BE1001281A5 - DETERGENT COMPOSITION CONTAINING AQUEOUS thickened LITTLE OR NO PHOSPHATE AND METHOD OF USING THE WASHING DISHES. - Google Patents

Abstract

A liquid detergent composition for automatic dishwasher having a zero or low phosphorus percentage (less than 0.01%) is based on a mixture of aluminosilicate zeolite and a polymer with a water-soluble carboxyl group and stable to bleaching agents , such as a relatively low molecular weight sodium polyacrylate, so as to achieve a cleaning performance comparable to a phosphate formulation. The compositions which contain an inorganic colloidal clay and an aliphatic fatty acid or a salt thereof are viscoelastic and physically stable with respect to phase separation.

Description

       

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   THICK AQUEOUS DETERGENT COMPOSITION CONTAINING LITTLE
NO PHOSPHATE AND DISHWASHING METHOD
USING IT.



   The present invention relates to aqueous compositions for washing dishes and the like, especially in an automatic dishwasher. More specifically, the invention relates to compositions which do not contain phosphate builders but which have a detergent power comparable or superior to similar liquid detergent compositions for automatic dishwashers containing phosphorus.



   The present invention specifically relates to thickened liquid detergent compositions for automatic dishwashers having viscoelastic properties, improved chemical and physical stability and increased detergency despite the absence of adjuvant phosphate salts and which are spontaneously dispersible in the washing medium to provide effective washing. dishes, glassware, porcelain etc.



   Detergents for household dishwashers commercially available in powder form have several drawbacks, e.g. a non-uniform composition: costly operations for their production; a tendency to agglomerate in storage for high humidity levels, and thus to form clusters which are difficult to disperse; dust, a particular source of irritation for allergic users and a tendency to agglomeration in the dishwasher dispenser. The liquid forms of these compositions, however, generally cannot be used in automatic dishwashers because of their high foam percentages, their unacceptably low viscosites and their far too high alkalinity.



   A recent research and development activity

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 looked at the gel or "thixotropic" form of such compositions, eg. degreasers and products for automatic dishwashers characterized by thixotropic liquids or pastes. Products for dishwashing thus obtained are essentially questionable in that they are insufficiently viscous to test "anchored" in the distribution pan of the dishwasher, and moreover leave stains on dishes, glassware, porcelain etc.



   The presentation of compositions for automatic dishwashers in gel form and having satisfactory stability and detergent properties has hitherto proved problematic, particularly with regard to compositions for use in domestic dishwashers.

   For effective use, we recommend
 EMI2.1
 generally that the automatic dishwasher detergent, hereinafter referred to as ADD, contains (1) sodium tripolyphosphate (NaTPP) to soften or fix the minerals with hard water and emulsify and / or peptise the dirt; (2) sodium silicate to provide the alkalinity necessary for effective cleaning and to protect varnish and pattern from fine porcelain; (3) sodium carbonate, generally considered optional, to increase the alkalinity;

   (4) a chlorine-releasing agent to aid in the removal of soils which lead to the formation of water spots; and (5) a defoamer / surfactant to reduce foam, thereby increasing the efficiency of the machine and providing proper cleaning. See, for example, SDA Detergents in Depth, "Formulations Aspects of Machine Dishwashing", Thomas Oberle (1974). The cleaning products corresponding roughly to the compositions described above are mostly liquids or powders. Combining such ingredients in thickened form suitable for household machines has proven difficult.



  Generally such compositions do not contain hypochlorite bleach, as it tends to react with other chemically active ingredients, in particular

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 surfactants, degrading the suspending agent or thickener and reducing its effectiveness.



   U.S. Patent 4,115,308 describes thixotropic pastes for automatic dishwashers containing a suspending agent, p. ex. CMC, synthetic clays etc. ; inorganic salts including silicates, phosphates and polyphosphates; a small amount of surfactant and an antifoam. There is no mention of bleach.



   On the other hand, U.S. Patent 3,684,722 describes a detergent composition based on alkaline hypochlorite and thickened using mixtures of C8-C18 alkaline soaps and hydrotropes, such as amine and betaine cxyks. The inventors describe tests which show that various classes of organic polymeric thickeners were either unstable or did not succeed in providing a suitable thickening or else caused a loss of available chlorine. The polyacrylates were capable of causing thickening for several weeks at room temperature, but then decomposed.
 EMI3.1
 



  U.S. Patent 3,985,668 describes gel consistency abrasive degreasers containing (1) a suspending agent, preferably clays of the smectite or attapulgite type; (2) an abrasive, p. ex. silica sand or perlite; and (3) a filler comprising low density powdered polymers, expanded perlite, etc., which has buoyancy and therefore a stabilizing effect on the composition in addition to its filler function, thus replacing the water moreover available for the formation of an undesirable supernatant layer due to oozing and phase destabilization. The above ingredients are the essential ingredients.

   Optional ingredients include a hypochlorite bleach, surfactant. resistant to bleaching and buffering, p. ex. silicates, carbonates and monophosphates. Adjuvants such as NaTPP may be included as additional optional ingredients to establish or supplement an auxiliary function not fulfilled by the buffer, the amount of such an adjuvant not exceeding 57. de

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 the total composition, according to the patent. Maintaining the pH level A at values of (more than) 10 is achieved by the buffer / adjuvant components. A high pH is expected to decrease the decomposition of the chlorine bleach and the undesirable interaction between the surfactant and the bleach.

   When present, NaTPP is limited to SX, as indicated. There is no mention of antifoam.



   In GB 2 Patent Applications. 116. 199A and GB
2.140.450A, both in the name of Colgate-Palmolive, mention is made of liquid ADD compositions (LADD) which have properties advantageously characteristic of a thixotropic gel-like structure and which contain various ingredients necessary for effective cleaning with an automatic dishwasher. The aqueous detergent composition for an automatic dishwasher normally in the form of a gel having thixotropic properties includes the following ingredients, on a weight basis: (a) 5 to 35% of alkaline tripolyphosphate (b) 2, S A 20X of sodium silicate;
 EMI4.1
 (c) 0 to 97. of alkaline carbonate; (d) 0.1 to 57. of active organic detergent material dispersible in water. ! and resistant to.

   K sgEnts of MLanchunent chlores: (e) 0 to 5X of antifoam stable with bleaching agents ChLa (f) compound dike bleaching agent in sufficient quantity to give approximately 0.2 to 4% of available chlorine; (g) thixotropic thickener in an amount sufficient to impart to the composition a thixotropy index of 2.5
 EMI4.2
 about 10; (h) sodium hydroxide in an amount necessary to adjust the pH; and (i) water;
The LADD compositions thus formulated are weakly foaming; and spontaneously soluble in the washing medium and of maximum efficiency for alkaline pH values.

   The compositions normally have the consistency of a gel, that is to say a highly viscous opaque jelly material having a Bingham plasticity and thus relatively high flow thresholds.

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    Consequently, a defined shear force is necessary to trigger or increase the flow, as it can be obtained within a distribution tank with stirring of an automatic dishwasher in action.



  ; Under such conditions the composition is quickly fluidized and easily dispersed. When one stops applying the shearing force, the fluid composition quickly regains a high viscosity, the plasticity of Bingham returning very close to its previous consistency.



  U.S. Patent 4,5ii,487, dated April 16, 1985, describes a low foaming detergent paste for dishwashers. The patented thixotropic detergent has a viscosity of at least 30 pa.s at 20 C determined using a rotary viscometer at a spindle speed of 5 revolutions per minute. The composition is based on a mixture of hydrated sodium tripolyphosphate and finely divided hydrated sodium metasilicate, an active chlorine compound and a thickening agent which is a hectorite type lamellar silicate. Small amounts of nonionic surfactants and alkali carbonates and / or alkali hydroxides may be used.



  Recently the applicant has developed various modifications and improvements in the liquid detergent compositions of automatic dishwashers of the patents GB 2 116. 199A and GB 2 140. 450A. For example the demam FR.N 86. 18377 describes thixotropic liquid detergent compositions of aqueous gel type and free from clay and thickener, which use a mono or polycarboxylic acid of 8 to 22 carbon atoms to confer physical stability and thixotropic properties.



  In the French application W 87. 12321 filed on 9/9/87 the physical stability of the detergent compositions for automatic dishwashers made up of thixotropic liquid based on clay is improved by the addition of small quantities, for example of approximately 0, 02 to 1% by weight, of a polyvalent metallic sei of a long chain fatty acid, such as aluminum stearate.

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   The majority of these detergent compositions and similar liquids for automatic dishwashers described and marketed depend on phosphate salts as adjuvants such as sodium tripolyphopshate, to increase the cleaning capacity. While these phosphate additives are very effective for this purpose, their use has a major drawback: they are harmful to aquatic life and to rivers, in general al. In fact many jurisdictions have already, or are in the process of, absolutely banning phosphate based cleaning products.



   Although there have been multiple attempts to produce alternative builders and many such salts are known for inorganic and organic non-phosphate detergents, very few are able in practice to provide cleaning benefits comparable to those of phosphate adjuvants.

   In addition, the choice of suitable adjuvants is all the more difficult in view of current aqueous compositions which contain bleaches, since the replacement adjuvant must be compatible with the bleaching agent chlorine
In addition to its function as a detergency builder, inorganic alkali metal phosphate has the important function of contributing to the rheological properties of liquid aqueous detergent compositions of the thickened thixotropic gel type as described in GB 2.16.199A and GB 2. 140.450A .

   Consequently, the replacement of the phosphate adjuvant by a non-phosphate adjuvant has not proved to be simple since there are many various factors to be taken into account in order to meet all the multifunctional missions of the phosphate adjuvant.



   Therefore it is the first c. It is the object of the invention to provide aqueous cleaning compositions containing a bleaching agent which avoid the use of phosphate additives and which do not contain, or only environmentally tolerable levels of phosphorus from 'other sources. it is another object of the invention to provide

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 Thickened liquid ADD compositions containing little or no phosphate and having improved physical stability and rheological properties.



     It is yet another object of the invention to provide thickened liquid ADD compositions having little or no phosphorus without adversely affecting, or improving, the cleaning capacity, in particular by the formation of a small amount of stains and movies.



   These and other objects of the invention, which will be more easily understood from the following detailed description of the invention and of its preferred embodiments, are achieved by means of a liquid aqueous detergent composition containing little or no phosphorus and comprising the water,
 EMI7.1
 an organic detergent dispersible in water and stable to cl ag = nts of blandTimen): ditores, m agänt of hLanciujiEnt cMc, a silicate ai'lin and a detergency builder, where the detergency builder is a mixture of aluminosilicate zeolite and of a water-soluble polymer stable to bleaching agents and having a carboxyl group, or a salt thereof.

   More particularly, according to a preferred and specific embodiment of the invention, a thickened viscoelastic liquid detergent composition for a dishwasher is produced, free from phosphate adjuvant salts and containing little or no phosphorus and effective in preventing the deposition of particles in it. water-insoluble suspension, such as adjuvant aluminosilicate zeolite particles and bleach, etc. The composition can include clay or other thickeners as well as other stabilizers and other conventional ADD additives.



   According to this particular aspect the present invention provides an aqueous detergent composition normally of gel type for automatic dishwasher and having viscous elastic properties, which comprises, by weight: (a) 5 to 35% of aluminosilicate zeolite; (b) 25 to 407. sodium silicate; (c) 0 to 9% alkali metal carbonate; (d) 0.1 to 5X active ingredient organic detergent

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 dispersible in water and stable to chlorinated bleaching agents; (e) 0 to 5% of antifoam resistant to chlorinated bleaching agents;
 EMI8.1
 (f) a chlorinating compound of whitish.

   EnquatititB sufficient to supply about 0.2 to 47 .. of available chlorine; (g) 0 to 0.57. of a long chain fatty acid or a salt thereof; (h) 0 bk 5% of a clay thickener; (i) 0 to 8X sodium hydroxide; and (j) complementary water.



   Also in relation to this specific aspect, the invention provides a method of cleaning the dishes in an automatic dishwasher with an aqueous washing bath containing an effective amount of the liquid detergent composition for automatic dishwasher (LADD) described above. -above. According to this aspect of the invention, the LADD composition can be poured directly into the dispensing tank of the automatic dishwasher and will be sufficiently viscous to remain safely inside the tank until? shear forces are applied to it, such as those coming from the water jet of the washing machine, forces making it possible to exceed the flow threshold of the composition which will then flow.



   The invention will now be described in more detail using specific embodiments.



   Considering the environmental problems caused by the elutriation of lakes, rivers and other watercourses attributed to the deposition of phosphorus from detergents and other products in watercourses, much emphasis was placed on the elimination of phosphorus in detergent products.



   However, attempts to replace the phosphate adjuvant in thixotropic liquid compositions for automatic dishwashers of the type used by the applicant and which typically contain 0 to 3% of clay thickener - generally of the smectite type swelling with water; 10 to 25'r. alkali silicate; 0 to 0.57 .. stabilizing fatty acid; small amounts of bleach, stable detergent

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   bleaching agent, bleach-stable antifoaming agent, sodium carbonate, caustic soda, etc., and approximately 20 to 25% alkaline phosphate as deteogsice adjuvant, have led to a loss of thixotropic properties and generally to a deterioration of the cleaning efficiency.

   Although the exact mechanism for the destruction of rheological properties causing loss of thixotropy has not been fully elucidated, it appears that there is at least one interaction between the particles of phosphate adjuvant in suspension and the other ingredients of the formulation. , specially
 EMI9.1
 the clay thickener and the fatty acid or the stabilizing fatty acid salt and this interaction contributes to increasing the shear stress and the plastic viscosity of the composition.



   The present invention is based on the surprising discovery that similar rheological properties and a similar physical stability, that is to say resistance to phase separation, to sedimentation, etc., can be achieved, as in liquid compositions. aqueous phosphates previously, including in the composition an aluminosilicate zeolite as an inorganic detergent adjuvant insoluble in water mixed with a polymer with water-soluble carboxyl group and resistant to bleaching agents as rheological agent and multifunctional detergent adjuvant, and by increasing the percentage of alkali silicate A more than 25% by weight.

   At the end of the day, it gets better results with regard to stains and films (that is to say, fewer stains and a reduction in films).



   Although the compositions of the present invention do not exhibit thixotropic properties, they exhibit viscoelastic properties and a sufficiently high flow threshold (the maximum tension on a shear tension curve as a function of the shear rate) so that they do not flow under the effect of the force exerted by their own weight, that is to say the gravitational forces. Consequently, the compositions according to the invention can be easily poured

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 in the dispenser of an automatic dishwasher and will not flow until a sufficiently strong shear force is applied such that the force of the water jets exerted on the tray during the detergent dispersion.



   Naturally, it is understood that when physical stability over extended periods such as several weeks or several months is not required and when it is not asked to produce a very thickened solution, the high rates can be subtracted from the formulation. silicate, clay thickener and / or fatty acid or its stabilizing salt without adversely affecting the cleaning capacity given by the aluminosilicate zeolite adjuvant and the bleach-stable polymer containing a water-soluble carboxyl group (or one of its salts) .



   The adjuvants useful here are the water-insoluble aluminosilicates, whether of the crystallized or amorphous type. Different zeolites are described in GB patent 1,504,168, U. S. patent 4,409,136 and Canadian patents 1,072,835 and 1,087,477, all taken into account here as a reference for such descriptions. An example of amorphous zeolites useful here can be found in the Belgian Patent
 EMI10.1
 835. 351 and this patent is also incorporated here for reference. Zeolites generally have the formula (M = 0). (Als03) y. <: SiO =.

   WH20 where x is 1, y is between 0, 8 and 1, 2 and preferably 1, z is between 1, 5 and 3, 5 or more and preferably 2 to 3 and M is between 0 and 9, preferably 2, 5 to 6 and M is an alkali metal, preferably sodium or potassium, preferably especially sodium. A typical zeolite is of type A or similar structure, type 4A having
 EMI10.2
 especially preference. Preferred aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents per gram or more, e.g. ex. 400 meq / g.



   The aluminosilicate zeolite adjuvant can be present in the formulations in the same amounts as those found useful for alkaline polyphosphate adjuvants,

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   generally in the range of about 5 to 35X by weight, preferably about 20 to 30% by weight.



   The water-soluble polymers used here, which are stable to bleaching and which contain carboxyl groups, are, for example, homopolymers and copolymers of acrylic acid and their salts. These materials are generally commercially available and can be streaked as described below.



   Polyacrylic polymers and their salts which may be used include low molecular weight water soluble polymers having the formula
 EMI11.1
 ott R2, R2, and R3 can be the same or different and
 EMI11.2
 may be hydrogen, lower alkyl, or combinations thereof; n is a number from 5 to 250, preferably from 10 to 150, and even better from 20 to 100; and M represents hydrogen or an alkali metal, such as sodium or potassium. The preferred substituent for M is sodium.



   Preferred groups R t, Rz and Rs are hydrogen, methyl, ethyl and propyl. The preferred acrylic monomer is that where R1 and R3 are hydrogen, e.g. ex. acrylic acid, or where R1 and R3 are hydrogen and R2 is methyl, for example the methacrylic acid monomer
The degree of polymerization, that is to say the value of n, is generally determined by the limit compatible with the solubility of the polymer or copolymer in water. The terminal or final groups of the polymer or copolymer are not critical and may be H, OH, CH3 or a low molecular weight hydrocarbon.



   Typically polyacrylic acid copolymers may contain copolymers of, for example, acrylic acid

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 or methacrylic acid and an acid anhydride or polycarboxylic acid such as succinic anhydride, succinic acid, maleic anhydride, maleic acid, citric acid, etc. Preference is given to acid copolymers
 EMI12.1
 acrylic or methacrylic with a. maleic nhydride.



  The acrylic acid or methacrylic acid monomer will usually contain from 40 to 60'1. by weight, p. ex. 50X by weight approximately of the copolymer with a polycarboxylic acid or anhydride.



   The polyacrylic acid polymer may have a molecular weight (average weight) of 500 or 1000 to 25,000, preferably 1,500 to 15,000 and more preferably 2,000 to 25,000.
10,000. The copolymers can have higher molecular weights, for example up to about 100,000.
Specific examples of the polyacrylic acid polymers which can be used include Acrysol LMW acrylic acid polymers from Rohm and Haas, such as Acrysol LMW-45NX, a neutralized sodium salt, which has a molecular weight of about 4500 and Acrysol LMW20-NX, a neutralized sodium salt, which has a molecular weight of approximately 2000.



   A specific example of copolymer c? acrylic acid that can be used is Sokalan CP5 (from BASF) which has a molecular weight of about 70,000 and is the product of the reaction of about an equal number of moles of methacrylic acid and maleic anhydride which has been completely neutralized to form its sodium salt.



   The above polymers and copolymers can be prepared according to methods known in the prior art.



  See, for example, patent U. S.4.203.858.



   The water-soluble carboxylic polymers which are stable to bleaching are intended to have three primary functions in the liquid detergent compositions for automatic dishwashers of this rheology control invention; calcium complexation; and dispersion of dirt;
As a rheological control agent, the polymer additive apparently functions as a thickener and,

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 with the help of high percentages of alkali silicate, clay (when present) and fatty acid (or acid) (when present), it communicates viscoelasticity to the composition and a plastic viscosity in the range of about 200 to 10,000 mpa. 2, preferably 2,000 to 8,000, p. ex. 5000 rrPa. s.

   The desired viscoelasticity and plastic viscosity ranges are best achieved when the molecular weight is not more than 10,000, especially from 2000 to 10,000, p. ex. around 4000 to 5000.



   As a calcium complexing agent it is important that the polymer has a particularly good water solubility. Here again, we arrive at the best results when the pc. lymer has a molecular weight not exceeding 10,000, especially 2,000 to 10,000.



   Similarly, in its action as a dirt dispersing agent contributing to anti-stain and anti-stain properties
 EMI13.1
 desired improved film, the molecular weights of the additive polymer are preferably in the range of 2000-10,000.



  The amount of additive polyacrylic acid polymer or copolymer necessary to achieve the desired increase in physical stability and cleaning performance will depend on factors such as the amount and nature of the fatty acid or its content. present risk), the nature and quantity of the clay thickener (when present), the active detergent component, the
 EMI13.2
 bleaching, as bisn as corfditi. vs. ns expected storage and shipping.



  Generally, however, the amounts of additive polyacrylic polymer or copolymer which can be used are in the range of about 0.5 to 10% by weight, preferably about 0.80 8.0% by weight. , and especially about 2 to 6% by weight.



   The detergent active material useful here must be stable in the presence of chlorinated bleaching agent, especially hypochlorite, and the types of surfactants are preferred.

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 dispersible in water such as organic anionics, amine oxides, phosphine oxides, sulfoxides or betaines, the first anionics mentioned having preference. They are
 EMI14.1
 used in amounts ranging from about 0.1 SX, preferably about 0.3 to 2.0%. Particularly preferred surfactants here are the mono- and / or disulfates of mono- and / or di- (C8-C14) alkoyldiphenyl alkali linear or branched, commercially available oxides, for example DOWFAX (trademark) 3B-2 and DOWFAX 2A-1.

   In general, paraffinic sulfonates tend to abnormally increase viscosity, causing serious shear force problems. In addition, the surfactant should be compatible with the other ingredients of the composition. Other suitable surfactants include alkyl sulfates, alkyl sulfonates, primary alkylarylsulfonates and secondary alkyl sulfates. Examples include sodium Crow alkyl sulfates, such as sodium dodecyl sulfate and tallow sodium alcohol sulfate; C10-C18 sodium alkanesulfonates, such as sodium hexadecyl-1-sulfonate and C11-C18 sodium alkylbenzenesulfonates, such as sodium dodecylbenzenesulfonates. The corresponding potassium salts can also be used.



   As other suitable surfactants or detergents, amine oxides typically have the structure RzR1NO, in which R represents an Inner alkyl group, for example methyl, and R1 represents a long chain alkyl group having from 8 to 22 carbon atoms, for example a lauryl, myristyle, palmityl or cetyl group. Instead of an amine oxide, a phosphine oxide R1R: 2PO can be used
 EMI14.2
 or a sulfoxide RR1SO tensioactit; correspondents. Betainic surfactants typically have the structure RRiNR "COO-, in which each R represents a lower allene group having from 1 to 5 carbon atoms.

   Specific examples of these surfactants are lauryldimethylamine oxide, myristyldimethylamine oxide, the corresponding phosphite oxides and sulfoxides, and the corresponding betaines, including acetate of

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 EMI15.1
 dodecyldimethylammonium, tetradecyldiethylammonium pentanoate, hexadecyladimethylammonium hexanoate, etc. For biodegradability, the alkyl groups of these surfactants should be linear, and it is these compounds that are preferred.



   Surfactants of the above type are well known in the prior art and are described, for example, in patents U. S. 3,985,668 and U. S. 4,271,030.



   Although any chlorine bleaching compound can be used in the compositions of this invention, such as dichloroisocyanurate, dichlorodimethylhydantoin, or chlorine TSP, an alkali metal hypochlorite, p. ex. potassium, lithium, magnesium, and especially sodium. The composition should contain sufficient chlorine bleaching compound to provide 0.2 to 4.0% by weight of available chlorine, dosed for example by acidification of 100 parts of the composition with an excess of hydrochloric acid. A solution containing about 0.2 to 4.0% by weight of sodium hypochlorite contains or supplies about the same percentage of available chlorine.

   Preference is given to about 0.8 to 1.6X by weight of available chlorine.



  For example, it is advantageous to use a solution of sodium hypochlorite (NaOCD having approximately 11 to approximately
 EMI15.2
 13% chlorine available in quantities of about 3 to 20%, preferably about 7 to 127 ..



   Sodium or potassium silicate, which provides alkalinity and protection to hard surfaces such as fine porcelain (varnish and pattern), is normally used in amounts ranging from about 2.5 to 20 or 25% by weight. At higher percentages than about 107. by weight, the silicate also has an improved stain-fighting action.



   However, for the physically stable and viscoelastic aqueous detergent dishwasher composites of this invention, it is essential to incorporate quantities of alkali silicate in excess relative to the quantities normally used, especially more than 25% by weight, for example from 28% to 40%,

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 more especially about 30 to 38% by weight of the composition.



   Sodium silicate is generally added in the form of an aqueous solution, preferably with a Na2O1SiO2 ratio of approximately 1: 2.2 to 1: 2, S, for example 1: 2, 4. Most of the components of the composition, in particular NaOH, sodium hypochlorite and antifoam can also be added in the form of an aqueous dispersion or solution.



   The inhibition of foam is important to increase the performance of the dishwasher and to reduce the destabilizing effects which could occur in the presence of excess foam in the machine during use. The foam can be sufficiently reduced by an appropriate choice of the type and / or the amount of active detergent material, the main foaming component. The amount of foam also depends to some extent on the hardness of the washing water in the machine, so that a proper adjustment of the proportions of NaTPP, which has a softening effect on the water, can help achieve the desired degree of inhibition of the foams. However, it is generally preferable to introduce a reducing agent or foam inhibitor resistant to discoloration by chlords.



  Particularly effective in this regard are the alkyl esters of phosphonic compounds of the following formula, when a certain percentage of phosphorus can be tolerated:
 EMI16.1
 and especially the following alkyl acid phosphates
 EMI16.2
 

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 EMI17.1
 r In the above formulas, Pun or the two R groups in each type of ester can independently represent a C12-C20 alkyl group. The ethoxylated derivatives of each type of ester, for example the condensation products of a mole of ester with, for example from 1 to 10 moles, preferably 2 to 6 moles, even better 3 or 4 moles, of oxide ethylene can also be used.

   Some of the above products are commercially available, such as SAP products from Hooker and LPKn-158 from Knapsack. We can use mixtures of both types, or all others
 EMI17.2
 types stable to KLartinjnant agents: cMQpes, or n & Lans of mono and diesters of the same type.

   We have a special preference for a mixture of mono and di-C16-C18 alkyl acid phosphates such as monostearyl / distearyl acid phosphates 1, 2/1, and their condensates with 3 to 4 moles of ethylene oxide . In the case where it is used, proportions of 0.01 to 0.5% by weight, preferably 0.02 to 0.4% by weight, in particular approximately 0.1 to 0.2% by weight, of foam reducing agent in the composition are typical proportions, the weight ratio of active detergent to antifoaming generally being between approximately 20: 1 and 4: 1 and preferably between approximately 10: 1 and 5:

   1. At these low percentages of anti-foaming agent, the total percentage of phosphorus in the composition will generally and preferably not exceed 0.01% by weight of the total of the composition.



   When it is desired to completely remove the phosphorus, any silicone anti-foaming agent compatible with the bleaching agent can be used.



   In the preferred thickened LADD compositions of this invention, thickening is caused by inorganic colloidal water-swelling clays of the smectite and / or attapulgite types. These materials can generally be used in amounts of about 0.1 to 10
 EMI17.3
 preferably 1 to SX by weight, to impart the desired properties. However, in the presence of fatty acid stabilizers or fatty acid salts, more quantities can be used.

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 weak inorganic colloidal clays of the smectite and / or attapulgite types.

   For example amounts of clay in
 EMI18.1
 the range of about 0.1 tek 3%, preferably 0, t to 2.51, or even better from 0.1 to 27. are generally sufficient to achieve the desired viscoelastic properties when used in combination with stabilizing fatty acid (or fatty acid salt), and other specified ingredients.



  Smectites include montmorillonite (bentonite), hectorite, attapulgite, smectite, saponite, etc. Montmorillonite-type clays are preferred and are available under trade names such as Thixogel (trademark) Not and Gelwhite (trademark) GP, H etc., of Georgia Kaolin Company; and ECCAGUM (trademark) GP, H etc., from Luthern Clay Products. Attapulgite clays include materials commercially available under the trade name Attagel (trademark), that is, Attagel 40, Attagel 50 and Attagel 150 from Engelhard Minerals and Chemicals Corporation. Mixtures of smectites and attapulgites in weight ratios of 4: 1 to 1: 5 are also useful here.

   Thickening or suspending agents of the preceding types are well known in the prior art.



   Physical stability, i.e. resistance to phase separation, sedimentation, etc. of these aqueous liquid ADD compositions can be significantly improved by adding to the composition a small but effective amount of a long chain fatty acid or a metal salt thereof. In fact, under the preferred alkaline pH conditions of the LADD composition, ie pH 10.5 to 13.5, the fatty acids will be transformed into the corresponding alkali metal salts.



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

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 saturated or unsaturated and can be linear or branched. Straight chain saturated fatty acids are preferred. Mixtures of fatty acids can be used, such as those derived from natural sources such as tallow fatty acid, coconut fatty acid, soy fatty acid, etc., or from synthetic sources such as industrial manufacturing processes.



   So examples of fatty acids are, for example, decancic acid, dodecancic acid, palmitic acid,
 EMI19.1
 myristic acid, stearic acid, oleic acid, eicosanoic acid, tallow fatty acid, coconut fatty acid, soy fatty acid, mixtures of these acids, etc. Stearic acid and mixed fatty acids are preferred.



   The metal salts of the fatty acids can also be used and any monovalent or versatile metal can be used. Monovalent metals include, for example, alkali metals, especially sodium and potassium. Sodium salts (soaps) are particularly preferred.



   The preferred polyvalent metals are the polyvalent metals of groups IIA, IIB and IIIB of the Periodic Table of the Elements, such as magnesium, calcium, aluminum and zinc, although other polyvalent metals, including those of
 EMI19.2
 groups IIIA, IVA, VA, IB, IVB, VB, VIB, VIIB and VIII of the Periodic Table can also be used. Specific examples of such other versatile metals are Ti, Zr, V, Nb, Mn, Fe, Co, Ni, Cd, Sn, Sb, Bi, etc. Generally, metals can be present in a divalent to pentavalent state. Preferably, the polyvalent metal salts are used in their higher oxidation states.



  Naturally, for the LADD compositions, as well as for all other applications where the composition according to the invention will intervene, or may intervene, in articles used for the handling, storage or presentation of food, or which may be in contact or consumed by people or animals, the metal salt should be chosen taking into account the toxicity of the metal.



  To this end, the calcium and magnesium salts benefit

  <Desc / Clms Page number 20>

 very particular preference as generally healthy food additives.



   Many of these metal salts are commercially available. For example, aluminum salts are available in triacid form, e.g. ex. aluminum stearate like
 EMI20.1
 aluminum tristearat, AKdHCOO. Monoacid salts, p. ex. aluminum monostearate, and the salts of diacids, p. ex. aluminum distearate, and mixtures of two or three of the mono-, di- and triacid salts can be used for metals, e.g. ex. AI, valences +3, and mixtures of the salts of the mono- and diacids can be used for the minds, eg. ex.

   Zn at valences +2. It is highly desirable that the valence metal diacids +2 and the valence metal triacids +3, the valence metal tetracids +4 and the valence metal pentacids +5, be used in predominant amounts.



   The metal salts mentioned above are
 EMI20.2
 generally commercially available, but can readily be produced, for example by saponification of a fatty acid, e.g. ex, animal fat, stearic acid etc., or the corresponding fatty ester, followed by treatment with a hydroxide or a polyvalent metal oxide, for example in the case of aluminum salt, with alum, alumina etc., or by reacting a soluble metal salt with a soluble fatty acid residue.



   Calcium stearate, i.e. calcium distearate, magnesium stearate, i.e. magnesium distearate, aluminum stearate, i.e. tristearate d aluminum and zinc stearate, i.e.
 EMI20.3
 zinc distearate, are the preferred polyvalent stabilizing fatty acid salts.



   Mixed fatty acids, such as acids were found in nature, eg copra acid as well as mixed fatty acids resulting from industrial manufacture are also advantageously used as a cheap but valuable source of fatty acid. long chain.



   In addition, the dimers or trimers of these acids can

  <Desc / Clms Page number 21>

 also Stre used.



   The amount of fatty acids or salts of stabilizing fatty acids required to achieve the desired improvement in physical stability will depend on such factors as the nature of the fatty acid (or its salt), the nature and amount of the clay thickener, active detergent component, inorganic salts, other LADD ingredients, as well as storage and shipping conditions.



   Generally, however, amounts of stabilizers of polyvalent fatty acid salts in the range of about 0.02 to 1X, preferably about 0.06 to 0.2%, more preferably d about 0.08-0.4% provide long term stability and lack of phase separation during storage or during transportation both at low and high temperatures as is desirable for a commercially available product acceptable.



   Although not wishing to be bound by any particular theory as to the mode of action of fatty acid stabilizers (metal salts), it is hypothesized that these stabilizers, which, under alkaline conditions, are anionic salts, act on the surface of the cationic clay particles used as a thickener, the fatty acid residues helping to keep the clay particles in suspension. In addition, depending on the quantities, proportions and types of physical stabilizers and clay thickeners, the addition of fatty acid (or its salt) not only increases physical stability but also causes a simultaneous increase in apparent viscosity .

   The ratios of fatty acid (or sei) to the clay thickener ranging from about 0.08 to 0.4% by weight of clay thickener are generally sufficient to give these simultaneous benefits and, therefore, these ingredients are advantageously used according to these reports.



     Generally, the effectiveness of LADD is directly related to (a) amounts of available chlorine; (b) alkalinity; (c) solubility in the washing medium and (d) inhibition of foams; It is preferred here that the pH of. the LADD composition

  <Desc / Clms Page number 22>

 or at least about 9.5, better still about 10.5 to 13.5 and even more preferably at least about 11.5. At relatively low pH values, the LADD product is often too viscous, i.e. almost solid, and thus
 EMI22.1
 therefore not spontaneously fluid under the effect of the shear forces created within the distribution tank under the normal operating conditions of the machine.



  Essentially, the composition loses much, if not all, of its viscoelastic character. The addition of NaOH is thus often necessary to increase the pH up to the intervals mentioned above, and to increase the rheological properties. The presence of carbonate is also often necessary here, as it acts as a buffer which helps maintain the desired pH. However, excess carbonate should be avoided, as it can cause the formation of crystals into carbonate needles, thus altering the stability, thixotropy and / or detergent power of the LADD product, at the same time as the distribution of the product from, by example, tubular pressure bottles.

   Caustic soda has the additional function of neutralizing the phosphoric ester or 1 phosphonic foam reducing agent when it is present. About 0.5 to 3% by weight of NaOH and about 2 to 9% by weight of sodium carbonate in the LADD composition are characteristic, although it should be noted that sufficient alkalinity can often be provided by the metal silicate alkaline.



   The amount of water contained in these compositions should, of course, not be too high to create an abnormally low viscosity and fluidity, nor too low to create an abnormally high viscosity and low flowability, the viscoelastic properties being in both cases diminished or destroyed. Such a value is readily determined by a routine test in each particular case, and is generally in the range of about 25 to 75% by weight, preferably about 55 to 65% by weight, in total, of all sources. The water should also be advantageously deionized or

  <Desc / Clms Page number 23>

 softened.



   Other conventional ingredients can be introduced into these compositions in small amounts, generally less than about 37% by weight, such as a perfume, hydrotropic agents, such as benzene-, toluene-, xylene-, and cumene sulfonates. sodium, preservatives, dyes and pigments, etc., all, of course, stable to chlorine bleach and to high alkalinity (properties of all components). Special preference is given for coloring with chlorinated phthalocyanines and aluminosilicate polysulphides which give pleasant green and blue tints respectively. TiO2 can be used to whiten or neutralize color deviations.

   Abrasives or polishing agents should be avoided in LADD compositions as they can damage the surface of fine dishes, crystal etc.



   According to a preferred method for making these compositions, one should first dissolve or disperse all inorganic salts, e.g. ex. carbonate (when used), silicate and zeolite, in the aqueous medium. The thickening components including polymer with carboxylic group and clay (when present) are added last.



  The antifoam (when present) is first introduced in the form of an aqueous dispersion, from mg to qua thickening agent. The antifoam dispersion, caustic soda (when present) and the inorganic salts are first mixed at high temperatures in aqueous solution (deionized water) and then cooled, with constant stirring.



  Bleach, surfactant, fatty acid (or its salt
 EMI23.1
 stabilizing metal), the polyirµre and the dispersion of, thickening at room temperature then add the cooled solution (2S-35'C). If the chlorine bleach compound is excluded, the total sei concentration (eg sodium silicate and sodium carbonate) is generally about
 EMI23.2
 20 to SOX by weight, preferably about 25 to 40X by weight of the composition.



   Another particularly preferred method of mixing

  <Desc / Clms Page number 24>

 
 EMI24.1
 of the ingredients in LADD formulations consists of c? first form a mixture of water, antifoam, detergent, polymer with a carboxyl group, fatty acid or salt of fatty acid and clay.



  These ingredients are mixed together under high shear conditions, preferably at room temperature at the start, to form a uniform dispersion. To this pre-mixed fraction the remaining ingredients are incorporated under low shear mixing conditions. For example, the required amount of premix is introduced into a low shear mixer and the remaining ingredients are then added, while mixing, either sequentially or simultaneously. Preferably, the ingredients are added sequentially, although it is not necessary to complete the addition of the entire ingredient before starting to add the next ingredient.

   In addition, one or more of the ingredients can be divided into parts and added at different times. Of
 EMI24.2
 good results have been obtained by adding the remaining ingredients in the following order: sodium hydroxide, alkali carbonate, sodium silicate, aluminosilicate zeolite, bleach (preferably sodium hypochlorite) and sodium hydroxide.



   The liquid ADD compositions of this invention are used directly, in a known manner for washing plates, other kitchen utensils, etc. in an automatic dishwasher provided with a suitable detergent dispenser, in an aqueous washing bath containing an effective amount of the composition.



   While the invention has been particularly described with respect to its application to liquid detergents for autc dishwashers. Any person skilled in the art will readily understand that, with or without the advantages of viscoelasticity and physical stability obtained thanks to the additional quantities of alkali silicate and to the interaction.
 EMI24.3
 clay and fatty acid, the cleaning benefits offered by the combination of a stable detergent with bleaching agents, a bleaching agent,

   zeolite builder and a water-soluble carboxylic group polymer resistant to

  <Desc / Clms Page number 25>

 bleaching agents make the compositions of this invention useful as a general type of liquid cleaning caulk for dishes, glassware, cutlery, pots, pans etc.



   The detergent performance of the composition of the invention, in terms of eliminating a wide spectrum of food spots, is comparable to or slightly better than that of detergents based on a similar alkaline polyphosphate, e.g. ex. sodium tripolyphosphate.

   For example, in cleaning tests on various food residues, some of them even being cooked on the walls, including egg, peanut butter, tea, coffee, milk, milk chocolate, tomato juice, rice, rice mixture / cheese, white sauce, oatmeal and Lspinards, the LADD composition of the invention carried out a slightly better cleaning or the same cleaning in 14 to 16 cases of food stains on different substrates (glasses, cups, knives, dishes, pots) and cleaning only slightly worse for milk chocolate and cooked rice on the containers.



   In addition, as will be shown in the following example, the compositions of this invention are generally superior to similar phosphate compositions in terms of staining and filming.



   The invention can be literally practiced in different ways and a number of specific embodiments have been described to illustrate the invention in the following example.



   All the amounts and proportions referred to therein are by weight of the composition, unless otherwise indicated.



  Example
The following two compositions are prepared so as to compare the properties of the composition according to the invention with a similar phosphate-based composition.

  <Desc / Clms Page number 26>

 
 EMI26.1
 
 <tb>
 <tb> Component <SEP> Invention <SEP> Comparison
 <tb> Lot <SEP> NO <SEP> 1 <SEP> Lot <SEP> N * 2
 <tb> Water Deionized <SEP> <SEP> 16, <SEP> 44 <SEP> 30, <SEP> 44
 <tb> Acid <SEP> stearic <SEP> 0, <SEP> 10 <SEP> 0, <SEP> 10
 <tb> Clay <SEP> smectite
 <tb> (Van <SEP> Gel <SEP> ES) <SEP> 1, <SEP> 50 <SEP> 1, <SEP> 50
 <tb> Silicate <SEP> from <SEP> sodium
 <tb> (solution <SEP> A <SEP> 47, <SEP> SX <SEP> from
 <tb> Na2O2SiO2.report <SEP> 1:

  2,4) <SEP> 35.00 <SEP> 25.00
 <tb> Tripolyphosphate <SEP> from
 <tb> sodium <SEP> (substantially <SEP> anhydrous, <SEP> either
 <tb> approx. 3% <SEP> humidity) <SEP> 12.00
 <tb> Tripolyphosphate <SEP> from
 <tb> sodium, <SEP> hexahydrate <SEP> 12.00
 <tb> Aluminosilicate <SEP> zeolite <SEP> 24, <SEP> 00
 <tb> Carbonate <SEP> Na, <SEP> anhydrous <SEP> 6, <SEP> 00 <SEP> 6, <SEP> 00
 <tb> Hypochlorite <SEP> from <SEP> sodium
 <tb> (IX <SEP> chlorine <SEP> available) <SEP> 9, <SEP> 00 <SEP> 9, <SEP> 00
 <tb> Surfactant <SEP> (Dowfax
 <tb> 3B-2, <SEP> solution <SEP> aqueous
 <tb> to <SEP> 45% <SEP> from <SEP> mono-and <SEP> dod6cyldisulfonate <SEP> from <SEP> Na) <SEP> 0, <SEP> 80 <SEP> 0, <SEP> 80
 <tb> Agent <SEP> defoamer
 <tb> Knapsack <SEP> LPKn <SEP> 158,
 <tb> mix <SEP> from <SEP> mono-and
 <tb> distearyl (C16-C18)
 <tb> alkylesters <SEP> of acid
 <tb> phosphoric, <SEP> report
 <tb> molar <SEP> approx. 1:

  1.3) <SEP> 0.16 <SEP> 0.16
 <tb> Solution <SEP> soda
 caustic <tb> <SEP> (NaOH <SEP> 50%) <SEP> 3.00 <SEP> 3.00
 <tb> Polyacrylate <SEP> from <SEP> Na
 <tb> (PM = 4,500) (50lut.45%) <SEP> 4.00
 <tb> 100, <SEP> 00 <SEP> 100, <SEP> 00
 <tb>
 Each of the formulations in lots 1 and 2 is tested

  <Desc / Clms Page number 27>

 to compare their cleaning performance (formation of stains and films on glassware) using a Kenmore dishwasher with 100 grams of glassware and tap water At a temperature of 55 C and a hardness of 120 ppm. The test procedure is described in ASTM D3S66-79, except that only four cleaning cycles are used.



  Film and task formations are evaluated according to the following scales: Film evaluation scale
 EMI27.1
 1. Very well, no visible film 2. Slight film, becoming visible 3. Visible film, increasing 4. Continuous growth of a large film 5. The film becomes excessive 6. Large film, excessive formation 7. Continuous growth Sun excessive film.



  Stain assessment scale A. Very good, no stains B. Very few visible stains C. Distinct stains D. Significant coverage around SOX.



  The results are presented below:
 EMI27.2
 
 <tb>
 <tb> Evaluation <SEP> from <SEP> the <SEP> performance
 <tb> Spots <SEP> Movies
 <tb> Cycle <SEP> NO <SEP> Lot <SEP> 1 <SEP> Lot <SEP> 2 <SEP> Lot <SEP> l <SEP> Lot <SEP> 2
 <tb> 1 <SEP> A, <SEP> B <SEP> B <SEP> 1, <SEP> 2 <SEP> 1, <SEP> 2
 <tb> 2 <SEP> A, <SEP> B <SEP> B <SEP> 1, <SEP> 2 <SEP> 1, <SEP> 2
 <tb> 3 <SEP> A, <SEP> B-B <SEP> B-C <SEP> 1, <SEP> 2 <SEP> 1, <SEP> 2
 <tb> 4 <SEP> B <SEP> B-C <SEP> 2 <SEP> 2
 <tb>
 Results similar to those described above will be obtained if the polyacrylate is replaced by a methacrylic acid / maleic anhydride copolymer, e.g. ex. the Sokolan CP5.


    

Claims (19)

 CLAIMS 1. Aqueous liquid detergent composition containing little or no phosphorus and consisting of water, organic detergent dispersible in water and stable to chlorine bleaches, alkali metal silicate, chlorine bleach and adjuvant detergency agent comprises a mixture of aluminosilicate zeolite and a polymer cA water-soluble carboxylic group, stable to bleaching agents, characterized in that the polymer stable to bleaching agents is a polyacrylic acid or a polyacrylate polymer and has a molecular weight in the range from about 1000 to about 25000.  EMI28.1   2. Composition according to claim 1, characterized in that the polymer stable to bleaching agents has a molecular weight of approximately 2000 to approximately 10000. 3. Composition according to claim 1, characterized in that the detergent adjuvant contains from about 5 to about 35% by weight of aluminosilicate zeolite and from about 0.5 to 10% by weight of polymer stable to bleaching agents.  4. Composition according to claim 1, further comprising an inorganic clay thickener forming colloid.  5. The composition of claim 4, further comprising a Cn to C22 aliphatic carboxylic acid or a salt thereof.  6. Composition according to claim 1, further comprising a foam reducer stable to bleaching agents.  7. Composition according to Claim 6, characterized in that the foam reducing agent consists of an alkyl acid phosphate or an acid ester  <Desc / Clms Page number 29>  alkylphosphonic containing one or two C12-C20 alkyl groups, or a mixture thereof.  8. Composition according to claim 1, characterized in that it is free of phosphorus.  9. The composition of claim 9, further comprising a silicone foam reducer.  10. A thickened aqueous detergent composition for an automatic dishwasher containing not more than about 0.01 by weight of phosphorus, and containing approximately by weight, (a) 5 to 35% of aluminosilicate zeolite; (b) more than 25% sodium silicate; (c) 0 to 9% alkali metal carbonate; (d) 0.1 to 5% of active ingredient of organic detergent dispersible in water and stable to bleaching agents; (e) 0 to 5% foam reducer stable to bleaching agents; (f) a chlorine bleach compound in sufficient quantity to produce about z 4 W of available chlorine; (g) 0 to 3% of an inorganic clay thickener forming a colloid;  (h) 0 to 0.5% of an aliphatic fatty acid having from 8 to 22 carbon atoms, its dimers, its trimeres, or its metal salts; (i) 0 to 8% sodium hydroxide; (j) 0.5 to 10% of polymer with a water-soluble carboxylic group and stable to bleaching agents; and (k) water; said composition having a pH of at least 9.5.  11. Composition according to claim 11, characterized in that the polymer which is stable to bleaching is polyacrylic acid or a polyacrylate and has a weight  <Desc / Clms Page number 30>  molecular from about 1000 to 25000.  12. Composition according to claim 11, characterized in that the bleach-stable polymer has a molecular weight of approximately 2000 to approximately 10000.  13. Composition according to claim 10, comprising 0.03 to 0.5 of said aliphatic fatty acid or its salt (h) and 0.1 to 3% of said clay thickener (g).  14. Composition according to claim 13, characterized in that the fatty acid is stearic acid or a salt of this acid and the clay is a smectite or an attapulgite.  15. Composition according to claim 10, characterized in that the chlorine-containing bleaching compound (f) is sodium hypochlorite.  16. Composition according to claim 10, characterized in that it contains at least about 0.1% by weight of the foam reducing agent (e).  17. Composition according to claim 16, characterized in that the foam reducer is an alkyl acid phosphate or an ester of alkylphosphonic acid containing one or two C 1 -C 4 alkyl groups, or their mixtures.  18. The composition of claim 10, having a pH of about 10.5 to about 13.5.  19. A method of cleaning dirty dishes in an automatic dishwasher which consists in contacting, in an automatic dishwasher, dirty dishes with an aqueous washing bath containing in dispersion an effective amount of the composition according to claim 10 .