WO2013088345A1 - Composition for cleaning hard surfaces at high pressure - Google Patents

Composition for cleaning hard surfaces at high pressure Download PDF

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Publication number
WO2013088345A1
WO2013088345A1 PCT/IB2012/057189 IB2012057189W WO2013088345A1 WO 2013088345 A1 WO2013088345 A1 WO 2013088345A1 IB 2012057189 W IB2012057189 W IB 2012057189W WO 2013088345 A1 WO2013088345 A1 WO 2013088345A1
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Prior art keywords
cellulose
composition
μηπ
discrete
particles
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PCT/IB2012/057189
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Spanish (es)
French (fr)
Inventor
Pere LLOBET PADRO
Miquel OSSET HERNÁNDEZ
David Amantia
Mirko FACCINI
Albert ALMARZA MARTÍNEZ
Minerva FERNÁNDEZ BLANCO
Original Assignee
Tecnoquimia Catalunya, S. L.
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Application filed by Tecnoquimia Catalunya, S. L. filed Critical Tecnoquimia Catalunya, S. L.
Priority to EP12856765.8A priority Critical patent/EP2792736A4/en
Publication of WO2013088345A1 publication Critical patent/WO2013088345A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/83Mixtures of non-ionic with anionic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/22Carbohydrates or derivatives thereof
    • C11D3/222Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/40Products in which the composition is not well defined
    • C11D7/44Vegetable products
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02Anionic compounds
    • C11D1/12Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols

Definitions

  • the present invention is framed in the field of compositions for cleaning hard surfaces under high pressure, and especially for cleaning the exterior surfaces of vehicles.
  • the problem generated by such cleaning has its origin both in the heterogeneous set of objects that constitute hard surfaces, and in the diversity of materials that form them, which include, for example, metals, glass, ceramics, porcelain, plastic, rubber, rubber or wood
  • a specific case of cleaning hard surfaces that motivates a particular interest is the exterior washing of vehicles.
  • the surface is mostly metallic, possibly galvanized, usually with an exterior coating based on paints and / or varnishes, which can also include chrome elements.
  • paints and / or varnishes which can also include chrome elements.
  • other materials such as plastic materials, rubber, and glass, is also common.
  • the exterior surface of vehicles clean is desirable not only for aesthetic reasons, but also for the purpose of preventing premature deterioration, avoiding wear, discoloration and corrosion.
  • One of the elements that contributes to the deterioration of the exterior surface of the vehicles is constituted by a particular type of dirt that adheres on said surface, forming a film, which is usually designated with the English term traffic film.
  • the composition of this dirt film includes a wide variety of substances, both organic and inorganic, of very different physical and chemical characteristics (in particular its high degree of adhesion on the surface, probably due to electrostatic attractions), which makes its particularly difficult elimination.
  • European patent application EP-A-1 184452 describes a detergent composition for use in cleaning hard surfaces by spraying, which comprises spherical particles, which produce an abrasive effect thanks to the kinetic energy of said particles. aimed at high pressure on the surface.
  • Said particles are constituted by silicic acid, derivatives of silicic acid, silicates or alumina.
  • a process for cleaning surfaces is described by high pressure treatment with a detergent solution which also comprises particles of a thermoplastic material such as, for example, polyethylene, polypropylene, polystyrene or acrylonitrile butadiene styrene (ABS) Said particles, preferably, have a spherical or rounded shape so as not to damage the surface to be cleaned.
  • a method for surface cleaning is described which consists of spraying under pressure a liquid comprising surfactants together with water-soluble abrasive particles, preferably sodium carbonate, bicarbonate or sulfate or potassium
  • a cleaning composition for use by spraying which comprises abrasive particles that can be soluble in water such as, for example, sodium bicarbonate, sodium tripolyphosphate pentahydrate, sodium tetraborate decahydrate, potassium sulfate or sodium citrate; or it can be water insoluble abrasive particles, such as silicon dioxide, silicates, calcium carbonate, dicalcium phosphate, iron oxide, calcium pyrophosphate, sodium metaphosphate, diatomite or aluminum oxide.
  • abrasive particles that can be soluble in water such as, for example, sodium bicarbonate, sodium tripolyphosphate pentahydrate, sodium tetraborate decahydrate, potassium sulfate or sodium citrate; or it can be water insoluble abrasive particles, such as silicon dioxide, silicates, calcium carbonate, dicalcium phosphate, iron oxide, calcium pyrophosphate, sodium metaphosphate, diatomite or aluminum oxide.
  • compositions and cleaning methods proposed in the state of the art there remains a need for new compositions for cleaning hard surfaces, applicable by high pressure spraying, which are effective for the removal of dirt, while not damaging the surface, especially in the case of more vulnerable surfaces, for example, those that have a paint, varnish or similar finish.
  • the object of the present invention is a composition for cleaning hard surfaces.
  • a process for cleaning hard surfaces is also part of the object of the present invention.
  • the object of the present invention is a composition for cleaning hard surfaces under high pressure, which comprises particles discrete cellulose whose average particle size is less than or equal to 200 ⁇ .
  • compositions for cleaning hard surfaces under high pressure which comprises discrete particles of cellulose and, surprisingly, is highly effective for the removal of dirt adhered to said surfaces. It has been found that said composition is particularly effective in removing significantly the traffic film of dirt film adhered to the exterior surfaces of the vehicles without deteriorating the cleaned surface.
  • discrete cellulose particles refer to insoluble cellulose particles.
  • Discrete cellulose particles suitable for use in the compositions of the present invention are selected from the group consisting of microcrystalline cellulose, powdered cellulose, nanocellulose, cellulose microfibers, and mixtures thereof. Preferably, they are selected from microcrystalline cellulose, cellulose microfibers, and mixtures of both.
  • Said discrete particles of cellulose may have an appearance of granules, of variable and irregular shapes, such as microcrystalline cellulose, powdery cellulose and nanocellulose; or it can be filaments, substantially cylindrical, as is the case with cellulose microfibers.
  • the average particle size of the microcrystalline cellulose, the powdered cellulose and the nanocellulose is usually characterized by its equivalent mean diameter, which is determined according to the usual analytical procedures for measuring the average particle size as described, for example, in the Book ME Aulton, Pharmacy. The science of the design of pharmaceutical forms, second edition, Elsevier, Madrid, 2004, according to the method of the area sensitive to electric current (Coulter counter), or by laser light scattering.
  • Substantially cylindrical cellulose microfibers are usually characterized by their length (L) and thickness (E).
  • cellulose microfibers are also characterized by their equivalent diameter, the value of which corresponds to the diameter of a hypothetical sphere having the same volume as the cylindrical filament defined by the aforementioned dimensions L and E.
  • the average particle size of the discrete cellulose particles refers to the equivalent average diameter determined according to the methods described above, depending on the type of cellulose particles in question.
  • Discrete cellulose particles that are part of the object of the present invention have an average particle size of less than or equal to 200 ⁇ , typically between 0.05 ⁇ and 200 ⁇ , preferably between 1 ⁇ and 150 ⁇ , and more preferably comprised between 10 ⁇ and 100 ⁇ .
  • Microcrystalline cellulose, powdered cellulose and cellulose microfibers are commercially available.
  • the nanocellulose can be obtained from the above, for example by means of an ultrasound treatment that reduces the average particle size to dimensions of approximately 1 ⁇ or less.
  • Microcrystalline cellulose is a crystalline powdery substance, obtained by controlled hydrolysis of ⁇ -cellulose, which has characteristics specified for example in the manual of pharmaceutical excipients, RC Rowe, PJ Sheskey and PJ Weller, Handbook or Pharmaceutical Excipient, fourth edition, Pharmaceutical Press, 2003.
  • Microcrystalline cellulose can be obtained commercially from various suppliers, for example through the company FMC Biopolymer, under the general trade name AVICEL®, and is available in different average particle sizes that are usually comprised between 1 ⁇ and 200 ⁇ . You can also obtain microcrystalline cellulose qualities with an average particle size of 50 ⁇ or 90 ⁇ from the Acros Organics company. It can also be obtained through the Sigma-Aldrich company under the name Cellulose microcrystalline 310697 with an average particle size of 20 ⁇ .
  • microcrystalline cellulose with an average particle size between 20 ⁇ and 100 ⁇ is used.
  • Powdered cellulose is a powder obtained by reducing the size of ⁇ -cellulose by mechanical means, which has characteristics specified in the book R. C. Rowe, already cited. Powdered cellulose can be obtained commercially, for example through the company J. Rettenmaier & Sóhne, under the general trade name ARBOCEL®. Said cellulose is available in different average particle sizes, which are usually between 1 ⁇ and 200 ⁇ .
  • Cellulose microfibers can be obtained by various mechanical and / or chemical treatments of cellulose until cellulose is obtained in the form of filaments.
  • Cellulose microfibers can be obtained commercially from various suppliers, for example through the company, J. Rettenmaier & Sóhne, under the general trade name ARBOCEL®.
  • Such microfibers are available in different sizes, and are usually characterized by their length (L) and thickness (E).
  • Cellulose microfibers suitable for use in the present invention may have a length between approximately 1 ⁇ and 220 ⁇ , and a thickness between approximately 0.01 ⁇ and 150 ⁇ , which is equivalent to an equivalent average diameter between 0 , 05 ⁇ and 195 ⁇ , according to the approximation explained above.
  • cellulose microfibers having an equivalent average diameter between 10 ⁇ and 30 ⁇ are used.
  • Cellulose nanoparticles can be obtained from any of the cellulose particles described above, that is, from microcrystalline cellulose, powdered cellulose, or cellulose microfibers, by subjecting them to a process to reduce their size. This reduction can be achieved, for example, by ultrasonic treatment of a liquid dispersion of said particles, until obtaining cellulose nanoparticles whose average size is equal to or less than 1 ⁇ , preferably between 0.05 ⁇ and 1 ⁇ .
  • the ultrasonic treatment is carried out at a power of 450 W, for a period of time between 5 minutes and 3 hours, using a dispersion of the cellulose particles preferably in distilled water with a concentration between 0.01% and 20%, expressed by weight.
  • the high pressure hard surface cleaning composition of the present invention comprises discrete cellulose particles, as defined above.
  • the composition object of the present invention comprises between 1% and 20% of discrete cellulose particles, percentage expressed by weight of cellulose with respect to the total weight of solids of the composition.
  • solids means all the ingredients of the composition, except water and, eventually, other co-solvents.
  • the cleaning effect of the discrete cellulose particles is so significant that in a preferred embodiment of the invention, the cleaning composition comprises only discrete particles of cellulose as an insoluble product, that is, the composition does not comprise additional abrasive products.
  • the composition comprises discrete particles of cellulose dispersed in water and preservatives.
  • the composition comprises between 1% and 20% by weight with respect to the total weight of the composition.
  • said composition further comprises surfactants, adjuvants and, optionally, other auxiliary products.
  • composition with surfactants, adjuvants and possibly other auxiliary components can be solid or liquid, without the presentation form influencing the cleaning result, since, such as explained below, the composition, whether solid or liquid, is dispersed in water before being applied at high pressure on the hard surface.
  • Surfactants as is well known to those skilled in the art, are amphiphilic substances that have a hydrophobic part and a hydrophilic part. This particular chemical structure of the surfactants plays an important role in the washing process, because they decrease the surface tension of the liquid, which favors the wetting of the surfaces and are also able to group together forming micelles, which allows dissolving, emulsifying or break up the dirt.
  • the surfactants suitable for use in the compositions of this invention are selected from the group consisting of anionic, nonionic, cationic, amphoteric surfactants, and mixtures thereof.
  • surfactant products can be obtained commercially from various suppliers, such as, for example, the companies Kao Corportation, BASF, Croda, Huntsman, Evonik, or Cognis (currently BASF), among others.
  • anionic surfactants suitable for use in the context of the present invention are, for example, soaps, alkylbenzenesulfonic acids and their salts, sulfonated ⁇ -olefins, sulfonated paraffins, alkyl sulfates, alkyl ether sulfates, ether sulfates of glycerin, alkyl sulfosuccinates, carboxylic acid ethers and salts thereof, alkyl phosphates, alkyl ether phosphates, alkylphenol sulfates, alkylphenol ether sulfates, isethionates, sarcosinates, taurates, and N-acylamino acid salts.
  • sodium lauryl ether sulfate is among the alkyl ether sulfates, such as that supplied by the Kao Corporation under the trade name EMAL® or the Cognis range of products TEXAPON® ( currently BASF); alkyl sulfates are marketed under the name SULFOPON ® of the Cognis company (currently BASF); among the ethers of carboxylic acids are those supplied by the company Kao Corporation under the trade name AKYPO®; or among the alkylbenzenesulfonic acids, For example, linear alkylbenzene sulfonic acids (LAS), especially n-dodecylbenzenesulfonic acid and its salts, such as that supplied by Cognis (currently BASF) under the trade name MARANIL®.
  • LAS linear alkylbenzene sulfonic acids
  • MARANIL® n-dodecylbenzenesulfonic acid and its salts
  • nonionic surfactants suitable for use in the context of the present invention are, for example, ethoxylated fatty alcohols, ethoxylated fatty acids, ethoxylated alkylphenols, fatty acid alkanolamides, ethoxylated fatty acid alkanolamides, ethoxylated fatty amines, oxides of fatty amine, fatty amidoamine oxides, glycerin esters and fatty acids, sorbitan esters, ethoxylated sorbitan esters, sucrose esters, alkyl polyglycosides, ethylene / propylene oxide copolymers, among others.
  • DEHYDOL® ethoxylated fatty alcohols
  • DEHYDOL® LT7 which is a Ci 2 -Ci 8 fatty alcohol with approximately 7 moles of ethylene oxide.
  • RHEODOL® ethoxylated sorbitan esters
  • ethoxylated alkylphenols products marketed under the name DEHYDROPHEN® by the company Cognis (currently BASF) may be mentioned.
  • amphoteric surfactants suitable for use in the context of the present invention are, for example, alkyldimethyl betaines, alkylamido betaines, alkylsulfobetaines, alkylamido sulfobetaines, imidazoline derivatives and alkylaminopropionates, among others.
  • alkylamido betaines those mentioned by the company Cognis (currently BASF) may be mentioned under the trade name DEHYTON®.
  • the cationic surfactants suitable for use in the context of the present invention are quaternary ammonium compounds having an antistatic effect, such as benzalkonium chloride, which is commercially available under the trade name DEHYQUART® supplied by the Cognis company (currently BASF).
  • DEHYQUART® supplied by the Cognis company (currently BASF).
  • polyphosphates especially alkali metal tripolyphosphates and pyrophosphates, alkali carbonates, alkali silicates, zeolites, alkali salts of nitrileacetic acid, EDTA and their salts, the current ecological substitutes of NTA / EDTA / phosphates, such as GLDA (Glutamic Acid ⁇ , ⁇ -Diacetic Acid) commercially available under the name of Disolvine® GL from Akzo Nobel, alkaline salts of citric acid, and mixtures thereof.
  • the alkaline salt that is preferably used is the sodium salt.
  • the cleaning composition object of the present invention may optionally contain other auxiliary products such as, for example, enzymes, dyes, foam stabilizers, thickening agents, solvents, and pH regulators.
  • auxiliary products such as, for example, enzymes, dyes, foam stabilizers, thickening agents, solvents, and pH regulators.
  • a liquid composition it generally also includes preservatives.
  • the cleaning composition comprises between 1% and 20% of discrete cellulose particles, preferably between 5% and 10%; between 5% and 50% of surfactants, preferably between 10% and 30%; and between 35% and 95% of adjuvants, preferably between 50% and 65%. These percentages are expressed in weight with respect to the total weight of solids of the composition. The percentages of the different components are selected so that the sum of them is 100% of the composition.
  • the cleaning composition comprises between 1% and 20% of discrete cellulose particles, preferably between 5% and 10%; between 2% and 20% of anionic surfactants, preferably between 2% and 10%; between 3% and 30% of non-ionic surfactants, preferably between 5% and 15%; and between 35% and 95% of adjuvants, preferably between 50% and 65%.
  • these percentages are expressed in weight with respect to the total weight of solids of the composition. The percentages of the different components they are selected so that the sum of them results in 100% of the composition.
  • the anionic surfactant is an alkaline salt of a linear alkylbenzenesulfonic acid, and more preferably it is the sodium salt of n-dodecylbenzenesulfonic acid;
  • the nonionic surfactant is an ethoxylated fatty alcohol, more preferably it is an ethoxylated Ci 2 -Ci 8 chain alcohol with about 7 moles of ethylene oxide, and the adjuvant is selected from the group consisting of sodium tripolyphosphate, sodium carbonate, and mixtures of both, more preferably the adjuvant is a mixture of sodium tripolyphosphate and sodium carbonate.
  • a characteristic solid cleaning composition according to the present invention comprises, for example, between 1% and 20% of discrete cellulose particles, between 5% and 45% of sodium tripolyphosphate, between 20% and 50% of sodium carbonate, between 2% and 10% anionic surfactant and between 5% and 15% non-ionic surfactant. These percentages are expressed in weight with respect to the total weight of solids of the composition. The percentages of the different components are selected so that the sum of them is 100% of the composition.
  • composition may also contain other ingredients, such as amphoteric surfactants, cationic surfactants, enzymes, dyes, foam stabilizers, among others.
  • other ingredients such as amphoteric surfactants, cationic surfactants, enzymes, dyes, foam stabilizers, among others.
  • a solid detergent composition can be prepared by direct mixing of all the ingredients when they are solid, also mixing directly with the discrete particles of cellulose. It can also be prepared by a process comprising an atomization step, for which a paste, or slurry in English, is previously prepared by dispersion in water of some of the components, usually anionic surfactants and adjuvants. Said paste is subjected to spray drying, for example, against a counter current of hot air. In this way particles of the powder detergent composition with an apparent density of approximately 300 g / l are obtained. and 1000 g / l.
  • the atomized detergent composition can be completed by the subsequent addition of other components such as, for example, non-ionic surfactants. Discrete cellulose particles can also be added in this final stage onto the already atomized detergent.
  • a characteristic liquid cleaning composition according to the present invention comprises, for example, between 0.5% and 5% discrete cellulose particles between 10% and 20% sodium tripolyphosphate, between 1% and 15% of nonionic surfactant and between 1% and 10% anionic surfactant, water being added, optionally combined with other co-solvents, until 100% of the composition is reached.
  • the percentages are expressed in weight of each ingredient with respect to the total weight of the composition including water and possibly co-solvents.
  • liquid detergent formulations of the invention are, for example, propylene glycol, 1-methoxy-2-propanol, glycerin, cumensulfonate, dipropylene glycol, dipropylene glycol monomethyl ether, butylglycol, or butyldiglycol.
  • the liquid detergent formulation may contain other ingredients, such as amphoteric surfactants, cationic surfactants, enzymes, dyes, foam stabilizers, thickeners, pH regulators, and preservatives among others.
  • the preparation of the liquid detergent is carried out according to procedures that are also well known in the field of detergent technology. For example, it can be prepared by dissolving the different components in water, with stirring until a homogeneous solution is achieved. Discrete cellulose particles can be added, for example, in a final stage, on the prepared detergent composition, by stirring mechanically or with other dispersion methods such as sonication, until obtaining a homogeneous dispersion of said particles in the liquid medium. .
  • hard surface is broadly understood, and comprises, for example, any metal surface, for example aluminum, chrome, steel, or stainless steel; surfaces glass, ceramic or porcelain; rubber or rubber surfaces; surfaces of any type of plastic, such as thermoplastic or thermosetting polymers, among other possible materials. Likewise, said surfaces that are coated with a layer of paint, varnish, enamel, or other type of finish are also included.
  • the hard surfaces to be cleaned according to the process of the present invention can correspond to a wide variety of objects, both domestically and industrially. These may include, for example, floors, walls, tiles, sinks, work surfaces, blinds, windows, bathrooms, any type of outdoor furniture, panels, containers, tarpaulins, machinery, or the exterior surface of any type of vehicle .
  • the cleaning composition and the cleaning process of the present invention are applied for cleaning the exterior surface of a vehicle. It has been observed that the composition of the invention is particularly effective in eliminating the so-called traffic film.
  • the traffic film may contain, for example, fuel combustion residues, fuel leaks, carbon black, lubricating substances, residues from previous washes, as well as very heterogeneous environmental substances present on the roads, such as salts, sand, or mud.
  • vehicle includes any means of transport, typically, cars, trucks, buses, trailers, wagons, motorcycles, airplanes, airplanes, or parts thereof, among others.
  • Cleaning procedure Also part of the object of this invention is a process for cleaning hard surfaces comprising the step of spraying at high pressure on the hard surface an aqueous dispersion of the composition of the invention comprising discrete cellulose particles whose average particle size is less than or equal to 200 ⁇ .
  • high pressure means a pressure equal to or greater than 10 bar.
  • the cleaning process is performed at a pressure between 20 and 200 bars, more preferably between 50 and 1 50 bars, and more preferably between 90 and 1 10 bars.
  • High pressure spraying can be carried out using a pressure washer such as those available on the market, for example, those supplied by the company Nilfisk-ALTO, Kárcher or piston pumps type "CAT”, or "Interpump".
  • a pressure washer such as those available on the market, for example, those supplied by the company Nilfisk-ALTO, Kárcher or piston pumps type "CAT”, or "Interpump”.
  • the aqueous dispersion that is sprayed is prepared by dispersion in water of the composition of the invention. That is, the process of the invention comprises a previous step of preparing an aqueous dispersion of the composition comprising discrete cellulose particles.
  • said machines have a reservoir in which a mother aqueous dispersion of the composition comprising discrete cellulose particles is prepared.
  • said aqueous dispersion is prepared by dispersion in water of the composition of the invention, either in solid or liquid form, to an approximate dilution of 1 to 10 g / l thereof, the particles of which remain suspension cellulose.
  • the concentration of the discrete cellulose particles at the spearhead is preferably between 0.005% and 0.2%, more preferably between 0.005% and 0.1%, and even more preferably between 0.005% and 0.05%, wherein the percentage is expressed by weight of cellulose with respect to the weight of the aqueous dispersion sprayed.
  • the cleaning devices used usually have a water heating system for subsequent application under pressure on the surface to be cleaned.
  • the cleaning method according to the present invention can be effected at a temperature between room temperature and about 90 Q C, preferably between 40 and 70 Q C Q C, and most preferably between 50 C and 60 Q Q C.
  • compositions of the invention including discrete cellulose particles, a washing efficiency of substantially higher hard surfaces is achieved with respect to detergent compositions which do not comprise said particles.
  • the spearhead concentration can be considerably reduced, cleaning times are optimized and wastewater is reduced.
  • the dispersion obtained was treated with ultrasound at a power of 450 W, for 1 hour.
  • dodecylbenzenesulfonic acid was first dispersed under stirring in a part of the water, then adding the sodium hydroxide necessary to neutralize said acid. Subsequently, the remaining components and the remaining water were added, and the mixture was kept under stirring until a homogeneous solution was obtained.
  • a solid detergent composition containing 40% by weight of sodium tripolyphosphate, 45% by weight of sodium carbonate, 10% by weight of DEHYDOL® LT-7 from Cognis (currently BASF) (Ci 2 -Ci 8 ethoxylated alcohol with 7 moles of ethylene oxide), and 5% by weight of dodecylbenzenesulfonic acid.
  • the mixture was kept under stirring until it obtained a homogeneous powder.
  • Example 1 Liquid detergent composition with microcrystalline cellulose
  • a liquid detergent composition was prepared by dissolving in water 20% by weight of sodium tripolyphosphate, 10% by weight of DEHYDOL® LT-7 from Cognis (currently BASF) (ethoxylated C12-C18 alcohol with 7 moles of oxide ethylene), 5% by weight of neutralized dodecylbenzenesulfonic acid with 0.6% by weight of sodium hydroxide, and 1.77% by weight of microcrystalline cellulose from the Sigma-Aldrich company with an average particle size of 20 ⁇ (Cellulose microcrystalline 310697).
  • dodecylbenzenesulfonic acid was first dispersed under stirring in a part of the water, then adding the sodium hydroxide necessary to neutralize said acid. Subsequently, sodium tripolyphosphate, the non-ionic surfactant and the remaining water, and the mixture was kept under stirring until a homogeneous solution was obtained. Finally, cellulose microfibers were added.
  • the cellulose content in this composition was 4.8% by weight on the weight of the active components, that is, all except water.
  • Example 2 Solid detergent composition with cellulose microfibers
  • a solid detergent composition containing 40% by weight of sodium tripolyphosphate, 45% by weight of sodium carbonate, 10% by weight of DEHYDOL® LT-7 from Cognis (currently BASF) (ethoxylated Ci 2 -Ci 8 alcohol with 7 moles of ethylene oxide), 5% by weight of dodecylbenzenesulfonic acid, and 1, 1 1% of cellulose microfibers 23 ⁇ in length and 17 ⁇ in thickness (ARBOCEL® BE 600-20), which represents an equivalent average diameter of 22 ⁇ .
  • the mixture was kept under stirring until a homogeneous powder was obtained.
  • the proportion by weight of the cellulose with respect to the total composition was 10%.
  • Example 3 Solid detergent composition with microcrystalline cellulose
  • a solid detergent composition containing 40% by weight of sodium tripolyphosphate, 45% by weight of sodium carbonate, 10% by weight of DEHYDOL® LT-7 from Cognis (currently BASF) (Ci 2 -Ci 8 ethoxylated alcohol with 7 moles of ethylene oxide), 5% by weight of dodecylbenzenesulfonic acid, and 1.1, 1% of microcrystalline cellulose with an average size of 90 ⁇ from Acros Organics.
  • the mixture was kept under stirring until a homogeneous powder was obtained.
  • the proportion by weight of the cellulose with respect to the total composition was 10%.
  • Example 4 Solid detergent composition with microcrystalline cellulose
  • a solid detergent composition containing 40% by weight of sodium tripolyphosphate, 45% by weight of sodium carbonate, 10% by weight of DEHYDOL® LT-7 from Cognis (currently BASF) (ethoxylated Ci 2 -Ci 8 alcohol with 7 moles of ethylene oxide), 5% by weight of dodecylbenzenesulfonic acid , and 1 1, 1 1% microcrystalline cellulose with an average size of 50 ⁇ HEWETEN® 101 from J. Rettenmeier & Sóhne.
  • the mixture was kept under stirring until a homogeneous powder was obtained.
  • the proportion by weight of the cellulose with respect to the total composition was 10%.
  • Example 5 Aqueous composition with microcrystalline cellulose
  • microcrystalline cellulose from the Sigma-Aldrich company with an average particle size of 20 ⁇ (Cellulose microcrystalline 310697) was dispersed in 190 g of water. The dispersion was kept under stirring until a homogeneous dispersion was achieved, then treated with ultrasound at a power of 450 W, for 90 minutes.
  • a surface of a previously painted vehicle soiled with Tra ⁇ Tic-film type dirt was cleaned, according to the method of the invention, using the compositions prepared in Examples 1 to 4.
  • a high pressure washer washer was used. the Nilfisk-ALTO brand.
  • compositions of the invention were carried out at two temperatures: ambient and 53 Q C, and at two pressures: 75 bar and 105 bar.
  • compositions of the reference examples described above were also tested.
  • Example 1 To test the liquid composition of Example 1, it was conveniently dosed in the feedwater of the pressure system to obtain a concentration of 0.40% at the spearhead, and the surface was cleaned at a pressure of 75 bar and room temperature. The high pressure spray was maintained for an approximate period of 1 minute over an area of 0.25 m 2 .
  • An analogous procedure was carried out to test the efficacy of the solid compositions of Examples 2 to 4, dispersing 10 g of each in 5 I of water and obtaining working solutions at the desired composition of 0.2% in weight. In this case, the cleaning procedure was carried out at a pressure of 105 bar, at a temperature of 53 QC and for a period of 1 minute over an area of 0.25 m 2 .
  • Example 5 The composition of Example 5 was conveniently dosed in the feedwater of the pressure system to obtain a concentration of 0.40% by weight at the spearhead, and the surface was cleaned, at a pressure of 75 bar and at a temperature ambient. The high pressure spray was maintained for an approximate period of 1 minute over an area of 0.25 m 2 . The high pressure spray was maintained for a period of 1 minute over an area of 0.25 m 2 .
  • Example 1 The efficacy of the liquid composition of Example 1 was evaluated by a 2 2 factorial design with the factors and levels shown in the matrix of Table 2:
  • Example 5 included microcrystalline cellulose with an average particle size of 20 ⁇ , but did not contain surfactants or adjuvants;
  • Reference Example 1 was a liquid detergent composition that did not contain cellulose particles, and
  • Example 1 was a detergent composition of the invention containing microcrystalline cellulose with an average particle size of 20 ⁇ .
  • Example 5 It can be seen that by incorporating microcrystalline cellulose into the water, Example 5, there is an improvement in the degree of cleaning, passing from a grade 5 to a grade 2-3.
  • Example 2 0.02% (microfibers of 1

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Abstract

The present invention relates to a composition for cleaning hard surfaces at high pressure, which comprises insoluble cellulose particles. The invention also relates to a cleaning method in which said composition is used, and to the use thereof for cleaning hard surfaces at high pressure. The composition is particularly useful for cleaning the exterior surfaces of vehicles that have a traffic film.

Description

COMPOSICIÓN PARA LA LIMPIEZA DE SUPERFICIES DURAS A ALTA  COMPOSITION FOR CLEANING HIGH HARD SURFACES
PRESIÓN  PRESSURE
Campo de la técnica Technical field
La presente invención se enmarca en el campo de las composiciones para la limpieza de superficies duras a alta presión, y de forma especial para la limpieza de las superficies exteriores de los vehículos.  The present invention is framed in the field of compositions for cleaning hard surfaces under high pressure, and especially for cleaning the exterior surfaces of vehicles.
Estado de la técnica anterior Prior art
La limpieza de superficies duras, tanto a nivel doméstico como industrial, es un problema que ha suscitado un gran interés a lo largo de muchas décadas.  Hard surface cleaning, both domestically and industrially, is a problem that has aroused great interest over many decades.
La problemática que genera dicha limpieza tiene su origen tanto en el conjunto heterogéneo de objetos que constituyen las superficies duras, como en la diversidad de materiales que las forman, que incluyen, por ejemplo, metales, vidrio, cerámica, porcelana, plástico, goma, caucho o madera.  The problem generated by such cleaning has its origin both in the heterogeneous set of objects that constitute hard surfaces, and in the diversity of materials that form them, which include, for example, metals, glass, ceramics, porcelain, plastic, rubber, rubber or wood
Un caso concreto de limpieza de superficies duras que motiva un particular interés es el lavado exterior de vehículos. En este caso, la superficie es mayoritariamente metálica, eventualmente galvanizada, normalmente con un revestimiento exterior a base de pinturas y/o barnices, que también puede incluir elementos cromados. Así mismo, es también habitual la presencia de otros materiales, tales como materiales plásticos, caucho, y vidrio.  A specific case of cleaning hard surfaces that motivates a particular interest is the exterior washing of vehicles. In this case, the surface is mostly metallic, possibly galvanized, usually with an exterior coating based on paints and / or varnishes, which can also include chrome elements. Likewise, the presence of other materials, such as plastic materials, rubber, and glass, is also common.
El mantener limpia la superficie exterior de los vehículos es deseable no tan solo por razones estéticas, sino también con la finalidad de prevenir su deterioro prematuro, evitando al máximo su desgaste, decoloración y corrosión. Uno de los elementos que contribuye al deterioro de la superficie exterior de los vehículos está constituido por un tipo particular de suciedad que se adhiere sobre dicha superficie, formando una película, que se designa habitualmente con el término inglés traffic film. La composición de esta película de suciedad incluye una gran variedad de sustancias, tanto orgánicas como inorgánicas, de características físico químicas muy diversas (en particular su elevado grado de adhesión sobre la superficie, probablemente debido a atracciones electrostáticas), lo que hace particularmente difícil su eliminación. Para conseguir una limpieza efectiva del traffic film, a menudo es necesario un tratamiento agresivo, tanto químico como mecánico, que puede repercutir negativamente sobre la superficie, particularmente sobre el recubrimiento de pintura y/o barniz. En general, es deseable evitar los sistemas de limpieza que impliquen eliminar de forma mecánica la suciedad de la superficie mediante frotado, puesto que tal tratamiento abrasivo comporta un riesgo de rayado y desgaste del revestimiento del automóvil. Keeping the exterior surface of vehicles clean is desirable not only for aesthetic reasons, but also for the purpose of preventing premature deterioration, avoiding wear, discoloration and corrosion. One of the elements that contributes to the deterioration of the exterior surface of the vehicles is constituted by a particular type of dirt that adheres on said surface, forming a film, which is usually designated with the English term traffic film. The composition of this dirt film includes a wide variety of substances, both organic and inorganic, of very different physical and chemical characteristics (in particular its high degree of adhesion on the surface, probably due to electrostatic attractions), which makes its particularly difficult elimination. To achieve an effective cleaning of the traffic film, aggressive treatment, both chemical and mechanical, is often necessary, which can have a negative impact on the surface, particularly on the paint and / or varnish coating. In general, it is desirable to avoid cleaning systems that involve mechanically removing dirt from the surface by rubbing, since such abrasive treatment involves a risk of scratching and wear of the car's coating.
En este sentido, se han desarrollado sistemas de limpieza sin frotado, basados en la pulverización a presión de composiciones limpiadoras sobre la superficie del vehículo. Sin embargo, se ha constatado que con composiciones detergentes simples, no se consigue la completa eliminación de la suciedad, y que para conseguir un grado de limpieza, que no siempre resulta aceptable, se requieren altas concentraciones de detergente, lo que supone un serio inconveniente, tanto desde un punto de vista económico como ambiental. En el estado de la técnica se han propuesto diversas composiciones o métodos más eficaces para la limpieza de superficies duras por pulverización a presión utilizando composiciones detergentes en combinación con determinadas partículas que confieren unas propiedades abrasivas a dichas composiciones.  In this sense, cleaning systems without rubbing have been developed, based on the pressure spraying of cleaning compositions on the surface of the vehicle. However, it has been found that with simple detergent compositions, the complete removal of dirt is not achieved, and that to achieve a degree of cleanliness, which is not always acceptable, high concentrations of detergent are required, which is a serious inconvenience , both from an economic and environmental point of view. Various more effective compositions or methods for cleaning hard surfaces by pressure spraying using detergent compositions in combination with certain particles that confer abrasive properties to said compositions have been proposed in the state of the art.
Así por ejemplo, la solicitud de patente europea EP-A-1 184452 describe una composición detergente para ser usada en la limpieza de superficies duras mediante pulverización, que comprende unas partículas esféricas, que producen un efecto abrasivo gracias a la energía cinética de dichas partículas dirigidas a alta presión sobre la superficie. Dichas partículas están constituidas por ácido silícico, derivados del ácido silícico, silicatos o alúmina.  Thus, for example, European patent application EP-A-1 184452 describes a detergent composition for use in cleaning hard surfaces by spraying, which comprises spherical particles, which produce an abrasive effect thanks to the kinetic energy of said particles. aimed at high pressure on the surface. Said particles are constituted by silicic acid, derivatives of silicic acid, silicates or alumina.
En la solicitud de patente británica GB1099701 se describe un proceso para la limpieza de superficies mediante el tratamiento a alta presión con una solución detergente que comprende así mismo unas partículas de un material termoplástico como, por ejemplo, polietileno, polipropileno, poliestireno o acrilonitrilo butadieno estireno (ABS). Dichas partículas, preferiblemente, tienen una forma esférica o redondeada para así no dañar la superficie a limpiar. En la solicitud de patente internacional WO-A-94/1 6831 se describe un método para la limpieza de superficies que consiste en pulverizar a presión un líquido que comprende tensioactivos juntamente con unas partículas abrasivas solubles en agua, preferiblemente carbonato, bicarbonato o sulfato sódico o potásico. In British patent application GB1099701 a process for cleaning surfaces is described by high pressure treatment with a detergent solution which also comprises particles of a thermoplastic material such as, for example, polyethylene, polypropylene, polystyrene or acrylonitrile butadiene styrene (ABS) Said particles, preferably, have a spherical or rounded shape so as not to damage the surface to be cleaned. In the international patent application WO-A-94/1 6831 a method for surface cleaning is described which consists of spraying under pressure a liquid comprising surfactants together with water-soluble abrasive particles, preferably sodium carbonate, bicarbonate or sulfate or potassium
Así mismo, en la solicitud de patente internacional WO-A- 98/29193 se describe una composición limpiadora para ser utilizada por pulverización que comprende partículas abrasivas que pueden ser solubles en agua como, por ejemplo, bicarbonato sódico, tripolifosfato sódico pentahidrato, tetraborato sódico decahidrato, sulfato potásico o citrato sódico; o bien puede tratarse de partículas abrasivas insolubles en agua, tales como dióxido de silicio, silicatos, carbonato cálcico, fosfato dicálcico, óxido de hierro, pirofosfato cálcico, metafosfato sódico, diatomita u óxido de aluminio.  Likewise, in the international patent application WO-A-98/29193 a cleaning composition is described for use by spraying which comprises abrasive particles that can be soluble in water such as, for example, sodium bicarbonate, sodium tripolyphosphate pentahydrate, sodium tetraborate decahydrate, potassium sulfate or sodium citrate; or it can be water insoluble abrasive particles, such as silicon dioxide, silicates, calcium carbonate, dicalcium phosphate, iron oxide, calcium pyrophosphate, sodium metaphosphate, diatomite or aluminum oxide.
A pesar de las diferentes composiciones y métodos de limpieza propuestos en el estado de la técnica, subsiste la necesidad de disponer de nuevas composiciones para la limpieza de superficies duras, aplicables por pulverización a alta presión, que sean efectivas para la eliminación de la suciedad, al tiempo que no deterioren la superficie, especialmente para el caso de superficies más vulnerables, por ejemplo, aquéllas que tienen un acabado de pintura, barniz o similar.  Despite the different compositions and cleaning methods proposed in the state of the art, there remains a need for new compositions for cleaning hard surfaces, applicable by high pressure spraying, which are effective for the removal of dirt, while not damaging the surface, especially in the case of more vulnerable surfaces, for example, those that have a paint, varnish or similar finish.
Objeto de la invención Object of the invention
El objeto de la presente invención es una composición para la limpieza de superficies duras.  The object of the present invention is a composition for cleaning hard surfaces.
Forma también parte del objeto de la presente invención un procedimiento para la limpieza de superficies duras.  A process for cleaning hard surfaces is also part of the object of the present invention.
También forma parte del objeto de la presente invención el uso de partículas discretas de celulosa para la limpieza de superficies duras. Descripción detallada de la invención  The use of discrete cellulose particles for cleaning hard surfaces is also part of the object of the present invention. Detailed description of the invention
El objeto de la presente invención es una composición para la limpieza de superficies duras a alta presión, que comprende partículas discretas de celulosa cuyo tamaño medio de partícula es inferior o igual a 200 μηπ. The object of the present invention is a composition for cleaning hard surfaces under high pressure, which comprises particles discrete cellulose whose average particle size is less than or equal to 200 μηπ.
Los autores de la presente invención han desarrollado una composición para la limpieza de superficies duras a alta presión, que comprende partículas discretas de celulosa y que, sorprendentemente, es altamente efectiva para la eliminación de la suciedad adherida a dichas superficies. Se ha comprobado que dicha composición es particularmente efectiva para eliminar de forma significativa la película de suciedad tipo traffic film adherida en las superficies exteriores de los vehículos sin que se produzca un deterioro de la superficie limpiada.  The authors of the present invention have developed a composition for cleaning hard surfaces under high pressure, which comprises discrete particles of cellulose and, surprisingly, is highly effective for the removal of dirt adhered to said surfaces. It has been found that said composition is particularly effective in removing significantly the traffic film of dirt film adhered to the exterior surfaces of the vehicles without deteriorating the cleaned surface.
Las partículas discretas de celulosa Discrete Cellulose Particles
En el ámbito de la presente invención, las partículas discretas de celulosa se refieren a partículas insolubles de celulosa.  Within the scope of the present invention, discrete cellulose particles refer to insoluble cellulose particles.
Las partículas discretas de celulosa apropiadas para ser utilizadas en las composiciones de la presente invención se seleccionan de entre el grupo formado por celulosa microcristalina, celulosa pulverulenta, nanocelulosa, microfibras de celulosa, y mezclas de las anteriores. Preferiblemente se seleccionan entre celulosa microcristalina, microfibras de celulosa, y mezclas de ambas.  Discrete cellulose particles suitable for use in the compositions of the present invention are selected from the group consisting of microcrystalline cellulose, powdered cellulose, nanocellulose, cellulose microfibers, and mixtures thereof. Preferably, they are selected from microcrystalline cellulose, cellulose microfibers, and mixtures of both.
Dichas partículas discretas de celulosa pueden presentar un aspecto de gránulos, de formas variables e irregulares, como es el caso de la celulosa microcristalina, la celulosa pulverulenta y la nanocelulosa; o bien puede tratarse de filamentos, de forma substancialmente cilindrica, como es el caso de las microfibras de celulosa.  Said discrete particles of cellulose may have an appearance of granules, of variable and irregular shapes, such as microcrystalline cellulose, powdery cellulose and nanocellulose; or it can be filaments, substantially cylindrical, as is the case with cellulose microfibers.
El tamaño medio de partícula de la celulosa microcristalina, la celulosa pulverulenta y la nanocelulosa se caracteriza habitualmente por su diámetro medio equivalente, que se determina según los procedimientos analíticos usuales para medir el tamaño medio de partículas tal como se describe, por ejemplo, en el libro M. E. Aulton, Farmacia. La ciencia del diseño de las formas farmacéuticas, segunda edición, Elsevier, Madrid, 2004, según el método de la zona sensible a la corriente eléctrica (contador Coulter), o por dispersión de la luz láser. Las microfibras de celulosa substancialmente cilindricas se caracterizan habitualmente por la longitud (L) y el espesor (E) de las mismas. En el contexto de la presente invención, las microfibras de celulosa se caracterizan también por su diámetro equivalente, cuyo valor corresponde al diámetro de una hipotética esfera que tiene el mismo volumen que el filamento de forma cilindrica definido por las dimensiones L y E antes mencionadas. The average particle size of the microcrystalline cellulose, the powdered cellulose and the nanocellulose is usually characterized by its equivalent mean diameter, which is determined according to the usual analytical procedures for measuring the average particle size as described, for example, in the Book ME Aulton, Pharmacy. The science of the design of pharmaceutical forms, second edition, Elsevier, Madrid, 2004, according to the method of the area sensitive to electric current (Coulter counter), or by laser light scattering. Substantially cylindrical cellulose microfibers are usually characterized by their length (L) and thickness (E). In the context of the present invention, cellulose microfibers are also characterized by their equivalent diameter, the value of which corresponds to the diameter of a hypothetical sphere having the same volume as the cylindrical filament defined by the aforementioned dimensions L and E.
Así pues, en el ámbito de esta invención, el tamaño medio de partícula de las partículas discretas de celulosa se refiere al diámetro medio equivalente determinado según los métodos arriba descritos, en función del tipo de partículas de celulosa de que se trate.  Thus, within the scope of this invention, the average particle size of the discrete cellulose particles refers to the equivalent average diameter determined according to the methods described above, depending on the type of cellulose particles in question.
Las partículas discretas de celulosa que forman parte del objeto de la presente invención tienen un tamaño medio de partícula inferior o igual a 200 μηπ, típicamente comprendido entre 0,05 μηπ y 200 μηπ, preferiblemente entre 1 μηπ y 150 μηπ, y más preferiblemente comprendido entre 10 μηπ y 100 μηπ.  Discrete cellulose particles that are part of the object of the present invention have an average particle size of less than or equal to 200 μηπ, typically between 0.05 μηπ and 200 μηπ, preferably between 1 μηπ and 150 μηπ, and more preferably comprised between 10 μηπ and 100 μηπ.
La celulosa microcristalina, celulosa pulverulenta y las microfibras de celulosa se encuentran disponibles comercialmente. La nanocelulosa se puede obtener a partir de las anteriores, por ejemplo mediante un tratamiento con ultrasonidos que reduce el tamaño medio de partícula hasta unas dimensiones de aproximadamente 1 μηπ o inferiores.  Microcrystalline cellulose, powdered cellulose and cellulose microfibers are commercially available. The nanocellulose can be obtained from the above, for example by means of an ultrasound treatment that reduces the average particle size to dimensions of approximately 1 μηπ or less.
La celulosa microcristalina es una sustancia pulverulenta cristalina, obtenida por hidrólisis controlada de α-celulosa, que presenta unas características especificadas por ejemplo en el manual de excipientes farmacéuticos, R. C. Rowe, P. J. Sheskey y P.J. Weller, Handbook oí Pharmaceutical Excipiente, cuarta edición, Pharmaceutical Press, 2003. La celulosa microcristalina puede obtenerse comercialmente de diversos proveedores, por ejemplo a través de la compañía FMC Biopolymer, bajo el nombre comercial general AVICEL®, y se encuentra disponible en diferentes tamaños medios de partícula que, habitualmente, están comprendidos entre 1 μηπ y 200 μηπ. También se pueden obtener a través de la compañía Acros Organics calidades de celulosa microcristalina con un tamaño medio de partícula de 50 μηπ o 90 μηπ. También se puede obtener a través de la compañía Sigma-Aldrich bajo la denominación Cellulose microcrystalline 310697 con un tamaño medio de partículas de 20 μηπ. Microcrystalline cellulose is a crystalline powdery substance, obtained by controlled hydrolysis of α-cellulose, which has characteristics specified for example in the manual of pharmaceutical excipients, RC Rowe, PJ Sheskey and PJ Weller, Handbook or Pharmaceutical Excipient, fourth edition, Pharmaceutical Press, 2003. Microcrystalline cellulose can be obtained commercially from various suppliers, for example through the company FMC Biopolymer, under the general trade name AVICEL®, and is available in different average particle sizes that are usually comprised between 1 μηπ and 200 μηπ. You can also obtain microcrystalline cellulose qualities with an average particle size of 50 μηπ or 90 μηπ from the Acros Organics company. It can also be obtained through the Sigma-Aldrich company under the name Cellulose microcrystalline 310697 with an average particle size of 20 μηπ.
Preferiblemente se emplea celulosa microcristalina con un tamaño medio de partícula comprendido entre 20 μηπ y 100 μηπ.  Preferably, microcrystalline cellulose with an average particle size between 20 μηπ and 100 μηπ is used.
La celulosa pulverulenta es un polvo obtenido por reducción del tamaño de la α-celulosa por medios mecánicos, que presenta unas características especificadas en el libro R. C. Rowe, ya citado. La celulosa en forma pulverulenta puede obtenerse comercialmente, por ejemplo a través de la compañía J. Rettenmaier & Sóhne, bajo el nombre comercial general ARBOCEL®. Dicha celulosa se encuentra disponible en diferentes tamaños medios de partícula que, habitualmente, están comprendidos entre 1 μηπ y 200 μηπ.  Powdered cellulose is a powder obtained by reducing the size of α-cellulose by mechanical means, which has characteristics specified in the book R. C. Rowe, already cited. Powdered cellulose can be obtained commercially, for example through the company J. Rettenmaier & Sóhne, under the general trade name ARBOCEL®. Said cellulose is available in different average particle sizes, which are usually between 1 μηπ and 200 μηπ.
Las microfibras de celulosa pueden obtenerse mediante diversos tratamientos mecánicos y/o químicos de la celulosa hasta conseguir celulosa en forma de filamentos. Las microfibras de celulosa pueden obtenerse comercialmente a través de diversos proveedores, por ejemplo a través de la compañía, J. Rettenmaier & Sóhne, bajo el nombre comercial general ARBOCEL®. Dichas microfibras se encuentran disponibles en diferentes tamaños, y habitualmente están caracterizadas por la longitud (L) y el espesor (E) de las mismas. Las microfibras de celulosa apropiadas para ser utilizadas en la presente invención pueden presentar una longitud comprendida aproximadamente entre 1 μηπ y 220 μηπ, y un espesor comprendido aproximadamente entre 0,01 μηπ y 150 μηπ, lo que equivale a un diámetro medio equivalente comprendido entre 0,05 μηπ y 195 μηπ, según la aproximación que se ha explicado anteriormente. Preferiblemente se emplean microfibras de celulosa que presentan un diámetro medio equivalente comprendido entre 10 μηπ y 30 μηπ.  Cellulose microfibers can be obtained by various mechanical and / or chemical treatments of cellulose until cellulose is obtained in the form of filaments. Cellulose microfibers can be obtained commercially from various suppliers, for example through the company, J. Rettenmaier & Sóhne, under the general trade name ARBOCEL®. Such microfibers are available in different sizes, and are usually characterized by their length (L) and thickness (E). Cellulose microfibers suitable for use in the present invention may have a length between approximately 1 μηπ and 220 μηπ, and a thickness between approximately 0.01 μηπ and 150 μηπ, which is equivalent to an equivalent average diameter between 0 , 05 μηπ and 195 μηπ, according to the approximation explained above. Preferably, cellulose microfibers having an equivalent average diameter between 10 μηπ and 30 μηπ are used.
Las nanopartículas de celulosa pueden obtenerse a partir de cualquiera de las partículas de celulosa anteriormente descritas, es decir, a partir de celulosa microcristalina, celulosa pulverulenta, o microfibras de celulosa, sometiéndolas a un procedimiento para reducir su tamaño. Esta reducción se puede conseguir, por ejemplo, mediante el tratamiento con ultrasonidos de una dispersión líquida de dichas partículas, hasta obtener nanopartículas de celulosa cuyo tamaño medio es igual o inferior a 1 μηπ, preferiblemente comprendido entre 0,05 μηπ y 1 μηπ. Preferiblemente, el tratamiento con ultrasonidos se efectúa a una potencia de 450 W, durante un período de tiempo comprendido entre 5 minutos y 3 horas, utilizando una dispersión de las partículas de celulosa preferiblemente en agua destilada con una concentración comprendida entre el 0,01 % y el 20%, expresado en peso. Cellulose nanoparticles can be obtained from any of the cellulose particles described above, that is, from microcrystalline cellulose, powdered cellulose, or cellulose microfibers, by subjecting them to a process to reduce their size. This reduction can be achieved, for example, by ultrasonic treatment of a liquid dispersion of said particles, until obtaining cellulose nanoparticles whose average size is equal to or less than 1 μηπ, preferably between 0.05 μηπ and 1 μηπ. Preferably, the ultrasonic treatment is carried out at a power of 450 W, for a period of time between 5 minutes and 3 hours, using a dispersion of the cellulose particles preferably in distilled water with a concentration between 0.01% and 20%, expressed by weight.
Composición Composition
La composición para la limpieza de superficies duras a alta presión de la presente invención comprende partículas discretas de celulosa, según se han definido anteriormente.  The high pressure hard surface cleaning composition of the present invention comprises discrete cellulose particles, as defined above.
Preferiblemente, la composición objeto de la presente invención comprende entre el 1 % y el 20% de partículas discretas de celulosa, porcentaje expresado en peso de celulosa respecto al peso total de sólidos de la composición. En el contexto de la invención se entiende por "sólidos" todos los ingredientes de la composición, exceptuando el agua y, eventualmente, otros co-solventes.  Preferably, the composition object of the present invention comprises between 1% and 20% of discrete cellulose particles, percentage expressed by weight of cellulose with respect to the total weight of solids of the composition. In the context of the invention, "solids" means all the ingredients of the composition, except water and, eventually, other co-solvents.
El efecto limpiador de las partículas discretas de celulosa resulta tan significativo que en una realización preferida de la invención, la composición limpiadora comprende únicamente partículas discretas de celulosa como producto insoluble, es decir, la composición no comprende productos abrasivos adicionales.  The cleaning effect of the discrete cellulose particles is so significant that in a preferred embodiment of the invention, the cleaning composition comprises only discrete particles of cellulose as an insoluble product, that is, the composition does not comprise additional abrasive products.
En la forma más simple de realización la composición comprende las partículas discretas de celulosa dispersadas en agua y agentes conservantes. En este caso la composición comprende entre el 1 % y el 20% en peso respecto del peso total de la composición.  In the simplest embodiment, the composition comprises discrete particles of cellulose dispersed in water and preservatives. In this case the composition comprises between 1% and 20% by weight with respect to the total weight of the composition.
Para obtener un grado de limpieza más significativo, preferiblemente dicha composición comprende además agentes tensioactivos, coadyuvantes y, opcionalmente, otros productos auxiliares.  To obtain a more significant degree of cleaning, preferably said composition further comprises surfactants, adjuvants and, optionally, other auxiliary products.
Esta composición con tensioactivos, adyuvantes y eventualmente otros componentes auxiliares puede ser sólida o líquida, sin que la forma de presentación tenga influencia en el resultado de la limpieza, ya que, tal como se explica más adelante, la composición, sea sólida o líquida, se dispersa en agua antes de ser aplicada a alta presión sobre la superficie dura. This composition with surfactants, adjuvants and possibly other auxiliary components can be solid or liquid, without the presentation form influencing the cleaning result, since, such as explained below, the composition, whether solid or liquid, is dispersed in water before being applied at high pressure on the hard surface.
Los agentes tensioactivos, como es bien conocido por el experto en la materia, son sustancias anfifílicas que poseen una parte hidrofobica y una parte hidrofílica. Esta estructura química particular de los tensioactivos juega un importante papel en el proceso de lavado, debido a que disminuyen la tensión superficial del líquido con lo que favorecen el mojado de las superficies y son también capaces de agruparse formando micelas, lo que permite disolver, emulsionar o disgregar la suciedad.  Surfactants, as is well known to those skilled in the art, are amphiphilic substances that have a hydrophobic part and a hydrophilic part. This particular chemical structure of the surfactants plays an important role in the washing process, because they decrease the surface tension of the liquid, which favors the wetting of the surfaces and are also able to group together forming micelles, which allows dissolving, emulsifying or break up the dirt.
Los tensioactivos apropiados para ser empleados en las composiciones de esta invención se seleccionan de entre el grupo formado por tensioactivos aniónicos, no iónicos, catiónicos, anfóteros, y mezclas de los anteriores.  The surfactants suitable for use in the compositions of this invention are selected from the group consisting of anionic, nonionic, cationic, amphoteric surfactants, and mixtures thereof.
Una gran variedad de productos tensioactivos puede obtenerse de forma comercial a partir de diversos suministradores, tales como, por ejemplo, las compañías Kao Corportation, BASF, Croda, Huntsman, Evonik, o Cognis (actualmente BASF), entre otras.  A wide variety of surfactant products can be obtained commercially from various suppliers, such as, for example, the companies Kao Corportation, BASF, Croda, Huntsman, Evonik, or Cognis (currently BASF), among others.
Entre los tensioactivos aniónicos apropiados para ser usados en el marco de la presente invención se encuentran, por ejemplo, jabones, ácidos alquilbencenosulfonicos y sus sales, α-olefinas sulfonadas, parafinas sulfonadas, sulfatos de alquilo, sulfatos de éteres de alquilo, sulfatos de éteres de glicerina, sulfosuccinatos de alquilo, éteres de ácidos carboxílicos y sus sales, fosfatos de alquilo, fosfatos de éteres de alquilo, sulfatos de alquilfenoles, sulfatos de éteres de alquilfenoles, isetionatos, sarcosinatos, tauratos, y sales de N-acilaminoácidos. Por sólo citar algunos ejemplos de este grupo, entre los sulfatos de éteres de alquilo se encuentra el lauril éter sulfato sódico, como el suministrado por la compañía Kao Corporation bajo la denominación comercial EMAL® o la gama de productos TEXAPON® de la compañía Cognis (actualmente BASF); los sulfatos de alquilo se encuentran comercializados bajo la denominación SULFOPON ® de la compañía Cognis (actualmente BASF); entre los éteres de ácidos carboxílicos se encuentran los suministrados por la compañía Kao Corporation bajo la denominación comercial AKYPO®; o entre los ácidos alquilbencenosulfonicos cabe citar, por ejemplo, los ácidos alquilbenceno sulfónicos lineales (LAS) especialmente el ácido n-dodecilbencenosulfónico y sus sales, como por ejemplo el suministrado por la compañía Cognis (actualmente BASF) bajo la denominación comercial MARANIL®. Among the anionic surfactants suitable for use in the context of the present invention are, for example, soaps, alkylbenzenesulfonic acids and their salts, sulfonated α-olefins, sulfonated paraffins, alkyl sulfates, alkyl ether sulfates, ether sulfates of glycerin, alkyl sulfosuccinates, carboxylic acid ethers and salts thereof, alkyl phosphates, alkyl ether phosphates, alkylphenol sulfates, alkylphenol ether sulfates, isethionates, sarcosinates, taurates, and N-acylamino acid salts. Just to name a few examples of this group, sodium lauryl ether sulfate is among the alkyl ether sulfates, such as that supplied by the Kao Corporation under the trade name EMAL® or the Cognis range of products TEXAPON® ( currently BASF); alkyl sulfates are marketed under the name SULFOPON ® of the Cognis company (currently BASF); among the ethers of carboxylic acids are those supplied by the company Kao Corporation under the trade name AKYPO®; or among the alkylbenzenesulfonic acids, For example, linear alkylbenzene sulfonic acids (LAS), especially n-dodecylbenzenesulfonic acid and its salts, such as that supplied by Cognis (currently BASF) under the trade name MARANIL®.
Entre los tensioactivos no iónicos apropiados para ser usados en el marco de la presente invención se encuentran, por ejemplo, alcoholes grasos etoxilados, ácidos grasos etoxilados, alquilfenoles etoxilados, alcanolamidas de ácidos grasos, alcanolamidas etoxiladas de ácidos grasos, aminas grasas etoxiladas, óxidos de amina grasos, óxidos de amidoaminas grasas, ésteres de glicerina y ácidos grasos, ésteres de sorbitán, ésteres de sorbitán etoxilado, ésteres de sacarosa, alquilpoliglicósidos, copolímeros de óxido de etileno/propileno, entre otros. Así, por ejemplo, entre los alcoholes grasos etoxilados pueden citarse los suministrados por la compañía Cognis (actualmente BASF) bajo la denominación comercial DEHYDOL®, por ejemplo el DEHYDOL® LT7 que es un alcohol graso Ci2-Ci8 con aproximadamente 7 moles de oxido de etileno. Entre los ésteres de sorbitán etoxilado pueden mencionarse los suministrados por la compañía Kao Corporation bajo la denominación comercial RHEODOL®. Entre los alquilfenoles etoxilados se pueden mencionar los productos comercializados bajo la denominación DEHYDROPHEN® por la compañía Cognis (actualmente BASF). Among the nonionic surfactants suitable for use in the context of the present invention are, for example, ethoxylated fatty alcohols, ethoxylated fatty acids, ethoxylated alkylphenols, fatty acid alkanolamides, ethoxylated fatty acid alkanolamides, ethoxylated fatty amines, oxides of fatty amine, fatty amidoamine oxides, glycerin esters and fatty acids, sorbitan esters, ethoxylated sorbitan esters, sucrose esters, alkyl polyglycosides, ethylene / propylene oxide copolymers, among others. Thus, for example, among the ethoxylated fatty alcohols, those supplied by Cognis (currently BASF) under the trade name DEHYDOL®, for example DEHYDOL® LT7 which is a Ci 2 -Ci 8 fatty alcohol with approximately 7 moles of ethylene oxide. Among the ethoxylated sorbitan esters, those supplied by the Kao Corporation under the trade name RHEODOL® may be mentioned. Among the ethoxylated alkylphenols, products marketed under the name DEHYDROPHEN® by the company Cognis (currently BASF) may be mentioned.
Entre los tensioactivos anfóteros adecuados para ser usados en el marco de la presente invención se encuentran, por ejemplo, alquildimetil betaínas, alquilamidobetaínas, alquilsulfobetaínas, alquilamidosulfobetaínas, derivados de imidazolina y alquilaminopropionatos, entre otros. Así, por ejemplo, entre las alquilamidobetaínas pueden mencionarse las suministradas por la compañía Cognis (actualmente BASF) bajo la denominación comercial DEHYTON®.  Among the amphoteric surfactants suitable for use in the context of the present invention are, for example, alkyldimethyl betaines, alkylamido betaines, alkylsulfobetaines, alkylamido sulfobetaines, imidazoline derivatives and alkylaminopropionates, among others. Thus, for example, among the alkylamido betaines those mentioned by the company Cognis (currently BASF) may be mentioned under the trade name DEHYTON®.
Los tensioactivos catiónicos adecuados para ser usados en el marco de la presente invención son compuestos de amonio cuaternario que presentan un efecto antiestático, como por ejemplo cloruro de benzalconio, que se encuentra disponible comercialmente bajo el nombre comercial DEHYQUART® suministrado por la compañía Cognis (actualmente BASF). En el libro M. Asch y I. Asch, Handbook of Industrial Surfactants, cuarta edición, Synapse Information Resources, 2005, puede encontrarse una extensa relación de los tensioactivos disponibles comercialmente. The cationic surfactants suitable for use in the context of the present invention are quaternary ammonium compounds having an antistatic effect, such as benzalkonium chloride, which is commercially available under the trade name DEHYQUART® supplied by the Cognis company (currently BASF). In the book M. Asch and I. Asch, Handbook of Industrial Surfactants, fourth edition, Synapse Information Resources, 2005, an extensive list of commercially available surfactants can be found.
Como agentes coadyuvantes pueden utilizarse, por ejemplo, polifosfatos, especialmente tripolifosfatos y pirofosfatos alcalinos, carbonatos alcalinos, silicatos alcalinos, zeolitas, sales alcalinas del ácido nitriloacético, EDTA y sus sales, los actuales sustitutos ecológicos de NTA/ EDTA/fosfatos, tales como el GLDA (del inglés Glutamic Acid Ν,Ν-Diacetic Acid) disponible comercialmente bajo el nombre de Disolvine® GL de Akzo Nobel, sales alcalinas del ácido cítrico, y sus mezclas. La sal alcalina que se emplea preferiblemente es la sal sódica.  As auxiliary agents, for example, polyphosphates, especially alkali metal tripolyphosphates and pyrophosphates, alkali carbonates, alkali silicates, zeolites, alkali salts of nitrileacetic acid, EDTA and their salts, the current ecological substitutes of NTA / EDTA / phosphates, such as GLDA (Glutamic Acid Ν, Ν-Diacetic Acid) commercially available under the name of Disolvine® GL from Akzo Nobel, alkaline salts of citric acid, and mixtures thereof. The alkaline salt that is preferably used is the sodium salt.
La composición limpiadora objeto de la presente invención puede contener, opcionalmente, otros productos auxiliares como, por ejemplo, enzimas, colorantes, estabilizadores de espuma, agentes espesantes, co- solventes, y reguladores del pH. En el caso de que se trate de una composición líquida generalmente ésta comprende también agentes conservantes.  The cleaning composition object of the present invention may optionally contain other auxiliary products such as, for example, enzymes, dyes, foam stabilizers, thickening agents, solvents, and pH regulators. In the case of a liquid composition, it generally also includes preservatives.
En una realización preferida de la presente invención, la composición limpiadora comprende entre el 1 % y el 20% de partículas discretas de celulosa, preferiblemente entre el 5% y el 10%; entre el 5% y el 50% de tensioactivos, preferiblemente entre el 10% y el 30%; y entre el 35% y el 95% de coadyuvantes, preferiblemente entre el 50% y el 65%. Estos porcentajes están expresados en peso con respecto al peso total de sólidos de la composición. Los porcentajes de los diferentes componentes se seleccionan de modo que la suma de los mismos resulta el 100% de la composición.  In a preferred embodiment of the present invention, the cleaning composition comprises between 1% and 20% of discrete cellulose particles, preferably between 5% and 10%; between 5% and 50% of surfactants, preferably between 10% and 30%; and between 35% and 95% of adjuvants, preferably between 50% and 65%. These percentages are expressed in weight with respect to the total weight of solids of the composition. The percentages of the different components are selected so that the sum of them is 100% of the composition.
En una realización más preferida de la presente invención, la composición limpiadora comprende entre el 1 % y el 20% de partículas discretas de celulosa, preferiblemente entre el 5% y el 10%; entre el 2% y el 20% de tensioactivos aniónicos, preferiblemente entre el 2% y el 10%; entre el 3% y el 30% de tensioactivos no iónicos, preferiblemente entre el 5% y el 15%; y entre el 35% y el 95% de coadyuvantes, preferiblemente entre el 50% y el 65%. Estos porcentajes están expresados en peso con respecto al peso total de sólidos de la composición. Los porcentajes de los diferentes componentes se seleccionan de modo que la suma de los mismos resulta el 100% de la composición. In a more preferred embodiment of the present invention, the cleaning composition comprises between 1% and 20% of discrete cellulose particles, preferably between 5% and 10%; between 2% and 20% of anionic surfactants, preferably between 2% and 10%; between 3% and 30% of non-ionic surfactants, preferably between 5% and 15%; and between 35% and 95% of adjuvants, preferably between 50% and 65%. These percentages are expressed in weight with respect to the total weight of solids of the composition. The percentages of the different components they are selected so that the sum of them results in 100% of the composition.
En una realización particularmente preferida el tensioactivo aniónico es una sal alcalina de un ácido alquilbencenosulfónico lineal, y más preferiblemente es la sal sódica del ácido n-dodecilbencenosulfónico; el tensioactivo no iónico es un alcohol graso etoxilado, más preferiblemente es un alcohol de cadena Ci2-Ci8 etoxilado con aproximadamente 7 moles de óxido de etileno, y el coadyuvante se selecciona entre el grupo formado por tripolifosfato sódico, carbonato sódico, y mezclas de ambos, más preferiblemente el coadyuvante es una mezcla de tripolifosfato sódico y carbonato sódico. In a particularly preferred embodiment the anionic surfactant is an alkaline salt of a linear alkylbenzenesulfonic acid, and more preferably it is the sodium salt of n-dodecylbenzenesulfonic acid; the nonionic surfactant is an ethoxylated fatty alcohol, more preferably it is an ethoxylated Ci 2 -Ci 8 chain alcohol with about 7 moles of ethylene oxide, and the adjuvant is selected from the group consisting of sodium tripolyphosphate, sodium carbonate, and mixtures of both, more preferably the adjuvant is a mixture of sodium tripolyphosphate and sodium carbonate.
Una composición limpiadora sólida característica según la presente invención, comprende, por ejemplo, entre el 1 % y el 20% de partículas discretas de celulosa, entre el 5% y el 45% de tripolifosfato sódico, entre el 20% y el 50% de carbonato sódico, entre el 2% y el 10% de tensioactivo aniónico y entre el 5% y el 15% de tensioactivo no iónico. Estos porcentajes están expresados en peso respecto al peso total de sólidos de la composición. Los porcentajes de los diferentes componentes se seleccionan de modo que la suma de los mismos resulta el 100% de la composición.  A characteristic solid cleaning composition according to the present invention comprises, for example, between 1% and 20% of discrete cellulose particles, between 5% and 45% of sodium tripolyphosphate, between 20% and 50% of sodium carbonate, between 2% and 10% anionic surfactant and between 5% and 15% non-ionic surfactant. These percentages are expressed in weight with respect to the total weight of solids of the composition. The percentages of the different components are selected so that the sum of them is 100% of the composition.
Opcionalmente, la composición puede contener también otros ingredientes, tales como tensioactivos anfóteros, tensioactivos catiónicos, enzimas, colorantes, estabilizadores de espuma, entre otros.  Optionally, the composition may also contain other ingredients, such as amphoteric surfactants, cationic surfactants, enzymes, dyes, foam stabilizers, among others.
La preparación de la composición detergente se realiza según procedimientos que son bien conocidos en el campo de la tecnología de los detergentes. Por ejemplo una composición detergente sólida puede prepararse por mezcla directa de todos los ingredientes cuando éstos son sólidos, mezclándose también directamente con las partículas discretas de celulosa. También puede prepararse mediante un procedimiento que comprende una etapa de atomización, para lo cual se prepara previamente una pasta, o slurry en inglés, por dispersión en agua de algunos de los componentes, habitualmente tensioactivos aniónicos y coadyuvantes. Dicha pasta es sometida a un secado por atomización, por ejemplo, a contracorriente de aire caliente. De esta forma se obtienen partículas de la composición detergente en polvo con una densidad aparente comprendida aproximadamente entre 300 g/l y 1000 g/l. La composición detergente atomizada puede completarse mediante la adición posterior de otros componentes como, por ejemplo, tensioactivos no iónicos. Las partículas discretas de celulosa también pueden añadirse en esta etapa final sobre el detergente ya atomizado. The preparation of the detergent composition is carried out according to procedures that are well known in the field of detergent technology. For example a solid detergent composition can be prepared by direct mixing of all the ingredients when they are solid, also mixing directly with the discrete particles of cellulose. It can also be prepared by a process comprising an atomization step, for which a paste, or slurry in English, is previously prepared by dispersion in water of some of the components, usually anionic surfactants and adjuvants. Said paste is subjected to spray drying, for example, against a counter current of hot air. In this way particles of the powder detergent composition with an apparent density of approximately 300 g / l are obtained. and 1000 g / l. The atomized detergent composition can be completed by the subsequent addition of other components such as, for example, non-ionic surfactants. Discrete cellulose particles can also be added in this final stage onto the already atomized detergent.
Una composición limpiadora líquida característica según la presente invención comprende, por ejemplo, entre el 0,5% y el 5% de partículas discretas de celulosa entre el 10% y el 20% de tripolifosfato sódico, entre el 1 % y el 15% de tensioactivo no iónico y entre el 1 % y el 10% de tensioactivo aniónico, añadiéndose agua, opcionalmente combinada con otros co-solventes, hasta alcanzar el 100% de la composición. En este caso, los porcentajes se expresan en peso de cada ingrediente respecto al peso total de la composición incluyendo el agua y eventualmente los co-solventes. Algunos co-solventes adecuados para ser usados en las formulaciones líquidas de la invención son, por ejemplo, propilenglicol, 1 -metoxi-2-propanol, glicerina, cumensulfonato, dipropilenglicol, dipropilenglicol monometiléter, butilgllicol, o butildiglicol. Opcionalmente, la formulación detergente líquida puede contener otros ingredientes, tales como tensioactivos anfóteros, tensioactivos catiónicos, enzimas, colorantes, estabilizadores de espuma, agentes espesantes, reguladores del pH, y conservantes entre otros.  A characteristic liquid cleaning composition according to the present invention comprises, for example, between 0.5% and 5% discrete cellulose particles between 10% and 20% sodium tripolyphosphate, between 1% and 15% of nonionic surfactant and between 1% and 10% anionic surfactant, water being added, optionally combined with other co-solvents, until 100% of the composition is reached. In this case, the percentages are expressed in weight of each ingredient with respect to the total weight of the composition including water and possibly co-solvents. Some co-solvents suitable for use in the liquid formulations of the invention are, for example, propylene glycol, 1-methoxy-2-propanol, glycerin, cumensulfonate, dipropylene glycol, dipropylene glycol monomethyl ether, butylglycol, or butyldiglycol. Optionally, the liquid detergent formulation may contain other ingredients, such as amphoteric surfactants, cationic surfactants, enzymes, dyes, foam stabilizers, thickeners, pH regulators, and preservatives among others.
La preparación del detergente líquido se realiza según procedimientos que son también bien conocidos en el campo de la tecnología de los detergentes. Por ejemplo se puede preparar por disolución de los diferentes componentes en agua, bajo agitación hasta conseguir una di solución homogénea. Las partículas discretas de celulosa pueden añadirse, por ejemplo, en una etapa final, sobre la composición detergente preparada, agitando mecánicamente o con otros métodos de dispersión como, por ejemplo, la sonicación, hasta obtener una dispersión homogénea de dichas partículas en el medio líquido. La superficie dura  The preparation of the liquid detergent is carried out according to procedures that are also well known in the field of detergent technology. For example, it can be prepared by dissolving the different components in water, with stirring until a homogeneous solution is achieved. Discrete cellulose particles can be added, for example, in a final stage, on the prepared detergent composition, by stirring mechanically or with other dispersion methods such as sonication, until obtaining a homogeneous dispersion of said particles in the liquid medium. . Hard surface
En el contexto de la presente invención, el término superficie dura se entiende de forma amplia, y comprende, por ejemplo, cualquier superficie metálica, por ejemplo de aluminio, cromo, acero, o acero inoxidable; superficies de vidrio, cerámica o porcelana; superficies de caucho o goma; superficies de cualquier tipo de plástico, tales como polímeros termoplásticos o termoestables, entre otros posibles materiales. Así mismo, también se incluyen dichas superficies que se encuentran recubiertas con una capa de pintura, barniz, esmalte, u otro tipo de acabado. In the context of the present invention, the term "hard surface" is broadly understood, and comprises, for example, any metal surface, for example aluminum, chrome, steel, or stainless steel; surfaces glass, ceramic or porcelain; rubber or rubber surfaces; surfaces of any type of plastic, such as thermoplastic or thermosetting polymers, among other possible materials. Likewise, said surfaces that are coated with a layer of paint, varnish, enamel, or other type of finish are also included.
Las superficies duras a limpiar según el procedimiento de la presente invención pueden corresponder a una amplia variedad de objetos, tanto a nivel doméstico como industrial. Entre ellos se pueden mencionar, por ejemplo, suelos, paredes, baldosas, fregaderos, superficies de trabajo, persianas, ventanas, baños, cualquier tipo de mobiliario exterior, paneles, contenedores, lonas, maquinaria, o la superficie exterior de cualquier tipo de vehículo.  The hard surfaces to be cleaned according to the process of the present invention can correspond to a wide variety of objects, both domestically and industrially. These may include, for example, floors, walls, tiles, sinks, work surfaces, blinds, windows, bathrooms, any type of outdoor furniture, panels, containers, tarpaulins, machinery, or the exterior surface of any type of vehicle .
En una realización preferida, la composición limpiadora y el procedimiento de limpieza de la presente invención se aplican para la limpieza de la superficie exterior de un vehículo. Se ha observado que la composición de la invención es particularmente efectiva para eliminar el denominado traffic film.  In a preferred embodiment, the cleaning composition and the cleaning process of the present invention are applied for cleaning the exterior surface of a vehicle. It has been observed that the composition of the invention is particularly effective in eliminating the so-called traffic film.
Se trata de un tipo particular de suciedad que se adhiere sobre la superficie exterior del vehículo formando una película y que resulta difícil de eliminar sin tocar la superficie en un proceso "touchless", es decir, sin ayuda de efecto mecánico: frotado, cepillado, etc., mediante los procedimientos descritos en el estado de la técnica porque tiene una composición muy heterogénea.  It is a particular type of dirt that adheres to the exterior surface of the vehicle forming a film and that is difficult to remove without touching the surface in a "touchless" process, that is, without the help of mechanical effect: rubbing, brushing, etc., by the procedures described in the state of the art because it has a very heterogeneous composition.
La película de traffic film puede contener, por ejemplo, residuos de combustión del combustible, fugas de combustible, negro de carbón, sustancias lubricantes, residuos de previos lavados, así como sustancias ambientales muy heterogéneas presentes en las carreteras, tales como sales, arena, o barro.  The traffic film may contain, for example, fuel combustion residues, fuel leaks, carbon black, lubricating substances, residues from previous washes, as well as very heterogeneous environmental substances present on the roads, such as salts, sand, or mud.
En el contexto de la presente invención, el término vehículo incluye cualquier medio de transporte, típicamente, automóviles, camiones, autobuses, remolques, vagones, motocicletas, aeroplanos, aviones, o sus partes, entre otros.  In the context of the present invention, the term "vehicle" includes any means of transport, typically, cars, trucks, buses, trailers, wagons, motorcycles, airplanes, airplanes, or parts thereof, among others.
Procedimiento de limpieza Forma también parte del objeto de esta invención un procedimiento para la limpieza de superficies duras que comprende la etapa de pulverizar a alta presión sobre la superficie dura una dispersión acuosa de la composición de la invención que comprende partículas discretas de celulosa cuyo tamaño medio de partícula es inferior o igual a 200 μηπ. Cleaning procedure Also part of the object of this invention is a process for cleaning hard surfaces comprising the step of spraying at high pressure on the hard surface an aqueous dispersion of the composition of the invention comprising discrete cellulose particles whose average particle size is less than or equal to 200 μηπ.
En el contexto de la presente invención, se entiende por alta presión una presión igual o superior a 10 bares. En una realización preferida, el procedimiento de limpieza se realiza a una presión comprendida entre 20 y 200 bares, más preferiblemente comprendida entre 50 y 1 50 bares, y más preferiblemente entre 90 y 1 10 bares.  In the context of the present invention, high pressure means a pressure equal to or greater than 10 bar. In a preferred embodiment, the cleaning process is performed at a pressure between 20 and 200 bars, more preferably between 50 and 1 50 bars, and more preferably between 90 and 1 10 bars.
La pulverización a alta presión puede realizarse empleando una máquina hidrolimpiadora a presión como las que existen en el mercado, por ejemplo, las suministradas por la compañía Nilfisk-ALTO, Kárcher o bombas de pistones tipo "CAT", o "Interpump".  High pressure spraying can be carried out using a pressure washer such as those available on the market, for example, those supplied by the company Nilfisk-ALTO, Kárcher or piston pumps type "CAT", or "Interpump".
En el procedimiento de la invención la dispersión acuosa que se pulveriza se prepara por dispersión en agua de la composición de la invención. Esto es, el procedimiento de la invención comprende una etapa previa de preparar una dispersión acuosa de la composición que comprende las partículas discretas de celulosa.  In the process of the invention the aqueous dispersion that is sprayed is prepared by dispersion in water of the composition of the invention. That is, the process of the invention comprises a previous step of preparing an aqueous dispersion of the composition comprising discrete cellulose particles.
Habitualmente, dichas máquinas disponen de un depósito en donde se prepara una dispersión acuosa madre de la composición que comprende las partículas discretas de celulosa.  Usually, said machines have a reservoir in which a mother aqueous dispersion of the composition comprising discrete cellulose particles is prepared.
En una realización de la invención, dicha dispersión acuosa se prepara mediante dispersión en agua de la composición de la invención, bien sea en forma sólida o líquida, hasta una dilución aproximada de 1 a 10 g/l de la misma, quedando las partículas de celulosa en suspensión.  In an embodiment of the invention, said aqueous dispersion is prepared by dispersion in water of the composition of the invention, either in solid or liquid form, to an approximate dilution of 1 to 10 g / l thereof, the particles of which remain suspension cellulose.
Típicamente dicha dispersión acuosa madre se dosifica en el seno de un chorro de agua a presión, mediante un dispositivo que a tal efecto poseen dichas máquinas hidrolimpiadoras, y que permite ajustar convenientemente la concentración final en el agua pulverizada, o concentración en punta de lanza, que es la que se propulsa efectivamente contra la superficie a limpiar. Según el procedimiento de limpieza de la presente invención, la concentración de las partículas discretas de celulosa en punta de lanza, está comprendida preferiblemente entre el 0,005% y el 0,2%, más preferiblemente entre el 0,005% y el 0,1 %, y aún más preferiblemente entre el 0,005% y el 0,05%, en donde el porcentaje viene expresado en peso de celulosa respecto del peso de la dispersión acuosa pulverizada. Typically said mother aqueous dispersion is dosed into a jet of pressurized water, by means of a device that such hydrolypiating machines possess, and which allows conveniently adjusting the final concentration in the sprayed water, or spearhead concentration, which is the one that is effectively propelled against the surface to be cleaned. According to the cleaning process of the present invention, the concentration of the discrete cellulose particles at the spearhead is preferably between 0.005% and 0.2%, more preferably between 0.005% and 0.1%, and even more preferably between 0.005% and 0.05%, wherein the percentage is expressed by weight of cellulose with respect to the weight of the aqueous dispersion sprayed.
Los dispositivos de limpieza empleados tienen habitualmente un sistema de calentamiento del agua para su posterior aplicación a presión sobre la superficie a limpiar. El procedimiento de limpieza según la presente invención puede efectuarse a una temperatura comprendida entre la temperatura ambiente y aproximadamente 90Q C, preferiblemente entre 40Q C y 70Q C, y aún más preferiblemente entre 50Q C y 60Q C. The cleaning devices used usually have a water heating system for subsequent application under pressure on the surface to be cleaned. The cleaning method according to the present invention can be effected at a temperature between room temperature and about 90 Q C, preferably between 40 and 70 Q C Q C, and most preferably between 50 C and 60 Q Q C.
Ensayos de eficacia Efficacy tests
Se realizaron diversos ensayos para valorar la eficacia del procedimiento de limpieza a alta presión que forma parte de la invención, en particular, usando las composiciones limpiadoras de la invención. Los resultados de dichos ensayos se explican detalladamente en el apartado de Ejemplos.  Various tests were performed to assess the efficacy of the high pressure cleaning process that forms part of the invention, in particular, using the cleaning compositions of the invention. The results of these tests are explained in detail in the Examples section.
A partir de los resultados obtenidos, los autores de la presente invención observaron que, sorprendentemente, con las composiciones de la invención incluyendo las partículas discretas de celulosa, se consigue una eficacia en el lavado de superficies duras substancialmente superior respecto a composiciones detergentes que no comprenden dichas partículas.  From the results obtained, the authors of the present invention observed that, surprisingly, with the compositions of the invention including discrete cellulose particles, a washing efficiency of substantially higher hard surfaces is achieved with respect to detergent compositions which do not comprise said particles.
También se ha observado que el empleo de las partículas de celulosa en la composición detergente para la limpieza de superficies duras puede permitir reducir la carga química de la misma sin disminuir la eficacia.  It has also been observed that the use of cellulose particles in the detergent composition for cleaning hard surfaces can reduce the chemical load thereof without decreasing the effectiveness.
Asimismo, se ha observado que con la composición de la invención se puede reducir considerablemente la concentración en punta de lanza, se optimizan los tiempos de limpieza y se reducen las aguas residuales.  Likewise, it has been observed that with the composition of the invention, the spearhead concentration can be considerably reduced, cleaning times are optimized and wastewater is reduced.
Es de destacar el efecto sinérgico que se observó al incorporar las partículas discretas de celulosa en una composición detergente. Como se explica en los ejemplos, con una menor concentración a punta de lanza de partículas de celulosa y de detergente se obtuvo un mayor grado de limpieza que el obtenido con un contenido más elevado de partículas de celulosa, pero sin detergente, o que el obtenido con una mayor concentración de detergente, pero sin partículas de celulosa. It is noteworthy the synergistic effect that was observed when incorporating discrete cellulose particles in a detergent composition. As explained in the examples, with a lower concentration at the spearhead of Cellulose and detergent particles a higher degree of cleaning was obtained than that obtained with a higher content of cellulose particles, but without detergent, or that obtained with a higher concentration of detergent, but without cellulose particles.
Es por ello, que es también un objeto de la presente invención el uso de partículas discretas de celulosa de tamaño medio de partícula inferior o igual a 200 μηπ para la limpieza a alta presión de superficies duras, como por ejemplo para la limpieza de la superficie exterior de un vehículo  That is why it is also an object of the present invention to use discrete cellulose particles of average particle size less than or equal to 200 μηπ for high pressure cleaning of hard surfaces, such as for surface cleaning exterior of a vehicle
La utilización de las partículas discretas de celulosa facilita la eliminación de la suciedad del tipo traffic film de los vehículos en procesos sin intervención de medios físicos o mecánicos como cepillos o gamuzas, que acostumbran a ser agresivos con las superficies tratadas ya que, por ejemplo, pueden generar rayas en la superficie pintada. Ejemplos  The use of discrete cellulose particles facilitates the removal of dirt from the traffic film type of vehicles in processes without the intervention of physical or mechanical means such as brushes or chamois, which tend to be aggressive with the treated surfaces since, for example, They can generate scratches on the painted surface. Examples
Ejemplo Preparativo: Preparación de nanocelulosa Preparative Example: Preparation of nanocellulose
Se incorporó 1 g de celulosa microcristalina de la compañía Sigma-Aldrich con un tamaño medio de partículas de 20 μηπ (Cellulose microcrystalline 310697), en 100 mi de agua destilada y se agitó hasta obtener una dispersión homogénea.  1 g of Sigma-Aldrich company microcrystalline cellulose with an average particle size of 20 μηπ (Cellulose microcrystalline 310697) was incorporated in 100 ml of distilled water and stirred until a homogeneous dispersion was obtained.
La dispersión obtenida se trató con ultrasonidos a una potencia de 450 W, durante 1 hora.  The dispersion obtained was treated with ultrasound at a power of 450 W, for 1 hour.
Transcurrido este tiempo, se tomó una muestra de la dispersión que se observó al microscopio, y se comprobó que se había producido una reducción significativa del tamaño medio de las partículas de celulosa, obteniéndose nanocelulosa, cuyo tamaño medio de partícula era inferior a 1 μηπ. Ejemplo de Referencia 1 : Preparación de una composición detergente líquida sin partículas discretas de celulosa Se preparó una composición detergente líquida por disolución en agua de un 20% en peso de tripolifosfato sódico, un 10% en peso de DEHYDOL® LT-7 de la compañía Cognis (actualmente BASF) (alcohol C12-C18 etoxilado con 7 moles de óxido de etileno), 5% en peso de ácido dodecilbencenosulfonico neutralizado con un 0,6% en peso de hidróxido sódico. After this time, a sample of the dispersion that was observed under the microscope was taken, and it was found that there was a significant reduction in the average size of the cellulose particles, obtaining nanocellulose, whose average particle size was less than 1 μηπ. Reference Example 1: Preparation of a liquid detergent composition without discrete cellulose particles A liquid detergent composition was prepared by dissolving in water 20% by weight of sodium tripolyphosphate, 10% by weight of DEHYDOL® LT-7 from Cognis (currently BASF) (ethoxylated C 12 -C 18 alcohol with 7 moles of ethylene oxide), 5% by weight of neutralized dodecylbenzenesulfonic acid with 0.6% by weight of sodium hydroxide.
Para la preparación de dicha composición, primeramente se dispersó el ácido dodecilbencenosulfonico bajo agitación en una parte del agua, añadiéndose a continuación el hidróxido sódico necesario para neutralizar dicho ácido. Posteriormente se añadieron el resto de componentes y el agua restante, y se mantuvo la mezcla bajo agitación hasta obtener una solución homogénea.  For the preparation of said composition, dodecylbenzenesulfonic acid was first dispersed under stirring in a part of the water, then adding the sodium hydroxide necessary to neutralize said acid. Subsequently, the remaining components and the remaining water were added, and the mixture was kept under stirring until a homogeneous solution was obtained.
Ejemplo de Referencia 2: Preparación de una composición detergente sólida sin partículas discretas de celulosa Reference Example 2: Preparation of a solid detergent composition without discrete cellulose particles
En un mezclador de sólidos de preparó una composición detergente sólida que contenía un 40% en peso de tripolifosfato sódico, un 45% en peso de carbonato sódico, un 10% en peso de DEHYDOL® LT-7 de la compañía Cognis (actualmente BASF) (alcohol Ci2-Ci8 etoxilado con 7 moles de óxido de etileno), y un 5% en peso de ácido dodecilbencenosulfonico. La mezcla se mantuvo en agitación hasta que obtuvo un polvo homogéneo. In a solid mixer prepared a solid detergent composition containing 40% by weight of sodium tripolyphosphate, 45% by weight of sodium carbonate, 10% by weight of DEHYDOL® LT-7 from Cognis (currently BASF) (Ci 2 -Ci 8 ethoxylated alcohol with 7 moles of ethylene oxide), and 5% by weight of dodecylbenzenesulfonic acid. The mixture was kept under stirring until it obtained a homogeneous powder.
Ejemplo 1 : Composición detergente líquida con celulosa microcristalina Example 1: Liquid detergent composition with microcrystalline cellulose
Se preparó una composición detergente líquida por disolución en agua de un 20% en peso de tripolifosfato sódico, un 10% en peso de DEHYDOL® LT-7 de la compañía Cognis (actualmente BASF) (alcohol C12- C18 etoxilado con 7 moles de óxido de etileno), 5% en peso de ácido dodecilbencenosulfonico neutralizado con un 0,6% en peso de hidróxido sódico, y un 1 ,77% en peso de celulosa microcristalina de la compañía Sigma- Aldrich con un tamaño medio de partículas de 20 μηπ (Cellulose microcrystalline 310697).  A liquid detergent composition was prepared by dissolving in water 20% by weight of sodium tripolyphosphate, 10% by weight of DEHYDOL® LT-7 from Cognis (currently BASF) (ethoxylated C12-C18 alcohol with 7 moles of oxide ethylene), 5% by weight of neutralized dodecylbenzenesulfonic acid with 0.6% by weight of sodium hydroxide, and 1.77% by weight of microcrystalline cellulose from the Sigma-Aldrich company with an average particle size of 20 μηπ (Cellulose microcrystalline 310697).
Para la preparación de dicha composición, primeramente se dispersó el ácido dodecilbencenosulfonico bajo agitación en una parte del agua, añadiéndose a continuación el hidróxido sódico necesario para neutralizar dicho ácido. Posteriormente se añadieron el tripolifosfato sódico, el tensioactivo no iónico y el agua restante, y se mantuvo la mezcla bajo agitación hasta obtener una solución homogénea. Finalmente se añadieron las microfibras de celulosa. For the preparation of said composition, dodecylbenzenesulfonic acid was first dispersed under stirring in a part of the water, then adding the sodium hydroxide necessary to neutralize said acid. Subsequently, sodium tripolyphosphate, the non-ionic surfactant and the remaining water, and the mixture was kept under stirring until a homogeneous solution was obtained. Finally, cellulose microfibers were added.
El contenido de celulosa en esta composición era del 4,8% en peso sobre el peso de los componentes activos, esto es, todos exceptuando el agua.  The cellulose content in this composition was 4.8% by weight on the weight of the active components, that is, all except water.
Ejemplo 2: Composición detergente sólida con microfibras de celulosa Example 2: Solid detergent composition with cellulose microfibers
En un mezclador de sólidos de preparó una composición detergente sólida que contenía un 40% en peso de tripolifosfato sódico, un 45% en peso de carbonato sódico, un 10% en peso de DEHYDOL® LT-7 de la compañía Cognis (actualmente BASF) (alcohol Ci2-Ci8 etoxilado con 7 moles de óxido de etileno), un 5% en peso de ácido dodecilbencenosulfónico, y 1 1 ,1 1 % de microfibras de celulosa de 23 μηπ de longitud y 17 μηπ de espesor (ARBOCEL® BE 600-20), que representa un diámetro medio equivalente de 22 μηπ. La mezcla se mantuvo en agitación hasta que se obtuvo un polvo homogéneo. La proporción en peso de la celulosa respecto al total de la composición era del 10%. Ejemplo 3: Composición detergente sólida con celulosa microcristalina In a solid mixer prepared a solid detergent composition containing 40% by weight of sodium tripolyphosphate, 45% by weight of sodium carbonate, 10% by weight of DEHYDOL® LT-7 from Cognis (currently BASF) (ethoxylated Ci 2 -Ci 8 alcohol with 7 moles of ethylene oxide), 5% by weight of dodecylbenzenesulfonic acid, and 1, 1 1% of cellulose microfibers 23 μηπ in length and 17 μηπ in thickness (ARBOCEL® BE 600-20), which represents an equivalent average diameter of 22 μηπ. The mixture was kept under stirring until a homogeneous powder was obtained. The proportion by weight of the cellulose with respect to the total composition was 10%. Example 3: Solid detergent composition with microcrystalline cellulose
En un mezclador de sólidos de preparó una composición detergente sólida que contenía un 40% en peso de tripolifosfato sódico, un 45% en peso de carbonato sódico, un 10% en peso de DEHYDOL® LT-7 de la compañía Cognis (actualmente BASF) (alcohol Ci2-Ci8 etoxilado con 7 moles de óxido de etileno), un 5% en peso de ácido dodecilbencenosulfónico, y 1 1 ,1 1 % de celulosa microcristalina con un tamaño medio de 90 μηπ de la compañía Acros Organics. La mezcla se mantuvo en agitación hasta que se obtuvo un polvo homogéneo. La proporción en peso de la celulosa respecto al total de la composición era del 10%. In a solid mixer prepared a solid detergent composition containing 40% by weight of sodium tripolyphosphate, 45% by weight of sodium carbonate, 10% by weight of DEHYDOL® LT-7 from Cognis (currently BASF) (Ci 2 -Ci 8 ethoxylated alcohol with 7 moles of ethylene oxide), 5% by weight of dodecylbenzenesulfonic acid, and 1.1, 1% of microcrystalline cellulose with an average size of 90 μηπ from Acros Organics. The mixture was kept under stirring until a homogeneous powder was obtained. The proportion by weight of the cellulose with respect to the total composition was 10%.
Ejemplo 4: Composición detergente sólida con celulosa microcristalina Example 4: Solid detergent composition with microcrystalline cellulose
En un mezclador de sólidos de preparó una composición detergente sólida que contenía un 40% en peso de tripolifosfato sódico, un 45% en peso de carbonato sódico, un 10% en peso de DEHYDOL® LT-7 de la compañía Cognis (actualmente BASF) (alcohol Ci2-Ci8 etoxilado con 7 moles de óxido de etileno), un 5% en peso de ácido dodecilbencenosulfonico, y 1 1 ,1 1 % de celulosa microcristalina con un tamaño medio de 50 μηπ HEWETEN® 101 de la compañía J. Rettenmeier & Sóhne. La mezcla se mantuvo en agitación hasta que se obtuvo un polvo homogéneo. La proporción en peso de la celulosa respecto al total de la composición era del 10%. In a solid mixer prepared a solid detergent composition containing 40% by weight of sodium tripolyphosphate, 45% by weight of sodium carbonate, 10% by weight of DEHYDOL® LT-7 from Cognis (currently BASF) (ethoxylated Ci 2 -Ci 8 alcohol with 7 moles of ethylene oxide), 5% by weight of dodecylbenzenesulfonic acid , and 1 1, 1 1% microcrystalline cellulose with an average size of 50 μηπ HEWETEN® 101 from J. Rettenmeier & Sóhne. The mixture was kept under stirring until a homogeneous powder was obtained. The proportion by weight of the cellulose with respect to the total composition was 10%.
Ejemplo 5: Composición acuosa con celulosa microcristalina Example 5: Aqueous composition with microcrystalline cellulose
En un recipiente provisto de agitación se dispersaron 10 g de celulosa microcristalina de la compañía Sigma-Aldrich con un tamaño medio de partículas de 20 μηπ (Cellulose microcrystalline 310697), en 190 g de agua. La dispersión se mantuvo bajo agitación hasta conseguir una dispersión homogénea, seguidamente se trató con ultrasonidos a una potencia de 450 W, durante 90 minutos.  In a vessel provided with stirring, 10 g of microcrystalline cellulose from the Sigma-Aldrich company with an average particle size of 20 μηπ (Cellulose microcrystalline 310697) was dispersed in 190 g of water. The dispersion was kept under stirring until a homogeneous dispersion was achieved, then treated with ultrasound at a power of 450 W, for 90 minutes.
Ejemplo 6: Ensayos comparativos de eficacia Example 6: Comparative efficacy trials
Se procedió a limpiar una superficie de un vehículo pintada previamente ensuciada con suciedad tipo traí Tic-film, según el procedimiento de la invención, utilizando las composiciones preparadas en los Ejemplos 1 a 4. Para ello, se utilizó una máquina hidrolimpiadora a alta presión de la marca Nilfisk-ALTO.  A surface of a previously painted vehicle soiled with Traí Tic-film type dirt was cleaned, according to the method of the invention, using the compositions prepared in Examples 1 to 4. For this purpose, a high pressure washer washer was used. the Nilfisk-ALTO brand.
Los ensayos de las composiciones de la invención se efectuaron a dos temperaturas: ambiente y a 53Q C, y a dos presiones: 75 bares y 105 bares. The tests of the compositions of the invention were carried out at two temperatures: ambient and 53 Q C, and at two pressures: 75 bar and 105 bar.
A fines comparativos también se ensayaron las composiciones de los ejemplos de referencia descritos anteriormente.  For comparative purposes, the compositions of the reference examples described above were also tested.
Para ensayar la composición líquida del Ejemplo 1 se dosificó convenientemente en el agua de alimentación del sistema de presión para obtener la concentración 0,40% en punta de lanza, y se procedió a la limpieza de la superficie, a una presión de 75 bares y a temperatura ambiente. La pulverización a alta presión se mantuvo durante un período aproximado de 1 minuto sobre un área de 0,25 m2. Se procedió de una forma análoga para ensayar la eficacia de las composiciones sólidas de los Ejemplos 2 a 4, dispersando 10 g de cada una de ellas en 5 I de agua y obtener sendas disoluciones de trabajo a la composición deseada del 0,2% en peso. En este caso, el procedimiento de limpieza se realizó a una presión de 105 bares, a una temperatura de 53Q C y durante un período de tiempo de 1 minuto sobre un área de 0,25 m2. To test the liquid composition of Example 1, it was conveniently dosed in the feedwater of the pressure system to obtain a concentration of 0.40% at the spearhead, and the surface was cleaned at a pressure of 75 bar and room temperature. The high pressure spray was maintained for an approximate period of 1 minute over an area of 0.25 m 2 . An analogous procedure was carried out to test the efficacy of the solid compositions of Examples 2 to 4, dispersing 10 g of each in 5 I of water and obtaining working solutions at the desired composition of 0.2% in weight. In this case, the cleaning procedure was carried out at a pressure of 105 bar, at a temperature of 53 QC and for a period of 1 minute over an area of 0.25 m 2 .
La composición del Ejemplo 5 se dosificó convenientemente en el agua de alimentación del sistema de presión para obtener la concentración 0,40% en peso en punta de lanza, y se procedió a la limpieza de la superficie, a una presión de 75 bares y a temperatura ambiente. La pulverización a alta presión se mantuvo durante un período aproximado de 1 minuto sobre un área de 0,25 m2. La pulverización a alta presión se mantuvo durante un período de 1 minuto sobre un área de 0,25 m2. The composition of Example 5 was conveniently dosed in the feedwater of the pressure system to obtain a concentration of 0.40% by weight at the spearhead, and the surface was cleaned, at a pressure of 75 bar and at a temperature ambient. The high pressure spray was maintained for an approximate period of 1 minute over an area of 0.25 m 2 . The high pressure spray was maintained for a period of 1 minute over an area of 0.25 m 2 .
También se ensayó la eficacia del detergente líquido preparado en el Ejemplo de Referencia 1 , que no contenía partículas de celulosa. Para ello se preparó se dosificó convenientemente en el agua de alimentación del sistema de presión para obtener la concentración 0,40% en peso en punta de lanza, y se procedió a la limpieza de la superficie, a una presión de 75 bares y a temperatura ambiente. La pulverización a alta presión se mantuvo durante un período aproximado de 1 minuto sobre un área de 0,25 m2 The efficacy of the liquid detergent prepared in Reference Example 1, which did not contain cellulose particles, was also tested. For this purpose, it was prepared conveniently dosed in the feedwater of the pressure system to obtain the concentration 0.40% by weight at the spearhead, and the surface was cleaned, at a pressure of 75 bar and at room temperature . The high pressure spray was maintained for an approximate period of 1 minute over an area of 0.25 m 2
Asimismo se realizaron pruebas de lavado con el detergente sólido preparado en el Ejemplo de Referencia 2, que también carecía de partículas de celulosa. Para ello se dispersaron 10 g en 5 I de agua y se obtuvo la composición deseada del 0,2% en peso. En este caso, el procedimiento de limpieza se realizó a una presión de 105 bares, a una temperatura de 53Q C y durante un período de tiempo de 1 minuto sobre un área de 0,25 m2 Wash tests were also performed with the solid detergent prepared in Reference Example 2, which also lacked cellulose particles. For this, 10 g were dispersed in 5 I of water and the desired composition of 0.2% by weight was obtained. In this case, the cleaning procedure was performed at a pressure of 105 bar, at a temperature of 53 Q C and for a period of 1 minute over an area of 0.25 m 2
Como ensayo Control se empleó agua sin partículas de celulosa, ni detergente.  As a Control test, water without cellulose particles or detergent was used.
A fin de cuantificar la eficacia limpiadora de las diferentes composiciones y condiciones ensayadas, se utilizó la escala de valoración según se muestra en la Tabla 1 : TABLA 1 In order to quantify the cleaning efficacy of the different compositions and conditions tested, the titration scale was used as shown in Table 1: TABLE 1
Figure imgf000022_0001
Figure imgf000022_0001
La eficacia de la composición líquida del Ejemplo 1 se evaluó mediante un diseño factorial 22 con los factores y niveles que se muestran en la matriz de la Tabla 2: The efficacy of the liquid composition of Example 1 was evaluated by a 2 2 factorial design with the factors and levels shown in the matrix of Table 2:
TABLA 2  TABLE 2
Figure imgf000022_0002
Figure imgf000022_0002
Todos los ensayos se efectuaron a temperatura ambiente, a una presión de 75 bares y durante 1 minuto sobre un área de 0,25 m2 All tests were carried out at room temperature, at a pressure of 75 bar and for 1 minute over an area of 0.25 m 2
En el ensayo Control se efectuó la limpieza con agua sin celulosa ni detergente; la composición del Ejemplo 5 incluía celulosa microcristalina con un tamaño medio de partículas de 20 μηπ, pero no contenía tensioactivos, ni adyuvantes; el Ejemplo de Referencia 1 era una composición detergente líquida que no contenía partículas de celulosa, y el Ejemplo 1 era una composición detergente de la invención que contenía celulosa microcristalina con un tamaño medio de partículas de 20 μηπ.  In the Control test, the cleaning was carried out with water without cellulose or detergent; the composition of Example 5 included microcrystalline cellulose with an average particle size of 20 μηπ, but did not contain surfactants or adjuvants; Reference Example 1 was a liquid detergent composition that did not contain cellulose particles, and Example 1 was a detergent composition of the invention containing microcrystalline cellulose with an average particle size of 20 μηπ.
En la Tabla 3 se presentan los resultados obtenidos en dichos ensayos: TABLA 3 Table 3 shows the results obtained in these tests: TABLE 3
Figure imgf000023_0001
Figure imgf000023_0001
Se puede observar que al incorporar la celulosa microcristalina al agua, Ejemplo 5, se produce una mejora en el grado de limpieza, se pasa de un grado 5 a un grado 2-3. It can be seen that by incorporating microcrystalline cellulose into the water, Example 5, there is an improvement in the degree of cleaning, passing from a grade 5 to a grade 2-3.
También se puede observar que al incorporar la composición detergente sin partículas de celulosa al agua se produce una cierta mejora, pero claramente insuficiente.  It can also be observed that incorporating the detergent composition without cellulose particles into the water produces a certain improvement, but clearly insufficient.
En cambio, si se comparan los resultados de los ejemplos de referencia con el grado de limpieza alcanzado con la composición del Ejemplo 1 de la invención, se observa que se produce un efecto sinérgico al incorporar celulosa microcristalina a la composición detergente, ya que con una menor concentración en punta de lanza de partículas de celulosa (0,019% vs 0,038%) y de detergente (0,375% vs 0,5%) se obtiene un mayor grado de limpieza.  On the other hand, if the results of the reference examples are compared with the degree of cleanliness achieved with the composition of Example 1 of the invention, it is observed that a synergistic effect is produced by incorporating microcrystalline cellulose into the detergent composition, since with a lower concentration of spearhead of cellulose particles (0.019% vs. 0.038%) and detergent (0.375% vs. 0.5%) results in a higher degree of cleanliness.
Los resultados obtenidos con las dispersiones obtenidas a partir de las composiciones sólidas de los Ejemplos 2 a 4 se muestran en la Tabla 4:  The results obtained with the dispersions obtained from the solid compositions of Examples 2 to 4 are shown in Table 4:
TABLA 4  TABLE 4
Ensayo Concentración en punta Valoración  Test Point concentration Assessment
de lanza  spear
Ejemplo de Referencia 2 0,20% (detergente sin 3  Reference Example 2 0.20% (detergent without 3
partículas de celulosa) Ensayo Concentración en punta Valoración cellulose particles) Test Point concentration Assessment
de lanza  spear
Ejemplo 2 0,02% (microfibras de 1  Example 2 0.02% (microfibers of 1
celulosa 20 μηπ)  cellulose 20 μηπ)
0,18% (detergente)  0.18% (detergent)
Ejemplo 3 0,02% (celulosa 1  Example 3 0.02% (cellulose 1
microcristalina 90 μηπ)  microcrystalline 90 μηπ)
0,18% (detergente)  0.18% (detergent)
Ejemplo 4 0,02% (celulosa 1  Example 4 0.02% (cellulose 1
microcristalina 50 μηπ)  microcrystalline 50 μηπ)
0,18% (detergente)  0.18% (detergent)
Se puede observar que se produce una mejora sustancial en la eficacia al incorporar partículas de celulosa a una composición detergente, tanto en composiciones líquidas (Ejemplo 1 en comparación con el Ejemplo de Referencia 1 ), o en composiciones sólidas (Ejemplos 2 a 4 con respecto al Ejemplo de Referencia 2). It can be seen that there is a substantial improvement in efficiency by incorporating cellulose particles into a detergent composition, both in liquid compositions (Example 1 compared to Reference Example 1), or in solid compositions (Examples 2 to 4 with respect to to Reference Example 2).
Se puede observar también que al comparar los resultados obtenidos con las composiciones detergentes sólidas, no se detectaron diferencias significativas entre los diferentes tipos de partículas de celulosa ensayados: microfibras de celulosa y celulosa microcristalina de diferentes tamaños medios.  It can also be observed that when comparing the results obtained with the solid detergent compositions, no significant differences were detected between the different types of cellulose particles tested: cellulose microfibers and microcrystalline cellulose of different average sizes.
En todos los ensayos con las composiciones de la invención se ha observado que las superficies tratadas no han observado alteraciones en el estado superficial como aparición de rayas o defectos, o disminución de brillo.  In all tests with the compositions of the invention it has been observed that the treated surfaces have not observed alterations in the surface state such as the appearance of scratches or defects, or decrease in brightness.

Claims

REIVINDICACIONES
1 . - Composición para la limpieza a alta presión de superficies duras, caracterizada porque comprende partículas discretas de celulosa cuyo tamaño medio de partícula es inferior o igual a 200 μηπ. one . - Composition for high pressure cleaning of hard surfaces, characterized in that it comprises discrete cellulose particles whose average particle size is less than or equal to 200 μηπ.
2. - Composición según la reivindicación 1 , caracterizada porque las partículas discretas de celulosa se seleccionan de entre el grupo formado por celulosa microcristalina, celulosa pulverulenta, nanocelulosa, microfibras de celulosa, y mezclas de las anteriores. 2. - Composition according to claim 1, characterized in that the discrete cellulose particles are selected from the group consisting of microcrystalline cellulose, powdered cellulose, nanocellulose, cellulose microfibers, and mixtures of the foregoing.
3. - Composición según la reivindicación 2, caracterizada porque las partículas discretas de celulosa se seleccionan entre celulosa microcristalina, microfibras de celulosa, y mezclas de ambas. 3. - Composition according to claim 2, characterized in that the discrete cellulose particles are selected from microcrystalline cellulose, cellulose microfibers, and mixtures of both.
4. - Composición según cualquiera de las reivindicaciones 1 a 3, caracterizada porque las partículas discretas de celulosa tienen un tamaño medio de partícula comprendido entre 1 μηπ y 150 μηπ. 4. - Composition according to any of claims 1 to 3, characterized in that the discrete cellulose particles have an average particle size between 1 μηπ and 150 μηπ.
5.- Composición según la reivindicación 4, caracterizada porque las partículas discretas de celulosa tienen un tamaño medio de partícula comprendido entre 10 μηπ y 100 μηπ. 5. Composition according to claim 4, characterized in that the discrete cellulose particles have an average particle size between 10 μηπ and 100 μηπ.
6. - Composición según las reivindicaciones 3 y 5, caracterizada porque las partículas discretas de celulosa son de celulosa microcristalina y tienen un tamaño medio de partícula comprendido entre 20 μηπ y 100 μηπ. 6. - Composition according to claims 3 and 5, characterized in that the discrete cellulose particles are microcrystalline cellulose and have an average particle size between 20 μηπ and 100 μηπ.
7. - Composición según las reivindicaciones 3 y 5, caracterizada porque las partículas discretas de celulosa son microfibras de celulosa y tienen un diámetro medio equivalente comprendido entre 10 μηπ y 30 μηπ. 7. - Composition according to claims 3 and 5, characterized in that the discrete cellulose particles are cellulose microfibers and have an equivalent average diameter between 10 μηπ and 30 μηπ.
8.- Composición según cualquiera de las reivindicaciones 1 a 7, caracterizada porque comprende además tensioactivos, coadyuvantes y, opcionalmente, otros productos auxiliares. 8. Composition according to any of claims 1 to 7, characterized in that it further comprises surfactants, adjuvants and, optionally, other auxiliary products.
9.- Composición según la reivindicación 8, caracterizada porque comprende entre el 1 % y el 20% de partículas discretas de celulosa, entre el 5% y el 50% de tensioactivos y entre el 35% y el 95% de coadyuvantes, porcentajes expresados en peso respecto al peso total de sólidos de la composición. 9. Composition according to claim 8, characterized in that it comprises between 1% and 20% of discrete cellulose particles, between 5% and 50% of surfactants and between 35% and 95% of adjuvants, expressed percentages by weight with respect to the total weight of solids of the composition.
10.- Composición según la reivindicación 9, caracterizada porque comprende entre el 1 % y el 20% de partículas discretas de celulosa, entre el 2% y el 20% de tensioactivos aniónicos, entre el 3% y el 30% de tensioactivos no iónicos, y entre el 35% y el 95% de coadyuvantes, porcentajes expresados en peso respecto al peso total de sólidos de la composición. 10. Composition according to claim 9, characterized in that it comprises between 1% and 20% of discrete cellulose particles, between 2% and 20% of anionic surfactants, between 3% and 30% of non-ionic surfactants , and between 35% and 95% of adjuvants, percentages expressed by weight with respect to the total solids weight of the composition.
1 1 . - Composición según la reivindicación 10, caracterizada porque el tensioactivo aniónico es una sal alcalina de un ácido alquilbencenosulfonico lineal, el tensioactivo no iónico es un alcohol graso etoxilado, y el coadyuvante se selecciona entre tripolifosfato sódico, carbonato sódico, y mezclas de ambos. eleven . - Composition according to claim 10, characterized in that the anionic surfactant is an alkaline salt of a linear alkylbenzenesulfonic acid, the nonionic surfactant is an ethoxylated fatty alcohol, and the adjuvant is selected from sodium tripolyphosphate, sodium carbonate, and mixtures of both.
12. - Procedimiento para la limpieza de superficies duras caracterizado porque comprende pulverizar a alta presión una dispersión acuosa de la composición de cualquiera de las reivindicaciones 1 a 1 1 . 12. - Process for cleaning hard surfaces characterized in that it comprises spraying an aqueous dispersion of the composition of any of claims 1 to 1 1 under high pressure.
13. - Procedimiento para la limpieza de superficies duras según la reivindicación13. - Procedure for cleaning hard surfaces according to claim
12, caracterizado porque la pulverización se efectúa a una presión igual o superior a 10 bares. 12, characterized in that the spraying is carried out at a pressure equal to or greater than 10 bar.
14.- Procedimiento para la limpieza de superficies duras según la reivindicación14.- Procedure for cleaning hard surfaces according to claim
13, caracterizado porque la pulverización se efectúa a una presión comprendida entre 50 y 150 bares. 13, characterized in that the spraying is carried out at a pressure between 50 and 150 bars.
15.- Procedimiento según cualquiera de las reivindicaciones 12 a 14, caracterizado porque se efectúa a una temperatura comprendida entre la temperatura ambiente y aproximadamente 90Q C. 15. Method according to any of claims 12 to 14, characterized in that it is carried out at a temperature between room temperature and approximately 90 QC .
1 6.- Procedimiento según la reivindicación 15, caracterizado porque se efectúa a una temperatura comprendida entre 50Q C y 60Q C. 1. Method according to claim 15, characterized in that it is carried out at a temperature between 50 Q C and 60 Q C.
17. - Procedimiento según cualquiera de las reivindicaciones 12 a 1 6, caracterizado porque la dispersión acuosa a pulverizar se prepara por dispersión en agua de una composición según cualquiera de las reivindicaciones 1 a 1 1 . 17. - Method according to any of claims 12 to 1 6, characterized in that the aqueous dispersion to be sprayed is prepared by dispersion in water of a composition according to any of claims 1 to 1 1.
18. - Procedimiento según cualquiera de las reivindicaciones 12 a 17, caracterizado porque la concentración de las partículas discretas de celulosa en el medio acuoso que se lanza a alta presión sobre la superficie, está comprendida entre el 0,005% y el 0,2%, porcentaje expresado en peso de celulosa respecto del peso de la dispersión acuosa pulverizada. 18. - Method according to any of claims 12 to 17, characterized in that the concentration of discrete cellulose particles in the aqueous medium that is released at high pressure on the surface is between 0.005% and 0.2%, percentage expressed by weight of cellulose with respect to the weight of the aqueous dispersion sprayed.
19. - Procedimiento según la reivindicación 18, caracterizado porque la concentración de las partículas discretas de celulosa en el medio acuoso está comprendida entre el 0,005% y el 0,05%, porcentaje expresado en peso de celulosa respecto del peso de la dispersión acuosa pulverizada. 19. - Method according to claim 18, characterized in that the concentration of the discrete particles of cellulose in the aqueous medium is comprised between 0.005% and 0.05%, percentage expressed by weight of cellulose with respect to the weight of the pulverized aqueous dispersion .
20. - Procedimiento según cualquiera de las reivindicaciones 12 a 19, caracterizado porque la superficie dura es la superficie exterior de un vehículo. 20. - Method according to any of claims 12 to 19, characterized in that the hard surface is the outer surface of a vehicle.
21 . - Uso de partículas discretas de celulosa de tamaño medio de partícula inferior o igual a 200 μηπ para la limpieza a alta presión de una superficie dura. twenty-one . - Use of discrete cellulose particles of average particle size less than or equal to 200 μηπ for high pressure cleaning of a hard surface.
22.- Uso según la reivindicación 21 , caracterizado porque las partículas discretas de celulosa se seleccionan de entre el grupo formado por celulosa microcristalina, celulosa pulverulenta, nanocelulosa, microfibras de celulosa, y mezclas de las anteriores. 22. Use according to claim 21, characterized in that the discrete cellulose particles are selected from the group consisting of microcrystalline cellulose, pulverulent cellulose, nanocellulose, cellulose microfibers, and mixtures thereof.
23. - Uso según la reivindicación 22, caracterizado porque las partículas discretas de celulosa se seleccionan entre celulosa microcristalina, microfibras de celulosa, y mezclas de ambas. 23. - Use according to claim 22, characterized in that the discrete cellulose particles are selected from microcrystalline cellulose, cellulose microfibers, and mixtures of both.
24. - Uso según cualquiera de las reivindicaciones 21 a 23, caracterizado porque superficie dura es la superficie exterior de un vehículo. 24. - Use according to any of claims 21 to 23, characterized in that the hard surface is the outer surface of a vehicle.
PCT/IB2012/057189 2011-12-14 2012-12-11 Composition for cleaning hard surfaces at high pressure WO2013088345A1 (en)

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ES2413565A1 (en) 2013-07-16

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