound, the total salt concentration (NaTPP, sodium silicate and carbonate, generally 20 to 50% by weight, preferably 30 to 40% by weight of the composition.

A preferred method of mixing the constituents of the LADD suspensions involves first forming a mixture of water, foam inhibitor, detergent, physical stabilizers, namely potassium tripolyphosphates and fatty acid salt, and thixotropic agent, e.g. Sound on. These ingredients are mixed under strong shear conditions, preferably starting at room temperature, to form a uniform dispersion. The remaining ingredients are added to this premixed portion under low shear mixing conditions. E.g. the required amount of the premix is placed in a low shear mixer and then the remaining ingredients are added with simultaneous or subsequent mixing. Preferably, the ingredients are added sequentially, although it is not necessary to add the entire amount of one ingredient before starting to add the next ingredient. In addition, one or more of the ingredients can be divided into portions and added at different times. Good results were obtained by adding the remaining ingredients in the following order: sodium hydroxide, alkali metal carbonate, sodium silicate, hydrated sodium tripolyphosphate, sodium tripolyphosphate, anhydrous or up to 5% water, bleach, preferably sodium hypochlorite and sodium hydroxide.

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Other conventional ingredients can also be added to the suspensions of the invention in small amounts, generally less than 3% by weight, e.g. Perfume, hydrotropic agents such as Sodium benzene, toluene, xylene and cumene sulfonates, preservatives, dyes and pigments and the like, all of which are naturally stable to the chlorine bleaching compound and the high alkalinity.

The chlorinated phthalocyanines and polysulfides of the aluminosilicates, which produce pleasing green or blue tints, are particularly preferred for coloring. TÌO2 can be used to whiten or remove shadows.

The liquid ADD suspensions according to the invention can easily be used in a known manner for washing dishes, other kitchen utensils in a dishwasher equipped with a suitable detergent dispenser in an aqueous washing bath which contains an effective amount of the composition according to the invention.

In the following, the invention is explained in more detail with reference to the examples, wherein all quantity data relate to the weight, unless stated otherwise.

example 1

In order to demonstrate the effect of the potassium tripolyphosphate and metal salt stabilizers, liquid ADD formulations with varying amounts of potassium tripolyphosphate and fatty acid salt stabilizers and thixotropic clay thickener were prepared as follows:

Thixotropic clay formulations

percent

Deionized water to 100% 33.06-42.55

Monostearyl phosphate 0.16

Dowfax 3B2 (45% Na monodecyl / didecyldiphenyloxide 0.8 disulfonate, aqueous solution)

Potassium TPP (50%) 0-1.6 aluminum stearate 0-0.4 Pharmagel H 0.25-2.0

These products were mixed under high shear at room temperature and the following ingredients were then added at room temperature.

percent

Sodium hydroxide solution (50% NaOH)

2.2-10.2

Sodium carbonate, anhydrous

5.00

Sodium silicate, 47.5% solution of Na20: Si02

15.74

in the ratio of 1: 2.4

Sodium TPP hexahydrate (Thermphos N hexa)

12.00

Sodium TPP (essentially anhydrous, i.e. 0.5%,

12.00

especially 3% moisture) (Thermphos NW)

Sodium hypochlorite solution (11% available chlorine)

9.00

The liquid ADD formulations 1 to 7 were prepared and the density, the apparent viscosity at 3 and 30 rpm and the physical stability with regard to phase separation on standing and in a freight test were determined. The results obtained are shown in Tables I and II below.

The following conclusions can be drawn from the data given in Tables I and II:

Incorporation of 0.1% aluminum stearate into a formulation Experiment 2 (comparison) containing 1.25% Pharmagel H leads to an increase in the physical stability without changing the apparent viscosity compared to experiment 1 (comparison).

The incorporation of 0.4% aluminum stearate into a formulation containing Experiment 5 (comparison) containing 0.25% Pharmagel H leads to an increase in physical stability and the apparent viscosity compared to experiment 1 (comparison) and 3 (comparison). The use of a larger amount

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Aluminum stearate of 0.4% in Experiment 3 (comparison) also allows the clay content to be reduced from 1.25% Experiment 2 (comparison) to 0.25% Experiment 3 (comparison), while maintaining the physical stability of the formulation.

The data from Table I also show that the simultaneous use of approximately 1.6% potassium TPP in a formulation containing Experiments 4 and 6 containing 0.5% or 0.3% Pharmagel H does not adversely affect the physical stability of the formulations , while changes in rheological properties decrease over time.

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Table I

Expe formulation riment

Dense Brook LVT-Vis- Without shaking, liquid separation {%)

(g / cm3) viscosity 1.103 / s'1 '(after 12 weeks)

3 30 glass bottle plastic bottle

Revolutions / min. 4 ° C (2) RT (Z) 35 ° C (2) 43 ° C (2) 4 ° C (3> RT (3) 35 ° C (3) 43 ° C (3)

Fraudulent

processing

Test (%) (4)

1

H2O = 41.10%

1.25

13

4th

1-3

1-2

0

0

-

1-5

-

-

1-5

(Ver

KTPP (50%) = 0%

equal)

NaOH solution (50%) - 2.2% aluminum stearate = 0% Pharmagel H = 2%

2nd

H20 = 41.75%

1.32

28

6.8

0

0

0

0

-

1

-

-

0

(Ver

KTPP (50%) = 0%

equal)

NaOH solution (50%) = 2.2% aluminum stearate = 0.1% Pharmagel H = 1.25%

3rd

H20 = 42.45%

1.35

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2.9

0

0

0

0

-

0

-

-

0

(Ver

KTPP (50%) = 0%

equal)

NaOH solution (50%) = 2.2% aluminum stearate = 0.4% Pharmagel H = 0.25%

4th

H20 = 40.60%

KTPP (50%) = 1.6% NaOH solution (50%) = 2.2% aluminum stearate = 0.4% pharmaceutical gel H = 0.5%

1.33

38

6.9

0

0

0

0

0

0

5

H20 = 38.5%

1.36

20th

3.9

0

0

0

0

_

-

__

__

(Ver

KTPP (50%) = 0%

equal)

NaOH solution (50%) = 6.2% aluminum stearate = 0.3% Pharmagel H = 0.3%

6

H2O = 37.06%

KTPP (50%) tn 1.6% NaOH solution (50%) = 6.2% aluminum stearate = 0.3% pharmaceutical gel H = 0.3%

1.36

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3.8

0

0

0

0

0

0

0

0

0

measured with spindle 4 after 3 minutes on 24 hour old samples (2 'in height (RT = room temperature = ■ 20 +/- 2 ° C)

(3j in weight (RT = room temperature = 20 +/- 2 ° C)

(4) Liquid wedge separation determined by weight after 6 weeks and 2000 km in a private car in a plastic bottle.

0 X

01

oi ro

CJl ro>

Oil

Ci Uì

Ol en en

^ 1 o co en ro en ro o

Table I (continued)

Expe formulation riment

Density Brook LVT-Vis- Without shaking, liquid separation (%)

(g / cm3) l.loW * (after 12 weeks)

3 30 glass bottle plastic bottle

Revolutions / min. 4 ° C (2) RT (2) 35 ° C (2 '43 ° C <2' 4 ° C (3) RT (3)

35 ° C (3) 43 ° C (3)

Freight test (%)

(4)

JO

H2O- 33.06%

KTPP (50%) = 1.6% NaOH solution (50%) = 10.2% aluminum stearate = 0.3% Pharmagel H = 0.3%

1.39

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4.1

0

0

0

0

0

(1) measured with spindle 4 after 3 minutes on 24 hour old samples (2 'in height (RT = room temperature = 20 +/- 2 ° C)

'3J in weight (RT = room temperature «20 +/- 2 ° C)

'' in uüwiuH i = ntturiiiüiiipt? raiur «£ U +/— c. O;

^ Liquid separation determined after 6 weeks and 2000 km in a private car in a plastic bottle by weight.

0 X o> tri

N>

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io £

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Table 11

Simultaneous use of potassium TPP and aluminum tristearate

Brookfield LVT experiment at 3 and 30 rpm. after specified duration at RT

(1,103 / s) (1)

1 day 2 weeks 4 weeks 6 weeks 12 weeks

2 (comparison)

28 / 6.8

24 / 3.4

34 / 8.9

53/7

41 / 6.7

3 (comparison)

10 / 2.9

51 / 6.4

(2)

48 / 7.6

200/20

4th

38 / 6.9

56/8

70 / 9.8

91/12

100/13

5 (comparison)

20 / 3.9

21 / 3.0

46 / 5.1

61 / 5.1

70 / 6.3

6

8 / 3.8

30/4

26 / 5.0

30 / 5.1

38 / 5.4

7

20 / 4.1

35 / 10.1

20 / 5.0

25/6

36/10

(1) Measured with spindle 4 after 3 minutes standing in a glass bottle (2> no measurement

Example 2

In order to determine the changes in the rheological properties with time, the apparent viscosities of the formulations of experiments 2 to 7 of Example 1 were determined at 3 and 30 rpm. measured after one day, two weeks, four weeks, six weeks and 12 weeks. The data obtained are given in Table II above.

The data from Table II show that the addition of 1.6% (Experiments 4, 6 and 7) leads to a large reduction in the changes in the rheological properties with time, without the physical stabilities of the formulations at a Pharmagel H clay content of 0.3 and 0.5% compared to experiments 3 (comparison) and 5 (comparison), in which significant changes in the apparent viscosity occur over time.

Example 3

The following gel-like, thixotropic, liquid ADD was prepared according to the general procedure of Example 1:

Component weight%

Sodium silicate (47.5% solution of Na20: SiC> 2, 7.48 ratio 1: 2.4)

Monostearyl phosphate 0.16

Dow Fax 3B-2 0.36

Thermphos NW 12.0

Thermphos N hexa 12.0

Potassium TPP (50%) 1.6

Aluminum stearate 0.25

Sodium carbonate, anhydrous 4.9

Sodium hydroxide solution (50% NaOH) 6.2

Pharmagel H 1.25

Sodium hypochlorite solution (11%) 1.0

Water to 100

pH = 13 to 13.4

Smaller amounts of perfume, dye, etc. can also be added to the formulation. The composition was found to have good thixotropic properties, good stability to phase separation and changes in rheological properties over time.

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Example 4

A gel-like, thixotropic, liquid ADD was prepared as in Example 3, using 1.6% (50%) potassium pyrophosphate instead of the potassium TPP. Results similar to those in Example 3 were obtained.

Example 5

The following gel-like, thixotropic, liquid ADD was prepared according to the general procedure of Example 1:

Component quantity

% By weight

Sodium silicate (47.5% solution of Na20: Si02,

7.48

Ratio 1: 2.4)

Monostearyl phosphate

0.16

Dow Fax 3B-2

0.36

Thermphos NW

12.0

Thermphos N hexa

12.0

Potassium TPP (50%)

1.6

Stearic acid

0.4

Sodium carbonate, anhydrous

5.0

Sodium hydroxide solution (50% NaOH)

3.1

Pharmagel H

0.5

Sodium hypochlorite solution (11%)

1.0

Water to 100

Smaller amounts of perfume, dye, etc. can also be added to the formulation.

Example 6

The following gel-like, thixotropic, liquid ADD was prepared according to the general procedure of Example 1.

Component quantity

% By weight

Sodium silicate (47.5% solution of Na20: Si02,

7.48

Ratio 1: 2.4)

Monostearyl phosphate

0.16

Dow Fax 3B-2

0.36

Thermphos NW

12.0

Thermphos N hexa

12.0

Potassium TPP (50%)

1.6

Behenic acid

0.2

Sodium carbonate, anhydrous

5.0

Sodium hydroxide solution (50% NaOH)

6.2

Pharmagel H

0.5

Sodium hypochlorite solution (11%)

1.0

Water to 100

Smaller amounts of perfume, dye, etc. can also be added to the formulation.

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Claims (26)

Claims 1. Aqueous suspension of thixotropic clay, characterized in that it contains a thixotropic clay, potassium polyphosphate and at least one long-chain fatty acid or a metal salt of a long-chain fatty acid, the potassium polyphosphate and the fatty acid or the fatty acid metal salt being present in an effective amount to ensure physical stability and increasing the stability based on the changes in the rheological properties with the time of the composition, water and at least one additional component from the group consisting of organic detergents, pH-changing agents, chlorine bleach detergent builder, gelling agents, foam inhibitors, abrasive particles and mixtures thereof contains. 2. Suspension according to claim 1, characterized in that it contains at least potassium tripolyphosphate, potassium pyrophosphate and / or potassium hexametaphosphate. 3. Suspension according to claim 1, characterized in that it contains potassium tripolyphosphate. 4. Suspension according to claim 1, characterized in that it contains, as the metal salt of a long-chain fatty acid, a salt of a metal of groups II, III or IV of the periodic table of the elements with one or more long-chain fatty acids with about 8 to 22 carbon atoms. 5. Suspension according to claim 1, characterized in that the polyvalent metal is aluminum, zinc, calcium or magnesium. 6. Suspension according to claim 1, characterized in that the fatty acid metal salt is aluminum stearate, calcium stearate or magnesium stearate. 7. Suspension according to claim 1 in the form of an aqueous thixotropic composition, for dishwashers, characterized in that it: a) 5 to 35% by weight sodium tripolyphosphate, b) 2.5 to 20% by weight of sodium silicate, c) 0 to 9% by weight of alkali metal carbonate, d) 0.1 to 5% by weight of chlorine bleach-stable, water-dispersible, organic, detergent-active material, e) 0 to 5% by weight of chlorine bleach-stable foam inhibitor, f) chlorine bleach compound in an amount to provide 0.2 to 4% by weight of available chlorine, g) thixotropic clay thickener in an amount sufficient to provide the composition with a thixotropic index of 2 to 10, h) 0 to 8% by weight of sodium hydroxide, i) a physical and rheological property stabilizing agent which contains at least one of potassium tripolyphosphate, potassium pyrophosphate and potassium hexametaphosphate and a polyvalent metal salt of a long-chain fatty acid and j) contains 100% by weight of water. 8. Suspension according to claim 7, characterized in that the stabilizer comprises potassium tripolyphosphate. 9. Suspension according to claim 7, characterized in that the stabilizer comprises potassium pyrophosphate. 10. Suspension according to claim 7, characterized in that the stabilizer comprises potassium hexametaphosphate. 11. Suspension according to claim 7, characterized in that the metal salt stabilizer is a polyvalent metal salt of an aliphatic fatty acid having 8 to 22 carbon atoms. 12. Suspension according to claim 7, characterized in that the acid has 12 to 18 carbon atoms. 13. Suspension according to claim 7, characterized in that the metal salt stabilizer is the aluminum or zinc salt of the fatty acid. 14. Suspension according to claim 7, characterized in that the metal salt stabilizer is aluminum stearate. 15. Suspension according to claim 7, characterized in that the metal salt stabilizer is zinc stearate. 16. Suspension according to claim 7, characterized in that it contains 0.1 to 0.5 wt .-% clay, 0.5 to 3.0 wt .-% potassium polyphosphate and 0.1 to 0.5 wt .-% fatty acid metal salt contains. 17. Suspension according to claim 7, characterized in that the thixotropic clay thickener is an inorganic colloid-forming clay. 18. Suspension according to claim 1 in the form of an aqueous thixotropic composition for dishwashers, characterized in that it: a) 5 to 35% by weight tripolyphosphate, b) 2.5 to 20% by weight of sodium silicate, c) 0 to 9% by weight of alkali metal carbonate, d) 0.1 to 5% by weight of chlorine bleach-stable, water-dispersible organic detergent-active material, e) 0 to 5% by weight of chlorine bleach-stable foam inhibitor, f) chlorine bleach compound in an amount to provide 0.2 to 4% by weight of available chlorine, 15 CH 675 252 A5 g) thixotropic clay thickener in an amount sufficient to provide the composition with a thixotropic index of 2 to 10, h) 0 to 8% by weight of sodium hydroxide, i) a physical and theological properties stabilizing agent which contains potassium poly-5 phosphate and a polyvalent metal salt of an aliphatic fatty acid with 12 to 18 carbon atoms, and j) contains 100% by weight of water. 19. Suspension according to claim 18, characterized in that it contains potassium tripolyphosphate. 20. Suspension according to claim 18, characterized in that it contains potassium pyrophosphate. 10th 21. Suspension according to claim 18, characterized in that the metal salt stabilizer is the aluminum or zinc salt of the fatty acid. 22. Suspension according to claim 18, characterized in that the metal salt stabilizer is aluminum stearate. 23. Suspension according to claim 18, characterized in that the metal salt stabilizer is zinc-15 stearate. 24. Suspension according to claim 18, characterized in that it contains 0.2 to 0.4% by weight of clay, 0.8 to 2.0% by weight of potassium polyphosphate and 0.2 to 0.4% by weight of the Contains fatty acid metal salt. 25. Suspension according to claim 18, characterized in that the thixotropic thickener is an inorganic, colloidal clay. 20th 26. Commercial process for cleaning soiled dishes in an automatic dishwasher, characterized in that this comprises contacting the soiled dishes with an aqueous washing bath in which an effective amount of the suspension according to claim 7 or 18 is dispersed. 30th 35 40 45 55 65 16