# Patent

## Title
Cleaning implement based on melamine-formaldehyde foam comprising hollow melamine-formaldehyde microspheres

## Abstract

The present invention relates to a cleaning implement that includes a melamine-formaldehyde foam and hollow microspheres. The hollow microspheres have a core that includes at least one benefit agent and a shell that includes at least one melamine-formaldehyde resin. Additionally the present invention encompasses a method for cleaning a hard surface with a cleaning implement according to the present invention.

## Background
TECHNICAL FIELD
The present invention relates to cleaning implement based on melamine-formaldehyde foams comprising hollow microspheres. The hollow microspheres having a shell that includes at least one melamine-formaldehyde resin.
BACKGROUND OF THE INVENTION
Recently, a novel application for such melamine-formaldehyde foams in the area of hard surface cleaning has been discovered. Indeed, cleaning implements of cut or molded pieces of such melamine-formaldehyde foam, and in particular melamine foam, have become popular to remove soils and/or stains from hard surfaces (i.e., cleaning of hard surfaces) such as tiles, walls, floors, sanitary fittings such as sinks, showers, shower curtains, wash basins, WCs, household appliances including, but not limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on. Indeed, melamine foam sponges are currently marketed under the tradename Mr. Clean Magic Eraser®.
It is has been observed that melamine-formaldehyde foam in particular shows good soil and/or stain removal performance when used to clean hard surfaces, on stains/soils such as marks on walls and furniture. Indeed, it has been observed that melamine foam in particular, when wetted with an appropriate solvent, such as tap water, removes soils and/or stains from a hard surface when said hard surface is brought into contacted with said wetted modified open-cell foam. By “bringing into contact” it is meant wiping, swiping, rubbing or the like. In order for the melamine foam in particular to optimally remove soils and/or stains from hard surfaces substantial amounts of an appropriate solvent, such as tap water, have to be used. Most commonly, tap water is used by the users of melamine foam when removing soils and/or stains from hard surfaces. When used with water or any other appropriate solvent, the melamine foam in particular comes off as small particles (meaning, the foam crumbles) when brought into contact with a hard surface. Indeed, a milky suspension of small modified melamine foam in particular particles in water is formed. However there has been the need for better soil and/or stain removal with better durability upon use.
It is therefore, an objective of the present invention to provide a cleaning implement, wherein said implement is capable of (improved) cleaning greasy soap scum soils and neat kitchen dirt (grease) from hard surfaces whilst providing a good surface safety profile and at the same time showing excellent durability upon use.
It has been now found that above objective can be met by use of cleaning implement that includes a melamine-formaldehyde foam and hollow microspheres. The hollow microspheres have a core that includes at least one benefit agent and a shell that includes at least one melamine-formaldehyde resin. Indeed, the objectives are met by cleaning implements according to present invention based on such melamine-formaldehyde foam, the method of cleaning hard surfaces with such a cleaning implement or the method of cleaning hard surfaces with the melamine-formaldehyde foams according to present invention.
The melamine-formaldehyde foams of the present invention have good mechanical foam properties and better fixation of the hollow microspheres in the foam particularly at high loadings, i.e., hollow microsphere contents and any associated benefit agent. Furthermore, the hollow microspheres can be incorporated in the foam in the course of foam production without additional process step.
The articles, processes and uses according to the present invention will now be described.
SUMMARY OF THE INVENTION
The present invention relates to a cleaning implement that includes a melamine-formaldehyde foam and hollow microspheres. The hollow microspheres have a core that includes at least one benefit agent and a shell that includes at least one melamine-formaldehyde resin.
The present invention further encompasses a method for cleaning a hard surface with a cleaning implement according to the present invention.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a cleaning implement 1.
FIG. 2 is a perspective view of a cleaning implement 1 comprising two layers.



DETAILED DESCRIPTION OF THE INVENTION
Cleaning Implement
The cleaning implement 1 herein is based on the melamine-formaldehyde foam comprising hollow microspheres 5, wherein the hollow microspheres 5 have a core that includes at least one benefit agent and a shell that includes at least one melamine-formaldehyde resin.
By a “cleaning implement” it is meant herein an article of manufacture of any suitable shape and/or size and/or volume suitable for cleaning, i.e., removing spots and/or stains from hard surfaces. In a highly preferred embodiment according to the present invention, the cleaning implement herein is in a shape and/or size and/or volume suitable for use by a consumer to clean hard surfaces therewith. Examples of cleaning implements are wipers, brushes, cleaning cloths or cleaning granules.
In a preferred embodiment, the cleaning implements herein are suitable for cleaning/cleansing inanimate surfaces selected from the group consisting of household hard surfaces; dish surfaces; surfaces like leather or synthetic leather; and automotive vehicles surfaces.
In a highly preferred embodiment, the cleaning implements herein are suitable to clean household hard surfaces.
By “household hard surface”, it is meant herein any kind of surface typically found in and around houses like kitchens, bathrooms, e.g., floors, walls, tiles, windows, cupboards, sinks, showers, shower plastified curtains, wash basins, WCs, fixtures and fittings and the like made of different materials like ceramic, vinyl, no-wax vinyl, linoleum, melamine, glass, Inox®, Formica®, any plastics, plastified wood, metal or any painted or varnished or sealed surface and the like. Household hard surfaces also include household appliances including, but not limited to refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on. Such hard surfaces may be found both in private households as well as in commercial, institutional and industrial environments.
Suitable shapes of the cleaning implements 1, such as a wiper, herein may be selected from the group consisting of: cube shape, rectangular shape, pyramid shape, cylindrical shape, cone shape, pencil eraser shape, cuboid shape, tetrahedron shape; sphere shape; globular shape; and ellipsoid shape. Preferably, said cleaning implement has a shape selected from the group consisting of: cube shape, rectangular shape, pencil eraser shape, and cuboid shape.
Suitable volumes of the cleaning implements herein may be from 1 cm3 to 10,000 cm3, preferably from 10 cm3 to 1,000 cm3, more preferably from 150 cm3 to 250 cm3.
In a highly preferred embodiment herein, the cleaning implement 1 herein has a cuboid shape defined by three groups of parallel and equal length sides, referred to as a, b and c, wherein a ranges from 2 cm to 20 cm, preferably 4 cm to 8 cm, b ranges from 2 cm to 20 cm preferably 8 cm to 15 cm, and c ranges from 1.5 cm to 5 cm, preferably 2 cm to 4 cm.
In a preferred embodiment according to present invention, the thickness of said melamine-formaldehyde foam comprising hollow microspheres foam 2 layer is from 5 mm to 100 mm, preferably from 7 mm to 50 mm, more preferably 10 mm to 50 mm even more preferably from 15 mm to 50 mm, still more preferably from 20 mm to 40 mm.
The cleaning implement 1 of a first embodiment of the present invention as shown in FIG. 1 comprises a single layer 2 of melamine-formaldehyde foam comprising hollow microspheres 5.
In a preferred embodiment according to the present invention the cleaning implements herein may comprise additional layers of material. Preferably, in the cleaning implement herein said melamine-formaldehyde foam 2 comprising hollow microspheres 5 forms a first layer and said cleaning implement additionally comprises a second layer of material. Even more preferably, said second layer of material is a second foam layer 3 made of a second foam material as discussed herein below. Such a cleaning implement according to this preferred embodiment is shown in FIG. 2.
The layers of melamine-formaldehyde foam 2 comprising hollow microspheres 5 and second foam 3 may be arranged in said cleaning implement in any way suitable. In a preferred embodiment according to present invention the layers of melamine-formaldehyde foam 2 comprising hollow microspheres 5 and second foam 3 are arranged parallel to at least one side, preferably two opposite sides, of the cleaning implement. However, the cleaning implement may also have an irregular shape. Indeed, the thickness of the layers may be constant or vary throughout the cleaning implement. The separation line 4 between the two layers may form a straight line or may form a bend or be completely irregular. In addition, the separation plane of the layers may be in the center of cleaning implement, dividing the implement in two equal parts, or may be in the upper or lower part of the implement. In addition, the cleaning implement may be in the shape of a sphere or a globule or an ellipsoid with the separation plane of the layers forming a spherical segment or one of the layers, preferably the layer of a second foam here, forming a sphere in a sphere (similar to the layers of an onion).
In this highly preferred embodiment of the present invention, wherein the cleaning implement 1 herein has a cuboid shape, the line indicating the separation 4 of the two layers (or the surface areas where the two layers are joined together) of the implement is preferably substantially parallel (preferably parallel) to the side of the cuboid shaped implement having the largest surface area (as shown in FIG. 2).
In another highly preferred embodiment herein the cleaning implement herein is in the shape of a pencil eraser. By “shape of a pencil eraser” it is meant herein a voluminous body having six walls, wherein three pairs of parallel and equally shaped and sized walls exist and wherein one pair of walls are in the shape of a parallelogram and the remaining two pairs of walls are of rectangular shape. In this preferred embodiment, wherein the cleaning implement herein has the shape of a pencil eraser, the line indicating the separation of the two layers (or the surface areas where the two layers are joined together) of the implement is preferably substantially parallel (preferably parallel) to the side of implement in the shape of a pencil eraser having the largest surface area.
In order to obtain suitable cleaning implements according to a preferred embodiment of the present invention, the melamine-formaldehyde foam layer 2 comprising hollow microspheres 5 and the second layer of second foam 3 have to be attached to each other. This attachment can be achieved by any attachment means suitable for joining the two layers. The attachment may be either a permanent attachment (wherein the two layers cannot be separated without inflicting substantial damage to the layers) or temporary attachment (wherein the two layers may be separated without inflicting substantial damage to the layers). Suitable attachment means providing a permanent attachment are selected from the group consisting of: foam flame laminating the two layers together; use of a permanent adhesive; sewing the two layers together; and needle-punching the two layers together; and combinations thereof. Suitable attachment means providing a temporary attachment are selected from the group consisting of: a weak adhesive; Velcro; and a water-based, water-soluble coating or adhesive; and combinations thereof.
In a preferred embodiment here, the attachment of layers herein is a permanent attachment.
Foam flame lamination is a continuous process that can adhere foams and additional materials, if any, to one or both sides of foam in a single pass. The process of flame lamination involves the passing of first foam (either the melamine-formaldehyde foam comprising hollow microspheres herein or the second foam herein) over an open flame, which creates a thin layer of molten foam/polymer. Second foam (either the second foam herein or the melamine-formaldehyde foam comprising hollow microspheres herein, depending on the first step) is pressed against the first foam while it is still in the molten state. Foams and additional material, if any, can be adhered to one or both sides of the foam in a single pass. Furthermore, additional passes are optional. The strength of the bond depends upon the foams and additional material, if any, selected and the processing conditions (i.e., gas type, flame height and spread, foam burn-off and nip pressure).
The cleaning implement according to the present invention may contain more than two layers, wherein said additional layers, if, any, may be of the same or similar materials as the melamine-formaldehyde foam comprising hollow microspheres or said second foam, or may be made of another material having similar properties as said second foam or different properties therefore. Indeed, the cleaning implement herein may be in a so-called sandwich configuration, wherein three layers are present. In a preferred embodiment, wherein the cleaning implement herein is in a sandwich configuration, the middle layer may be said second foam and at least one of the two outer layers is melamine-formaldehyde foam comprising hollow microspheres with the second outer layer being either melamine-formaldehyde foam comprising hollow microspheres or another material providing other feature, such as abrasiveness or increased rigidity. In a highly preferred embodiment according to the present invention the cleaning implement herein comprises two outer layers of said melamine-formaldehyde foam comprising hollow microspheres and an inner layer, preferably of a second foam material, as discussed herein below.
The layers of the cleaning implement according to the present invention may cover each other either partially or fully. By a “partial coverage” it is meant that at least one of the layers overlaps the other layer (or other layers, if any) and is not fully covered by said other layer (or other layers, if any). By a “full coverage” it is meant that the layers of the cleaning implement do fully cover each other and that none of the layers substantially overlap the other layer (or other layers, if any).
The ratio of said melamine-formaldehyde foam comprising hollow microspheres to said second foam in the cleaning implement according to the present invention is preferably from 20:1 to 1:20 by volume, more preferable from 10:1 to 1:10 by volume, even more preferably 5:1 to 1:1, still more preferably 5:1 to 2:1, and most preferably from 4:1 to 3:1 by volume.
In order to obtain suitable cleaning implements according to the present invention, the melamine-formaldehyde foam comprising hollow microspheres—and second foam-raw materials may have to be modified in shape and/or size. This modification can be done by any means known to those skilled in the art. Suitable means of modifying the shape and/or size of melamine foam- and second foam-raw materials may be selected from the group consisting of: cutting, breaking, and tearing, and combinations thereof.
Melamine-formaldehyde foams as such and their production and also hollow microspheres as such and their production are known to a person skilled in the art and described in the literature.
The melamine-formaldehyde foams of the present invention comprise hollow microspheres and these hollow microspheres in accordance with an essential requirement have a median particle diameter (D50, volume averaged, Malvern, Fraunhofer diffraction) in the range from 100 μm to 1000 μm, preferably in the range from 200 μm to 800 μm and more preferably in the range from 300 μm to 700 μm.
The hollow microsphere content is generally in the range from 0.1% to 60% by weight, preferably in the range from 5% to 50% by weight and more preferably in the range from 10% to 30% by weight, the weight all being based on the total weight of hollow microspheres and melamine-formaldehyde precondensate used for foam production.
The melamine-formaldehyde foams have an open-cell foam scaffold comprising a multiplicity of interconnected, three-dimensionally branched struts (the points of connection between the struts being known as “nodes” or “nodal points”). The hollow microsphere median particle diameter which is essential to the present invention and the herein below described production process for the melamine-formaldehyde foams of the present invention cause the hollow microspheres to become preferentially embedded into the open-cell pores of the foam structure. Incorporation into the struts or nodes of the foam scaffold does not take place to any significant extent, if at all. As a result, good fixation of the hollow microspheres in the foam is achieved even at high hollow microsphere contents without the mechanical properties of the foam becoming excessively affected.
The melamine-formaldehyde foams of the present invention comprising hollow microspheres are preferably obtainable by the consecutive process steps a) and b):

    
    
        a) heating to foam up and crosslink a mixture comprising a melamine-formaldehyde precondensate having a molar ratio of melamine:formaldehyde in the range of typically from 1:1.3 to 1:5 and preferably from 1:2.5 to 1:3.5, the hollow microspheres, a curative, a dispersant and a blowing agent, and
        b) drying the foam obtained in process step a),

wherein these process steps and also the melamine-formaldehyde precondensates, curatives, dispersants and blowing agents useful in step a) are known in principle to a person skilled in the art and are described in the literature.

    
    


The melamine-formaldehyde precondensate in addition to melamine and formaldehyde may comprise up to 50% by weight and preferably up to 20% by weight (all based on the weight of cocondensed melamine) of other thermoset-formers and up to 50% by weight and preferably up to 20% by weight (all based on the weight of cocondensed formaldehyde) of other aldehydes in cocondensed form. Useful thermoset-formers include for example: alkyl- and aryl-alkyl-substituted melamine, urea, urethanes, carboxamides, dicyandiamide, guanidine, sulfurylamide, sulfonamides, aliphatic amines, glycols, phenol and its derivatives. Examples of useful other aldehydes are acetaldehyde, trimethylolacetaldehyde, acrolein, benzaldehyde, furfurol, glyoxal, gluteraldehyde, phthalaldehyde and terephthalaldehyde. Particular preference is given to an unmodified melamine-formaldehyde precondensate, i.e., a melamine-formaldehyde precondensate devoid of any other thermoset-formers or other aldehydes. Further details concerning melamine-formaldehyde condensation products may be found in Houben-Weyl, Methoden der organischen Chemie, volume 14/2, 1963, pages 319 to 402.
Commercially available melamine-formaldehyde precondensates are useful for a multiplicity of fields of use, for example for further processing into glues. Melamine-formaldehyde precondensates comprising sulfite groups are advantageous for use in some of these fields. Such sulfite group-containing melamine-formaldehyde precondensates are obtainable for example as described in EP-B 37470 whereby from 1% to 20% by weight of sodium disulfite is incorporated in the course of the condensation of melamine and formaldehyde to obtain cocondensed sulfite groups.
For the processes of the present invention, however, it is advantageous that step a) utilizes a precondensate which is free of the sulfite groups.
Emulsification of the blowing agent and stabilization of the foam in step a) requires the addition of a dispersant, e.g., an emulsifier or emulsifier mixture. Useful emulsifiers include anionic, cationic and nonionic surfactants and also mixtures thereof.
Suitable anionic surfactants are diphenylene oxide sulfonates, alkane- and alkylbenzenesulfonates, alkylnaphthalenesulfonates, olefinsulfonates, alkyl ether sulfonates, fatty alcohol sulfates, ether sulfates, alpha-sulfo fatty acid esters, acylaminoalkanesulfonates, acyl isethionates, alkyl ether carboxylates, N-acylsarcosinates, alkyl and alkyl ether phosphates. Useful nonionic surfactants include alkylphenol polyglycol ethers, fatty alcohol polyglycol ethers, fatty acid polyglycol ethers, fatty acid alkanolamides, EO-PO block copolymers, amine oxides, glycerol fatty acid esters, sorbitan esters and alkylpolyglucosides. Useful cationic emulsifiers include alkyltriammonium salts, alkylbenzyldimethylammonium salts and alkylpyridinium salts. The emulsifiers are preferably added in amounts of 0.2% to 5% by weight, based on the melamine-formaldehyde precondensate.
For the melamine-formaldehyde precondensate, which is preferably used in the form of an aqueous solution or dispersion, to produce foam in step a), it has to comprise a blowing agent, the amount depending on the desired density of the foam. In principle, the process of the present invention can utilize both physical blowing agents and chemical blowing agents. Useful physical blowing agents include, for example, hydrocarbons, halogenated and more particularly fluorinated hydrocarbons, alcohols, ethers, ketones and esters in liquid form or air and CO2 as gases. Useful chemical blowing agents include, for example, isocyanates mixed with water, in which case CO2 is released as an effective blowing agent, moreover carbonates and bicarbonates mixed with acids, which likewise produce CO2, and also azo compounds, such as azodicarbonamide. In one preferred embodiment of the present invention, the aqueous solution or dispersion of the melamine-formaldehyde precondensate is admixed with between 1% and 40% by weight, based on the melamine-formaldehyde precondensate, of a physical blowing agent having a boiling point of between 0 and 80° C.; in the case of pentane, the amount used is preferably in the range from 5% to 15% by weight.
Curatives used in step a) comprise acidic compounds catalyzing the continued condensation of the melamine-formaldehyde precondensate. The amounts are between 0.01% and 20% by weight and preferably between 0.05% and 5% by weight, based on the melamine-formaldehyde precondensate. Organic and inorganic acids can be used, examples being hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, oxalic acid, toluenesulfonic acids, amidosulfonic acids and also acid anhydrides.
The aqueous solution or dispersion of the melamine-formaldehyde precondensate used in step a) is preferably free of further added substances. However, it can be beneficial for some purposes to add up to 20% by weight, and preferably less than 10% by weight, based on the melamine-formaldehyde precondensate, of customary added substances, such as dyes, flame retardants, UV stabilizers, agents to lower combustion gas toxicity or to promote carbonization. Since the foams are generally open celled and capable of imbibing water, some applications make it necessary to add hydrophobicizers in amounts of 0.2% to 5% by weight. Useful hydrophobicizers include for example silicones, paraffins, silicone surfactants, fluorosurfactants, hydrophobic hydrocarbonaceous surfactants, silicone emulsions and fluorocarbon emulsions.
The concentration of the melamine-formaldehyde precondensate in the mixture of precondensate and solvent/dispersant, more particularly water, can vary within wide limits between 55% and 85% by weight and preferably between 63% and 80% by weight, all based on the total weight of melamine-formaldehyde precondensate and solvent/dispersant. The preferred viscosity of the mixture of precondensate and solvent/dispersant is between 1 and 3000 dPa·s and preferably between 5 and 2000 dPa·s.
The hollow microspheres and further mixture components are mixed with the aqueous solution or dispersion of the melamine-formaldehyde precondensate to form a homogeneous mixture, with the blowing agent being forced in under pressure if necessary. However, it is also possible to start with a solid, for example spray-dried, melamine-formaldehyde precondensate and to subsequently mix it with a dispersion of the hollow microspheres and/or with an aqueous solution of the emulsifier, with the curative and also with the blowing agent. After mixing, the heated resin mixture with the dispersed blowing agent is discharged through a die and foams up thereafter.
Foaming of the blowing agent-containing solution or dispersion upon emergence from the die is augmented—as described in EP-B 17671—by means of hot air or high frequency irradiation. Preferably, the energy can be input by electromagnetic radiation, for example by high frequency irradiation with 5 to 400 kW, preferably 5 to 200 kW, particularly preferably 9 to 120 kW per one kilogram of the mixture used in a frequency range of 0.2 to 100 GHz, preferably 0.5 to 10 GHz. Magnetrons are a suitable source of radiation for dielectric radiation, with one or more magnetrons being able to be irradiated at the same time.
The mixture to be foamed is irradiated immediately on emerging from the foaming die. The blowing agent evaporates the resin mixture foams up and at the same time cures through.
The foams produced are finally dried to remove water and blowing agent remaining in the foam.
In a further embodiment of the process according to the present invention, process step b) may be followed by a process step c) in which the dried foam is press molded to make it elastic.
Process step c) is known in principle to a person skilled in the art and is described in the literature, for example in EP-A 1 505 105 and EP-B 37470.
The foam blocks or sheets obtained can optionally be thermocompressed in a further process step. Thermocompression as such is known to a person skilled in the art and described for example in WO 2007/031944, EP-A 451 535, EP-A 111 860 and U.S. Pat. No. 6,608,118. Thermocompression can often provide better fixation of the hollow microspheres in the foam structure.
Preferred hollow microspheres for producing the melamine-formaldehyde foams of the present invention have walls comprising at least one melamine-formaldehyde resin. In one preferred embodiment of the present invention the melamine-formaldehyde foams walls are melamine-formaldehyde resin.
The microspheres that are used according to the present invention may be prepared according to any process that is known to the skilled artisan.
A preferred process for the preparation of the microspheres according to the present invention comprises at least the following steps:

    (1) Providing a solution comprising at least one melamine-formaldehyde precondensate and optionally further additives, and
    (2) Coating of the benefit agent with the solution of step (1) to obtain microspheres having a core comprising at least one benefit agent and a shell comprising at least one melamine-formaldehyde resin.


The melamine-formaldehyde precondensate that is used for the preparation of the shell of microspheres according to the present invention has in general a molar ratio of formaldehyde to melamine of more than 2, preferably 2.5 to 3.5.
The melamine-formaldehyde precondensate that is used to prepare the shell of the microspheres according to the present invention in addition to melamine and formaldehyde may comprise 0.1 to 50% by weight and preferably 0.5 to 20% by weight (all based on the weight of the melamine-formaldehyde precondensate) of other thermoset-formers and 0.1 to 50% by weight and preferably 0.5 to 20% by weight (all based on the weight of the melamine-formaldehyde precondensate) of other aldehydes in cocondensed form.
Examples of useful other thermoset-formers are alkyl- and aryl-alkyl-substituted melamine, urea, urethanes, carboxamides, dicyandiamide, guanidine, sulfurylamide, sulfonamides, aliphatic amines, glycols, phenol and its derivatives.
Examples of useful other aldehydes are acetaldehyde, trimethylolacetaldehyde, acrolein, benzaldehyde, furfurol, glyoxal, glutaraldehyde, phthalaldehyde and terephthalaldehyde.
Regarding the shell of the microspheres, particular preference is given to an unmodified melamine-formaldehyde precondensate, i.e., a melamine-formaldehyde precondensate devoid of any other thermoset-formers or other aldehydes. Further details concerning melamine-formaldehyde condensation products may be found in Houben-Weyl, Methoden der organischen Chemie, volume 14/2, 1963, pages 319 to 402.
According to step (1) of the process for the preparation of microspheres according to the present invention, the melamine-formaldehyde precondensate is provided in solution, in particular in an aqueous solution, more preferably at about 30 to 50% by weight, most preferably about 35 to 45% by weight, which is treated with a curing agent afterwards. Preferably, the solution further comprises further additives; in particular a curing agent is conducted preferably at room temperature. Higher temperatures reduce the durability of the melamine-formaldehyde resin solution due to polymerization of the melamine-formaldehyde resin.
According to a preferred embodiment of the present invention the reaction of the melamine-formaldehyde precondensate to obtain a corresponding melamine-formaldehyde resin occurs essentially during the coating of the core material.
The core of the microspheres that are used according to the present invention comprises at least one benefit agent. Benefit agents are for example a detergent compositions, hence are capable of improving the cleaning properties of the cleaning implement 1 based on melamine-formaldehyde foams; or else surfactants; dyes, for example inks and pigments; scents; acids; bases; oils; salts; bleach; antimicrobial agents; fragrances; solvents; biocides, which are released by destruction of the hollow microsphere walls to develop their benefit for the particular desired use and mixtures thereof. Further usable benefit agents known per se to a person skilled in the art are for example hydrophobicizing agents; agents influencing haptics or the soil release behavior (to obtain the so-called lotus effect for example); formaldehyde scavengers; abrasives such as inorganic nanoparticles for example (see WO 2009/021963 for example) or synthetic abrasives; or catalysts and mixtures thereof.
The ratio by weight of core to shell of the microspheres that are used according to the present invention, the so called core/shell-ratio, is in general 50:50 to 95:5, preferably 60:40 to 95:5, more preferably 65:35 to 90:10.
For applying the shell onto the core of the microspheres that are used according to the present invention, according to step b), numerous processes are known to the skilled artisan. The skilled artisan may differentiate between methods in which particles are moved mechanically or fluidized bed processes, see for example H. Uhlemann, L. Mörl, Fluidized Bed Spray Granulation, Berlin 2000, pages 466 ff.
A preferred method for the preparation of the microspheres in step (2) of the process according to the present invention is a fluidized bed spray granulation. The principle of said method is based on flowing of gas through a powdery bed of solids until fluidized bed is obtained after overcoming gravity by the single particles, whereas this bed acts analogously to a fluid. These fluidized particles are preferably treated with the melamine-formaldehyde precondensate or resin comprising solution as mentioned above, preferably via spray nozzles. After coating of the melamine-formaldehyde precondensate or resin onto the cores, the obtained particles agglomerate. Spraying can be conducted according to, for example, H. Uhlemann, L. Mörl, Fluidized Bed Spray Granulation, Berlin 2000, pages 69 to 125.
If a core material is used as a powder, this powder is agglomerated using aqueous melamine-formaldehyde resin mixtures by fluidized bed methods (granulation), before these agglomerates are coated with aqueous melamine-formaldehyde resins (coating). If the core material is used in the form of larger granulates, coating with the shell material can be conducted by spray granulation immediately.
Within the process for coating according to the present invention, powders and/or granulates of the core material are used in generally known apparatuses, for example fluidized bed spray granulation apparatuses of Glatt. Particle sizes of 30 to 300 μm, preferably 50 to 200 μm for granulation and 200 to 700 μm, preferably 250 to 500 μm, for coating, are preferred.
Within the process for the preparation of the core-shell microspheres according to the present invention, the benefit agents are provided and then a spray granulation/coating using fluidized bed technology using melamine-formaldehyde resins, which are preferably in solution, particularly preferred in aqueous solution, preferred about 30 to 50% by weight, more preferred about 35 to 45% by weight, is conducted. Doing so, the benefit agents are fluidized using a hot air stream at a temperature of 50 to 130° C. and are sprayed with a melamine-formaldehyde resin solution, which dries and coats the benefit agents, or these benefit agents are first granulated and are coated afterwards.
In general the melamine-formaldehyde foams according to the present invention have a density of 3 to 100 g/l, preferably 5 to 50 g/l, more preferably 5 to 25 g/L.
According to the present invention the melamine-formaldehyde foams comprising microspheres are obtainable batch wise or preferably continuously as sheets or webs generally in any desired thickness, advantageously in layered thicknesses ranging from 0.1 to 500 cm, preferably from 0.5 to 200 cm, more preferably from 1 to 100 cm, more particularly from 3 to 80 cm and most preferably from 5 to 50 cm. Moldings comprising melamine-formaldehyde foams according to the present invention are obtainable in a continuous manner or preferably in a batch wise manner.
The melamine-formaldehyde foams in the form of webs, sheets, moldings or some other form can be laminated or endowed with surface layers by generally customary methods on one, two, more or all sides, for example with paper, paper board, glass overlay mat, wood, plaster board, metal sheet or metal foil, plastic or self-supporting plastics foam/sheet which may optionally also be foamed. The surface layers can be applied in the course of foaming or subsequently. In the case of subsequent application, it is advantageous to use an adhesion promoter.
Because the melamine-formaldehyde foams of the present invention comprise microspheres at least partially filled with benefit agents to be released, this release can be affected at any desired time by applying a suitable mechanical or thermal action to the foam. For example, the above-described benefit agents, for example detergent compositions, surfactants, inks, scents or biocides, acids, bases, bleaches, water, solvents, waxes, pigments, dyes, fragrances, oils, salts and mixtures thereof, can be released through thermal (e.g., hot air, various forms of radiation, for example infrared or microwave radiation) or mechanical destruction (pressing, rolling, ultrasound, etc) of the hollow microsphere walls. This releases the contents of the hollow microspheres uniformly or almost uniformly and causes wetting of the surface structure (struts and nodes) even in the interior of the open-cell melamine-formaldehyde foam structure. The processes for thermal or mechanical destruction of microcapsule walls are known in principle to a person skilled in the art, and are described in the literature. For example, the foam can be compression molded to destroy the microcapsule walls, as described in EP-A 0451535 for example, by leading the foam through a defined gap between two contra-rotating rolls in parallel alignment. In addition to leading the foam through a gap between two co-rotating rolls, it is also possible for the foam to be transported on a conveyor belt and for a roll—turning at the same circumferential speed as the speed of movement of the foam—to press down on the foam. The pressure on the foam can further be exerted by placing the foam for example into a press in which a ram presses down on the foam. In this case, however, continuous pressing is not possible.
The cleaning implement based on melamine-formaldehyde foams comprising hollow microspheres are used for cleaning hard surfaces.
The melamine-formaldehyde foams of the present invention exhibit more particularly even at high loadings, i.e., hollow microsphere contents and optionally associated benefit agent contents, good mechanical properties for the foam and better fixing of the hollow microspheres in the foam. Furthermore, the hollow microspheres can be incorporated in the foam in the course of foam production without additional process step.
Second Layer
In a highly preferred embodiment, as discussed above, the cleaning implement 1 herein may comprises (at least) one additional layer 3. The second layer 3 may comprise a foam, a film, a synthetic nonwoven, a cellulosic sheet, sustainable sheets and combinations thereof. Plural layers may comprise one or more of these materials and laminates thereof, including the same and/or different materials.
If a foam is selected for one or more of the layers, suitable foams are selected from the group consisting of polyurethane foams; polypropylene foams; polyethylene foams; cellulose foam sponges; naturally occurring sponges; open-cell polyester foams; and cross-linked polyethylene foams; and combinations thereof.
If a film is selected for one or more of the layers, the layer may comprise a polyolefinic sheet, as is known in the art. The sheet may comprise polyethylene terephthalate, polypropylene, polyethylene naphthalate, low-density polyethylene, high-density polyethylene, etc. as are known in the art. The film layer may be smooth or textured, as described in commonly assigned U.S. Pat. No. 4,846,821. A film layer may have a basis weight of about 15 to about 60 gsm and/or a thickness ranging from about 0.01 to about 3 mm.
A synthetic nonwoven may be carded, thermally bonded, spunbonded, hydroentagled, etc., as are known in the art. The nonwoven may be of constant or variable basis weight and/or density. The nonwoven may be textured and/or comprise discrete apertures, as disclosed in commonly assigned U.S. Pat. No. 6,936,330. A nonwoven layer may have a basis weight of about 15 to about 120 gsm and/or a thickness ranging from about 0.01 to 3 mm.
A cellulosic sheet may be wet laid and comprise permanent and/or temporary wet strength resins, as are known in the art. The cellulosic sheet may comprise kraft grade or tissue grade paper. The cellulosic sheet may be of constant or variable basis weight and/or density, as disclosed in commonly assigned U.S. Pat. No. 5,277,761 or commonly assigned U.S. Pat. No. 4,637,859. A tissue grade cellulosic sheet may have a basis weight of about 15 to about 45 gsm and/or a thickness ranging from about 0.01 to about 3 mm.
If desired, the one or more of the layers may be made of sustainable materials and/or combinations and blends of sustainable and other materials, including polymers derived from Biorenewable materials. Sustainable materials may include polylactic acid (PLA), polyglycolic acid (PGA), polybutylene succinate (PBS), an aliphatic-aromatic copolyester optionally with high terephthalic acid content, an aromatic copolyester optionally with high terephthalic acid content, polyhydroxyalkanoate (PHA), thermoplastic starch (TPS) and mixtures thereof. Suitable materials are disclosed in commonly assigned U.S. Pat. No. 8,083,064.
If desired, the layer may comprise a laminate of two or more materials. For example, the second layer 3 may comprise a layer of polyolefinic film. This layer may be reinforced with a woven layer or yarn layer attached thereto. A woven layer may comprise a loose weave, providing loop material suitable for attachment to a hook surface. A yarn layer may comprise plural parallel or randomly laid yards, also providing loop material suitable for attachment to a hook surface. The woven and/or yarn layers may be thermally bonded to the second layer 3.
In another embodiment the second layer 3 may comprise any sheet which is flexible, impermeable to fluid and, in one embodiment, hydrophobic. As used herein, the term “impermeable” means that the material resists and, in some embodiments, prevents diffusion of moisture therethrough.
The thickness of said second layer 3, if any, is preferably up to 30 mm, preferably from 0.5 mm to 20 mm, more preferably from 1 mm to 15 mm, even more preferably from 2 mm to 10 mm, and most preferably from 4 mm to 8 mm. Furthermore, in the preferred embodiment herein, wherein the cleaning implement comprises a second layer 3 the thickness of said layer is preferably from 7 mm to 100 mm, more preferably from 15 mm to 25 mm.
In a preferred embodiment herein, the total volume of said second layer 3 in the cleaning implement herein is preferably from 10 cm3 to 100 cm3, more preferably from 20 cm3 to 70 cm3, even more preferably from 30 cm3 to 60 cm3, and most preferably from 40 cm3 to 50 cm3.
Active Agent
The cleaning implements herein may contain an active agent, other than the benefit agent discussed above, located anywhere as known in the art. In one embodiment, the active agent is impregnated in the melamine-formaldehyde foam layer 2 comprising the hollow microspheres 5. In another embodiment, the active agent is embedded in the second foam layer 3. In yet another embodiment, the active agent is impregnated in the attachment means, as discussed above, that attaches the foam layer 2 to the foam layer 3. It will be understood, however, that in still further embodiment that the active agent can be located in any or all of the foam layer 2, foam layer 3 or attachment means, as known in the art. Suitable active agents are selected among a surfactant, a bleaching agent, a limescale reducing agent, a biocide, a solvent and a mixture thereof. In one embodiment, the active agent may have an HLB greater than about 5, alternatively greater than about 8 to about 14, alternatively greater than about 12. In another embodiment, the active agent may be present in free form in an amount from about 5% to about 20%, or from about 10% to about 15% by weight of the active agent. An active agent in free form means that the active agent is supplied to the cleaning implement in its neat form whose release from the cleaning implement is not purposefully controlled, delayed, or sustained.
Surfactants that are suitable for the present invention can be nonionic, anionic, cationic, amphoteric and/or a zwitterionic surfactant. Suitable nonionic surfactants include alkoxylated fatty alcohol having the formula of RO(EO)e(PO)pH, where R is a hydrocarbon chain of from 2 to 24 carbon atoms, EO is ethylene oxide and PO is propylene oxide, e and p respectively representing the average degree of ethoxylation and propoxylation, are independently from 0 to 24, or R is a straight alkyl chain having from 6 to 22 carbon atoms, e is 5-12 and p is 0 (e.g. LutensolTM). Suitable cationic surfactants herein include derivatives of quaternary ammonium, phosphonium, imidazolium and sulfonium compounds. Preferred cationic surfactants herein are trimethyl quaternary ammonium compounds. Suitable amphoteric surfactants herein include amine oxides, betaine or ammonium sulfate or ammonium carboxylate, having the following formula R1R2R3NO, R1R2R3NR4SO4 or R1R2R3NR4CO2 wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched alkyl groups of from 1 to 30, or from 8 to 18 carbon atoms, except for R4 which preferably contain 3 saturated carbons. Preferred amine oxides herein are for instance natural blend C8-C10 amine oxides, and C12-C16 amine oxides, such as cetyl dimethyl amine oxide. Preferred betaine herein is cocamidopropyl betaine and lauramidopropyl betaine. Suitable anionic surfactants include alkyl diphenyl ether sulphonate and alkyl carboxylate. Other suitable anionic surfactants herein include water soluble salts or acids of the formula ROSO3M wherein R is preferably a C10-C24 hydrocarbyl, or C12-C18 alkyl or hydroxyalkyl, and M is H or a cation, such as sodium, potassium, lithium, or ammonium or substituted ammonium. Other suitable anionic surfactants include soap salts, C9-C20 linear alkylbenzenesulfonates, C8-C22 primary or secondary alkylsulfonates, sulfonated polycarboxylic acids, C8-C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates, sulfates of alkylpolysaccharides, alkyl polyethoxy carboxylates, such as those of the formula RO(CH2CH2O)kCH2COO−M+ wherein R is a C8-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable. Further examples are given in “Surface Active Agents and Detergents” (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Pat. No. 3,929,678.
Bleaching agents herein may be selected from a hydrogen peroxide source, a preformed peroxycarboxylic acid, a hypohalite bleach source, and a mixture thereof. Hydrogen peroxide sources herein include persulfate, dipersulphate, persulfuric acid, percarbonate, perborate, metal peroxide, perphosphate, persilicate, urea peroxyhydrate and a mixture thereof. Preformed peroxycarboxylic acids herein include those containing one, two or more peroxy groups, and can be aliphatic or aromatic. When the organic percarboxylic acid is aliphatic, the unsubstituted acid suitably has the linear formula: HO—O—C(O)—(CH2)n—Y, wherein Y is H, CH3, CH2Cl, COOH or C(O)OOH; n is an integer of 1-20. Branched analogs are also acceptable. When the organic percarboxylic acid is aromatic, the unsubstituted acid suitably has formula: HO—O—C(O)—C6H4—Y wherein Y is hydrogen, alkyl, alkyhalogen, halogen, —COOH or —C(O)OOH. Monoperoxycarboxylic acids useful as oxygen bleach herein are further illustrated by alkyl percarboxylic acids and aryl percarboxylic acids such as peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g., peroxy-α-naphthoic acid; aliphatic, substituted aliphatic and arylalkyl monoperoxy acids such as peroxylauric acid, peroxystearic acid, and N,N-phthaloylaminoperoxycaproic acid (PAP); and 6-octylamino-6-oxo-peroxyhexanoic acid. Peracids can be used in acid form or any suitable salt with a bleach-stable cation. Suitable hypohalite bleaching agents herein include those that form positive halide ions and/or hypohalite ions, and bleaching agents that are organic based sources of halides, such as chloroisocyanurates. Suitable hypohalite bleaching agents herein include alkali metal and alkaline earth metal hypochlorite, hypobromite, hypoiodite, chlorinated trisodium phosphate dodecahydrate, potassium and sodium dichloroisocyanurates, potassium and sodium trichlorocyanurates, N-chloroimides, N-chloroamides, N-chloroamines and chlorohydantoins.
Limescale reducing agents herein include, but are not limited to, acids and chelating agents. Exemplary acids useful herein include hydrochloric acid, phosphoric acid, sulfuric acid, sulfamic acid, acetic acid, hydroxyacetic acid, citric acid, benzoic acid, tartaric acid, formic acid and mixtures thereof. A mixture of organic and inorganic acid is preferred. Chelating agents useful herein can include, but are not limited to, carboxylates, phosphates, phosphonates, polyfunctionally-substituted aromatic compounds, polyamines, biodegradable compounds, the alkali metal, ammonium or substituted ammonium salts or complexes of these chelating agents, and mixtures thereof. Further examples of suitable chelating agents and levels of use are described in U.S. Pat. Nos. 3,812,044; 4,704,233; 5,292,446; 5,445,747; 5,531,915; 5,545,352; 5,576,282; 5,641,739; 5,703,031; 5,705,464; 5,710,115; 5,710,115; 5,712,242; 5,721,205; 5,728,671; 5,747,440; 5,780,419; 5,879,409; 5,929,010; 5,929,018; 5,958,866; 5,965,514; 5,972,038; 6,172,021; and 6,503,876.
Biocide means any known ingredient having the ability of reducing or even eliminating by killing or removing the micro-organisms existing on a surface, such as those described in U.S. Pat. No. 6,613,728. Biocide useful herein includes a quaternary surface active compound, a guanidine, an alcohol, a glycerol, a phenolic compound, a heavy metal salt, an inorganic and organic acid, a halogen, a halogen-containing compound, a dye, an essential oil, an oxidizing compound, an adsorbent, a fungicide, an algaecide and a mixture thereof. Exemplary quaternary surface active compounds include benzalkonium chloride, benzethonium chloride, cetyl pyridinium chloride, sodium tetradecyl sulfate, sichlorobenzalkonium chloride, methylbenzethonium chloride, cetyl dimethyl ethyl ammonium bromide. Exemplary guanidines include chlorohexidine hydrochloride, chlorohexidine gluconate, dodecylguanidine hydrochloride, polyhexmethylenebiguanidine hydrochloride, and 6-acetoxy-2,4-dimethylmetadioxane. Exemplary alcohols include methanol, ethanol, propanol, isopropanol, etc. Exemplary phenolic compounds include cresol, resolcinols and related compounds, phenol; substituted phenols—cresols, meta-cresylacetate, creosote, quaiacol, resorcinol, hexylresorcinol, pyrogallol, thymol, thymol iodide, picric acid, chlorinated phenols—dichlorophene, hexachlorophene, tars. Exemplary halogens and halogen-containing compounds include iodine and iodoform. Exemplary oxidizing agents include peroxide, sodium perporate, potassium permanganate, zinc permanganate, potassium chlorate. Exemplary heavy metal salts include mercuric chloride, miscellaneous ionizable mercuric salts, organic mercurials, silver nitrate, silver lactate, silver picrate, silver proteins, silver halides, zinc oxide, zinc stearate, copper sulfate and organic tin derivatives. Exemplary dyes include azo dyes, acridene dyes, fluorescein dyes, phenolphthalein dyes and triphenylmethane dyes. Exemplary inorganic and organic acids include hydrochloric acid, sulfuric acid, nitric acid, citric acid, sorbic acid, acetic acid, boric acid, formic acid, maleic acid, adipic acid, lactic acid, malic acid, malonic acid, glycolic acid, and mixtures thereof. Exemplary essential oils are thyme oil, clove oil, cinnamon oil, geranium oil, eucalyptus oil, peppermint oil, citronella oil, ajowan oil, mint oil or mixtures thereof. Other useful biocide herein includes furan derivatives, nitrofurantoin, sulfur, sulfur dioxide, ichthamol, chrysarobin, anthralin, betanaphthol, balsams, volatile oils, chlorophyl.
Biocides useful herein also include fungicides and algaecides which act against molds and mildew. Removal of algae and fungi from hard surfaces is difficult. Moreover, fungi and algae reappear promptly if not completely removed or inhibited. Suitable fungicides and algaecides include metal salts, such as zinc sulfate, zinc acetate, zinc bromide, zinc chloride, zinc iodide, zinc nitrate, zinc bromate and zinc chlorate, cooper halide, copper sulfate, organic tin derivatives, water-insoluble or partially water-soluble fungicides and algaecides, such as diiodomethyl p-tolyl sulfone, N-(trichloromethyl thio) phthalimide, N,N-dimethyl-N′-phenyl N′-(fluorodichloromethyl thio) sulphamide, 2-(thiocyanomethylthio) benzothiazole/methylene bis(thiocyanate), 3-iodo-2-propynyl butyl carbamate, etc., all available from ALDRICH chemical. Above biocides are optionally mixed with concentrated acids, such as acetic acid, formic, propionic, n-butanoic, n-pentanoic, trimethylacetic, n-hexanoic, lactic, methoxyacetic, cyanoacetic, chloroacetic, citric, partaric, etc.
The active agent may be a solvent having a good dissolving ability for greasy stains. Solvents useful herein include those which are at least partially water-miscible, such as alcohols, ethers, such as diethylene glycol diethylether, diethylene glycol dimethylether, propylene glycol dimethylether, propylene glycol monomethylether, propylene glycol monoethylether, propylene glycol monopropylether, propylene glycol monobutylether, ethylene glycol monobutylether, dipropylene glycol monomethylether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, diethyleneglycol monobutylether, lower esters of monoalkylethers of ethylene glycol or propylene glycol, such as propylene glycol monomethyl ether acetate, N-methyl pyrolidone and tetrahydrofuran. Mixtures of several solvents can also be used.
Packaging Means
The cleaning implement herein may be combined in an article of manufacture with a packaging means.
The packaging means herein may be any suitable means known to package cleaning implements. Indeed, particularly suitable packaging means herein are selected from the group consisting of: paper bags, plastic bags, cartons, carton boxes, flow wraps, plastic wraps, and paper wraps, and the like and combinations thereof.
The packaging means herein may be printed and/or modified. In particular, such printing and/or other modification may be used to associate a brand-name and/or logo of a hard surface cleaner with said cleaning implement.
Method of Cleaning a Hard Surface
In another embodiment the present invention encompasses method of cleaning a hard surface with a cleaning implement as described herein above.
In yet another embodiment herein, the present invention encompasses a method of cleaning a hard surface by bringing a cleaning implement according to the present invention into contact with said hard surface. By “cleaning” it is meant herein removing spots and/or stains from hard surfaces.
In still another embodiment herein, the present invention encompasses a method of cleaning a hard surface with cleaning implement according to the present invention.
Suitable hard surfaces herein are tiles, walls, floors, sanitary fittings such as sinks, showers, shower curtains, wash basins, WCs, household appliances including, but not limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on.
The methods of cleaning a hard surface according to the present invention may additionally include the step of wetting said cleaning implement or said foam with an appropriate solvent, preferably tap water, more preferably water in combination with a detergent composition, prior to bringing said cleaning implement into contact with said hard surface.
EXAMPLES
Methods of Measurement:
Mechanical Properties, Elasticity:
Ram pressure measurements for evaluating the mechanical quality of the melamine resin foams were all carried out as described in U.S. Pat. No. 4,666,948. A cylindrical ram having a diameter of 8 mm and a height of 10 cm was pressed into a cylindrical sample having a diameter of 11 cm and a height of 5 cm in the direction of foaming at an angle of 90% until the sample tore. The tearing force [N], hereinafter also referred to as ram pressure value, provides information as to the quality of the foam.
Comparative Example V-A
Producing a melamine/-formaldehyde-foam without microspheres.
75 parts by weight of a spray-dried melamine-formaldehyde precondensate (molar ratio 1:3) were dissolved in 25 parts by weight of water, then 3% by weight of formic acid, 2% by weight of a sodium C12/C14-alkyl sulfate, 38% by weight of pentane, all % by weight being based on the weight of the precondensate, were added, this was followed by stirring and then foaming in a propylene mold (for foaming) by irradiation with microwave energy. After foaming, the foam was dried for 30 minutes.
This melamine-formaldehyde foam has a density of 8.7 g/l and a ram pressure value of 20.9 N.
Comparative Example V-B
Producing a melamine-formaldehyde foam comprising 20% by weight of foam glass (being based on the melamine-formaldehyde precondensate) as benefit agent.
75 parts by weight of a spray-dried melamine-formaldehyde precondensate (molar ratio 1:3) were dissolved in 25 parts by weight of water, then 3% by weight of formic acid, 2% by weight of a sodium C12/C14-alkyl sulfate, 20% by weight of pentane and 25% by weight of foam glass (Poraver, particle size 0.4 to 0.6 mm), wherein all % by weight being based on the weight of the precondensate, were added, followed by stirring and then foaming in a polypropylene mold (for foaming) by irradiation with microwave energy. After foaming, the foam was dried for 30 minutes.
This melamine-formaldehyde foam had a density of 11.2 g/l and a ram pressure value of 17.1 N.
Comparative Example V-C
Producing a melamine-formaldehyde foam with 25% by weight of foam glass having an acrylate coating (based on the melamine-formaldehyde precondensate) as benefit agent.
75 parts by weight of a spray-dried melamine-formaldehyde precondensate (molar ratio 1:3) were dissolved in 25 parts by weight of water, then 3% by weight of formic acid, 2% by weight of a sodium C12/C14-alkyl sulfate, 20% by weight of pentane and 25% by weight of foam glass with an acrylate-coating (preparation according to WO 04/006689, example 3d, particle size 0.4 to 0.6 mm), all % by weight being based on the weight of the precondensate, were added, this was followed by stirring and then foaming in a polypropylene mold (for foaming) by irradiation with microwave energy. After foaming, the foam was dried for 30 minutes.
This melamine-formaldehyde foam had a density of 10.9 g/l and a ram pressure value of 16.9 N.
Comparative Example V-D
Producing a melamine-formaldehyde foam with 25% by weight of foam glass having a polyurethane coating (based on the melamine-formaldehyde precondensate) as benefit agent.
75 parts by weight of a spray-dried melamine-formaldehyde precondensate (molar ratio 1:3) were dissolved in 25 parts by weight of water, then 3% by weight of formic acid, 2% by weight of a sodium C12/C14-alkyl sulfate, 20% by weight of pentane and 25% by weight of foam glass with a polyurethane coating (preparation according to WO 06/097389, example 1, particle size 0.4 to 0.6 mm), all % by weight being based on the weight of the precondensate, were added, this was followed by stirring and then foaming in a polypropylene mold (for foaming) by irradiation with microwave energy. After foaming, the foam was dried for 30 minutes.
This melamine-formaldehyde foam had a density of 10.7 g/l and a ram pressure value of 15.4 N.
Comparative Example V-E
Producing a melamine-formaldehyde foam with 25% by weight of sodium sulfate (based on the melamine-formaldehyde precondensate) as benefit agent.
75 parts by weight of a spray-dried melamine-formaldehyde precondensate (molar ratio 1:3) were dissolved in 25 parts by weight of water, then 3% by weight of formic acid, 2% by weight of a sodium C12/C14-alkyl sulfate, 20% by weight of pentane and 25% by weight of sodium sulfate (particle size 0.4 to 0.6 mm), all % by weight being based on the weight of the precondensate, were added, this was followed by stirring and then foaming in a polypropylene mold (for foaming) by irradiation with microwave energy. After foaming, the foam was dried for 30 minutes.
This melamine-formaldehyde foam had a density of 10.8 g/l and a ram pressure value of 15.1 N.
Comparative Example V-F
Producing a melamine-formaldehyde foam with 25% by weight of sodium sulfate having a polyester coating (based on the melamine-formaldehyde precondensate) as benefit agent.
75 parts by weight of a spray-dried melamine-formaldehyde precondensate (molar ratio 1:3) were dissolved in 25 parts by weight of water, then 3% by weight of formic acid, 2% by weight of a sodium C12/C14-alkyl sulfate, 20% by weight of pentane and 25% by weight of sodium sulfate with a polyester coating (preparation according to WO 1998/14413, example 1, particle size 0.4 to 0.6 mm), all % by weight being based on the weight of the precondensate, were added, this was followed by stirring and then foaming in a polypropylene mold (for foaming) by irradiation with microwave energy. After foaming, the foam was dried for 30 minutes.
This melamine-formaldehyde foam had a density of 10.5 g/l and a ram pressure value of 16.7 N.
Comparative Example V-G
Producing a melamine-formaldehyde foam with 25% by weight of sodium lauryl sulfate (based on the melamine-formaldehyde precondensate) as benefit agent.
75 parts by weight of a spray-dried melamine-formaldehyde precondensate (molar ratio 1:3) were dissolved in 25 parts by weight of water, then 3% by weight of formic acid, 2% by weight of a sodium C12/C14-alkyl sulfate, 20% by weight of pentane and 25% by weight of sodium lauryl sulfate (particle size 0.4 to 0.6 mm), all % by weight being based on the weight of the precondensate, were added, this was followed by stirring and then foaming in a polypropylene mold (for foaming) by irradiation with microwave energy. After foaming, the foam was dried for 30 minutes.
This melamine-formaldehyde foam had a density of 9.7 g/l and a ram pressure value of 15.3 N.
Comparative Example V-H
Producing a melamine-formaldehyde foam with 25% by weight of sodium lauryl sulfate having a polyamide coating (based on the melamine-formaldehyde precondensate) as benefit agent.
75 parts by weight of a spray-dried melamine-formaldehyde precondensate (molar ratio 1:3) were dissolved in 25 parts by weight of water, then 3% by weight of formic acid, 2% by weight of a sodium C12/C14-alkyl sulfate, 20% by weight of pentane and 25% by weight of sodium lauryl sulfate with a polyester coating (preparation according to WO 2012072545, example 1, particle size 0.4 to 0.6 mm), all % by weight being based on the weight of the precondensate, were added, this was followed by stirring and then foaming in a polypropylene mold (for foaming) by irradiation with microwave energy. After foaming, the foam was dried for 30 minutes.
This melamine-formaldehyde foam had a density of 9.9 g/l and a ram pressure value of 18.3 N.
Example 1
Producing of melamine-formaldehyde coated foam glass-granulate with 20% by weight melamine-formaldehyde (being based on the foam glass granulate).

    
    
        35 parts by weight of a spray-dried melamine-formaldehyde precondensate are dissolved in water and are treated with 0.1% by weight Basantol 762 liquid, wherein the % by weight are based on the weight of the precondensate, to be able to evaluate the coating of the granulate and the distribution in the foam. 4.6% by weight of formic acid, the % by weight being based on the precondensate, are added to this resin solution. The resin solution was transferred to a fluidized bed-spray granulating apparatus, type GPCG by Glatt. The foam glass (Poraver, particle size 0.4 to 0.6 mm) that is present therein is coated in the fluidized bed at a temperature of 80° C. with 20% by weight of melamine-formaldehyde resin.
        Light microscopic recordings showed a homogeneous coating. The foam glass with melamine-formaldehyde coating was sieved. The particle size of 0.4 to 0.6 mm was used for the following producing of melamine-formaldehyde foam:
    
    


Producing a melamine-formaldehyde foam having 25% by weight foam glass with a melamine-formaldehyde coating (being based on melamine-formaldehyde precondensate) as benefit agent.

    
    
        75 parts by weight of a spray-dried-melamine-formaldehyde precondensate (molar ratio 1:3) were dissolved in 25 parts by weight of water, 3% by weight of formic acid, 2% by weight of a Na—C12/C14-alkyl sulfate, 20% by weight of pentane and 25% by weight of foam glass having a melamine-formaldehyde coating (0.4 to 0.6 mm), all % by weight being based on the precondensate, were added, this was followed by stirring and then foaming in a polypropylene mold (for foaming) by irradiation with microwave energy. After foaming, the foam was dried for 30 minutes.
        The melamine-formaldehyde foam had a density of 11.0 g/l and a ram pressure value of 22.3 N.
    
    


Example 2
Producing of melamine-formaldehyde coated sodium sulfate with 20% by weight melamine-formaldehyde (being based on the sodium sulfate).

    
    
        35 parts by weight of a spray-dried melamine-formaldehyde precondensate are dissolved in water and are treated with 0.1% by weight Basantol 762 liquid, wherein the % by weight are based on the weight of the precondensate, to be able to evaluate the coating of the granulate and the distribution in the foam. 4.6% by weight of formic acid, all % by weight being based on the precondensate, are added to this resin solution. The resin solution was transferred to a fluidized bed-spray granulating apparatus, type GPCG by Glatt. The sodium sulfate (particle size 0.4 to 0.6 mm) that is present therein is coated in the fluidized bed at a temperature of 80° C. with 20% by weight of melamine resin.
        Light microscopic recordings showed a homogeneous coating. The sodium sulfate with melamine-formaldehyde coating was sieved. The particles size of 0.4 to 0.6 mm was used for the following producing of melamine-formaldehyde foam.
    
    


Producing a melamine-formaldehyde foam having 25% by weight of sodium sulfate with a melamine-formaldehyde coating (being based on melamine-formaldehyde precondensate) as benefit agent.

    
    
        75 parts by weight of a spray-dried melamine-formaldehyde precondensate (molar ratio 1:3) were dissolved in 25 parts by weight of water, 3% by weight of formic acid, 2% by weight of a Na—C12/C14-alkyl sulfate, 20% by weight of pentane and 25% by weight of sodium sulfate having a melamine-formaldehyde coating (0.4 to 0.6 mm), all % by weight being based on the precondensate, were added, this was followed by stirring and then foaming in a polypropylene mold (for foaming) by irradiation with microwave energy. After foaming, the foam was dried for 30 minutes.
        The melamine-formaldehyde foam had a density of 11.4 g/l and a ram pressure value of 26.1 N.
    
    


Example 3
Producing of melamine-formaldehyde coated sodium lauryl sulfate with 20% by weight melamine-formaldehyde (being based on the sodium lauryl sulfate).

    
    
        35 parts by weight of a spray-dried melamine-formaldehyde precondensate are dissolved in water and are treated with 0.1% by weight Basantol 762 liquid, wherein the % by weight are based on the weight of the precondensate, to be able to evaluate the coating of the granulate and the distribution in the foam. 4.6% by weight of formic acid, all % by weight being based on the precondensate, are added to this resin solution. The resin solution was transferred to a fluidized bed-spray granulating apparatus, type GPCG by Glatt. The sodium lauryl sulfate (particle size 0.4 to 0.6 mm) that is present therein is coated in the fluidized bed at a temperature of 80° C. with 20% by weight of melamine resin.
        Light microscopic recordings showed a homogeneous coating. The sodium lauryl sulfate with melamine-formaldehyde coating was sieved. The particles size of 0.4 to 0.6 mm was used for the following producing of melamine-formaldehyde foam.
    
    


Producing a melamine-formaldehyde foam having 10% by weight of sodium lauryl sulfate with a melamine-formaldehyde coating (being based on melamine-formaldehyde precondensate) as benefit agent.

    
    
        75 parts by weight of a spray-dried melamine-formaldehyde precondensate (molar ratio 1:3) were dissolved in 25 parts by weight of water, 3% by weight of formic acid, 2% by weight of a Na—C12/C14-alkyl sulfate, 20% by weight of pentane and 25% by weight of sodium lauryl sulfate having a melamine-formaldehyde coating (0.4 to 0.6 mm), all % by weight being based on the precondensate, were added, this was followed by stirring and then foaming in a polypropylene mold (for foaming) by irradiation with microwave energy. After foaming, the foam was dried for 30 minutes.
        The melamine-formaldehyde foam had a density of 9.6 g/l and a ram pressure value of 26.9 N.
    
    




















TABLE 1






V-A
V-B
V-C
V-D
V-E
V-F
V-G
V-H
1
2
3


























density
8.7
11.2
10.9
10.7
10.8
10.5
9.7
9.9
11.0
11.4
9.6


[g/l]













ram
20.9
17.1
16.9
15.4
15.1
16.7
15.3
18.3
22.3
26.1
26.9


pressure













value













[N]









Result:

The comparison between example 1 and comparative example V-B shows that in the case of foam glass having a melamine-formaldehyde coating, the mechanical characteristics (herein acquired using the ram pressure value) are improved. The mechanical characteristics of comparative example V-C (acrylate coating) and V-D (polyurethane coating) are significantly worse compared to example 1.
The comparison between example 2 and comparative examples V-D and V-E show that the mechanical characteristics of sodium sulfate being coated with melamine-formaldehyde coating are significantly improved compared to an uncoated salt (V-E) or a salt having a polyester coating (V-F).
The comparison between example 3 and comparative example V-G and V-H show that the mechanical characteristics of sodium lauryl sulfate having a melamine-formaldehyde coating is essentially improved compared to an uncoated anionic sodium lauryl sulfate (V-G) and a sodium lauryl sulfate having a polyamide-coating (V-H).
Furthermore, it is clear that comparative examples V-B to V-H show reduced mechanical characteristics compared to V-A (foam without microspheres). In contrast thereto, mechanical characteristics of example 1 to 3 are improved compared to comparative example V-A.
Use of Melamine-Formaldehyde Foam Comprising Hollow Microspheres as Cleaning Implements or to Clean Hard Surfaces.
Cleaning Implement A
A single layer cleaning implement having a cuboid shape defined by three groups of parallel and equal length sides, referred to as a, b and c, with a being 6.5 cm, b being 12 cm, and c being 3 cm is cut from the foam according to present invention. The overall shape of Cleaning Implement A is similar to the cleaning implement of FIG. 1. Cleaning implement A comprising hollow microspheres comprising benefit agent.
Cleaning Implement A is used to clean hard surfaces. Indeed, Cleaning Implement A is wetted with water and thereafter brought into contact with the hard surface to be cleaned. Cleaning Implement A shows an excellent performance in removing greasy soap scum and neat kitchen dirt from said hard surface whilst providing adequate surface safety.
Cleaning Implement B
A dual layer cleaning implement having a cuboid shape defined by three groups of parallel and equal length sides, referred to as a, b and c, with a being 6.5 cm, b being 12 cm, and c being 4 cm is made by foam flame laminating a first layer of the foam according to present invention, having a thickness—side c—of 2 cm to a second layer of commercially available polyurethane foam, having a thickness—side c—of 1 cm. The two layers are joined together at the plane formed by sides a and b. The overall shape of Cleaning Implement B is similar to the cleaning implement of FIG. 2. Cleaning implement B comprising hollow microspheres comprising benefit agent.
Cleaning Implement B is used to clean hard surfaces. Indeed, Cleaning Implement B is wetted with water and thereafter the foam according to present invention side of Cleaning Implement B is brought into contact with the hard surface to be cleaned by rubbing said side over the area to be cleaned. The excessive amount of water is thereafter absorbed by the polyurethane layer of Cleaning Implement B by swiping the cleaned surface with said layer. Cleaning Implement B shows an excellent performance in removing greasy soap scum and neat kitchen dirt from said hard surface whilst providing adequate surface safety.
Cleaning Implement C
A dual layer cleaning implement having a cuboid shape defined by three groups of parallel and equal length sides, referred to as a, b and c, with a being 6.5 cm, b being 12.5 cm, and c being 2.5 cm is made by a permanent adhesive a first layer of hybrid foam according to present invention, having a thickness—side c—of 2 cm to a second layer of commercially available polyurethane foam, having a thickness—side c—of 0.5 cm. The two layers are joined together at the plane formed by sides a and b. The overall shape of Cleaning Implement C is similar to the cleaning implement of FIG. 2. Cleaning implement C comprising hollow microspheres comprising benefit agent.
Cleaning Implement C is used to clean hard surfaces. Indeed, Cleaning Implement C is wetted with water and thereafter the foam according to present invention side of Cleaning Implement C is brought into contact with the hard surface to be cleaned by rubbing said side over the area to be cleaned. The excessive amount of water is thereafter absorbed by the polyurethane layer of Cleaning Implement C by swiping the cleaned surface with said layer. Cleaning Implement C shows an excellent performance in removing greasy soap scum and neat kitchen dirt from said hard surface whilst providing adequate surface safety.
Use of Melamine-formaldehyde Foam Comprising Hollow Microspheres According to Present Invention to Clean a Hard Surface
A piece of melamine-formaldehyde foam comprising hollow microspheres according to present invention is used to clean a hard surface by wetting a piece of said foam with water and thereafter bringing it into contact with the hard surface to be cleaned. The foam according the present invention shows an excellent performance in removing greasy soap scum and neat kitchen dirt from said hard surface, whilst providing surface safety.
The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” is intended to mean “about 40 mm”.
Every document cited herein, including any cross referenced or related patent or application, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

## Claims

1. A cleaning implement comprising:
a) a melamine-formaldehyde foam and
b) hollow microspheres,
wherein the hollow microspheres have a core comprising at least one benefit agent and a shell comprising at least one melamine-formaldehyde resin.

2. The cleaning implement according to claim 1, wherein the cleaning implement comprises from about 0.1% to about 60%, by weight of the hollow microspheres and melamine-formaldehyde precondensate used for foam production, of the hollow microsphere.

3. The cleaning implement according to claim 2, wherein the hollow microspheres are embedded into open-cell pores of the melamine-formaldehyde foam.

4. The cleaning implement according to claim 1, wherein the benefit agent is selected from the group consisting of a detergent composition; surfactants; dyes; inks; pigments; scents; acids; bases; oils; salts; bleach; antimicrobial agents; fragrances; solvents; biocides; hydrophobicizing agents; agents influencing haptics; agents influencing soil release behavior; formaldehyde scavengers; inorganic nanoparticles abrasives; synthetic abrasives; catalysts and mixtures thereof.

5. The cleaning implement according to claim 1, wherein the microspheres have an average diameter (D50, averaged by volume, Malvern, Fraunhofer-Diffraction) in the range of 100 μm to 1000 μm.

6. The cleaning implement according to claim 1, wherein the shell is melamine-formaldehyde resin.

7. The cleaning implement according to claim 1, wherein the melamine-formaldehyde foam comprises an active agent.

8. The cleaning implement according to claim 1 having a first layer, and further comprising a second layer joined to said first layer.

9. The cleaning implement according to claim 8, wherein the second layer comprises an active agent.

10. The use of cleaning implement based on melamine-formaldehyde foam comprising hollow microspheres according to claim 1 to clean a hard surface.