WO1997000935A1 - Improvements relating to lavatory cleaning blocks - Google Patents

Improvements relating to lavatory cleaning blocks Download PDF

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Publication number
WO1997000935A1
WO1997000935A1 PCT/EP1996/002273 EP9602273W WO9700935A1 WO 1997000935 A1 WO1997000935 A1 WO 1997000935A1 EP 9602273 W EP9602273 W EP 9602273W WO 9700935 A1 WO9700935 A1 WO 9700935A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
alcohol
preferred
alkoxylated
block according
Prior art date
Application number
PCT/EP1996/002273
Other languages
French (fr)
Inventor
Francesco Maria Puerari
Original Assignee
Unilever Plc
Unilever N.V.
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 Plc, Unilever N.V. filed Critical Unilever Plc
Priority to AU60015/96A priority Critical patent/AU6001596A/en
Publication of WO1997000935A1 publication Critical patent/WO1997000935A1/en

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
    • 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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3955—Organic bleaching agents
    • 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
    • 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
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to lavatory blocks including those which are intended, in use, to be located under the rim of a lavatory bowl or urinal such that, during a flushing cycle, water from the cistern flows over the block thereby dissolving a portion of the block.
  • Such blocks are generally known in the art as 'rim blocks' and will be referred to as such or simply as 'blocks' herein.
  • the invention also relates to so-called 'in-cistern' blocks which sit in the cistern of a lavatory or urinal and slowly dissolve in the water contained therein.
  • WO 92/03532 discloses that rim blocks generally comprise a surfactant component and a solubility retarding component.
  • the surfactant is an anionic present at a level of 5-85% by weight of the block, although other surfactant components such as nonionics can be present: levels of less than 10% of nonionics being preferred.
  • Blocks can also comprise inert fillers, water softening agents, colouring agent and perfumes. The document discloses a common process for the manufacture of these blocks, by extrusion of the components into a bar which is subsequently cut into blocks.
  • WO 92/03532 discloses that the extrusion of the blocks is assisted by the presence of polysaccharide gums, which function as lubricant processing aids.
  • EP-A-341836 discloses an extruded lavatory cleansing block with a good sanitising and cleansing effect, which block comprises an anionic surfactant and a chlorinated cyanuric acid derivative.
  • the preferred method of manufacture is again by extrusion in which case less than 25% wt and preferably 3-15% wt of a processing aid is added.
  • Suitable processing agents are described as lower ethoxylated alcohol or alkyl phenols, higher alcohols or chlorinated hydrocarbons.
  • EP-A-526437 discloses the use of stabilisers selected from the group comprising mineral oils, silicone fluids and polybutene.
  • the preferred method of manufacture is again by extrusion in which case less than 25% wt and preferably 1-15% wt of a processing aid is added.
  • Suitable processing agents are described as lower ethoxylated alcohol or alkyl phenols.
  • the present invention provides a lavatory block comprising 0.5-10%wt of an alkoxylated C8-C18 alcohol having, on average, 25-75 alkoxy units per alkyl moiety.
  • the alkoxylated alcohol is an ethoxylated alcohol.
  • the preferred level of alkoxylated alcohol is 0.75-2%wt.
  • the preferred ethoxy chain length is 40-60 with an average ethoxy chain length of around 50 being preferred.
  • Suitable materials include Empilan KM 50/KF (TM) ex. Albright & Wilson.
  • blocks according to the present invention comprise, in addition to the above-mentioned, alkoxylated alcohol 30 to 80% by weight of an anionic surfactant; 0 to 50% by weight of an inert and/or electrolyte filler and 5 to 50% by weight of a water-soluble bleaching agent.
  • the anionic surfactants which may be used in the present invention include for example alkali metal salts of alkyl substituted benzene sulphonates, alkali metal long chain alkyl sulphates, alkali metal ether sulphates derived from long chain alcohols and alkyl phenols, alkali metal alkane sulphonates, alkali metal olefin sulphonates and alkali metal sulphosuccinates, whereby the sodium salts are generally preferred.
  • anionics are sodium alkyl benzene sulphonates.
  • the anionic surfactant used in the block is present at a level of 40-60%wt, with levels of 40-50% being particularly preferred.
  • Suitable materials include Nansa HS 80/GPF (TM) ex. Albright & Wilson.
  • Suitable fillers include ionic fillers and inert fillers.
  • Suitable fillers include one or more of urea, sodium, magnesium and calcium carbonates, sodium chloride, borax, talc and sodium, magnesium and calcium sulphates.
  • Preferred ionic fillers include sodium sulphate.
  • Preferred inert fillers include calcium carbonate.
  • Typical levels of filler range from 5-30%wt in total.
  • Preferred levels of filler are 5-15% of ionic filler and 5-15% of inert filler. It is particularly preferred to use an approximately 50:50 mixture of sodium sulphate and calcium carbonate as the filler.
  • the weight ratio between the anionic surfactant and the filler, if electrolytic, is greater than 2.
  • Suitable bleaching agents active-halide and active-oxygen bleaching agents are at least sparingly soluble in water.
  • Halide bleaching agents are preferred. Suitable water ⁇ soluble, active chlorine, bleaching agents used in accordance with the invention include chlorinated cyanurates, phthalimides, p-toluene sulphonamides, azodicarbonamides, hydantoins, glycoluracils, amines and melamines.
  • the alkali metal salts of cyanurates are preferred.
  • a particularly preferred bleaching agent is sodium dichlorocyanurate.
  • the bleaching agent is most preferably present in an amount of 10 to 25% by weight.
  • Oxidan DCN/WSG (TM) ex Sigma has been found to be a suitable bleaching agent.
  • the blocks further comprise 1 to 15% by weight of a hydrophobic oily liquid perfume.
  • the blocks more preferably comprise 4-9% by weight of the perfume. Levels of around 6% are particularly preferred.
  • This is preferably the liquid oily perfume of the kind described in the European patent application EP 167,210. It will be understood that the liquid oily perfume must be stable in the presence of the water-soluble, active chlorine, bleaching agent. Suitable oily perfumes can be easily selected by testing them in combination with the water- soluble, active chlorine, bleaching agent. Examples of suitable bleach-stable perfumes are Verdeo 898, Bonanza 048 and Ponderosa 431 all ex IFF, and LB 132 ex Quest. Particularly preferred perfumes are Icebreaker Super Mod, Oxygen Supra Mod, Motebianco Supra and lemonfit Supra (all TM) ex Givaudan Roure.
  • Minor components will generally be present but are optional. These include colouring agents, and/or whiteners. These materials should be chosen such that they are compatible with the bleaching agent and do not react therewith to a significant extent.
  • TM 'Sudangelb 150'
  • Sandoz is an acceptable colouring agent as are Colanyl Green (TM) ex Hoechst and Dispers Blue (TM) ex BASF. Titanium dioxide is an acceptable whitener.
  • An optional minor component is a foam-boosting surfactant.
  • Suitable surfactants include nitrogen-containing surfactants including amphoteric surfactants such as betaines, amine oxides and ethanolamides.
  • Blocks according to the present invention are manufactured by an extrusion process as known in the art: i.e. the ingredients are mixed to form a dough, which is then extruded into a rod or bar which is cut into blocks of suitable lengths.
  • the term block is not intended to limit the shape of the eventual product.
  • the rod is generally cut into lengths which are long relative to their diameter and for cistern blocks the rod is cut into lengths which are short relative to their diameter.

Abstract

The invention provides a lavatory block comprising 0.5-10 wt.% of an alkoxylated C8-C18 alcohol having, on average, 25-75 alkoxy units per alkyl moiety. It is preferred that the alkoxylated alcohol is an ethoxylated alcohol. The preferred level of alkoxylated alcohol is 0.75-2 wt.%. The preferred ethoxy chain length is 40-60 with an average ethoxy chain length of around 50 being particularly preferred. Typically, blocks according to the present invention comprise, in addition to the above-mentioned alkoxylated alcohol, 30 to 80 % by weight of an anionic surfactant; 0 to 50 % by weight of an inert and/or electrolyte filler and 5 to 50 % by weight of a water-soluble bleaching agent.

Description

IMPROVEMENTS RELATING TO LAVATORY CLEANING BLOCKS
Technical Field
The present invention relates to lavatory blocks including those which are intended, in use, to be located under the rim of a lavatory bowl or urinal such that, during a flushing cycle, water from the cistern flows over the block thereby dissolving a portion of the block. Such blocks are generally known in the art as 'rim blocks' and will be referred to as such or simply as 'blocks' herein. The invention also relates to so-called 'in-cistern' blocks which sit in the cistern of a lavatory or urinal and slowly dissolve in the water contained therein.
Background to the Invention
WO 92/03532 (JEYES) discloses that rim blocks generally comprise a surfactant component and a solubility retarding component. Typically, the surfactant is an anionic present at a level of 5-85% by weight of the block, although other surfactant components such as nonionics can be present: levels of less than 10% of nonionics being preferred. Blocks can also comprise inert fillers, water softening agents, colouring agent and perfumes. The document discloses a common process for the manufacture of these blocks, by extrusion of the components into a bar which is subsequently cut into blocks. WO 92/03532 discloses that the extrusion of the blocks is assisted by the presence of polysaccharide gums, which function as lubricant processing aids. EP-A-341836 (JEYES) discloses an extruded lavatory cleansing block with a good sanitising and cleansing effect, which block comprises an anionic surfactant and a chlorinated cyanuric acid derivative. The preferred method of manufacture is again by extrusion in which case less than 25% wt and preferably 3-15% wt of a processing aid is added. Suitable processing agents are described as lower ethoxylated alcohol or alkyl phenols, higher alcohols or chlorinated hydrocarbons.
EP-A-526437 (KIWI) discloses the use of stabilisers selected from the group comprising mineral oils, silicone fluids and polybutene. The preferred method of manufacture is again by extrusion in which case less than 25% wt and preferably 1-15% wt of a processing aid is added. Suitable processing agents are described as lower ethoxylated alcohol or alkyl phenols.
Brief Description of the Invention
We have determined that improved blocks can be manufactured by the extrusion process using a higher ethoxylated alcohol as a processing aid.
Accordingly the present invention provides a lavatory block comprising 0.5-10%wt of an alkoxylated C8-C18 alcohol having, on average, 25-75 alkoxy units per alkyl moiety.
Detailed Description of the Invention
It is preferred that the alkoxylated alcohol is an ethoxylated alcohol. The preferred level of alkoxylated alcohol is 0.75-2%wt. The preferred ethoxy chain length is 40-60 with an average ethoxy chain length of around 50 being preferred. Suitable materials include Empilan KM 50/KF (TM) ex. Albright & Wilson.
Typically, blocks according to the present invention comprise, in addition to the above-mentioned, alkoxylated alcohol 30 to 80% by weight of an anionic surfactant; 0 to 50% by weight of an inert and/or electrolyte filler and 5 to 50% by weight of a water-soluble bleaching agent.
The anionic surfactants which may be used in the present invention include for example alkali metal salts of alkyl substituted benzene sulphonates, alkali metal long chain alkyl sulphates, alkali metal ether sulphates derived from long chain alcohols and alkyl phenols, alkali metal alkane sulphonates, alkali metal olefin sulphonates and alkali metal sulphosuccinates, whereby the sodium salts are generally preferred.
The most favoured anionics are sodium alkyl benzene sulphonates. Desirably, the anionic surfactant used in the block is present at a level of 40-60%wt, with levels of 40-50% being particularly preferred. Suitable materials include Nansa HS 80/GPF (TM) ex. Albright & Wilson.
Suitable fillers include ionic fillers and inert fillers.
Suitable fillers include one or more of urea, sodium, magnesium and calcium carbonates, sodium chloride, borax, talc and sodium, magnesium and calcium sulphates.
Preferred ionic fillers include sodium sulphate.
Preferred inert fillers include calcium carbonate.
Typical levels of filler range from 5-30%wt in total.
Preferred levels of filler are 5-15% of ionic filler and 5-15% of inert filler. It is particularly preferred to use an approximately 50:50 mixture of sodium sulphate and calcium carbonate as the filler.
Preferably, the weight ratio between the anionic surfactant and the filler, if electrolytic, is greater than 2.
Suitable bleaching agents active-halide and active-oxygen bleaching agents. It is important that the bleaching agent is at least sparingly soluble in water.
Halide bleaching agents are preferred. Suitable water¬ soluble, active chlorine, bleaching agents used in accordance with the invention include chlorinated cyanurates, phthalimides, p-toluene sulphonamides, azodicarbonamides, hydantoins, glycoluracils, amines and melamines. The alkali metal salts of cyanurates are preferred. A particularly preferred bleaching agent is sodium dichlorocyanurate. The bleaching agent is most preferably present in an amount of 10 to 25% by weight. Oxidan DCN/WSG (TM) ex Sigma has been found to be a suitable bleaching agent.
Preferably, the blocks further comprise 1 to 15% by weight of a hydrophobic oily liquid perfume. The blocks more preferably comprise 4-9% by weight of the perfume. Levels of around 6% are particularly preferred. This is preferably the liquid oily perfume of the kind described in the European patent application EP 167,210. It will be understood that the liquid oily perfume must be stable in the presence of the water-soluble, active chlorine, bleaching agent. Suitable oily perfumes can be easily selected by testing them in combination with the water- soluble, active chlorine, bleaching agent. Examples of suitable bleach-stable perfumes are Verdeo 898, Bonanza 048 and Ponderosa 431 all ex IFF, and LB 132 ex Quest. Particularly preferred perfumes are Icebreaker Super Mod, Oxygen Supra Mod, Motebianco Supra and lemonfit Supra (all TM) ex Givaudan Roure.
Minor components will generally be present but are optional. These include colouring agents, and/or whiteners. These materials should be chosen such that they are compatible with the bleaching agent and do not react therewith to a significant extent. We have determined that 'Sudangelb 150' (TM) ex. Sandoz is an acceptable colouring agent as are Colanyl Green (TM) ex Hoechst and Dispers Blue (TM) ex BASF. Titanium dioxide is an acceptable whitener.
An optional minor component is a foam-boosting surfactant. Suitable surfactants include nitrogen-containing surfactants including amphoteric surfactants such as betaines, amine oxides and ethanolamides.
Blocks according to the present invention are manufactured by an extrusion process as known in the art: i.e. the ingredients are mixed to form a dough, which is then extruded into a rod or bar which is cut into blocks of suitable lengths. As used herein the term block is not intended to limit the shape of the eventual product. For rim-blocks the rod is generally cut into lengths which are long relative to their diameter and for cistern blocks the rod is cut into lengths which are short relative to their diameter.
In order that the invention may be further understood it will be described hereafter by way of example. Examples
The components listed in Table 1 below were mixed in the proportions specified and extruded in the form of a bar which was then cut into blocks. All proportions are given in weight % as throughout the specification unless stated otherwise.
Table 1
Example Component 1 2 3 4
Anionic Nansa HS 47.8 47.8 47.8 47.8 80/GPF
Nonionic Empilan 1.00 1.00 1.00 1.00 KM50/KF
Bleaching Oxidan 15.0 15.0 15.0 15.0 Agent DCN/WSG
Ionic Sodium 8.95 8.70 8.95 .8.95 Filler Sulphate
Inert Calcium 8.95 8.75 8.95 8.95 Filler Carbonate
Perfume Oxygen 6.00 - - - Supra Mod
Montebianco - 6.50 - - Supra
Lemonfit - - 6.00 - Supra
Icebreaker - - - 6.00 Supra Mod
Colour Dispers 0.025 - - - Blue
Colanyl - 0.024 - - Green GG130
Sudangelb - - 0.025 - 150
Dispers - - - 0.005 Blue
Whitener Titanium 0.07 0.07 0.07 0.07 Dioxide
Water to 100 to 100 to 100 to 100 In order to demonstrate the advantages of the present invention, blocks were prepared with and without the addition of the highly ethoxylated nonionic surfactant. Table 2 shows the temperature (in degrees Celcius) of the mixtures during the process both in the presence and the absence of the nonionic in a pilot plant heating mixer and extruder.
Table 2
Stage With 1% nonionic Without nonionic
Initial 29 29
+3 minutes 39 40
+8 minutes 40 42
Perfume added 41 46
+8 minutes 43 50
+13 minutes 43 52
Extrusion 46 51
+8 minutes 49 55
Finel 56 6.8
It can clearly be seen from Table 2 that the addition of the nonionic reduces the overall exposure of the composition to elevated temperatures and thereby would be expected to reduce the extent to which the bleaching agent is decomposed by these temperatures.

Claims

Claims
A lavatory block comprising 0.5-10%wt of an alkoxylated C8-C18 alcohol having, on average, 25-75 alkoxy units per alkyl moiety.
2. A block according to claim 1 wherein the level of alkoxylated alcohol is 0.75-2%wt.
A block according to claim 1 wherein the alkoxylated alcohol is an ethoxylated alcohol having an average ethoxy chain length of 40-60.
A block according to claim 1 which comprises 30 to 80% by weight of an anionic surfactant; 0 to 50% by weight of an inert and/or electrolyte filler and 5 to 50% by weight of a water-soluble bleaching agent.
A block according to claim 1 which comprises 5-15% of ionic filler and 5-15% of inert filler.
A block according to claim 1 which further comprises 1 to 15% by weight of a hydrophobic oily liquid perfume.
A block according to claim 1 manufactured by a process wherein the ingredients are mixed to form a dough, which is then extruded into a rod or bar.
PCT/EP1996/002273 1995-06-22 1996-05-23 Improvements relating to lavatory cleaning blocks WO1997000935A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU60015/96A AU6001596A (en) 1995-06-22 1996-05-23 Improvements relating to lavatory cleaning blocks

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9512714.8 1995-06-22
GBGB9512714.8A GB9512714D0 (en) 1995-06-22 1995-06-22 Improvements relating to lavatory cleaning blocks

Publications (1)

Publication Number Publication Date
WO1997000935A1 true WO1997000935A1 (en) 1997-01-09

Family

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Family Applications (1)

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PCT/EP1996/002273 WO1997000935A1 (en) 1995-06-22 1996-05-23 Improvements relating to lavatory cleaning blocks

Country Status (4)

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AR (1) AR006303A1 (en)
AU (1) AU6001596A (en)
GB (1) GB9512714D0 (en)
WO (1) WO1997000935A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998036049A1 (en) * 1997-02-14 1998-08-20 Lonza Inc. Bleaching and cleaning compositions containing fragrances
WO1998037171A1 (en) * 1997-02-20 1998-08-27 Reckitt & Colman Of India Limited Toilet cleaning block
EP0879877A1 (en) * 1997-05-22 1998-11-25 Buck-Chemie GmbH & Co. Toilet cleaning block releasing active chlorine
WO2003042462A2 (en) * 2001-11-13 2003-05-22 Reckitt Benckiser Inc Improvements relating to toilet bowl cleaning articles
US11851632B2 (en) 2020-05-14 2023-12-26 Reckitt Benckiser Finish B.V. Solid composition comprising an ethoxylated alcohol with from 30 to 40 ethoxy groups

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0014979A1 (en) * 1979-02-23 1980-09-03 Henkel Kommanditgesellschaft auf Aktien Process for producing rinsing blocks for the hygiene of water-closets
DE3209333A1 (en) * 1982-03-15 1983-09-15 Henkel KGaA, 4000 Düsseldorf Process for the production of a floatable acid tablet for WC cleaning
DE3407456A1 (en) * 1984-02-29 1985-09-05 Werner & Mertz Gmbh, 6500 Mainz COMBINED CLEANING / BLEACHING AGENT FOR THE TREATMENT OF THE RINSE WATER OF TOILET MACHINES AND THEIR USE
EP0167085A2 (en) * 1984-07-02 1986-01-08 Henkel Kommanditgesellschaft auf Aktien Toilet cleaning agent
WO1992003532A1 (en) * 1990-08-28 1992-03-05 Jeyes Limited Lavatory cleansing
WO1995011958A1 (en) * 1993-10-29 1995-05-04 Henkel Kommanditgesellschaft Auf Aktien Use of detergent mixtures for toilet freshening blocks

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0014979A1 (en) * 1979-02-23 1980-09-03 Henkel Kommanditgesellschaft auf Aktien Process for producing rinsing blocks for the hygiene of water-closets
DE3209333A1 (en) * 1982-03-15 1983-09-15 Henkel KGaA, 4000 Düsseldorf Process for the production of a floatable acid tablet for WC cleaning
DE3407456A1 (en) * 1984-02-29 1985-09-05 Werner & Mertz Gmbh, 6500 Mainz COMBINED CLEANING / BLEACHING AGENT FOR THE TREATMENT OF THE RINSE WATER OF TOILET MACHINES AND THEIR USE
EP0167085A2 (en) * 1984-07-02 1986-01-08 Henkel Kommanditgesellschaft auf Aktien Toilet cleaning agent
WO1992003532A1 (en) * 1990-08-28 1992-03-05 Jeyes Limited Lavatory cleansing
WO1995011958A1 (en) * 1993-10-29 1995-05-04 Henkel Kommanditgesellschaft Auf Aktien Use of detergent mixtures for toilet freshening blocks

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998036049A1 (en) * 1997-02-14 1998-08-20 Lonza Inc. Bleaching and cleaning compositions containing fragrances
US5972864A (en) * 1997-02-14 1999-10-26 Lonza Inc. Bleaching and cleaning compositions containing fragrances
US6255268B1 (en) 1997-02-14 2001-07-03 Lonza Inc. Bleaching and cleaning compositions containing fragrances
WO1998037171A1 (en) * 1997-02-20 1998-08-27 Reckitt & Colman Of India Limited Toilet cleaning block
EP0879877A1 (en) * 1997-05-22 1998-11-25 Buck-Chemie GmbH & Co. Toilet cleaning block releasing active chlorine
WO2003042462A2 (en) * 2001-11-13 2003-05-22 Reckitt Benckiser Inc Improvements relating to toilet bowl cleaning articles
WO2003042462A3 (en) * 2001-11-13 2003-11-20 Reckitt Benckiser Inc Improvements relating to toilet bowl cleaning articles
US11851632B2 (en) 2020-05-14 2023-12-26 Reckitt Benckiser Finish B.V. Solid composition comprising an ethoxylated alcohol with from 30 to 40 ethoxy groups

Also Published As

Publication number Publication date
AU6001596A (en) 1997-01-22
AR006303A1 (en) 1999-08-25
GB9512714D0 (en) 1995-08-23

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