EP2205689A1 - Composition liquide de nettoyage et procédé de nettoyage d'une surface - Google Patents

Composition liquide de nettoyage et procédé de nettoyage d'une surface

Info

Publication number
EP2205689A1
EP2205689A1 EP07848801A EP07848801A EP2205689A1 EP 2205689 A1 EP2205689 A1 EP 2205689A1 EP 07848801 A EP07848801 A EP 07848801A EP 07848801 A EP07848801 A EP 07848801A EP 2205689 A1 EP2205689 A1 EP 2205689A1
Authority
EP
European Patent Office
Prior art keywords
cleaning composition
liquid cleaning
microparticles
solid inorganic
inorganic microparticles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07848801A
Other languages
German (de)
English (en)
Inventor
Giancarlo Gazzaniga
Norberto Roveri
Marcello Tedino
Luca Tabanelli
Tommaso Zuccheri
Elisabetta Foresti
Antonio Corallo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Coswell SpA
Original Assignee
Coswell SpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Coswell SpA filed Critical Coswell SpA
Publication of EP2205689A1 publication Critical patent/EP2205689A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1454—Abrasive powders, suspensions and pastes for polishing
    • C09K3/1463—Aqueous liquid suspensions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C09K3/1409—Abrasive particles per se
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures

Definitions

  • the present invention relates to homogenous aqueous liquid cleaning compositions containing low abrasive particles which are suited to the cleaning of hard surfaces.
  • the present invention relates to liquid cleaning compositions suited to the cleaning of hard surfaces such as ceramic, steel, plastic, glass and/or painted surfaces. According to another aspect thereof, the present invention relates to a method of cleaning a surface of an article which is also capable of rendering hydrophilic the cleaned surface.
  • the present invention relates to solid inorganic microparticles and uses thereof as low abrasive material in cleaning compositions and for imparting hydrophilic properties to a substrate.
  • Liquid compositions for cleaning hard surfaces are widely available on the market.
  • compositions are used for two purposes, the first being to clean soil from the surface and the second being to leave the surface with an aesthetically pleasing finish e.g. spot-free or shiny.
  • Typical liquid abrasive cleaning compositions are disclosed for example in International patent application WO 03/031554 and generally comprise one or more surfactants and a plurality of abrasive particles dispersed therein.
  • the surfactants may form a lamellar micelle aqueous phase which acts as a suspending system to keep the abrasive particles in a stable suspension.
  • Typical abrasive materials include minerals such as calcite or dolomite and other materials of relatively high density.
  • abrasive materials are generally obtained by grinding naturally occurring minerals or ores obtaining crystalline microparticles having a particle size ranging from 20 to 300 ⁇ m and an irregular outer surface formed by sharp-cornered edges formed during the grinding operations.
  • the known liquid cleaning compositions containing abrasive particles may damage in the long run delicate surfaces, such as the chromium plated surfaces of taps and fittings used in kitchens and bathrooms, forming micro scratches which irreversibly impair the luster and gloss over time giving a dull look to the surface.
  • the known liquid cleaning compositions containing abrasive particles have a tendency to leave residues which are difficult to rinse away and often leave water-marks, smears or spots on the cleaned surface which is believed may be due to the evaporation of water from the surface leaving behind deposits of minerals which were present as dissolved solids in the water, for example calcium, magnesium and sodium ions and salts thereof or may be deposits of water-carried soils, or even remnants of abrasive particles.
  • the present invention aims at overcoming at least in part one or more of the drawbacks mentioned with reference to the cited prior art and, more specifically, aims at providing a liquid cleaning composition for hard surfaces containing low abrasive particles which allows both to reduce in a substantial way the abrasive action on the surface to be cleaned and to facilitate the rinsing operations while attaining at the same time a satisfactory cleaning action.
  • the present invention provides a liquid cleaning composition for hard surfaces as defined in attached claim 1.
  • liquid cleaning composition of the present invention comprises: - a carrier, at least some of which is aqueous;
  • Y diffracted peaks net area + background area
  • X diffracted peaks net area of the microparticles X-ray diffraction pattern.
  • the liquid cleaning composition of the invention is capable of exerting an effective cleaning action by interacting in a mechanical way with the soil and dirt particles lying even in the tiniest microscratches formed in the surface to be cleaned without abrading in any detectable way the surface to be cleaned and without affecting the ability of the liquid cleaning composition of being rinsed away easily.
  • the liquid cleaning composition of the invention is also capable of imparting to the cleaned surface hydrophilic characteristics which render the surface even more rinsable thereby preventing the formation of water spots or streaks which tend to drift away from the surface.
  • hydrophilic it is meant herein that the surface has a high affinity for water.
  • the liquid cleaning composition of the invention is capable of hydrophilically modify a hard surface on which it is applied to the extent that the hard surface exhibits surprising and significantly improved rinsability, wetting and sheeting, quick drying, uniform drying, anti-spotting, anti-soil deposition, cleaner appearance, enhanced gloss, enhanced color, minor surface defect repair, improved smoothness, anti-hazing properties, modification of surface friction, release of actives, reduced damage to abrasion and improved transparency properties.
  • the surface cleaned with the liquid cleaning composition of the invention exhibits some advantageous "self-cleaning" properties (dirt removal via water rinsing, e. g. from rainwater) and/or soil release benefits (top layers are strippable via mild mechanical action).
  • the hydrophilicity can also provide the cleaned surface with resistance to soiling by hydrophobic types of soils.
  • liquid cleaning composition is used to indicate compositions in the form of liquids, aqueous gels, phase-separated liquid compositions (such as suspensions) and/or colored liquid compositions.
  • hard surface is used to indicate any kind of rigid surfaces typically found in houses like kitchens, bathrooms, or the exterior surfaces of a vehicle, e. g., floors, walls, tiles, windows, sinks, showers, shower plastified curtains, wash basins, WCs, dishes, fixtures and fittings and the like made of different materials like ceramic, vinyl, nowax vinyl, linoleum, melamine, glass, any plastics, plastified wood, metal, especially steel and chrome metal or any painted or varnished or sealed surface and the like.
  • Surfaces also include household appliances including, but not limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, . dishwashers and so on.
  • the present composition is especially efficacious in the cleaning of ceramic, enamel, steel, plastic, glass surfaces found in kitchens, bathrooms and the like.
  • the non-abrasive effective cleaning action of the liquid cleaning composition is due to a reduced size of the microparticles, while the ability of the liquid cleaning composition of being easily washed away and of imparting hydrophilic characteristics to the cleaned surface may be attributed to the large surface area and to the low crystallinity degree of the microparticles, which features impart to the microparticles a highly indented and irregular outer surface.
  • the microparticles are capable of modifying the surface by adhering or in some way associating with the surface to be cleaned such that they preferably remain on the surface during and after the cleaning process. Such adhesion or association may be due for example to electrostatic interaction, hydrogen bonding or Van der Waals forces.
  • the microparticles modify the surface by rendering it hydrophilic meaning that the contact angle (measured as will be explained later on) between water and the surface, after the surface has been treated with the polymer-containing composition is less than 33°, more preferably less than 30°, still more preferably, less than 25°.
  • the particle size of the solid inorganic microparticles can be measured according to known methods, such as, for example, by using transmission electron microscopy (TEM).
  • TEM transmission electron microscopy
  • crystallinity degree is intended to indicate the percentage of the compound or compounds forming the microparticles present in the crystalline state.
  • crystallinity degree can be measured according to known methods, such as, for example, by using X-ray diffraction analysis.
  • crystallinity degree CD is measured according to the method reported by Z. E. Erkmen "The effect of heat treatment on the morphology o/D-Gun Sprayed Hydroxyapatite coatings", J. Biomed
  • the carrier medium can form part of the liquid cleaning composition, or it can comprise the medium in which the microparticles are carried (or transported) for application to the hard surface.
  • the carrier medium is contained in the liquid cleaning composition in an amount suitable to transport and/or solubilize the various ingredients described herein.
  • amount is readily ascertained by one of ordinary skill in the art and is based on many factors, such as the physical and chemical nature of the ingredients, the application technique of the cleaning composition, and the like.
  • the liquid cleaning composition can be provided in the form of an aqueous liquid or gel in a container, and the liquid or gel can be poured, applied by means of a cloth or sponge or sprayed (if liquid) onto a hard surface.
  • the aqueous liquid or gel carrier in the container holding the coating composition may be referred to herein as the "static carrier”.
  • the liquid droplets in the spray may be referred to herein as the "dynamic carrier” (the medium that transports the ingredients to the surface in order to contact the surface).
  • carrier includes both static and dynamic carriers.
  • Suitable carrier mediums include liquids.
  • One suitable carrier medium is water, which can be distilled, deionized, or tap water. Water is valuable due to its low cost, availability, safety, and compatibility, hi certain embodiments in which the carrier medium is aqueous, it may be preferred that at least some of the aqueous carrier is purified beyond the treatment it received to convert it to tap water (that is, the tap water is post-treated, e. g., deionized or distilled).
  • the purified water could comprise: all or part of the static carrier for the composition; all or part of the dynamic carrier; or, all or part of both.
  • carrier mediums which may be used in combination with water are low molecular weight organic solvents that are highly soluble in water, e.g., ethanol, methanol, propanol, isopropanol and the like, and mixtures thereof.
  • Low molecular weight alcohols can allow the treated hard surface to dry faster.
  • the optional water soluble low molecular weight solvent can be used at a level of up to about 50% by weight, typically from about 0.1% to about 25% by weight, alternatively from about 2% to about 15% by weight, alternatively from about 5% to about 10%, by weight of the suitable carrier medium.
  • Factors that need to consider when a high level of solvent is combined with the suitable carrier medium are odor, flammability, dispersancy of the microparticle and environment impact.
  • the liquid cleaning composition comprises solid inorganic microparticles having a particle size of from 0.5 to 5 ⁇ m, preferably from 0.5 to 1.5 ⁇ m. hi this way, the ability of the microparticles of reaching dirt and soil located in the tiniest scratches of the surface to be cleaned and the ability of the liquid cleaning composition of exerting its cleaning action without affecting the surface integrity and its gloss are advantageously enhanced.
  • the solid inorganic microparticles are contained in the liquid cleaning composition in an effective amount to provide one or more of the benefits described herein.
  • an effective amount of the solid inorganic microparticles refers to the quantity of microparticles of the present invention described herein necessary to achieve at least one of the desired cleaning action, ability of the cleaning composition to be rinsed away and hydrophilic characteristics of the cleaned surface in the specific composition. Such effective amount is readily ascertained by one of ordinary skill in the art and is based on many factors, such as the particular microparticles used, the application technique of the cleaning composition, the specific composition of the cleaning composition, and the like.
  • the concentration of microparticles in the liquid cleaning compositions described herein is comprised between 0.1 and 60% by weight as a function of the application technique of the cleaning composition.
  • a liquid cleaning composition that is to be applied to the hard surface by pouring or by means of a sponge or cloth may comprise from 5 to 50% by weight, more preferably from 10 to 40% by weight, of solid inorganic microparticles
  • a liquid cleaning composition that is to be applied to the hard surface by spraying may comprise from 0.1 to 15% by weight, more preferably from 0.5 to 5% by weight, of solid inorganic microparticles in order not to clog the spraying device.
  • the solid inorganic microparticles of the liquid cleaning composition have a surface area of from 20 to 40 m 2 /g.
  • the ability of the liquid cleaning composition of being easily washed away and of imparting hydrophilic characteristics to the cleaned surface may be advantageously enhanced.
  • the surface area of the microparticles can be measured according to known methods, such as, for example, by the BET method. In connection with this parameter, the inventors have observed that the average values of the surface area of the microparticles may vary within the aforementioned range as a function of the total amount of microparticles synthesized per each production batch, the higher values being more easily reached the smaller is the entity of the production batch.
  • the solid inorganic microparticles of the liquid cleaning composition have a crystallinity degree CD comprised between 25% and 35%. In this way, the ability of the liquid cleaning composition of being easily washed away and of imparting hydrophilic characteristics to the cleaned surface may be advantageously enhanced.
  • suitable solid inorganic microparticles are inorganic microparticles selected from phosphates, oxides, silicates, carbonates, hydroxides, and mixtures thereof.
  • the solid inorganic microparticles are inorganic microparticles selected from acid phosphates, calcium phosphates, hydroxyapatite, modified hydroxyapatite, alkaline earth metal phosphates, ammonium phosphates, brushite, monetite, feldspar, quartz, topaz, calcite, alumina, limonite, kimenite, ceramic, leucite, glass, taconite, silica sand, flint, vermiculite, fire clay, diaspore, bauxite, limestone, magnetite, hematite, and mixtures thereof.
  • the solid inorganic microparticles are microparticles of a carbonate-substituted non-stoichiometric hydroxyapatite having the formula: Ca 10 (P ⁇ 4 ) 6 - y (CO 3 ) y+z (OH) 2-z wherein y is a number comprised between 0.065 and 0.9 and z is a number comprised between 0 and 0.32.
  • the carbonate-substituted non-stoichiometric hydroxyapatite microparticles possess negatively " charged carbonate and phosphate moieties which enhances the ability of the liquid cleaning composition of being easily washed away and of imparting hydrophilic characteristics to the cleaned surface.
  • the carbonate ions incorporated in the apatite structure which contribute to lower the crystallinity degree of the microparticles consequent to the incorporation of these ions in the apatite structure.
  • the carbonate ion can occupy two different sites in the hydroxyapatite structure: namely, it can partially substitute the OH-ion (site A) and/or the PO 4 3" ion (site B).
  • the carbonation preferably takes place at site B 5 as this results in a reduction of the crystallinity with the consequent beneficial effect on the aforementioned ability of the liquid cleaning composition of being easily washed away and of imparting hydrophilic characteristics to the cleaned surface.
  • the carbonate-substituted non- stoichiometric hydroxyapatite microparticles comprise from 1 to 15% by weight and, more preferably, from 1 to 10% by weight based on the total weight of the microparticles, of carbonate substituted into the hydroxyapatite structure.
  • the ratio A/B between the carbonate substitution at the hydroxyl site (A) and the carbonate substitution at the phosphate site (B) of the hydroxyapatite microparticles is comprised between 0.05 and 0.5 and, still more preferably, comprised between 0.18 and 0.33.
  • the carbonate substitution at the phosphate site (B) of the hydroxyapatite is greater than or equal to 65% by weight and, still more preferably, comprised between 90% and 100% by weight, of the total carbonate present in the hydroxyapatite.
  • the carbonate-substituted non-stoichiometric hydroxyapatite microparticles have a molar ratio Ca/P comprised between 1.6 and 1.9. hi this way, the rinsing ability of the liquid cleaning composition may be further enhanced.
  • suitable carbonate-substituted non-stoichiometric hydroxyapatite microparticles may be prepared by processes known in the art and disclosed, for example, by L. Rimondini, B. Palazzo, M. Iafisco, L. Canegallo, F. Demarosi, M. Merlo, N. Roveri, "The remineralizing effect of carbonate-hydroxyapatite nanocrystals on dentine", Materials Science Forum, VoIs. 539-543 (2007) pp. 602-605.
  • a preferred process for preparing carbonate-substituted non-stoichiometric hydroxyapatite microparticles comprises the steps of: a) preparing an aqueous solution or suspension comprising a Ca compound; b) forming nanoparticles of a carbonate-substituted hydroxyapatite by adding
  • the aforementioned step a) of preparing an aqueous solution or suspension comprising a Ca compound may be carried out in any conventional manner, such as by dissolving or suspending the Ca compound in water.
  • the Ca compound is a calcium salt selected from the group comprising: calcium hydroxide, calcium carbonate, calcium acetate, calcium oxalate, calcium nitrate, and mixtures thereof.
  • step a) is preferably carried out in order to achieve a suspension of nanoparticles having a basic pH.
  • the aqueous solution or suspension of step a) has a pH comprised between 8 and 12.
  • nanoparticles of carbonate-substituted hydroxyapatite are formed in step b) by adding PO 4 3" ions to the aqueous solution or suspension of step a) and by simultaneously agitating this solution or suspension in order to capture the carbon dioxide present in the atmosphere and achieve the desired carbonate substitution at the phosphate site (B) of the hydroxyapatite compound being formed.
  • the carbonate substitution may be advantageously carried out by simply agitating the solution or suspension for example by means of a mechanical stirrer.
  • the required agitation of the solution or suspension may be achieved by bubbling air, a CO 2 -containing gas or a mixture thereof into the liquid phase or by combining a mechanical stirring with a gas bubbling.
  • the PO 4 3" ions are added to the aqueous solution or suspension of step a) over a time which generally depends on the amount of the used phosphoric solution with respect to the amount of the basic, calcium solution or suspension, and which may be selected by those skilled in the art.
  • step b) is carried out over a time comprised between 30 minutes and 2 hours in order to keep the reaction time and the operating costs as low as possible.
  • step b) is carried out while maintaining said solution or suspension at a temperature lower than or equal to 60 0 C.
  • the inventors have observed that in this way the crystallinity degree CD of the nanoparticles may be kept below the aforementioned maximum value of 50%.
  • step b) is carried out while maintaining said solution or suspension at a temperature lower than or equal to 4O 0 C and more preferably comprised between 25° and 4O 0 C.
  • step b) is carried out by adding, preferably dropwise, an aqueous solution including PO 4 3" ions to the aqueous solution or suspension of step a).
  • the aqueous solution including PO 4 3" ions added in step b) may further comprise HCO 3 " ions. hi this way, it may be possible to adjust to the proper extent the desired carbonate substitution at the phosphate site (B) of the hydroxyapatite compound being formed.
  • the aforementioned aqueous solution including HCO 3 " and PO 4 3" ions may be prepared by bubbling air, CO 2 or a mixture thereof through water to obtain a solution of carbonic acid and then adding
  • step b) may be carried out by simultaneously adding a first solution containing CO 3 2" ions and a second solution containing PO 4 3" ions to the aqueous solution or suspension of step a).
  • the process is carried out such that the suspension of microparticles obtained from step c) has a pH comprised between 7 and 8 and, more preferably, between 7 and 7.4.
  • the preparation process of the microparticles allows to produce a suspension which may be advantageously directly used as such or mixed with other ingredients in the formulation of effective liquid cleaning compositions with a remarkable simplification of the manufacturing operations of the compositions and a remarkable cost reduction.
  • step c) promotes the growth and aggregation of the nanoparticles of carbonate-substituted hydroxyapatite to form microparticles of the desired particle size.
  • the microparticles obtained in this way are aggregate or clusters of nanoparticles as will be described in greater detail hereinbelow.
  • step c) is accomplished by agitating the suspension obtained from step b) (during which mainly a nucleation of the nanoparticles is taking place) over a time of at least 2 hours at a temperature lower than or equal to 60 0 C.
  • step c) is carried out over a time comprised between 2 and 24 hours and more preferably between 2 and 12 hours, as required by the circumstances in order to have a growing time of the microparticles sufficient to reach the desired size and in order to obtain a single phase.
  • step c) is carried out while mamtaining the suspension of microparticles at a temperature comprised between 25° and 40°C. In a preferred embodiment of the invention, step c) is carried out while mamtaining the suspension of microparticles at the same temperature of step b).
  • the separation step d) is carried out by decantation, centrifugation or filtration using apparatuses and techniques well known to those skilled in the art.
  • the drying step e) is carried out by freezing the wet solid microparticles at a temperature lower than 0°C until reaching a constant weight.
  • the drying step e) is preferably carried out by freeze-drying the wet solid microparticles at a temperature comprised between -20° and -50 0 C, most preferably at about -40°C.
  • the process may also comprise the additional step f) of washing the separated solid microparticles with water or a basic solution prior to effecting the drying step e).
  • this additional washing step f) serves the useful function of removing any acid residues possibly absorbed or trapped by the microparticles.
  • solid inorganic microparticles suitable for the purposes of the present invention are layered clay minerals and inorganic metal oxides.
  • the layered clay minerals suitable for use in the present invention include those in the geological classes of the smectites, the kaolins, the illites, the chlorites, the attapulgites and the mixed layer clays.
  • Typical examples of specific clays belonging to these classes are the smectites, kaolins, illites, chlorites, attapulgites and mixed layer clays.
  • Smectites for example, include montmorillonite, bentonite, pyrophyllite, hectorite, saponite, sauconite, nontronite, talc, beidellite, volchonskoite and vermiculite.
  • Kaolins include kaolinite, dickite, nacrite, antigorite, anauxite, halloysite, indellite and chrysotile.
  • Illites include bravaisite, muscovite, paragonite, phlogopite and biotite.
  • Chlorites include corrensite, penninite, donbassite, sudoite, pennine and clinochlore.
  • Attapulgites include sepiolite and polygorskyte.
  • Mixed layer clays include allevardite and vermiculitebiotite. Variants and isomorphic substitutions of these layered clay minerals offer unique applications.
  • the layered clay minerals of the present invention may be either naturally occurring or synthetic.
  • An example of one embodiment of the present invention uses natural or synthetic hectorites, montmorillonites and bentonites. Another embodiment uses the hectorites clays commercially available.
  • the inorganic metal oxides of the present invention may be silica-or alumina-based microparticles that are naturally occurring or synthetic. Aluminum can be found in many naturally occurring sources, such as kaolinite and bauxite. The naturally occurring sources of alumina are processed by the Hall process or the Bayer process to yield the desired alumina type required.
  • alumina Various forms of alumina are commercially available in the form of Gibbsite, Diaspore, and Boehmite.
  • Natural clay minerals typically exist as layered silicate minerals and less frequently as amorphous minerals.
  • a layered silicate mineral has SiO 4 tetrahedral sheets arranged into a two-dimensional network structure.
  • a 2: 1 type layered silicate mineral has a laminated structure of several to several tens of silicate sheets having a three layered structure in which a magnesium octahedral sheet or an aluminum octahedral sheet is sandwiched between two sheets of silica tetrahedral sheets.
  • a sheet of an expandable layer silicate has a negative electric charge, and the electric charge is neutralized by the existence of alkali metal cations and/or alkaline earth metal cations.
  • microparticles described above may be prepared by processes known in the art.
  • the solid inorganic microparticles and most preferably the microparticles of the carbonate-substituted non-stoichiometric hydroxyapatite mentioned above are aggregates or "clusters" of inorganic nanoparticles.
  • nanoparticle is used to indicate a particle having a size generally below l ⁇ m.
  • the microparticles are characterized by an elevated disorder of their outer surface which is believed to account for to the enhanced ability of the liquid cleaning composition of being easily washed away and of rendering hydrophilic the cleaned surface. Also, this aggregation of smaller particles is deemed to contribute to reducing the abrasive action on the surface to be cleaned thanks to their tendency to disgregate if subjected to the mechanical rubbing action exerted during cleaning.
  • the liquid cleaning composition of the invention achieves the additional advantage that the nanoparticles are aggregated in clusters without the need of any binding agent but are simply reversibly kept together by electrostatic interaction, hydrogen bonding or Van der Waals forces.
  • the nanoparticles forming the aggregates or "clusters" have a particle size ranging from 5 to 200 nm.
  • the aforementioned aggregates are aggregates of nanoparticles, most preferably aggregates of nanoparticles of a carbonate-substituted non-stoichiometric hydroxyapatite, having: a) a length L ranging from 20 to 200 nm and a width W ranging from 5 to 30 nm; and b) an aspect ratio AR comprised between 2 and 40, the aspect ratio being defined as
  • length L of the nanoparticles is intended to mean the dimension of the nanoparticle as measured along the major axis thereof
  • width W of the nanoparticles is intended to mean the dimension of the nanoparticle as measured along the minor axis thereof.
  • the length L and the width W of the nanoparticles can be measured according to known methods, such as, for example, by using transmission electron microscopy (TEM).
  • TEM transmission electron microscopy
  • the solid inorganic nanoparticles forming the aforementioned aggregates, and preferably the carbonate-substituted non- stoichiometric hydroxyapatite nanoparticles have a substantially acicular or platelet shape. having a length L comprised between 50 and 150 nm and a width W comprised between 5 and 20 nm.
  • the nanoparticles have a thickness T as measured by the TEM technique ranging from 2 to 15 nm.
  • the aspect ratio AR of the nanoparticles is preferably comprised between 2 and 16 and, still more preferably, between 5 and 10.
  • the liquid cleaning composition of the invention may further include additional solid inorganic microparticles, selected from the materials disclosed above, and having a particle size higher than 5 ⁇ m and preferably comprised between 5 and 25 ⁇ m.
  • additional solid inorganic microparticles need not comply with the aforementioned requirements of surface area and crystallinity degree and may be added to regulate the content of abrasive particles contained in the composition to optimal values reducing at the same time the overall cost of the liquid cleaning composition.
  • concentration of these additional solid inorganic microparticles in the liquid cleaning compositions described herein should be suitably selected to such low values as not to trigger the noted problems of surface damage and progressive loss of surface gloss which affect the liquid cleaning compositions of the prior art.
  • concentration of these additional solid inorganic microparticles in the liquid cleaning compositions described herein is preferably comprised between 0.1 and 15% by weight, more preferably, between 0.5 and 5% by weight, as a function of the concentration in the cleaning composition of the above-described solid inorganic microparticles of the invention. .
  • the weight ratio between the additional solid inorganic microparticles and the solid inorganic microparticles of the invention is maintained at a value lower than 0.3 and preferably lower than 0.15 in order not to trigger the noted problems of surface damage and progressive loss of surface gloss which affect the liquid cleaning compositions of the prior art.
  • surfactants The presence of a surfactant in the liquid cleaning compositions of the present invention have been found to not only improve the cleaning performance, but also facilitate the dispersion of the solid inorganic microparticles and other adjunct ingredients such as antimicrobial actives and perfumes.
  • the liquid cleaning composition of the invention may do without the suspending systems usually required in the compositions of the prior art to keep the solid abrasive in a stable suspension.
  • Suitable surfactant useful in the present invention is surfactant selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.
  • the surfactant is contained in the liquid cleaning composition in an effective amount to provide one or more of the benefits described herein.
  • effective amount of the surfactant refers to the quantity of surfactant described herein necessary to achieve at least one of the desired cleaning action, ability of dispersing the solid inorganic microparticles and other optional adjunct ingredients.
  • Such effective amount may be readily ascertained by one of ordinary skill in the art and is based on many factors, such as the specific composition of the cleaning composition, the application technique of the cleaning composition, and the like.
  • the concentration of surfactant in the liquid cleaning compositions described herein is preferably comprised between 0.1 and 40% by weight as a function of the application technique of the cleaning composition.
  • a liquid cleaning composition that is to be applied to the hard surface to be cleaned by pouring or by means of a sponge or cloth may preferably comprise firom 0.3 to 20% by weight, more preferably from 1.5 to 10% by weight, of surfactant
  • a liquid cleaning composition that is to be applied to the hard surface to be cleaned by spraying may preferably comprise from 0.5 to 10% by weight, more preferably from 1.0 to 6.0% by weight, of surfactant in order to reduce the formation of foam, enhance the rinsability characteristics and reduce costs.
  • Suitable anionic surfactants for use in the compositions herein include water-soluble salts or acids of the formula ROSO 3 M wherein R preferably is a C 7 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 7 -C 24 alkyl component, more preferably a C 12 -C 18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylarnine, triethylamine, and mixtures thereof, and the like).
  • R
  • Suitable anionic surfactants for use herein are water-soluble salts or acids of the formula RO(A) 1n SOaM wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C 2O alkyl or hydroxyalkyl, more preferably C 12 -C 18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is a number greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate, C 12 -C 18 E(LO)M), C 12 -C 18 alkyl polyethoxylate (2.25) sulfate, C 12 -C 18 E(2.25)M), C 12 -C 18 alkyl polyethoxylate (3.0) sulphate, C 12 -C 18 E(3.0), and C 12 -C 18 alkyl polyethoxylate (4.0) sulfate C 12 -C 18 E(4.0)M), wherein M is conveniently selected from sodium and potassium.
  • alkyl sulphonates including water-soluble salts or acids of the formula RSO 3 M wherein R is a C 6 -C 22 linear or branched, saturated or unsaturated alkyl group, preferably a C 1 O-Ci 6 alkyl group and more preferably a C 12 -C 16 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethylammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • R is a C 6 -C 22 linear or branched, saturated
  • Suitable alkyl aryl sulphonates for use herein include water-soluble salts or acids of the formula RSO 3 M wherein R is an aryl, preferably a benzyl, substituted by a C 6 -C 22 linear or branched saturated or unsaturated alkyl group, preferably a C 10 -C 18 alkyl group and more preferably a C 12 -C 16 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc) or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and ⁇ rimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, tri
  • alkylsulfonates and alkyl aryl sulphonates for use herein include primary and secondary alkylsulfonates and primary and secondary alkyl aryl sulphonates.
  • secondary C 6 -C 22 alkyl or C 6 -C 22 alkyl aryl sulphonates it is meant herein that in the formula as defined above, the SO 3 M or aryl-SO 3 M group is linked to a carbon atom of the alkyl chain being placed between two other carbons of the said alkyl chain (secondary carbon atom).
  • Other anionic surfactants useful for detersive purposes can also be used herein.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • soap of natural fatty acids, such as coconut oil, C 8 -C 24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, C 8 -C 24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as C 14 -C 16 methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N
  • alkyl carboxylates and alkyl alkoxycarboxylates having from 4 to 24 carbon atoms in the alkyl chain, preferably from 8 to 18 and more preferably from 8 to 16, wherein the alkoxy is propoxy and/or ethoxy and preferably is ethoxy at an alkoxylation degree of from 0.5 to 20, preferably from 5 to 15.
  • Suitable amphoteric surfactants for use herein include amine oxides having the following formula R 1 R 2 R 3 NO wherein each of R 1 , R 2 and R 3 is independently a saturated substituted or unsubstituted, linear or branched hydrocarbon chain of from 1 to 30 carbon atoms.
  • Preferred amine oxide surfactants to be used according to the present invention are amine oxides having the following formula R 1 R 2 R 3 NO wherein Ri is a hydrocarbon chain comprising from 1 to 30 carbon atoms, preferably from 6 to 20, more preferably from 8 to 16, most preferably from 8 to 12, and wherein R 2 and R 3 are independently substituted or unsubstituted, linear or branched hydrocarbon chains comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and more preferably are methyl groups.
  • R 1 may be a saturated, substituted or unsubstituted linear or branched hydrocarbon chain.
  • Suitable amine oxides for use herein are for instance natural blend C 8 -C 10 amine oxides as well as C 12 -Ci 6 amine oxides commercially available from Hoechst.
  • Suitable zwitterionic surfactants for use herein contain both a cationic hydrophilic group, i.e., a quaternary ammonium group, and anionic hydrophilic group on the same molecule at a relatively wide range of pH's.
  • the typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups like sulfates, phosphonates, and the like can be used.
  • R 1 are aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chains that can contain linking groups such as amido groups, ester groups. More preferred R 1 is an alkyl group containing from 1 to 24 carbon atoms, preferably from 8 to 18, and more 20 preferably from 10 to 16. These simple alkyl groups are preferred for cost and stability reasons.
  • the hydrophobic group Rl can also be an amido radical of the formula R 2 -C(O)-NH- (C(R b )2) m , wherein R a is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain, preferably an alkyl group containing from 8 up to 20 carbon atoms, 25 preferably up to 18, more preferably up to 16, R b is selected from the group consisting of hydrogen and hydroxy groups, and m is from 1 to 4, preferably from 2 to 3, more preferably 3, with no more than one hydroxy group in any (C(R b )2) moiety.
  • R 2 is hydrogen, or a C 1 -C 3 alkyl and more preferably methyl.
  • Preferred R 3 is a C 1 -C 4 carboxylic acid group or C 1 -C 4 sulfonate group, or a C 1 -C 3 alkyl and more preferably methyl.
  • Preferred R 4 is (CH 2 ) n wherein n is an integer from 1 to 10, preferably from 1 to 6, more preferably is from 1 to 3.
  • alkyldimethyl betaines examples include coconut-dimethyl betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2-(N-decyl-N,N-dimethyl- ammonia)acetate, 2-(N-coco-N,N-dimethylammonio)acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine.
  • coconut dimethyl betaine is commercially available from Seppic under the trade name of Amonyl 265®.
  • Lauryl betaine is commercially available from Albright & Wilson under the trade name Empigen BB/L®.
  • amidobetaines include cocoamidoethylbetaine, cocoamidopropyl betaine or C 1O -C 14 fatty acylamidopropylene(hydropropylene)sulfobetaine.
  • C 10 -C 14 fatty acylamidopropylene(hydropropylene)sulfobetaine is commercially available from Sherex Company under the trade name "Varion CAS® sulfobetaine".
  • betaine is lauryl-imino-dipropionate commercially available from Rhone-Poulenc under the trade name Mirataine H2C-HA®.
  • Suitable cationic surfactants for use herein include derivatives of quaternary ammonium, phosphonium, imidazolium and sulfonium compounds.
  • Preferred cationic surfactants for use herein are quaternary ammonium compounds wherein one or two of the hydrocarbon groups linked to nitrogen are a saturated, linear or branched alkyl group of 6 to 30 carbon atoms, preferably of 10 to 25 carbon atoms, and more preferably of 12 to 20 carbon atoms, and wherein the other hydrocarbon groups (i.e.
  • alkoxylated nonionic surfactants are suitable for use herein.
  • alkoxylated nonionic are preferably alkoxylated hydrocarbons, such as alkoxylated terpene, or alkoxylated alcohols having a carbon chain containing from 8 to 20 carbon atoms, more preferably from 10 to 18 carbon atoms and most preferably from 10 to 15 carbon atoms.
  • the alkoxylation may be provided by ethoxylate, propoxylate or butoxylate groups, preferably ethoxylate groups.
  • the ethoxylated alcohol comprises from 0.5 to 20, more preferably from 2 to 10, most preferably from 4 to 6 ethoxy groups.
  • Suitable capped alkoxylated nonionic surfactants for use herein are according to the formula:
  • Rl(O-CH 2 -CH 2 V(OR 2 VO-R 3 wherein R 1 is a C 8 -C 24 linear or branched alkyl or alkenyl group, aryl group, alkylaryl group, preferably R 1 is a C 8 -C 18 alkyl or alkenyl group, more preferably a C 1O -C 15 alkyl or alkenyl group, even more preferably a C 10 -C 15 alkyl group; wherein R 2 is a C 1 -C 10 linear or branched alkyl group, preferably a C 2 -C 10 linear or branched alkyl group, wherein R 3 is a C 1 -C 10 alkyl or alkenyl group, preferably a C 1 -C 5 alkyl group, more preferably methyl; and wherein n and m are integers independently ranging in the range of from 1 to 20, preferably from 1 to 10, more preferably from 1 to 5; or mixtures thereof.
  • surfactants are commercially available from BASF under the trade name Plurafac®, from HOECHST under the trade name Genapol® or from ICI under the trade name Symperonic®.
  • Preferred capped nonionic alkoxylated surfactants of the above formula are those commercially available under the trade name Genapol® L 2.5 NR from Hoechst, and Plurafac® from BASF.
  • suitable surfactants include the alkyl polysaccharide surfactants.
  • the alkyl polysaccharide surfactants have a hydrophobic group containing from 8 to 20 carbon atoms, preferably from 10 to 18 carbon atoms, and a polysaccharide hydropbilic group containing from 1.5 to 10, preferably from 1.5 to 4 saccharide units.
  • Suitable saccharide units include galactoside, glucoside, fructoside, glycosyl, fructosyl and/or galactosyl. Mixtures of saccharide units may be used in the alkyl polysaccharide.
  • Typical hydrophobic groups include alkyl groups, either saturated or nonsaturated, branched or unbranched containing from 6 to 20, preferably from 8 to 18 carbon atoms.
  • the alkyl group is a linear, saturated alkyl group.
  • the alkyl group can contain up to 3 hydroxy groups and/or the polyalkoxide chain can contain up to 30, preferably less than 10 alkoxide groups.
  • Suitable alkyl polysaccharides are octyl, decyl, dodecyl, tetradcyl, pentadecyl, hexadecyl and actadecyl, di-, tri-, terra-, penta- and hexa-glucosides, lactosides, fructosides, fructosyls, lactosyls, glucosyls, galactosyls, and mixtures thereof.
  • Suitable surfactants include silicone surfactants such as organsilane or organosiloxane.
  • silicone surfactants have molecular weight of from 600 to 10000, more preferably from 900 to 6000, most preferably about 3000.
  • Such compounds are well known in the art, examples of which can be found in for example US 3 299 112, US 4 311 695, US 4 782 095 the disclosures of which are incorporated herein by reference.
  • Suitable siloxane oligomers are described in US 4 005 028.
  • Suitable silicone surfactants include poly siloxane polyethylene glycol copolymers, polyalkylene oxide-modified polydimethylsiloxane copolymers.
  • Suitable surfactants include the fiuorosurfactants which comprise a hydrophilic and a hydrophobic section.
  • the hydrophilic section comprises an alkyl group having from 2 to 12 carbons and an ester, sulfonate or carboxylate moiety.
  • the hydrophobic section is fluorinated.
  • Preferred fiuorosurfactants include alkyl fluorocarboxylates for example ammonium perfluroalkyl carboxylate and potassium fluroalkyl carboxylate.
  • a particularly suitable fluorosurfactants is an aqueous mixture of potassium fluoroalkyl carboxylate and has from 40-44% fluoroalkyl carboxylate having 8 carbon atoms in the alkyl chain, from 1-5% fluoroalkyl carboxylates having 6 carbon atoms in the alkyl chain, from 1-5% fluoroalkyl carboxylates having 4 carbon atoms in the alkyl chain, from 1-3% fluoroalkyl carboxylates having 7 carbon atoms in the alkyl chain and from 0.1-1% fluoroalkyl carboxylates having 5 carbon atoms in the alkyl chain.
  • the surfactant is a system comprising at least one anionic surfactant in combination with a non ionic surfactant.
  • anionic surfactants are the alkyl sulfates and the salts of natural fatty acids surfactants.
  • Particularly preferred non ionic surfactants are the alkoxylated hydrocarbons, such as alkoxylated terpene.
  • the surfactant is a system comprising at least one non ionic surfactant.
  • Particularly preferred non ionic surfactants are alkoxylated hydrocarbons, such as alkoxylated terpene, and alkoxylated alcohols such as Laureth-4 (ethoxylated dodecyl alcohol).
  • Optional ingredients are alkoxylated hydrocarbons, such as alkoxylated terpene, and alkoxylated alcohols such as Laureth-4 (ethoxylated dodecyl alcohol).
  • liquid cleaning compositions described herein may comprise a variety of optional ingredients depending on the technical benefit required and the surface treated.
  • Suitable optional ingredients for use herein can be selected from anti-resoiling ingredients, solvents, pH adjusting agents, rheology regulators, perfumes and minor ingredients such as colorants, preservatives and/or disinfectants. Suitable amounts of these optional ingredients may be easily selectable by those skilled in the art as a function of the specific characteristics to be imparted to the liquid cleaning composition.
  • Anti-resoiling ingredients can be selected from anti-resoiling ingredients, solvents, pH adjusting agents, rheology regulators, perfumes and minor ingredients such as colorants, preservatives and/or disinfectants. Suitable amounts of these optional ingredients may be easily selectable by those skilled in the art as a function of the specific characteristics to be imparted to the liquid cleaning composition.
  • Anti-resoiling ingredients may be easily selectable by those skilled in the art as a function of the specific characteristics to be imparted to the liquid cleaning
  • composition comprises one or more anti-resoiling ingredients.
  • the anti-resoiling ingredients are contained in the liquid cleaning composition in an effective amount to provide one or more of the benefits described herein.
  • an effective amount of the anti-resoiling ingredient refers to the quantity of this ingredient necessary to impart anti-resoling properties to the cleaned surface thanks to the film-forming action of this ingredient.
  • Such effective amount is readily ascertained by one of ordinary skill in the art and is based on many factors, such as the particular anti-resoiling ingredient used, the application technique of the cleaning composition, the specific composition of the cleaning composition, and the like.
  • concentration of the anti-resoiling ingredients in the liquid cleaning compositions described herein is preferably comprised between 0.1 and 2% by weight, more preferably between 0.25% and 1.5% by weight, as a function of the application technique of the cleaning composition.
  • Suitable anti-resoiling ingredients include those well known to those skilled in the art, amongst which include polyalkoxylene glycol diesters, vinylpyrrolidone homopolymers or copolymers, polysaccharide polymers, polyalkoxylene glycols, mono- or di-capped polyalkoxylene glycols, as defined hereinafter, or a mixture thereof.
  • Suitable vinylpyrrolidone homopolymers for use herein are homopolymers of N- vinylpyrrolidone ("PVP") having an average molecular weight of from 1,000 to 100,000,000, preferably from 2,000 to 10,000,000, more preferably from 5,000 to 1,000,000, and most preferably from 50,000 to 500,000.
  • PVP N- vinylpyrrolidone
  • Suitable copolymers of vinylpyrrolidone for use herein include copolymers of N- 15 vinylpyrrolidone and alkylenically unsaturated monomers or mixtures thereof.
  • the alkylenically unsaturated monomers of the copolymers herein include unsaturated dicarboxylic acids such as maleic acid, chloromaleic acid, fumaric acid, itaconic acid, citraconic acid, phenylmaleic acid, aconitic acid, acrylic acid, and vinyl acetate. Any of the anhydrides of the unsaturated acids may be employed, for example acrylate, methacrylate.
  • Aromatic monomers like styrene, sulphonated styrene, alpha-methyl styrene, vinyl toluene, t-butyl styrene and similar well known monomers may be used.
  • polysaccharide polymers including substituted cellulose materials like carboxymethylcellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxymethyl cellulose, succinoglycan and naturally occurring polysaccharide polymers like xanthan gum, guar gum, locust bean gum, tragacanth gum or derivatives thereof, or mixtures thereof.
  • Particularly preferred polysaccharide polymers to be used in the liquid cleaning composition disclosed herein are xanthan gum and derivatives thereof.
  • Suitable additional anti-resoiling ingredients for use herein further include alkyl ether glycols, polyalkoxylene glycols, mono- and dicapped polyalkoxylene glycols or a mixture thereof, as defined herein after.
  • Suitable alkyl ether glycols for use herein are according to the following formula R 1 -
  • Suitable polyalkoxylene glycols for use herein are according to the following formula HO-(CH 2 -CHR 2 O) n -H.
  • Suitable monocapped polyalkoxylene glycols for use herein are according to the following formula R 1 -O-(CH 2 -CHR 2 O) n -H.
  • Suitable dicapped polyalkoxylene glycols for use herein are according to the formula
  • R 1 -O-(CH 2 -CHR 2 O) n -R 3 the substituents R 1 and R 3 each independently are substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbon chains having from 1 to 30 carbon atoms, or amino bearing linear or branched, substituted or unsubstituted hydrocarbon chains having from 1 to 30 carbon atoms, R 2 is hydrogen or a linear or branched hydrocarbon chain having from 1 to 30 carbon atoms, and n is an integer greater than 0.
  • alkyl ether glycol to be used in the liquid cleaning composition disclosed herein is butyl glycol.
  • compositions described herein may further optionally comprise one or more solvents.
  • the solvents are contained in the liquid cleaning composition in an effective amount to provide one or more of the benefits described herein.
  • effective amount of the solvents refers to the quantity of this ingredient necessary to solubilize the soil or dirt removed from the surface preventing its redeposition on the cleaned surface.
  • Such effective amount is readily ascertained by one of ordinary skill in the art and is based on many factors, such as the particular solvents used, the application technique of the cleaning composition, the specific composition of the cleaning composition, and the like.
  • the solvents are contained in the liquid cleaning composition also exert the useful function of stabilizing the suspension of microparticles present therein.
  • concentration of the solvents in the liquid cleaning compositions described herein is preferably comprised between 0.1 and 5% by weight as a function of the application technique of the cleaning composition.
  • a liquid cleaning composition that is to be applied to the hard surface by pouring or by means of a sponge or cloth may comprise from 1.0 to 5% by weight, more preferably from 1.5 to 2.5% by weight, of one or more solvents
  • a liquid cleaning composition that is to be applied to the hard surface by spraying may comprise from 0.75 to 5% by weight, more preferably from 1.0 to 2.5% by weight, of one or more solvents.
  • Solvents for use herein include all those known to those skilled in the art. Suitable solvents for use herein include ethers and diethers having from 4 to 14 carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably from 8 to 10 carbon atoms, glycols, alkylated or alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C 1 -C 5 alcohols, linear C 1 -C 5 alcohols, C 8 -C 14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, C 6 -C 16 glycol ethers, and mixtures thereof.
  • Preferred solvents among the above-identified ones are selected from dodecaneglycol, propanediol, methoxy octadecanol, ethoxyethoxyethanol, benzoxyethanol, benzoxypropanol, benzyl alcohol, 2-ethylbutanol, 2-methylbutanol, 1- methylpropoxyethanol, 2-methyl butoxyethanol, butoxy propoxy propanol (n-BPP), butoxyethanol, butoxypropanol, ethoxyethanol, methanol, ethanol, propanol, butyl diglycol ether (BDGE), butyltriglycol ether, ter-amilic alcohol, or mixtures thereof.
  • pH adjusting agents In the embodiment of the present invention the liquid cleaning compositions are preferably formulated at basic pH range, typically from 10 to 12.
  • this basic pH allows to achieve two beneficial technical effects: enhance the degreasing action of the liquid cleaning compositions thereby enhancing the cleaning efficacy of the same and stabilize the suspension of microparticles, especially if the latter are hydroxyapatite microparticles, thereby enhancing the stability of the liquid cleaning compositions.
  • the liquid cleaning compositions may further comprise an effective amount of a suitable compound or a combination of compounds adapted to regulate the pH of the composition to such range of values.
  • an effective amount of the pH adjusting agent refers to the quantity of this ingredient necessary to achieve the desired pH value of the liquid composition. Such effective amount is readily ascertained by one of ordinary skill in the art and is based on many factors, such as the particular pH adjusting agents used, the application technique of the cleaning composition, the specific composition of the cleaning composition, and the like.
  • the concentration of the pH adjusting agents in the liquid cleaning compositions described herein is preferably comprised between 2 and 5% by weight, more preferably between 2.5 and 3.5% by weight, as a function of the application technique of the cleaning composition.
  • pH adjusting agents for use herein include all those known to those skilled in the art.
  • Suitable pH adjusting agents for use herein include inorganic bases, such as sodium hydroxide, potassium hydroxide, phosphates, such as potassium diphosphates, carbonates, such as sodium carbonate, or any other compound or mixture of compounds known to those skilled in the art and suitable to achieve the desired pH value of the liquid composition.
  • inorganic bases such as sodium hydroxide, potassium hydroxide, phosphates, such as potassium diphosphates, carbonates, such as sodium carbonate, or any other compound or mixture of compounds known to those skilled in the art and suitable to achieve the desired pH value of the liquid composition.
  • compositions described herein may further optionally comprise one or more rheology regulators.
  • the rheology regulators are contained in the liquid cleaning composition in an effective amount to provide one or more of the benefits described herein.
  • rheology regulators refers to the quantity of this ingredient necessary to regulate the rheology characteristics of the liquid cleaning composition, such as for example viscosity and thixotropicity, as a function of the application techniques.
  • Such effective amount is readily ascertained by one of ordinary skill in the art and is based on many factors, such as the particular rheology regulators used, the application technique of the cleaning composition, the specific composition of the cleaning composition, and the like.
  • liquid cleaning compositions are preferably formulated at a viscosity comprised between 2000 and 30000 cps at 20 0 C, and more preferably, between 6000 and 10000 cps at 20 0 C as a function of the application technique of the cleaning composition.
  • the concentration of the rheology regulators in the liquid cleaning compositions described herein is preferably comprised between 0.1 and 2% by weight as a function of the application technique of the cleaning composition.
  • a liquid cleaning composition that is to be applied to the hard surface by pouring or by means of a sponge or cloth may comprise from 0.25 to 1.5% by weight, more preferably from 0.3 to 0.8% by weight, of one or more rheology regulators
  • a liquid cleaning composition that is to be applied to the hard surface by spraying may comprise from 0.1 to 3.0% by weight, more preferably from 0.25 to 1.5% by weight, of one or more rheology regulators.
  • Rheology regulators for use herein include all those known to those skilled in the art. Suitable rheology regulators for use herein include thickeners, adapted to adjust the viscosity of the composition, as well as thixotroping agents, adapted to impart suitable thixotropic properties to the composition.
  • Suitable thickening agents are those known in the art.
  • thickening agents include gum-type polymers (e.g. xanthan gum), polyvinyl alcohol and derivatives thereof, cellulose and derivatives thereof and polycarboxylate polymers.
  • the thickening agent comprises a polymeric sulfonic acid, gum-type polymer or a polycarboxylate polymer.
  • the gum-type polymer may be selected from the group consisting of polysaccharide hydrocolloids, xanthan gum, guar gum, succinoglucan gum, Cellulose, derivatives of any of the above, and mixtures thereof, hi a preferred aspect of the present invention the gum-type polymer is a xanthan gum or derivative thereof.
  • the polycarboxylate polymer can be a homo or copolymer of monomer units selected from acrylic acid, methacrylic acid, maleic acid, malic acid, maleic anhydride. Suitable polymers have molecular weight in the range of from 10,000 to 100,000,000 most preferably 1,000,000 to 10,000,000. Particularly preferred examples of these thickening agents are polymeric sulfonic acid, xanthan gum and cross-linked polycarboxylate polymers.
  • Suitable thixotroping agents are those known in the art. Examples of thixotroping agents include vinylpyrrolidone homopolymer or copolymers, xanthan gum, acrylic homo polymers or copolymers, or mixtures thereof.
  • Suitable vinylpyrrolidone homopolymers for use herein is an homopolymer of N- vinylpyrrolidone ("PVP") having an average molecular weight of from 1,000 to 100,000,000, preferably from 2,000 to 10,000,000, more preferably from 5,000 to 1,000,000, and most preferably from 50,000 to 500,000.
  • PVP N- vinylpyrrolidone
  • Suitable vinylpyrrolidone copolymers for use herein is an ammonium acryloyldimethylaurate/VP Copolymer. Perfumes
  • compositions described herein may further optionally comprise one or more perfumes.
  • the perfumes are contained in the liquid cleaning composition in an effective amount to provide the benefits disclosed herein.
  • "effective amount of the perfumes” refers to the quantity of this ingredient necessary to attain the aforementioned effect as a function of the application techniques. Such effective amount is readily ascertained by one of ordinary skill in the art and is based on many factors, such as the particular perfumes used, the application technique of the cleaning composition, the specific composition of the cleaning composition, and the like.
  • concentration of the perfumes in the liquid cleaning compositions described herein is preferably comprised between 0.01 and 5% by weight.
  • Suitable perfumes for use herein include materials which provide an olfactory aesthetic benefit and/or cover any "chemical" odor that the product may have.
  • the main function of a small fraction of the highly volatile, low boiling (having low boiling points), perfume components in these perfumes is to improve the fragrance odor of the product itself, rather than impacting on the subsequent odor of the surface being cleaned.
  • perfume components in these perfumes provide a fresh and clean impression to the surfaces, and it is desirable that these ingredients be deposited and present on the dry surface.
  • Perfume ingredients can be readily solubilized in the compositions, for instance by the surfactants.
  • the perfume ingredients and compositions suitable to be used herein are the conventional ones known in the art.
  • compositions described herein may further optionally comprise one or more minor ingredients selected among colorants, preservatives and disinfectants.
  • these minor ingredients are contained in the liquid cleaning composition in an effective amount to provide the benefits disclosed herein.
  • effective amount of the minor ingredients refers to the quantity of these ingredients necessary to attain the desired effect as a function of the application techniques.
  • Such effective amount is readily ascertained by one of ordinary skill in the art and is based on many factors, such as the particular ingredient used, the application technique of the cleaning composition, the specific composition of the cleaning composition, and the like.
  • the concentration of the minor ingredients in the liquid cleaning compositions described herein is preferably comprised between 0.01 and 2% by weight.
  • Suitable colorants are those known in the art. Examples of colorants include well known water soluble dyes and pigments both of natural and of synthetic origin.
  • Suitable preservatives are those known in the art.
  • preservatives are any compound that can be stably added to the composition that kills or at least inactivates microbes, for example bacteria and fungi.
  • Particularly preferred preservatives are 5- choloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one available from Rohm & Haas under the trade name KATHON® CG, imidazolidinylurea, C 1 -C 4 paraoxybenzoates in phenoxyethanol, chloroacetamide, sodium benzoate, 4,4- dimethyloxazolidine, l,2-benzisothiazolin-3-one available from Avecia under the trade name Proxel GXL, phenoxyethanol available from BASF under the trade name Protectol PP or gluteraldehyde available from BASF under the trade name Protectol GDA.
  • Suitable disinfectants are those known in the art.
  • disinfectants are any compound that can be stably added to the composition that kills or at least inactivates microbes, for example bacteria, thereby exerting sanitizing effect on the cleaned surface.
  • Particularly preferred disinfectants are quaternary ammonium salts such as benzalconium chloride and tertiary amines such as bis-(3-aminopropyl) dodecylamine.
  • one or more of the ingredients illustrated hereinabove may exert more than one function at the same time thereby advantageously reducing the number of total ingredients and the production costs.
  • liquid cleaning compositions may include xanthan gum which may act both as an anti-resoiling agent and as a thickener adjusting the viscosity characteristics of the composition.
  • surfactants may act both as cleaning agents and as suspending agents of the microparticles and/or of other ingredients such as the perfumes.
  • the liquid cleaning compositions described herein may be prepared using mixing procedures of the ingredients well known to those skilled in the art.
  • the present invention relates to a method of cleaning a surface of an article and of imparting hydrophilic properties to said surface comprising the steps of: applying to said surface a liquid cleaning composition as described above, and rinsing the composition applied to the surface.
  • the method of the invention allows to render the cleaned surface hydrophilic once the liquid cleaning composition described above is applied to the surface to be cleaned.
  • hydrophilic it is meant that the surface has a high affinity for water. Because of the affinity between water and the surface, water spreads out on the surface to maximize contact. The higher the hydrophilicity the greater the spread and the smaller the contact angle.
  • Hydrophilicity can be determined by measuring the contact angle between the surface and a droplet of water on the surface. Contact angle is measured according to procedures known in the art for measuring contact angle, for example using the apparatus commercially sold under the trade name DigiDrop, Model DS by GBX, Romans-sur- Isere, France and the software WINDR0P++ also commercially available from GBX.
  • the liquid cleaning composition applied to the surface is capable of modifying the cleaned surface to render it hydrophilic, providing a contact angle between water and the cleaned surface of less than 33°, more preferably the surface has a contact angle of less than 30°, still more preferably, less than 25°.
  • the liquid cleaning composition is preferably also capable of durably modifying the surface to render it hydrophilic, meaning with the term "durably" that the hydrophilic surface modification is maintained for at least one rinse, preferably at least three rinses.
  • the liquid cleaning composition may be applied to the surface of an article by pouring the composition over the surface, by applying the composition on the surface by means of a cloth or sponge or by spraying the composition on the surface.
  • the surface can then be left to dry naturally.
  • a particular benefit of the present composition is that the surface is cleaned and rinsed as described above and the surface then left to dry naturally without the formation of water spots or streaks.
  • the surface may be dried using a cloth or chamois.
  • the present invention relates to solid inorganic microparticles as described above.
  • the present invention relates to the use of solid inorganic microparticles as described above as low abrasive material in a cleaning composition.
  • the cleaning composition may be in form of liquid, gel, foam, particulate or tablet.
  • the present invention relates to the use of solid inorganic microparticles as described above for imparting hydrophilic properties to a substrate.
  • substrate is used to indicate any kind of hard surface as previously disclosed or any kind of soft and/or flexible surface, such as fabric, textiles, fibers, woven materials, non- woven materials, and carpets.
  • the substrate is a hard surface as illustrated above.
  • Fig. 1 shows an X-Ray diffraction pattern of one example of solid inorganic microparticles according to the invention
  • Fig. 2 shows an X-Ray diffraction pattern of one example of solid inorganic microparticles according to the prior art
  • Figs. 3 show a SEM image of one example of solid inorganic microparticles according to the invention
  • Figs. 4 show a SEM image of one example of solid inorganic microparticles according to the prior art
  • - Figs. 5 show a TEM image of the solid inorganic microparticles according to the invention shown in Fig. 3 which display the aggregate structure of nanoparticles;
  • Fig. 6 shows a thermogravimetric plot of one example of solid inorganic microparticles according to the invention
  • Fig. 7 shows a FTIR spectrum of one example of solid inorganic microparticles according to the invention
  • Fig. 8 shows an image of a drop placed on a hard surface and of the contact angle formed between the drop and the surface before applying the liquid cleaning composition according to the invention
  • Fig. 9 shows an image of a drop placed on a hard surface cleaned by means of a liquid cleaning composition according to the invention and of the contact angle formed between the drop and the cleaned surface;
  • Fig. 10 shows an image of a rinsed surface of mirrored stainless steel after application of a liquid cleaning composition according to the invention
  • Fig. 11 shows an image of a rinsed surface of mirrored stainless steel after application of a liquid cleaning composition according to the prior art.
  • percentages and parts are by weight unless otherwise indicated.
  • Liquid cleaning compositions in cream form adapted to be poured and applied to a surface to be cleaned by means of a cloth or sponge according to Examples 1-2 in Table 1 below were prepared.
  • compositions were prepared by first dissolving the bentonite and xanthan gum in deionized water (aqua) until complete solubilization and then adding under agitation potassium cocoate, terpene ethoxylated propoxylated, butoxyethanol, tetrapotassium pyrophosphate and sodium carbonate.
  • the low abrasive carbonate-substituted non-stoichiometric hydroxyapatite microparticles used in Examples 1-2 were prepared as follows.
  • an aqueous suspension comprising 356 g of Ca(OH) 2 and 94 g of Ca(CO 3 ) in 1100 g Of H 2 O was prepared in a conventional reaction vessel while agitating the ingredients with a mechanical stirrer.
  • the resulting suspension was brought to a temperature of 40° ⁇ 2 °C by means of an electrical resistance or by any other suitable heating element such as for example a thermostated jacket in which a heating fluid, such as oil or vapor, is circulated.
  • nanoparticles of a carbonate-substituted hydroxyapatite were formed by adding dropwise PO 4 3" ions to the aqueous suspension of the preceding step while simultaneously agitating the same.
  • 600 g of an acid solution constituted by a mixture 70/30 of H 3 PO 4 (75%)/H 2 O were added with a dripping speed of 22 g "min '1 (0,4 g "sec '1 ), while continuously stirring and maintaining constant the temperature of the reaction vessel.
  • a suspension of nanoparticles was obtained which was subsequently agitated over a period of time of 2h, after which a suspension having a total content of about 30-31% by weight of microparticles having a mean particle size of 2 ⁇ m, a surface area of 40 m 2 /g and a crystallinity degree CD of 30% was obtained.
  • the solid microparticles were separated from the liquid by filtering on a Millipore paper with a pore diameter of 45 ⁇ m and then were repeatedly washed with a diluted water solution OfCaCO 3 to remove any acid residues.
  • microparticles thus obtained which had the aspect of a white powder, were then characterized as follows. n X-rav diffraction fXRD)
  • X-ray powder patterns were collected using a Philips PW 1710 powder diffractometer equipped with a secondary graphite monochromator using Cu Ka radiation generated at 40 kV and 40 niA.
  • the instrument was configured with a 1° divergence and 0.2 mm receiving slits.
  • the samples were prepared using the front loading of standard aluminium sample holders which are 1 mm deep, 20 mm high and 15 mm wide. The 20 range was from 5° to 60° with a step size (2 ⁇ ) of 0.05° and a counting time (s) of 3.
  • Fig. 1 the XRD pattern of the microparticles, which allows to determine the crystallinity degree of the microparticles, is shown.
  • the line intensity is related to its intensity percentage (arbitrary units), considering the highest line equal to 100.
  • the crystallinity degree, was evaluated according to the aforementioned Erkmen method was of about 30%.
  • CM 100 The powdered samples were ultrasonically dispersed in ultrapure water and then a few droplets were dropped on holey-carbon foils supported on conventional copper microgrids.
  • the average aspect ration A/R was 10.
  • Thermal Analysis SDT Q 600 Heating was performed in nitrogen flow (100 ml/min) using an alumina sample holder at a rate of 10°C/min up to 1000 0 C. The weight of the samples was around 10 mg.
  • Fig. 6 reports the results of a thermogravimetric analysis of the microparticles showing the weight decreases relating to the decomposition of the inorganic phase.
  • Line a corresponds to percentage weight loss as a function of the treatment temperature and line b represents the derivative of the percentage weight loss respect to the temperature.
  • Line b shows a broad peak between 15O 0 C and 300 0 C due to the loss of the physically absorbed water (weight loss of 2.2 ⁇ 0.5%).
  • the peak between 800 0 C and 1000 0 C can be attributed to the dehydroxylation process (weight loss of 1.5 ⁇ 0.5%).
  • the peak broadness is partially due to the low crystallinity degree of the microparticles.
  • the specific surface area of the microparticles was evaluated by the Brunauer, Emmet,
  • the average surface area of the microparticles was of about 40 m 2 /g.
  • the amount of calcium and phosphorous in the samples of nanoparticles was obtained using and Inductively Coupled Plasma - Optical Emission Spectrometry (ICP- OES) technique.
  • ICP-OES Inductively Coupled Plasma - Optical Emission Spectrometry
  • the ICP-OES measurements were carried out with a Perkin Elmer Optima 4200 DV instrument. The samples had been previously dissolved in ultrapure nitric acid
  • microparticles exhibited a bulk Ca/P molar ratio of about 1.8.
  • FTIR Fourier Transform Infrared
  • the FTIR spectrum of the microparticles is shown in Fig. 7.
  • the spectrum shows the signals related to the groups PO 4 3" (1037 cm “1 ), HPO 4 2" (955 cm “1 ), OH ' (3444 cm “1 and 1630 cm “1 ), CO 3 2" (870 cm “1 ).
  • a comparison between the peak area at 870 cm “1 of the nanoparticles and the peak area at 870 cm “1 of a CaCO 3 reference standard allowed to evaluate a CO 3 2" amount of about 8% by weight based on the total weight of the nanoparticles.
  • the band at 870 cm “1 provides information about the apatite carbonation type.
  • the deconvolution profile of the carbonate peak at 870 cm “1 allows to deduce that the hydroxy apatite carbonation is predominantly of type B (A/B ratio of approximately 1).
  • the low abrasive carbonate-substituted non-stoichiometric hydroxyapatite microparticles used in Examples 3-4 were prepared as follows.
  • the resulting suspension was brought to a temperature of 40° ⁇ 2 °C by the same method of the preceding Example 5. Once the desired temperature was reached, nanoparticles of a carbonate-substituted hydroxyapatite were formed by adding dropwise PO 4 3' ions in the same way and in the same amounts as described in preceding Example 5.
  • microparticles were then separated from the aqueous suspension thus obtained according to the separation method described in the preceding Example 5.
  • the microparticles thus obtained were then characterized according to the procedures and methods described in Example 5.
  • the relevant characterization data of the nanoparticles are reported in the following Table 3.
  • Figs. 2 and 4 The XRD diffraction pattern and a SEM image of the microparticles used are shown in Figs. 2 and 4 respectively, from which it may visually appreciated the greater particle size and the greater crystallinity possessed by these microparticles.
  • the contact angle between the horizontal flat surface of the drop placed onto the untreated surface and the tangent to the drop itself was calculated utilizing the software WINDROP++ also commercially available from GBX, Romans-sur-Isere, France. A value of the contact angle of 33.3° was obtained.
  • Test 2 (invention). The same a glass slide was then cleaned with the liquid cleaning composition of Example 1 by pouring a small amount of the composition on a cloth, wiping the surface with a cloth, rinsing and letting the surface to dry naturally.
  • the liquid cleaning compositions of the invention advantageously allow not only to clean the surface, but also to impart to the cleaned surface characteristics of hydrophilicity which allow to reduce resoiling phenomena and water stagnation on the cleaned surface thereby enhancing the rinsability and "self-cleaning" properties and maintaining the gloss and luster characteristics of the cleaned surface.
  • the loss in gloss of this substrate was measured using 2 g of product using a cloth tool under 1.5 Kg load for 100 alternative wiping cycles on a to and fro head adding one drop of cleaning composition every 5 cycles. At the end of the wiping cycles, the surface was rinsed with tap water and dried by means of a cotton cloth in order to eliminate possible traces of the compositions.
  • the reflectance of the surface treated with the two compositions was then measured using the same colorimeter (mean value of three measurements). The higher the loss in terms of reflectance of the surface, the higher is the damage potential of the product.
  • the abrasion characteristics of the tested liquid cleaning compositions is presented in the following Table 4.
  • the loss in gloss of this substrate was measured using 3 g of product using a cloth tool for 200 circular wiping cycles carried out manually adding one drop of cleaning composition every 5 cycles. At the end of the wiping cycles, the surface was rinsed with tap water and dried by means of a cotton cloth in order to eliminate possible traces of the compositions.
  • the reflectance of the surface treated with the two compositions was then measured using the same apparatus (mean value of three measurements). The higher the loss in terms of reflectance of the surface, the higher is the damage potential of the product.
  • the abrasion characteristics of the tested liquid cleaning compositions is presented in the following Table 5.
  • the abrasion tests show that the liquid cleaning compositions of the invention have markedly lower abrasion characteristics with respect to the comparative cleaning compositions and achieve superior properties in terms of maintaining the surface integrity of the substrate.
  • Black enamelled surface A model black enamelled surface of metal with an initial reflectance of 4.405 (mean value of four measurements) as measured on the commercially available colorimeter mentioned above was chosen for this study.
  • the loss of shine of this substrate was measured using 2 g of product using an Erichsen apparatus model 494 (Erichsen GmbH, Hemer, Germany) under 1 Kg load for 5 alternative wiping cycles on a to and fro head. At the end of the wiping cycles, the surface was rinsed with tap water for 30" and dried by leaving the surface in vertical position in open air for three hours.
  • the reflectance of the surface treated with the two compositions was then measured using the same apparatus (mean value of three measurements). The higher the loss in terms of reflectance of the surface, the higher is the amount of product residues on the surface.
  • the reflectance values of the treated surfaces are presented in the following Table 6.
  • a model stainless steel surface with an initial reflectance of 63.7125 (mean value of four measurements) as measured on the commercially available colorimeter mentioned above was chosen for this study.
  • the loss of shine of this substrate was measured using 2 g of product using the Erichsen apparatus mentioned above under 1 Kg load for 5 alternative wiping cycles on a to and fro head.
  • the surface was rinsed with tap water for 30" and dried by leaving the surface in vertical position in open air for three hours.
  • the reflectance of the surface treated with the two compositions was then measured using the same colorimeter (mean value of three measurements). The higher the loss in terms of reflectance of the surface, the higher is the amount of product residues on the surface.
  • the reflectance values of the treated surfaces are presented in the following Table 7.
  • the product applied on the surface was then left to dry in open air for 30' at room temperature and the surface was then rinsed with tap water for 30" and dried by leaving the surface in vertical position in open air for three hours.

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Abstract

L'invention concerne une composition liquide de nettoyage pour surfaces dures qui comprend un excipient dont au moins une partie est aqueuse, au moins un tensio-actif, des micro-particules inorganiques solides qui ont une granulométrie comprise entre 0,5 et 5 μm, une aire de surface allant de 10 à 50 m2/g et un degré de cristallinité (CD) inférieur à 50%, le degré de cristallinité (CD) étant défini par CD = (X/Y) • 100, où Y = surface nette de pics diffractés + surface de fond, X = surface nette de pics diffractés du motif de diffraction des rayons X propre aux microparticules. La composition liquide de nettoyage selon l'invention permet de diminuer substantiellement l'action abrasive sur la surface à nettoyer et de faciliter les opérations de rinçage, tandis qu'elle a également une action de nettoyage satisfaisante. Un autre aspect de l'invention porte sur un procédé conçu pour nettoyer une surface d'un article et pour conférer des propriétés hydrophiles à la surface, ledit procédé consistant à appliquer sur la surface une composition liquide de nettoyage comme décrit ci-dessus et à rincer la composition appliquée sur la surface.
EP07848801A 2007-09-28 2007-09-28 Composition liquide de nettoyage et procédé de nettoyage d'une surface Withdrawn EP2205689A1 (fr)

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CN103725454A (zh) * 2012-10-11 2014-04-16 3M创新有限公司 清洁剂和该清洁剂用于清洁硬质制品的应用
FR3011005B1 (fr) * 2013-09-26 2016-08-19 Ge Energy Products France Snc Agents de nettoyage mineraux mis en oeuvre sous forme de suspensions
NO2883573T3 (fr) 2013-12-13 2018-03-24
ITPD20130357A1 (it) 2013-12-23 2015-06-24 Pirelli Tyre Spa Metodo e dispositivo per gestire elementi longiformi in un impianto di confezionamento di pneumatici
EP3177690B1 (fr) * 2014-08-05 2019-09-04 Unilever NV Composition de traitement de surface dure
CA2998356C (fr) 2015-09-17 2022-04-26 Ecolab Usa Inc. Procedes de fabrication de matieres solides a base de triamine
WO2017049076A1 (fr) 2015-09-17 2017-03-23 Ecolab Usa Inc. Solidification de triamine à l'aide de diacides
CA3053175C (fr) * 2017-02-24 2023-02-28 Illumina, Inc. Suspension epaisse de carbonate de calcium
KR102261151B1 (ko) * 2020-02-27 2021-06-07 비드오리진(주) 표면 돌기가 형성된 구형 무기 입자 및 그 제조 방법

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DK2029480T3 (en) * 2006-05-30 2017-08-14 Coswell Spa Biologically active nanoparticles of a carbonate-substituted hydroxyapatite, process for their preparation, and compositions comprising the same.

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CN110982645A (zh) * 2019-12-18 2020-04-10 苏州东方之宝生物药业有限公司 一种洗衣皂液的配方及其生产工艺

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