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EP0619367A1 - Blocs pour toilettes contenant des enzymes - Google Patents

Blocs pour toilettes contenant des enzymes Download PDF

Info

Publication number
EP0619367A1
EP0619367A1 EP93201007A EP93201007A EP0619367A1 EP 0619367 A1 EP0619367 A1 EP 0619367A1 EP 93201007 A EP93201007 A EP 93201007A EP 93201007 A EP93201007 A EP 93201007A EP 0619367 A1 EP0619367 A1 EP 0619367A1
Authority
EP
European Patent Office
Prior art keywords
lavatory
block according
cleansing block
lavatory cleansing
present
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.)
Withdrawn
Application number
EP93201007A
Other languages
German (de)
English (en)
Inventor
Stefano Scialla
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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 Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP93201007A priority Critical patent/EP0619367A1/fr
Priority to JP6522179A priority patent/JPH08508770A/ja
Priority to CA 2159820 priority patent/CA2159820A1/fr
Priority to PCT/US1994/003164 priority patent/WO1994023006A1/fr
Priority to AU65516/94A priority patent/AU6551694A/en
Publication of EP0619367A1 publication Critical patent/EP0619367A1/fr
Withdrawn legal-status Critical Current

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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-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
    • C11D1/14—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
    • C11D1/29—Sulfates of polyoxyalkylene ethers

Definitions

  • the present invention relates to solid lavatory cleansing blocks containing enzymes.
  • the block is designed to have good stain removal capacity.
  • Lavatory blocks for cleansing and deodourizing the lavatory bowl are well known in the art.
  • Such lavatory blocks typically comprise surfactants and chlorinating compounds which provide the desired cleansing and deodourizing properties.
  • the lavatory blocks disclosed in the prior art do not efficiently address the problem of stain removal of physiological soils which are frequently found in the lavatory bowl.
  • the surfactants contained in the lavatory blocks on the market are not present in sufficiently high concentrations in order to achieve optimum improved stain removal.
  • Chlorinating agents due to their bleaching action are known for their stain removal ability.
  • the in-bowl stain removal action of said chlorinating agents is limited at low concentrations.
  • the present invention proposes to formulate a lavatory block comprising an enzyme system as a stain removal active.
  • the blocks according to the present invention progressively dissolve in water, thereby releasing the ingredients in solution.
  • a permanent aqueous solution is provided in the lavatory bowl which comprises a constant and predetermined amount of various ingredients.
  • An advantage of the present invention is that the enzymes are permanently active in the lavatory bowl water during the whole period in between lavatory flushes.
  • the present invention is a solid lavatory block characterized in that it comprises from 0.1% to 50% of an enzyme system, whereby said lavatory block provides a permanent aqueous solution comprising an effective amount of said enzyme system as said block is progressively dissolved in said lavatory bowl water.
  • the present invention relates to a solid lavatory cleansing block.
  • lavatory blocks available on the market at present, in-rim and in-cistern type lavatory blocks.
  • the in-rim type blocks are distinct from in-cistern type blocks in that they are designed to be hung from the rim of the lavatory bowl, in a conventional type rim cage.
  • the in-cistern type blocks are designed to be placed in the cistern itself. Depending on the positioning of the block the properties of the active ingredients will vary, depending on the length of time the block is immersed in water.
  • the lavatory blocks according to the present invention are designed to be used as both in-rim and in-cistern type lavatory blocks.
  • the blocks according to the present invention progressively dissolve in water, thereby releasing the ingredients in solution.
  • a permanent aqueous solution is provided in the lavatory bowl which comprises a constant and predetermined amount of various ingredients.
  • the lavatory blocks of the present invention comprise as an essential feature from 0.1% to 50%, preferably from 1% to 40%, more preferably from 2% to 25% of an enzyme system.
  • Suitable enzymes which may be used are selected from lipases, proteases, cellulases, amylases, polysaccharide hydrolases and mixtures thereof.
  • the preferred enzyme for use herein is lipase.
  • lavatory blocks according to the present invention comprise a lipase enzyme such that the lipolytic activity of the lavatory block is from 0.01 to 5000 KLU, preferably from 0.1 to 1000 KLU, most preferably from 1 to 150 KLU per gram of the lavatory block.
  • KLU are standard kilo units defined by Novo for measuring lipase activity.
  • the lavatory blocks according to the present invention typically comprise a protease enzyme such that the protolytic activity of the lavatory block is from 0.01 to 500 KNPU, preferably from 0.05 to 200 KNPU, most preferably from 1 to 100 KNPU per gram of the lavatory block.
  • KNPU denotes Kilo Novo Protease Units.
  • the lavatory blocks according to the present invention typically comprise an amylase enzyme such that the amylolytic activity of the lavatory block is from 0.01 to 500 KNU, preferably from 0.1 to 250, most preferably from 1 to 100 KNPU per gram of the lavatory block.
  • KNU are Kilo Novo units used for measuring amylase activity.
  • lavatory blocks according to the present invention comprise a cellulase enzyme such that the cellulytic activity of the lavatory block is from 0.01 to 50 000 CEVU, preferably from 0.1 to 10 000 CEVU, more preferably from 1 to 1500 CEVU per gram of the lavatory block.
  • CEVU are standard units for measuring cellulase activity.
  • Commercially available enzymes for use herein include :
  • the enzyme system assists in the removal of faecal, urine and grease stains which are found in the lavatory bowl. It is believed that enzymes, especially lipases are effective in removing the stains found in the lavatory bowl by attacking the components present in faeces which represent a significant fraction of the faecal soil.
  • the lavatory blocks according to the present invention may also contain a number of optional ingredients.
  • One such ingredient is a surfactant system.
  • the incorporation of a surfactant provides increased cleansing of the lavatory blocks and provides a solid matrix in which all the other ingredients can be incorporated.
  • the block comprises at least 10% of a surfactant system.
  • the surfactants that may be used herein can be anionic and nonionic surfactants or mixtures thereof.
  • the anionic surfactants which may be used in the present invention include for example alkali metal salts of alkyl substituted benzene sulphonates, alkali metal alkyl sulphonates, alkali metal alkyl sulphonates and alkali metal alkyl ether sulphates derived for example from fatty alcohols and alkyl phenols, alkali metal alkane sulphonates, alkali metal olefin sulphonates and alkali metal sulphosuccinates, whereby the sodium salts are preferred. Most preferred are sodium alkyl metal sulphonates and sulphates.
  • nonionic surfactants which may be used can be chosen from any liquid or solid ethoxylated C6-C24 fatty alcohol nonionic surfactant, fatty acid C6-C24 alkanolamides, C6-C20 polyethylglycol ethers, polyethyleneglycol with molecular weight 1000 to 80000 and C6-C24 amine oxides.
  • the lavatory blocks of the present invention may further comprise from 0.001% to 10%, preferably from 0.001% to 3% soluble calcium salts.
  • the calcium salts can be used to stabilize the enzymes.
  • the lavatory blocks of the invention may further comprise 0% to 50%, preferably from 5% to 30%, fillers of inorganic salts such as sodium sulphate, sodium carbonate, sodium silicate and less preferably phosphorous sodium salts, for example sodium triphosphate, or inert fillers such as clay, urea or calcite.
  • inorganic salts such as sodium sulphate, sodium carbonate, sodium silicate and less preferably phosphorous sodium salts, for example sodium triphosphate, or inert fillers such as clay, urea or calcite.
  • composition differences in the composition of the in-rim and in-cistern type lavatory blocks of the present invention can be exclusively but not necessarily dependant upon the type of surfactants, fillers and polymers used therein, to determine the dissolution rate.
  • the composition differences are well known in the art.
  • In-cistern type lavatory blocks can preferably contain surfactants with a lower solubilization rate and may be chosen from long chain higher anionics or nonionics with a high degree of ethoxylation.
  • In-cistern type lavatory blocks may also contain specific ingredients to decrease the solubilization rate such as slowly dissolving polymers or oils.
  • the lavatory blocks of the present invention may further comprise as an optional feature from 1ppm to 500ppm, preferably from 5ppm to 300ppm, more preferably from 10ppm to 200ppm active oxygen in the lavatory bowl water.
  • the source of active oxygen can be selected from hydrogen peroxide or sources thereof, preformed peroxyacids, organic peroxides and mixtures thereof.
  • active oxygen concentration refers to the percentage concentration of elemental oxygen, with an oxidation number zero, that being reduced to water would be stoichiometrically equivalent to a given percentage concentration of a given peroxide compound, when the peroxide functionality of the peroxide compound is completely reduced to oxides.
  • a hydrogen peroxide source according to the present invention refers to any compound which produces hydrogen peroxide when said compound is in contact with water.
  • Suitable water-soluble sources of hydrogen peroxide for use herein include persulphates, percarbonates, metal oxides and perborates.
  • Suitable preformed peroxyacids for use in the lavatory blocks according to the present invention include diperoxydodecandioic acid DPDA, magnesium perphthalate, perlauric acid, perbenzoic acid, diperoxyazelaic acid and mixtures thereof.
  • the blocks according to the present invention comprise from 0.01% to 30% of said preformed peroxyacids.
  • Suitable organic peroxides for use in the lavatory blocks according to the present invention include diacyl and dialkyl peroxides such as dibenzoyl peroxide, dilauroyl peroxide, dicumyl peroxide and mixtures thereof.
  • the blocks according to the present invention comprise from 0.01% to 30% of said organic peroxides.
  • the lavatory blocks may additionally comprise peracid precursors, i.e. compounds that upon reaction with hydrogen peroxide produce peroxyacids.
  • peracid precursors suitable for use in the present invention can be found among the classes of esters, amides, imides and anhydrides such as acetyl triethyl citrate (ATC), tetra acetyl ethylene diamine (TAED), succinic or maleic anhydrides. All of these bleaching agents are environmentally compatible and odourless.
  • Another optional component of said system is an acid or alkali.
  • the acid or alkali is used to ensure that the pH of the lavatory bowl water is in the range of pH 4 to pH 10.
  • the stability and activity of the enzymes of the present invention can be optimized by ensuring that the pH of said lavatory bowl water is at the optimum level for the enzyme used herein.
  • the acids of the present invention may in addition have the advantage that they can form small concentrations of the corresponding peracids by reaction with hydrogen peroxide in-situ, thus enhancing the overall performance of the lavatory block. These acids can be further selected so as to have chelating and/or building properties, which results in limescale removal.
  • the acids that can be used in the present invention are organic or inorganic acids, preferably organic acids such as citric, maleic, oxalic succinic and tartaric acids, more preferably citric and maleic acids.
  • the alkalis that may be used in the present invention include sodium hydroxide, potassium hydroxide, alkali metal hydroxides, alkaline earth metal hydroxides and amines, for example monoethylamine, monoethanolamine and triethanolamine.
  • a chelant system improves the overall limescale/rust removal performance. Furthermore, the chelant system may improve the stability of the bleaching agent in the formulation. Suitable chelants may be chosen from EDTA, NTA or preferably from biodegradable chelants such as s,s-ethylene diamino disuccinate and dipicolinic acid.
  • Further optional ingredients include perfumes and dyes used to improve the aesthetics of the lavatory block. These perfumes and dyes contained in the lavatory block are selected for their stability in the presence of the source of active oxygen.
  • said blocks comprise perfumes and dyes
  • the lavatory cleansing block is formed by conventional methods well known in the art as described for instance in EP-A 462 643.
  • the ingredients are mixed to form a dough of suitable consistency which can then be extruded and cut into lengths to form blocks.
  • the extrusion process can be carried out by using simple conventional extrusion equipment such as usually used for manufacturing soap bars.
  • the lavatory blocks may be prepared by compressing all of the ingredients into a block.

Landscapes

  • 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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP93201007A 1993-04-06 1993-04-06 Blocs pour toilettes contenant des enzymes Withdrawn EP0619367A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP93201007A EP0619367A1 (fr) 1993-04-06 1993-04-06 Blocs pour toilettes contenant des enzymes
JP6522179A JPH08508770A (ja) 1993-04-06 1994-03-23 酵素を含有したラバトリーブロック
CA 2159820 CA2159820A1 (fr) 1993-04-06 1994-03-23 Bloc lavabo contenant des enzymes
PCT/US1994/003164 WO1994023006A1 (fr) 1993-04-06 1994-03-23 Blocs detergents a base d'enzymes pour wc
AU65516/94A AU6551694A (en) 1993-04-06 1994-03-23 Lavatory blocks containing enzymes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP93201007A EP0619367A1 (fr) 1993-04-06 1993-04-06 Blocs pour toilettes contenant des enzymes

Publications (1)

Publication Number Publication Date
EP0619367A1 true EP0619367A1 (fr) 1994-10-12

Family

ID=8213747

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93201007A Withdrawn EP0619367A1 (fr) 1993-04-06 1993-04-06 Blocs pour toilettes contenant des enzymes

Country Status (5)

Country Link
EP (1) EP0619367A1 (fr)
JP (1) JPH08508770A (fr)
AU (1) AU6551694A (fr)
CA (1) CA2159820A1 (fr)
WO (1) WO1994023006A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995011958A1 (fr) * 1993-10-29 1995-05-04 Henkel Kommanditgesellschaft Auf Aktien Utilisation de melanges detergents pour la fabrication de blocs desodorisants pour toilettes
WO1996006910A3 (fr) * 1994-08-31 1996-03-21 Ecolab Inc Composition de nettoyage amelioree contenant une enzyme proteolytique
WO1997047721A1 (fr) * 1996-06-12 1997-12-18 Unilever Plc Perfectionnements relatifs aux blocs nettoyants pour w.-c.
US5830839A (en) * 1995-05-17 1998-11-03 Sunburst Chemicals, Inc. Solid detergents with active enzymes and bleach
WO1999053012A1 (fr) * 1998-04-09 1999-10-21 Unilever Plc Blocs nettoyants pour w-c
WO1999053013A1 (fr) * 1998-04-09 1999-10-21 Unilever Plc Blocs nettoyants pour w-c
EP0999263A1 (fr) * 1998-11-05 2000-05-10 Buck-Chemie GmbH & Co. Compositions de nettoyage pour toilettes sous forme de pains
WO2005041659A1 (fr) * 2003-10-24 2005-05-12 Novapharm Research (Australia) Pty Ltd Pastille utilisable dans un bac recepteur
AU2004284836B2 (en) * 2003-10-24 2010-08-05 Novapharm Research (Australia) Pty Ltd Drip tray tablet

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0004130D0 (en) * 2000-02-23 2000-04-12 Procter & Gamble Detergent tablet
JP5047385B1 (ja) * 2011-08-26 2012-10-10 都市拡業株式会社 尿石除去剤

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0258068A2 (fr) * 1986-08-29 1988-03-02 Novo Nordisk A/S Additif enzymatique pour détergent
EP0271152A2 (fr) * 1986-12-10 1988-06-15 Unilever N.V. Composition détergente et de blanchiment à base d'enzymes
EP0462643A1 (fr) * 1990-06-18 1991-12-27 Unilever N.V. Bloc de nettoyage pour cabinets d'aisance

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3798181A (en) * 1970-11-03 1974-03-19 Colgate Palmolive Co Enzymatic detergent bar
US4248827A (en) * 1978-06-12 1981-02-03 The Procter & Gamble Company Method for sanitizing toilets
JPH0788519B2 (ja) * 1985-06-07 1995-09-27 ダウブランズ・インコーポレーテッド 洗濯用汚れおよびしみ除去剤
GB8813687D0 (en) * 1988-06-09 1988-07-13 Unilever Plc Enzymatic dishwashing & rinsing composition
GB9015503D0 (en) * 1990-07-13 1990-08-29 Unilever Plc Detergent composition
US5178787A (en) * 1991-03-11 1993-01-12 Block Drug Company, Inc. Lavatory cleaning block comprising n,n-dichloro dialkyl hydantoin and aluminum hydroxide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0258068A2 (fr) * 1986-08-29 1988-03-02 Novo Nordisk A/S Additif enzymatique pour détergent
EP0271152A2 (fr) * 1986-12-10 1988-06-15 Unilever N.V. Composition détergente et de blanchiment à base d'enzymes
EP0462643A1 (fr) * 1990-06-18 1991-12-27 Unilever N.V. Bloc de nettoyage pour cabinets d'aisance

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 9217, Derwent Publications Ltd., London, GB; AN 92-138570 & JP-A-4 082 560 (DAISO KK) 16 March 1992 *
DATABASE WPI Week 9305, Derwent Publications Ltd., London, GB; AN 93-042674 & JP-A-4 370 200 (ASAHI PEN KK) 22 December 1992 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5939372A (en) * 1993-10-29 1999-08-17 Henkel Kommanditgesellschaft Auf Aktien Use of detergent mixtures for the production of toilet blocks
WO1995011958A1 (fr) * 1993-10-29 1995-05-04 Henkel Kommanditgesellschaft Auf Aktien Utilisation de melanges detergents pour la fabrication de blocs desodorisants pour toilettes
WO1996006910A3 (fr) * 1994-08-31 1996-03-21 Ecolab Inc Composition de nettoyage amelioree contenant une enzyme proteolytique
US6197739B1 (en) 1994-08-31 2001-03-06 Ecolab Inc. Proteolytic enzyme cleaner
US5858117A (en) * 1994-08-31 1999-01-12 Ecolab Inc. Proteolytic enzyme cleaner
US5830839A (en) * 1995-05-17 1998-11-03 Sunburst Chemicals, Inc. Solid detergents with active enzymes and bleach
WO1997047721A1 (fr) * 1996-06-12 1997-12-18 Unilever Plc Perfectionnements relatifs aux blocs nettoyants pour w.-c.
WO1999053012A1 (fr) * 1998-04-09 1999-10-21 Unilever Plc Blocs nettoyants pour w-c
WO1999053013A1 (fr) * 1998-04-09 1999-10-21 Unilever Plc Blocs nettoyants pour w-c
EP0999263A1 (fr) * 1998-11-05 2000-05-10 Buck-Chemie GmbH & Co. Compositions de nettoyage pour toilettes sous forme de pains
WO2005041659A1 (fr) * 2003-10-24 2005-05-12 Novapharm Research (Australia) Pty Ltd Pastille utilisable dans un bac recepteur
AU2004284836B2 (en) * 2003-10-24 2010-08-05 Novapharm Research (Australia) Pty Ltd Drip tray tablet
US8795740B2 (en) 2003-10-24 2014-08-05 Novapharm Research (Australia) Pty Ltd Drip tray tablet

Also Published As

Publication number Publication date
JPH08508770A (ja) 1996-09-17
AU6551694A (en) 1994-10-24
CA2159820A1 (fr) 1994-10-13
WO1994023006A1 (fr) 1994-10-13

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