JP2009522078A - Cleaning tool having an erodible foam substrate and a controlled release system of active agent - Google Patents

Abstract

  The cleaning implement (1) includes an erodible foam substrate (2), such as a melamine foam substrate (2), and a controlled release system comprising an active agent. The controlled release system includes a component selected from the group consisting of a polymer matrix, microcapsules, a particulate porous carrier, a complexing agent, a semipermeable film, and combinations thereof, wherein the active agent is a surfactant, a bleaching agent. Selected from the group consisting of agents, limescale reducing agents, biocides, solvents, and mixtures thereof.

Description

  The present invention relates to a cleaning tool. More specifically, the present invention relates to a cleaning implement containing an erodible foam substrate, such as a melamine foam substrate.

  The use of erodible foams, such as melamine formaldehyde resin foam, referred to herein as melamine foam, and phenolic foam in hard surface cleaning is well known. Indeed, cut / molded melamine foam cleaning tools are popular for removing dirt and / or stains from hard surfaces. Melamine foam is currently marketed in several countries under the trade name Mr. Clean Magic Eraser ™.

  Melamine foam exhibits excellent soil and / or stain removal performance when it is wetted with a suitable solvent such as tap water and used to wipe in contact with a soiled surface when cleaning hard surfaces . “Wipe off”, “wiped off”, “wiping off” means wiping, wiping, rubbing, etc., to apply hand force on the surface to be cleaned. Melamine foam is generally quite effective at removing dirt and / or stains from hard surfaces, but consumers can remove certain types of nuisance stains with melamine foam, even with an extra rubbing force It can still be difficult to do. For example, everyday adhesive resin-like or semi-solid modified oil stains from food, colored stains such as tea, coffee, fruit juice, grass, and carotenoid stains, oily magic and ink, mold and mildew, fungi etc. It is often difficult to remove with melamine foam.

  To improve the cleaning performance of a sponge, such as melamine foam, on certain types of troublesome stains, the sponge may be used with a detergent composition. The sponge and detergent can be provided separately in the kit, or the sponge may be impregnated with the detergent. However, consumers may find it inconvenient to rub after applying the detergent composition. Sponges impregnated with active agent tend to release the active agent too quickly, resulting in considerable loss of active agent after the first few uses. Therefore, a decrease in cleaning properties is observed when the active agent is used up. Also, if the active agent releases very rapidly on the first or second use, an extra rinse may be required with a high concentration of active agent.

  There is therefore a need for an improved cleaning tool that can clean nuisance stains, provides controlled release of active agents, and is convenient to use.

  The present invention includes an erodible foam substrate and a controlled release system comprising an active agent selected from the group consisting of surfactants, bleaches, limescale reducing agents, biocides, solvents, and mixtures thereof. Includes cleaning tools.

  The present invention further includes a method for cleaning a hard surface using the cleaning tool of the present specification.

  Surprisingly, it has now been found that combining a controlled release system with an active agent and an erodible foam substrate greatly improves the cleaning performance of the cleaning tool against nuisance stains on hard surfaces. At the same time, the life of the active agent in the cleaning tool is extended, resulting in improved cleaning performance over an extended period of time.

  Unless otherwise indicated, all percentages, ratios and proportions herein are “by weight” and all temperatures herein are in degrees Celsius (° C.).

  As used herein, “average particle size” means the average particle size by volume of a given particulate material as measured by conventional analytical techniques, such as microscopic measurements.

Cleaning Tool The cleaning tool herein is an article of manufacture of any suitable shape and / or size and / or volume suitable for cleaning, i.e. removing stains and / or stains from a hard surface. The cleaning implement herein includes an erodible foam substrate and a controlled release system having an active agent therein. As used herein, “erodible foam” means a foam that breaks into small particles and peels off by friction. Useful erodible foams herein include, but are not limited to, melamine foam, phenolic foam, and the like. In one embodiment herein, the erodible foam has a density in the range of about 5 to about 1000 kg / m ³ , or about 6 to about 500 kg / m ³ , or about 7 to about 300 kg / m ³ , and An open cell foam having a BET surface area, measured according to DIN 66131, in the range of about 0.1 to about 50 m ² / g, preferably about 0.5 to about 20 m ² / g. As used herein, “open cell foam” means at least 50%, or from about 60% to about 100%, or from about 65% to about 99.% of all thin layers, as measured according to DIN ISO 4590. 9% means open form. The bubbles can be shaped like channels, for example, and have an average pore diameter (number average) in the range of about 1 μm to about 1 mm, or about 50 μm to about 500 μm, as determined by evaluation of cross-sectional micrographs. Can have.

  In another embodiment herein, about 5 wt% to 20 wt%, or about 10 wt% to 15 wt% of the active agent contained in the cleaning implement is present in free form in the cleaning implement and is controlled. Ensure that the active agent is usable in the first few uses where the active agent in the release system may not yet be fully released. As used in contrast to controlled release systems, “free form active agent” means that the active agent is supplied to the cleaning implement in a pure form where release from the cleaning implement is not intentionally controlled or sustained. Means that.

  Shapes suitable for the cleaning tool of the present specification include a cubic shape, a rectangular shape, a pyramid shape, a cylindrical shape, a conical shape, an oblique quadrangular prism shape, a parallelepiped shape, a tetrahedral shape, a spherical shape, a spherical shape, and an ellipse. It may be selected from the group consisting of body shapes. The “slanting quadrangular prism shape” in the present specification has six wall surfaces, three parallel wall surfaces having the same shape and size, and a pair of wall surfaces are parallelogram shapes. It means a bulky object in which the remaining two pairs of wall surfaces are rectangular.

The cleaning implement may have any thickness and volume appropriate for its intended use. The erodible foam substrate may have a thickness of less than about 30 mm, or about 2 mm to about 15 mm, or about 5 mm to about 10 mm, and about 50 mm ³ to about 600 cm ³ , or about 80 cm ³ to about 300 cm. ³ , or a total capacity of about 150 cm ³ to about 275 cm ³ . Where the cleaning implement includes one or more additional substrates, each additional substrate can have any thickness and volume appropriate for its intended use. In one embodiment herein, each additional substrate has a thickness of less than about 30 mm, or from about 2 mm to about 15 mm, or from about 5 mm to about 10 mm. “Thickness” means the length in mm (the height of the substrate) of the side having the shortest extension compared to the other sides of the substrate. If the cleaning tool is based on an irregular shape and / or the substrate thickness varies widely, the substrate thickness extends at least once beyond the thickness herein. It is enough.

  The erodible foam substrate may be a commercially available melamine foam substrate, such as Basotect ™ from BASF. The preparation of melamine foam is known in the art and is described, for example, in PCT International Patent WO 2006/017298. Melamine foam typically has a pore size of about 20 μm to about 500 μm, or about 50 μm to about 200 μm. A controlled release system of beads or powder can be filled into a melamine foam substrate by dry spray. In such cases, the melamine foam herein may have a larger pore size compared to the pore size of the bead or powder to facilitate penetration of the controlled release system into the melamine foam substrate. Good. According to another embodiment herein, the erodible foam substrate is a phenolic foam substrate.

  The cleaning implements herein may include one or more additional substrates, such as a second erodable foam substrate or a substrate of a material different from the erodable foam substrate. Such additional substrate (s) may be attached directly to the first erodable foam substrate or another additional substrate (s). FIG. 1 shows a cleaning tool (1) having a melamine foam substrate (2) and a second substrate (3) attached to the melamine foam substrate (2) by adhesive bonding means (4). The additional substrate serves a different function than the first erodible foam substrate, for example, serving as an absorbent substrate, a wipe substrate, a support substrate, a rubbing substrate, or a gripping substrate. Also good. If the additional substrate is designed as a gripping substrate, the controlled release system is filled into the first erodable foam substrate and is ejected from the first erodable foam substrate during use. By gripping only the gripping substrate, it is possible to minimize contact of the hand with the active agent. Preferably, indicia such as different colors, markings, words, etc. are included to grip the gripping substrate and guide the user to contact the surface to be cleaned with the first erodible foam substrate.

  If the additional substrate (s) is not an erodible foam substrate, this additional substrate can be a cellulose foam sponge, a naturally occurring sponge or nonwoven, or even polyurethane, polypropylene, polyethylene, polyvinyl acetate Selected from the group consisting of urethane, propylene, ethylene, vinyl acetate, esters, acrylates, ethers and mixtures thereof, such as polyester, polyurethane-ether, polyurethane-ester, polyethylene-vinyl acetate, polyethylene-methacrylate, etc. It can be produced from a polymer foam containing monomers. The second substrate can absorb liquid, but does not swell so as to be visible. P. It may be a hydrophilic ester polyurethane foam, such as Cellulex ™ from (Foamex L.P.). See U.S. Patent No. 6,756,416.

  The additional substrate may be more hydrophobic than the melamine foam and can be used as a gripping substrate. Typical hydrophobic substrates are urethane, propylene, ethylene, butadiene, styrene, vinyl acetate, silicone, ester, acrylate, ether, cellulose acetate, styrene, silicone, natural latex, rubber, vinyl chloride, fluoroethylene and their Examples include closed cell foams of polymers having monomers selected from the group consisting of mixtures, Plastazote ™, Evazote available from Zotefoams plc (Croydon, UK) ) (TM), Supazote (TM), Propazote (TM), and FR, FM, CN or SD foam grades made with a significant proportion of hydrophobic polymers / materials.

  FIG. 2 shows a cleaning tool (10) having a sandwich-type shape with a rectangular prism shape and having three layers of substrates, at least one of the two outer substrates (11) and (12) being a melamine foam substrate It is a material. The intermediate substrate (13) is a liquid impermeable substrate and the controlled release system is contained in one of the substrates (11) and (12). For example, this controlled release system containing the active agent may be filled only within the substrate (12) and the intermediate substrate (13) is a liquid impermeable substrate. In this case, the active agent is released only from the substrate (12) and the substrate (11) can be used as a gripping substrate. Materials useful as liquid-impermeable substrates such as the above-mentioned hydrophobic foam substrates or high barrier hydrophobic nonwoven fabrics or plastic films such as polyethylene, polypropylene, polyamide, polyester, Teflon (trademark), etc. are known .

  Where the cleaning tool of the present invention includes one or more substrates or semi-permeable films, the erodible foam substrate, semi-permeable film and additional substrate (s) are substrate and film May be attached by any coupling means suitable for joining together. This bonding means can be used to make the two substrates permanent (cannot separate the two substrates without substantial damage to the substrates) or temporarily (without substantial damage to the substrates) as desired. Can be separated). Suitable permanent bonding means include permanent adhesive, foam frame lamination, stitching or needle punching together the substrate and / or film, and combinations thereof. The substrate or film can also be joined together by a permanent adhesive. Useful adhesives include vinyl emulsions such as vinyl acetates or other vinyl esters, such as homopolymers and copolymers of ethylene and / or acrylic monomers (vinyl acrylics); homopolymers of acrylic emulsions Reactive comonomers (eg, monomers containing functionality such as carboxyl, hydroxyl, epoxy, amide, isocyanate, etc.) that can crosslink the polymer itself (eg, carboxyl groups that react with hydroxyl, epoxy, or isocyanate groups) Cross-linking adhesives including those produced by inclusion or by reaction with external cross-linking agents (eg urea formaldehyde resins, isocyanates, polyols, epoxides, amines and metal salts, especially zinc). It is. The adhesives of this invention can also contain a limited amount of tackifying resin to improve adhesion, such as the addition of hydrogenated rosin ester tackifiers to vinyl acetate / ethylene copolymer latex. . See also the adhesive composition described in US Pat. No. 5,969,025. The adhesive can be applied, for example, by spray coating to produce a discontinuous bond, coating, roll coating, slot coating or lick coating to produce a continuous bond.

  Suitable temporary bonding means include low adhesive strength adhesives, weak adhesives such as repositionable adhesives such as “PSA” (pressure sensitive adhesive) with permanent tack (National Starch ( Some are also referred to as soft gel or hydrogel adhesives such as Dispomelt ™ available from National Starch); hook and loop fastening devices (eg Velco ™; water-based, water-soluble coatings) Or adhesives; interlock substrate shapes that provide stability and interlock fit, and combinations thereof.

  Referring to FIG. 1, the controlled release system has an active agent in the adhesive bonding means (4). In another embodiment, the adhesive bonding means (4) is liquid impermeable and a controlled release system with an active agent is included in the melamine foam substrate (2). In this case, the active agent is released only from the substrate (2), so the second substrate (3) can be used as a gripping substrate. Useful liquid impervious adhesive materials include PM17 and LA hot melt from Savare (Milano, Italy), Propel from Fuller (Minnesota, USA) ), Solar Cure (TM), Optimelt (TM), Clarity (TM), Fullback (TM) hotmelts, fullerene from Fuller ( Fulaprene, Bondseal solvent adhesive, and Rakoll (TM), AirSperse (TM), LiquiLoc (TM), Casemate (Fuller) from Fuller Trademark), water-based adhesives, and the like.

Controlled Release System The controlled release system herein contains an active agent and is in communication with an erodible foam substrate. The controlled release system may be impregnated or dispersed within an erodible foam substrate, applied on a bonding means for attaching the substrate, and / or a semi-permeable film attached to the erodible foam substrate. It can be applied in the middle of the second film. Exemplary controlled release systems useful herein include those having a polymer matrix, microcapsules, particulate porous carrier, complexing agent, and / or semipermeable film. The controlled release system of the present invention can be a liquid, gel, paste, bead, powder or film, etc. and can be applied to the cleaning tool by any conventional means such as dipping, spraying, dousing, coating, etc. Can be applied. If the controlled release system is a bead or powder, the bead or powder may be deposited or dry sprayed onto the substrate while vibrating the substrate so that the bead or powder can better penetrate the interior of the substrate. Preferably, the average particle size of the beads or powder is less than the average pore diameter of the melamine foam substrate, i.e., the average particle size of the controlled release system is from about 1 μm to about 400 μm, or from about 10 μm to about 100 μm, or about 1 μm. ˜about 30 μm. If the controlled release system includes a semi-permeable film, it can be attached to the substrate by an adhesive.

  The controlled release system may further comprise plasticizers, tackifiers, solid organic or mineral fillers, and / or preservatives. These materials have several additional features such as bonding substrates or films together, facilitating the immobilization of the controlled release system within the substrate, further controlling the release of the active agent, etc. May provide the benefits.

  Suitable plasticizers include citrate esters such as acetyl tributyl citrate and triethyl citrate, low molecular weight polyesters, polyethers, liquid rosin esters (eg, Foralyn ™ 5020F), aromatic Sulfonamides, phthalic acids, benzoates, sucrose esters, diacetin, polyfunctional alcohol derivatives, adipates, tartrate, sebacate, phosphoric acid, esters of fatty acids and dibasic acids, fatty alcohols And diols, epoxidized vegetable oils, and mixtures thereof.

Tackifiers are used in hot melt adhesives to improve adhesive properties, and they are generally organic compounds having a polycyclic structure. Tackifier, stable at about 200 ° C., and an amorphous glassy thermoplastic at room temperature greater than about 50 ° C., or from about 80 ° C. ~ about 125 ° C. T _g and about 8.30E-22g It has a molecular weight of (500 Daltons) to about 3.32E-21 g (2000 Daltons). The tackifier is a rosin or derivative thereof that is solid at room temperature, such as an α-methylstyrene copolymer commercially available from Hercules as Kristalex ™, having an average molecular weight of about 1200. It may be. When present, the tackifier represents from about 2% to about 60%, or from about 5% to about 40% by weight of the controlled release system.

Suitable solid organic or mineral fillers are Mg, Mn, Ba, Ca, W, Zr, Ti, Si, Mo oxides, chlorides, sulfates, phosphates, carbonates, especially TiO ₂ , It can be SiO ₂ and Al ₂ O ₃ . Further suitable materials are water-insoluble sodium polymetaphosphate, hydrated alumina, dicalcium orthophosphate dihydrate, calcium pyrophosphate, tricalcium phosphate, calcium polymetaphosphate.

  The amount of controlled release system in the cleaning tool depends on various factors including the volume of erodible foam and any additional substrate (s) to absorb the controlled release system, the viscosity of the controlled release system, etc. Can vary greatly. In one embodiment herein, the cleaning implement is about 0.1 to 500 parts by weight, or about 0.5 to 100 parts by weight, or about 1 to 50 parts by weight per 100 parts by weight of erodible foam substrate. Containing a controlled release system.

Polymer Matrix In one embodiment of the present invention, the controlled release system comprises a polymer matrix and an active agent. The active agent is absorbed or dissolved in the polymer matrix or chemically linked to the polymer matrix. The weight ratio of polymer matrix to active agent is about 19: 1 to about 1:19, or about 3: 2 to 2: 3. A controlled release system comprising a polymer matrix and an active agent may be prepared by any known method of making a thermoplastic polymer composition, and melts the polymer to provide a tackifier, if present, and / or a plasticizer. The process typically includes the step of intimately blending the agent and the active agent to form a homogeneous material, which is then cooled to produce a controlled release system. Preferred polymer matrices have a low melting temperature and viscosity and are therefore suitable for use as a hot melt. Controlled release systems may also be prepared using polymer solutions. A typical process is necessary to dissolve the polymer, tackifier and / or plasticizer, if present, and the active agent in an effective solvent, to prepare a solution or gel. If present, heating and removing the solvent by evaporation can be mentioned. Alternatively, the controlled release system may be prepared in the form of an aqueous emulsion or dispersion.

  The active agent is controlled release through migration, moisture activation prior to use, degradation, eg hydrolysis of weak chemical bonds linking the active agent to the polymer matrix, and / or physical erosion of the polymer matrix by friction. Can be released from the system. Polymers useful as the polymer matrix of the present invention include thermoplastic hydrophilic polymers, water-soluble polymers, water-swellable polymers, polymers that can be eroded by mechanical friction, at least one primary and / or Examples include polymers containing secondary amine groups and nanoparticulate polymers containing cationic monomers. As used herein, “water-soluble polymers” refers to polymers whose solubility in water (pH is 7, 25 ° C.) exceeds 1.5 g / L, preferably exceeds 2 g / L. As used herein, “water-swellable polymers” refers to polymers having a water absorption capacity of at least 10 wt%, or at least 20 wt% at 20 ° C., as measured according to ISO 8361.

  The polymers useful herein are selected from the group consisting of olefins, acrylic acids, acrylates, ethers, vinyl alcohols, vinyl pyrrolidones, urethanes, siloxanes, sugars, ethyleneimines, amides, esters, and / or vinyl acetates. Can have monomers and can be, for example, 500-1,000,000 g / mol, or 1,500-500,000 g / mol, or 2,000, as determined by gel permeation chromatography (GPC) It may have a molecular weight (Mn) in the range of up to 200,000 g / mol, or 20,000 g / mol.

  Suitable thermoplastic hydrophilic polymers are disclosed in PCT International Patents WO 99/64077, 99/64505 and EP 1193289. Particularly preferred thermoplastic hydrophilic polymers have thermoplastic ethylene-vinyl acetate copolymers (eg, Elvax ™ 250 from DuPont, 28 wt% vinyl acetate and 72 wt% ethylene. Random ethylene vinyl acetate copolymer resin), thermoplastic polyetheramide block copolymers (eg Pebax ™ MH1657 from Atofina, polyethylene oxide block co-poly-ε-caprolactam polymer, each block being Mw of about 1500 g / mol Melting point according to ASTM D3418: 204 ° C., thermoplastic polyester block copolymers (eg, Hytrel ™ 8171 from Dupont, hydrophilic butylenes Polyethylene glycol phthalate block copolyester), thermoplastic polyurethanes, typically non-reactive polyurethanes (eg, Estane ™ 5170 from Noveon, polyethylene glycol block polyurethane) and mixtures thereof is there.

Suitable water soluble or water swellable polymers are polyethylene glycols (polyethylene oxide) that are solid at room temperature (eg, Pluriol ™ E9000 having a Mw of about 9000 g / mol and a Mw of about 400 g / mol). Pluriol ™ E400), polyvinyl pyrrolidone, polyvinyl alcohol and partially hydrolyzed polyvinyl acetate, polyacrylamide, agar, dextran, gati gum, acacia, guar, starch and other polysaccharides, polynucleotides, Polypeptide (polyglutamine), polyacrylate, cross-linked polyacrylate, physically cross-linked polyethylene oxide, eg Aquacalk ™ from Sumitomo, polyalkylene glycol-vinyl acetate Graft copolymers, copolymers of (meth) acrylic acid and (meth) acrylates, such as _C1-10 alkyl esters of (meth) acrylic acid, and (meth) acrylic acid and ethylenically unsaturated dicarboxylic acids Copolymers such as fumaric acid, itaconic acid, and in particular maleic acid can be used.

  Suitable erodible polymers can be waxes. Examples of waxes are natural waxes such as paraffin wax, microcrystalline wax, biowax such as lanolin, candelilla, carnauba, mineral wax such as montain wax, and average molecular weights in the range of 500-20,000 g / mol ( Synthetic waxes such as polyethylene waxes with Mn) and polypropylene waxes with an average molecular weight (Mn) in the range of 500 to 20,000 g / mol.

  Suitable nanoparticulate polymers comprising cationic monomers can contain from about 0.1 wt% to about 50 wt%, or from about 1 wt% to about 10 wt% cationic monomers, about 100 nm Have a particle size of ˜50 μm. Cationic monomers useful herein include cationic units. Cationic unit is understood to mean a moiety that can maintain a cationic charge within a pH range of about 2 to about 8 when incorporated into the structure of the polymer particle. The cationic unit need not be protonated at all pH values within the range of about 2 to about 8. Suitable cationic monomers include dimethylaminoalkyl acrylates, in particular dimethylaminoethyl methacrylate, vinyl pyrrolidones, vinyl imidazolyls, vinyl ethers having a dialkylamino group, vinyl pyridines, alkyl acrylamides, dialkyl acrylamides, dialkyls. Examples include aminoalkyl acrylamide and aminoalkyl acylamides.

  Suitable polymers containing at least one primary and / or secondary amine group can be linear homo-, copolymers, and optionally branched, grafted and / or cross-linked polymers. Preferably, these polymers contain more than 10 amino groups and have a number average molecular weight (Mn) ranging from about 150 to about 2.10E6, or from about 600 to about 40,000. Examples of such polymers include polyethyleneimine, polyvinylamine, polyvinylamine-vinyl alcohol copolymer, polyvinylamine-vinylformamide copolymer, polyamino acid (10: 1) commercially available from BASF as Lupasol ™. L-lysine / lauric acid in a molar ratio of L-lysine / aminocaproic acid / adipic acid in a molar ratio of 5: 5: 1, L-lysine / aminocaproic acid / ethylhexanoic acid in a molar ratio of 5: 3: 1) , Polylysine-cocaprolactan, polylysine hydrobromide, cross-linked polylysine, amino-substituted polyvinyl alcohol.

  In one embodiment herein, the polymer matrix is a polyalkylene glycol-vinyl acetate graft copolymer having an average molecular weight (Mn) of 3,000-100,000 g / mol. An example of a polyalkylene glycol-vinyl acetate graft copolymer can be produced from a base polymer (A) selected from:

(A1) Polyethylene glycols which may be end-protected with one or two C _1-25 alkyl groups, or non-end-protected polyethylene glycols, 1,500-20,000 g / mol, or 2, Having an average molecular weight Mn in the range of 500-15,000 g / mol,
(A2) Copolymers of ethylene oxide and propylene oxide and / or butylene oxide end-protected with one or two C _1-25 alkyl groups, or end-protected, having an ethylene oxide content of at least 50% by weight Having an average molecular weight Mn in the range of 1,500 to 20,000 g / mol, or 2,500 to 15,000 g / mol,
(A3) Polyethylene glycols (A1) or copolymers of ethylene oxide and propylene oxide and / or butylene oxide (A2) are converted into C _2-12 dicarboxylic acid or C _2-12 dicarboxylic acid (me) ethyl esters or C ₆ Chain extension products obtainable by conversion with _{~ 18} diisocyanate. Particularly preferably, the chain extension product (A3) has an average molecular weight Mn in the range of 2,500 to 25,000 g / mol.

  For grafting any of the base polymers (A1) to (A3), vinyl esters such as vinyl acetate or vinyl propionate are preferred. In one embodiment herein, vinyl esters are the only monomers for grafting. In another embodiment herein, 1 to 50 mol% of the vinyl ester is replaced by (meth) acrylic acid.

Microcapsules In one embodiment herein, the controlled release system includes microcapsules that encapsulate an active agent. The microcapsule can be any ruptureable capsule containing an active agent therein or a capsule in which the active agent encapsulated therein is controllably penetrable. The burst strength of the microcapsules should be within a range that can withstand processing and spraying without rupture but can be broken by external forces of friction or moisture.

  The microcapsule shell can be made from a wide variety of materials known in the art. Suitable microcapsule shell materials and / or methods for producing microcapsules are, for example, U.S. Pat. Nos. 2,800,458, 3,159,585, 3,516,846, 516,941, 3,533,958, 3,697,437, 3,778,383, 3,888,689, 3,965,033, 3,996,156, 4,010,036, 4,016,098, 4,087,376, 4,089,802, 4,100 No. 103, No. 4,251,386, No. 4,269,729, No. 4,303,548, No. 4,460,722, No. 4,610,927, and No. 5,591,146, British Patent No. 1,156,725 No. 1,483,542, No. 2,006,709, No. 2,041,319, No. 2,048,206 and No. 2,062,570, and Benita , Simon (edit), microencapsulation: methods and industrial applications (Marcel Dekker, Inc. 1996).

  The microcapsules herein have an average size of about 0.1 μm to about 1,000 μm, or 1 μm to about 500 μm, or about 10 μm to about 100 μm. The active agent is contained in the microcapsule at a concentration of about 1% to about 99%, or about 10% to about 95%, or about 30% to about 90% by weight of the microcapsule.

Particulate Porous Carrier In one embodiment herein, the controlled release system contains a particulate porous carrier, and the active agent is releasably loaded into the pores of the carrier. This particulate porous carrier absorbs the active agent and then releases it either over time or as a result of external pressure, moisture, and the like. The particulate porous carrier is typically silica, silicate, clay, metal oxide, zeolite, sodalite, chitin microbeads, carboxyalkyl cellulose, starch, sugar, porous carbon, and / or Selected from the following derivatives: Preferably, the particulate porous support is zeolite A having a primary particle size of about 0.1 μm to about 10 μm.

  A typical method for filling an active agent into a particulate porous carrier is to spray the active agent or a solution of the active agent onto the particulate porous carrier, followed by particles loaded with the active agent. Stirring the solid mixture or suspension to obtain a porous support in the form of a solid. Alternatively, a particulate porous carrier may be deposited on the substrate and then the active agent or solution of the active agent may be sprayed onto the substrate. The weight ratio of the particulate porous carrier to the active agent is about 100: 1 to 1: 1, or about 100: 20 to 100: 60.

Complexing Agent In one embodiment herein, the controlled release system includes a complexing agent that binds the active agent. A useful complexing agent can be a cyclodextrin.

  Naturally or chemically modified, such as α-, β-, and γ-cyclodextrin, glucosyl-α-cyclodextrin, maltosyl-α-cyclodextrin, glucosyl-β-cyclodextrin, and maltosyl-β-cyclodextrin Both of the cyclodextrins that can be used can be used herein. Polymerized cyclodextrins may be used and may form complexes with active agents. A suitable solubility of the cyclodextrin / activator complex in water is from about 0.1 g to about 100 g, or from about 0.5 g to 20 g, or from about 1 g to 5 g of complex per 100 g of water at 25 ° C. In one embodiment herein, the cyclodextrin is β-cyclodextrin having a water solubility of about 1.8 g to about 2 g per 100 g of water at 25 ° C. The same method as described above for packing the active agent into the particulate porous carrier can be used for the method of combining cyclodextrin with the active agent. In one embodiment herein, the molar ratio of cyclodextrin to active agent is from about 20: 1 to about 1: 1 molar equivalent, or from about 10: 3 to about 10: 8 molar equivalent.

Semi-permeable film The controlled release system includes a first semi-permeable film attached to an erodible foam substrate, a second film of semi-permeable film or liquid impermeable film attached to a second substrate, and It may contain an active agent applied in the middle between the one semi-permeable film and the second film. The active agent can be used in its pure form or in any form of the controlled release system herein. 3 and 4 are laminated together with a melamine foam substrate (21) and a second substrate (22) and attached separately to the melamine foam substrate (21) and the second substrate (22). Figure 2 shows a cleaning tool (20) having a two-layer semi-permeable film (23) formed. The activator (24) is applied between the two semi-permeable films (23).

Suitable translucent films herein include open films such as polyolefin films based on polyethylene and polypropylene, polyesters, polyamides, polyester-ether copolymers, polyamide-ethers, Teflon (TM) films, and the like. A flexible liquid impervious film having pores. These films typically have a basis weight of 1 to 250 g / m ² , or ² to 60 g / m ² . Translucent films are commercially available from Clopay, RKW, Mitsui, Tacolin, 3M (3M), Dupont, International plastic and the like. The pore size and density (number of pores per square meter of film) can be adjusted to match the release kinetics of the active agent through the pores. Typically, the hole diameter is from about 100 μm to about 10 mm, or from about 0.5 mm to about 2 mm, and the hole density is from about 100 holes / m ² to about 500,000 holes / m ² , or about 3000 holes / m ^2. ~ About 30,000 holes / m ² . Microporous films are typically defined by their water vapor transmission rate (WVTR) as measured, for example, by PERMATRAN-W ™ model 398 (eg, ASTM standard E-398) manufactured by Mocon. Suitable microporous films have a WVTR of about 100 to about 25,000 g / m ² / day, or about 2000 to about 6,000 g / m ² / day. Another suitable semi-permeable film is a high liquid barrier nonwoven containing a high percentage of fibers made of a hydrophobic material. Typical high liquid barrier nonwoven has a basis weight of 1 to 500 g / m ^2, or 10 to 150 g / m ^2, or 40 and 80 g / m ^2. Preferred high liquid barrier nonwovens are made of 100% polypropylene fibers and are formed by spunbond (S), meltblown (M), and combinations thereof, such as SMS, SMMS, and the like. High liquid barrier nonwovens are commercially available from BBA, PGI, Freudenberg, Alsthom, Jacob holm, and the like.

Activator The cleaning tool herein contains an activator selected from surfactants, bleaches, limescale reducing agents, biocides, solvents, and mixtures thereof.

The surfactant can be a nonionic, anionic, cationic, amphoteric, and / or zwitterionic surfactant. Suitable nonionic surfactants include alkoxylated fatty alcohols having the formula RO (EO) e (PO) pH, where R is a hydrocarbon chain of 2 to 24 carbon atoms; EO is ethylene oxide, PO is propylene oxide, and e and p, each representing the average degree of ethoxylation and propoxylation, are independently 0-24, or R is 6-22 carbon atoms. Where e is 5 to 12 and p is 0. Suitable cationic surfactants herein include quaternary ammonium, phosphonium, imidazolium and sulfonium compound derivatives. Preferred cationic surfactants herein are trimethyl quaternary ammonium compounds. Suitable amphoteric surfactants herein include amine oxides having the formula R ₁ R ₂ R ₃ NO, R ₁ R ₂ R ₃ NR ₄ SO ₄ , or R ₁ R ₂ R ₃ NR ₄ CO ₂ , Examples include betaine sulfate or ammonium sulfate, or ammonium carboxylate, wherein each of R ₁ , R ₂ , and R ₃ is independently 1-30, except for R _4, which preferably contains three saturated carbons. A saturated, substituted or unsubstituted, linear or branched alkyl group of from 8 to 18 carbon atoms. Preferred amine oxides herein are, for example C ₈ -C ₁₀ amine oxides natural blends and C ₁₂ -C ₁₆ amine oxides, such as cetyl dimethyl amine oxide. Preferred betaines herein are cocamidopropyl betaine and lauramidopropyl betaine. Suitable anionic surfactants include alkyl diphenyl ether sulfonates and alkyl carboxylates. Other suitable anionic surfactants herein include water-soluble salts or acids of the formula ROSO ₃ M, where R is preferably C ₁₀ -C ₂₄ hydrocarbyl, or C ₁₂ -C _18. Alkyl or hydroxyalkyl, M is H or a cation such as sodium, potassium, lithium, or ammonium or substituted ammonium. Other suitable anionic surfactants include soap salts _{(soap salts), C 9 ~C} 20 linear alkylbenzenesulfonates, C ₈ -C ₂₂ primary or secondary alkyl sulfonates, sulfonated polycarboxylic acids , C ₈ -C ₂₄ alkyl polyglycol ether sulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates, sulfates of alkyl polysaccharides, alkyl polyethoxycarboxylates such as the formula RO (CH) ₂ CH ₂ 0) _k CH ₂ COO ⁻ M ⁺ , wherein R is C ₈ -C ₂₂ 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” (Volumes I and II, Schwartz, Perry and Berch). Such surfactant variants are also generally disclosed in US Pat. No. 3,929,678.

The bleaching agent herein is selected from a hydrogen peroxide source, a preformed peroxycarboxylic acid, a hypohalite bleach source, and mixtures thereof. The hydrogen peroxide source in the present specification includes persulfate, dipersulfate, persulfate, percarbonate, perborate, metal peroxide, perphosphate, persilicate, urea peroxidation. And hydrides and mixtures thereof. The 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 logical formula HO—O—C (O) — (CH ₂ ) _n —Y, where Y is H, CH ₃ , CH ₂ Cl, COOH, or C (O) OOH, and n is an integer of 1-20. Branched analogs are also acceptable. When the organic percarboxylic acid is aromatic, the unsubstituted acid suitably has the formula HO—O—C (O) —C ₆ H ₄ —Y, where Y is hydrogen, alkyl, alkylhalogen. ), Halogen, —COOH, or —C (O) OOH. Monoperoxycarboxylic acids useful as oxygen bleaches herein are peroxybenzoic acids and ring-substituted peroxybenzoic acids, for example, alkylpercarboxylic acids and arylpercarboxylic acids, such as peroxy-α-naphthoic acid; Aliphatic, substituted aliphatic and arylalkyl monoperoxy acids such as acids, peroxystearic acid, and N, N-phthaloylaminoperoxycaproic acid (PAP); and 6-octylamino-6-oxo-peroxyhexanoic acid Thus further illustrated. Peracids can be used in acid form or in any suitable salt having a cation that is stable to bleach. Suitable hypohalite bleaching agents herein include those that form positive halide ions and / or hypohalite ions, and organic sources of halides such as chloroisocyanurates. Some bleaching agents are mentioned. Suitable hypohalite bleaching agents herein include alkali metal and alkaline earth metal hypochlorite, hypobromite, hypoiodite, chlorinated trisodium phosphate Examples include hydrates, potassium dichloroisocyanurate and sodium dichloroisocyanurate, potassium trichlorocyanurate and sodium trichlorocyanurate, N-chloroimide, N-chloroamide, N-chloroamine, and chlorohydantoin.

  Lime scale reducing agents herein include, but are not limited to acids and chelating agents. Representative 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 acids is preferred. Chelating agents useful herein include carboxylates, phosphates, phosphonates, polyfunctional substituted aromatic compounds, polyamines, biodegradable compounds, alkali metals, ammonium or substituted ammonium salts, or these But not limited to these chelating agent complexes, and mixtures thereof. Further examples of suitable chelating agents and concentrations used are disclosed in U.S. Pat. Nos. 3,812,044, 4,704,233, 5,292,446, 5,445,747. No. 5,531,915, No. 5,545,352, No. 5,576,282, No. 5,641,739, No. 5,703,031, No. 5, No. 705,464, No. 5,710,115, No. 5,710,115, No. 5,712,242, No. 5,721,205, No. 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, 6,172,0 No. 1, and is described in the No. 6,503,876.

  A biocide is any that also has the ability to reduce or even eliminate by killing or removing microorganisms present on the surface, such as those described in US Pat. No. 6,613,728 Means known ingredients. Biocides useful herein include quaternary surfactant compounds, guanidines, alcohols, glycerol, phenolic compounds, heavy metal salts, inorganic and organic acids, halogens, halogen-containing compounds, dyes, essential oils, oxidizing compounds, adsorbents , Fungicides, algicides, and mixtures thereof. Representative quaternary surface active compounds include benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, sodium tetradecyl sulfate, dichlorobenzalkonium chloride, methylbenzethonium chloride, and cetyldimethylethylammonium bromide. Representative guanidines include chlorohexidine hydrochloride, chlorohexidine gluconate, dodecylguanidine hydrochloride, polyhexamethylene biguanidine hydrochloride, and 6-acetoxy-2,4-dimethylmetadioxane. Typical alcohols include methanol, ethanol, propanol, isopropanol and the like. Representative phenolic compounds include cresol, resorcinol and related compounds, phenol; substituted phenols-cresols, meta-cresyl acetate, creosote, quaiacol, resorcinol, hexyl resorcinol, pyrogallol, thymol, thymol iodide , Picric acid, chlorinated phenols-dichlorophen, hexachlorophene, tars. Representative halogens and halogen-containing compounds include iodine and iodoform. Representative oxidizing agents include peroxide, sodium perporate, potassium permanganate, zinc permanganate, and potassium chlorate. Typical heavy metal salts include mercuric chloride, other ionizable mercuric salts, organic mercury agents, silver nitrate, silver lactate, silver picrate, protein silver, silver halide, zinc oxide, zinc stearate, Examples thereof include copper sulfate and organotin derivatives. Representative dyes include azo dyes, acridene dyes, fluorescein dyes, phenolphthalein dyes, and triphenylmethane dyes. Typical 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. Is mentioned. Typical 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 biocides useful herein include furan derivatives, nitrofurantoin, sulfur, sulfur dioxide, ictamol, chrysarobin, anthralin, β-naphthol, balsams, volatile oils, chlorophyll.

  Biocides useful herein also include fungicides and algicides that act against mold and mildew. Removal of algae and fungi from hard surfaces is difficult. Furthermore, if the fungi and algae are not completely removed or controlled, they reappear immediately. Suitable fungicides and algicides include, for example, metal salts such as zinc sulfate, zinc acetate, zinc bromide, zinc chloride, zinc iodide, zinc nitrate, zinc bromate and zinc chlorate, copper halides (cooper halide), copper sulfate, organotin derivatives, water-insoluble or partially water-soluble fungicides and algicides such as diiodomethyl para-tolyl sulfone, N- (trichloromethylthio) phthalimide, N, N-dimethyl -N'-phenyl N '-(fluorodichloromethylthio) sulfamide, 2- (thiocyanomethylthio) benzothiazole / methylenebis (thiocyanate), 3-iodo-2-propynylbutylcarbamate, etc., all of which are Aldrich Chemical (ALDRICH chemical). The biocides are optionally acetic acid, formic acid, propionic acid, n-butanoic acid, n-pentanoic acid, trimethylacetic acid, n-hexanoic acid, lactic acid, methoxyacetic acid, cyanoacetic acid, chloroacetic acid, citric acid, Mixed with concentrated acids, such as tartaric acid.

  The activator can be a solvent having an excellent dissolving ability with respect to a stain stained with fat. Solvents useful herein include those that are at least partially water miscible, such as alcohols, ethers such as diethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, Propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, diethylene glycol monobutyl ether, ethylene glycol or monoalkyl ethers of propylene glycol Lower ester Such as propylene glycol monomethyl ether acetate, include N- methylpyrrolidone and tetrahydrofuran. Mixtures of several solvents can also be used.

Packaging means The cleaning tool of the present description may be combined in a product with packaging means known for packaging cleaning tools. Particularly suitable packaging means herein can be paper bags, plastic bags, paper packs, paper pack boxes, flow wraps, plastic wraps, paper wraps, and the like, and combinations thereof.

Hard Surface Cleaning Method In another embodiment, the present invention includes a hard surface cleaning method using the cleaning tool herein. In yet another embodiment, the present invention includes a method of cleaning a hard surface by contacting a cleaning tool herein with the hard surface. “Cleaning” means removing stains and / or stains from a hard surface.

  Suitable hard surfaces herein include tiles, walls, floors, sanitary appliances (sinks, showers, shower curtains, basins, toilets, etc.), household appliances (refrigerators, freezers, washing machines, automatic dryers, ovens) , Microwave ovens, dishwashers, and the like).

  The method for cleaning a hard surface herein may further comprise a step of wetting the cleaning tool with a suitable solvent, preferably tap water, before contacting the cleaning tool with the hard surface.

The invention is further illustrated by the following examples. In all the examples below, the erodible foam substrate has an open cell ratio of 99.6% according to DIN ISO 4590, a density of 10.0 kg / m ³ as measured according to EN ISO 845, a cross-sectional photomicrograph. An open-celled foam with an average pore diameter of 210 μm determined by evaluation and a BET surface area of 6.4 m ² / g measured by DIN 66131. This open cell foam is commercially available from BASF as Basotec ™ melamine foam. All melamine foam substrates and any additional substrate (s), if present, have a cubic shape having a length of about 125 mm and a width of about 65 mm.

(Examples 1-8)
A controlled release system comprising a low melting hot melt polymer matrix and an active agent comprises the composition shown in Table 1 below in a high shear hot melt blender (TM20 twin screw extruder from Maris, Turin, Italy). Prepared by mixing. All percentages in the table are by weight based on the total weight of the controlled release system. Approximately 1.5 g of controlled release system is achieved by slot coating nozzle (EP-11 from Nordson, Germany or LH-3 laboratory coater / laminator from Acumeter, USA) And extruded at about 70 ° C. in a series of separate lanes on the surface of a melamine foam substrate having a thickness of about 23 mm and a weight of about 1.85 g. After applying the molten controlled release system onto the melamine foam substrate, a second substrate of open cell polyurethane foam (Sweetane ™ series by Recticel) having a thickness of about 6 mm is obtained. Adhered to the melamine foam substrate along the surface coated with a controlled release system by a liquid impermeable polyamide hot melt adhesive (Fullback ™ from Fuller). After bonding the two substrates, the substates are pressed several times or heated to a higher temperature to facilitate penetration of the controlled release system into the melamine foam substrate and polyurethane foam substrate. Is done. A cleaning tool is obtained having a controlled release system located at the interface between the melamine foam substrate and the open cell polyurethane foam substrate.

１． デュポン（DuPont）社製エチレン−ビニルアセテートコポリマー
２． アトフィナケミカルズ（Atofina Chemicals）社製ポリエーテル−ブロックアミドポリマー
３． デュポン（DuPont）社製ポリエーテル−ポリエステルブロックコポリマー
４． ノベオン（Noveon）社製熱可塑性弾性ポリウレタン
５． ＢＡＳＦ社製ポリエチレングリコール
６． イーストマンケミカル（Eastman Chemical）社製ロジンエステル粘着付与剤
７． ハーキュレス（Hercules）社製α−メチルスチレンコポリマー炭化水素樹脂粘着付与剤
８． ＢＡＳＦ社製で７のエトキシル化度のＣ₁₀アルキルポリエチレン（polyethelene）グリコールエーテル
９． ＢＡＳＦ社製で８のエトキシル化度のＣ₁₀アルキルポリエチレン（polyethelene）グリコールエーテル
１０． ＢＡＳＦ社製で１０のエトキシル化度のＣ₁₀アルキルポリエチレン（polyethelene）グリコールエーテル
１１． ＢＡＳＦ社製非イオン性直鎖一級オキシエチル化アルコール

1. 1. Ethylene-vinyl acetate copolymer manufactured by DuPont 2. Polyether-block amide polymer from Atofina Chemicals. 3. Polyether-polyester block copolymer manufactured by DuPont 4. Noveon thermoplastic elastic polyurethane 5. Polyethylene glycol manufactured by BASF Corp. 6. Rosin ester tackifier from Eastman Chemical Co. 7. α-Methylstyrene copolymer hydrocarbon resin tackifier from Hercules. C ₁₀ alkyl polyethylene made by BASF 7 degrees of ethoxylation (polyethelene) glycol ether 9. C ₁₀ alkyl polyethylene degrees of ethoxylation made by BASF 8 (polyethelene) glycol ether 10. _10. C10 alkyl polyethylene glycol ether manufactured by BASF and having a degree of ethoxylation of 10. Nonionic linear primary oxyethylated alcohol manufactured by BASF

(Examples 9 to 16)
A liquid controlled release system comprising a polymer matrix and an active agent is prepared by mixing the compositions shown in Table 2. All percentages in Table 2 are by weight based on the controlled release system. About 1 g of liquid controlled release system is sprayed onto the surface of two melamine foam substrates each having a thickness of about 10 mm using a Nordso A7A spray gun or AD hand gun. The melamine foam substrates each weigh about 0.8 g before applying the controlled release system. The surface coated with the controlled release system of the melamine foam substrate is adhered in a sandwich-type configuration to a third substrate of closed cell polypropylene foam (Zotefoam, UK) having a thickness of about 10 mm. The third substrate is bonded to the middle of the two melamine foam substrates by a polyamide hot melt (commercially available from Fuller as liquid impervious Fullback ™ hot melt adhesive). This three-layer laminate is then compressed by hand so that the controlled release system penetrates into the melamine foam substrate, and the resulting cleaning implement is then used to evaporate water and ethanol. Air dried.

１． ビニルアセテートとグラフト化された７０重量％のポリエチレングリコール、２０重量％のエタノール及び１０重量％の水を含有する粘稠な溶液混合物
２． ６０重量％のポリビニルアルコール（そのうち８８％が加水分解される）、１０重量％のエタノール及び３０重量％の水を含有するハーローケミカル社（Harlow Chemical Company Ltd）から入手可能な粘稠な溶液混合物
３． ステパン（Stepan）から入手可能なナッコノール（Nacconol）（商標）

1. 1. A viscous solution mixture containing 70% by weight polyethylene glycol grafted with vinyl acetate, 20% by weight ethanol and 10% by weight water. A viscous solution mixture available from Harlow Chemical Company Ltd containing 60% by weight polyvinyl alcohol (of which 88% is hydrolyzed), 10% by weight ethanol and 30% by weight water 3 . Nacconol ™ available from Stepan

(Examples 17 to 19)
A controlled release system comprising β-cyclodextrin particles having an average particle size of about 150 microns, water and an active agent is prepared by mixing and stirring the compositions shown in Table 3 for 4 hours to form a suspension. Is done. This suspension is then sprayed onto the surface of a melamine foam substrate having a thickness of about 14 mm and a weight of about 1.1 g before being filled with the controlled release system. This melamine foam substrate is then attached to a second melamine foam substrate of equal thickness using a Fuller ™ Fullback ™ adhesive from Fuller. A cleaning tool is thus obtained.

１． ワッカー（Wacker）社製カバマックス（Cavamax）Ｗ７
２． シェル（Shell）社製で約８のエトキシル化度のＣ_9〜11アルキルポリエチレングリコール界面活性剤であるネオドール（Neodol）９１−８

1. Wacker's Cavamax W7
2. Neodol 91-8, a C _9-11 alkyl polyethylene glycol surfactant with a degree of ethoxylation of about 8 manufactured by Shell

(Example 20)
A particulate porous support mixture of 0.15 g Zeolite A and 0.15 g mesoporous silica ZSM-5 having a particle size of about 150 microns is about 14 mm thick before being filled with the controlled release system. And deposited on one of the two largest surfaces of a melamine foam substrate having a weight of about 1.1 g. 0.067 g non-ionic C _12-13 primary alcohol ethoxylate surfactant (Neodol ™ 23-3 from Shell), 0.033 g cocoamide, about 3 ethoxylated A mixture of propyl betaine surfactant (Amphosol ™ from Stepan) and 1 g of water-containing active agent was then deposited on the zeolite / silica particles deposited on the surface of the melamine foam substrate. Sprayed on. A second melamine foam substrate of approximately equal thickness is then adhered to the active-filled surface of the first melamine foam substrate with a Fullback ™ adhesive. A cleaning tool is thus obtained in which a particulate porous carrier and a controlled release system of active agent are located across the interface of the two melamine foam substrates.

(Examples 21 to 22)
The same process is repeated as in Example 20, but the mixture of activators was dissolved in 0.1 g N, N-phthaloylaminoperoxycaproic acid (Example 21) dissolved in 1 g water and 1 g water. Except 0.1 g cetylpyridinium chloride (Example 22).

(Example 23)
A controlled release system produces 0.3 g of polyethyleneimine (BASF Lupasol ™) and 0.15 g of Nacconol ™ in 5 mL of water to produce a suspension. And are mixed. This suspension is then deposited on one of the two largest surfaces of a melamine foam substrate having a thickness of about 14 mm and a weight of about 1.1 g before being filled with the controlled release system. A second melamine foam substrate of approximately equal thickness and weight is then adhered to a surface filled with a controlled release system of the first melamine foam. A cleaning tool is thus obtained.

(Example 24)
The active agent described in the above examples is sprayed in an amount of about 25 g / m ² onto a polyethylene film having a basis weight of 30 g / m ^{2 from} Tacolin or Clopay. The polyethylene film filled with the activator is then laminated to another unused polyethylene film in an ultrasonic discontinuous bond pattern, followed by needle punching at a hole density of 1500 holes / m ² with a 1 mm diameter needle. (Needle punching may be performed prior to ultrasonic lamination). The perforated and laminated polyethylene film is then laminated between two melamine foam substrates each having a thickness of 14 mm and a weight of about 1.1 g before being filled with the controlled release system. A cleaning tool is thus obtained.

(Example 25)
The same steps are taken as in Example 24, except that the polyethylene film is replaced by a polypropylene nonwoven (100% PP Melten 65 g / m ² SMS from Tenotext).

(Example 26)
The same steps are taken as in Example 24, but one side of the polyethylene film is not subjected to needle punching, and the polyethylene film laminate (thin layer) is then about 23 mm thick and about before being applied with the controlled release system. Lamination between a melamine foam substrate having a weight of 1.85 g and an open cell polyurethane foam substrate having a thickness of about 6 mm (Sweetane ™ series by Recticel ™) Except that an unperforated film is attached to the polyurethane foam substrate.

(Example 27)
The same steps as in Example 26 are taken except that the needle punched polyethylene film is replaced by a microporous polyethylene film (MD stretched HBBS 40 g / m ^{2 from} RKW).

  All documents cited in “Best Mode for Carrying Out the Invention” are incorporated herein by reference in their relevant parts, and any citation of any document is prior art with respect to the present invention. It should not be interpreted as approval. 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 given to that term in this document shall apply And

  While particular embodiments herein 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. Accordingly, it is intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

1 is a perspective view of an embodiment of a cleaning implement herein having an erodible foam substrate and a second substrate. FIG. The perspective view of embodiment of the cleaning tool of this specification which has a base material of three layers of a slanting square pillar shape. FIG. 3 is a perspective view of an embodiment of a cleaning implement herein having a second substrate and two layers of semi-permeable film. FIG. 4 is an exploded view of the cleaning tool shown in FIG. 3.

Claims (21)

(A) an erodible foam substrate;
(B) a cleaning tool comprising a controlled release system comprising an active agent selected from the group consisting of surfactants, bleaches, limescale reducing agents, biocides, solvents, and mixtures thereof.   The cleaning implement of claim 1, wherein the controlled release system comprises a component selected from the group consisting of a polymer matrix, microcapsules, a particulate porous carrier, a complexing agent, a semipermeable film, and combinations thereof. .   The cleaning implement according to claim 1, wherein the erodible foam substrate is a melamine foam substrate.   The cleaning implement according to claim 1, wherein the controlled release system is in the form of beads or powder having a particle size of about 1 micron to about 400 microns.   3. A cleaning implement according to claim 2, wherein the controlled release system comprises a polymer matrix and the active agent is absorbed or dissolved in the polymer matrix or chemically linked to the polymer matrix.   6. The polymer matrix of claim 5, wherein the polymer matrix comprises a monomer selected from the group consisting of olefin, acrylic acid, acrylate, ether, vinyl alcohol, vinyl pyrrolidone, urethane, siloxane, sugar, ethyleneimine, and mixtures thereof. Cleaning tool.   The cleaning implement according to claim 2, wherein the controlled release system comprises a microcapsule comprising a shell encapsulating the active agent.   The cleaning implement according to claim 2, wherein the controlled release system comprises a particulate porous carrier, and the active agent is releasably filled into the pores of the particulate porous carrier.   9. A cleaning implement according to claim 8, wherein the particulate porous support is selected from the group consisting of zeolite, silica, porous carbon, and mixtures thereof.   The cleaning implement according to claim 2, wherein the controlled release system comprises a complexing agent that binds the active agent.   11. A cleaning implement according to claim 10, wherein the complexing agent is cyclodextrin.   The controlled release system includes a first semipermeable film and a second film, a semipermeable film or a liquid impermeable film, wherein the active agent is a first semipermeable film and a second film; The cleaning tool according to claim 2, which is applied in the middle of the above.   The cleaning implement according to claim 1, comprising a second substrate attached to the erodible foam substrate by adhesive bonding means.   14. The cleaning implement of claim 13, wherein the second substrate is a polymer closed cell foam substrate comprising a monomer selected from the group consisting of urethane, propylene, ethylene, vinyl acetate, esters, and mixtures thereof. .   14. A cleaning implement according to claim 13, wherein the controlled release system comprising an active agent is contained in the adhesive bonding means.   The cleaning tool includes a three-layer substrate in a sandwich-type configuration, wherein the erodible foam substrate is disposed as at least one of the outer layers attached to the intermediate layer by adhesion. The cleaning tool described in 1.   The cleaning tool according to claim 16, wherein the intermediate layer is a liquid impermeable layer.   The cleaning tool of claim 1, wherein from about 5% to about 20% by weight of the active agent contained in the cleaning tool is present in the cleaning tool in free form.   A method for cleaning the hard surface by bringing the cleaning tool of claim 1 into contact with the hard surface.   20. The method of cleaning a hard surface according to claim 19, wherein the method further comprises the step of wetting the cleaning tool with a suitable solvent before contacting the cleaning tool with the hard surface.   21. A method of cleaning a hard surface according to claim 20, wherein the suitable solvent is water.

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