EP4305136B1 - Geformter toilettenreinigerblock - Google Patents

Geformter toilettenreinigerblock

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Publication number
EP4305136B1
EP4305136B1 EP22708952.1A EP22708952A EP4305136B1 EP 4305136 B1 EP4305136 B1 EP 4305136B1 EP 22708952 A EP22708952 A EP 22708952A EP 4305136 B1 EP4305136 B1 EP 4305136B1
Authority
EP
European Patent Office
Prior art keywords
toilet
toilet cleaner
block
block according
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP22708952.1A
Other languages
English (en)
French (fr)
Other versions
EP4305136C0 (de
EP4305136A1 (de
Inventor
Koushik ACHARYA
Olivier LONTOUO TAKEMLON
Paolo Mondani
Michele STEFANONI
Ivan Valcarenghi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever Global IP Ltd
Unilever IP Holdings BV
Original Assignee
Unilever Global IP Ltd
Unilever IP Holdings BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever Global IP Ltd, Unilever IP Holdings BV filed Critical Unilever Global IP Ltd
Publication of EP4305136A1 publication Critical patent/EP4305136A1/de
Application granted granted Critical
Publication of EP4305136C0 publication Critical patent/EP4305136C0/de
Publication of EP4305136B1 publication Critical patent/EP4305136B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0056—Lavatory cleansing blocks
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds

Definitions

  • 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.
  • 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.
  • 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.
  • cageless blocks may be solid blocks that are e.g. formed by moulding a heated pourable or malleable composition that hardens upon cooling.
  • 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.
  • 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 2 872 613 discloses self-adhesive sanitary compositions comprising a saccharide component selected from mono- or disaccharide, sugar alcohols or mixtures thereof, surfactant and residual water in an amount of 1 to 5 wt%.
  • US 2010/299818 discloses lavatory treatment blocks with good foaming benefits wherein the said blocks contain an amount of glycerine.
  • the blocks are used to deliver a composition which also comprises surfactants to a sanitary appliance , e.g. a toilet bowl.
  • 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.
  • a shaped toilet cleaner block comprising:
  • the invention further provides a method of making a shaped toilet cleaner block according to the present invention comprising the steps of:
  • 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.
  • FIG. 1A to 1D show possible block shapes of the shaped toilet cleaner blocks of the present invention.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • ABS Alkylbenzene sulphonates
  • Alkylbenzene sulphonates 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.
  • the alkyl benzene sulfonate is C 8-18 alkyl benzene sulfonate and more preferably C 10-14 alkyl benzene sulfonate.
  • Sodium C 10-14 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%.
  • the primary alcohol sulphate is a surfactant of the formula (Formula I): (R 1 -O-SO 3 - ) x M x+ , wherein:
  • 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 poly glycosides are compounds according to the formula (Formula II): R 1 O(R 2 O) b (Z) a , wherein R 1 is a alkyl radical, having from about 1 to about 30 carbon atoms; R 2 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).
  • 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.
  • 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, R 1 is an alkyl group that contains 4 to 22 carbon atoms, and the average value of a is about 1 to 2.
  • R 1 is an alkyl group that contains 8 to 18 carbon atoms, and more preferred R 1 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%.
  • 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.
  • 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.
  • further nonionic surfactants include cocamide monoethanolamine (CMEA) and alcohol ethoxylates.
  • amphoteric surfactant include betaines and aminoxide surfactant.
  • 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.
  • the toilet cleaner block comprises 20 to 60 wt% filler, more preferably 40 to 50 wt%.
  • 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.
  • 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.
  • the polyol has a carbon chain length of 3 and more preferably is glycerol.
  • the toilet cleaner block comprises 0.5 to 10 wt% polyol, more preferably 0.5 to 2.5 wt%.
  • 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.
  • 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.
  • 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.
  • 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.
  • a material is commercially available, for example, as CARBOPOL ® 974P NF Polymer or CARBOPOL ® 690 POLYMER, ex Lubrizol Advanced Materials, Inc.
  • carboxyvinyl polymer for use in the compositions of the present invention is a homopolymer of acrylic acid crosslinked with pentaerythritol triallylether.
  • 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.
  • the toilet cleaner block should not contain more than 2 wt% water.
  • the amount of water is 0 to 1 wt% and more preferably 0 to 0.5 wt%.
  • the toilet cleaner block of the present invention may comprise further ingredients like for example 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.
  • 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.
  • 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.
  • 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.
  • 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 .
  • dimension 'a' is 25 to 90 mm, more preferably 30 to 70 mm, and even more preferably 35 to 50 mm.
  • 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. 1A .
  • 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.
  • 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°, 72°, 60°, 51 3/7°, etc.) does not change the object.
  • a "1-fold" symmetry is no symmetry (all objects look alike after a rotation of 360°).
  • the shape of the toilet block may have an overall circular shape like for example hexagonal or octagonal. Hexagonal cylinders are a preferred.
  • the present invention further provides for a method of making a shaped toilet cleaner block according to the present invention comprising the steps of:
  • the current shaped toilet cleaner block comprises a specific surfactant mix.
  • the alkyl poly glycoside surfactant is preferably provided as a solid that does not contain a noticeable amount of water.
  • 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.
  • a barrier in the form of an applicator may be used.
  • a typical barrier can be a piece of paper or carton.
  • 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.
  • extrusion conditions employed during manufacture were: Extrusion speed: 0.6-1m/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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Molecular Biology (AREA)
  • Detergent Compositions (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)

Claims (15)

  1. Geformter Toilettenreinigerblock, umfassend:
    a. eine Tensidmischung, umfassend:
    i. 10 bis 60 Gew.-% Alkylbenzolsulfonat;
    ii. 1 bis 40 Gew.-% Primäralkoholsulfat;
    iii. 1 bis 15 Gew.-% Alkylpolyglykosid;
    b. 10 bis 60 Gew.-% Füllstoff;
    c. 0,5 bis 15 Gew.-% Polyol mit einer Kohlenstoffkettenlänge von 2 bis 4;
    d. 0 bis 3 Gew.-% haftungsvermittelndes Polymer;
    e. 0 bis 2 Gew.-% Wasser;
    wobei das Gewichtsverhältnis von (Alkylbenzolsulfonat + Primäralkoholsulfat) / Alkylpolyglykosid 6:1 bis 19:1 beträgt.
  2. Toilettenreinigerblock nach Anspruch 1, wobei das Gewichtsverhältnis von (Alkylbenzolsulfonat + Primäralkoholsulfat) / Alkylpolyglykosid 7:1 bis 17:1, vorzugsweise 8:1 bis 14:1 beträgt.
  3. Toilettenreinigerblock nach Anspruch 1 oder 2, umfassend 12 bis 65 Gew._% Tensidmischung, vorzugsweise 15 bis 60 Gew.-%, bevorzugter 20 bis 50 Gew.-% und noch bevorzugter 25 bis 40 Gew.-%.
  4. Toilettenreinigerblock nach irgendeinem der Ansprüche 1 bis 3, umfassend 20 bis 40 Gew.-% Alkylbenzolsulfonat, vorzugsweise 10 bis 20 Gew.-%.
  5. Toilettenreinigerblock nach irgendeinem der Ansprüche 1 bis 4, umfassend 5 bis 30 Gew.-% Primäralkoholsulfat, vorzugsweise 10 bis 20 Gew.-%.
  6. Toilettenreinigerblock nach irgendeinem der Ansprüche 1 bis 5, umfassend 1 bis 10 Gew.-% Alkylpolyglykosid, vorzugsweise 2,5 bis 7,5 Gew.-%.
  7. Toilettenreinigerblock nach irgendeinem der Ansprüche 1 bis 6, umfassend 20 bis 60 Gew.-% Füllstoff, vorzugsweise 40 bis 50 Gew.-%.
  8. Toilettenreinigerblock nach irgendeinem der Ansprüche 1 bis 7, umfassend 0,5 bis 10 Gew.-% Polyol, vorzugsweise 0,5 bis 2,5 Gew.-%.
  9. Toilettenreinigerblock nach irgendeinem der Ansprüche 1 bis 8, wobei das Polyol eine Kohlenstoffkettenlänge von 3 aufweist und vorzugsweise Glycerin ist.
  10. Toilettenreinigerblock nach irgendeinem der Ansprüche 1 bis 9, umfassend 0,05 bis 2 Gew.-% haftungsvermittelndes Polymer, vorzugsweise 0,1 bis 0,75 Gew.-%.
  11. Toilettenreinigerblock nach irgendeinem der Ansprüche 1 bis 10, wobei das haftungsvermittelnde Polymer unter natürlichen und synthetischen Cellulosepolymeren ausgewählt ist, wie Carboxymethylcellulose, Polyacrylaten, Polyvinylpyrrolidon, Malein-/ Vinylcopolymeren, Polymeren auf Silikonbasis, Alkyl (C8-C22)-Polysorbatderivaten und Mischungen davon.
  12. Toilettenreinigungsblock nach irgendeinem der Ansprüche 1 bis 11 in Blockform, die durch eine maximale Abmessung "a" und eine minimale Abmessung "b" gekennzeichnet ist, wobei das Verhältnis von a/b 3,5 bis 12,5, vorzugsweise 4 bis 9 und bevorzugter 5 bis 7 beträgt, wobei "a" und "b" als gerade Linie zwischen zwei Punkten auf der dreidimensionalen Form definiert sind, wobei "a" der längste Abstand zwischen zwei Punkten und "b" der kürzeste Abstand zwischen zwei Punkten ist.
  13. Toilettenreinigungsblock nach irgendeinem der Ansprüche 1 bis 12 in Blockform, die dadurch gekennzeichnet ist, dass sie eine diskrete Rotationssymmetrie von mindestens C = 3, vorzugsweise C = 6, aufweist.
  14. Verfahren zur Herstellung eines geformten Toilettenreinigerblocks nach einem der Ansprüche 1 bis 13, umfassend die Schritte:
    a. Bereitstellen des Alkylpolyglykosids in fester Form;
    b. Mischen der Bestandteile;
    c. Extrudieren der gemischten Bestandteile.
  15. Verfahren zum Reinigen und/oder Desinfizieren und/oder Desodorieren des Inneren einer Toilettenschüssel, umfassend die Schritte: Bereitstellen eines geformten Toilettenreinigerblocks nach irgendeinem der Ansprüche 1 bis 13 und Anbringen des Blocks auf der Oberfläche der Innenseite der Toilettenschüssel.
EP22708952.1A 2021-03-08 2022-03-02 Geformter toilettenreinigerblock Active EP4305136B1 (de)

Applications Claiming Priority (2)

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EP21161255 2021-03-08
PCT/EP2022/055276 WO2022189228A1 (en) 2021-03-08 2022-03-02 Shaped toilet cleaner block

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EP4305136B1 true EP4305136B1 (de) 2025-10-15

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CN (1) CN117120586A (de)
AU (1) AU2022233781B2 (de)
BR (1) BR112023018191A2 (de)
PL (1) PL4305136T3 (de)
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Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4337032C1 (de) * 1993-10-29 1995-05-24 Henkel Kgaa Verwendung von Detergensgemischen zur Herstellung von Toilettensteinen
BRPI0718778B1 (pt) * 2006-11-16 2017-11-21 Unilever N.V. Self-adhesive block for rigid surface cleaning, method for hygienizing a sanitary and method for dishwasher disposal
US7709433B2 (en) * 2007-02-12 2010-05-04 S.C. Johnson & Son, Inc. Self-sticking disintegrating block for toilet or urinal
GB0719712D0 (en) 2007-10-09 2007-11-21 Reckitt Benckiser Inc Lavatory treatment block compositions with substantive foaming benefits and improved lifespan
US8444771B2 (en) * 2008-02-29 2013-05-21 Buck-Chemie Gmbh Method for cleaning and/or deodorizing toilet bowl or urinal using an adhesive agent
EP2601283B1 (de) * 2010-08-06 2014-11-19 RE.LE.VI. S.p.a. Hygienemittel
DE102010043848A1 (de) * 2010-11-12 2012-05-16 Henkel Ag & Co. Kgaa Kugelförmige WC-Steine auf Aniontensidbasis
US8658588B2 (en) 2012-01-09 2014-02-25 S.C. Johnson & Son, Inc. Self-adhesive high viscosity cleaning composition
PL2872613T3 (pl) 2013-05-10 2021-07-05 Eurvest S.A. Nowa kompozycja sanitarna
EP3168284A1 (de) * 2015-11-13 2017-05-17 Unilever N.V. Geformter toilettenreinigerblock
CN110591833B (zh) * 2019-10-09 2021-08-20 广州超威生物科技有限公司 一种洁厕清洁剂及其制备方法

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EP4305136C0 (de) 2025-10-15
PL4305136T3 (pl) 2025-12-22
BR112023018191A2 (pt) 2023-12-12
CN117120586A (zh) 2023-11-24
AU2022233781B2 (en) 2024-10-17
EP4305136A1 (de) 2024-01-17
ZA202307721B (en) 2024-12-18
AU2022233781A1 (en) 2023-08-24
WO2022189228A1 (en) 2022-09-15

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