EP4788782A1

EP4788782A1 - Solid hard surface cleaning composition

Info

Publication number: EP4788782A1
Application number: EP24765681.2A
Authority: EP
Inventors: Koushik ACHARYA; Valentina LA MOLA; Shanthi APPAVOO
Original assignee: Unilever Global IP Ltd; Unilever IP Holdings BV
Current assignee: Unilever Global IP Ltd; Unilever IP Holdings BV
Priority date: 2023-10-05
Filing date: 2024-09-09
Publication date: 2026-08-12
Also published as: WO2025073430A1

Abstract

The present invention relates to a solid hard surface cleaning composition comprising: a. a biocidal quaternary ammonium compound; b. an anionic surfactant comprising alkyl sulfate; and c. an effervescence base comprising a carbonate salt and an acid; wherein, • the weight ratio of biocidal quaternary ammonium compound to anionic surfactant is from 1.5:1 to 7:1; • at least 50 wt% of the total amount of acid present in the cleaning composition is sulfamic acid calculated on total amount of acid present in the cleaning composition; • the cleaning composition comprises from 0 to 1 wt% water; and • 25 grams of the cleaning composition dissolved in 1.5 litres of water of 20° Celsius provides an aqueous solution with a pH of 1.5 to 4.5. The invention further relates to a method of cleaning the inside surface of a toilet bowl using the composition of the present invention.

Description

Solid Hard Surface Cleaning Composition

Field of the invention

The present invention relates to solid hard surface cleaning compositions, more particularly to shaped solid hard surface cleaning compositions, comprising a biocidal quaternary ammonium compound, an anionic surfactant comprising alkyl sulfate, and an effervescence base.

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).

Toilet cleaner blocks, i.e. shaped solid cleaning compositions, are commonly used to impart cleansing and/or other components to the flush water of toilets, like lavatories or urinals. Such blocks may be immersed in the water tank (so called in-tank blocks or cistern blocks) or held under the rim of a toilet in a suitable holder for intermittent contact of the toilet cleaner block with flush water (so called rim blocks).

Rim blocks typically contain active ingredients such as surfactants, perfume, acids, bases, salts, thickeners, antimicrobials, preservatives, sequestrants, bleaching agents, corrosion inhibitors, flush regulators, enzymes, microorganisms, active substances for biofilm removal, lime-scale inhibitors, soil-adhesion inhibitors etc. Rim blocks also often contain a substantial amount of filler, such as sodium sulphate or sodium carbonate.

Solid toilet blocks are typically manufactured and shaped by an extrusion process. In case of rim blocks the shaped toilet blocks may be inserted into a suitable holder, like for example a basket, for use in the toilet bowl.

In-use characteristics of a toilet block include:

• Lifespan - how long the block lasts, usually measured as number of flushes before the block is completely dissolved;

• 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;

• 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 mm of foam;

• Fragrance performance - fragrance development during a flush as well a fragrance perception between flushes.

Solid toilet blocks are thus useful for continuously cleaning the inside of a toilet bowl but may not be suitable for performing a ‘deep clean’ of the inside of the toilet bowl as the flush water comprising the cleansing and/or other components is only briefly in contact with the inside surface of the toilet bowl.

Solid hard surface cleaning compositions containing an effervescent base are known for use on household surfaces like e.g. in toilets and dishwashing machines, for one time deep cleaning. The effervescent base usually comprises a carbonate salt capable of releasing CO2 when reacting with an acid. When in contact with water, e.g. by submerging in water, the effervescent base in the composition produces CO2 thereby creating a foam. The surface of e.g. the inside of a toilet bowl is therefore in contact with a cleaning liquor or foam. This allows for cleaning of the hard surface without the need of manually scrubbing, wiping or otherwise touching the hard surface. In-use characteristics of such solid compositions include:

• Foam development - how much visible foam develops during dissolution as well as how much and how long visible foam is present after dissolution. This is usually measured as mm of foam and visually assessed as ‘foam quality’;

• Fragrance performance - fragrance development during dissolution as well a fragrance perception after flush;

• Dissolution time - how long it takes for the composition to completely dissolve;

• Effective organic soil removal; and

• Effective limescale removal.

Existing hard surface cleaning compositions may not always address all of the above mentioned in-use characteristics. Usually there is a trade-off between these in-use characteristics. For example, a harder toilet block will have a longer lifespan but may not perform well on foam development.

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.

Despite efforts thus far, there is still a need for solid hard surface cleaning compositions with improved in-use characteristics.

Summary of the invention

Accordingly, in a first aspect the invention relates to a solid hard surface cleaning composition comprising: a. a biocidal quaternary ammonium compound; b. an anionic surfactant comprising alkyl sulfate; and c. an effervescence base comprising a carbonate salt and an acid; wherein, the weight ratio of biocidal quaternary ammonium compound to anionic surfactant is from 1.5:1 to 7:1; • at least 50 wt% of the total amount of acid present in the cleaning composition is sulfamic acid calculated on total amount of acid present in the cleaning composition;

• the cleaning composition comprises from 0 to 1 wt% water; and

• 25 grams of the cleaning composition dissolved in 1.5 litres of water of 20° Celsius provides an aqueous solution with a pH of 1.5 to 4.5.

The invention also provides for a method of cleaning the inside surface of a toilet bowl comprising the steps of a. adding the hard surface cleaning composition according to the invention to water present inside the toilet bowl; b. allowing the composition to dissolve in the water to provide for a cleaning solution and/or foam; c. optionally leaving the surface into contact with the cleaning solution and/or foam; and d. flushing the toilet with water.

Detailed description of the invention

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 degrees Celsius. Biocidal quaternary ammonium compound

The solid hard surface cleaning composition of the present invention comprises a biocidal 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 BARDACTM, 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 BARDACTM 2250 R and BTC® 1010, both 50% active; and BARDACTM 2280 R and BTC® 1010- 80, both 80% active), dioctyl dimethyl ammonium chloride (available as BARDACTM LF, 50% active; BARDACTM 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 BARDACTM 205M, 50% active; and available as BARDACTM 208M, 80% active), a mixture of octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride; and dioctyl dimethyl ammonium chloride (available as BARDACTM 2050, 50% active; and available as BARDACTM 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 preferably comprises from 0.1 to 20% by weight of the quaternary ammonium compound, more preferably from 0.5 to 15%, even 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

The solid hard surface cleaning composition of the present invention comprises an anionic surfactant comprising 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 wt%, more preferably 0.2 to 10 wt%, even more preferably from 0.3 to 5 wt% and most preferably from 0.4 to 3 wt%, 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 7:1, like for example 1.5:1 to 6:1 , preferably from 2:1 to 5:1, more preferably from 3:1 to 5:1.

Effervescent base

The solid hard surface cleaning composition of the present invention comprises an effervescent base.

Typically, the effervescent base comprises an acid and a carbonate salt which upon combining in the presence of water produce an effervescent reaction (i.e. generate carbon dioxide). At least 50 wt% of the total amount of acid present in the cleaning composition is sulfamic acid calculated on total amount of acid present in the cleaning composition. The acid may further comprise tartaric acid, citric acid, fumaric acid, malic acid and/or oxalic acid. Preferably at least 60 wt% of the total amount of acid present in the cleaning composition is sulfamic acid calculated on total amount of acid present in the cleaning composition, more preferably at least 80 wt% and even more preferably essentially all.

Preferably the amount of adipic acid is kept low as it was found that adipic acid negatively influences foam formation and/or quality thereof. Preferably the composition comprises 0 to 1 wt% adipic acid and more preferably is free of adipic acid.

The carbonate salt is preferably selected from sodium carbonate, calcium carbonate, magnesium carbonate, ammonium carbonate, potassium carbonate, sodium bicarbonate, calcium bicarbonate and mixtures thereof. Preferably the amount of acid is in stoichiometric excess over the carbonate salt. The stoichiometric excess of acid over the carbonate salt also allows for providing the desired acidic pH, wherein the pH is determined as defined herein.

The solid hard surface cleaning composition of the present invention preferably comprises from 10 to 95 wt% of the effervescent base, more preferably from 20 to 90 wt%, even more preferably from 30 to 90 wt% and most preferably from 45 to 85 wt%. 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. Preferably the shape is selected from ballshaped, cubical, rectangular, circular, disc, cylindrical, flower-shaped, hemispherical, lentil-shaped, oblong, star-shaped and hexagonal. More preferably the composition is ball-shaped, cylindrical, cubical, rectangular or hexagonal shaped. Hexagonal shaped solid compositions are particularly preferred.

Preferably, the solid hard surface cleaning composition is provided as a water soluble or water dispersible unit dose, like for example an amount of powder or granulate packed in a water-soluble polymer like e.g. poly vinyl alcohol (PVA), or as a shaped solid like for example a hexagonal. The unit dose 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 15 to 50 grams.

Alternatively, the solid hard surface cleaning composition is provided as a unit dose, like for example an amount of powder or granulate packed in a unit dose packaging like plastic or carton sachet or container.

It is not preferred that the 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 shaped solid hard surface cleaning composition is preferably packaged in a blister pack or a multidose container which is preferably equipped with a child-safe locking mechanism.

Formation/shaping of the hard surface cleaning composition into various solid forms 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 wt% of the composition, more preferably from 0 to 0.5 wt% and even more preferably from 0 to 0.2 wt%. 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 an electric or hydraulic tableting 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.

Preferably the hard surface cleaning composition of the present invention is a shaped hard surface cleaning composition with a hardness of 40 to 300 Newton, more preferably 45 to 250 Newton, and even more preferably 50 to 200. pH

The solid hard surface cleaning composition of the present invention has a pH from 1.5 to 4.5, preferably 1.5 to 4, more preferably from 1.6 to 3 and even more preferably from 1.7 to 2.5.

The pH is determined by dissolving 25 grams of solid cleaning composition in 1.5 litre demin water of about room temperature and determining the pH of the resulting aqueous solution.

Further ingredients

The hard surface cleaning composition of the invention may further comprise: a. a hydrophobic fragrance component; b. further surfactant selected from nonionic surfactant and/or amphoteric surfactant; and c. optionally a disintegrant polymer.

Hydrophobic fragrance component

Hydrophobic fragrance components are often utilized in cleaning compositions but may negatively influence the amount of foam and quality thereof. The composition of the present invention has an improved tolerance of hydrophobic fragrance.

Preferably the fragrance component is selected from the groups consisting of (4Z)- cyclopentadec-4-en-1-one, rose oxide, ethyl-2-methyl valerate (manzanate), limonene, dihyro myrcenol, dimethyl benzyl carbonate acetate, benzyl acetate, geraniol, methyl nonyl acetaldehyde, cyclacet (verdyl acetate), cyclamal, beta ionone, hexyl salicylate, tonalid, phenafleur, octahydrotetramethyl acetophenone (OTNE), the benzene, toluene, xylene (BTX) feedstock class such as 2-phenyl ethanol, phenoxanol and mixtures thereof, the cyclododecanone feedstock class, such as habolonolide, the phenolics feedstock class such as hexyl salicylate, the C5 blocks or oxygen containing heterocycle moiety feedstock class such as gamma decalactone, methyl dihydrojasmonate and mixtures thereof, the terpenes feedstock class such as dihydromycernol, linalool, terpinolene, camphor, citronellol and mixtures thereof, the alkyl alcohols feedstock class such as ethyl-2-methylbutyrate, the diacids feedstock class such as ethylene brassylate, and mixtures of these components.

Preferably the hard surface cleaning composition comprises from 0.01 to 2 wt% hydrophobic fragrance component, more preferably 0.05 to 1 wt%, even more preferably 0.1 to 0.5 wt%.

Further surfactants

Further surfactant is selected from nonionic surfactant and/or amphoteric surfactant.

The further surfactant preferably is present in an amount from 0.1 to 5 wt%, more preferably from 0.2 to 4 wt%, even more preferably 0.3 to 3 wt% and still more preferably from 0.4 to 2 wt%.

Nonionic surfactant

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, endcapped 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): R1O(R2O)b(Z)a, wherein R1 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.

Amphoteric surfactant

Preferably the amphoteric surfactant comprises betaine. Suitable betaines include alkyl betaine, alkyl amido betaine, alkyl amidopropyl betaine, alkyl sulphobetaine and alkyl phosphobetaine, wherein the alkyl groups preferably have from 8 to 19 carbon atoms.

Examples include cocodimethyl sulphopropyl betaine, cetyl betaine, laurylamidopropyl betaine, caprylate/caprate betaine, capryl/capramidopropyl betaine, cocamidopropyl hydroxysultaine, cocobutyramido hydroxysultaine, and preferably lauryl betaine, cocamidopropyl betaine and sodium cocamphopropionate. Preferably the betaine is cocamidopropyl betaine (CAPB).

It is preferred that the further surfactant is amphoteric surfactant. Preferably the further surfactant is betaine amphoteric surfactant.

Disintegrant polymer

The cleaning composition of the present invention may comprise a disintegrant polymer. Disintegrants include organic materials such as starches, for example, corn, maize, rice and potato starches and starch derivatives, such as carboxymethyl starch, modified or pre-gelatinized starch and sodium starch glycolate; celluloses and cellulosic derivatives, for example, sodium carboxymethyl cellulose, cross-linked modified cellulosic, and microcrystalline cellulosic fibres; natural gums (for example, acacia, tragacanth, carrageenan, xanthan, agar, guar, locust bean, karaya, pectin, gellan); sugars (for example, glucose, sucrose); and various synthetic organic polymers, notably polyethylene glycol, polyvinyl alcohol, polyvinyl acetate and crosslinked polyvinyl pyrrolidone, and crosslinked polyacrylic acid.

Typical disintegrants suitable for the cleaning composition of the present invention include synthetic polymers including, for example, polyvinyl pyrrolidone, polyacrylates and polyvinyl sulfonates; and native or modified biopolymers including alginates, starches and cellulose, derivatives thereof and combinations thereof. On contact with water the disintegrant will rapidly absorb water and swell. Disintegrant polymers are usually added to shaped solid hard surface cleaning compositions, as the swelling thereof upon contact with water creates stress points that will aid in breaking up the tablet. We have surprisingly found that disintegrants may provide for better foam quality and/or quantity, for example in formulations comprising hydrophobic fragrance, in shaped solid hard surface cleaning compositions as well as free flowing powder solid hard surface cleaning compositions.

Preferably the disintegrant polymer is chosen from crosslinked polyvinyl pyrrolidone (PVP) homopolymer, cellulosic polymer and combinations thereof. Examples of such disintegrants include Disintex™ 75 from Ashland, a cross linked crosslinked polyvinyl pyrrolidone also known as polyvinyl polypyrrolidone; and sodium carboxymethyl cellulose, a cellulosic polymer. A preferred disintegrant polymer is crosslinked polyvinyl pyrrolidone (PVP) homopolymer.

The disintegrant polymer preferably is present in an amount from 0.1 to 3 wt%, more preferably from 0.2 to 2 wt%, even more preferably 0.3 to 1.5 wt% and still more preferably from 0.4 to 1 wt%.

Weight ratio of further surfactant and disintegrant polymer

Preferably the hard surface cleaning composition of the invention comprises the further surfactant and disintegrant polymer in a weight ratio from 1 :5 to 5:1 .

More preferably the hard composition comprises the further surfactant and disintegrant polymer in a weight ration from 1 :3 to 3:1 , even more preferably 1 :2 to 2:1 , still more preferably 1 :1.5 to 1.5:1 and still even more preferably 1 :1.1 to 1.1 :1 , like for example 1 :1.

Fillers

The hard surface cleaning composition of the invention may comprise fillers, wherein the filler is an inorganic salt selected from sulphates, halides, phosphates and combinations thereof. For the purpose of the present invention carbonates and bicarbonates are part of the effervescent base and are not part of the total amount of fillers.

Preferably, said inorganic salt is selected from sulphates. The inorganic salt that may be employed as a filler in the toilet cleaner block is preferably selected from alkali metal salts, earth alkaline metal salts, ammonium salts and combinations thereof, even more preferably it is selected from alkali metal salts, most preferably it is selected from sodium salts.

Preferably the composition of the invention only comprises a minimal amount of filler. Preferably the amount of fillers is from 0 to 5 wt%, more preferably from 0.1 to 4 wt%, even more preferably from 0.2 to 3 wt% and still more preferably from 0.5 to 2 wt%.

Method of cleaning

The present invention also concerns a method of cleaning the inside surface of a toilet bowl comprising the steps of a. adding the hard surface cleaning composition of the invention to water present inside the toilet bowl; b. allowing the composition to dissolve in the water to provide for a cleaning solution and/or foam; c. optionally leaving the surface into contact with the cleaning solution and/or foam; and d. flushing the toilet with water.

The advantage of this method of cleaning is that ‘deep cleaning’ is realized without the need of manually scrubbing, wiping or otherwise touching the hard surface. It will be understood that the method of cleaning is equally suitable for cleaning the inside surface of any apparatus comprising a housing and an inner space such as a machine dishwasher. The present method is especially suitable for cleaning the inside of a machine dishwasher the hard surface cleaning composition of the invention is added to water present inside the machine dishwasher, more specifically to the water present at the drain side of the machine dishwasher.

Figures

Figure 1 shows a plexiglass toilet bowl model. Dimensions in parentheses are the internal dimensions.

The invention will now be illustrated by means of the following non-limiting examples.

Examples

Tablet pressing

The solid cleaning formulation is pressed into tablets of hexagonal shape with the longest diameter being 38 mm using a pressure of about 20 KN. The height of the tablet will depend on the physical characteristics of the formulation (e.g. density) but is about 14 mm.

Foam and tablet disintegration

Foam development and tablet disintegration are measured using a plexiglass toilet bowl model as depicted in Figure 1 using the following protocol.

The model is filled with 1.5 litre demin water of about room temperature. 25 grams of the solid formulation to be tested is added to the water. This is time zero (TO).

The required time for the solid formulation to dissolve is measured using a stopwatch.

Foam height is measured along axis A as indicated in Figure 1.

For each formulation to be measured the protocol is executed 3 times and the average calculated. pH

Example 1

Solid cleaning formulations were prepared according to the base composition as in Table 1 with further ingredients as in Table 2. The thus prepared cleaning formulations were pressed into tablets of 25 grams according to the method described above.

The foam quality and tablet disintegration were tested using the protocol described above. The results are compiled in Table 3.

TABLE 1 (wt% calculated on total product)

^# C12-14 Alkyl dimethyl benzyl ammonium chloride (ADBAC)

TABLE 2 (wt% calculated on total product)

¹ Lutensol AT 25;² Disintex 75; ³ Tween 80-LQ; ⁴ Carbopol 2984; ⁵ Glucopon 50G; ⁶ Tegobain CK D.

TABLE 3

Example 2

Solid cleaning formulations were prepared as in Table 4. The thus prepared cleaning formulations were pressed into tablets of 25 grams according to the method described above. The foam quality and tablet disintegration were tested using the protocol described above. The results are compiled in Table 5.

TABLE 4 (wt% calculated on total product) ^# C12-14 Alkyl dimethyl benzyl ammonium chloride (ADBAC)

TABLE 5

Example 3 Solid cleaning formulations were prepared as in Table 6. The thus prepared cleaning formulations were pressed into tablets of 25 grams according to the method described above. The foam quality and tablet disintegration were tested using the protocol described above. The results are compiled in Table 7.

TABLE 6 (wt% calculated on total product) ^# C12-14 Alkyl dimethyl benzyl ammonium chloride (ADBAC)

12 $: WO 2022/175695 example 2/532B

13 $: WO 2022/1756954/17

TABLE 7

Example 4

Solid cleaning formulations were prepared as in Table 8. The thus prepared cleaning formulations were used as a powder in an amount of 25 grams. TABLE 8 (wt% calculated on total product)

14 WO 03/064579 A1 Example 2

15 modified sample 14, according to the invention

TABLE 9

Claims

1. A solid hard surface cleaning composition comprising: a. a biocidal quaternary ammonium compound; b. an anionic surfactant comprising alkyl sulfate; and c. an effervescence base comprising a carbonate salt and an acid; wherein,

• the weight ratio of biocidal quaternary ammonium compound to anionic surfactant is from 1.5:1 to 7:1;

• at least 50 wt% of the total amount of acid present in the cleaning composition is sulfamic acid calculated on total amount of acid present in the cleaning composition;

• the cleaning composition comprises from 0 to 1 wt% water; and

2. The hard surface cleaning composition according to claim 1 further comprising: a. a hydrophobic fragrance component; b. further surfactant selected from nonionic surfactant and/or amphoteric surfactant; and c. optionally a disintegrant polymer.

3. The hard surface cleaning composition according to claim 2 wherein the further surfactant is selected from amphoteric surfactant, preferably betaine amphoteric surfactant.

4. The hard surface cleaning composition according to claim 2 or claim 3 wherein the composition comprises the further surfactant and disintegrant polymer in a weight ratio from 1 :5 to 5:1.

5. The hard surface cleaning composition according to claim 2 or claim 3 wherein the hard composition comprises the further surfactant and disintegrant polymer in a weight ration from 1 :3 to 3:1 , preferably 1:2 to 2:1 , more preferably 1:1.5 to 1.5:1 and even more preferably 1:1.1 to 1.1:1.

6. The hard surface cleaning composition according to any one of claims 2 to 5 wherein the disintegrant polymer is selected from crosslinked polyvinyl pyrrolidone (PVP) homopolymer, cellulosic polymer and combinations thereof.

7. The hard surface cleaning composition according to any one of claims 1 to 6 wherein the hard surface cleaning composition is a shaped hard surface cleaning composition with a hardness of 40 to 300 Newton.

8. The hard surface cleaning composition according to claim 7 wherein the hard surface cleaning composition is a shaped hard surface cleaning composition with a hardness of 145 to 250 Newton, preferably 150 to 230 more preferably 155 to 220 and even more preferably 160 to 210.

9. The hard surface cleaning composition according to any one of claims 1 to 8 wherein at least 60 wt% of the total amount of acid present in the cleaning composition is sulfamic acid calculated on total amount of acid present in the cleaning composition, preferably at least 80 wt% and more preferably essentially all.

10. The hard surface cleaning composition according to any one of claims 1 to 9 wherein the composition comprises 0 to 1 wt% adipic acid, preferably is free of adipic acid.

11. The hard surface cleaning composition according to any one of claims 1 to 10 wherein 25 grams of the cleaning composition dissolved in 1.5 litres of water of 20° Celsius provides an aqueous solution with a pH of 1.5 to 4, preferably 1.6 to 3, and more preferably 1.7 to 2.5.

12. The hard surface cleaning composition according to any one of claims 1 to 11 wherein the composition comprises from 0 to 0.5 wt% water, preferably 0 to 0.2 wt%.

13. Method of cleaning the inside surface of a toilet bowl comprising the steps of a. adding the hard surface cleaning composition according to any one of claims 1 to 12 to water present inside the toilet bowl; b. allowing the composition to dissolve in the water to provide for a cleaning solution and/or foam; c. optionally leaving the surface into contact with the cleaning solution and/or foam; and d. flushing the toilet with water.