ES2413565B1 - Composition for cleaning hard surfaces under high pressure - Google Patents

Abstract

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

Description

Composition for cleaning hard surfaces under high pressure

Technical field

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.

Prior art

Hard surface cleaning, both domestically and industrially, is a problem that has aroused great interest over many decades.

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. 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.

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 to said surface, forming a film, which is usually designated by 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.

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.

Thus, for example, European patent application EP-A-1184452 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.

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-94/16831 a method for surface cleaning is described which consists of spraying under pressure a liquid comprising surfactants together with water-soluble abrasive particles, preferably carbonate, bicarbonate or sodium sulfate or potassium

Likewise, in the international patent application WO-A-98/29193 a cleaning composition is described for use by spraying comprising abrasive particles that can be soluble in water such as, for example, sodium bicarbonate, sadic tripolyphosphate pentahydrate, tetraborate sadistic decahydrate, potassium sulfate or sadic citrate; or it may be water insoluble abrasive particles, such as carbon dioxide

silicon, silicates, calcium carbonate, dichloric phosphate, iron oxide, calcium pyrophosphate, sadic metaphosphate, diatomite or aluminum oxide.

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.

Object of the invention

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 use of discrete cellulose particles for cleaning hard surfaces is also part of the object of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The object of the present invention is a composition for the cleaning of hard surfaces under high pressure, which comprises discrete cellulose particles whose average particle size is less than or equal to 200 μm.

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.

Discrete Cellulose Particles

Within the scope of the present invention, 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 scattering of laser light.

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, whose value corresponds to the diameter of a hypothetical sphere having the same volume as the cylindrical filament defined by the aforementioned dimensions L and E.

Thus, in 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.

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 μm, typically between 0.05 μm and 200 μm, preferably between 1 μm and 150 μm, and more preferably comprised between 10 μm and 100 μm.

Microcrystalline cellulose, powdered cellulose and cellulose microfibers are commercially available. The nanocellulose can be obtained from the foregoing, for example by an ultrasound treatment that reduces the average particle size to dimensions of approximately 1 µm or less.

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Microcrystalline cellulose is a crystalline powdery substance, obtained by controlled hydrolysis of a-cellulose, which has characteristics specified for example in the manual of pharmaceutical excipients, R. C. Rowe, P. J. Sheskey and P.J. Weller, Handbook of Pharmaceutical Excipients, fourth edition, Pharmaceutical Press, 2003. Microcrystalline cellulose can be obtained commercially from various suppliers, for example through the company FMC Biopolymer, under the general brand name AVICEL�, and is available in different average particle sizes that are usually between 1 μm and 200 μm. You can also obtain microcrystalline cellulose qualities with an average particle size of 50 μm or 90 μm from the Acros Organics company. It can also be obtained through the company Sigma-Aldrich under the name Cellulose microcrystalline 310697 with an average particle size of 20 į

Preferably, microcrystalline cellulose with an average particle size between 20 μm and 100 μm is used.

Powdered cellulose is a powder obtained by reducing the size of a-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 & S�hne, under the general trade name ARBOCEL�. Said cellulose is available in different average particle sizes, which are usually between 1 μm and 200 μm.

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 & S�hne, 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 μm and 220 μm, and a thickness between approximately 0.01 μm and 150 μm, which is equivalent to an equivalent average diameter between 0 , 05 μm and 195 μm, according to the approach explained above. Preferably, cellulose microfibers having an equivalent average diameter between 10 μm and 30 μm 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 μm, preferably between 0.05 μm and 1 μm 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 in weight.

Composition

The high pressure hard surface cleaning composition of the present invention comprises discrete cellulose particles, as defined above.

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.

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.

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.

To obtain a more significant degree of cleaning, preferably said composition further comprises surfactants, adjuvants and, optionally, other auxiliary products.

This composition with surfactants, adjuvants and possibly other auxiliary components can be solid or liquid, without the presentation form influencing the cleaning result, since, as explained below, the composition, whether solid or liquid, it disperses 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 possess 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

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liquid with which they favor the wetting of the surfaces and are also able to group together forming micelles, which allows dissolving, emulsifying or disintegrating the dirt.

The surfactants suitable for use in the compositions of this invention are selected from the group consisting of anionic, nonionic, cationic, amphoteric, and mixtures thereof.

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.

Among the suitable anionic surfactants for use in the context of the present invention are, for example, soaps, alkylbenzenesulfonic acids and their salts, sulfonated a-olefins, sulfonated paraffins, alkyl sulfates, ether sulfates of alkyl, glycerin ether sulfates, alkyl sulphosuccinates, carboxylic acid ethers and salts thereof, alkyl phosphates, alkyl ether phosphates, alkylphenol sulfates, alkylphenol ether sulfates, isethionates, sarcosinates, taurates, and salts of N-acylamino acids. Just to name a few examples of this group, among the alkyl ether sulfates is lauryl sodium sulfate ether, such as that supplied by the company Kao Corporation under the trade name EMAL� or the TEXAPON� product range of the Cognis company (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 the company Cognis (currently BASF) ) under the trade name MARANIL�.

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 the Cognis company (now BASF) under the trade name DEHYDOL, may be mentioned, for example the DEHYDOL� LT7 which is a C12-C18 fatty alcohol with approximately 7 moles of ethylene oxide. Among the esters of ethoxylated sorbiton, mention may be made of those supplied by the company Kao Corporation under the trade name RHEODOL. Among the ethoxylated alkylphenols, products marketed under the name DEHYDROPHEN� by the Cognis company (currently BASF) may be mentioned.

Among the amphoteric surfactants suitable for use in the context of the present invention are, for example, alkyl dimethyl betaines, alkylamido betaines, alkyl sulfobethanes, alkylamido sulfobethanes, imidazoline derivatives and alkylaminopropionates, among others. Thus, for example, among the alkylamido betaines those mentioned by the Cognis company (currently BASF) may be mentioned under the trade name DEHYTON.

Suitable cationic surfactants 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 company. Cognis (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.

As auxiliary agents, for example, polyphosphates, especially alkali metal tripolyphosphates and pyrophosphates, alkali carbonates, alkali silicates, zeolites, alkali salts of nitriloacetic acid, EDTA and their salts, the current ecological substitutes of NTA / EDTA / phosphates, such as such as GLDA (Glutamic Acid N, N-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 sadistic 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, cosolvents, and pH regulators. In the case of a liquid composition, it generally also includes preservatives.

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.

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 by 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.

In a particularly preferred embodiment, the anionic surfactant is an alkaline salt of a linear alkylbenzenesulfonic acid, and more preferably it is the sadistic salt of n-dodecylbenzenesulfonic acid; The nonionic surfactant is an ethoxylated fatty alcohol, more preferably it is an ethoxylated C12-C18 chain alcohol with about 7 moles of ethylene oxide, and the adjuvant is selected from the group consisting of sadic tripolyphosphate, sadic carbonate, and mixtures of both , more preferably the adjuvant is a mixture of sadic tripolyphosphate and sadic 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 sadic tripolyphosphate, between 20% and 50% of sadic carbonate, between 2% and 10% of anionic surfactant and between 5% and 15% of 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.

Optionally, the composition may also contain other ingredients, such as amphoteric surfactants, cationic surfactants, enzymes, dyes, foam stabilizers, among others.

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 dispersing in water 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 to 1000 g / l are obtained. 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% of discrete cellulose particles between 10% and 20% of sadic tripolyphosphate, between 1% and 15% of non-ionic surfactant and between 1% and 10% of 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.

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 a homogeneous dispersion of said particles in the liquid medium.

Hard surface

In the context of the present invention, the term "hard surface" is broadly understood, and comprises, for example, any metallic surface, for example aluminum, chrome, steel, or stainless steel; glass, ceramic or porcelain surfaces; rubber or rubber surfaces; surfaces of any type of plastic, such as thermoplastic or thermosetting polymers, among other possible materials. Likewise, said surfaces are also included that are coated with a layer of paint, varnish, enamel, or other type of finish.

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 .

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.

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.

The traffic film may contain, for example, combustion residues of the fuel, fuel leaks, carbon black, lubricating substances, residues of previous washes, as well as very heterogeneous environmental substances present on the roads, such as salts, sand , or mud.

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.

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 size of particle is less than or equal to 200 μm.

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 150 bars, and more preferably between 90 and 110 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, Krrcher or piston pumps type "CAT", or " Interpump. "

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.

Usually, said machines have a reservoir in which an aqueous mother dispersion of the composition comprising discrete cellulose particles is prepared.

In one 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, up to an approximate dilution of 1 to 10 g / l thereof, leaving the cellulose particles in suspension.

Typically said mother aqueous dispersion is dosed into a jet of pressurized water, by means of a device that for this purpose possesses such pressure washers, and which allows to conveniently adjust the final concentration in the sprayed water, or concentration in spearhead, 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 pulverized aqueous dispersion.

The cleaning devices used usually have a water heating system for subsequent application under pressure on the surface to be cleaned. The cleaning process according to the present invention can be carried out at a temperature between room temperature and about 90 ° C, preferably between 40 ° C and 70 ° C, and even more preferably between 50 ° C and 60 ° C.

Efficacy tests

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.

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.

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 diminishing efficiency.

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.

The synergistic effect that was observed when incorporating discrete cellulose particles in a detergent composition is noteworthy. As explained in the examples, with a lower spearhead concentration of cellulose particles and detergent, 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.

Therefore, it is also an object of the present invention to use discrete cellulose particles of average particle size less than or equal to 200 μm for high pressure cleaning of hard surfaces, such as for surface cleaning. exterior of a vehicle

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

Preparative Example: Preparation of nanocellulose

1g of microcrystalline cellulose from the Sigma-Aldrich company with an average particle size of 20 (Cellulose microcrystalline 310697) was incorporated into 100 ml of distilled water and stirred until a homogeneous dispersion was obtained.

The dispersion obtained was treated with ultrasound at a power of 450 W, for 1 hour.

After this time, a sample of the dispersion that was observed under a microscope was taken, and it was verified that there had been a significant reduction in the average size of the cellulose particles, obtaining nanocellulose, whose average particle size was less than 1 μm.

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 sadic tripolyphosphate, 10% by weight of DEHYDOL� LT-7 of the Cognis company (currently BASF) (ethoxylated C12-C18 alcohol with 7 moles of ethylene oxide), 5% by weight of neutralized dodecylbenzenesulfonic acid with 0.6% by weight of sadic hydroxide.

For the preparation of said composition, dodecylbenzenesulfonic acid was first dispersed under stirring in a part of the water, then adding the sadic hydroxide necessary to neutralize said acid. Subsequently, the rest of the components and the remaining water were added, and the mixture was kept under stirring until a homogeneous solution was obtained.

Reference Example 2: Preparation of a solid detergent composition without discrete cellulose particles

In a solid mixer, I prepared a solid detergent composition containing 40% by weight of sadic tripolyphosphate, 45% by weight of sadic carbonate, 10% by weight of DEHYDOL� LT-7 of the Cognis company (currently BASF) (ethoxylated C12-C18 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.

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Example 1: Liquid detergent composition with microcrystalline cellulose

A liquid detergent composition was prepared by dissolving in water 20% by weight of sadic tripolyphosphate, 10% by weight of DEHYDOL� LT-7 of the Cognis company (currently BASF) (ethoxylated C12-C18 alcohol with 7 moles of ethylene oxide), 5% by weight of neutralized dodecylbenzenesulfonic acid with 0.6% by weight of sadic hydroxide, and 1.77% by weight of microcrystalline cellulose from the Sigma-Aldrich company with an average particle size of 20 (Cellulose microcrystalline 310697).

For the preparation of said composition, dodecylbenzenesulfonic acid was first dispersed under stirring in a part of the water, then adding the sadic hydroxide necessary to neutralize said acid. Subsequently, the sadic tripolyphosphate, the non-ionic surfactant and the remaining water were added, 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

In a solid mixer, I prepared a solid detergent composition containing 40% by weight of sadic tripolyphosphate, 45% by weight of sadic carbonate, 10% by weight of DEHYDOL� LT-7 of the Cognis company (currently BASF) (ethoxylated C12-C18 alcohol with 7 moles of ethylene oxide), 5% by weight of dodecylbenzenesulfonic acid, and 11.11% of cellulose microfibers 23 μm long and 17 μm thick ( ARBOCEL� BE 600-20), which represents an equivalent average diameter of 22 μm. 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

In a solid mixer, I prepared a solid detergent composition containing 40% by weight of sadic tripolyphosphate, 45% by weight of sadic carbonate, 10% by weight of DEHYDOL� LT-7 of the Cognis company (currently BASF) (ethoxylated C12-C18 alcohol with 7 moles of ethylene oxide), 5% by weight of dodecylbenzenesulfonic acid, and 11.11% of microcrystalline cellulose with an average size of 90 μm of the compand� to 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

In a solid mixer, I prepared a solid detergent composition containing 40% by weight of sadic tripolyphosphate, 45% by weight of sadic carbonate, 10% by weight of DEHYDOL� LT-7 of the Cognis company (currently BASF) (ethoxylated C12-C18 alcohol with 7 moles of ethylene oxide), 5% by weight of dodecylbenzenesulfonic acid, and 11.11% of microcrystalline cellulose with an average size of 50 μm HEWETEN� 101 of the Company J. Rettenmeier & S�hne. 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

In a vessel equipped with stirring, 10 g of microcrystalline cellulose from the Sigma-Aldrich company with an average particle size of 20 (Cellulose microcrystalline 310697) were 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.

Example 6: Comparative efficacy trials

A surface of a previously painted vehicle soiled with traffic-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 pressure washer Nilfisk-ALTO was used.

The tests of the compositions of the invention were carried out at two temperatures: ambient and at 53 C, and at two pressures: 75 bar and 105 bar.

For comparative purposes, the compositions of the reference examples described above were also tested.

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 proceeded to the

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surface cleaning, at a pressure of 75 bars and at room temperature. The high pressure spray was maintained for an approximate period of 1 minute over an area of 0.25 m2.

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 l of water and obtaining working solutions at the desired composition of 0.2% in weight. In this case, the cleaning procedure was performed at a pressure of 105 bar, at a temperature of 53 ° C and for a period of 1 minute over an area of 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 room temperature. The high pressure spray was maintained for an approximate period of 1 minute over an area of 0.25 m2. The high pressure spray was maintained for a period of 1 minute over an area of 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, the pressure system feed water was dosed conveniently to obtain a concentration of 0.40% by weight 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 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 l 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� C and for a period of 1 minute over an area of 0.25 m2

As a Control test, water without cellulose particles or detergent was used.

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

Value

Degree of cleanliness observed

one

Completely clean

2

Small, hardly noticeable marks still appear

3

Faint marks remains

4

Brand Remains

5

Clear and visible remains of brands

The efficacy of the liquid composition of Example 1 was evaluated by a factorial design 22 with the factors and levels shown in the matrix of Table 2:

TABLE 2

Test

 Cellulose particles Detergent composition

Control (Water)

Do not Do not

Example 5

Yes Do not

Reference Example 1

Do not Yes

Example 1

Yes Yes

All tests were carried out at room temperature, at a pressure of 75 bar and for 1 minute over an area of 0.25 m2

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 μm, 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 µm.

Table 3 shows the results obtained in these tests:

TABLE 3

Test

Spearhead Concentration Assessment

Control (Water)

- 5

Example 5

0.038% (microcrystalline cellulose) 2-3

Reference Example 1

0.5% (detergent without cellulose particles) 4

Example 1

0.019% (microcrystalline cellulose) 0.375% (detergent) one

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.

It can also be seen that incorporating the detergent composition without cellulose particles 10 into the water produces some improvement, but clearly insufficient.

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 spearhead concentration of cellulose particles (0.019% vs. 0.038%) and detergent (0.375% vs. 0.5%) a higher grade is obtained

15 cleaning.

The results obtained with the dispersions obtained from the solid compositions of Examples 2 to 4 are shown in Table 4:

TABLE 4

Test

Spearhead Concentration Assessment

Reference Example 2

0.20% (detergent without cellulose particles) 3

Example 2

0.02% (cellulose microfibers 20) 0.18% (detergent) one

Example 3

0.02% (90 μm microcrystalline cellulose) 0.18% (detergent) one

Example 4

0.02% (50 μm microcrystalline cellulose) 0.18% (detergent) one

It can be seen that there is a substantial improvement in efficiency by incorporating particles of

Cellulose to a detergent composition, both in liquid compositions (Example 1 compared to Example

of Reference 1), or in solid compositions (Examples 2 to 4 with respect to Reference Example 2).

It can also be observed that when comparing the results obtained with the compositions

solid detergents, no significant differences were detected between the different types of cellulose particles

tested: microfibre cellulose and microcrystalline cellulose of different average sizes.

In all tests with the compositions of the invention it has been observed that the surfaces

treated have not observed alterations in the superficial state such as appearance of streaks or defects, or decrease

of brightness

Claims (23)

1.- 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 μm. 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. Composition according to claim 2, characterized in that the discrete cellulose particles are selected from microcrystalline cellulose, cellulose microfibers, and mixtures of both. 4. Composition according to any of claims 1 to 3, characterized in that the discrete cellulose particles have an average particle size between 1 μm and 150 μm. 5. Composition according to claim 4, characterized in that the discrete cellulose particles have an average particle size between 10 μm and 100 μm. 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 μm and 100 μm. 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 μm and 30 μm. 8. Composition according to any of claims 1 to 7, characterized in that it further comprises surfactants, adjuvants and, optionally, other auxiliary products. 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. 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 surfactants non-ionic, and between 35% and 95% adjuvants, percentages expressed by weight with respect to the total weight of solids of the composition. 11. 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 sadic tripolyphosphate, sadic carbonate, and mixtures of both. 12. Process for cleaning hard surfaces characterized in that it comprises spraying an aqueous dispersion of the composition of any of claims 1 to 11 under high pressure. 13. Method for cleaning hard surfaces according to claim 12, characterized in that the spraying is carried out at a pressure equal to or greater than 10 bar. 14. Method for cleaning hard surfaces according to claim 13, characterized in that the spraying is carried out at a pressure between 50 and 150 bar. 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� C. 16. Method according to claim 15, characterized in that it is carried out at a temperature between 50� C and 60� C. 17. Method according to any of claims 12 to 16, 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 11. 18. Method according to any of claims 12 to 17, characterized in that the concentration of discrete particles of cellulose 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 pulverized aqueous dispersion. 19. Method according to claim 18, characterized in that the concentration of the discrete particles of cellulose in the aqueous medium is between 0.005% and 0.05%, percentage expressed by weight of cellulose with respect to the weight of the dispersion n aqueous spray. 20. Method according to any of claims 12 to 19, characterized in that the hard surface is the outer surface of a vehicle. 21.- Use of discrete cellulose particles of average particle size less than or equal to 200 μm for high pressure cleaning of a hard surface. 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. Use according to claim 22, characterized in that the discrete cellulose particles are selected from microcrystalline cellulose, cellulose microfibers, and mixtures of both. 10. Use according to any of claims 21 to 23, characterized in that the hard surface is the exterior surface of a vehicle. SPANISH OFFICE OF THE PATENTS AND BRAND Application No.: 201132012 SPAIN Date of submission of the application: 14.12.2011 Priority Date: REPORT ON THE STATE OF THE TECHNIQUE 51 Int. Cl.: C11D7 / 44 (2006.01) C11D3 / 22 (2006.01) RELEVANT DOCUMENTS

Category

56 Documents cited Claims Affected

X

WO 0032726 A1 (KAERCHER GMBH & CO ALFRED et al.) 08.06.2000, 1-24

pages 3-8; example 3; claims 1-3,5,8,9,12-14,16.

X

US 4693840 A (TRINH TOAN et al.) 15.09.1987, 1-12,20-24

column 2, lines 40-64; column 3, lines 42-61; column 4, lines 14-16,31-41; column 5,

lines 26-44; claims 1-6,8-9.

X

US 5704991 A (MARCUS THOR) 06.01.1998, 1-7,12-24

column 1, lines 39-52; column 2, lines 16-19; column 4, lines 54-65;

claims 1,8,9,13.

TO

GB 1403919 A (BASF WYANDOTTE CORP) 28.08.1975, 1-24

page 1, lines 37-53,75-88; Example 1; claims 1.6.

TO

ES 2064510 T3 (VORWERK CO INTERHOLDING) 01.02.1995, 1-24

column 1, lines 3-20; column 3, lines 29-59; Example 1; claims 1,6,8.

TO

ES 2334781 T3 (HENKEL AG & CO KGAA) 16.03.2010, 1-24

page 2, lines 3.32-42; claim 1.

Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the submission of the application E: previous document, but published after the date of submission of the application

This report has been prepared • for all claims • for claims no:

Date of realization of the report 25.04.2013

Examiner M. González Rodríguez Page 1/4

REPORT OF THE STATE OF THE TECHNIQUE Application number: 201132012 Minimum documentation searched (classification system followed by classification symbols) C11D Electronic databases consulted during the search (name of the database and, if possible, terms of search used) INVENES, EPODOC, WPI. State of the Art Report Page 2/4  WRITTEN OPINION Application number: 201132012 Date of Completion of Written Opinion: 04.25.2013 Statement

Novelty (Art. 6.1 LP 11/1986)

Claims Claims 6, 11, 14-16 1-5, 7-10, 12, 13, 17-24 IF NOT

Inventive activity (Art. 8.1 LP11 / 1986)

Claims Claims 1-24 IF NOT

The application is considered to comply with the industrial application requirement. This requirement was evaluated during the formal and technical examination phase of the application (Article 31.2 Law 11/1986).  Opinion Base.- This opinion has been made on the basis of the patent application as published. State of the Art Report Page 3/4  WRITTEN OPINION Application number: 201132012  1. Documents considered.- The documents belonging to the state of the art taken into consideration for the realization of this opinion are listed below.

Document

Publication or Identification Number publication date

D01

WO 0032726 A1 (KAERCHER GMBH & CO ALFRED et al.) 08.06.2000

D02

US 4693840 A (TRINH TOAN et al.) 15.09.1987

D03

US 5704991 A (MARCUS THOR) 06.01.1998

 2. Statement motivated according to articles 29.6 and 29.7 of the Regulations for the execution of Law 11/1986, of March 20, on Patents on novelty and inventive activity; quotes and explanations in support of this statement The object of the invention is a composition for high pressure cleaning of hard surfaces (i.e. vehicles), which comprises discrete particles of cellulose of average size equal to or less than 200 im. Likewise, the process for cleaning hard surfaces based on the high-pressure spraying of a solution of the above composition and the use of cellulose particles of average size equal to or less than 200 im for high-level cleaning is a subject of the invention pressure of said surfaces. Document D01 is considered the closest in the state of the art to the object of the invention, and discloses a product for high pressure cleaning of vehicles, comprising cellulose fibers of medium length 40-400 im and thickness 5-200 im (equivalent average diameter 10-300 im), surfactants and adjuvants. In example 3, the following composition is proposed: 14% cellulose fibers (18 and 200 im); 12% surfactants (anionic surfactant: alkylbenzenesulfonic acid derivative; nonionic surfactant: ethoxylated fatty alcohol); 56.5% adjuvant (chelating agent) -percentages indicated by dry weight-. With respect to the cleaning procedure, pressure ranges of 1-300 bar and temperature ranges of 0-140 �C are allowed, where the cleaning agent is applied diluted to 0.02% by weight of fiber. (See pages 3-8; example 3; claims 1-3, 5, 8, 9, 12-14, 16). Therefore, the object of claims 1-5 and 7-10, relating to the composition, has been disclosed identically in D01 and is not new (Art. 6.1 LP). Claim 6, relating to the use of microcrystalline cellulose particles in the composition, does not meet the requirement of inventive activity since it is one of several obvious possibilities within the types of cellulose that one skilled in the art could select without the exercise of inventive activity (Art. 8.1 LP). Claim 11, relating to the use of sadic tripolyphosphate, sadic carbonate or mixtures thereof as adjuvants, also does not meet the requirement of inventive activity, since these are compounds widely known in the technical field and used as adjuvants in the formulation of detergents (Art. 8.1 LP). The object of the invention set forth in claims 12-20 is a process for cleaning hard surfaces in which an aqueous dispersion of the described cellulose composition is sprayed. The object of claims 12, 13, 17-20 has been disclosed identically in D01 and is not new (Art. 6.1 LP). On the other hand, claims 14-16, relating to the pressure and application temperature conditions, establish pressure and temperature ranges that constitute a selection of values within the range described in document D01; This selection cannot be considered inventive in the absence of unexpected effects or properties with respect to the rest of the range (Art. 8.1 LP). Finally, claims 21-24 relate to the use of cellulose particles for cleaning hard surfaces. The use of cellulose particles of size equal to or less than 200 im for high pressure cleaning of hard surfaces (eg vehicles) is already known from document D01 and therefore, claims 21-24 are not new to the light of the state of the known art (Art. 6.1 LP). Similar reasons can be followed with documents D02 and D03 which also disclose compositions for cleaning vehicles with cellulose particles (See D02: column 2, lines 40-64; column 3, lines 42-61; column 4, lines 14- 16 and 31-41; column 5, lines 26-44; claims 1-6, 8-9. See D03: column 1, lines 39-52; column 2, lines 16-19; column 4, lines 54-65; claims 1, 8, 9, 13). State of the Art Report Page 4/4