CS252459B2 - Agent for ice prevention and ice melting - Google Patents

Abstract

1. Anti-freeze and ice-release agent, containing water-soluble ammonium ions and/or sulphate ions and, optionally, additional anions which form with calcium ions largely water-soluble calcium compounds, characterized by a content of anions, selected from the group of phosphate anions, organic carboxylic acid anions, polycarboxylic acid anions, fluoride anions or silicofluoride anions, the calcium compounds of which have a water solubility of less than 0.1 gram per 100 gram of water at 20 degrees C, and by a content of organic and/or inorganic substances, forming agglomerated systems (micelles), dispersed in water and having a particle size of less than 1 000 micrometres, selected from the group of ultra-fine silica, magnesium silicates, aluminium silicates, polyelectrolytes, such as, in particular, higher-molecular polyethyleneoxides, polyacrylates or polyacrylamides.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifreeze and ice melting agent.

Antifreeze and ice melting agents are used to lower the freezing point of aqueous solutions of the liquids by preventing the formation of ice on one scratch ε on the other hand by melting the ice already formed. These compositions generally include inorganic salts such as sodium chloride, magnesium chloride, calcium chloride, potassium, sodium or ammonium phosphate, ammonium nitrate, magnesium, alkaline earth nitrates, ammonium sulfate, alkali metal sulfates with organic compounds such as low molecular weight alcohols, glycols , glycerol, lectates or urea.

While these compositions reduce the freezing point of the water, they generally have an adverse effect on the environment, and in some cases these effects are very significant. Up to now, sodium, calcium and magnesium chloride are known to be the most widespread compound for this use, and they are also the cheapest. The chlorine content of the aqueous solution causes strong corrosion of iron and other metals, as well as concrete and masonry, and further damages plants. Chlorine content in both solutions and salt, directly used for scattering, makes it more difficult to absorb water from the roots of trees and lower plants. Chlorides get into leaves that damage. The leaves turn brown at the edges ε prematurely. Children in melting snow wash the chlorides from fallen leaves again and the harmful cycle continues. Further damage to the chloride content can also be observed on footwear and clothing, and chloride also harms the paws of domestic animals.

The use of organic compounds does not cause corrosion because the organic compounds are far less aggressive. However, these substances are far more expensive than inorganic substances and, in addition, the use of some of these compounds causes considerable environmental pollution. When monoethylene glycol is used as an antifreeze agent in chillers, the water is highly contaminated. Alcohols in some cases have adverse effects, for example in the case of methyl alcohol, and in particular when using a low molecular weight alcohol, they are volatile substances, causing a risk of fire. If higher alcohols are used, oxidation of oxygen from the air can lead to the formation of acids, which in turn cause stronger corrosion. Buffers such as potassium phosphate or sodium boronite and, consequently, metal corrosion inhibitors such as benzotriazoles, tolyltriazoles, phosphates, alpha-amine phosphates or molybdemams are added to the organic substances used in these compositions. , it should be pointed out that these phosphates did not in any case contain, in addition to anionic and sulphate ions, an additional agent to protect certain substances, such as baton against the effects of these ions ·

A typical antifreeze and ice melting agent has been described CA-PS 969 345. Compositions of this type are also used in airport runways and consist, for example, of mixtures of foraanide, urea, water and chromene (Ca-PS 981 440). According to the present findings, the adverse effects on water have been found to be adverse and the environment is mainly formanide and chronanes, so it is recommended that these substances be discarded for this purpose. DAS 1,459,639 recommends mixtures of formamide or formamide derivatives and water ^- soluble alcohols and esters to rapidly dissolve ice and to dissolve snow on snowy surfaces. ^{In MS} - I8 ^{PS 4} D8 isuje ^p o ^{p p} ou ^F APPLICATION etoano-urea together with inhibitors of the melting ice ns airports and streets.

It is known from DOS 2 933 318 to use a mixture of sodium and potassium chloride together with calcium oxide, calcium carbonate, magnesium oxide and / or magnesium carbonate. In this case too, the composition contains harmful chlorides in addition to the soluble proportions of limestone and dolomite. Longer publications also reduce the corrosion of sodium chloride by adding, for example, 0.1 to 10% calcium nitrate. A composition of this type is described, for example, in German Patent 2,847,350 in which the use of calcium nitrate reduces metal corrosion, but does not reduce the harmful effects of sodium chloride on plants, animals, buildings and the like. The same applies to a composition containing 80 to 99.9% by weight of chlorides and with the addition of a corrosion inhibitor according to DOS 2,161,522.

Because of the problems associated with the use of formulations containing chlorides, other compounds having a similar effect and not harmful have been sought, such as ammonium sulfate, urea and sodium nitrate. Mixtures of this type containing various corrosion inhibitors have been described, for example, in Austrian Patent Specification S. 191,383 and U.S. Patent Specification No. 2,980,625.

A mixture of urea, ammonium chloride, ammonium phosphate and ammonium sulphate is described as an antifreeze agent, in particular for extinguishing fluids, in Fransau Patent 2,102,933. U.S. Pat. No. 3,624,243 discloses a mixture of urea and ammonium nitrate together with ethylene glycol.

All of the above compositions are intended to protect iron and light metals at the same time from corrosion. Urea alone has this effect is relatively good activity against corrosion. ^P s te ^{pl rt} c ^h nižšíc ^h - ⁸ ° ^C, the VSA ^{to a} span ^ i ^ ^l e ^d in non ^EFFECTIVE mounted, ^PRICE EMZ te ^pl OTA here ^{h ¹H} by forcing it in ^{eh d} n of ^the mites is at -11, ⁵ ° ^C.

Ammonium salts having a lower melting point in solution break up concrete, masonry and other calcium-containing building materials, such as runways, bridge structures, drain pipes, canal linings, and the like. For this reason, a number of regulations limit the content of these substances in water and soil. For example, an ammonium content below 15 mg / liter is reported as the concentration. with a harmful effect on concrete, 15 to 30 mg / liter as a concentration at slight damage, a concentration of 30 to 60 mg / liter as a concentration at very severe damage, above 60 mg / liter is completely inadmissible. In particular, calcium hydroxide from the cement dissolves the ammonium salts, releasing ammonia. Taking into account the sulphate content of the solutions according to the same standard, a content of 200 mg / liter for Portland cement, a content below 400 mg / liter for cement used in blast furnaces and below 602 mg / liter for cement, with a special treatment increases its resistance to sulphates. In the case of conventional types of building materials, a sulphate content of 200-300 mg / liter is considered weakly corrosive, 400-500 mg / liter strongly corrosive and 600-1,500 mg / liter completely impermissible. It has been shown that in the case of Portland cement there is severe damage in the range of 300-400 mg / liter, blast furnace linings at a sulphate concentration of 500-600 mg / liter, and cements with special sulphate treatment at a concentration of 1,500-3,000 mg / liter . Above 3000 mg / liter, the sulphate content is therefore also unacceptable even in cement with a special treatment against the action of these salts.

Sulfates react with calcium aluminate in the cement and cause an increase in volume, so that cement products are bursting.

The above range is generally exceeded when using conventional antifreeze and ice melting agents. When using ammonium sulphate, which is the most inexpensive ... · most commonly used, there are other adverse effects, since it contains both a harmful emonium and a too high sulphate ion content, so that it has an adverse effect on concrete and construction. compositions comprising calcium aluminate and calcium hydroxide.

The invention seeks to provide means for melting ice and anti mrsnutí, ^{kt s} er than would ^{be the Copper} of the ros ^^ y, z ^and l ^IR ATA ^{driver. Tyr} about prostl ^ DTY would Mil ^y amortize sn ^iz ene ^even the ^pl ot ^y aqueous flux ^b ez freezing to - ²⁰ ° C and sweep ^{they should} ovlťvnovat strength of concrete, masonry and other building materials containing calcium in strength nor in structure. Also, metals, especially iron and light metals, should not be affected by the product or be neglected to a limited extent. Accordingly, the present invention provides a means for protecting against freezing and melting ice containing water-soluble ammonium and / or sulfur

252419 linseed N ions or other anions, characterized in that it further comprises a phosphate anions, carbonate anions, bicarbonate ions, anions of polycarboxylic acids, or fluoride anions silikofluoridové, _ _tvořící- calcium salts having a water solubility of N ^and IB ^have less ^{than 0.1 g} per 100 ^g water s ^{yp p} te ture of 20 ° C. the abundance of ^0.5 to about 50 $ by weight, preferably 2-25% by weight based on the total weight of the composition and organic 'or inorganic substances, forming highly water systems sglomerované (aicels) having a particle size of less than 1000 µm from the group of highly dispersed silicic acid, magnesium or aluminum silicate, electrolyte poles, especially high molecular weight polyethylene oxides, polynacrylates in an amount of 0.1 to 25% by weight, preferably 0.25 to 5% by weight %, based on the total weight of the composition.

It is therefore essential for the composition according to the invention that the antifreeze and ice-melting composition containing ammonium compounds and / or sulphates further contains such anions that, when the composition is used, insoluble salts are formed that neither calcium aluminum nor calcium hydroxide. This means that both ammonium and calcium ions lose their aggressiveness. This protective effect on building materials, which recently contain a large number of pores and crevices, is further enhanced by the use of pore blocking agents, so that solutions containing ammonium ε / or sulfate ions are prevented from entering the interior of the building materials.

The water-soluble compounds whose anions form with the calcium cation a low water solubility compound are in particular ammonium phosphate and / or alkali metal phosphate and also organic monocarbonates and polycarbonates. Fluorides or fluorosilicates which form water-insoluble calcium compounds may also be used in this case, but their use is limited due to the limitation of their environmental concentration.

Solubility hy^drox^idu vá^pCe (OH) 2 is at rt^plm.p. 18 ° C^celk^em 0^,118^G C^and0 or 0.152 g of Cs (OH) 2, the solubility of the gypsum CaSO4 • H2O is 0.2036 g per 100 g of water. In order to prevent the formation of calcium hydroxide which does not dissolve in water and react with ammonium ions, calcium hydroxide is converted to water-insoluble compounds on the surface of the building materials so that it is not attacked by the ammonium salts contained in the antifreeze and ice dissolving agents. The same principle can be used for calcium aluminate in concrete. Relatively water-insoluble calcium compounds are, for example, the above-mentioned orthophosphates. Reaction of calcium ions in aqueous solution with phosphate snion^Eand h^ydro^Glime phosphate^tý,^který m^and pH^tep^lmp 24 ° C dec a permeability of 0.02 g / 100 g of water and in the presence of ammonia forms a stable hydroxyepatite Ca in the water₃CP0₄)₂JCa (OH)₂<

Similar water-insoluble calcium compounds are also formed in the presence of organic carboxyl and polycarboxylic anions, whereby the effect on the insolubility of the resulting calcium compounds can be enhanced by carbon chain extension. Preferably, the use of salts of dicarboxylic acids, for example potassium or ammonium salts of melonic, succinic, glutaric or sdipic acid is contemplated, these salts being preferable to salts of monocarboxylic acids, for example alkaline or ammonium soaps of palmitic and / or stearic acid, The dicarboxylic acids themselves have a good effect in lowering the freezing point of the water, which means that less ammonium and / or sulfate salts can be used. Alkali metal phosphates and ammonium phosphate also have the same effect of lowering the freezing point of water, so that they are not only a protective agent against the corrosion of building materials, but also an effective part of anti-softening or ice-dissolving agents.

These additives also prevent gypsum formation when the composition contains a sulphate ion, since the water solubility of the secondary calcium phosphate constitutes only 1/10 of the gypsum solubility.

The protective effect on building materials containing water-soluble calcium compounds can be improved by using ammonium and / or sulphate ionic formulations which, compared to calcium hydroxide, calcium aluminate and gypsum, form insoluble calcium compounds, gypsum formation and other thus, the reaction of the calcium hydroxide with the ammonium salts under the above compounds is prevented.

in particular they contain salts of orthophosphoric acid and the salts of organic dicarboxylic acids are somewhat more expensive than, for example, ammonium sulfate. However, it is necessary to take into account that these substances enclose pores of building materials which would otherwise be attacked by the composition and that the composition may therefore be in contact with said materials for a long period of time. Due to this protective effect, it was necessary to use a relatively high proportion of more expensive preservatives, as otherwise the volume of the composition could change in contact with the building materials. It is surprising that water-soluble colloidal dispersions, for example dispersions of silicic acid, aluminum silicate and magnesium silicate with a high surface area, and organic high molecular weight compounds have a synergistic effect with phosphates with dicarbonates which are present as preservatives in the composition of the invention. This may be due to the fact that these highly dispersive substances of high molecular weight or strong agglomeration capability close the pores in the building materials and prevent the ingress of the ammonium and / or sulfate ions contained in the antifreeze or ice melting agent. In this way, the efficacy of the composition according to the invention is increased and it is therefore possible to reduce the content of the more expensive additives somewhat while achieving the same

These cases that effect.

The invention will be illustrated by the following examples

An example of the apparatus is mixed homogeneously with a mixture of 50% by weight urea sulphate, 10% by weight ammonium hydrogen phosphate and

In a mixing weight% of highly disperse silicic acid with a mean particle diameter of 12 microns (Aerosil 200). To this solid ice melting agent is added 1: 2 ice, for example 100 g of the composition is mixed with 200 g of crushed ice. Upon cooling, this mixture can be demonstrated ^{that with} me ^ ^s and ^{p is} ALN ^{and PR} as the temperature ^of 5 ° C -1 ^for new solidification e ^{d d} e drawbar to ^P s. mp -24 ° C. Urea for stejnýc ^{hp d} of m ^greater than ^the zaj ^ Herein ^p and ^k and ^{l of} the mixture nose ^{t id} -8 ° ^C к ^pl p n ^{s t s} u ^h nut occurs te ^p s ^p lo ^I '- ^11.5 ° C.

ammonium, 39.5

0.5 wt

No damage to these materials was observed when the mixture was in contact with the building material for two winter periods; all surfaces were completely unchanged.

A mixer produces a mixture of powdered urea, ammonium sulfate and ammonium hydrogen phosphate containing 42.98 wt% sulfate ion, 16.61 wt% ammonium ion, 3.30 wt% phosphate ion, and 7.53 wt% organic carbon and 2.00 % by weight of the insoluble fraction consisting of aluminum silicate having an average particle size of 0.2 microns (Kaophil 2). 5 cm thick ice layer with an area of 135x200 mm is sprinkled with this agent. 0.405 g of the composition, i.e., 0.25 g of the composition, are used for sprinkling^{15 g /}m².^pand^to se s^lE^dtán^{í pri} temp^{20 May}Deň: 32 ° C.^INni^tonu^tí prostřenu^dabout surface le du lasts 30 seconds, penetrating to the bottom of the ice plate 3 minutes. After 6 minutes, melting occurred, thawing was complete after 8 minutes. Analogous values when using sodium chloride are 30 seconds to penetrate the surface, 3.5 minutes to reach the underside of the plate,

8.5 minutes to thaw © 1-4 minutes to complete thaw. It will be appreciated that the compositions of the present invention can provide faster melting than sodium chloride. At the same time, even after prolonged contact with building materials, they are not disturbed. In contrast, the sodium chloride-containing composition caused considerable damage to the concrete slabs when used for the same period of time, i.e. three times 6 months.

Ο

Example 3 '

A solid mixture is formed containing 63.5% by weight ammonium sulfate, 15.00% by weight urea and 1.5% by weight hydrophilic silica with a mean micrometer particle size (Sipernsit 22 S). Further, it dissolves in water 10% by weight of potassium dicarboxylic acid salts, ε to 30 to 35% by weight of edipic acid salt, 40 to 45% by weight of gluteric acid salt e 20 to 25% by weight of succinic acid salt, this mixture is commonly used as by-product in the manufacture of edipic acid. This amount is dissolved in 20% by weight of water. The solid mixture is used simultaneously with said aqueous solution of potassium salts of dicarboxylic acids as an antifreeze agent and for dissolving ice on concrete surfaces in the form of simultaneous spraying. The advantage of this composition is that it is easy to remove the active substance by wind or road traffic and, moreover, to dissolve the ice very rapidly. The concrete pavement on the streets or bridges are using 1 5-2 ° ^gp ROS ^cl u ed ^to 1 m ² not fully resistant PrOH nemrzání ^{s, p} * rostrata e ^d e is ^the effective EŽ to ^t e ^pl Ota -26 ° C. ¹

Example

The mixture of Example 1 is formed except that 0.5 wt% ethylene oxide polymer with a molecular weight of about 4,000,000 (Polyex 301) is used instead of highly disperse silicic acid (Aerosol 200). The antifreeze protection and the protective effect of concrete and longer building surfaces are analogous to those in Example 1.

Example 5

Mixture of 45% by weight urea, 45% by weight ammonium sulphate, 9% by weight of a mixture consisting of 50% by weight of dibasic phosphate and potassium dihydrogenphosphate and 1% by weight of dispersed silicic acid with an average particle size of 0.021 microns. (Hi-Sil T 600 Thickner Silicon) is used as a protective means against freezing ^{and I} · ^P for ^the extended ^{TEN or} ice. К rozpouě ^I n ^{e l} edu ocház ^{d i} to ^d on te ^pl of ^the -20-ene snor ^{g i c y} are construction materials coronal alkylated ^{y d i} n ^{t yšší} pH EPLO ^d +3 ⁰ C.

Example 6

Mixture of 80% by weight ammonium sulphate, 19% by weight of a mixture of ammonium carbonate and bicarbonate and 1% by weight of sodium polyecrylate with a molecular weight

000 (Good-rite K-739) is used as an ice-freezing agent. The results are comparable to the product of Example 2.

Example 7

A solution containing 35 weight% ammonium nitrate, 10 weight% hydrogenfosforečnenu ammonium E 3 wt% colloidal silica having a solids content of approximately 30% E medium containing silica of a particle size ⁸ mik ^r © m ^{(Nalcoa g} 1 ¹ 3 ⁰⁾ stay ^and alný ^{e p} e ^t to ^{the pl} © - ² 5 ° C is e ly ^from n ^o for a ^live example JEKO heat transfer fluid. This composition protects metals against corrosion when used in the presence of building materials and does not break them even if these materials contain water-soluble calcium compounds.

Example of use

In order to monitor the effect of the antifreeze agent e to dissolve the ice according to the example, it was applied in the form of a 3% aqueous solution not for 6 months on concrete slabs containing a large proportion of pores. The solution was refreshed every month. For comparison, the same boards were immersed only in neutral water, degree of hardness 12. After half a year it was possible to prove that all corners e edges of the boards were straight and sharp and that there were no cracks or change in the volume of the boards.

The flexural strength after 6 months of exposure to the 3% aqueous solution of the above formulation was at an average density of 2.30 kg / d and gave an average of 11.6 N / mm ² , for boards submerged in water at a density of 2.39 kg / dm 3 on average. 7 N / mm ² .

Since the test plates in the above experiment were not damaged by the composition of Example 1 in spite of their relatively high pore content, the composition of Example 1 was applied to the high pore content concrete using a composition containing ^both ammonium and sulphate ions. was carried out for 30 days using a 3% aqueous solution, but at a temperature of + 40 ° C. Even with such increased exposure to the composition, after one month all corners and edges of the test plates were sharp and there were also no cracks, undulations or changes in the plate volume.

Example 8

A solid mixture is formed containing 90 parts by weight of ammonium sulfate, 6 parts by weight of potassium bicarbonate, 3 parts by weight of potassium dihydrogen phosphate KHgPO4 and 1 part by weight of silicic acid (Sipernat 22). The mixture is homogenized in a rotary mixer. The pH of the aqueous solution of the above mixture is close to 7, which indicates the formation of a neutral solution. Sipernat 22 comprises spray dried silica with high suction power and an optimum particle size spectrum. The mean diameter of the primary particles is 18nm, the mean diameter of the secondary particles (agglomerated form) is approximately 100 microns, the particle surface is 190 m ² / g according to BET (DIN 66131), the SiO ₂ content is 98%.

Said mixture can be used for defrosting well below -20 ° C. The 3% solution can be subjected to a 50-fold freeze-thaw cycle on the concrete surface without any detectable changes in the concrete surface.

The mixture is well flowable and at high atmospheric humidity and can be stored either in silos or in bags.

Example 9

Forming a solid mixture comprising 50 parts by weight ^of mo5o ins, 6 parts of sodium bicarbonate, 3 parts by weight of citric acid and 1 part of the material forming the micelles. The micelle-forming agent may be a sodium salt of polyacrylate (white free-flowing powder) having a molecular weight of 5,100 on average, a pH of 1% aqueous solution ranging from 6.0 to 8.0, a polymer content of 71.1% by weight, sodium 18.9%, water content 10%.

The solid mixture thus obtained is used on rails and rails. It defrosts the ice considerably slowed down even during further snowfall.

to defrost electric rails on ulii frozen snow and mileage. Another freeze is

Example 10

Blending gives a solid mixture containing 72 parts by weight of ammonium nitrate, 15 parts by weight of ammonium bicarbonate, 10 parts by weight of potassium dihydrogen carbonate and 3 parts by weight of Hectorite. Hectorite is a micelle forming substance c; pilgrimages to min tmor and lioni here. It consists essentially of magnesium silicates and contains 17% magnesium oxide, a free-flowing powder with a medium particle size of pos 200 mesh (75 microns), most of the particles to a diameter in the range of 10 to 20 microns.

This product can be used for thawing wherever water gets into the soil after it has been bred ε where good nitrogen, potassium and phosphorus fertilization is desirable for plant growth in the following year.

EXAMPLE 11 parts by weight of ammonium sulphate, 3 parts by weight of sodium lauric acid, 1 part by weight of polyacrylamide having a molecular weight in the range of 650,000 to 800,000 are mixed into a powdered thawing composition. On concrete and on calcium-containing building materials, a water-insoluble calcium salt of lueric acid is formed whose solubility in 100 g of water at only 15 ° C is only 0.004 g.

Polyacrylamide, which is a micelle-forming substance in the mixture, can be used up to a median particle size of about 000,000 with the same effect (e.g., Superfloc, Cynamid Company.)

The composition of the above composition may be used to thaw even to -24 ° C.

Example of use

To monitor the effect of the antifreeze composition to dissolve the ice of the example, the composition was applied as a 3% aqueous solution for 6 months to large pore concrete slabs. The solution was refreshed every month. For comparison, the same boards were immersed only in neutral water, degree of hardness 12. After half a year it was possible to prove that all corners p of the board edge were straight ε sharp and that there were no cracks or change in the board volume.

The bending strength after b months of treatment with the 3% aqueous solution of the above formulation was at an average of 11.6 N / mm at a density of 2.30 kg / dm, for slabs immersed in water at an average of 2.39 kg / d &lt; 11.7 N / mm ² .

Since the test plates in the above experiment were not damaged by the composition of the Example in spite of their relatively high pore content, the composition of Example 1 was still supported on a high pore content concrete using both ammonium and sulphate ion compositions. carried out for 30 days using a 3% aqueous solution, but at a temperature of + 40 ° C. .1 in such enhanced application, all corners f of the test plate edges were sharp after one month and there were also no cracks, undulations or changes in the plate volume.

Thus, it will be appreciated that when the composition of the present invention is used to dissolve ice and to protect against freezing, it is possible to provide a high protective effect on concrete with a high pore content, so that both sulphate and ammonium ion compositions can be used. By using phosphate-free comparative solutions and highly disperse silicic acid, a significant reduction in flexural strength and cracks, ripple and volume changes were already observed on the test plates at room temperature.

Application example В

In 1000 ml of an aqueous solution of sodium chloride in the solution of the composition of Example 1, a black plate in strips at 20 ° C was stored for 10 days with agitation. Using a 5% sodium chloride solution, the weight loss was 470 mg / dm @ 2, the loss using a 5% anti-freezing solution of the invention was 4.5 mg / dm @ 2. d. In the solutions described above, and in addition in a 5% aqueous urea solution, the precipitate was collected by filtration, ashed after 4 days, and the oxidized ash was weighed and analyzed. The following amount of ash by weight was obtained.

NaCl; 1, B0%, urea: 0.20%, Example 1: 0.05%.

In general, it is preferred that the anionic content of the low-permeability calcium compounds is in the range of 0.5 to 50% by weight, preferably 2 to 25% by weight, and the proportion of highly dispersing substances is 0.1 to 25% by weight. %, preferably 0.25 to 5% by weight, based on the total weight of the composition. The substances forming the dispersion systems can also be polyelectrolytes, in particular high molecular weight polyethylene oxides, polyacrylates or polyacrylamides.

Claims (3)

A composition for the protection against freezing and melting of ice containing water-soluble ammonium and / or sulfate ions and optionally other anions, characterized in that it further comprises phosphate anions, carbonate anions, bicarbonate ions, polycarboseylic acid anions, fluoride or silicofluoride calcium-forming anions having a water solubility of less than 0.1 g per 100 g of water at 20 ° C in an amount of 0.5 to 50% by weight, preferably 2 to 25% by weight, based on the total weight of the composition and organic or inorganic substances forming highly agglomerated systems in water - micelles having a particle size of less than 1000 .mu.m, from the group of highly dispersed silicic acid, magnesium or aluminum silicate, polyelectrolytes, in particular high molecular weight polyethylene oxides, polyacrylates or polyacrylamides in an amount of 0.1 to 25% by weight, preferably 0.25 to 5% by weight based on the total weight of the composition. 2. A composition according to claim 1, wherein the anion with low solubility of the calcium salts in water is an organic dicarboxylic acid salt or an organic dicrboxylate containing at least three carbon atoms. 3. A composition according to claim 2, wherein the organic dicarboxylate comprises a potassium salt and / or an ammonium salt of a mixture of a balloon, succinic, glutaric and / or adipic acid.