Composition for making compressed cleaning articles

Abstract

The present invention is a cleaning composition comprising a binder, a gas generating agent, an acid, and at least about 0.1% water. The cleaning article has an aged Shore A hardness of at least about 10, an aged Shore D hardness of up to about 100, and a dissolution time of about 1 minute to about 60 minutes.

Description

[Technical field]

[0001] The present invention relates generally to the field of cleaning compositions. In particular, the present invention is a toilet cleaning composition. [Background technology]

[0002] Cleaning toilets is an unpleasant but necessary task. Current methods of cleaning toilets typically involve applying a cleaning agent into the toilet bowl and then scrubbing the bowl with a handheld tool. The handheld tool typically includes bristles or a cleaning head that can be used to scrub the interior surface of the toilet bowl to remove debris and soil. The need to manually clean the toilet bowl requires the person cleaning the toilet to be in close proximity to the toilet, a condition that most people find unappealing.

[0003] In an attempt to achieve greater distance from the toilet bowl while still cleaning it, various products have been developed that can be dropped into the toilet bowl to clean debris and dirt without the need to scrub the bowl by hand. However, most of these products contain bleach or other harsh chemicals with their unpleasant, harsh odors and problematic environmental profiles to kill microbial soils. Other products do not contain bleach but do not clean the toilet bowl adequately. Summary of the Invention

[0004] In one embodiment, the present invention is a cleaning composition comprising a binder, a gas generating agent, an acid, and at least about 0.1% water. The cleaning article has an aged Shore A hardness of at least about 10, an aged Shore D hardness of up to about 100, and a dissolution time of about 1 minute to about 60 minutes.

[0005] In another embodiment, the invention is a solid cleaning composition that includes an inorganic binder that hardens upon reaction with water, a gas generating agent, an acid, and a water-containing liquid. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0006] The present invention is a composition that can be used to manufacture compressed cleaning articles. The composition provides foaming, effervescence, and acidity after dissolving in water. Furthermore, the composition can be compressed into a solid article at low temperature. The composition has good stability at both room temperature and high temperature. In one embodiment, the composition can be used with other materials such as surfactants, fragrances, abrasives, minerals, and colorants to allow the creation of a wide range of cleaning articles. Furthermore, the composition of the present invention is environmentally friendly and harmless to humans and the environment. The composition is completely soluble in water and leaves minimal residue after cleaning. The important characteristics of the composition can be tailored to specifically enhance the oxidizing power, acidity, or foaming required by product development needs. The composition can be molded into a cleaning article under pressure at room temperature. The cleaning article can be gradually dissolved in the presence of water and provides foaming, effervescence, acidity, and abrasive properties that allow for effective cleaning. In one embodiment, the composition is used to clean and / or remove stains such as hard water stains from a toilet bowl.

[0007] The composition generally includes a binder, a gas generating agent, an acid, and a water-containing liquid. In one embodiment, the composition includes about 1% to about 50% by weight of the binder, about 10% to about 50% by weight of the gas generating agent, about 15% to about 70% by weight of the acid, and about 0.1% to about 20% by weight of the water-containing liquid. In particular, the solid state composition includes about 5% to about 30% by weight of the binder, about 20% to about 30% by weight of the gas generating agent, about 15% to about 45% by weight of the acid, and about 1% to about 5% by weight of the water-containing liquid.

[0008] Binders function to hold the components of the composition together. They must be strong enough to retain mechanical integrity and provide hardness to the composition until it comes into contact with water, at which point the composition can dissolve. Binders can form covalent bonds, ionic bonds, hydrogen bonds, van der Waals interactions, or other secondary interactions in the presence of water-containing liquids to chemically or physically hold the components of the composition together. Binders can be inorganic or organic, or a combination of both. Binders can be chemically reactive or non-reactive during the bonding process.

[0009] In one embodiment, the binder is an inorganic binder that reacts with water to harden the composition. Hardening means that the binder reacts with water to form a new hydrated form or that the binder condenses and crosslinks in the presence of water. The hardened binder provides structural support to the composition, making it resistant to degradation caused by water. During the hardening process, the binder can form hydrogen bonds with other components, improving the structural integrity of the composition. Compared to non-reactive binders, the use of inorganic binders that are reactive with water can significantly improve the hardness and mechanical integrity of the composition after the composition is compressed at room temperature under the same amount of force. After forming a compressed article, a composition containing a reactive inorganic binder can maintain sufficient hardness, mechanical integrity, and durability for scrubbing and cleaning, while minimizing swelling of the formed shape when contacted with water, for example, in a toilet bowl. The strong binding ability of reactive inorganic binders allows the durability of the compressed article when used in water or in a wet environment. The durability of the compressed article in the wet state can be quantified by the number of cycles that the compressed article can move back and forth linearly at a selected path length (5 cm, 10 cm, 20 cm) and speed, or the selected number of cycles and speed on a circular path, under a specific applied weight (0.5 kg, 1.0 kg, 2.0 kg, 5 kg, 10 kg) in the wet state on a suitable machine, such as a Taber Linear Abraser or Taber Rotary Platform Abrasion Tester (North Tonawanda, NY). By wet state, it is meant that the compressed article is immersed in water and then removed or remains immersed in water during the test. To simulate the use of the compressed article in water or in a wet environment, a compressed article having a cylindrical shape (diameter 4 cm, height 0.25 cm, 0.38 cm, 0.50 cm or 0.56 cm) is first immersed in water to allow complete penetration of the water into the compressed article, pressed against a hard surface, and then held by hand and moved back and forth over a path length of about 20 cm. The compressed articles are believed to exhibit sufficient "wet firmness," i.e., sufficient mechanical integrity and durability, when used in a wet state.The compressed article lathers and foams when rubbed against a hard surface with manually applied force, and gradually loses mass during the simulated cleaning process.

[0010] Compressed articles containing non-reactive binders lose their hardness and mechanical integrity or swell when used in water for a short period of time, for example within about 2 minutes. The hardness of the composition can be measured by compressing a durometer of Shore A or D on the surface of the composition, for example according to the following procedure described in ASTM D 2240-00. The aged hardness is the hardness measured on a compressed composition that has been aged in air at room temperature for 2 weeks. Examples of particularly suitable reactive inorganic binders include, but are not limited to, calcium sulfate hemihydrate, anhydrous calcium sulfate, sodium silicate, sodium metasilicate, potassium silicate, potassium metasilicate, lithium metasilicate, lithium silicate, cement, and combinations thereof. Examples of particularly suitable reactive inorganic binders include, but are not limited to, calcium sulfate hemihydrate-based compounded binder compositions such as DURABOND 20, DURABOND 45, and DURABOND 90 available from USG, Chicago, IL.

[0011] Examples of particularly suitable organic binders include, but are not limited to, sugars (such as glucose, fructose, galactose, sucrose, lactose, maltose, and liquid glucose), organic acid salts (such as sodium acetate, calcium acetate, sodium propanoate, sodium glycolate, and sodium citrate), polymers (such as hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose, gelatin, gum arabic, chitosan, alginic acid, starch, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, acrylate polymers, polyurethanes, styrene butadiene rubber, polyesters, polyamides, polyethyleneimines, vinyl polymers, and the like), and combinations thereof.

[0012] Water or water-containing liquids function as reactants with the binder, serve as a medium for other components in the composition to react, and serve as a carrier for additives. Reactive inorganic binders can react with the water in the water-containing liquid to harden and provide hardness and mechanical integrity to the composition. Water in the water-containing liquid can also function as a medium for acids and gas generating agents to react to produce more water, which creates hydrogen bonds in the composition to improve hardness and mechanical integrity. The water-containing liquid has a water content sufficient to react with the binder. In one embodiment, the water-containing liquid has a water content of at least about 0.1%, particularly at least about 1% by weight. Examples of suitable water-containing liquids include, but are not limited to, water, aqueous solutions of inorganic compounds, aqueous solutions of polymers, aqueous dispersions of polymers, aqueous dispersions of organic molecules, liquid organic compounds, mixtures of liquid water and organic compounds, aqueous solutions of organic compounds, and combinations thereof. Examples of suitable liquids include, but are not limited to, deionized water, an aqueous solution of calcium chloride, an aqueous solution of calcium acetate, an aqueous solution of sodium acetate, an aqueous solution of polyacrylic acid and its sodium salts, an aqueous solution of polyvinyl alcohol, an aqueous solution of polyvinylpyrrolidone, an aqueous solution of polyethylene glycol, an aqueous solution of polyethyleneimine, an aqueous solution of polystyrene sulfonic acid, an aqueous solution of polyester, an aqueous dispersion of polyurethane, an aqueous dispersion of polyvinyl acetate, an aqueous dispersion of styrene butadiene rubber, an aqueous dispersion of polyacrylate, an aqueous dispersion of polyamide, an aqueous dispersion of polyolefin, an aqueous dispersion of rosin and its derivatives, a mixture of water and acetic acid, a mixture of water and lactic acid, an aqueous solution of glycolic acid, and an aqueous solution of gluconic acid, an aqueous dispersion of fragrance, an aqueous dispersion of pigment, an aqueous solution of dye, and combinations thereof.

[0013] The gas generating agent functions as a foaming agent to create bubbles / foam. By generating bubbles and / or foam, the composition can reach additional surface area. Examples of suitable gas generating agents include, but are not limited to, carbon dioxide generating agents and oxygen generating agents. Examples of suitable carbon dioxide generating agents include, but are not limited to, bicarbonates of Group I metals, Group II metals and other cations, including ammonium, alkyl (mono-, di-, or tri-) ammonium, or transition metals; carbonates of Group I metals, Group II metals and other cations, including ammonium, alkyl (mono-, di-, or tri-) ammonium, or transition metals; and percarbonates of Group I metals, Group II metals and other cations, including ammonium, alkyl (mono-, di-, or tri-) ammonium, or transition metals. Examples of particularly suitable carbon dioxide generating agents include, but are not limited to, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, and calcium bicarbonate.

[0014] Examples of suitable oxygen generating agents include, but are not limited to, hydrogen peroxide; peracetic acid generated from sodium percarbonate / TAED (tetraacetylethylenediamine); percarbonate salts of Group I metals, Group II metals, and other cations, including ammonium, alkyl (mono-, di-, or tri-) ammonium, or those of the transition metals; chloride and peroxide salts of Group I metals, Group II metals, and other cations, including ammonium, alkyl (mono-, di-, or tri-) ammonium, or those of the transition metals; superoxide salts of Group I metals, Group II metals, and other cations, including ammonium, alkyl (mono-, di-, or tri-) ammonium, or those of the transition metals; peroxide salts of Group I metals, Group II metals, and other cations, including ammonium, alkyl (mono-, di-, or tri-) ammonium, or those of the transition metals.

[0015] The acid functions as both a foaming agent and a cleaning agent. The acid can be any solid form of organic or inorganic acid. Examples of suitable acids include, but are not limited to, sodium bisulfate, sulfamic acid, glycolic acid, maleic acid, benzoic acid, and succinic acid.

[0016] Other additives can be included in the composition to perform various functions. Examples include, but are not limited to, chelating agents, surfactants, oxidizing agents, biocides, antimicrobial agents, anti-caking agents, hydrophilic agents, dispersing agents, co-binders, fillers / tougheners, softeners, abrasive particles, drying agents, release agents, lubricants, disintegrants, detergents, coupling agents, photoinitiators, thermal initiators, viscosity modifiers, adhesion promoters, grinding aids, wetting agents, dispersing agents, light stabilizers, antioxidants, defoamers, colorants, dyes, pigments, and fragrances. Particularly suitable additives include ingredients that help improve the stability of the composition before compression and formation of the compressed article. Examples include anti-caking agents, dispersing agents, and co-binders. Additives that are particularly suitable for aiding in the release of the compressed article include, but are not limited to, release agents and lubricants.

[0017] When a chelating agent is included in the composition, it functions primarily as a complexing agent with metal ions dissolved in water or precipitated on toilet surfaces as soil. It also promotes cleaning and foaming. Examples of suitable chelating agents include, but are not limited to, citric acid and its sodium salt, ethylenediaminetetraacetic acid (EDTA) and its sodium salt, ethyleneglycoltetraacetic acid (EGTA) and its sodium salt, and maleic acid and its sodium salt.

[0018] When surfactant is included in the composition, it is used as a cleaning agent and foaming agent.Suitable examples of surfactants include, but are not limited to, anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, oligomeric and polymeric surfactants.Suitable examples of anionic surfactants include, but are not limited to, alkyl and alkyl ether sulfates, sulfated monoglycerides, sulfonated olefins, alkylarylsulfonates, primary or secondary alkane sulfonates, alkyl sulfosuccinates, acid taurates, alkyl sulfoacetates, acid isethionates, alkyl glyceryl ether sulfonates, sulfonated methyl esters, sulfonated fatty acids, alkyl phosphates, acyl glutamates, acyl sarcosinates, alkyl lactylates, anionic fluorosurfactants, sodium lauroyl glutamate, and combinations thereof. Additional suitable anionic surfactants include those disclosed in U.S. Patent Application No. 61 / 120,765 and those disclosed in McCutcheon's Detergents and Emulsifiers, North American Edition (1992), Allured Publishing Corp. Examples of suitable nonionic surfactants include, but are not limited to, polyoxyethylenated alkylphenols, polyoxyethylenated alcohols, polyoxyethylenated polyoxypropylene glycols, glyceryl esters of alkanoic acids, polyglyceryl esters of alkanoic acids, propylene glycol esters of alkanoic acids, sorbitol esters of alkanoic acids, polyoxyethylenated sorbitol esters of alkanoic acids, polyoxyethylene glycol esters of alkanoic acids, polyoxyethylenated alkanoic acids, alkanolamides, N-alkylpyrrolidones, alkyl glycosides, alkyl polyglucosides, alkyl amine oxides, and polyoxyethylenated silicones.Examples of suitable cationic surfactants include, but are not limited to, those selected from the class of "quaternary ammonium" substances, including, but not limited to, cetyltrimethylammonium chloride, behenyltrimethylammonium chloride, stearyltrimethylammonium chloride, cetylpyridinium chloride, octadecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octyldimethylbenzylammonium chloride, decyldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride, didodecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, distearyldimethylammonium chloride, tallowtrimethylammonium chloride, cocotrimethylammonium chloride, dipalmitoylethyldimethylammonium chloride, PEG-2 oleylammonium chloride, and salts thereof where the chloride is replaced by a halogen (e.g., bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfate, or alkyl sulfate. Examples of suitable zwitterionic and amphoteric surfactants include, but are not limited to, amine oxides, betaines (carboxylic acid / quaternary ammonium or carboxylic acid / phosphonium), sulfobetaines or carboxybetaines, sultaines (sulfonic acid / quaternary ammonium or sulfonic acid / phosphonium), amino acid derivatives, imidazoline derivatives, lecithins, and phospholipids. Examples of suitable polymeric surfactants include, but are not limited to, block copolymers of ethylene oxide and aliphatic alkyl residues, block copolymers of ethylene oxide and propylene oxide, hydrophobically modified polyacrylates, hydrophobically modified celluloses, silicone polyethers, silicone copolyol esters, diquaternary polydimethylsiloxanes, and co-modified amino / polyether silicones.

[0019] When the composition includes an oxidizing agent, the oxidizing agent functions to oxidize organic soils and remove bacteria. Examples of suitable oxidizing agents include, but are not limited to, sodium persulfate, potassium persulfate, ammonium persulfate, sodium percarbonate, carbamide peroxide, polyvinylpyrrolidone-hydrogen peroxide complex, sodium perborate, peracetic acid, and combinations thereof. Examples of suitable commercially available oxidizing agents include, but are not limited to, Oxone available from Dupont, Wilmington, DE. In one embodiment, when the solid state composition includes an oxidizing agent, the solid state composition includes up to about 15% by weight of oxidizing agent, particularly up to about 5% by weight of oxidizing agent.

[0020] The composition may optionally include a biocide to eliminate bacteria. Examples of suitable biocides include, but are not limited to, benzalkonium chloride, sodium dichloroisocyanurate, benzoisothiazolinone chlorhexidine, quaternary ammonium derivatives, and combinations thereof. In one embodiment, when the composition includes a biocide, the solid state composition includes up to about 5% by weight of the biocide, particularly up to about 2% by weight of the biocide.

[0021] The composition has an acidic pH, making it favorable for cleaning surfaces such as toilet bowls that are etched by protons in aqueous solutions. Furthermore, hard water stains and limescale can be dissolved under acidic conditions. A basic pH is favorable for the formation of hard water stains and organic deposits on toilet bowls. It is therefore desirable for the composition to have an acidic pH. In one embodiment, the composition has a pH of about 0 to about 6, particularly about 1 to about 5, and especially about 2 to about 5, when dissolved in water.

[0022] Due in part to its low pH, the composition can effectively remove a variety of debris and soils, such as hard water soils and limescale. In practice, the composition must come into contact with a sufficient amount of water or a mixture of water and a polar solvent to initiate the necessary reaction to clean the intended surface. When the composition is exposed to water, it dissolves and begins to foam. The water serves as the medium in which the reaction occurs. The acid and gas generating agent react to release carbon dioxide, which rises through the aqueous solution of the surfactant to the surface, generating bubbles in the solution and forming a foam layer on the surface. The foaming allows the composition to contact hard-to-reach surfaces, such as the underside of the inner surface of a toilet bowl. In one embodiment, a sufficient amount of foam is generated to have a foam height of at least about 0.1 cm, at least about 0.5 cm, at least about 0.75 cm, at least about 1 cm, at least about 1.25 cm, at least about 1.5 cm, at least about 1.75 cm, at least about 2 cm, and at least about 3 cm.

[0023] The composition has two important features: cleaning efficacy and the ability to be molded into various shapes at room temperature. Cleaning efficacy includes foaming, effervescence, acidity, and abrasive properties to remove hard water soils, limescale, and organic soils from the surface being cleaned. In one embodiment, the composition can be added to water, and the cleaning efficacy is static, without the use of mechanical force. In one embodiment, the composition can be used as a scrubber on a surface, and the cleaning efficacy is a complex combination of electrostatic cleaning efficacy and mechanical force scrubbing. Additional features of the composition, including fragrance, color, oxidizing power, and antimicrobial properties, can be incorporated into the base formulation of the composition to allow for the creation of a wide range of cleaning products. In one embodiment, the composition can remove at least about 25%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95% of hard water soils. In one embodiment, the solid form composition is capable of removing at least about 25%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95% of the limescale.

[0024] After being molded into a condensed solid form, the composition provides sufficient mechanical integrity, hardness, toughness, and durability to be used on hard surfaces. In one embodiment, the solid state composition is in the form of a tablet or pod that can be dropped, for example, into a toilet bowl to provide cleaning. In one embodiment, the composition can be molded into a cleaning head and used with a handheld tool. This provides a dissolvable head that functions as a cleaning tool and also provides the chemicals required for cleaning. Thus, the solid state composition has the dual functionality of being used as a tablet and / or used on a handle. The solid state composition can also be first used on a handle to clean with mechanical force and then released into water for static cleaning.

[0025] The composition must have a certain hardness and durability such that it does not immediately dissolve or decompose when in contact with water, and must remain in solid state form for a sufficient time to contact and clean the surface. In one embodiment, the composition has an aged Shore A hardness of at least about 30, specifically at least about 30, more specifically at least about 50 to about 100, and even more specifically at least about 80. In one embodiment, the solid state composition has an aged Shore D hardness of about 10 to about 100, particularly about 20 to about 70. The amount of time that the composition remains in solid state form can be measured as dissolution time, which is defined as the time it takes for 5 grams of the solid state composition to disintegrate and dissolve when immersed in 195 grams of water without agitation after aging in air at ambient conditions for 2 weeks. The solid state composition has a dissolution time that is optimal for scrubbing the surface to be cleaned. In one embodiment, the solid state composition has a dissolution time of about 1 minute to about 60 minutes, particularly about 5 minutes to about 40 minutes, and particularly about 10 minutes to about 30 minutes.

[0026] To produce the solid state composition of the present invention, the ingredients are mixed together. If a fragrance is present, the composition must include an anti-caking agent. In one embodiment, the anti-caking agent is hydrophobic. Examples of suitable anti-caking agents include, but are not limited to, fumed silica, fumed alumina, clay, and cornstarch. The anti-caking agent and fragrance are mixed first, then mixed with an optional surfactant to form a premix, and the premix is ​​then mixed with the remaining mixture of ingredients. The final mixture of the composition is added to a cavity or mold where mechanical force is applied to compress the mixture into a compressed article. The compressed article can take any shape without departing from the intended scope of the present invention. After the compressed article is removed from the cavity or mold, it is aged in air or in a closed environment at ambient conditions to harden over time. In one embodiment, the resulting solid state composition is compressed to form a tablet. In one embodiment, the solid state composition is wrapped by a water-soluble polymeric film to form a pod. EXAMPLES

[0027] Unless otherwise stated or readily apparent from the context, all parts, percentages, ratios, etc. in the examples and elsewhere in the specification are by weight.

[0028] [Table 1]

[0029] Test Method Tablet Hardness - Shore Hardness Shore hardness is a measure of the resistance a material has to indentation. A higher value indicates greater resistance to indentation and therefore a harder material. A lower number indicates less resistance and a softer material. A handheld durometer was used to measure the Type A and Type D Shore hardness of the example tablets (Model 3000 by Rex Gauge, Buffalo Grove, IL) according to the ASTM D2240-00 testing protocol. Unless otherwise noted below, the example tablets tested had a diameter of about 4 cm, a thickness of 0.63 cm, and a density of about 1.5 g / cm. 3 Unless otherwise stated below, the values ​​in the tables are the average of at least three measurements taken on a single tablet.

[0030] Tablet properties - dissolution time, pH, foaming, residue: Prior to testing, the tablets to be tested were aged in air at ambient conditions for 2 weeks. 5 g tablet pieces were broken off from the tablets. Approximately 195 g of water was added to a 1 liter glass beaker and the tablet pieces were dropped into the water. The time it took for the tablet pieces to dissolve to the maximum amount in the beaker without stirring was recorded. After dissolution was complete, the pH was measured using pH paper. Effervescence (foam height) and residue remaining in the water were visually assessed.

[0031] Preparation Example Preparation Example 1 (PEx1): Preparation of a sodium carbonate-based powder formulation 2.7 g of sodium persulfate, 23.6 g of sodium bisulfate, 26.1 g of sodium carbonate, 42.1 g of citric acid, 1.3 g of SIPERNAT 50S, and 0.007 g of Duasyn Ink Blue SLK were added to a glass vial followed by hand swirling. 2.5 g of LATHANOL LAL, 1.5 g of STEPANOL WA-100 NF / USP, and 0.30 g of SZ 41894 Citrus were added to another glass vial followed by hand swirling and then further mixing with a spatula until a homogenous mixture was obtained. The two separate mixtures were combined, then swirled by hand and mixed with a spatula. The resulting powder mixture was free flowing.

[0032] [Table 2]

[0033] Working Example Example 1 (Ex1T Tablet) 40.0 g of the prepared PEx1 mixture was added to a glass jar, followed by 5.0 g of DURABOND 45. The resulting mixture was rolled by hand, followed by the addition of 1.0 g of DI water. A spatula was then used to stir the mixture until it was a uniform solid mixture. 15.0 g of the mixture was added to the cylindrical cavity of a Teflon die of a tablet press (Hydraulic Unit Model #3912, Carver Inc. Wabash, IN). The diameter of the cavity was 4.0 cm and the fill height of the cavity was 5.0 cm. The weight applied to the plunger was 2500 pounds, applying a pressure of 1284 psi. The mixture was allowed to dwell in the die for 1 minute at 1284 psi before the pressure was released. The tablets (Ex1T) were removed from the cavities and inspected. The tablets were observed to have good initial strength and integrity. After inspection, the fresh tablets were stored in air at ambient conditions followed by a second inspection after 24 hours. The tablets were again observed to have good strength and integrity. The dry aged tablets were held in the hand and rubbed against a hard surface to assess their integrity for use as a handheld tool. The tablets held up well under the forces typically used for effective cleaning. The aged tablets were immersed in water to make them wet, pressed against a hard surface, and then held in the hand and moved back and forth over a path length of approximately 20 cm. The wet tablets exhibited good hardness, mechanical integrity and durability. They foamed and effervescent when rubbed against a hard surface with force from the hand.

[0034] [Table 3]

[0035] Example 2 (Ex2T tablets) 40.0 g of the prepared PEx1 mixture was added to a glass jar, followed by 5.0 g of DURABOND 45. The resulting mixture was rolled by hand, followed by 2.0 g of DI water. A spatula was then used to stir the mixture until it was a uniform solid mixture. 15.0 g of the mixture was added to a cylindrical die of a tablet press, and tablets were prepared under the same conditions as described for ExT1 above. The tablets (Ex2T) were removed from the cavities and inspected. The tablets were observed to have good initial strength and integrity. After inspection, the fresh tablets were stored in air at ambient conditions, followed by a second inspection after 24 hours. The tablets were again observed to have good strength and integrity. The aged tablets were held in the hand and rubbed against a hard surface to assess their integrity for use as a handheld tool. The tablets held well under forces typically used for effective cleaning. The aged tablets were moistened by immersion in water, pressed against a hard surface, and then manually moved back and forth over a path length of approximately 20 cm. The moist tablets exhibited good hardness, mechanical integrity, and durability. They foamed and effervescent when rubbed against a hard surface with manual force.

[0036] [Table 4]

[0037] Example 3 (Ex3T tablets) 40.0 g of the prepared PEx1 mixture was added to a glass jar, followed by 5.0 g of DURABOND 45. The resulting mixture was rolled by hand, followed by 2.6 g of DI water. A spatula was then used to stir the mixture until it was a uniform solid mixture. 15.0 g of the mixture was added to the cylindrical die of a tablet press, and tablets were prepared under the same conditions as described for ExT1 above. The tablets (Ex3T) were removed from the cavities and inspected. The tablets were observed to have good initial strength and integrity. After inspection, the fresh tablets were stored in air at ambient conditions, followed by a second inspection after 24 hours. The tablets were again observed to have good strength and integrity. The aged tablets were held in the hand and rubbed against a hard surface to assess their integrity for use as a handheld tool. The tablets held well under forces typically used for effective cleaning. The aged tablets were moistened by immersion in water, pressed against a hard surface, and then manually moved back and forth over a path length of approximately 20 cm. The moist tablets exhibited good hardness, mechanical integrity, and durability. They foamed and effervescent when rubbed against a hard surface with manual force.

[0038] [Table 5]

[0039] Example 4 (Ex4T tablets) 40.0 g of the prepared PEx1 mixture was added to a glass jar, followed by 5.0 g of DURABOND 45 and 1.0 g of POLYOX WSR 205. The resulting mixture was rolled by hand, followed by 2.0 g of DI water. A spatula was then used to stir the mixture until it was a uniform solid mixture. 15.0 g of the mixture was added to the cylindrical die of a tablet press and tablets were prepared under the same conditions as described for ExT1 above. The tablets (Ex4T) were removed from the cavities and inspected. The tablets were observed to have good initial strength and integrity. After inspection, the fresh tablets were stored in air at ambient conditions followed by a second inspection after 24 hours. The tablets were again observed to have good strength and integrity. The aged tablets were held in the hand and rubbed against a hard surface to assess their integrity for use as a handheld tool. The tablets held well under forces typically used for effective cleaning.

[0040] [Table 6]

[0041] Example 5 (Ex5T tablets) 40.0 g of the prepared PEx1 mixture was added to a glass jar, followed by 5.0 g of DURABOND 45 and 1.0 g of poly(acrylic acid) (Mv approx. 1,250,000). The resulting mixture was rolled by hand, followed by 2.0 g of DI water. A spatula was then used to stir the mixture until it was a uniform solid mixture. 15.0 g of the mixture was added to a cylindrical die of a tablet press and tablets were prepared under the same conditions as described for ExT1 above. The tablets (Ex5T) were removed from the cavities and inspected. The tablets were observed to have good initial strength and integrity. After inspection, the fresh tablets were stored in air at ambient conditions followed by a second inspection after 24 hours. The tablets were again observed to have good strength and integrity. The aged tablets were held in the hand and rubbed against a hard surface to assess their integrity for use as a handheld tool. The tablets held well under forces typically used for effective cleaning.

[0042] [Table 7]

[0043] Example 6 (Ex6T tablets) 40 g of the prepared PEx1 mixture was added to a glass jar, followed by 5.0 g of DURABOND 45. The resulting mixture was rolled by hand, followed by 3.65 g of SOKALAN CP10. A spatula was then used to stir the mixture until it was a uniform solid mixture. 15.0 g of the mixture was added to a cylindrical die of a tablet press, and tablets were prepared under the same conditions as described for ExT1 above. The tablets (Ex6T) were removed from the cavities and inspected. The tablets were observed to have good initial strength and integrity. After inspection, the fresh tablets were stored in air at ambient conditions, followed by a second inspection after 24 hours. The tablets were again observed to have good strength and integrity. The aged tablets were held in the hand and rubbed against a hard surface to assess their integrity for use as a handheld tool. The tablets held well under forces typically used for effective cleaning. The aged tablets were moistened by immersion in water, pressed against a hard surface, and then manually moved back and forth over a path length of approximately 20 cm. The moist tablets exhibited good hardness, mechanical integrity, and durability. They foamed and effervescent when rubbed against a hard surface with manual force.

[0044] [Table 8]

[0045] Example 7 (Ex7T tablets) 40 g of the prepared PEx1 mixture was added to a glass jar, followed by 5.0 g of DURABOND 45. The resulting mixture was rolled by hand, followed by 4.0 g of SOKALAN CP10S. A spatula was then used to stir the mixture until it was a uniform solid mixture. 15.0 g of the mixture was added to the cylindrical die of a tablet press, and tablets were prepared under the same conditions as described for ExT1 above. The tablets (Ex7T) were removed from the cavities and inspected. The tablets were observed to have good initial strength and integrity. After inspection, the fresh tablets were stored in air at ambient conditions, followed by a second inspection after 24 hours. The tablets were again observed to have good strength and integrity. The aged tablets were held in the hand and rubbed against a hard surface to assess their integrity for use as a handheld tool. The tablets held well under forces typically used for effective cleaning.

[0046] [Table 9]

[0047] Shore A and Shore D hardness measurements were performed on the tablets of Examples ExT4-ExT7 after aging for 1 day according to the tablet hardness test method described above. The results are summarized in Table 9.

[0048] [Table 10]

[0049] Examples 8 to 15 (Ex8T to Ex15T tablets) Compositions containing various amounts of calcium sulfate hemihydrate and SOKALAN CP10 were prepared according to the formulations shown in Table 10. For each example formulation, LATHANOL LAL and STEPANOL WA-100 NF / USP were first mixed together and then SIPERNAT 50S was added to the mixture. This was followed by sequential addition of citric acid, sodium bisulfate, sodium carbonate, calcium sulfate hemihydrate and pumice to the mixture. After each component was added, the resulting mixture was mixed for approximately 30 to 60 seconds either manually or with a spatula or mechanical blender. Finally, SOKALAN CP10 was added to the powder mixture and the final mixture was further mixed until it was uniform and free-flowing.

[0050] To prepare tablets of each composition, 30.0 g of the final mixture was added to the cylindrical die of a tablet press as described for ExT1 above. The weight applied to the plunger was 2500 lbs, exerting a pressure of 1284 psi. The mixture was allowed to reside in the die for 1 minute at 1284 psi before the pressure was released. The tablets were removed from the cavities and inspected. Tablets Ex8T-Ex15T were observed to have good initial strength and integrity.

[0051] [Table 11]

[0052] Shore D hardness measurements were performed on the tablets of Examples ExT8-ExT15 after aging for 24 hours according to the tablet hardness test method described above. The results are summarized in Table 11.

[0053] [Table 12]

[0054] Additional Shore D hardness measurements were performed on tablets of Examples Ex12T-Ex15T according to the Tablet Hardness Test Method described above, including additional aging after 4, 7 and 14 days. The results are summarized in Table 12. Each value is the average of four data points for one tablet.

[0055] [Table 13]

[0056] Examples 16 to 23 (Tablets Ex16T to 23T) The compositions of Examples 16-23 were prepared according to the formulations shown in Table 13, and tablets were formed for each composition using the procedure described above for Examples 8 to 15. Tablets Ex16T-Ex23T were observed to have good initial strength and integrity.

[0057] [Table 14]

[0058] Shore D hardness measurements were performed on tablets of Examples ExT16-ExT23 after aging for 24 hours according to the Tablet Hardness Testing Method described above. The results are summarized in Table 14. N / A means that the hardness value was not measured.

[0059] [Table 15]

[0060] Further properties of some example tablets were investigated as described in the Tablet Property Test Methods above. The results are summarized in Table 15.

[0061] [Table 16]

[0062] Comparative Example Comparative example CEx1 (CEx1T) 40 g of the prepared PEx1 mixture was added to a glass jar, followed by 5.0 g of calcium carbonate. The resulting mixture was rolled by hand, followed by 2.0 g of DI water. A spatula was then used to stir the mixture until it was a uniform solid mixture. 15.0 g of the mixture was added to a cylindrical die of a tablet press, and tablets were prepared under the same conditions as described for ExT1 above. The tablets (CEx1T) were removed from the cavities and inspected. The tablets were broken by applying gentle force by hand. After inspection, the broken tablets were stored in air at ambient conditions, followed by a second inspection after 24 hours. The tablets were broken again by applying gentle force by hand.

[0063] [Table 17]

[0064] Comparative example CEx2 (CEx2T) 40 g of the prepared PEx1 mixture was added to a glass jar, followed by 5.0 g of calcium sulfate dihydrate. The resulting mixture was rolled by hand, followed by 2.0 g of DI water. A spatula was then used to stir the mixture until it was a uniform solid mixture. 15.0 g of the mixture was added to the cylindrical die of a tablet press, and tablets were prepared under the same conditions as described for ExT1 above. The tablets (CEx2T) were removed from the cavity and inspected. The tablets were broken by applying gentle force by hand. After inspection, the broken tablets were stored in air at ambient conditions at room temperature in a fume hood, followed by a second inspection after 24 hours. The tablets were broken again by applying gentle force by hand.

[0065] [Table 18]

[0066] Comparative example 3T (CEx3T) 40 g of the prepared PEx1 mixture was added to a glass jar, followed by 2.0 g of DI water. A spatula was then used to stir the mixture until it was a uniform solid mixture. 15.0 g of the mixture was added to the cylindrical die of a tablet press and tablets were prepared under the same conditions as described for ExT1 above. The tablets (CEx3T) were removed from the cavity and inspected. Initial strength was low and some of the tablets broke upon removal from the die. After inspection, the fresh tablets were stored in air at ambient conditions followed by a second inspection after 24 hours. Tablet strength improved after aging. Aged tablets were rubbed against a hard surface held by hand to assess their integrity as a handheld tool and broke during the rub test.

[0067] [Table 19]

[0068] Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes can be made in form and detail without departing from the spirit and scope of the invention.

Claims

Claim 1 A cleaning article, comprising: a binder; a gas generating agent; an acid; at least about 0.1% water; and the cleaning article has a Shore A hardness after aging of at least about 10, a Shore D hardness after aging of at most about 100, and a dissolution time of about 1 minute to about 60 minutes. Claim 2 The cleaning article according to claim 1, wherein when the cleaning article contains an anti-caking agent, the anti-caking agent is hydrophobic. Claim 3 The cleaning article according to claim 1, wherein the binder is an inorganic binder. Claim 4 The cleaning article according to claim 3, wherein the inorganic binder reacts with the water. Claim 5 The cleaning article according to claim 1, wherein the binder is one of calcium sulfate hemihydrate, silicate, anhydrous calcium sulfate, metasilicate, or cement. Claim 6 The cleaning article according to claim 1, wherein the cleaning article has a Shore A hardness after aging of at least about 30. Claim 7 The cleaning article according to claim 1, wherein the cleaning article has a dissolution time of about 5 minutes to about 40 minutes. Claim 8 The cleaning article according to claim 1, wherein the cleaning article has a pH of about 0 to about 6 when dissolved in water. Claim 9 The cleaning article according to claim 1, wherein the cleaning article has cleaning efficiency when used with or without mechanical force. Claim 10 A solid cleaning composition, comprising: an inorganic binder that reacts with water to harden and form a hardened structure; a gas generating agent; an acid; and a water-containing liquid.