TOILET CLEANING COMPOSITIONS

Abstract: A toilet composition comprising at least 50 % by weight of a relatively inert thermoplastic moldable water soluble organic polymer. Additional components of the toilet composition will be active components such as cleansing and disinfecting agents, and certain inert materials such as fillers. The composition is formed into a shaped element by a process involving melting the polymer component.

Description: TOILET CLEANING COMPOSITIONS Technical Field This invention relates to compositions for use as toilet bowl cleaners. These compositions are provided in the form of blocks which can either be for in-cistern use or for rim-block use i.e. the block can be immersed in the water in the cistern which flushes the toilet or can be placed beneath the rim ofthe toilet so that, on flushing, water fed to the toilet through the rim passes over the block. Background Art Toilet cleansing blocks have traditionally been sold as blocks as such or incorporated in structures which are positioned under the surface the cistern water to dissolve slowly and release the content into the cistern water. Release can be improved by incorporating the block into an in-tank release system. By enclosing the block in a container a more accurate dose can be delivered particularly since the enclosure ofthe block in a container will limit the contact with the amount of water rather than the full cistern content so improving block duration. These blocks generally comprise a combination of solid surfactants, usually anionic, particularly linear alkyl benzene sulphonates. This is particularly true of blocks used for location at the toilet rim. The blocks can also contain sequestrants or chelating agents such as phosphates to prevent deposition of or to remove limescale; acids such as a sulphamic acid to prevent deposition or to remove limescale and possibly to provide bactericidal properties; bactericides, germicides, preservatives, quaternaries, bleach or other materials providing disinfectant properties; surface property affecting components such as silanes which can interact with the toilet surface to provide long term cleaning action or a reduced surface adhesion for stains; enzymes or other stain removing agents. Also bonding agents can be included to assist in forming the structure ofthe block and to bind the components together, such binding agents have usually comprised a minor proportion ofthe total block. Other optional components can be additional surfactants; and bleaching agents such as dichloroisocyanurates and fragrances. In patent applications corresponding to U.S. patent application 08/253,243 there is disclosed the possibility of using a polyvinyl alcohol or polyvinyl acetate as a water soluble or relatively easily water dispersible polymer in a toilet cleanser block. There is no appreciation that other water soluble polymers may be desirable as these agents nor that addition of use of other water soluble or easily water dispersible materials may have advantages because of compatibility ofthe other components in these compositions and providing for greater control over duration, hardness and degree of swelling under hydration. Compositions of this general type in block form have been prepared which contained polymers to act as a binding agent as to affect the rheostatic properties but these have been in minor proportions and there has been no reason to add a major proportion of such polymers so as to constitute the principal component ofthe composition. Polymers in this manner is described for example in EP-A-18344 WO 92/03,532 and WO 82/01319. See also Japanese specification JP 3224923 and US-A-4,861,511, US-A-4, 765,921 and US-A- 4,269,723. In US-A-5,1 10,868 there is described a solid composition containing a hydroxy acetic acid/lactic acid polymer which can be used in a toilet bowl cleaning material. Description ofthe Invention According to the present invention there is provided a solid shaped toilet composition comprising at least 50% of a relatively inert thermoplastic moldable water soluble organic polymer, the remainder ofthe composition comprising active components and inert filler components the composition being in the form of shaped elements which have been formed by a shaping process involving heating to melt the polymer. Preferably the block contains at least 60% of the water soluble polymer. Preferably the shaped element is a shaped block. Best Modes for Carrying Out the Invention By a water soluble polymer is meant a polymer which in solid form when exposed to water will dissolve or disperse in the water without leaving any significant solid residue. A relatively inert polymer is used which unlike the other components does not contribute to cleansing, fragrance or surface activity. Such polymers include hydroxypropylmethylcellulose, methylcellulose, hydroxypropylcellulose, polyethyleneoxides but can include water soluble synthetic polymers such as acrylic polymers, polyvinylpyrrolidone and certain water soluble natural products such as arabic gum, karaya gum or pectins and gelatins. Not included in the invention is a composition comprising primarily polyvinyl alcohol or polyvinyl acetate with from 1 to 20% of fragrance, 0 to 20% of foaming agents, 0 to 20% of hydrophobic silica and 0 to 5% of at least one surfactant. Particular polymers which can be used include water soluble polymerized acrylonitrile; butadiene and styrene polymers; acetal copolymers; acetal homopolymers; acrylics; alkyds; allyls; aminos; cellulosics; epoxies; fluoroplastics; furans; ionomers; nitrile barrier resins; nylons; phenolics; phenylene-oxide based resins; poly (amide-imide); polyaryl ethers; polyaryl sulfones; polybutadienes; polybutylenes; polycarbonates; polyesters; polyethersulfones; polyethylenes; polyimides; polyphenylene sulfides; polypropylenes; polystyrenes; polysulfones; polyurethanes; polyvinyls; silicones; salts of heavy metals cellulose sulfates; other water soluble materials such as gelatin and gelatin derivatives of which gelatin is the main radical; colloidal albumen; hydrolyzed polyvinyl acetate; hydrolysed cellulose acetate hydrolysed to an acetyl content of 19 - 26%; polyacrylamide or an imidized polyacrylamide; zein; polyvinyl alcohol; a vinyl alcohol polymer containing urethane carboxylic acid groups; or containing cyanoacetyl groups such as the vinyl alcohol-cyanoacetate vinyl copolymer; or a polymer material which results from polymerizing protein with a monomer having a vinyl group. Other naturally occurring colloids such as agar-agar, Irish moss, pectin, starch, shellac, rosin, xanthene gums, gum arabic, guar gum, naturally occurring or synthetic alginates such as salts of water soluble heavy metals of sodium, potassium and magnesium; and any combination of mixtures thereof. The most suitable members of these classes comprise those colloids which have pronounced water soluble, water sensitive or water swellable properties such as gelatin, zein, xanthene gums, guar gum, gum arabic, alginates, cellulose acetate, metal salts of cellulose sulfate, cellulose acetate, metal salts of cellulose sulfate, cellulose ether phthalate, copolymer of 80% acrylic acid and 20% ethyl acrylate, polytriglycol adipamide, polyvinyl alcohol, poly (ethylene) oxide, polyacrylic acid, styrene-maleic anhydrite copolymer, polyurethanes, polyacrylamides, poly (vinyl pyrroiidone) and mixtures thereof. It must be noted however that certain of these polymers do have forms which are not water-soluble and these are not included in the present invention. Also the polymer must be resistant to degradation on heating so as to be meltable for forming of the shaped elements. A blend of two or more polymers may be employed. In selecting polymers of different solubility one could use a blend of polymers of different solubility one could use a blend of polymers for example polyvinylacetate and polymer of lower solubility. The additional components ofthe block will be active components by which is meant that they will have some cleansing, disinfecting or other property recognized as desirable in a block of this type. Also included can be certain inert materials which are fillers, for example, silica. Thus, as indicated active components which are usable in this type of block are anionic, nonionic, cationic or amphoteric surfactants, water-soluble bleaching agents, fragrance materials, sequestrants or chelating agents such as phosphonates, acids such as sulphamic acid, bactericides, germicides, preservatives, quaternaries, surface modifying agents such as silanes, stain removing agents such as enzymes and other active components. A block according to the invention can be provided with an appropriate dispensing structure, for example, a cage or suspension means for a rim block. The water soluble polymer must be chosen to be compatible with the remaining components of the system and, particularly if bleaches are to be included, polymers other than polyvinylalcohol/polyvinylacetate may be desirable. Thus, hydroxypropylmethylcellulose or polyvinylpyrrolidone in combination with bleach components as will as other components such as surfactants, fragrances, fillers would provide an improved rim block structure bleaching agent. There could be employed bleach polymers in which chlorine/oxygen releasing groups are incorporated into the polymer backbone, for example, polyvinyl pyrroiidone peroxide. In another embodiment ofthe invention the block ofthe invention will be incorporated in a dispensing unit formed with walls of water soluble polymeric sheet. In a particularly preferred embodiment ofthe invention a block according to the invention is provided which is stored between opposite heat sealed sheets to provide a control over the release ofthe components ofthe block on exposure to water. A structure of this type is disclosed in US-A 4,797,221. The block comprises the water soluble polymer specified above which can be formed from water-insoluble soft monomer; water-soluble anionic monomer; water-soluble nonionic monomer and water-insoluble hard monomer. The exact composition ofthe polymer would depend on the desired solubility characteristics ofthe final product block. By adjusting the components ofthe monomers a polymer is obtained for the block which has the desired solubility characteristics. The block can then contain the above other components being active and inert components as specified. This block can then be placed between two sheets which are heat sealed and which are water soluble sheets produced from an additional polymer comprising: i) A water-insoluble soft monomer such as alkyl acrylates with an inclusion level from O to 85%; ii) A water-soluble anionic monomer such as acrylic acid with an inclusion level from 15 to 100%; iii) A water-soluble nonionic monomer such as hydroxyalkyl acrylates with an inclusion level from 0 to 25%; iv) A water-insoluble hard monomer such as the polymerisable ethylenically unsaturated monomers (for example methacrylate) with an inclusion level of from 0 to 40%. The block to be included in such a structure could include the block described in US application 08/253,243 as described above. Such a combination would take advantage of both the properties ofthe block and surrounding walls ofthe structure of envelope of water soluble polymer. In a modification of this concept there could be used a conventional surfactant block. In another embodiment ofthe invention the blocks include high foaming agents. Such foaming agents would not have been incorporated in blocks comprising predominantly surfactants since the foaming would be unnecessary and in fact might have been regarded as counter-productive. Included in the blocks ofthe present invention they increase the foam and cleaning properties ofthe water soluble based polymer blocks. The specialized high foaming materials include saponins, high molecular weight polyethyleneglycols, high molecular weight celluloses, fluoro surfactants, amine oxides, betaines, sarcosinanes, taurates and protein based foam boosters. These cooperate with the blocks containing a high proportion of water soluble polymer to ensure delivery of foam when cleaning. If the shaped elements particularly blocks according to the invention are combined with an in-tank container system such as is described in U.S. patent application 08/398,040 a more accurate dosing is provided arising from the combination ofthe nature ofthe block and the surrounding container. The enclosed and limited water contact provided by an in- system container system benefits the duration ofthe blocks ofthe invention. Because ofthe soluble nature of certain ofthe polymers such as polyvinylacetate there is reduced life is used as simple in-system blocks as compared to one installed in a surrounding container structure. One particular method of producing the shaped elements involves absorbing components such as fragrance components on to silica or other inert filler in a blender, for example a ribbon-blender, combining the remaining components particularly surfactants, foaming agent and the soluble polymer in for example a main extruder feed hopper to which is then added the silica fragrance components for example through a side feeder. The resulting melt can be pressurized into strands, cooled and pelletized. These pellets can be used as such or they can then be injection molded. Accordingly, this embodiment of the invention comprises forming the material to be used in the blocks into pellets either simultaneously or in stages including blending the components either simultaneously or in stages and optionally injection molding the resulting pellets. In this process if one uses polymers of different water solubility one can combine with the initial basic polymers such as polyvinylacetate and, as mentioned above, a polymer of lower solubility either by direct feed into the original extruder or by introduction as pellets in the mix fed to the injection molding system. Blocks according to the present invention can also be combined with blocks of other materials for example traditional surfactant based blocks. Also a block according to the present invention in which the main components are fragrance based rather than cleansing components could be combined with a standard surfactant based room block structure to enhance the properties such as fragrance ofthe total structure. Industrial Applicability Advantages ofthe blocks according to the present invention are that they are smaller and more robust and have a more dense structure that hitherto available. These smaller blocks are advantageous over surfactant based blocks because they are more easily fittable into the modern smaller slim-lined in-cistern containers. Previous in-cistern containers of larger size created problems because ofthe lack of space within the cistern which made it difficult to mount the container without interference with the cistern mechanism. The blocks being injection molded rather than extruded allows for greater flexibility in shaping ofthe sizing ofthe finished block. Moreover the components ofthe block particularly in view of components such as polyvinyl acetate can ensure a major proportion is bio-degradable as compared to alkyl benzene sulfonates. It is a particular feature ofthe invention that the blocks are formed by heating to melt method for example injection molding. Blocks formed by injection molding are prepared over pellets formed by heat extrusion. However, the invention includes use by heat extrusion. However, the invention includes use of heat extruded elements e.g. pellets which can be placed in a container (which also can be ofthe water soluble polymer).

Claims: Claims: 1. A toilet composition comprising at least about 50% by weight of a relatively inert thermoplastic moldable water soluble organic polymer; and at least one active component. 2. The toilet composition of claim 1, wherein the composition is a shaped element. 3. The toilet composition of claim 2, wherein the shaped element is a block. 4. The toilet composition of claim 1, wherein the water soluble polymer comprises about 60% by weight ofthe composition. 5. The toilet composition of claim 1 , wherein the water soluble polymer is selected from the group consisting of hydroxypropylmethylcellulose, methylcellulose, hydroxypropylcellulose, polyethyleneoxides, acrylic polymers, polyvinylpyrrolidone, arabic gum, karaya gum, pectins, gelatins and mixtures thereof. 6. The toilet composition of claim 1 , wherein the water soluble polymer is selected from the group consisting of water soluble polymerized acrylonitrile; butadiene and styrene polymers; acetal copolymers; acetal homopolymers; acrylics; alkyds; allyls; aminos; cellulosics; epoxies; fluoroplastics; furans; ionomers; nitrile barrier resins; nylons; phenolics; phenylene-oxide based resins; poly (amide-imide); polyaryl ethers; polyaryl sulfones; polybutadienes; polybutylenes; polycarbonates; polyesters; polyethersulfones; polyethylenes; polyimides; polyphenylene sulfides; polypropylenes; polystyrenes; polysulfones; polyurethanes; polyvinyls; silicones; salts of heavy metals cellulose sulfates; gelatin; gelatin derivatives of which gelatin is the main radical; colloidal albumen; hydrolyzed polyvinyl acetate; hydrolysed cellulose acetate hydrolysed to an acetyl content of 19 - 26%; polyacrylamide; imidized polyacrylamide; zein; polyvinyl alcohol; a vinyl alcohol polymer containing urethane carboxylic acid groups; a vinyl alcohol polymer containing cyanoacetyl groups; agar-agar, Irish moss, pectin, starch, shellac, rosin, xanthene gums, gum arabic, guar gum, naturally occurring or synthetic alginates; and mixtures thereof. 7. The toilet composition of claim 1 , wherein the water soluble polymer is selected from the group consisting of gelatin, zein, xanthene gums, guar gum, gum arabic, alginates, cellulose acetate, metal salts of cellulose sulfate, cellulose acetate, metal salts of cellulose sulfate, cellulose ether phthalate, copolymer of 80% acrylic acid and 20% ethyl acrylate, polytriglycol adipamide, polyvinyl alcohol, poly (ethylene) oxide, polyacrylic acid, styrene-maleic anhydrite copolymer, polyurethanes, polyacrylamides, poly (vinyl pyrroiidone) and mixtures thereof. 8. The toilet composition of claim 1 further comprising a foaming agent. 9. A method of cleaning a toilet comprising introducing the composition of claim 1 into a toilet. 10. A process for forming a shaped solid toilet composition comprising introducing a sufficient amount of heat to the composition of claim 1 to melt the polymer, and shaping the composition. 11. The process for forming a shaped solid toilet composition according to claim 10 wherein the heating to melt is achieved by injection molding.

Inventors: CAMPBELL STUART J, FERRANDO JEAN-CHRISTOPHE, CAMPBELL, STUART, J., FERRANDO, JEAN-CHRISTOPHE
Applicants: CAMPBELL STUART J, FERRANDO JEAN CHRISTOPHE, JOHNSON & SON INC S C, CAMPBELL, STUART, J., FERRANDO, JEAN-CHRISTOPHE, S.C. JOHNSON & SON, INC.
Application year: 1996
Main classification: C11D17
IPC codes: C11D3, C11D17