A solid toilet block composition

Abstract

The present invention is in the fields of hard surface cleaning compositions, particularly it relates to a solid toilet block composition that sustains for a longer time in use. It provides enhanced long-lasting cleaning and hygiene benefit. There is a need to provide an improved solid toilet block composition., The present invention provides a composition having a combination of select silane and a quaternary ammonium compound, in presence of an anionic surfactant comprising at least an alkyl benzene sulphonate and a non-ionic surfactant, provides a toilet block composition. The composition is obtained by extrusion process. It provides superior cleaning and hydrophobicity to a hard surface. It reduces water retention and / or soil deposition on the surface, thereby delays the requirement of frequent cleaning.

Description

[0001] A SOLID TOILET BLOCK COMPOSITION

[0002] Field of the Invention

[0003] The present invention is in the fields of hard surface cleaning compositions. Particularly it relates to a solid toilet block composition that sustains for a longer time in use. It provides enhanced long-lasting cleaning and hygiene benefit.

[0004] Background of the Invention

[0005] Cleaning hard surfaces like, kitchen tops, tiles, table-top, cupboards, wash basin and toilet bowls are part of house-hold chores. Often consumers spend considerable amount of time and effort in such cleaning activities. They prefer to use various cleaning products for the same. Such products differ in their constituents, such as detersive actives, acids, builder, colourants; as well, they are available in different formats, such as powder, liquid, toilet block, spray, foam, and wipe.

[0006] Hard surfaces, particularly like, toilet bowls, urinals, bathroom tiles or wash basin are continuously in contact with water, they are prone to scaling, microbial growth, and deposition of soil. Thus, consumers may require frequent cleaning of those surfaces adding to their efforts. It is desired that a cleaning product provides a cleaning performance, which sustains for a longer period, thereby reduces requirement of frequent cleaning, and subsequently reduces consumer efforts. One of the ways to deliver long-lasting cleaning benefit is by depositing a layer of a hydrophobic material on a surface while cleaning. It reduces water retention on the surface and thus reduces the accumulation of scaling, dirt deposition and microbial growth.

[0007] It is further desired to provide a product in a solid format, such as toilet block. Toilet block is one of the product formats, where a composition is formulated in a solid shape. Consumers often dose one of such blocks in the flush tank of a toilet or placed inside the toilet bowl or urinals attaching to the rim. Typically, it provides cleaning benefit with each flush or flowing of the water. Consumer often find a toilet block is convenient to use for maintaining clean and hygienic toilet, as it requires minimal intervention.

[0008] A toilet block differs from other solid shaped product format, like a tablet, particularly in terms of dissolution time. Tablets are primarily formulated to dissolve quickly and release a cleaning active rapidly. On the other hand, a toilet block is supposed to dissolve at significantly slower and constant rate with each flush and doses a portion of cleaning active. It is desired that a toilet block sustains several flushes and last for a longer period in use.

[0009] In this regards, US 2019 / 0375871 A1 describes copolymers obtainable form free-radical copolymerisation at least of the following components: (a)cationic monomers selected from the group consisting of cationic (meth)acrylamide monomers and diallyl dimethyl ammonium chloride, (b)polyethylene glycol macromonomers, and (c)uncharged acrylamide monomers. The copolymers are suitable for using in detergent compositions providing advantageous shine results.

[0010] EP 1 767 554 A1 describes a water-soluble amphoteric terpolymers containing acrylic or methacrylic acid, alkyl acrylamides, and N-isopropylacrylamide as monomer building blocks. The polymers are suitable for using in hard surface cleaners.

[0011] EP 2 872 613 discloses self-adhesive sanitary compositions comprising a saccharide component selected from mono- or disaccharide, sugar alcohols or mixtures thereof, surfactant and residual water in an amount of 1 to 5% by weight.

[0012] WO 2022 / 175695 discloses effervescent solid compositions for cleaning and / or disinfecting all surfaces in the form of a compressed tablet containing an effervescing component, a germicidal agent and a non-ionic surfactant, but free of any anionic surfactant.

[0013] Further WO 2023 / 180053 discloses a solid hard surface cleaning composition comprising from 0.1 to 20% by weight of a quaternary ammonium compound and an alkyl sulfate, wherein the weight ratio of the quaternary ammonium compound to the alkyl sulfate ranges from 1.5:1 to 3.5:1 ; and wherein the quaternary ammonium compound comprises didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium saccharinate, octyl decyl dimethyl ammonium chloride, alkyl dimethyl ethyl benzyl ammonium chloride, methyldodecylbenzyl ammonium chloride, methyldodecylxylene- bis-trimethyl ammonium chloride, methyl benzethonium chloride, cetyl pyrinidinium chloride, cetrimonium bromide or mixtures thereof. Despite the prior art documents, still there is a need for an improved solid toilet block composition providing that sustains for a longer time in use and provides an enhanced long- lasting cleaning and hygiene benefit.

[0014] Surprisingly it has been found that a combination of select silane compound and a quaternary ammonium compound, in presence of an anionic surfactant comprising at least an alkyl benzene sulphonate, and a non-ionic surfactant provides a toilet block composition. The composition is obtained by extrusion process. It sustains several flushes and last for a longer period in use. It provides superior cleaning and hydrophobicity to the surface of a toilet bowl or urinal, such that it reduces water retention and / or soil deposition on the surface. Thereby it delays the requirement of frequent cleaning.

[0015] Summary of the Invention

[0016] According to the first aspect of the present invention, there is provided a solid hard surface cleaning composition comprising: a) 5 to 65% by weight of an anionic surfactant comprising at least an alkyl benzene sulphonate; b) a non-ionic surfactant; c) a quaternary ammonium compound; and d) 0.01 to 5% by weight of a silane having formula:

[0017] (ORi)3-x(R2)x-Si-R3;

[0018] Wherein,

[0019] Ri is hydrogen or a C2 to C4 alkyl group,

[0020] X has value of 0 or 1 or 2, R2 is a C1 to C6 alkyl group, R3 is a C1 to C18 hydrocarbon group selected from alkyl, phenyl, allyl, vinyl, at least one oxygen or nitrogen substituted non-ionic or cationic hydrocarbon group, and O is oxygen, C is carbon and Si is silicone.

[0021] In another aspect of the present invention, there is provided a process of making the toilet block composition comprising steps of: a) providing:

[0022] (i) 5 to 65% by weight of an anionic surfactant comprising at least an alkyl benzene sulphonate;

[0023] (ii) a non-ionic surfactant; (iii) a quaternary ammonium compound; and

[0024] (iv) 0.01 to 5% by weight of a silane having formula(l):

[0025] (OR1)3-x(R2)x-Si-R3;

[0026] Wherein,

[0027] R1 is hydrogen or a C1 to C4 alkyl group,

[0028] X has value of 0 or 1 or 2,

[0029] R2 is a C1 to C6 alkyl group,

[0030] R3 is a C1 to C18 hydrocarbon group selected from alkyl, phenyl, allyl, vinyl, at least one oxygen or nitrogen substituted non-ionic or cationic hydrocarbon group, and O is oxygen, C is carbon and Si is silicone, in a container; b) mixing the ingredients thoroughly, thereby proving a solid mass; and c) extruding the solid mass to form the toilet block.

[0031] According to another aspect of the present invention, there is provided a process for treating a surface comprising steps of: a) providing a solid hard surface cleaning composition according to the first aspect; b) placing the composition in contact with the surface; and, c) flushing composition with water.

[0032] Detailed Description of the Invention

[0033] Any feature of one aspect of the present invention may be utilized in any other aspect of the invention. The word “comprising” is intended to mean “including” but not necessarily “consisting of” or “composed of.” In other words, the listed steps or options need not be exhaustive. Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and / or use are to be understood as modified by the word “about”. Numerical ranges expressed in the format "from x to y" are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format "x to y", it is understood that all ranges combining the different endpoints are also contemplated. Unless specified otherwise, amounts as used herein are expressed in percentage by weight based on total weight of the composition and is abbreviated as “wt%”. The use of any and all examples or exemplary language e.g. “such as” provided herein is intended merely to better illuminate the invention and does not in any way limit the scope of the invention otherwise claimed. Room temperature is defined as a temperature of about 20° Celsius.

[0034] Accordingly, there is provided a solid toilet block composition comprising an anionic surfactant, a non-ionic surfactant, a quaternary ammonium compound and a silane. The anionic surfactant comprises at least an alkyl benzene sulphonate.

[0035] Anionic surfactant

[0036] The composition comprises 5 to 65% by weight of an anionic surfactant. More preferably the composition comprises 7 to 60% by weight, even more preferably 10 to 55% and most preferably 15 to 50% by weight of the anionic surfactant.

[0037] The anionic surfactant comprises at least an alkyl benzene sulphonate. Preferably the alkyl benzene sulphonate in the composition constitutes 20 to 100% by weight, more preferably 30 to 100% by weight and most preferably 40 to 100% by weight of the total amount of the anionic surfactant.

[0038] The anionic surfactant comprises alkyl benzene sulphonates that include water-soluble alkali metal salts of organic sulphonates having alkyl radicals typically containing from about 8 to about 22 carbon atoms, preferably 8 to 18 carbon atoms, still more preferably 12 to 15 carbon atoms and may be saturated or unsaturated. The alkyl benzene sulphonate preferably is a salt selected from alkali metal salts, earth alkaline metal salts, ammonium salts and combinations thereof. More preferably, the alkyl benzene sulphonate is an alkali metal salt, most preferably a sodium salt. Preferably the alkyl benzene sulphonate is C8-18 alkyl benzene sulphonate, and more preferably C10-14 alkyl benzene sulphonate. Sodium C10-14 alkyl benzene sulphonate is a preferred alkyl benzene sulphonate suitable for the invention.

[0039] Examples of other sulphonated surfactant that may additionally present in the composition include alkyl toluene sulphonate, alkyl xylene sulphonate, alkyl phenol sulphonate, alkyl naphthalene-sulphonate, ammonium di-amyl naphthalene-sulphonate and sodium di-nonyl naphthalene-sulphonate and mixtures with olefin sulphonates.

[0040] The anionic surfactant may further comprise other anionic surfactant, such as alkyl ether sulphate or primary alcohol sulphate, alkyl sulphate and combinations thereof. The anionic surfactant may further comprise an alkyl ether sulphate or primary alcohol sulphate having the formula:

[0041] (Ri-(OR2)n-O-SC>3')x Mx+, wherein:

[0042] Ri is saturated or unsaturated Cs to Ci6, preferably C12 to C14 alkyl chain; preferably, R1 is a saturated Csto Cie, more preferably a saturated C12 to C14 alkyl chain; R2is ethylene; n is from 1 to 18; preferably from 1 to 15, more preferably from 1 to 10, still more preferably from 1 to 5; x is 1 or 2. Mx+is a suitable cation which provides charge neutrality selected from sodium, calcium, potassium, magnesium, or organic counterions.

[0043] The alkyl ether sulphates are typically made as condensation products of ethylene oxide and monohydric alcohols having from about 8 to about 24 carbon atoms. The alcohols can be synthetic, or they can be derived from fats, e.g., coconut oil, palm kernel oil, tallow. Synthetic alcohols may include the grades available via Shell Chemical Co under the NEODOL trade name as NEODOL 91 (C9-11 alcohols), NEODOL 23 (C12-13 alcohols), NEODOL 25 (C12-15 alcohols), NEODOL 45 (C14-15 alcohols), and NEODOL 135 (C11-C13-C15 alcohols). Lauryl alcohol and straight chain alcohols derived from coconut oil or palm kernel oil are preferred. Such alcohols are reacted with between 0 and 10, preferably from 2 to 5, or preferably 3, molar proportions of ethylene oxide, and the resulting mixture of molecular species having, for example, an average of 3 moles of ethylene oxide per mole of alcohol, is sulphated and neutralized.

[0044] Preferably the alkyl ether sulphate comprises 1 to 18, more preferably 1 to 15, even more preferably 1 to 10, yet more preferably 1 to 5 and most preferably 1 to 3 ethylene oxide units per molecule. Preferred alkyl ether sulphate is sodium lauryl ether sulphate having 1 to 3 ethylene oxide units per molecule, more preferred sodium lauryl ether sulphate having 1 to 2 ethylene oxide units per molecule.

[0045] Suitable alkyl sulphates include those having Cs to Cis, more preferably C10 to C16, even more preferably C12 to C14 alkyl chain. Preferably the counterion is a monovalent alkali metal, such as sodium, potassium; or polyvalent metal cations, such as magnesium; or an ammonium, alkanolamines, such as triethanolamine, such as sodium and potassium, and, and calcium. Suitable examples include alkyl sulphates from synthetic origin with the trade name Alfol 1412S. Further suitable examples, and preferred, include alkyl sulphates commercially available from natural sources with trade names Galaxy 689, Galaxy 780, Galaxy 789, Galaxy 799 SP, and Ufarol TCL 92N.

[0046] Examples of further anionic surfactants that may be considered in the present invention include alkyl suphfoacetate like e.g. sodium lauryl sulphoacetate, alkyl isothionae like e.g. sodium coco- isothionate, alky taurate like e.g. sodium methyl cocoyl taurate, secondary alkane sulphonate, and alpha olefin sulphonate like e.g. sodium C14-16 alpha olefin sulphonate.

[0047] The alkyl benzene sulphonate, alkyl sulphate, alkyl ether sulphate may be linear or branched, substituted or un-substituted. The alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzene sulphonate surfactant may be derived from petrochemical material, biomaterial, or a waste material.

[0048] Non-ionic surfactant

[0049] The composition comprises a non-ionic surfactant. Preferably the non-ionic surfactant is selected from alcohol ethoxylate, alkyl polyglycoside and combinations thereof.

[0050] Preferably the non-ionic surfactant is present in an amount from 0.5 to 10% by weight of the composition. More preferably the non-ionic surfactant is present in an amount from 1 to 9% by weight, even more preferably from 1 .5 to 8% by weight and most preferably from 2.0 to 7% by weight of the composition.

[0051] Preferably the non-ionic surfactant comprises alcohol ethoxylate. Suitable alcohol ethoxylates include water soluble aliphatic ethoxylated non-ionic surfactants including the primary aliphatic alcohol ethoxylates and secondary aliphatic alcohol ethoxylates. This includes the condensation products of a higher alcohol (e.g., an alkanol containing about 8 to 16 carbon atoms in a straight or branched chain configuration) condensed with about 4 to 20 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with about 10 moles of ethylene oxide (EG), tridecanol condensed with about 6 to 15 moles of EO, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to about 14 carbon atoms in length and wherein the condensate contains either about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol. Examples of the foregoing non-ionic surfactants include, but are not limited to, the Neodol (trade mark, ex Shell), which are higher aliphatic, primary alcohol containing about 9 to 15 carbon atoms, such as C9 to C11 alkanol condensed with 4 to 10 moles of ethylene oxide (Neodol 91-8 or Neodol 91-5), C12 to C13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C12 to C15 alkanol condensed with 12 moles ethylene oxide (Neodol 25-12), C14 to C15 alkanol condensed with 13 moles ethylene oxide (Neodol 45-13), and the like.

[0052] Examples of the non-ionic surfactant include the class of the fatty alcohol ethoxylate and are sold under the trade names of Brij 35, Brij 97, Brij700, Brij 99, Brij 56, Brij 76, C12EO7, and Brij S10. Preferred non-ionic surfactants of the fatty acid ethoxylate class are sold under the brand names of Myrj S20, Myrj S40, Myrj S40, Myrj S50, and PEG-100 stearate. Preferred non-ionic surfactants of the polyoxyethylene sorbitan alkyl esters class are sold under the brand names of Tween 21, Tween20, Tween40, Tween 60, Tween 65 tristearate, Tween 85 trioleate, and Tween 80. Preferred non-ionic surfactants of the alkyl phenol ethoxylate class are sold under the brand names of Triton X114, Triton X100, Triton X102, TritonX165, Triton X305, TritonX405 or Triton X705. It is observed that the above-mentioned non-ionic surfactants all have an HLB value higher than 10. Preferably the non-ionic surfactant is selected from the class of polyoxyethylene sorbitan alkyl ester. These surfactants are available under the trade name Tween or Triton, for example, Tween 20 (polyoxyethylene sorbitan monolaurate, HLB=16.7), Tween 40(polyoxyethylene sorbitan monopalmitate, HLB=15.6),Tween60 (polyoxyethylene sorbitan monostearate, HLB=14.9), Tween65 (polyoxyethylene sorbitan tristearate, HLB=10.5), TweenSO (polyoxyethylene sorbitan monooleate, HLB=15.0), Tween85 (polyoxyethylene sorbitan trioleate, HLB=11.0),Triton(octylphenol Ethoxylates), e.g., HLB=12.3), TritonX114 (HLB = 12.3), Triton ( HLB=13.4), Triton X102(HLB= 14.4), Triton X305(HLB=17.3), TritonX405( HLB=17.3), Triton X705 ( HLB=18.4) etc.

[0053] The other non-ionic surfactants suitable for the present invention include alkyl polyglycoside, poly-oxyethylene sorbitan alkyl esters, alkyl phenol ethoxylates.

[0054] The non-ionic surfactant in the composition may be an alkyl plolyglycoside. As used herein alkyl polyglycosides are compounds having formula RiO(R2O)b(Z)a, wherein Ri is a alkyl radical, having from about 8 to about 10 carbon atoms; R2is an alkylene radical having from 2 to 4 carbon atoms; Z is a saccharide residue having 5 or 6 carbon atoms; b is a number having a value from 0 to about 12; and a is a number having a value from 1 to about 6 (the degree of polymerization). Due to the method by which they are synthesized, alkyl polyglycosides are generally present as mixtures of alkyl polyglycosides having varying amounts of carbon atoms in the alkyl radical and varying degrees of polymerization. Thus, when referring to alkyl polyglycosides, the alkyl radical is generally referred to as having a range of carbon atoms (e.g., C8 / 10 referring to a range of alkyl radicals having from 8 to 10 carbon atoms) and the degree of polymerization is generally referred to as the average degree of polymerization of the mixture.

[0055] Preferred alkyl polyglycosides suitable for the invention include those having the formula RiO(R2O)b(Z)a, wherein Ri is a alkyl radical, having from about 8 to about 10 carbon atoms; R2is an alkylene radical having from 2 to 4 carbon atoms; Z is a saccharide residue having 5 or 6 carbon atoms; b is a number having a value from 0 to about 12; and a is a number having a value from 1 to about 6 (the degree of polymerization). Preferred alky polyglycoside are those where Z is a glucose residue, b is zero, Ri is an alkyl group that contains 8 to 10 carbon atoms, and the average value of a is about 1 to 2. Such alkyl polyglucosides are commercially available, for example, as Glucopon® branded alkyl polyglucoside compositions from BASF (formerly Cognis Corporation), including Glucopon® 215CS UP and 225 DK.

[0056] Quaternary ammonium compound

[0057] The composition comprises a quaternary compound. Preferably the composition comprises 0.01 to 7% by weight, more preferably 0.05 to 6% by weight, even more preferably 0.05 to 5% and most preferably 0.1 to 5% by weight of the quaternary ammonium compound.

[0058] Examples of quaternary ammonium compounds include alkyl ammonium halides such as cetyl trimethyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl ammonium bromide, N-alkyl pyridinium halides such as N-cetyl pyridinium bromide, and the like. One suitable type of quaternary ammonium compound includes, for example, those in which the molecules contain amine, ether or ester linkages such as octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, N-(lauryl coco amino formyl methyl)-pyridinium chloride, and the like. Another effective type of quaternary ammonium compound includes, for example, those in which the hydrophobic radical is characterized by a substituted aromatic nucleus as the case of lauryl oxyphenyl trimethyl ammonium chloride, cetyl amino phenyl trimethyl ammonium methosulphate, dodecyl phenyl trimethyl ammonium methosulphate, dodecyl benzyl trimethylammonium chloride, chlorinated dodecyl benzyl trimethyl ammonium chloride, and the like. Preferably, the quaternary ammonium compound utilized in the practice of the present technology exhibit biocidal activity or are biocidal in nature.

[0059] Particularly useful quaternary ammonium compound includes compositions which include a single quaternary compound, as well as mixtures of two or more different quaternary compounds. Such useful quaternary compounds are available under the EMPIGEN, BARDAC, BARQUAT, HYAMINE, LONZABAC, and ONYXIDE trademarks, which are more fully described in, for example, McCutcheon's Functional Materials (Vol. 2), North American Edition, 1998, as well as the respective product literature from the suppliers identified below.

[0060] For example, BARDAC 205M is described to be a liquid containing alkyl dimethyl benzyl ammonium chloride (BKC), octyl decyl dimethyl ammonium chloride; didecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloride (50% active) (also available as 80% active (BARDAC 208M)); described generally in McCutcheon's as a combination of alkyl dimethyl benzyl ammonium chloride and dialkyl dimethyl ammonium chloride); BARDAC 2050 is described to be a combination of octyl decyl dimethyl ammonium chloridedidecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloride (50% active) (also available as 80% active (BARDAC 2080)); BARDAC 2250 is described to be didecyl dimethyl ammonium chloride (50% active); BARDAC LF (or BARDAC LF-80), described as being based on dioctyl dimethyl ammonium chloride (BARQUAT MB-50, MX-50, OJ-50 (each 50% liquid) and MB-80 or MX-80 (each 80% liquid) are each described as an alkyl dimethyl benzyl ammonium chloride; BARDAC 4250 and BARQUAT 4250 Z (each 50% active) or BARQUAT 4280 and BARQUAT 4280Z (each 80% active) are each described as alkyl dimethyl benzyl ammonium chloride / alkyl dimethyl ethyl benzyl ammonium chloride. Also, HYAMINE 1622, described as diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride (50% solution); HYAMINE 3500 (50% actives), described as alkyl dimethyl benzyl ammonium chloride (also available as 80% active (HYAMINE 3500-80)); and HYMAINE 2389 described as being based on methyldodecylbenzyl ammonium chloride and / or methyldodecylxylene-bis-trimethyl ammonium chloride. (BARDAC, BARQUAT and HYAMINE are presently commercially available from Lonza, Inc., Fairlawn, N. J.). BTC 50 NF (or BTC 65 NF) is described to be alkyl dimethyl benzyl ammonium chloride (50% active); BTC 99 is described as didecyl dimethyl ammonium chloride (50% active); BTC 776 is described to be myrisalkonium chloride (50% active); BTC 818 is described as being octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloride (50% active) (available also as 80% active (BTC 818-80%)); BTC 824 and BTC 835 are each described as being of alkyl dimethyl benzyl ammonium chloride (each 50% active); BTC 885 is described as a combination of BTC 835 and BTC 818 (50% active) (available also as 80% active (BTC 888)); BTC 1010 is described as didecyl dimethyl ammonium chloride (50% active) (also available as 80% active (BTC 1010- 80)); BTC 2125 (or BTC 2125 M) is described as alkyl dimethyl benzyl ammonium chloride and alkyl dimethyl ethyl benzyl ammonium chloride (each 50% active) (also available as 80% active (BTC 2125 80 or BTC 2125 M)); BTC 2565 is described as alkyl dimethyl benzyl ammonium chlorides (50% active) (also available as 80% active (BTC 2568)); BTC 8248 (or BTC 8358) is described as alkyl dimethyl benzyl ammonium chloride (80% active) (also available as 90% active (BTC 8249)); ONYXIDE 3300 is described as n-alkyl dimethyl benzyl ammonium saccharinate (95% active). (BTC and ONYXIDE are presently commercially available from Stepan Company, Northfield, III). Benzyl-C12-14-alkyldimethylammonium chlorides benzyl C12- C16- alkyl dimethyl chlorides also available as EMPIGEN BAC 50 and EMPIGEN BAC 80. It is an aqueous solution of benzalkonium chloride at ca. 50% or 80% in water respectively.

[0061] EMPIGEN BAC 50 and EMPIGEN 80 are readily biodegradable, EMPIGEN is commercially available from Innospec Performance Chemicals

[0062] Polymeric quaternary ammonium salts based on these monomeric structures may also be considered for the present invention. One example is POLYQUAT, described as being a 2- butenyldimethyl ammonium chloride polymer. Examples of polymeric quaternary ammonium compound suitable for the invention include polyquaternium-10, quaternary ammonium salt of hydroxyethyl cellulose (available as UCARE™ Extreme Polymer form Dow chemicals), Polyquaternium-10, quaternary ammonium salts of hydroxyethyl cellulose ( available as UCARE™ JR-30M Polymer form Dow chemicals), a cationic laundry conditioning polymer, Cationic hydroxyethyl cellulose-Low Charge Density (available as SupraCare™ 133 Polymer from Dow chemicals), guar hydroxy propyl trimonium chloride (available Jaguar® C-500 STD form Solvay), guar hydroxypropyl trimonium chloride (available as Jaguar® Excel from Solvay) and combinations thereof.

[0063] Preferably the quaternary ammonium compound is selected from di-decyl dimethylammonium chloride, dioctyl dimethylammonium chloride, alkyl dimethyl benzyl ammonium chloride, diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium saccharinate, octyl decyl dimethyl ammonium chloride, alkyl dimethyl ethyl benzyl ammonium chloride, methyl dodecyl benzyl ammonium chloride, methyl dodecyl xylene-bis- trimethyl ammonium chloride, methyl benzethonium chloride, cetyl pyrinidinium chloride, cetrimonium bromide, polyquaternium-10, quaternary ammonium salt of hydroxyethyl cellulose (available as UCARE™ Extreme Polymer form Dow chemicals), Polyquaternium-10, quaternary ammonium salts of hydroxyethyl cellulose ( available as UCARE™ JR-30M Polymer form Dow chemicals), a cationic laundry conditioning polymer, Cationic hydroxyethyl cellulose-Low Charge Density (available as SupraCare™ 133 Polymer from Dow chemicals), guar hydroxy propyl trimonium chloride (available Jaguar® C-500 STD form Solvay), guar hydroxypropyl trimonium chloride (available as Jaguar® Excel from Solvay) and combinations thereof.

[0064] Most preferably the quaternary ammonium compounds are selected from benzalkonium chloride, di-decyl dimethylammonium chloride, quaternary ammonium salt of hydroxyethyl cellulose (available as UCARE™ Extreme Polymer form Dow chemicals), quaternary ammonium salts of hydroxyethyl cellulose ( available as UCARE™ JR-30M Polymer form Dow chemicals), a cationic laundry conditioning polymer, Cationic hydroxyethyl cellulose-Low Charge Density (available as SupraCare™ 133 Polymer from Dow chemicals), guar hydroxy propyl trimonium chloride (available Jaguar® C-500 STD form Solvay) and combinations thereof.

[0065] Preferably the composition comprises the quaternary ammonium compound in an amount less than that of the anionic surfactant. Preferably the ratio of the quaternary ammonium compound to the anionic surfactant is at least 1 : 1.5, more preferably at least 1: 2, even more preferably at least 1 : 5 and most preferably at least 1 : 7 by weight. Preferably the ratio of the quaternary ammonium compound to the anionic surfactant is in the range of 1:1.5 to 1: 40, more preferably 1 :2 to 1 :35 by weight and most preferably 1 : 5 to 1 : 30 by weight.

[0066] Silane

[0067] The composition comprises a silane of formula (I): (ORi)3-x(R2)x-Si-R3; wherein,

[0068] Ri is hydrogen or a C1 to C4 alkyl group,

[0069] X has value of 0 or 1 or 2, R2is a C1 to C6 alkyl group, R3 is a C1 to C18 hydrocarbon group selected from alkyl, phenyl, allyl, vinyl, at least one oxygen or nitrogen substituted non-ionic or cationic hydrocarbon group, and O is oxygen, C is carbon and Si is silicone.

[0070] Preferably R1 is linear or branched methyl, ethyl, propyl or butyl group. Most preferably R1 is ethyl or methyl group. Preferably R2 is C2 to C4 linear or branched alkyl group. Most preferably R2 is ethyl group. Preferably R3 is C4 to C18 linear or branched alkyl group. More preferably R3 is C6 to C18 linear alkyl group. Most preferably R3 is selected from isobutyl, octyl, hexadecyl, octadecyl group. Preferably the silane is non-ionic silane.

[0071] Preferably the silane is selected from isobutyl tri-ethoxy silane, isobutyl trimethoxy silane, octyl tri-ethoxy silane, octyl trimethoxy silane, octadecyl tri-ethoxy silane, octadecyl trimethoxy silane, octadecyl trimethoxy silane, octyl trimethoxy silane, hexadecyl trimethoxy silane and combinations thereof. Most preferred silane are selected from isobutyl tri-ethoxy silane, isobutyl trimethoxy silane, octyl tri-ethoxy silane, octyl trimethoxy silane and combinations thereof. Most preferred silane is isobutyl tri-ethoxy silane and / or isobutyl trimethoxy silane.

[0072] The composition comprises 0.01 to 5% by weight of the silane. Preferably the composition comprises 0.01 to 4% by weight, more preferably 0.01 to 3% by weight and event more preferably 0.01 to 2% by weight and most preferably 0.01 to 1% by weight of the silane.

[0073] It is observed that the quaternary ammonium compound along with the silane synergistically enhances the hydrophobicity on a surface. That is, the combination of the silane and the quaternary ammonium compound delivers a hydrophobicity benefit significantly higher than that of delivered by the silane and the quaternary ammonium compound individually.

[0074] Filler

[0075] Preferably the composition comprises a filler. Preferably the filler is selected from an inorganic salt of sulphate, carbonate, halide, phosphate and combination thereof. More preferably, said inorganic salt is selected from sulphate, carbonate and combinations thereof. If the composition comprises a carbonate filler, it is so chosen that it does not courses effervescence in contact with water.

[0076] The inorganic salt that may be employed as a filler in the composition is selected from alkali metal salts, earth alkaline metal salts, ammonium salts and combinations thereof. Preferably the filler is selected from alkali metal salts and most preferably it is selected from sodium salts. The composition may comprise 10 to 80% by weight of the filler. Preferably the composition comprises 15 to 70% by weight and most preferably 20 to 60% by weight of the filler.

[0077] In a preferred way, the filler in the composition contains at least 50% by weight, more preferably at least 60% by weight, even more preferably at least 70% by weight and more preferably at least 80% by weight of sodium sulphate. Most preferred filler is sodium sulphate.

[0078] Preferably the composition is free of an effervescent. Typically, an effervescent is in a solid composition is considered for faster dissolution. Often it comprises a carbonate or bicarbonate salt optionally with an acid, which in presence of water generates fizz, thereby accelerates disintegration of a solid composition. However, the composition according to the present invention is a solid toilet block, that dissolves significantly slow rate and releases a cleaning active with each flush. An effervescent may affect adversely said dissolution process, thus it is not preferred. The term “free of” herein refers as the composition comprises less than 3% by weight, more preferably less than 1 % by weight and most preferably less than 1 % by weight of an effervescent. In a most preferred scenario, the composition does not contain an effervescent.

[0079] Polyol

[0080] The composition may comprise a polyol. Preferably the polyol has a carbon chain length of 2 to 4. Suitable polyols include ethylene glycol, propylene glycol, 1 ,3-propanedio, glycerol, 1 ,3- butanediol, 1,2-butanediol, 1,4-butanediol, 2,3-butanediol and combinations thereof. Preferably the polyol has a carbon chain length of 3 and more preferably is glycerol.

[0081] Preferably, composition may comprise 0.5 to 15% by weight, more preferably 0.5 to 10% by weight and most preferably 0.5 to 8% by weight of the polyol.

[0082] Polymer

[0083] The composition according to the present inventions may comprises a polymer. It is observed that certain polymers aide in self-adhesiveness of the ingredients in the solid cleaning compositions, particularly in shaped toilet blocks.

[0084] Polymers that are suitable for the inventions are those known by the skilled person in the area of toilet blocks. Preferably the polymer is selected from natural and synthetic cellulosic polymers, such as carboxymethyl cellulose, polyacrylates, polyvinyl pyrrolidone, maleic / vinyl copolymers, silicon-based polymers, alkyl (C8-C22) polysorbate derivates and mixtures thereof.

[0085] Polyacrylates are also preferred. A suitable chemical class of such carboxy vinyl polymers for use in the invention includes crosslinked polymers having a polymer backbone derived from acrylic acid, substituted acrylic acid, or salts or esters thereof, in which the crosslinking agent contains two or more carbon-carbon double bonds and is derived from a polyhydric alcohol. Specific examples of such materials are homopolymers of acrylic acid cross-linked with allyl ethers of sucrose or pentaerythritol and homopolymers of acrylic acid cross-linked with divinyl glycol. An example of a suitable carboxy vinyl polymer for use in the compositions of the present invention is a homopolymer of acrylic acid crosslinked with allyl ethers of pentaerythritol, which is slightly pre-neutralised (1 to 3%) by potassium salt. This preneutralisation is done in order to precipitate polyacrylic acid in the presence of the polymerisation solvent. Such a material is commercially available, for example, as CARBOPOL® 974P NF Polymer or CARBOPOL® 690 POLYMER, ex Lubrizol Advanced Materials, Inc. For ease of processing, the most preferred carboxy vinyl polymer for use in the compositions of the present invention is a homopolymer of acrylic acid crosslinked with pentaerythritol tri allyl ether. Such a material is commercially available, for example, as SYNTHALEN® KP, ex 3V Sigma. Mixtures of any of the above-described materials may also be used.

[0086] Preferably, the composition comprises 0.05 to 3% by weight, more preferably 0.1 to 2% by weight and most preferably 0.1 to 1% by weight of the polymer.

[0087] Other ingredients

[0088] Other ingredients that may be included in the composition include colorant, perfume, bleaching agents, polymers, corrosion inhibitors, flush regulators, adhesion inhibitors, pH regulators, enzymes and preservatives.

[0089] The composition may be coloured using any conventional means of colouring in the area of hard surface cleaning compositions, particularly toilet blocks. Preferably the colorant is a polymeric colorant, and / or a pigment dispersion colorant. Preferably the composition comprises 0.01 to 3 % by weight, more preferably 0.01 to 2% by weight and most preferably 0.05 to 1% by weight of the colorant. Perfume or fragrance may be present in an amount of 0.1 to 7% by weight, more preferably 0.1 to 6% by weight and most preferably 0.2 to 5% by weight of the composition.

[0090] Bleaching agents that may be present in the composition include bleach hypo chlorite donors, peroxides, peracids and / or perborates. A bleach activator can also be used in addition to the bleaching agent.

[0091] Enzymes that may be included in the composition include proteases, lipases, amylases, hydrolases and / or cellulases.

[0092] Toilet block

[0093] The solid hard surface cleaning composition is provided in the form of a shaped toilet block. Toilet block is one of the product formats, where a composition is formulated in a solid shape. Consumers often dose one of such blocks in the flush tank of a toilet or placed inside the toilet bowl or urinals attaching to the rim. Typically, it provides cleaning benefit with each flush or flowing of the water.

[0094] The toilet block can either be held under the rim of the toilet using a suitable holder, often termed as rim block or placed directly on the surface of the toilet bowl without a holder, often termed as cageless block for intermittent contact of the toilet block with flush water. Solid toilet blocks are typically manufactured and shaped by an extrusion process. Rim blocks may be inserted into a suitable holder, like a basket, for use in the toilet bowl.

[0095] Cageless blocks may be solid blocks that are e.g., formed by moulding a heated pourable or malleable composition that hardens upon cooling. To ensure adhesion to the toilet bowl surface, adhesion promoting ingredients may be added to the toilet block composition or included as part of an additional adhesive layer, like a gel strip, at the back of the toilet cleaner block.

[0096] In-use characteristics of a toilet block include:

[0097] - Lifespan: how long the block lasts, usually measured as number of flushes before the block is completely dissolved;

[0098] - 3D shape: how the 3D shape of the block changes during its lifetime. The block gradually dissolves under the influence of flush water. Ideally the block dissolves symmetrically such that the overall 3D shape of the block is maintained during its lifetime. It may happen that a block dissolves asymmetrically, for example one side erodes excessively, the block develops holes, or may become porous such that part of the block breaks off;

[0099] - Foam development: how much visible foam develops during a flush as well as how much and how long visible foam is present after a flush. This is usually measured as cm of foam;

[0100] - Fragrance performance: fragrance development during a flush as well a fragrance perception between flushes.

[0101] Preferably the toilet block according to the present invention has a geometrical shape. The shape may be characterized by a maximum dimension ‘a’ and a minimum dimension ‘b’ wherein the ratio ‘a’ to ‘b’ may be in the range 3.5 to 12.5, more preferably 4 to 9 and most preferably 5 to 7 by length. Dimensions ‘a’ and ‘b’ are defined as a straight line between 2 points on the 3-dimensional shape with ‘a’ being the longest distance between two points and ‘b’ being the shortest distance between two points.

[0102] Preferably dimension ‘a’ is in the range 25 to 90 mm, more preferably 30 to 70 mm, and most preferably 35 to 50 mm. Preferably dimension ‘b’ is in the range 2 to 14 mm, more preferably 3 to 12 mm, even more preferably 4 to 10 mm, still more preferably 5 to 9 mm and most preferably 6 to 8 mm.

[0103] The toilet block may have any shape, that includes an ornamental design, like a flower design, a geometric design, like circular, cuboidal, or hexagonal. To ensure proper adhesion to the toilet bowl surface, the side supposed to be in contact with the surface may be flat allowing maximum contact area. Preferably the surface facing away from the surface of the toilet bowl and visible may have ornamental design, however, preferably is flat as flush water may quickly erode any intricate details.

[0104] Preferably the composition being a toilet block has certain hardness and suitable for withstand flushes of water. It is observed that the desired hardness helps in maintaining physical integrity of the block while in use and helps in dosing the cleaning active uniformly over the life span of the toilet block. The term “cleaning active”, herein include the ingredients present in the composition for delivering cleaning, hygiene benefit or sensory benefit. Example of such ingredients includes but not limited to surfactant, antimicrobial agent, perfume and silane. Preferably the composition has a hardness value in the range 15 to 70 Newton, more preferably 20 to 60 Newton, even more preferably 20 to 50 Newton and most preferably 20 to 40 Newton. Hardness measurement of toilet blocks is known in the art, and part of common general knowledge. One of the examples of measurement method is using a Universal Testing Machine (UTM) to press or penetrate a solid toilet block and measure the force.

[0105] Preferably the toilet block sustains at least 30 flushes, more preferably at least 50 flushes, even more preferably at least 70 flushes and most preferably at least 100 flushes. The toilet block may run for 70 to 500 flushes, more preferably 70 to 400 flushes, and most preferably 70 to 300 flushes.

[0106] There is provided a process of making the toilet block composition comprising steps of providing (i) 5 to 65% by weight of an anionic surfactant comprising at least an alkyl benzene sulphonate, (ii) a non-ionic surfactant, (iii) a quaternary ammonium compound, and (iv) 0.01 to 5% by weight of a silane having formula(l) in a container and subsequently mixing the ingredients thoroughly, thereby proving a solid mass. The solid mass thereon extruded to form the toilet block. The process may involve standard mixing and extrusion parameters known in the art.

[0107] According to the present invention there is provided a process for treating a surface comprising steps of: providing the solid hard surface cleaning composition, placing the composition in contact with the surface and flushing the composition with water. Preferably the composition is formed as a toilet block, that can be placed in a toilet commode. With each flush, the composition erodes a part of the composition and applies to the surface. The treatment herein refers to providing hydrophobicity to the surface.

[0108] The invention is further illustrated by the following non-limiting examples.

[0109] Examples

[0110] Two group of formulations, namely Ex-1 A to 1 and Ex-2A to Ex-2 were prepared following the recipe provided in table 1 below: Table 1

[0111] 1Nansa HS 80 / L from Innospec;2Barquat™ MS 100; and3UCARE™ JR-30M.

[0112] Ex-1 and Ex- 2 are according to the invention. Ex-1A to 1C are comparative for Ex -1 whereas Ex-2A to 2C are comparative for Ex-2. Formulations were prepared by mixing thoroughly the ingredients and extruding thereon to form shaped toilet blocks. All formulations described above were evaluated for delivering hydrophobicity to a surface. Hydrophobicity herein was assessed by the amount of water retained on the surface after certain number of flushes. Each formulation was formulated as toilet block weighing 11 gm. Five of such blocks in a cage was placed in a test toilet commode. The toilet commode was flushed at regular intervals for a preset number of times. A dry tissue (fixed size) was weighed and placed on the commode surface, thereby absorbing remaining water on the surface. The wet or soaked tissue was weighed, and the amount of water retention was estimated by subtracting the weight recorded earlier for the dry tissue.

[0113] Form the above table it is evident, that Ex-1 and Ex- 2 shows significantly less water retention, i.e. , improved hydrophobicity compared to Ex-1A to 10 and Ex-2A to 2C respectively. Further, Ex-D and Ex-3, 4 were prepared following the recipe provided in table 2:

[0114] Table 2

[0115] 1Nansa HS 80 / L from Innospec;2Barquat™ MS 100.

[0116] Above examples were prepared by mixing thoroughly the ingredients and extruding thereon to form shaped toilet blocks. Hardness of each block was evaluated using Universal Testing machines, Model LS5, Ametek, USA. In the hardness measurement process, a preload of 0.5 N at a speed of 30 millimetre / seconds was applied with a 6 millimetres cylindrical probe. After contacting the surface of each block, the probe was programmed to penetrate 4 millimetres, hold for 10 seconds and returned to initial position. The maximum force recorded by the probed was reported as hardness in table 2.

[0117] Ex-D led to soft mass, does not sustain for long, and is not suitable as a toilet block. Ex-3, 4 result in solid block with significantly higher hardness value.

Claims

Claims1. A solid toilet block composition comprising: a) 5 to 65% by weight of an anionic surfactant comprising at least an alkyl benzene sulphonate; b) a non-ionic surfactant; c) a quaternary ammonium compound; and d) 0.01 to 5% by weight of a silane having formula(l):(ORi)3-x(R2)x-Si-R3;Wherein,Ri is hydrogen or a C1 to C4 alkyl group,X has value of 0 or 1 or 2,R2is a C1 to C6 alkyl group,R3is a C1 to C18 hydrocarbon group selected from alkyl, phenyl, allyl, vinyl, at least one oxygen or nitrogen substituted non-ionic or cationic hydrocarbon group, andO is oxygen, C is carbon and Si is silicone.

2. A composition as claimed in claim 1 wherein the toilet block is obtained by extrusion process.

3. A composition as claimed in claim 1 or 2 wherein the alkyl benzene sulphonate constitutes 20 to 100% by weight of the total anionic surfactant.

4. A composition as claimed in any one of claims 1 to 3 wherein the amount of the non-ionic surfactant is in the range 0.5 to 10% by weight of the composition.

5. A composition as claimed in any one of claims 1 to 4 wherein the non-ionic surfactant comprises alcohol ethoxylate.

6. A composition as claimed in any one of claims 1 to 5, wherein the amount of the quaternary ammonium compound is in the range 0.1 to 7% by weight of the composition.

7. A composition as claimed in any one of claims 1 to 6 wherein the quaternary ammonium compound is selected from di-decyl dimethylammonium chloride, dioctyl dimethylammonium chloride, alkyl dimethyl benzyl ammonium chloride, di-isobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium saccharinate, octyldecyl dimethyl ammonium chloride, alkyl dimethyl ethyl benzyl ammonium chloride, methyl dodecyl benzyl ammonium chloride, methyl dodecyl xylene-bis-trimethyl ammonium chloride, methyl benzethonium chloride, cetylpyridinium chloride, cetrimonium bromide, cetyltrimethylammonium chloride, polyquaternium-10, quaternary ammonium salt of hydroxyethyl cellulose, guar hydroxy propyl trimonium chloride, guar hydroxypropyl trimonium chloride and combinations thereof.

8. A composition as claimed in any one of claims 1 to 7 wherein the ratio of the quaternary ammonium compound to the anionic surfactant is at least 1 : 1.5 by weight.

9. A composition as claimed in any one of claims 1 to 8 wherein X is 0 and R1 is methyl or ethyl group in the silane with formula (I).

10. A composition as claimed in claim 9 wherein the silane is selected from isobutyl tri-ethoxy silane, isobutyl trimethoxy silane, octyl tri-ethoxy silane, octyl trimethoxy silane, octadecyl tri-ethoxy silane, octadecyl trimethoxy silane, , octyl trimethoxy silane, hexadecyl trimethoxy silane and combinations thereof.11 . A composition as claimed in any one of claims 1 to 10 further comprising a filler selected from an inorganic salt of sulphate, carbonate, halide, phosphate and combinations thereof.

12. A composition as claimed in claim 11 wherein the filler is sodium sulphate.

13. A composition as claimed in any one of claims 1 to 12 wherein the composition is free of an effervescent.

14. A process of making a toilet block composition as claimed in any one of claims 1 to 13 comprising steps of: a) providing:(i) 5 to 65% by weight of an anionic surfactant comprising at least an alkyl benzene sulphonate;(ii) a non-ionic surfactant;(iii) a quaternary ammonium compound; and(iv) 0.01 to 5% by weight of a silane having formula(l):(OR1)3-x(R2)x-Si-R3;Wherein,R1 is hydrogen or a C1 to C4 alkyl group,X has value of 0 or 1 or 2,R2 is a C1 to C6 alkyl group,R3 is a C1 to C18 hydrocarbon group selected from alkyl, phenyl, allyl, vinyl, at least one oxygen or nitrogen substituted non-ionic or cationic hydrocarbon group, andO is oxygen, C is carbon and Si is silicone, in a container; b) mixing the ingredients thoroughly, thereby proving a solid mass; and c) extruding the solid mass to form the toilet block.

15. A process for treating a surface of the toilet bowl comprising steps of: a) providing a solid toilet block composition as claimed in any one of claims 1 to 12; b) placing the composition in contact with the surface; and, c) flushing the composition with water.