DK170538B1 - Thickened toilet bowl cleaner - Google Patents

Abstract

A thickened aqueous composition comprising at least one compound acid or acidic salt, a thickening agent which is at least one of the compounds selected from the group consisting of compounds of the formula: <CHEM> wherein R, R1 R2, R3, R4 and R5 are specified substituent groups, and optionally a strong ionic salt, the thickening agent and the acid or acidic salt being together substantially water soluble, and wherein the thickened aqueous composition has a viscosity of not less than 30 centipoise at 25 DEG C when measured with a Brookfield RVT viscometer at 50 rpm using a No. 1 spindle.

Description

The present invention relates to aqueous formulations of acids or acid salts and, more particularly, to novel formulations of these acids or acid salts containing a thickener.

In this specification, acidic salts denote the substances which, in an aqueous solution, release protons.

Aqueous solutions of acids and acidic salts have long been used in detergents. Such agents include WC basin cleaners, metal cleaners and polishes, rust stain removers, denture cleaners, metal coating removal agents, common hard surface cleaners and disinfectants.

15

It has been found that a desirable property of many of the aforementioned agents is that they have sufficient viscosity to effectively apply the agent to surfaces, for example by brushing, or to allow the agent 20 to remain in contact. with the surface in sufficient time for it to work. The last feature is of particular relevance when cleaning sloping surfaces, such as those found in WC basins, where long-term contact between the agent and the basin is necessary for effective cleaning.

25

Many such agents are known in the art which have the necessary viscosity characteristics. Most of such agents achieve their viscosity using one or more of the following thickeners: (a) cellulose derivatives, for example sodium carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose; 35 DK 170538 B1 2 *? (b) rubbers such as xanthan gum, (c) acrylic acid polymers such as Carbopol (registered trademark of B.F. Goodrich) (d) nonionic surfactants such as nonylphenol ethoxylates; (e) poly (ethylene oxide) resins such as Polyox (registered trademark of Union Carbide); (f) anionic surfactants such as alkylbenzenesulfonates and alkyl ether sulfates; and (g) sodium silicates such as sodium metasilicate.

Most of these thickening agents, although capable of effectively increasing the viscosity of agents containing aqueous acid or acidic salts, have some drawbacks in their use.

The cellulose derivatives and rubbers tend to hydrolyze upon storage, resulting in a decrease in the viscosity of the agent. They are also generally difficult to dissolve, as intensive mixing is sometimes required to dissolve.

Acrylic acid polymers are generally useful only in solutions having a pH near neutral and higher. They are also prone to hydrolyze upon storage, and to obtain viscosity, they must be neutralized with fairly strong alkali.

Nonionic surfactants have the disadvantage that high concentrations of about 5 in DK 170538 B1 are usually required 3 to 10% of them to obtain satisfactory viscosity, making them expensive to use.

The water-soluble poly (ethylene oxide) resins also require 5 high concentrations to achieve the desired viscosity of the agent and further exhibit significant instability in some acid solutions.

Sodium silicates can provide gels with aqueous acids or aqueous acidic salts. However, in the development of viscosity in an agent, it has been found that viscosity generally develops over a long period of time, for example as much as 12 hours. In commercial fabrication processes, this is often inconvenient. It should also be noted that such gels, upon storage, tend to be broken down into small pieces, which is in many cases undesirable.

Other thickening agents and formulations described in the art related to formulations of an aqueous acid and / or an acidic salt include:

British Patent No. 1,443,244 (Reckitt & Colman Products Limited) disclosing a thickening agent of the formula:

(A) x-H

30 R - W

35 for thickening aqueous solutions of mineral acids and acidic salts of strong inorganic acids.

British Patent No. 2,071,688 (Jeyes Limited), which describes as a thickener a mixture of: (a) a compound of formula (I) or (II) which is substantially insoluble in acid; and (b) a substantially acid-soluble, cationic or nonionic surfactant for thickening aqueous formulations of inorganic acids or acid salts of strong inorganic acids.

R, R, / R-N R - N -> 0/2 2 2 20 (I) (II)

These formulations require a substantially acid-soluble cationic or anionic surfactant to obtain thickening.

U.S. Patent No. 3,786,091 (Boising), disclosing a phosphoric acid-containing paste base, prepared by preparing a finely divided aqueous dispersion of a long chain amine, heat this dispersion, adding the preheated phosphoric acid thereto with vigorous stirring at elevated temperature. until neutral, and then stir the resulting mixture until cold.

U.S. Patent No. 4,021,377 (Borchert et al.), Which discloses a citric acid amine reaction product obtained by mixing citric acid and water-soluble or water-dispersible amine in water. until all the citric acid is dissolved. Generally, the reaction is accompanied by a temperature increase to about 40 ° C over an hour. The resulting solution containing amine salts of citric acid and citric acid amides is viscous. It should be noted that the concentrations of citric acid and the exemplified amines are extremely high, for the exemplified amines being in the range of 12-45 wt-10% and for the citric acid 19.2 wt%. In addition, only the amines monoethanolamine, diethanolarain and triethanolamine are exemplified.

U.S. Patent No. 3,520,820 discloses amine-containing corrosion inhibitors containing aliphatic amines and acetic acid, which are mixed with nonionic emulsifiers to form liquid emulsions which can be dispersed in cold water. The formulations contain only from 0.1 to 0.6 moles of acid per day. moles of the fat amine and are thus not acidic formulations.

U.S. Patent No. 3,925,229 describes the preparation of a phosphoric acid-containing paste to be used for the purification of metals. No non-paste formulations are disclosed.

25

French Patent No. 2,459,830 discloses cleaning formulations that can be used for cleaning and removing coating from sanitary equipment such as toilet sinks. The invention is directed to aqueous solutions of sulfamic acid whose viscosity is adjusted and stabilized by the addition of four types of viscosity adjusting or thickening agents.

U.S. Patent No. 4,021,377 discloses liquid detergent formulations containing the reaction product of citric acid 35 and a water-soluble or water-dispersible amine. The reaction product 170 is said to be a mixture of amine salts of citric acid and citric acid amides.

European Patent No. 0,228,501 discloses a thickened aqueous liquid toilet bowl detergent which may include citric acid or a citrate and an amine as a thickening agent. The script also suggests that the citric acid may be replaced by another dicarboxylic acid.

The present inventor has recognized the difficulties of the prior art thickeners for such formulations of aqueous acids or acid salts. Accordingly, the present invention seeks to provide formulations that are alternative to the prior art.

Accordingly, the present invention provides a thickened aqueous liquid formulation for cleaning toilet sinks having a pH not exceeding 6.5 and having a viscosity of not less than 30 mPa * s at 25 ° C, measured with a Brookfield 20 RVT viscometer at 50 rpm using a spindle # 1, the formulation comprising at least one acid or an acid salt, optionally a strong ionic salt, and as the only organic means to thicken the formulation and impart the said viscosity in an amount of 0 , 1 to 10% by weight of at least one compound of the formula / R1, R - N (I) 30, R2 wherein R contains 8 to 24 carbon atoms and is a substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or alkenyl group, Rx is hydrogen or a substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or alkenyl group, R2 is hydrogen or a substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or alkenyl group, with the proviso that if either R, R 2 or R 2 is an alkyl or alkenyl group derived from a fatty acid 5 obtained from a natural oil or natural fat or equivalent synthetic fatty acid or is an alkaryl group containing from 8 to 12 carbon atoms in the alkyl moiety . then the other substituents are not respectively of the formula:

10 (A) x-H and (A) y-H

wherein A is either ethoxy or propoxy and x, y are independently 1, 2 or 3, the thickener and the acid or acid salt together being substantially water-soluble; with the exception that the acid is not citric or not a dicarboxylic acid, or that the acidic salt is not a citrate or the salt of a dicarboxylic acid.

In another aspect, the present invention consists in a process for forming a thickened aqueous solution consisting of dissolving in water (a) at least one compound selected from the group consisting of acids and acid salts, (b) a thickening agent wherein at least one of the compounds is selected from the group consisting of compounds of formula: 25 / R1 R - N (I) 30 in which R, Rx and R 2 have the above meanings, and optionally (c) a highly ionized salt, wherein the thickener and the salts together are substantially water-soluble in amounts sufficient to give a viscosity of not less than 30 mPa * s at 25 ° C, measured with a 35 Brookfield viscometer at 50 rpm. minute, DK 170538 B1 8 using a spindle # 1; with the exception that the acid is not citric acid or is not a dicarboxylic acid, or that the acidic salt is not a citrate or the salt of a dicarboxylic acid.

In the context of this specification, substantially water-soluble means that a thickening agent and an acid or an acid salt selected according to the invention together will either be soluble in water at 25 ° C or at least form a foggy solution which does not separate into two phases during normal storage.

It will be appreciated that the formulations of the present invention are readily distinguishable from those described in the aforementioned British Patent Application No. 2,071,668 (Jeyes Limited) in that the formulations desired to be protected therein are addressed. largely acid-insoluble amines or amine oxides which require a mainly acid-soluble, cationic or nonionic surfactant 20 to obtain the thickening.

In contrast, the present invention is limited to either amines or amine oxides which together with the selected acid or acid salt are substantially water-soluble without requiring a cationic or nonionic surfactant to obtain the solution. and thickening. It should also be noted that British Patent No. 2,071,688 states that neither the amine, the amine oxide, the cationic, surfactant nor the nonionic surfactant alone with an aqueous solution of an inorganic acid or an acid salt will cause thickening.

It will also be noted that the aforementioned U.S. Patent No. 4,021,377 (Borschert et al.) Does not disclose, nor does it suggest, that thickening will occur in the formulations which are contemplated in the present invention. , without resorting to heating the amine with citric acid to form various reaction products. The present inventor believes that the teachings of this US patent known that the reaction products 5 of citric acid and an amine are viscous in solution were merely an observation made by the inventors, and perhaps not unexpectedly, given the high concentration of reactants obtained used. In fact, there is no teaching in this US patent showing that the inventors are aware that concentrations of amines as low as those preferred and exemplified in the present invention will form thickened acid solution formulations or solutions of acid salts. The real thrust of this patent is a process for preparing a concentrated solution of desired reaction products which appears to be viscous at this high concentration.

To show this, the present invention prepared aqueous solutions containing 5% by weight of anhydrous citric acid and 2% by weight of mono-, di- or triethanolamine. No thickening was noticed in any of these solutions.

Similarly, U.S. Patent No. 3,786,091 (Boising) states that it is necessary to prepare a paste to obtain the reaction products between the selected amine and phosphoric acid by heating them together.

Thus, in the simplest embodiment of its invention, Boising disperses the selected amine in water, heats the dispersion to between 40 ° C and 100 ° C, and then adds at least a neutralizing amount of phosphoric acid first heated to between 40 ° C and 50 ° C. 120 ° C. Stirring is continued until the temperature drops to between 5 ° C and 25 ° C, and the resulting formulation is a paste consisting of the reaction products between phosphoric acid and the selected amine. Bolsen DK 170538 Bl 10 also discloses that other acids, such as sulfuric acid, hydrochloric acid, tartaric acid, oxalic acid, hydrofluoric acid and nitric acid, can be used as an addition to a paste base according to his invention. He further describes that other amines can also be used as additives.

The present invention can be distinguished from Boising when it is taken into account that the amines of the Boising invention must be derivatives of substituted or unsubstituted hydrocarbons having 8 to 24 carbon atoms, the selected amine must react with phosphoric acid upon heating to obtain viscosity, and there is no suggestion or suggestion that acids other than phosphoric acid are useful. Further, with respect to acid salts, it is noted that Boising refers to ammonium chloride as an adjuvant.

In contrast, the present invention demonstrates that thickening can be achieved with a variety of acids and acidic salts, no heating is required to obtain thickening, and the present inventor believes that amines other than Boisings are useful.

In the above formula I, the group R contains from 8 to 24 carbon atoms. Preferably the group R contains from 8 to 24 carbon atoms in an unsubstituted alkyl or alkenyl group.

Preferably, the groups Rx and R2 are independently a hydrogen atom or a lower, unsubstituted alkyl group, wherein lower refers to groups containing 1 to 4 carbon atoms, or a substituted alkyl group. More preferably, the groups R 1 and R 2 are independently a hydrogen atom or a lower, unsubstituted alkyl group. Most preferably, the groups Rx and R2 are independently a hydrogen atom or a methyl group.

DK 170538 B1 11

Preferred thickeners of the present invention which are primary amines include Farmin 0 (Farmin is a registered trademark of Kao Soap Co.) or Gen-5 amine OL-IOOD (Genamine is a registered trademark of Hoechst), both of which are mainly oleylamine, and Farmin T or Genamin TA100D, both of which are distilled sebaceous fat amines. These thickening agents are capable of thickening organic acids including formic acid, acetic acid, DL lactic acid, glycolic acid, pentetic acid, ascorbic acid, chloroacetic acid and propionic acid. In some cases, a small addition of a highly ionized salt, such as sodium chloride, is required to obtain sufficient viscosity of the formulation in the preferred concentration range of the thickening agent. Naturally, increasing the concentration of the thickener will increase the viscosity in many cases. However, due to the relatively low cost of such salts, it is preferred to use a mixture of thickening agent and highly ionized salt to obtain the desired viscosity. However, it must also be taken into account that the addition of extra thickening agent can raise the pH and thereby reduce the effectiveness of the agent.

Preferred thickeners of the present invention, which are tertiary amines, include Genamine SO302D (distilled dimethyl soybean oil grease) and Genamine TA302D (distilled dimethyl sebaceous fatamine). These amines can thicken organic acids including formic acid, acetic acid, DL lactic acid, ethylenediaminetetraacetic acid, glycolic acid and propionic acid 30, and inorganic acids including sulfamic acid, phosphoric acid, boric acid, hydrofluoric acid and sulfuric acid. For the reasons outlined above, these amines generally require the addition of a highly ionized salt, such as sodium chloride, to obtain sufficient viscosity of the formulation in the preferred concentration range of the thickening agent.

DK 170538 B1 12

Preferred thickening agents of the present invention which are tertiary amines capable of thickening acidic salts include Genamine TA302D and Genamine SO302D. Genamine 5 SO302D may thicken aqueous solutions of aluminum sulfate, sodium hydrogen sulfate, sodium dihydrogen orthophosphate, di-sodium ethylenediamine tetraacetate and aluminum potassium sulfate, with a small addition of a highly ionized salt such as sodium chloride being required in some cases; the sodium chloride is necessary to obtain appropriate viscosity of the agent as previously described.

Preferred thickening agents of the present invention, which are primary amines capable of thickening acidic salts, include Farmin O, Genamin OL-IOOD, Farmin T and Genamine TA-100D. These amines can thicken aqueous solutions of aluminum acetate.

Other amines considered by the present invention to be within the scope of the invention include;

Farmin DMON (Dimethyloleylamine),

Onamine R 1416 (N-alkyl (Cu-C 16) -dimethylamine);

Genamine 14R302D (tetradecyldimethylamine, distilled); Genamine 16R302D (hexadecyldimethylamine, distilled);

Genamine 14R100D (tetradecylamine, distilled);

Genamine 16R100D (hexadecylamine, distilled);

The following amines available from KenoGard: 30 Amine 2MOL (dimethyloleylamine)

Amine 28 (dioctylamine)

Amine 210 (didecylamine)

Amine M28 (methyldioctylamine) and Amine M210 (methyldidecylamine).

35 DK 170538 B1 13

It should be noted that the aforementioned preferred amines are in fact mixtures of a number of amines with an amine as the dominant one. The present inventor believes that the dominant amine may function by solubilizing the 5 amines present in smaller amounts in the formulations of the present invention.

For example, Farmin 0 is predominantly oleylamine having an approximate alkyl content of 6% C14, 13% C16 and 81% C18, while Genamin SO302D has an approximate average chain length distribution of 2% C14, 15% C16 and 83% C18 and Genamin TA302D has an approximate average chain length distribution of 5% C14, 30% C16 and 65% C18.

Furthermore, amines and amine oxides of the invention can generally be derived from natural or synthetic sources of sebum, soybean oil, oleic acid, palmitic acid, myristic acid, linoleic acid, linolenic acid, castor oleic acid or hexadecanoic acid.

In general, the acids directed by the present invention include inorganic acids such as sulfuric acid, hydrofluoric acid, boric acid, sulfamic acid and phosphoric acid, and the organic acids formic acid, acetic acid, DL-lactic acid, propionic acid and ethylenediaminetetraacetic acid, glycolic acid, , ascorbic acid, pentetic acid and chloroacetic acid.

The acidic salts to which the present invention is directed include acid salts of inorganic or organic acids such as sodium hydrogen sulfate, sodium dihydrogen orthophosphate, disodium ethylenediaminetetraacetate, aluminum acetate, aluminum sulfate and aluminum potassium sulfate.

The concentration of acid or acidic salt can be varied over a wide range, depending on the final use of the formulation. In some cases, particularly where a strong acid such as hydrofluoric acid is used and an almost neutral product is required, the concentration of acid or acidic salt may be as low as 0.01% by weight.

In other cases, the concentration of acid or acidic salt may be above 90%.

In general, the concentration of acid or acid salt 10 will range from 0.1 to 30% by weight.

In use, the thickener will generally be present at a concentration in the formulation of 0.1 to 10% by weight. Preferably, the concentration in formulation 15 will range from 0.4 to 5.0% by weight.

To obtain a desired viscosity in the formulation, the concentration of the thickener can be varied accordingly. However, in some cases it has been found that it is not possible to obtain sufficient viscosity of the formulation for certain applications. In such cases, addition of a salt having a high ionic strength has been found to increase the viscosity of these formulations. However, in most cases, the concentration of thickening agent and high ionic strength salt will be optimized to produce a cost-effective formulation with the desired viscosity. Generally, the ionized salts will be selected from alkali metal halides or sulfates and ammonium halides or sulfates. Such suitable salts include sodium chloride, sodium sulfate, potassium sulfate, potassium chloride, ammonium chloride and the like.

It has further been found in some cases that while the formulation is thick, clear and stable at room temperature, it is necessary to obtain a satisfactory upper and lower cloud point for the formulation to add another ingredient such as a salt with a strong ionic effect of the type mentioned above, a cationic, nonionic or amphoteric surfactant or solvent miscible with the formulation, for example ethanol, isopropanol, butyl Icionol and the like (Icionol is a trademark of ICI) and Dowanol DPM (dipropylene glycol methyl ether. Dowanol is a trademark of Dow Chemicals). Such addition of salt, surfactant 10 or solvent ensures that the formulation will remain stable under hot and cold weather conditions.

A variety of other ingredients can be added to the formulations of the invention depending on their end use. Thus, bactericidal agents, surfactants including anionic, nonionic, cationic and amphoteric, complex binders, corrosion inhibitors, perfumes and dyes can be added.

A principal advantage of the present invention is that an aqueous acid or aqueous solution of an acidic salt can be readily and conveniently thickened. In general, the steps for obtaining such thickened formulations will be - (a) adding an appropriate amount of acid or acid salt to water and stirring to dissolve, (b) adding a thickening agent of the present invention to the solution and stirring until is dissolved, and (c) add other ingredients if necessary, stirring to dissolve.

It will be appreciated that since the thickener of the present invention is defined as being soluble in the selected solution of acidic salt or acid, and since it will generally be easy to moisten, step (b) above will proceed relatively quickly, in contrast. for many thickening agents according to the prior art which, although DK 170538 B1 16 may be soluble, are often difficult to moisten.

Other advantages of the thickening agents of the present invention are that they are relatively inexpensive and in use provide even, homogeneous, instantaneous thickening. Further, the thickened formulations are stable in viscosity. For example, the present inventor has found that a citric acid formulation thickened with Farmin 0 did not undergo any significant change in viscosity when stored at room temperature for 12 months.

A further advantage is that the present inventor has found that the formulations of the invention have certain surfactant and corrosion inhibiting properties. The first discovery means that substances which are immiscible with water, such as fragrances, can be solubilized directly in a formulation according to the invention without requiring the addition of emulsifiers or auxiliary solvents, and in formulations in which surfactant properties are required. less or no additional surfactant is required.

The present inventor has also found that if there is just enough of an acid or an acid salt present to dissolve just a thickener of the present invention, then a pH-neutral formulation can be obtained. Thus, Farmin 0 can be used to thicken lactic acid at pH 6.5. The advantage of this discovery is that it can be used in liquid aqueous detergents in general.

The present inventor has further found that an acid or an acid salt, which is generally considered insoluble in water at room temperature, can be dissolved using a thickening agent according to the present invention, thickening occurs. The viscosity can be increased by using a highly ionized salt, such as sodium chloride. To prepare such formulations, the acid is dispersed in the water and the thickener is added with mixing. It will be seen that as the acid and thickener dissolve, the viscosity of the solution increases.

Preferred formulations of this type include ethylenediaminetetraacetic acid with Genamin SO302D as a thickener and pentetic acid with Farmin 0 as a thickener.

Following are a number of Examples 1 to 35 of the present invention along with Comparative Examples 1A and 1B, in which the viscosity, in mPa · s, was determined by a Brookfield RVT viscometer using a spindle and a speed which fit at 25 ° C. Note that the thickener is marked with an asterisk in each case.

All the examples (except Nos. 17 and 27) were prepared by dissolving the acid or acid salt, adding the thickener and mixing until dissolved, and then adding the other ingredients while mixing until dissolved.

25

Examples 17 and 27 were prepared by dispersing the acid or acidic salt in water, adding the thickener and mixing until the solution occurred, followed by sodium chloride (if necessary) until a satisfactory viscosity was obtained.

Note that all examples were prepared under normal laboratory conditions.

DK 170538 B1 18

For comparison 5 Example 1A

Water

Viscosity, spindle 1 speed 20 rpm: 3.5 mPa * s speed 50 rpm: 6.5 mPa * s 10 spindle 2 speed 20 rpm: 0 mPa * s speed 50 rpm: 5.5 mPa.s

Example IB 15 5% by weight aqueous solution of anhydrous citric acid

Viscosity, spindle 2 speed 20 rpm: 0 mPa * s speed 50 rpm: 5.5 mPa * s DK 170538 B1

Example 1 19% by weight DL lactic acid 88% 5.0 * Farmin O 2.0 5 Sodium chloride 0.3

Water 92.7

Viscosity (spindle # 2, speed 20 rpm at 25 ° C) 820 mFa * pH 2.9 10

Example 2 wt% DL lactic acid 88% 0.85 * Farmin O 2.0 Sodium Chloride 0.1

Water 97.05

Viscosity (spindle # 2, speed 20 rpm at 25 ° C) 740 mPa * pH 6.5 20

Example 3% by weight

Formic acid 88% 4.1 * Farmin 0 2.0 25 Sodium chloride 0.05

Water 93.85

Viscosity (spindle # 2, speed 50 rpm at 25 ° C) 58 mPa * pH 2.5 DK 170538 B1

Example 4 20% by weight

Formic acid 88% 4.1 * Genamine TA100D 2.0 5 Sodium Chloride 0.05

Water 93.85

Viscosity (spindle # 1, speed 50 rpm at 25 ° C) 30 mPa * pH 2.45 10

Example 5% by weight

Glacial acetic acid 4.7 * Farmin O 2.0 Sodium chloride 0.25

Water 93.05

Viscosity (spindle # 2, speed 50 rpm at 25 ° C) 160 mPa * pH 3.6 20

Example 6% by weight

Glacial acetic acid 4.7 * Genamine TA100D 2.0 Sodium chloride 0.3

Water 93.0

Viscosity (spindle # 2, speed 20 rpm at 25 ° C) 660 mPa * pH 3.6 30 DK 170538 B1

Example 7 21% by weight

Propionic acid 5.8 * Farmin 0 2.0 5 Sodium chloride 0.3

Water 91.9

Viscosity (spindle # 1, speed 50 rpm at 25 ° C) 58 mPa * pH 3.7 10

Example 8% by weight

Formic acid 88% 4.1 * Genamine SO302D 2.0 Sodium chloride 1.3

Color 0.005

Water 92.6

Viscosity (spindle # 2, speed 50 rpm at 25 ° C) 160 mPa * s 20 pH 2.4

Example 9% by weight

Formic acid 4.1 25 * Genamine TA302D 2.0

Sodium chloride 1.6

Water 92.3

Viscosity (spindle # 2, speed 20 rpm at 25 ° C) 500 mPa * s 30 pH 2.5 DK 170538 B1 22

Example 10 - wt% DL lactic acid 88% 5.0 * Genamine 16R302D 2.0 Sodium chloride 2.0

Perfume 0.2

Color 0.005

Water 88.8

Viscosity (spindle # 1, 10 speed 20 rpm at 25 ° C) 100 mPa * s pH 2.75

Example 11% by weight Sulfamic acid 7.6 * Genamine SO302D 2.0

Sodium Chloride 1.1

Water 89.3

Viscosity (spindle # 1, 20 speed 50 rpm at 25 ° C) 77 mPa * pH 0.8

Example 12% by weight Sulfamic acid 7.6 * Genamine TA302D 2.0

Sodium Chloride 1.7

Water 88.3

Viscosity (spindle # 2, 30 speed 20 rpm at 25 ° C) 390 mPa * pH 0.9

Example 13 DK 170538 B1 23% by weight

Phosphoric acid 85% 5.9 5 * Genamine SO302D 2.0

Sodium Chloride 1.1

Water 91.0

Viscosity (spindle # 2, speed 50 rpm at 25 ° C) 170 mPa * s 10 pH 1.35

Example 14

Phosphoric acid 85% 5.9 15 * Genamine TA302D 2.0

Sodium Chloride 1.5

Water 90.6

Viscosity (spindle # 2, speed 20 rpm at 25 ° C) 395 mPa * s 20 pH 1.35

Example 15% by weight

Sulfuric acid, wife. 3.83 25 * Genamin SO302D 2.0

Water 94.17

Viscosity (spindle # 2, speed 20 rpm at 25 ° C) 890 mPa pH 0.85 30 DK 170538 B1

Example 16 24% by weight

Sulfuric acid, wife. 3.83 5 * Genamin TA302D 2.0

Water 94.2

Viscosity (spindle # 2, speed 20 rpm at 25 ° C) 375 mPa pH 0.9

Example 17% by weight

Ethylenediaminetetraacetic acid 0.8 * Genamine SO302D 2.0 Sodium chloride 1.7

Water 95.5

Viscosity (spindle # 2, speed 20 rpm at 25 ° C) 730 mPa * pH 5.55 20

Example 18 wt% A12 (SO4) 3 16H2O 6.7 * Genamine SO302D 2.0 Sodium Chloride 0.3

Water 91.0

Viscosity (spindle # 2, speed 20 rpm at 25 ° C) 390 mPa * pH 3.65 30 5¾ DK 170538 B1

Example 19 25% by weight Alk (SO4) 2-12H20 10.0 * Genamine SO302D 2.0 Sodium Chloride 0.1

Water 87.9

Viscosity (spindle # 2, speed 50 rpm at 25 ° C) 240 mPa * pH 3.75 10

Example 20% by weight

Sodium Hydrogen Sulfate 9.5 * Genamine SO302D 2.0 15 Water 88.5

Viscosity (spindle # 2, speed 20 rpm at 25 ° C) 1500 mPa * pH 0.9 20 Example 21 wt%

Sodium dihydrogen ortho-phosphate dihydrate 12.0 * Genamine SO302D 2.0 25 Water 86.0

Viscosity (spindle # 2, speed 20 rpm at 25 ° C) 585 mPa s pH 5.2 DK 170538 B1

Example 22 26% by weight

Disodium ethylenediamine tetraacetate 6.6 5 * Genamine SO302D 2.0

Sodium Chloride 1.7

Water 89.7

Viscosity (spindle # 2, speed 20 rpm at 25 ° C) 785 mPa * s 10 pH 5.8

Example 23 wt% DL lactic acid 88% 8.0 15 * Genamine TA100D 2.0

Sodium chloride 0.6

Water 89.4

Viscosity (spindle # 2, speed 20 rpm at 25 ° C) 1255 mPa * s 20 pH 2.7

Example 24% by weight

Glycolic acid, 70% 8.5 * Farmin 0 2.0

Sodium chloride 0.2

Water 89.3

Viscosity (spindle # 2, speed 20 rpm at 25 ° C) 660 mPa * s 30 pH 2.5 0 DK 170538 B1

Example 25 27% by weight

Glycolic Acid, 70% 8.5 * Genamine SO302D 2.0 Sodium Chloride 1.8

Water 87.7

Viscosity (spindle # 2, speed 50 rpm at 25 ° C) 290 mPa * pH 2.3 10

Example 26 wt% L (+) - Ascorbic Acid 13.75 * Farmin 0 2.0 15 Sodium Chloride 0.5

Water 83.75

Viscosity (spindle # 2, speed 20 rpm at 25 ° C) 705 mPa pH 2.9

Example 27% by weight DTPA (Pentetic Acid) 1.3 * Farmin 0 2.0 25 Water 96.7

Viscosity (spindle # 2, speed 20 rpm at 25 ° C) 1185 mPa * pH 3.2

Example 28 DK 170538 B1 28% by weight

Chloroacetic acid 8.6 * Farmin 0 2.0 5 Water 89.4

Viscosity (spindle # 1, speed 50 rpm at 25 ° C) 96 mPa * pH 1.7 10 Example 29 wt%

Hydrochloric acid, 50% 3.1 * Genamine SO302D 2.0

Sodium chloride 0, 6 15 Water 94.3

Viscosity (spindle # 2, speed 50 rpm at 25 ° C) 370 mPa * pH 1.2 20 Example 30 wt%

Boric Acid 5.0 * Genamine SO302D 2.0

Sodium Chloride 1.4 Water 91.6

Viscosity (spindle # 1, speed 20 rpm at 25 ° C) 280 mPa * s pH 6.2 DK 170538 B1

Example 31 29% by weight

Aluminum acetate 5.3 * Farmin O 2.0 5 Water 92.7

Viscosity (spindle # 2 speed 20 rpm at 25 ° C) 1055 mPa * pH 5.2 10 Example 32 wt%

Sulfuric acid, wife. 3.83 * Genamine 14R302D 1.00 * Genamine 16R302D 1.00 Sodium Chloride 3.00

Water 91.17

Viscosity (spindle # 1, speed 20 rpm at 25 ° C) 212 mPa * s

pH

20

Example 33% by weight

Sulfuric acid, wife. 7.7 * Genamin 16R302D 2.0 25 Water 90.3

Viscosity (spindle # 2, speed 20 rpm at 25 ° C) 556 mPa * s

pH

DK 170538 B1

Example 34 30% by weight

Hydrochloric acid, 30% technical 9.5 * Genamine 14R302D 2.0 Sodium chloride 3.0

Water 85.5

Viscosity (spindle # 1, speed 50 rpm at 25 ° C) 105 mPa * s

pH

10

Example 35% by weight

Hydrochloric acid, 30% technical 53.0 * Genamine TA302D 2.0 15 Water 45.0

Viscosity (spindle # 2, speed 50 rpm at 25 ° C) 380 mPa * s

pH

It should be noted that the viscosity of Example 1, compared to the viscosity of water (1A) and 5% by weight of citric acid (IB), is significantly greater. A comparison with an aqueous solution of the thickener was not possible in this case, as the thickener is water insoluble.

25

Examples 1 to 35 described herein can be used for, for example, WC basin cleaners, metal and polish cleaners and the like, as well as applications such as gel batteries.

ft

Claims (16)

1. Thickened aqueous liquid formulation for the purification of 5 toilet sinks having a pH not exceeding 6.5 and having a viscosity of not less than 30 mPa * s at 25 ° C, measured with a Brookfield RVT viscometer at 50 rpm. using a spindle # 1, the formulation comprising at least one acid or an acid salt, optionally a strong ionic salt, and as the only organic means to thicken the formulation and impart the said viscosity in an amount of 0 1 to 10% by weight of at least one compound of formula 15 R - (I) 2 wherein R contains 8 to 24 carbon atoms and is a substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or alkenyl group, Rx is hydrogen or a substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or alkenyl group, R 2 is hydrogen or a substituted or unsubstituted alkyl, aryl, alkaryl, aralkyl or alkenyl group, with the proviso that if either R, Rx or R 2 is an alkyl or alkenyl group derived from a fatty acid obtained from a natural oil or natural fat or equivalent synthetic fatty acid or is an alkaryl group containing from 8 to 12 carbon atoms in the alkyl moiety, then the other 30 e substituents, respectively, of the formula: (A) xH and (A) yH where A is either ethoxy or propoxy and x, y is independently 1, 2 or 3, the thickener and acid DK 170538 B1 32 or the acidic salt together they are largely water-soluble; with the exception that the acid is not citric or not a dicarboxylic acid, or that the acidic salt is not a citrate or the salt of a dicarboxylic acid. 5 Formulation according to claim 1, characterized in that the thickener is insoluble in water. Formulation according to claim 1 or 2, characterized in that the group R is a substituted or unsubstituted alkyl or alkenyl group. Formulation according to claim 3, characterized in that R is derived from either a natural or a synthetic source of sebum, soybean oil, oleic acid, palmitic acid or myristic acid. The formulation according to claim 3, characterized in that R is derived from either a natural or a synthetic source of linolenic acid, castor oleic acid, linoleic acid or hexadecanoic acid. Formulation according to any of the preceding claims, characterized in that the groups Rx and R2 are independently a hydrogen atom, a lower unsubstituted alkyl group containing one to four carbon atoms, preferably methyl, or a substituted alkyl group. Formulation according to any one of the preceding claims, characterized in that the thickener is a mixture of compounds of formula I. Formulation according to any one of the preceding claims, characterized in that the acid is phosphoric acid, sulfuric acid, boric acid, sulfamic acid, lactic acid, formic acid, acetic acid, glycolic acid, pentacetic acid, ethylenediaminetetraacetic acid, fluoroacetic acid, ascorbic acid, ascorbic acid, ascorbic acid, ascorbic acid, ascorbic acid or ascorbic acid. chloroacetic. Formulation according to any one of the preceding claims, characterized in that the acidic salt is sodium hydrogen sulfate, sodium dihydrogen orthophosphate, disodium methylenediaminetetraacetate, aluminum potassium sulfate, aluminum acetate or aluminum sulfate. Formulation according to any one of the preceding claims, characterized in that the concentration of the thickener is in the range of 0.1 to 10% by weight, preferably 0.4 to 5.0% by weight. Formulation according to any one of the preceding claims, characterized in that the concentration of the acid or acid salt is not less than 0.01% by weight, preferably 0.1 to 30% by weight. A formulation according to any one of the preceding claims, characterized in that it further contains a perfume, a dye, a complexing agent, a surfactant or a bactericide. Formulation according to any one of the preceding claims, characterized in that the highly ionic salt is an alkali metal halide, an alkali metal sulfate, an ammonium halide, ammonium sulfate or a long chain quaternary ammonium compound. 30 Formulation according to any one of the preceding claims, characterized in that it further contains a compound effective to adjust the upper and / or lower cloud point of the formulation, preferably a strong ionic salt, an anionic surfactant, an B1 cationic surfactant, a nonionic surfactant, an amphoteric surfactant, a solvent miscible with the formulation or a mixture thereof. 5 The formulation according to claim 14, characterized in that the solvent is ethanol, isopropanol, butoxyethanol or dipropylene glycol methyl ether. Process for preparing a formulation according to any one of the preceding claims, characterized in that water (a) dissolves at least one acid or an acid salt, (b) a thickening agent as defined in claim 1, and optionally ( c) a strong ionic salt, the thickener and the acid or acid salts together being substantially water-soluble, in amounts sufficient to produce a viscosity of not less than 30 mPa * s at 25 ° C; measured with a Brookfield RVT viscometer at 50 rpm. using a spindle # 1. 25