WO2023180053A1

WO2023180053A1 - A solid hard surface cleaning composition

Info

Publication number: WO2023180053A1
Application number: PCT/EP2023/055615
Authority: WO
Inventors: Yanchao CHEN; hejian JIANG; Jun Shen; Minhua Zhang; Jiayu ZHAO
Original assignee: Unilever Ip Holdings B.V.; Unilever Global Ip Limited; Conopco, Inc., D/B/A Unilever
Priority date: 2022-03-22
Filing date: 2023-03-06
Publication date: 2023-09-28

Abstract

A solid hard surface cleaning composition is disclosed 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. Methods of cleaning and/or disinfecting and/or deodorizing a hard surface or inside of a toilet bowl are also disclosed.

Description

A SOLID HARD SURFACE CLEANING COMPOSITION

Technical Field of the Invention

The present invention relates to solid hard surface cleaning compositions and their use. In particular, the present invention relates to toilet cleaning compositions.

Background of the Invention

Hard surface cleaning is important for people inhabiting homes and using other common spaces like offices, restaurants, hotels and public places like bus and train stations and airports. In particular, hard surface cleaning includes cleaning of hard surfaces like e.g. utensils, dishes, sinks, platforms, kitchen tops, tiles, floors, toilets, cupboards, doors, machines like dishwash machines, washing machines. Typically, hard surfaces like these are cleaned by applying a hard surface cleaning composition in neat or diluted form followed by cleaning the hard surface with a suitable means like e.g. scrub, sponge, paper, cloth, wipes and simply by using hands. Optionally, the cleaning activity involves rinsing the surface with water.

Hard surfaces such as toilets are usually contaminated by various organic materials that contain or support the growth of various microorganisms, which require frequent cleaning and disinfection. Toilet cleaning compositions usually include harsh chlorine bleaching agents for disinfection which generate unpleasant smell during use and are often not liked by many consumers. For example, the use of sodium dichloroisocyanurate as a disinfecting agent is known in the art. sodium dichloroisocyanurate hydrolyzed in water to produce hypochlorous acid (HOCI) and hypochlorite (OCT).

US2013/0239313A1 (Henkel) discloses a toilet cleaning block which comprises perfume, at least one alkylbenzene sulfonate and at least one olefin sulfonate and not more than 2.5% by weight of nonionic surfactants. Sodium dichloroisocyanurate is disclosed as the most preferred antimicrobial active ingredients.

GB2315761A discloses a detergent composition, preferably in granular form, comprises (percentages by weight): (I) a surfactant; (II) a system, which liberates a gas on reaction, comprising: (i) a particulate acid source, preferably comprising up to 15% of the composition, at least 80% having a particle size of from 150 to 710 microns, with at least 37% having a particle size of not more than 350 microns, which may be selected from organic acids (especially citric acid, glutaric acid, succinic acid and adipic acid) and inorganic (including mineral) acids (especially monosodium phosphate, sodium hydrogen sulphate and boric acid); (ii) an alkaline source, preferably comprising from 2 to 75% by weight of the composition, preferably selected from an alkali metal carbonate, alkali metal bicarbonate, alkali metal sesquicarbonate, alkali metal percarbonate, alkaline earth metal carbonate, alkaline earth metal bicarbonate and alkaline earth metal sesquicarbonate.

GB2310851A discloses a cationic ester surfactant comprising at leat one ester linkage and at least one cationically charged group characterized in that said cationically charged group is an ammonium group substituted by at least one hydroxyalkyl group. Surfactant systems and detergent compositions suitable for use in laundry and dishwashing methods containing the cationic ester surfactants are also provided.

WO2021/180936A1 discloses a unit-dose cleaning composition for use in cleaning surfaces, in particular for cleaning submerged surfaces such as toilet bowls. The composition comprises a surfactant system comprising a cationic surfactant, one or more substituted phenols selected from thymol, sec-butylphenol, carvacrol, eugenol, propylphenol or mixtures thereof, one or more aliphatic terpene alcohols; and one or more unsaturated terpenes selected from limonene, alpha-terpinene, terpinolene, cymene, phellandrene or mixtures thereof.

WO03/064579A1 discloses a cleansing product with an outstanding in-use performance comprising an excellent distribution of a detergent as well as an intensive fresh odour is provided by a product comprising a granulated composition consisting of a core material consisting of particles of a mixture of effervescent material and acid substance, said particles being dispersed within a matrix of non-aqueous binder material.

It is always desired by the consumer that the cleaning products are formulated with milder antimicrobial agents like quaternary ammonium compounds which are not considered harsh i.e. are mild on skin and have acceptable sensory properties like having no unpleasant chlorine smell.

Anionic surfactants are commonly included in cleaning compositions to help cleaning and cause foaming during use of the composition. The generation of foam is desired as an indicator to the user of the cleaning action of the composition and high levels of foam may be associated by the user with cleaning performance of the composition. For example, for a toilet cleaning composition, the foam level approximately one inch above the water line in a toilet bowl is considered as an indication of good cleaning performance by the user. But when an anionic surfactant and a cationic compound such as quaternary ammonium compounds are present together in the composition, they would interact to form a complex and therefore reduce the antimicrobial effect.

Furthermore, consumers are becoming more conscious of the environmental impact of the products they use. In particular, consumers are concerned with the vast amount of packaging used in their everyday lives. There is a need for more concentrated products, which can provide the same consumer benefits, but with a lower environmental impact. One solution is to use solid products which have the dual benefit of firstly not requiring the transport of large quantities of water and secondly having reduced packaging requirements.

Compositions in form of a shaped solid become increasingly popular with consumers as they offer simple dosing, easy storage and handling. A shaped solid such as a tablet or a block usually contains a unit dose of concentrated cleaning composition which dissolves in water to form a wash liquor. It is often required that a shaped solid should dissolve relatively fast when in contact with water to improve user experience.

Therefore, there remains a need to develop a solid hard surface cleaning composition which provides excellent antimicrobial efficacy without compromising consumer satisfaction in terms of dissolution time and cleaning performance.

Summary of the Invention

In a first aspect, the present invention is directed to a solid hard surface cleaning composition comprising: a) from 0.1 to 20% by weight of a quaternary ammonium compound; and b) 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.

In a second aspect, the present invention is directed to a method of cleaning and/or disinfecting and/or deodorizing a hard surface comprising the steps of:

(i) adding the solid hard surface cleaning composition of any embodiment of the first aspect into water to form a wash liquor;

(ii) contacting the surface with the wash liquor; and

(iii) optionally rinsing the surface with water; and

(iv) optionally drying the surface.

In a third aspect, the present invention is directed to a method of cleaning and/or disinfecting and/or deodorizing inside of a toilet bowl comprising the steps of:

(a) adding the solid hard surface cleaning composition of any embodiment of the first aspect into the toilet bowl;

(b) allowing the composition to dissolve in water to obtain a solution;

(c) optionally, soaking the toilet bowl in the solution of step (b); and

(d) flushing the toilet with water.

All other aspects of the present invention will more readily become apparent upon considering the detailed description and examples which follow.

Detailed description of the invention

Except in the 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 may optionally be understood as modified by the word “about”.

All amounts are by weight of the final composition, unless otherwise specified.

It should be noted that in specifying any range of values, any particular upper value can be associated with any particular lower value. For the avoidance of doubt, 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.

The disclosure of the invention as found herein is to be considered to cover all embodiments as found in the claims as being multiply dependent upon each other irrespective of the fact that claims may be found without multiple dependency or redundancy.

Where a feature is disclosed with respect to a particular aspect of the invention (for example a composition of the invention), such disclosure is also to be considered to apply to any other aspect of the invention (for example a method of the invention) mutatis mutandis.

The term “hard surface”, as used in the context of the present invention, refers to any surface in household including the window, kitchen, bathroom, toilet, furniture, or floor including windows, mirrors, sinks, basins, toilet bowls, baths/shower trays, wall tiles, floor tiles, cooker tops, oven interiors, cookware, washing machine drums, cooker hoods, extractor fans. These surfaces, for example, may be made of glass, glazed ceramics, metal, stone, plastics, lacquer, wood, or combination thereof. Preferably, the hard surface cleaning composition according to the invention is a toilet cleaning composition.

The term “water soluble”, as used in the context of the present invention, refers to a material that dissolves in water to give a solution with a concentration of at least 0.1 moles per litre.

Quaternary ammonium compound

The solid hard surface cleaning composition of the present invention comprises a quaternary ammonium compound. The quaternary ammonium compound present in the composition acts as an antimicrobial agent.

Suitable quaternary ammonium compound for use in this invention includes, for example, 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.

Preferably, the quaternary ammonium compound comprises alkyl dimethyl benzyl ammonium chloride e.g. benzalkonium chloride (BKC), diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride (benzethonium chloride; BZC), methyl benzethonium chloride, cetyl pyrinidinium chloride, cetrimonium bromide or mixtures thereof. Benzalkonium chloride is particularly preferred.

The quaternary ammonium compounds mentioned above, are available as a single quaternary ammonium compound, as well as mixtures of two or more different quaternary ammonium compounds e.g. under trademarks BARDAC™, BARQUAT® and HYAMINE® (all by Lonza); and BTC® and ONYXIDE® (both by Stepan).

Quaternary ammonium compounds available as a single quaternary ammonium compound include didecyl dimethyl ammonium chloride (available as BARDAC™ 2250 R and BTC® 1010, both 50% active; and BARDAC™ 2280 R and BTC® 1010-80, both 80% active), dioctyl dimethyl ammonium chloride (available as BARDAC™ LF, 50% active; BARDAC™ LF-80, 80% active), alkyl dimethyl benzyl ammonium chloride (available as BARQUAT® MB-50, BARQUAT® MX-50, BARQUAT® QJ-50, HYAMINE® 3500, BTC® 50, BTC® 50E, BTC® 65, BTC® 776, BTC® 824, BTC® 835; each 50% active; and the same is available as BARQUAT® MB-80, BARQUAT® MX-80, HYAMINE® 3500-80, BTC® 8248, BTC® 8358; each 80% active), diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride (50% active - HYAMINE® 1622); and n-alkyl dimethyl benzyl ammonium saccharinate (available as ONYXIDE® 3300, 95% active).

Quaternary ammonium compounds that are available as a mixture of two or more quaternary ammonium compounds include a mixture of alkyl dimethyl benzyl ammonium chloride, octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride; and dioctyl dimethyl ammonium chloride (available as BARDAC™ 205M, 50% active; and available as BARDAC™ 208M, 80% active), a mixture of octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride; and dioctyl dimethyl ammonium chloride (available as BARDAC™ 2050, 50% active; and available as BARDAC™ 2080, 80% active), a mixture of alkyl dimethyl benzyl ammonium chloride and alkyl dimethyl ethyl benzyl ammonium chloride (available as BARQUAT® 4250 and BARQUAT® 4250 Z, each 50% active; and available as BARQUAT®4280 and BARQUAT® 4280Z, each 80% active), a mixture of methyldodecylbenzyl ammonium chloride and/or methyldodecylxylene-bis- trimethyl ammonium chloride available as HYMAINE® 2389), a mixture of octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride; and dioctyl dimethyl ammonium chloride (available as BTC® 818, 50% active; and available as BTC® 818-80%, 80% active), a mixture of alkyl dimethyl benzyl ammonium chloride, octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium choride; and dioctyldimethylammonium chloride (available as BTC® 885, 50% active; also available as BTC® 888, 80% active), a mixture of alkyl dimethyl benzyl ammonium chloride and alkyl dimethyl ethylbenzyl ammonium chloride (available as BTC® 2125 M and BTC® 2125 M 50, each 50% active, available as BTC® 2125M 80, 80% active; and available as BTC® 2125 M 80E, 81 % active).

The composition comprises from 0.1 to 20% by weight of the quaternary ammonium compound, preferably from 0.5 to 15%, more preferably from 1 to 10% and most preferably from 1 .5 to 5%, based on total weight of the composition and including all ranges subsumed therein.

Alkyl Sulfate

Alkyl sulfates are anionic surfactants which are water soluble salts containing a hydrocarbon hydrophobic group and a hydrophilic sulfate group.

Preferably, the alkyl sulfate has an alkyl group having 8 to 18 carbon atoms, more preferably from 10 to 18 carbon atoms, even more preferably from 10 to 16 carbon atoms. It will be appreciated that both branched and straight chained alkyl groups are encompassed. The alkyl substituent is preferably linear, i.e. normal alkyl, however, branched chain alkyl sulfates can be employed, although they are less preferred from a biodegradability perspective.

Preferably, the alkyl sulfate comprises a salt of an alkyl sulfate. In this way, the alkyl sulfate comprises a positively charged ion and a negatively alkyl sulfate moiety. The positively charged ion may be a metal ion such as sodium, potassium or magnesium; or an ammoniacal ion such as ammonium, monoethanolamine, diethanolamine or triethanolamine. Mixtures of such ions may also be employed. Sodium and potassium are preferred. It is preferred that the alkyl sulfate comprises sodium, potassium, calcium, magnesium, ammonium or ethanolamine salts of alkyl sulfate having 8 to 18 carbon atoms, more preferably 10 to 18 carbon atoms, even more preferably from 10 to 16 carbon atoms. Illustrative yet non-limiting examples of alkyl sulfates include sodium lauryl sulfate (also known as sodium dodecyl sulfate), ammonium lauryl sulfate, diethanolamine (DEA) lauryl sulfate. Suitable examples also include alkyl sulfates commercially available from natural source with trade names Galaxy 689, Galaxy 780, Galaxy 789, Galaxy 799 SP, and llfarol TCL 92N and from synthetic origin with trade names Safol 23, Dobanol 23A or 23S, Lial 123 S, Alfol 1412S, Empicol LC3, Empicol 075SR.

Sodium lauryl sulfate (SLS), also known as sodium dodecyl sulfate, is particularly preferred as the alkyl sulfate.

Typically, the amount of alkyl sulfate employed in the composition is in the range of from 0.1% to 15%, more preferably 0.5% to 10%, even more preferably from 0.8 to 8% and most preferably from 1 to 5%, based on total weight of the composition and including all ranges subsumed therein.

The weight ratio of the quaternary ammonium compound to the alkyl sulfate is from 1.5:1 to 3.5:1 , preferably from 1.5:1 to 3:1 , more preferably from 1.8:1 to 2.5:1.

The composition of the present invention may also comprise other surfactants in addition to the quaternary ammonium compound and the alkyl sulfate.

Other surfactants

Anionic surfactants in addition to the alkyl sulfate surfactants may be included in the composition of the present invention. Suitable anionic surfactants include, for example, alkyl sulfoacetate (such as sodium lauryl sulfoacetate), alkyl taurate (such as sodium methyl cocoyl taurate), alkyl ether sulfates, alkyl sulfonates, alkaryl sulfonates, alpha-olefin sulfonates, alkyl isethionates (such as sodium coco-isothionate), alkanoyl isethionates, alkyl succinates, alkyl sulphosuccinates, alkyl ether sulphosuccinates, N-alkyl sarcosinates, alkyl phosphates, alkyl ether phosphates, alkyl ether carboxylic acids and salts thereof, especially their sodium, magnesium, ammonium and mono-, di-, and triethanolamine salts. The alkyl ether sulfates, alkyl ether sulphosuccinates, alkyl ether phosphates and alkyl ether carboxylic acids and salts thereof may contain from one to twenty ethylene oxide (EO) or propylene oxide (PO) units per molecule.

A preferred class of anionic surfactant for use in the invention includes alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates (LAS) with an alkyl chain length of from 10 to 18 carbon atoms. Commercial LAS is a mixture of closely related isomers and homologues alkyl chain homologues, each containing an aromatic ring sulfonated at the “para" position and attached to a linear alkyl chain at any position except the terminal carbons. The linear alkyl chain typically has a chain length of from 11 to 15 carbon atoms, with the predominant materials having a chain length of about C12. Each alkyl chain homologue consists of a mixture of all the possible sulfophenyl isomers except for the 1- phenyl isomer. LAS is normally formulated into compositions in acid (i.e. HLAS) form and then at least partially neutralized in-situ. Examples include sodium salt of linear alkylbenzene sulphonate, alkyl toluene sulphonate, alkyl xylene sulphonate, alkyl phenol sulphonate, alkyl naphthalene-sulphonate, ammonium diamylnaphthalene-sulphonate and sodium dinonylnaphthalene-sulphonate and mixtures with olefin sulphonates.

Another anionic surfactant may be used in compositions of the invention are alkyl ether sulfates having a straight or branched chain alkyl group having 10 to 18, more preferably 12 to 14 carbon atoms and containing an average of 1 to 3EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES) in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 2EO units per molecule.

Preferably, the composition is substantially free of alkyl ether sulfates. “Substantially free of”, as used herein, means less than 1.5%, preferably less than 1.0%, more preferably less than 0.75%, more preferably still less than 0.5% and even more preferably less than 0.1 % and most preferably from 0 to 0.01 % by weight, based on total weight of the composition, including all ranges subsumed therein. Alkyl ether sulfates are too sticky which would cause problems with processing since they may stick to the mould. For the reasons of processability, it is preferred that the composition does not comprise any alkyl ether sulfates.

When the composition of the present invention comprises other anionic surfactants in addition to the alkyl sulfate, it is preferred if the alkyl sulfate is present in an amount of from 50 to 100%, more preferably from 70% to 100%, even more preferably from 80 to 100% and most preferably from 95 to 100%, based on the weight of total anionic surfactants in the composition. Preferably, the composition of the present invention does not comprise other anionic surfactants in addition to the alkyl sulfate which is included in the composition.

The total amount of anionic surfactants in the composition is preferably from 0.1 % to 15%, more preferably 0.5% to 10%, even more preferably from 0.8 to 8% and most preferably from 1 to 5%, based on total weight of the composition and including all ranges subsumed therein.

The solid hard surface cleaning composition may also comprise non-ionic surfactants. Suitable non-ionic surfactants that may be used in this invention include, for example, fatty acid alkoxylates, ethylene oxide/propylene oxide block polymers, fatty acid alkanolamides, fatty acid polyglycol ethers, alkyl polyglycosides, fatty acid glucamides, polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, fatty acid polyglycol esters, amine oxides, fatty acid amides, rhamnolipids or mixtures thereof.

A preferred class of non-ionic surfactants which can be used in accordance with this invention are alkyl polyglycosides. Alkyl polyglycosides are compounds according to the formula (Formula I): RiO(R2O)b(Z)_a, wherein Ri is a alkyl radical, having from about 1 to about 30 carbon atoms; R2 is 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 poly glycosides, the alkyl radical is generally referred to as having a range of carbon atoms (e.g. C4/22 referring to a range of alkyl radicals having from 4 to 22 carbon atoms) and the degree of polymerization is generally referred to as the average degree of polymerization of the mixture.

Preferred alkyl polyglycosides suitable for use in the composition include those having the formula I wherein Z is a glucose residue, b is zero, R1 is an alkyl group that contains 4 to 22 carbon atoms, and the average value of a is about 1 to 2. Preferably R1 is an alkyl group that contains 8 to 18 carbon atoms, and more preferred R1 is an alkyl group that contains 10 to 16 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).

Another preferred class of non-ionic surfactants for use in the invention includes fatty alcohol alkoxylates. The fatty alcohol alkoxylate preferably is selected from C8-22 alcohols alkoxylated with ethylene oxide (EO) and/or propylene oxide (PO) with a degree of alkoxylation of 12 to 30. The fatty alcohol alkoxylate is preferably selected from alkoxylated C12-20 fatty alcohols, more preferably from alkoxylated C16-18 fatty alcohols. The fatty acid alkoxylate is preferably selected from ethoxylated fatty alcohols with a degree of ethoxylation of 16 to 28, even more preferably with a degree of ethoxylation of 20 to 27. A preferred fatty alcohol alkoxylate is ethoxylated C16-18 fatty alcohol with a degree of ethoxylation of 24 to 26.

The composition may also comprise one or more types of amphoteric surfactant including betaines and aminoxide surfactants.

Disintegrant

The solid hard surface cleaning composition of the present invention may further comprise a disintegrant. Disintegrant, as used herein, refers to materials which are added to the solid composition to make it disintegrate and thus release the actives on contact with water. The use of disintegrant provides a quick-dissolving solid composition. The solid hard surface cleaning composition of the present invention preferably comprises from 10 to 95% by weight of the disintegrant, more preferably from 20 to 90%, even more preferably from 30 to 90% and most preferably from 45 to 85% by weight of the disintegrant. It is preferred that the disintegrant comprises effervescent disintegrant. More preferably the disintegrant is effervescent disintegrant. The effervescent disintegrant generates effervescence during dissolution in water which provides a cue to consumers about dissolution of the solid hard surface cleaning composition. Furthermore, the effervescence generated may agitate the water to accelerate the dissolution of the solid composition.

Suitable effervescent disintegrant includes a carbonate salt and an acid. Preferably the acid is selected from an organic acid, a salt of organic acid, a salt of inorganic acid and mixtures thereof. More preferably the acid is organic acids. The organic acid suitable for use in the composition of the present invention can be any organic acid. Particularly good results were achieved with organic acids being polyacids (i.e. acids having more than one carboxylic acid group), and more particularly with di- or tricarboxylic organic acids. The organic acid used in the invention has a weight average molecular mass of at most 500 Dalton, more preferably of at most 400 Dalton and most preferably of at most 300 Dalton, the molecular mass being based on the free acid equivalent. In any case, preferably the organic acid is not a polymer-based acid. The organic acid employed in accordance with the invention preferably comprises 3 to 25 carbon atoms, more preferably 4 to 15 carbon atoms.

In view of consumer acceptance and reducing environmental impact, the organic acids preferably are those which are also found naturally occurring, such as in plants. Examples of suitable organic acids include acetic acid, citric acid, aspartic acid, lactic acid, adipic acid, succinic acid, glutaric acid, gluconic acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acid, their salts or mixtures thereof. Of particular interest are citric acid, aspartic acid, acetic acid, lactic acid, succinic acid, glutaric acid, gluconic acid, their salts or mixtures thereof. Most preferably, the organic acid is citric acid, succinic acid, their salts or a mixture thereof.

Preferably, the solid hard surface cleaning composition of the present invention comprises from 10 to 80% by weight of the acid, more preferably from 20 to 75%, even more preferably from 30 to 70% and most preferably from 40 to 60% by weight of the acid.

Preferably the carbonate salt comprises sodium carbonate, sodium bicarbonate, sodium glycine carbonate, potassium carbonate, potassium bicarbonate, potassium glycine carbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate or mixtures thereof. More preferably the carbonate salt comprises sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate or mixtures thereof. Most preferably the carbonate salt comprises sodium carbonate, sodium bicarbonate or mixtures thereof.

It is particularly preferred that the effervescent disintegrant is a combination of sodium bicarbonate, citric acid and succinic acid.

It is preferred that the amount of carbonate salt is related to the amount of acid. More specifically it is desired that the weight ratio of the carbonate salt to the acid is from 1 : 10 to 10:1 , more preferably from 1 :5 to 5:1 , even more preferably from 1 :3 to 3:1 . The composition may also comprise a non-effervescent disintegrant. The non-effervescent disintegrant may be selected from polyvinylpyrrolidone, starch, such as wheat, rice, potato, tapioca starch; starch derivatives such as starch glycolate, carboxymethyl starch; cellulose; cellulose derivatives such as hydroxyalkyl cellulose, calcium carboxymethyl cellulose, cross-linked modified cellulose, microcrystalline cellulose; clays, such as bentonite; alginates; gums such as agar, Arabic, xanthan, guar, locust bean, karaya, pectin and tragacanth, non-carbonate salt such as sodium chloride, potassium chloride, magnesium sulfate, calcium silicate or a combination thereof. Polyvinylpyrrolidone is particularly preferred.

Filler

The solid hard surface cleaning composition may comprise a water soluble filler material. Preferably the solid hard surface cleaning composition comprises from 1 to 50% by weight of the filler materials, more preferably from 3 to 40%, even more preferably from 5 to 30% and most preferably from 8 to 20%, based on total weight of the composition and including all ranges subsumed therein.

Suitable water soluble filler materials comprise water soluble alkali metal salt, water soluble alkaline earth metal salt, water soluble organic alkali metal salt, water soluble organic alkaline earth metal salt, water soluble carbohydrate, water soluble silicate, water soluble urea or mixtures thereof. Preferably, the water soluble filler materials comprise alkali metal and/or alkali earth metal sulfates, halides, phosphates or mixtures thereof, more preferably alkali metal chlorides, alkali metal sulfates, alkaline earth metal chlorides, alkaline earth metal sulfates or mixtures thereof, even more preferably the water soluble filler materials comprise sodium sulfate, magnesium sulfate, sodium chloride or mixtures thereof. Sodium sulfate is most preferred.

Bleaching agents

Suitable bleaching agents include chlorine-containing bleaching agents, peroxides, peracids and/or perborates. Sodium percarbonate or phthalimidoperoxyhexanoic acid is particularly preferred. Chlorine-containing bleaching agents such as trichlororisocyanuric acid or sodium dichloroisocyanurate may also be employed in the composition.

Preferably, the solid hard surface cleaning composition of the present invention is substantially free of bleaching agents and/or bleach activator. “Substantially free of”, as used herein, means less than 1.5%, preferably less than 1.0%, more preferably less than 0.75%, more preferably still less than 0.5% and even more preferably less than 0.1 % and most preferably from 0 to 0.01 % by weight, based on total weight of the composition, including all ranges subsumed therein. It is preferred that the composition of the invention does not comprise any bleaching agents and/or bleach activator.

Lubricant

The solid hard surface cleaning composition of the invention may further comprise a lubricant, which may act as a processing aid to make the composition less sticky and allow for improved manufacturing. Suitable lubricant includes stearates such as magnesium stearate and calcium stearate, sodium benzoate, mineral oil, silicates, algenic acid, polyethylene glycols, dipropylene glycol or mixtures thereof.

Preferably the solid hard surface cleaning composition comprises from 0.01 to 10% by weight of the lubricant, more preferably from 0.1 to 8%, even more preferably from 0.5 to 5%, based on total weight of the composition and including all ranges subsumed therein.

Other ingredients

The solid hard surface cleaning composition of the present invention may comprise other ingredients which are common in the art to enhance physical properties and performance in addition to those materials described above. These ingredients include colorant, perfume, polymers, corrosion inhibitors, flush regulators, adhesion inhibitors, pH regulators, enzymes, preservatives, sequestrants, builders or mixtures thereof. Such ingredients typically and collectively make up less than 20% by weight of the composition, preferably from 0 to 15% by weight, most preferably from 0.01 to 10% by weight of the composition, including all ranges subsumed therein.

The solid hard surface cleaning composition may be colored using any conventional means of coloring in the area of hard surface cleaning especially toilet cleaning but preferably the colorant is a polymeric colorant, or pigment dispersion colorant. Preferably the composition comprises 0 to 3% by weight of the colorant, more preferably 0.01 to 2%.

Perfume or fragrance may be present in an amount of 0 to 7% by weight of the composition, preferably 0.05 to 6% and more preferably 0.1 to 5%. Polymers, such as acrylic polymers, can suitably be incorporated in the composition to reduce formation of lime scale and soil re-deposition.

Enzymes that may be applied in the composition include proteases, lipases, amylases, hydrolases and/or cellulases.

Form of the solid hard surface cleaning composition

The solid hard surface cleaning composition of the present invention may be provided in any suitable form, for example, a powder, a granulated particle or a shaped solid. Preferably the composition is a shaped solid which may have any shape selected from ball-shaped, cubical, rectangular, circular, disc, cylindrical, flower-shaped, hemispherical, lentil-shaped, oblong, star-shaped and any combinations thereof. More preferably the composition is ballshaped, cylindrical, cubical or rectangular shaped. Ball-shaped solid compositions are particularly preferred.

Preferably, the ball-shaped solid hard surface cleaning composition is provided as a water soluble or water dispersible unit dose. The ball-shaped solid composition preferably has a weight of from 1 to 200 grams, more preferably from 5 to 100 grams, even more preferably from 10 to 80 grams and most preferably from 20 to 60 grams. The density of the ballshaped solid composition is preferably from 1 to 2 g/cm³, more preferably from 1.1 to 1.8 g/cm³, even more preferably from 1.3 to 1.5 g/cm³.

It is not preferred that the ball-shaped solid composition is wrapped in a water soluble film. It was found that the presence of water soluble film can lead to residues during dissolution in water which is not preferred in some cases such as in a toilet bowl. The ball-shaped solid hard surface cleaning composition is preferably packaged in a blister pack or a multi-dose container which is preferably equipped with a child-safe locking mechanism.

Formation/shaping of the hard surface cleaning composition into various solid form may be achieved by using known methods and equipment, such as those in the field of detergent product manufacturing, machine dishwash tablet manufacturing, or toilet cleaning block manufacturing. If the ingredients of the composition are provided in liquid form, they may be dehydrated by any means known to those skilled in the art for removing liquid from a composition. Preferably the amount of water in the composition is from 0 to 1 % by weight of the composition, more preferably from 0 to 0.5%. Preferably, the solid composition of the present invention can be made by combining the ingredients together to provide a homogeneous mixture and compressing the mixture into a desired solid using electric or hydraulic tabletting machine. Compression pressure is typically from 50 MPa to 1000 MPa. The solid composition of the present invention may also be made by combining the ingredients together to provide a homogeneous mixture, extruding the mixture into an extruded strand, and cutting/shaping the extruded strand into a desired solid.

Use for the solid hard surface cleaning composition

The solid composition of the present invention is for use in the field of hard surface cleaning. The solid hard surface cleaning composition, as described herein may be used in method of cleaning and/or disinfecting and/or deodorizing a hard surface comprising the steps of:

(i) adding the solid hard surface cleaning composition into water to form a wash liquor;

(ii) contacting the surface with the wash liquor;

(iii) optionally rinsing the surface with water; and

(iv) optionally drying the surface.

Preferably, the composition of the invention is used for toilet cleaning or machine dish washing. It is particularly preferred that the composition of the invention is a toilet cleaning composition. When the composition of the invention is a toilet cleaning composition, it is preferred that the present invention also provides a method of cleaning and/or disinfecting and/or deodorizing inside of a toilet bowl comprising the steps of:

(a) adding the solid hard surface cleaning composition into the toilet bowl;

(b) allowing the composition to dissolve in water to obtain a solution;

(c) optionally, soaking the toilet bowl in the solution of step (b); and

(d) flushing the toilet with water.

In particular, the solid hard surface cleaning composition is placed directly into the toilet bowl without the use of a holder to provide a convenient-to-use toilet cleaning composition.

The duration of step (b) is preferably between 1 second and 24 hours. However, it is preferred that the method is suitable for consumer’s daily use of toilets where rapid dissolution of the cleaning composition is desired. Thus it is preferred that the duration of this step is from 1 second to 2 hours, more preferably from 5 seconds to 1 hour, even more preferably from 10 seconds to 45 minutes and most preferably from 1 minute to 35 minutes. Following step (b), the method preferably comprises a step (c) of soaking the toilet bowl in the solution of step (b), which may maximise the cleaning and/or disinfecting and/or deodorizing efficacy of the composition. To reduce the impact on consumer’s daily use of toilets, the toilet bowl is preferably soaked in the solution of step (b) for a duration of 1 second to 24 hours, more preferably from 1 minute to 2 hours, more preferably still from 5 minutes to 1 hour, even more preferably still from 10 minutes to 45 minutes and most preferably from 15 minutes to 30 minutes.

When the method comprises a step (c), it is preferred that the total duration of step (b) and step (c) is from 1 second to 24 hours, more preferably from 1 minute to 3 hours, more preferably still from 10 minutes to 2 hours, even more preferably still from 15 minutes to 1 .5 hour and most preferably from 20 minutes to 1 hour.

The following examples are provided to facilitate an understanding of the invention. The examples are not intended to limit the scope of the claims.

Examples

Example 1

Solid hard surface cleaning compositions for toilet cleaning were prepared as shown in table 1. All ingredients are expressed by weight percent of the total formulation.

Table 1

Preparation of toilet cleaning composition in the form of a ball

The ingredients were added one by one into a double-cone mixer and mixed evenly. A measured amount (50 gram) of the powder mixture was poured into a mould and pressed using a compression roll for ball shape-up. After some time, the ball was ejected out of the mould and collected.

It was found that samples comprising BKC and SLS in a weight ratio higher than 4:1 resulted in a sticky powder mixture that was not able to be pelletized in a semi-auto production line.

Method to test dissolution time

Toilet bowl and pipe usually store around 1.5L to 2.0L water after each flush. One ballshaped sample as prepared above was dropped into 2L tap water. The dissolution time was measured from To (when the sample is dosed into the 2L tap water) to Ti (when no visible solid and fizzing is observed).

It is required that the toilet cleaning composition should completely dissolve in 30 minutes, followed by at least 20 minutes soaking time in a toilet bowl to deliver organic stain (feces stain) removal benefit and 99.9% antimicrobial benefit. Total application time of the toilet cleaning composition in a toilet bowl should be within 50 minutes to reduce the impact on consumer’s daily use of toilets.

It can be seen in table 1 that sample C had an unacceptable dissolution time of 42 minutes.

Method to test antimicrobial efficacy

Staphylococcus aureus (S. aureus) and Escherichia coli (E.coli) are commonly found conditional pathogens in human living areas. Antimicrobial efficacy is tested against Staphylococcus aureus and Escherichia coli according to Light Industry Standard of the People’s Republic of China QB/T 2738-2012 (7.2).

Preparation of test sample solution

Test sample solution was prepared by dissolving one test sample (50 gram) into 2L tap water to mimic the toilet environment. Preparation of test bacterial suspension

Standard bacteria E.coli (ATCC25922) or S. aureus (ATCC6538) suspension was dispersed in 5 to 10 mL nutrient broth and incubated at 37 °C for 18 to 24 h. The suspension was streak inoculated on nutrient agar culture medium plate and cultured at 37 °C for 18 to 24h. Typical colony was picked, streak inoculated, cultured at 37 °C for 18 to 24h. The same procedure was repeated to obtain more than three generation colonies. Colonies of 3 to 14 generation were diluted with PBS (phosphate buffered saline) to suspensions with required concentrations. The required concentration of a test bacterial suspension is defined as: when 0.1 mL of the test bacterial suspension is taken and added into 5 mL PBS, the recovered colony count is from 1 *10⁴ to 9*10⁴ cfu/mL.

Determination of antimicrobial efficacy

0.1 mL of test bacterial suspension was added into 5 mL of test sample solution, the contact time was set for 15 minutes. At the end of contact time, 0.5 mL of test mixture was added to 4.5 mL sterilized neutralizer quickly. After neutralizing for 10 minutes, 1 mL of resulted mixture was inoculated in a sterilized Petri dish. 15 mL of nutrient agar culture medium was poured into the Petri dish and the Petri dish was rotated and incubated at (35 ± 2) °C for 48 hours. After that, the viable counts of bacterial colony were counted. Replaced the test sample solution with PBS and followed the above steps as the control sample.

The antimicrobial efficacy (%) of test sample was calculated as:

Antimicrobial efficacy (%)= (l-ll)/l *100

I: average colony count of control sample

II: average colony count of test sample

Results

The results are shown in table 2. The antimicrobial efficacy greater than or equal to 90% is considered as acceptable.

Table 2

Claims

1. A solid hard surface cleaning composition comprising: a) from 0.1 to 20% by weight of a quaternary ammonium compound; and b) 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.

2. The composition according to claim 1 , wherein the quaternary ammonium compound comprises alkyl dimethyl benzyl ammonium chloride, diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, methyl benzethonium chloride, cetyl pyrinidinium chloride, cetrimonium bromide or mixtures thereof, preferably benzalkonium chloride.

3. The composition according to claim 1 or claim 2, wherein the alkyl sulfate comprises sodium, magnesium, ammonium or ethanolamine salts of alkyl sulfate having 8 to 18 carbon atoms.

4. The composition according to any of the preceding claims, wherein the quaternary ammonium compound is present in an amount of from 0.5 to 15% by weight of the composition.

5. The composition according to any of the preceding claims, wherein the weight ratio of the quaternary ammonium compound to the alkyl sulfate ranges from 1.5:1 to 3:1 , preferably from 1.8:1 to 2.5:1.

6. The composition according to any of the preceding claims, wherein the alkyl sulfate is present in an amount of from 50 to 100% by the weight of total anionic surfactants in the composition.

7. The composition according to any of the preceding claims, wherein the composition further comprises a disintegrant comprising effervescent disintegrant. The composition according to claim 7, wherein the effervescent disintegrant comprises a carbonate salt and an acid. The composition according to claim 8, wherein the acid is organic acid comprising acetic acid, citric acid, aspartic acid, lactic acid, adipic acid, succinic acid, glutaric acid, gluconic acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acid, their salts or mixtures thereof, preferably citric acid, aspartic acid, acetic acid, lactic acid, succinic acid, glutaric acid, gluconic acid, their salts or mixtures thereof. The composition according to claim 8 or claim 9, wherein the carbonate salt comprises sodium carbonate, sodium bicarbonate, sodium glycine carbonate, potassium carbonate, potassium bicarbonate, potassium glycine carbonate, calcium carbonate, calcium bicarbonate, magnesium carbonate or mixtures thereof, preferably sodium carbonate, sodium bicarbonate or mixtures thereof. The composition according to according to claim 10, wherein the weight ratio of the carbonate salt to the acid is from 1 :10 to 10:1 , preferably from 1 :5 to 5:1. The composition according to any of the preceding claims, wherein the composition is in the form of a powder, a granulated particle or a shaped solid, preferably a shaped solid, more preferably a ball-shaped solid. The composition according to claim 12, wherein the ball-shaped solid has a weight of from 1 to 200 grams, preferably from 5 to 100 grams. A method of cleaning and/or disinfecting and/or deodorizing a hard surface comprising the steps of

(i) adding the solid hard surface cleaning composition according to any of the preceding claims into water to form a wash liquor;

(ii) contacting the surface with the wash liquor;

(iii) optionally rinsing the surface with water; and

(iv) optionally drying the surface. A method of cleaning and/or disinfecting and/or deodorizing inside of a toilet bowl comprising the steps of

(a) adding the solid hard surface cleaning composition according to any of the preceding claims into the toilet bowl; (b) allowing the composition to dissolve in water to obtain a solution;

(c) optionally, soaking the toilet bowl in the solution of step (b); and

(d) flushing the toilet with water.