EA031894B1 - Paste composition for cleaning hard surfaces - Google Patents

Abstract

The proposed composition of the cream for cleaning hard surfaces, including: (i) from 0.5 to 15 wt.% Anionic surfactant, of which at least 90 parts are the calcium or magnesium salt of a linear alkyl benzene sulfonic acid or a mixture of two salts; and (ii) from 10 to 50 wt.% of an abrasive having a Mohs hardness in the range of from 2.5 to 6, in which said composition comprises from 0.5 to 4 wt.% of mineral oil and in which the pH of said composition is in the range of 6 to 7.5. The composition of the cream is useful for removing deposits from patched oil and grease stains from a hard surface.

Description

FIELD OF THE INVENTION

The invention relates to a composition for removing residues of coated oily or greasy stains from a hard surface.

Level of invention

Compositions for cleaning hard surfaces are intended for cleaning surfaces such as stoves, sinks, burners, chimneys, tables and soiled items such as cutting tools, cutlery and crockery.

Such surfaces are prone to severe contamination, as they often come in contact with oily or greasy substances, such as cooking media. Over time, such residues tend to harden or acquire plaque. Oil stains and greases are usually easily removed when they are not hardening or coating, but when coated, for example during aging or heat treatment, the spots become especially difficult to remove. Cleaning is easier until the spots are covered with a coating. If not cleaned quickly, plaque-coated oils or fats can firmly bond with a hard surface.

Compositions for cleaning hard surfaces usually have a high pH. However, low pH formats are also known. High pH compositions are better suited for stain removal, due to their largely alkaline nature. However, such compositions are harsh. On the other hand, compositions having a neutral to slightly acidic pH are not so harsh, but they are also not so effective. Therefore, such compositions often contain more solid abrasive particles, typically particles having a Mohs hardness greater than 3.5.

Patent IN 204326 discloses compositions in the form of bars of detergents having approximately 14% anionic surfactants which are prepared by reacting linear alkylbenzenesulfonic acid (LAB sulfonic acid) with a stoichiometric excess of dolomite. The reaction leads to a mixture of LABS calcium and LABS magnesium, leaving a significant portion of free dolomite, which serves as an abrasive. In view of the specific product format, which is given as an example, the composition contains more than 70% of the total amount of abrasive materials. Usually the bars are used with a tool or brush made of nylon. Such a tool increases the intrinsic abrasive effect of the composition and at levels in the range of 70%, the composition essentially has a high abrasive effect.

WO 2015/078679 A1 (Unilever) discloses a paste composition suitable for cleaning plates. The composition helps remove stubborn stains, such as burnt soot and / or burnt food and fats, with noticeably less effort and time compared to at least some known products. The paste has an inorganic alkaline material with a pH of more than 11 and retains an alkalinity of more than 45 in a 1% solution and the abrasive has a Mohs hardness of more than 3.5. The strong alkaline nature of the composition enhances the cleaning effect of the abrasive.

Patent WO 2015/067438 A1 (Unilever) discloses a cleaning paste, where the primary surfactant is the Ca / Mg salt of LABS obtained by the reaction of LABS with dolomite. The composition also contains fatty acids or esters that give a non-grainy feel and removal of the top stain. Compositions contain abrasive material.

WO 2004013268 A1 (Unilever) discloses a synergistic cleaning composition having from 0.1 to 40% by weight of a surfactant and from 0.1 to 40% by weight of a crushed abrasive in the form of particles of a certain shape having a roundness factor of 0, 6 to 1.0. Dolomite is used to neutralize linear alkylbenzenesulfonic acid (LABS), resulting in a mixture of linear alkylbenzenesulfonates having a mixture of calcium and magnesium as counterions.

Therefore, with regard to the prior art relating to cleaning compositions for hard surfaces in the form of a paste, on the one hand, there are highly alkaline compositions containing a high level of sodium salt of linear alkylbenzenesulfonic acid as an anionic surfactant, and on the other hand, there are neutral or low acid compositions containing LABS calcium salt and / or LABS magnesium salt, which either contain high levels of durable abrasives or do not contain any abrasive at all.

Thus, there is an unmet need for a cleaning composition in the form of a paste or cream with a neutral or slightly acidic pH, having an optimal level and type of abrasive, but which is still very effective against deposits of coated oily / greasy stains on hard surfaces.

SUMMARY OF THE INVENTION

It has now been found that neutral or slightly acidic paste or cream compositions can be made more effective against deposits of plaque-coated oil / grease stains on a hard surface by combining an abrasive with a Mohs hardness greater than 2.5 with mineral oil.

According to a first aspect of the invention, there is disclosed a cream composition for cleaning hard surfaces, comprising:

(i) from 0.5 to 15 wt.% anionic surfactant, of which at least 90

- 1 031894 parts are a calcium or magnesium salt of linear alkylbenzenesulfonic acids, or a mixture of these two salts; and, (ii) from 10 to 50% by weight of an abrasive having a Mohs hardness in the range of from 2.5 to 6, in which said composition comprises from 0.5 to 4% by weight of mineral oil and in which the pH of said composition is in the range from 6 to 7.5.

According to a second aspect, a method for preparing a cream composition for cleaning hard surfaces is disclosed, comprising the steps of: (i) neutralizing at least 90 parts by weight linear alkylbenzenesulfonic acids by dolomite group mineral; (ii) adding from 0.5 to 4 parts by weight mineral oil and 1050 parts by weight an abrasive having a Mohs hardness in the range of 2.5 to 6 to a neutralized mass.

According to a third aspect, the use of the cream composition of the first aspect is disclosed for removing deposits from plaque-coated oil or grease stains from a hard surface.

According to a fourth aspect, there is disclosed a method for removing deposits from plaque-coated oil or grease stains from a hard surface, the method comprising the steps of applying the composition of the first aspect and cleaning the soiled part with a hard brush or rag and wiping it with a damp cloth.

DETAILED DESCRIPTION OF THE INVENTION

The disclosed cream composition for cleaning hard surfaces has:

(i) from 0.5 to 15% by weight of an anionic surfactant, of which at least 90 parts are a linear alkylbenzenesulfonic acid calcium or magnesium salt or a mixture of the two; and, (ii) from 10 to 50% by weight of an abrasive having a Mohs hardness in the range of from 2.5 to 6, in which said composition comprises from 0.5 to 4% by weight of mineral oil and in which the pH of said composition is in the range from 6 to 7.5.

Hard surface.

The compositions disclosed herein are generally suitable for cleaning hard surfaces. A hard surface can be any household or industrial surface, but domestic surfaces are definitely considered, and the invention will be explained further with respect to this application. Typical hard surfaces include glass, wood, tile and other ceramic materials, metal surfaces, polished stones and polished concrete; more preferably stone or concrete kitchen surfaces, burners, chimneys, tables, sinks, glass windows, kitchen coatings and tiles.

Composition.

The disclosed composition is in the form of a cream. The term cream, as used here, also includes a similar paste format and all references to the term cream should be interpreted to include an equivalent paste format.

Such products are usually packaged in paste tubes, plastic bottles, sachets, vessels, and other forms of packaging.

Anionic and other surfactants.

The composition essentially comprises from 0.5 to 15% by weight of an anionic surfactant, which is primarily responsible for the cleaning effect. Excess anionic surfactant often leads to too much foam, resulting in more water used for washing. At least 90% of the total anionic surfactant is a calcium or magnesium salt of a linear alkyl benzene sulfonic acid or a mixture of two salts. This product can be obtained by neutralizing the corresponding precursor of an anionic surfactant, such as linear alkylbenzenesulfonic acid, with an alkaline salt of calcium or magnesium, for example carbonate. A preferred method of producing a mixture of calcium and magnesium salts by neutralizing the acid precursor of a surfactant (linear alkylbenzenesulfonic acid) with a dolomite group mineral. When a stoichiometric excess of mineral is used, part of it is used to neutralize, and the unreacted part usually remains in the neutralized mass, which then becomes combined into a cleaning composition to serve as a solid abrasive.

Preferred compositions have a total amount of surfactant from 2 to 12 wt.%, More preferably from 3 to 8 wt.%. In further preferred compositions, the entire content of the anionic surfactant is derived from the calcium or magnesium salts of linear alkylbenzenesulfonic acids or a mixture of two salts.

The term dolomite group, or usually dolomites, refers to minerals with unusual trigonal symmetry and with the general formula AB (CO ₃ ) ₂ , where A is calcium and B is magnesium. Dolomites can be selected from the natural materials present, such as Ankerite Ca (Fe, Mg, Mn) (CO ₃ ) ₂ , Benstonite (Ba, Sr) ₆ (CaMn) ₆ Mg (CO ₃ ) ₁₃ , Dolomite CaMg (CO ₃ ) ₂ and Huntit CaMg ₃ (CO ₃ ) ₄ . The term dolomite refers to a specific mineral from the dolomite class and its molecular formula is given earlier. The basic anionic (negatively charged) unit of this class consists of a triangle, where the carbon atom occupies the center. At each corner of the triangle is an oxygen atom. The triple symmetry of a triangle explains the trigonal symmetry that many members of this class possess. The mineral structure of the dolomite group minerals is layered such that metal A ions occupy one layer, followed by a carbonate layer, followed by a layer of metal B ions, followed by another carbonate layer.

The remainder of the anionic surfactant may be any suitable surfactant, such as a water-soluble salt of organic sulfur reaction products having an alkyl radical containing from 8 to 22 carbon atoms and sulfuric acid ester. Non-limiting examples of anionic surfactants include alkyl polyols (ethoxylates), sodium lauryl ether sulfate, and methyl sulfonate esters.

The composition may also contain other surfactants (other than anionic). They include nonionic, cationic, amphoteric, zwitterionic surfactants. However, their role is limited to providing secondary benefits, such as reduced foaming or increased cleaning effect of anionic surfactants. Accordingly, it is preferred that, if present, their combined weight% is less than 15% by weight, more preferably less than 10% by weight, and most preferably from 1.5 to 5% by weight.

Preferred compositions have from 0.5 to 5% by weight of a nonionic surfactant. Suitable nonionic surfactants can be broadly described as compounds obtained by condensation of alkylene oxide groups that are hydrophilic in nature, with an organic hydrophobic compound, which may be aliphatic or alkylaromatic in nature. The length of the hydrophilic or polyoxyalkylene radical that condenses with any particular hydrophobic group can be easily adjusted to produce a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

Specific examples include the condensation product of aliphatic alcohols having from 8 to 22 carbon atoms in a linear or branched chain with ethylene oxide, such as a condensate of coconut oil ethylene oxide having from 2 to 15 mol of ethylene oxide per mole of coconut alcohol; alkyl phenol condensates having alkyl groups containing from 6 to 12 carbon atoms, from 5-25 moles of ethylene oxide per mole of alkyl phenol; condensates of the reaction product of ethylenediamine and propylene oxide with ethylene oxide, wherein the condensates contain from 40 to 80% by weight polyoxyethylene radicals and have a molecular weight of from 5000 to 11000; tertiary amine oxides of structure R ₃ NO, where one R group is an alkyl group with 8-18 carbon atoms and the other groups are methyl, ethyl or hydroxyethyl groups, for example dimethyldodecylamine oxide; tertiary phosphine oxides of structure R ₃ PO, where one R group is an alkyl group with 10-18 carbon atoms, and the other groups are alkyl or hydroxyalkyl groups with 1-3 carbon atoms, for example dimethyldodecylphosphine oxide; and dialkyl sulfoxides of structure R2SO, where the R group is an alkyl group with 10-18 carbon atoms, and the other is methyl or ethyl, for example methyl tetradecyl sulfoxide, fatty acid alkylolamides; condensates of alkylene oxide with fatty acid alkylolamides and alkyl mercaptans. Nonionic surfactants can be selected from a number of alkyl polyglucosides.

Suitable amphoteric surfactants are derivatives of aliphatic secondary and tertiary amines containing alkyl groups of 8 to 18 carbon atoms, and aliphatic radicals substituted with an anionic water-soluble group, for example sodium 3-dodecylaminopropionate, sodium 3-dodecylaminoropanesulfonate and sodium No. 2-hydroxydicycid . Suitable cationic detergent surfactants are quaternary ammonium salts having an aliphatic radical of 8-18 carbon atoms, for example cetyltrimethylammonium bromide.

The corresponding zwitterionic surfactants that can be used are derivatives of aliphatic quaternary ammonium, sulfonium and phosphonium having an aliphatic radical with 8 to 18 carbon atoms and an aliphatic radical substituted with an anionic water-soluble group, for example 3-Sh, no. Dimethyl-No. hexadecylammonium) propane-1-sudonate betaine, 3- (dodecylmethylsulfonium) propane-1-sulfonate betaine and 3- (cetylmethylphosphonium) ethanesulfonate betaine.

Further examples of suitable surfactants are provided in the well-known books of Surface Active Agents Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958 and / or current edition of McCutcheon's Emulsifiers and Detergents published by Manufacturing Confectioners Company or Tenside-Taschenbuch (Surfactants Handbook), H. Stache, 2nd Edn. , Carl Hauser Verlag, 1981.

Abrasives.

The composition of the cream for cleaning solid includes from 10 to 50 wt.% Abrasive. An abrasive that is ground material may be soluble or insoluble in water.

Water-soluble abrasives, when used, may be present in such excess to any

- 3 031894 the amount of water present in the composition, that the solubility of the abrasive in the aqueous phase is excessive, and therefore, the abrasive exists in the composition.

Preferred compositions contain from 30 to 50% by weight of an abrasive, which may be a single abrasive or a mixture of different abrasives.

Mohs hardness of the abrasive is in the range from 2.5 to 6.0. In preferred compositions, the abrasive is clay, calcite, dolomite, feldspar, apatite, fluorite and hematite, kyanite, magnetite, orthoclase or pumice.

More preferred abrasives are clay, calcite, dolomite and feldspar, and a combination of calcite and dolomite is optimal.

In preferred compositions, the average particle size of each abrasive is from 0.5 to 400 microns, more preferably from 10 to 200 microns.

The viscosity of the preferred cream compositions is in the range of 600 to 1200 cps. Viscosity can be measured by any known means. Preferably, the viscosity is measured with a Controlled-stress rheometer, Ex series viscometer. TA instrument AR 1000. The parallel geometry of a flat plate with a diameter of 4 cm is used. The gap between the plate and the base is set to 1000 mm. Data is analyzed by TA data analysis software. A sample of the paste is placed on the base and the plate is placed in the gap of a given geometry. Viscosity is measured at a shear rate varying from 10 to 25 s ^-1 and recorded at 20 s ^-1 .

The pH of the composition is in the range from 6 to 7.5, more preferably 6-7. The pH is measured at 25 ° C on a clean (undiluted) sample.

Water.

The paste / cream composition further comprises 20-60 wt.% Water, preferably 30-65 wt.% And more preferably 40-65 wt.%.

Mineral oil.

Disclosed compositions include from 0.5 to 4 wt.% Mineral oil. Preferably, the composition comprises from 2 to 4 wt.% Mineral oil. Preferably, the mineral oil is a hydrocarbon having from 14 to 40 carbon atoms.

Light or heavy mineral oil or mixtures are preferably used. Examples of alkanes are tetradecane, pentadecane, hexadecane, octadecane, nonadecane, eicosan and genecozan, and examples of alkane mixtures are light liquid paraffin / light mineral oil (14-16 carbon atoms), heavy liquid paraffin / heavy mineral oil (more than 20 carbon atoms ) Other mineral oils include white medical oil, liquid paraffin, liquid paraffin paraffin (liquid paraffin), liquid petroleum gas, and fragrant mineral oil. Hydrocarbons may have a linear, branched on any carbon atom or a cyclic structure. A preferred mineral oil is a light liquid paraffin oil with 14-16 carbon atoms.

Not wanting to be bound by theory, it is believed that mineral oil acts synergistically with an abrasive and provides a higher degree of removal of coated oils / fats.

Optional ingredients.

The composition may accordingly contain other ingredients that increase the cleaning efficiency. For example, the composition may contain components such as citrates, dicarboxylic acids, water-soluble phosphates, especially polyphosphates, mixtures of ortho and pyrophosphates, zeolites, sodium carbonate, sodium silicate, disodium silicate, sodium metasilicate and mixtures thereof. Such components may additionally function as abrasives if present in an amount in excess of their solubility in water. In addition to the ingredients already mentioned, various other optional ingredients such as builders, coloring agents, mud suspending agents, washing enzymes, fragrances and preservatives may be included due to their known benefits.

In accordance with a second aspect, a method for preparing a cream composition for cleaning hard surfaces is disclosed, comprising the steps of:

(i) neutralizing at least 90 parts by weight linear alkylbenzenesulfonic acid mineral dolomite group;

(ii) adding from 0.5 to 4 parts by weight mineral oil and 10-50 parts by weight an abrasive having a Mohs hardness in the range of 2.5-6 to a neutralized mass.

In accordance with a third aspect, the use of the cream composition of the first aspect is disclosed for removing deposits from plaque-coated oil or grease stains from a hard surface.

In accordance with a fourth aspect, a method is disclosed for removing deposits from plaque-coated oil or grease stains from a hard surface, the method comprising the steps of applying the composition of the first aspect, cleaning the contaminated part with a hard brush or cloth and wiping with a damp cloth.

The composition is distributed evenly over the surface. The paste is left on the surface for some time, brushed and then washed or wiped with a paper towel / cloth until completely dry. The dried treated surface exhibits excellent removal of contaminants.

The invention will now be clarified by the following non-limiting examples.

Examples

Example 1. Obtaining a control composition.

A pre-prepared mixture is obtained by mixing 5 g of commercial grade sodium carbonate with 92 g of demineralized water at 50 ° C. To this pre-prepared mixture was added 32 g of LABS (Linear alkylbenzenesulfonic acid (Reliance Industry, India)) and the contents were further stirred for five minutes to neutralize. The completion of the reaction was confirmed by checking the pH of the mixture; and a pH of 8 or more indicates complete neutralization: 5 g of methyl laurate is added to this neutralized mass and mixed, then 18 g of C12-3EO (triethylene oxide) nonionic surfactant are added. . This premix is stored in an incubator maintained at 50 ° C.

In a separate vessel, 0.06 g of antifoam silicone emulsion was mixed with 358 g of demineralized water at 50 ° C. To this aqueous mixture was added 35 g of sodium carbonate and stirred, followed by the addition of 450 g of calcite. 153 g of the previously prepared mixture described above is added to this mixture, stirring is continued for five minutes. The compositions were allowed to cool for one hour. Then other ingredients, such as pigments and perfumes, were added to the composition.

Example 2. Obtaining a cream composition according to the invention.

A pre-prepared mixture is prepared by mixing 10 g of dolomite with 91 g of demineralized water at 50 ° C. To this mixture was added 32 g of LABS acid (as mentioned above) and stirred further for 5 minutes to achieve complete neutralization. The completion of the reaction is confirmed by checking that the pH of the mixture is in the range from 6 to 7.5. To this neutralized mass, add 5 g of methyl laurate ether and mix further, followed by a mixture of 17 g of non-ionic surfactant g (as described above). This pre-prepared mixture (245 g) is stored in a thermostat at 50 ° C.

In a separate vessel, 350 g of calcite is added to 360 g of demineralized water at 50 ° C and stirred for two minutes. To this mixture was added 285 g of the above pre-prepared mixture and stirred for five minutes. The composition is cooled for 1 hour. Then other ingredients, such as pigments and perfumes, are added to the composition.

Obtaining model spots coated with plaque, and a method for cleaning them.

The compositions described above are tested on a steel tile (hard surface) on which castor oil is applied. This oil (0.05-0.07 g) is applied to a stainless steel tile (pre-weighed) using a pipette. The oil is spread over a tile which is left horizontal at room temperature for 12 hours to allow the oil to form a regular, even film. The tiles are then placed in a thermostat for one hour and the thermostat is maintained at 100 ° C. The tiles are then removed, allowed to cool for one hour and weighed again to know the exact weight of the bloomed oily / greasy stain.

Contaminated tiles are placed in the support area of the sample machine Test Forces (MIU). Cotton fabric is attached to the head of the MIU. A predetermined weight is fixed on the top of the head and the machine allows you to work with a constant number of rotations. The tiles are then removed from the machine and washed under tap water, then with demineralized water and dried in a thermostat at 50 ° C for approximately thirty minutes. The tile is weighed. The percentage of contaminants removed is calculated using the difference in weights.

Some more control compositions and compositions according to the invention are obtained by making corresponding changes in the procedure described previously.

Details of all such compositions and cleaning data are shown in the table.

Ingredient wt.% / control composition wt.% / composition according to the invention 1 2 3 4 5 1 2 3 Water 45.0 45.0 45.0 45.0 45.0 45.0 45.0 45.0 Do-LABS * - - - 3.2 3.2 3.2 3.2 3.2 Na-LABS * 3.2 3.2 3.2 - - - - - Dolomite (clean) - - - 9.7 9.7 9.7 9.7 9.7 Sodium carbonate 3,5 3,5 - - - - - - Nonionic surfactant 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Calcite 45.0 45.0 45.0 35.0 35.0 35.0 35.0 35.0 Mineral oil - 5,0 - - 5,0 s oh 4.0 2.0 Fragrance, Pigment, Methyl Laurate, Antifoam remedy and other small additives 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 PH value 10.5 10.5 7.0 6.5 6.5 6.5 6.5 6.5 Fat Removal /% 69 - 68 60 72 83 89 74 Phase separation Not Yes Not Not Yes Not Not Not

- 5 031894

Note.

Do-LABS means a mixture of calcium and magnesium salts of linear alkylbenzenesulfonic acids obtained by neutralizing linear alkylbenzenesulfonic acids with a stoichiometric excess of dolomite, thereby leaving a significant amount of unreacted (free) dolomite for abrasive action.

Na-LABS is the sodium salt of alkylbenzenesulfonic acid obtained by the usual neutralization reaction.

The table contains a number of control compositions and a number of compositions according to the invention.

In the case of all control compositions, either the removal of fat is low, or the composition tends to phase separation even at room temperature. No phase separation was observed in the case of using any composition according to the invention, and these compositions also provide a high degree of fat removal.

The illustrated examples clearly indicate how the need is met for cleaning compositions in the form of a paste or cream with a pH from neutral to weakly acid, having an optimal level of mineral oil, but which are still highly effective against deposits of coated oily / greasy stains on a hard surface.

Claims (10)

CLAIM 1. The composition of the cream for cleaning hard surfaces, including: (i) from 0.5 to 15% by weight of an anionic surfactant, of which at least 90 parts are a mixture of the calcium and magnesium salts of a linear alkyl benzene sulfonic acid; and, (ii) from 10 to 50 wt.% abrasive having a Mohs hardness in the range from 2.5 to 6, wherein said composition comprises from 0.5 to 4 wt.% mineral oil and wherein the pH of said composition measured at 25 ° C is in the range of 6 to 7.5. 2. The composition according to claim 1, comprising from 2 to 4 wt.% Mineral oil. 3. The composition according to claim 1 or 2, in which the specified mineral oil is a hydrocarbon having 14-40 carbon atoms. 4. The composition according to any one of claims 1 to 3, in which the abrasive is clay, calcite, dolomite, feldspar, apatite, fluorite, hematite, kyanite, magnetite, orthoclase and pumice. 5. The composition according to any one of claims 1 to 4, in which the anionic surfactant is obtained by neutralizing a linear alkylbenzenesulfonic acid with a dolomite group mineral. 6. The composition according to claim 5, in which the mineral is dolomite. 7. The composition according to any one of claims 1 to 5, which includes a nonionic surfactant. 8. A method of obtaining a cleaner for a hard surface according to any one of the preceding paragraphs, comprising the steps of: (i) neutralizing at least 90 parts by weight linear alkylbenzenesulfonic acid mineral dolomite group; (ii) adding from 0.5 to 4 parts by weight mineral oil and 10-50 parts by weight an abrasive having a Mohs hardness in the range of 2.5-6 to a neutralized mass. 9. The use of the cream composition according to claim 1 for removing deposits from plaque-coated oil or grease stains from a hard surface. 10. A method of removing deposits from plaque-coated oil or grease stains from a solid surface, which includes the steps of applying the composition of claim 1, cleaning the contaminated part with a hard brush or cloth and wiping with a damp cloth.