EP4305136A1

EP4305136A1 - Shaped toilet cleaner block

Info

Publication number: EP4305136A1
Application number: EP22708952.1A
Authority: EP
Inventors: Koushik ACHARYA; Olivier LONTOUO TAKEMLON; Paolo Mondani; Michele STEFANONI; Ivan Valcarenghi
Original assignee: Unilever Global IP Ltd; Unilever IP Holdings BV
Current assignee: Unilever Global IP Ltd; Unilever IP Holdings BV
Priority date: 2021-03-08
Filing date: 2022-03-02
Publication date: 2024-01-17
Anticipated expiration: 2042-03-02
Also published as: EP4305136C0; BR112023018191A2; WO2022189228A1; ZA202307721B; CN117120586A; AU2022233781B2; EP4305136B1; PL4305136T3; AU2022233781A1

Abstract

The present invention relates to a shaped toilet cleaner block comprising a surfactant mix, wherein the surfactant mix comprises i. 10 to 60 wt% alkyl benzene sulphonate; ii. 1 to 40 wt% primary alcohol sulphate; and iii. 1 to 15 wt% alkyl poly glycoside; wherein the weight ratio of (alkyl benzene sulphonate + primary alcohol sulphate) / alkyl poly glycoside is from 6:1 to 19:1. The invention further relates a method of making the toilet cleaner block of the present invention as well as a method of cleaning and/or disinfecting and/or deodorizing the inside of a toilet bowl using said toilet block.

Description

Shaped toilet cleaner block

Field of the invention

The present invention relates to toilet cleaner blocks, more particularly to toilet cleaner blocks comprising a surfactant mix of alkyl benzene sulfonate, primary alcohol sulphate and alkyl poly glycoside.

Background of the invention

Toilet cleaner blocks 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 placed inside the toilet bowl. For the latter, the block can either be held under the rim of the toilet in a suitable holder (so called rim blocks) or placed directly on the surface of the toilet bowl without a holder (so called cageless blocks) for intermittent contact of the toilet cleaner block with flush water.

Toilet cleaner 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 often also 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.

Cageless blocks may be gel like compositions that can be applied to the toilet surface using an applicator comprising one or (usually) more doses. The gel like consistency allows the use of an applicator that applies the gel by squeezing the gel out of the applicator. Alternatively, 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 e.g. a gel strip, at the back of the toilet cleaner block. The latter requiring a more complicated manufacturing process.

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 cm of foam;

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

Existing toilet block formulations 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.

WO2013/106372 discloses gel like cleaning compositions having a viscosity of about 600,000 cP to about 1 ,500, 000 cP comprising a first nonionic surfactant, polyalcohol, hydrophilic polymer, mineral oil, a second nonionic surfactant being an ethoxylated or non-ethoxylated blend of linear primary alcohols and water.

EP 2 872613 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 wt%. Despite efforts thus far, there is still a need for shaped toilet cleaner blocks with improved in-use characteristics. Especially 3D shape retention for shaped toilet cleaner blocks that can be used a cageless toilet blocks. Summary of the invention

We have found that shaped toilet cleaner blocks comprising a surfactant system of alkyl benzene sulphonate, primary alcohol sulphate and alkyl poly glycoside allow for improved in-use characteristics. Accordingly, in a first aspect the invention relates to a shaped toilet cleaner block comprising: a. a surfactant mix comprising: i. 10 to 60 wt% alkyl benzene sulphonate; ii. 1 to 40 wt% primary alcohol sulphate; iii. 1 to 15 wt% alkyl poly glycoside; b. 10 to 60 wt% filler; c. 0.5 to 15 wt% polyol with a carbon chain length of 2 to 4; d. 0 to 3 wt% adhesion promoting polymer; e. 0 to 2 wt% water; wherein the weight ratio of (alkyl benzene sulphonate + primary alcohol sulphate) / alkyl poly glycoside is from 6:1 to 19:1.

The invention further provides a method of making a shaped toilet cleaner block according to the present invention comprising the steps of: a. providing the alkyl poly glycoside as a solid; b. mixing the ingredients; c. extruding the mixed ingredients.

The invention also provides for a method of cleaning and/or disinfecting and/or deodorizing the inside of a toilet bowl comprising the steps of providing a shaped toilet cleaner block according to the present invention and placing said block on the surface of the inside of the toilet bowl. Brief description of the drawings

FIG. 1 A to 1 D show possible block shapes of the shaped toilet cleaner blocks of the present invention. 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.

The shaped toilet cleaner block of the present invention preferably is designed for use inside the toilet bowl, where the toilet cleaner block is positioned in the toilet bowl such that it is wetted when the toilet is flushed. This may be achieved by placing the toilet cleaner block in a suitable holder for placement under the toilet rim of the toilet bowl. Alternatively, and preferably, the toilet cleaner block is placed directly on the inside of the toilet bowl without a holder as a self-adhesive toilet block, optionally with the use of an adhesive layer at the back of the toilet cleaner block, like e.g. a gel strip, but preferably without such an additional layer.

The shaped toilet cleaner block of the present invention has the advantage of easy manufacturing as it can be manufactured by extrusion. Alternative self-adhesive toilet blocks may be gels that need to be contained in an applicator or require more elaborate manufacturing like for example mould casting.

Surfactant ratios

The toilet cleaner block comprises a surfactant mix comprising alkyl benzene sulphonate, primary alcohol sulphate and alkyl poly glycoside surfactant. It was surprisingly found that specific weight ratios of these surfactants allow for toilet cleaner blocks with improved and better balanced in-use characteristics, including life span, foam development and retention of 3D shape. Preferably the toilet cleaner block comprises 12 to 65 wt% surfactant mix, more preferably 15 to 60 wt%, even more preferably 20 to 50 wt% and still even more preferably 25 to 40 wt%.

The weight ratio of of (alkyl benzene sulphonate + primary alcohol sulphate) / alkyl poly glycoside is from 6:1 to 19:1. Preferably the weight ratio of (alkyl benzene sulphonate + primary alcohol sulphate) / alkyl poly glycoside is from 7:1 to 17:1, and more preferably 8:1 to 14:1.

Alkylbenzene sulphonates (ABS) Alkylbenzene sulphonates (ABS) and derivatives thereof 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. 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.

The alkyl benzene sulfonate employed in the surfactant mix preferably is a salt selected from alkali metal salts, earth alkaline metal salts, ammonium salts and combinations thereof. More preferably, the alkyl benzene sulfonate is an alkali metal salt, most preferably a sodium salt. Preferably the alkyl benzene sulfonate is Ce-ie alkyl benzene sulfonate and more preferably C10-14 alkyl benzene sulfonate. Sodium C10-14 alkyl benzene sulfonate is a preferred alkyl benzene sulfonate for use in the surfactant mix.

The surfactant mix comprises 10 to 60 wt% alkyl benzene sulphonate calculated on total weight of toilet cleaner block, preferably 20 to 40 wt% alkyl benzene sulphonate and more preferably 10 to 20 wt%.

Primary alcohol sulphate

The primary alcohol sulphate is a surfactant of the formula (Formula I): (R_I-0-S0₃ )_XM^x+, wherein:

Ri is saturated or unsaturated C8-C16, preferably C12-C14 alkyl chain; preferably, Ri is a saturated C8-C16, more preferably a saturated C12-C14 alkyl chain; x is equal to 1 or 2; M^x+ is a suitable cation which provides charge neutrality selected from sodium, calcium, potassium and magnesium.

Examples of primary alcohol sulphate include sodium lauryl sulphate. 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.

The surfactant mix comprises 1 to 40 wt% primary alcohol sulphate calculated on total amount of toilet cleaner block, preferably 5 to 30 wt%, more preferably 10 to 20 wt%.

Alkyl polyqlvcoside surfactant

As used herein alkyl poly glycosides are compounds according to the formula (Formula II): R₁0(R₂0)_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 poly glycosides are generally present as mixtures of alkyl poly glycosides 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 poly glycosides suitable for use in the disclosed toilet cleaner block include those having the formula II wherein Z is a glucose residue, b is zero, Ri is an alkyl group that contains 4 to 22 carbon atoms, and the average value of a is about 1 to 2. Preferably Ri is an alkyl group that contains 8 to 18 carbon atoms, and more preferred Ri is an alkyl group that contains 10 to 16 carbon atoms and the average value of a is about 1 to 2. Such alkyl poly glucosides are commercially available, for example, as GLUCOPON branded alkyl poly glucoside compositions from BASF (formerly Cognis Corporation).

The surfactant mix comprises 1 to 15 wt% alkyl poly glycoside calculated on total amount of toilet cleaner block, preferably 1 to 10 wt%, more preferably 2.5 to 7.5 wt%.

Further surfactants The toilet cleaner block may comprise further surfactants in addition to the surfactants making up the defined surfactant mix as above. The total amount of further surfactants calculated on total amount of toilet cleaner block is from 0 to 10 wt%, preferably 0.5 to 8 wt% and more preferably 1 to 5 wt%. Further surfactants may include further anionic surfactants in addition to the alkyl benzene sulphonate and primary alcohol sulphate, further nonionic surfactants in addition to the alkyl poly glycoside, amphoteric surfactants and combinations thereof.

Examples of further anionic surfactants include alkyl sulfoacetate like e.g. sodium lauryl sulfoacetate, 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. Examples of further nonionic surfactants include cocamide monoethanolamine (CMEA) and alcohol ethoxylates. Examples of amphoteric surfactant include betaines and aminoxide surfactant.

Fillers Preferably the filler in the toilet cleaner block is an inorganic salt selected from sulphates, carbonates, halides, phosphates and combinations thereof. More preferably, said inorganic salt is selected from sulphates, carbonates and combinations thereof.

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.

The toilet cleaner block comprises 10 to 60 wt% filler. Preferably the toilet cleaner block comprises 20 to 60 wt% filler, more preferably 40 to 50 wt%.

In a preferred toilet cleaner block of the present invention the filler contains at least 50 wt%, preferably at least 80 wt%, more preferably at least 90 wt% and even more preferably at least 95 wt% sodium sulphate.

Polyol

The toilet cleaner block comprises from 0.5 to 15 wt% polyol with a carbon chain length of 2 to 4. The polyol provides for processability on an extrusion line and imparts some pliability to the extruded toilet cleaner block such that it can be placed directly on the curved surface inside a toilet bowl. 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. Preferably, the toilet cleaner block comprises 0.5 to 10 wt% polyol, more preferably 0.5 to 2.5 wt%. Adhesion promoting polymer

The toilet cleaner block of the present invention comprises 0 to 3 wt% adhesion promoting polymer to further aide the self-adhesiveness of the toilet cleaner block and thereby to suitably stick to the inside surface of a toilet bowl. Preferably the toilet block comprises 0.05 to 2 wt% adhesion promoting polymer and more preferably 0.1 to 0.75 wt%.

Adhesion promoting polymers are suitably known by the skilled person in the area of self-adhesive toilet blocks. Preferably the adhesion promoting polymer is selected from natural and synthetic cellulosic polymers, such as carboxymethyl cellulose, polyacrylates, polyvinyl pyrolidone, maleic/vinyl copolymers, silicon based polymers, alkyl (C8-C22) polysorbate derivates and mixtures thereof.

Polyacrylates are preferred adhesion promoting polymers. A suitable chemical class of such carboxyvinyl 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 carboxyvinyl 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 pre neutralisation 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 carboxyvinyl polymer for use in the compositions of the present invention is a homopolymer of acrylic acid crosslinked with pentaerythritol triallylether. 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. Water

To aide processability the toilet cleaner block should not contain more than 2 wt% water. Preferably the amount of water is 0 to 1 wt% and more preferably 0 to 0.5 wt%. Further ingredients

The toilet cleaner block of the present invention may comprise further ingredients like for example builder.

Builder Examples of builders that may be included in the toilet cleaner block include low molecular weight polycarboxylic acids and salts thereof, the homopolymeric and copolymeric polycarboxylic acids and salts thereof, citric acid and salts thereof, carbonates, phosphates, silicates, zeolites and combinations thereof.

Preferably, the toilet cleaner block contains 0.5 to 20 wt%, more preferably 0.8 to 15 wt%, and even more preferably 1 to 10 wt.% builder.

A preferred toilet cleaner block contains at least 0.8 wt%, preferably at least 1 wt% of builder selected from phosphate, citrate and combinations thereof. Other ingredients

Other ingredients that may applied in the toilet cleaner block of the present invention include colorant, perfume, bleaching agents, polymers, corrosion inhibitors, flush regulators, adhesion inhibitors, pH regulators, enzymes and preservatives. The toilet cleaner block may be colored using any conventional means of coloring in the area of toilet block compositions but preferably the colorant is a polymeric colorant, or pigment dispersion colorant. Preferably the toilet cleaner block comprises 0 to 3 wt% colorant, more preferably 0.01 to 2 wt%. Perfume or fragrance may be present in an amount of 0 to 7 wt%, preferably 0.1 to 6 wt% and more preferably 0.5 to 5 wt%. Bleaching agents that may suitably be applied in the toilet cleaner blocks of the present invention include bleach hypo chlorite donors, peroxides, peracids and/or perborates. A bleach activator can also be used in addition to the bleaching agent. Polymers, such as acrylic polymers, can suitably be incorporated in the toilet cleaner block to reduce formation of lime scale and soil re-deposition.

Flush regulators can be employed in the toilet cleaner block to regulate degradation of the block. Solid long-chain fatty acids, such as stearic acid, are preferred regulators. Enzymes that may be applied in the toilet cleaner block include proteases, lipases, amylases, hydrolases and/or cellulases.

Toilet block shape

Preferably the toilet cleaning block of the present invention has a block shape that is characterized by a maximum dimension ‘a’ and a minimum dimension ‘b’ wherein the ratio of a/b is from 3.5 to 12.5, preferably 4 to 9 and more preferably 5 to 7. 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. Minimum dimension ‘b’ is perpendicular to the maximum dimension ‘a’ as can be seen in FIG. 1A to 1D.

Preferably dimension ‘a’ is 25 to 90 mm, more preferably 30 to 70 mm, and even more preferably 35 to 50 mm. Preferably dimension ‘b’ is 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 still even more preferably 6 to 8 mm.

The toilet block may have any particular shape as long as it complies with the dimensions ‘a’ and ‘b’. It may be an ornamental design, like for example a flower design, or geometric design, like for example circular or hexagonal. It will be understood that circular in this respect refers to a flat shaped cylinder as illustrated in FIG. 1B and hexagonal refer to a flat shaped hexagonal cylinder as illustrated in FIG.

1 A. To allow for proper adhesion to the toilet bowl surface, the back of the toilet block, i.e. the side that is facing and in contact with the surface of the toilet bowl, is flat to allow for a maximum contact area. The upper surface of the toilet block, i.e. the surface facing away from the surface of the toilet bowl, may be ornamental but preferably is flat as flush water will quickly erode any intricate details.

Preferably the shape of the toilet cleaning block of the present invention has a discrete rotational symmetry of the n^th order with respect to the axis of the shape, meaning that rotation by an angle of 360 n (180°, 120°, 90°, 12°, 60°, 51 3/7°, etc.) does not change the object. It will be understood that a "1-fold" symmetry is no symmetry (all objects look alike after a rotation of 360°). FIG. 1A shows a n=6 rotational symmetry; FIG. 1B shows a n=1 symmetry, so no symmetry; FIG.1C shows a n=3 rotational symmetry; and FIG. 1D shows a n=2 rotational symmetry.

Preferably the toilet cleaning block has block shape that is characterized in that it has a discrete rotational symmetry of at least n=3 and preferably n=6. The shape of the toilet block may have an overall circular shape like for example hexagonal or octagonal. Hexagonal cylinders are a preferred.

Method of making

The present invention further provides for a method of making a shaped toilet cleaner block according to the present invention comprising the steps of: a. providing the alkyl poly glycoside as a solid; b. mixing the ingredients; c. extruding the mixed ingredients. To allow for the improved in-use characteristics, the current shaped toilet cleaner block comprises a specific surfactant mix. To suitably make the toilet cleaner block the alkyl poly glycoside surfactant is preferably provided as a solid that does not contain a noticeable amount of water. Method of cleaning and/or disinfecting and/or deodorizing

The present invention also provides for a method of cleaning and/or disinfecting and/or deodorizing the inside of a toilet bowl comprising the steps of providing a shaped toilet cleaner block according to the present invention and placing said block on the surface of the inside of the toilet bowl. That is, the toilet block is placed directly inside the toilet bowl as a self-adhesive toilet block without the use of a holder.

The toilet block may be placed on the surface of the inside of the toilet bowl by pressing the toilet block on the toilet bowl surface. The toilet bowl surface may be wetted, e.g. post flushing, but preferably the toilet bowl surface is reasonably dry, i.e. pre flushing. To prevent direct contact with the toilet block, a barrier in the form of an applicator may be used. A typical barrier can be a piece of paper or carton. The invention is further illustrated by the following non-limiting examples.

Examples

Lifespan test protocol

To determine the number of flushes a toilet rim block the following protocol is used.

• Three different flush type toilets are used: o Laminar water flow type toilet (ex Ideal Standard); o Back to front water flow type toilet (ex KOL O); o T urbulent water flow type toilet (ex Villeroy & Boch).

• The cageless shaped toilet cleaner block is placed inside the toilet directly on the surface of the toilet bowl where the maximum water flow is. Per toilet type 3 tests are done resulting in 9 tests in total (3 tests x 3 toilets).

• The toilet is flushed using water having a hardness of 24° F. The water is at room temperature.

• The toilet is flushed 15 times at regular intervals during a time period of 14.5 hours followed by 9.5 hours without flushing.

• Flushing is repeated until the toilet block is completely dissolved.

• The average number of flushes is then calculated based on the data of the 9 tests.

Foam profile protocol

To determine the foam profile the following protocol is used.

• A shaped toilet cleaner block is prepared and placed in the toilet as for the lifespan test protocol. • After the toilet is flushed the height of the foam in the toilet is determined by measuring the foam height taking the water line as off set (i.e. zero point).

• The foam height is measured at T=0 (i.e. right after flushing) and at T=5 minutes (i.e. 5 minutes after flushing). Average foam height is the average of foam height at T=0 and T=5 minutes.

• The foam height is reported in cm.

3D shape retention

To determine the 3D shape retention the following protocol is used. · A shaped toilet cleaner block is prepared and placed in the toilet as for the lifespan test protocol.

• After a predetermined number of flushes the shape of the block is visually assed and rated on a scale of 1 to 5 with 1 indicating 80 to 100% symmetry and 5 indicating 20 to 0% symmetry as compared to the starting shape.

Example 1

Toilet cleaner blocks according to the present invention were manufactured by means of extrusion on the basis of the formulations 1 to 3 shown in Table 1. A comparative example with formulation A as shown in Table 1 was also made. The extrusion conditions employed during manufacture were: Extrusion speed: 0.6- 1 m/minute; Extrusion temperature: 10-25 °C; and Cutting frequency 80-130 pieces/minute.

The shaped toilet blocks had a hexagonal cylindrical shape of 0.6-0.7 mm (height) x 40 mm (widest diameter); and 10 gram in weight.

The lifespan, foam profile and 3D shape retention of the toilet blocks was determined using the protocols as described above. The results are shown in Table 1.

TABLE 1 (wt% calculated on total product)

BASF; ⁴ Synthalen^® KP ex 3VSigma; ⁵ not measured.

Example 2 Using the same protocol as described for Example 1, toilet cleaner blocks according to the present invention were manufactured by means of extrusion on the basis of the formulations 4 and 5 shown in Table 2. Comparative examples with formulation B and C as shown in Table 2 were also made. Comparative examples B and C are similar to components E and F of US 2010/299818 A1.

The foam profile of the toilet blocks was determined using the protocols as described above, with the modification that the foam profile was measured for a back to front water flow type toilet (ex KOL-O) and turbulent water flow type toilet (ex Villeroy & Boch). The results are shown in Table 1.

TABLE 2 (wt% calculated on total product)

BASF; ⁴ Synthalen^® KP ex 3VSigma; ⁵ not measured; ⁶ Bioterge AS 90 coarse ex

Stepan; ⁷ PEG 8000; ⁸ Sorbosil AC 43; ⁹ Comperlan 100.

Claims

1. Shaped toilet cleaner block comprising: a. a surfactant mix comprising: i. 10 to 60 wt% alkyl benzene sulphonate; ii. 1 to 40 wt% primary alcohol sulphate; iii. 1 to 15 wt% alkyl poly glycoside; b. 10 to 60 wt% filler; c. 0.5 to 15 wt% polyol with a carbon chain length of 2 to 4; d. 0 to 3 wt% adhesion promoting polymer; e. 0 to 2 wt% water; wherein the weight ratio of (alkyl benzene sulphonate + primary alcohol sulphate) / alkyl poly glycoside is from 6:1 to 19:1.

2. Toilet cleaner block according to claim 1 wherein the weight ratio of (alkyl benzene sulphonate + primary alcohol sulphate) / alkyl poly glycoside is from 7:1 to 17:1, preferably from 8:1 to 14:1.

3. Toilet cleaner block according to claim 1 or 2 comprising 12 to 65 wt% surfactant mix, preferably 15 to 60 wt%, more preferably 20 to 50 wt% and even more preferably 25 to 40 wt%.

4. Toilet cleaner bock according to any one of claims 1 to 3 comprising 20 to 40 wt% alkyl benzene sulphonate, preferably 10 to 20 wt%.

5. Toilet cleaner block according to any one of claims 1 to 4 comprising 5 to 30 wt% primary alcohol sulphate, preferably 10 to 20 wt%.

6. Toilet cleaner block according to any one of claims 1 to 5 comprising 1 to 10 wt% alkyl poly glycoside, preferably 2.5 to 7.5 wt%.

7. Toilet cleaner lock according to any one of claims 1 to 6 comprising 20 to 60 wt% filler, preferably 40 to 50 wt%.

8. Toilet cleaner block according to any one of claims 1 to 7 comprising 0.5 to 10 wt% polyol, preferably 0.5 to 2.5 wt%.

9. Toilet cleaner block according to any one of claims 1 to 8 wherein the polyol has a carbon chain length of 3 and preferably is glycerol.

10. Toilet cleaner block according to any one of claims 1 to 9 comprising 0.05 to 2 wt% adhesion promoting polymer, preferably 0.1 to 0.75 wt%.

11. Toilet cleaner block according to any one of claims 1 to 10 wherein the adhesion promoting polymer is selected from natural and synthetic cellulosic polymers, such as carboxymethyl cellulose, polyacrylates, polyvinyl pyrolidone, maleic/vinyl copolymers, silicon based polymers, alkyl (C8-C22) polysorbate derivates and mixtures thereof.

12. Toilet cleaning block according to any one of claims 1 to 11 having a block shape that is characterized by a maximum dimension ‘a’ and a minimum dimension ‘b’ wherein the ratio of a/b is from 3.5 to 12.5, preferably 4 to 9 and more preferably 5 to 7.

13. Toilet cleaning block according to any one of claims 1 to 12 having a block shape that is characterized in that it has a discrete rotational symmetry of at least C=3, preferably C=6.

14. Method of making a shaped toilet cleaner block according to any one of claims 1 to 13 comprising the steps of: a. providing the alkyl poly glycoside as a solid; b. mixing the ingredients; c. extruding the mixed ingredients.

15. Method of cleaning and/or disinfecting and/or deodorizing the inside of a toilet bowl comprising the steps of providing a shaped toilet cleaner block according to any one of claims 1 to 13 and placing said block on the surface of the inside of the toilet bowl.