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WO1999053012A1 - Blocs nettoyants pour w-c - Google Patents

Blocs nettoyants pour w-c Download PDF

Info

Publication number
WO1999053012A1
WO1999053012A1 PCT/EP1999/001899 EP9901899W WO9953012A1 WO 1999053012 A1 WO1999053012 A1 WO 1999053012A1 EP 9901899 W EP9901899 W EP 9901899W WO 9953012 A1 WO9953012 A1 WO 9953012A1
Authority
WO
WIPO (PCT)
Prior art keywords
bleaching agent
toilet block
block according
microns
toilet
Prior art date
Application number
PCT/EP1999/001899
Other languages
English (en)
Inventor
Giuseppe Vincenzo Bolzoni
Ronald Meredith Morris
Marco Oliva
Roberto Tummiolo
Original Assignee
Unilever Plc
Unilever N.V.
Hindustan Lever Limited
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., Hindustan Lever Limited filed Critical Unilever Plc
Priority to BR9909499-1A priority Critical patent/BR9909499A/pt
Priority to CA002320170A priority patent/CA2320170A1/fr
Priority to PL99343345A priority patent/PL343345A1/xx
Priority to HU0101314A priority patent/HUP0101314A3/hu
Priority to EP99915682A priority patent/EP1070114A1/fr
Priority to AU34166/99A priority patent/AU3416699A/en
Publication of WO1999053012A1 publication Critical patent/WO1999053012A1/fr

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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • 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 blocks.
  • Toilet blocks are blocks of a slowly soluble material either in containers attached to the rim of a toilet (so called 'rim-blocks') or in the cistern of the toilet (so-called 'cistern-blocks') .
  • the slowly soluble material can comprise a mixture of surfactant and optional filler as well as various functional ingredients such as perfumes dyestuffs and bleaches. Both types of block dissolve slowly in use: the rim block dissolving in the flush water that meets with it when the toilet is flushed and the cistern block dissolving in the water contained in the cistern between flushes.
  • Toilet blocks containing bleaching agents based on halogen release agents are known to be unstable, one way of countering this effect has been to include a source of certain metal ions as described in EP 0 341 836.
  • the present invention provides a toilet block comprising solid bleaching agent or precursor thereof wherein 75% of the granules of said bleaching agent have a granule size greater than 400 microns.
  • the present invention also relates to a method of preventing thermal heating within a toilet block by incorporation of a bleaching agent wherein 75% of the granules of said bleaching agent have a granule size greater than 400 microns.
  • the toilet blocks of the invention contain a bleaching agent having a defined granule size.
  • the blocks are thermally stable when stored in bulk.
  • the toilet blocks of the invention contain a bleaching agent.
  • the blocks comprise up to 50% by weight of an at least sparingly water soluble bleaching agent. Typical levels of bleaching agents are 2-30%wt on product.
  • bleaching agent is used to mean both a bleaching agent and a precursor which produces a bleaching agent unless the context demands otherwise.
  • the bleaching agent or precursor thereof have a granule size greater than 400 microns, more preferably 95% of the particulate bleaching agent or precursor thereof having a granule size greater than 400 microns .
  • the bleaching agent or precursor thereof has a granule size greater than 200 microns .
  • granule encompasses material of both a granular and particulate nature .
  • the bleaching granules have a granular size less than 2000 microns, more preferably 95% of the particles having a granular size less than 2000 microns, most preferably 99% of the granules having a granule size less than 2000 microns.
  • Suitable bleaching agents active-halide and active-oxygen bleaching agents particularly the so-called 'halogen release agents'.
  • Chlorine bleaching agents are preferred. Suitable water- soluble, active chlorine, bleaching agents used in accordance with the invention include chlorinated cyanurates, phthalimides, p-toluene sulfonamides, azodicarbonamides, hydantoins, glycoluracils, amines and melamines. The alkali metal salts of cyanurates are preferred.
  • a particularly preferred bleaching agent is sodium dichlorocyanurate (NaDCCA) .
  • the bleaching agent is typically present in an amount of 10-30% and most preferably at around 25%.
  • Oxidan DCN/WSG (TM) ex Sigma has been found to be a suitable bleaching agent .
  • the bleaching agent may be coated and/or co-granulated with polymer to further mitigate the risk of thermal heating.
  • Suitable polymers include soluble or insoluble polycarboxylate/co-polymers of the polycarboxylic acid, both in acidic form or neutralized with alkaline and/or earth metal ions.
  • the polymer molecular weight preferably ranges from 200 to 3000000, more preferably from 3000 to 1000000 most preferably from 50000 to 500000.
  • the polymer used is polyacrylic acid. If present it is preferred if the ratio of bleaching agent to polymer is from 1:10 to 10:1.
  • a surfactant may be present in the toilet block.
  • the surfactant component of the block may be anionic or nonionic in nature.
  • the surfactant serves to provide a cleansing and foaming effect and may, also act synergistically with the polymer component.
  • surfactant comprises up to 50%wt of the composition.
  • the surfactant component comprises one or more anionic surface active agents, optionally in combination with one or more nonionic surface active agents.
  • Suitable anionic surface active agents include alkali metal or ammonium alkylaryl sulphonates (especially alkyl benzene sulphonates), alkane sulphonates, alkyl sulphates and sarcosinates .
  • a surfactant system which comprises primary alkyl sulphate (PAS) together with other anionic surfactants.
  • PAS primary alkyl sulphate
  • the present invention provides a lavatory cistern block comprising l-15%wt (more preferably l-5%wt) of a primary alkyl sulphate and 15-50%wt (more preferably 30-50%wt) of other anionic surfactants.
  • this mixed surfactant system is advantageous in that it reduces the stickiness of the block during manufacture.
  • the blocks with 1-5% PAS show improved wear characteristics.
  • said other anionic surfactants is a sulphonate.
  • Suitable sulphonates include alkyl benzene sulphonate (ABS) . It is believed that the combination of relatively low levels of PAS together with higher levels of ABS promotes the foaming and the perfume delivery from the block. PAS is also believed to be environmentally more acceptable than alkyl benzene sulphonate.
  • Suitable nonionic surfactants include polyethoxylated fatty alcohols, polyethoxylated fatty acids, polyethoxylated alkyl phenols, amine oxides and ethylene oxide/propylene oxide block copolymers .
  • the total amount of surfactant when present may lie within wide limits.
  • the surfactant will generally for 10 to 70% by weight of the composition, but more preferable that surfactant comprises from 20 to 50% by weight thereof.
  • the blocks according to the invention further comprise a processing aid to assist in extrusion.
  • processing aids include oils (including both mineral and silicone oils) , esters (other than those derived from ethylenically unsaturated carboxyl group-containing monomers) and polybutene .
  • One particularly suitable processing aid is an alkoxylated alcohol . 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. Another suitable process aid is a PEG monostearate . PEG 4000 Monostearate (100%) ex DAC is a suitable raw material .
  • polymers used to coat/mix with the bleaching agent may be present in the formulation to prevent rapid dissolution of the block.
  • preferred polymers are polycarboxylic acids derived from one or more ethylenically unsaturated carboxyl group-containing monomers, especially ethylenically unsaturated carboxylic acids such as acrylic acid or maleic acid.
  • the carboxyl group-containing monomers may be polymerized alone or in combination with other ethylenically unsaturated monomers.
  • Preferred polymers are polymers of acrylic or methacrylic acid or maleic anhydride, or a co-polymer of one or more of the same either together or with other monomers. In general, polymers derived largely or wholly from the acidic monomers are preferred.
  • Suitable polymers include polyacrylic acid, polymaleic anhydride and copolymers of either of the aforementioned with ethylene, styrene and methyl vinyl ether.
  • the polymer is crosslinked.
  • Such materials are available from a number of sources including materials available under the tradename CARBOPO (TM) from B. F. Goodrich Company, the tradename SOKOLAN (TM) from the BASF Corporation and under the tradename POLYGEL (TM) from 3V Sigma.
  • the polymer is suitably present in an amount of from 0.5 to 20% by weight, more preferably from 1 to 5% by weight, most preferably around 2-3% by weight thereof.
  • blocks according to the present invention comprise 0 to 50% by weight of an inert non-polymeric and/or electrolyte filler.
  • blocks Preferably contain 5-50%wt, more preferably 10-30% of filler.
  • 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, non-polymeric fillers include calcium carbonate. - 8 -
  • Typical levels of total filler range from 10-40%wt on product in total .
  • the toilet block is an in-cistern blocks
  • 10-30%wt of an ionic filler as the sole filler present to ensure stability and solubility of the block.
  • preferred levels of filler are 10-20%wt on product of ionic filler and 10-20% on product of inert filler. It is particularly preferred to use an approximately 50:50 mixture of sodium sulphate and calcium carbonate as the filler.
  • typical levels in product are 15%wt of each of calcium carbonate and sodium sulphate .
  • the blocks comprise 2-15%wt of a hydrophobic oily liquid perfume.
  • the blocks more preferably comprise, 2-10%, more preferably 3-6%wt of the perfume. Levels of around 4%wt perfume are particularly preferred.
  • This oily perfume is typically 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 .
  • bleach-stable perfumes examples include Verdeo 898, Bonanza 048 and Ponderosa 431 all ex IFF, and LB 132 ex
  • perfumes are Icebreaker Super Mod, Oxygen Supra Mod, Motebianco Supra and lemonfit Supra (all TM) ex Givaudan Roure .
  • the most preferred perfume is Green Tank Harder (TM) ex. Givaudan Roure. Minors :
  • 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.
  • a particularly preferred colouring agent is P. Green (CI 74260) .
  • Titanium dioxide is an acceptable whitener.
  • Levels of colouring agents and/or whiteners as typically below 5%wt. For colouring agents levels are typically in the range 0.0001-0. l%wt .
  • chelating agent such as ethylene diamine tetra-acetic acid or a derivative thereof, nitrolotriacetic acid, phosphonates of polyphosphates, metasilicates, boroheptonates, s.s- thylene-diamino disuccinate, dipicolinic acid, 2- phosphonobutane-1, 2 , 4-tricarboxylic acid, or lower molecular weight polymeric materials capable of inhibiting crystal growth.
  • Further reducing agents such as alkali metal metabisulphates may be present to assist in the reduction of staining due to metals such as iron.
  • An optional minor component is a foam-boosting surfactant.
  • Suitable surfactants include amine oxides. - 10 -
  • compositions in accordance with the invention are formed by an extrusion process in which the mixture of the components which comprises is extruded as a plastified mass through an aperture to form a billet.
  • compositions of the invention are used as free-standing lavatory cleansing blocks, they have a weight from 30 to 150 grams, preferably 40-80 grams.
  • the invention also provides a method of cleaning a lavatory or urinal using a block of a composition in accordance with the invention.
  • Blocks were produced by mixing the raw materials together with the exception of perfume and NaDCC. The perfume was then added to the mix followed by the addition of NaDCC. The resulting dough was extruded and then cut into blocks of the desired shape.
  • ABS is Alkyl benzene sulphonate NANSA HS 80/LPF (TM) ex
  • PAS is Primary alkyl sulphate Empicol LZ-V (TM) ex
  • Polymer is Polygel DB (TM) high molecular weight-water insoluble, partially cross linked acrylic acid polymer ex Sigma
  • NaDCCA Granules with fines removed ie 99% of the material has a particulate size greater than 400 microns .

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un bloc pour W-C comprenant un agent blanchissant solide ou un précurseur de celui-ci, dans lequel 75 % des granules composant cet agent blanchissant présentent une dimension supérieure à 400 microns.
PCT/EP1999/001899 1998-04-09 1999-03-22 Blocs nettoyants pour w-c WO1999053012A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BR9909499-1A BR9909499A (pt) 1998-04-09 1999-03-22 Bloco de vaso sanitário, e, processo de prevenção do aquecimento térmico num bloco de vaso sanitário
CA002320170A CA2320170A1 (fr) 1998-04-09 1999-03-22 Blocs nettoyants pour w-c
PL99343345A PL343345A1 (en) 1998-04-09 1999-03-22 Toilet cleaning blocks
HU0101314A HUP0101314A3 (en) 1998-04-09 1999-03-22 Toilet cleaning blocks and method prevent the heat-developing therein
EP99915682A EP1070114A1 (fr) 1998-04-09 1999-03-22 Blocs nettoyants pour w-c
AU34166/99A AU3416699A (en) 1998-04-09 1999-03-22 Toilet cleaning blocks

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP98302785.5 1998-04-09
EP98302785 1998-04-09

Publications (1)

Publication Number Publication Date
WO1999053012A1 true WO1999053012A1 (fr) 1999-10-21

Family

ID=8234772

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/001899 WO1999053012A1 (fr) 1998-04-09 1999-03-22 Blocs nettoyants pour w-c

Country Status (9)

Country Link
EP (1) EP1070114A1 (fr)
AR (1) AR018837A1 (fr)
AU (1) AU3416699A (fr)
BR (1) BR9909499A (fr)
CA (1) CA2320170A1 (fr)
CZ (1) CZ20003728A3 (fr)
HU (1) HUP0101314A3 (fr)
PL (1) PL343345A1 (fr)
WO (1) WO1999053012A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1621606A1 (fr) * 2004-07-28 2006-02-01 Buck-Chemie GmbH . Agent nettoyant et odorisant pour les toilettes

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3166513A (en) * 1963-04-04 1965-01-19 Economics Lab Stable detergent composition
US4249274A (en) * 1979-12-03 1981-02-10 The Procter & Gamble Company Apparatus for sanitizing toilets
US4324677A (en) * 1980-01-12 1982-04-13 Henkel Kommanditgesellschaft Auf Aktien Stable dishwashing agent compositions containing active chlorine
US4861511A (en) * 1987-06-26 1989-08-29 Nalco Chemical Company Toilet bowl cleaner and stain-inhibiting composition
EP0341836A2 (fr) * 1988-04-13 1989-11-15 JEYES GROUP plc Blocs de nettoyage pour cabinets d'aisance
WO1992000369A1 (fr) * 1990-06-26 1992-01-09 The Procter & Gamble Company Produit a nettoyer granulaire pour surfaces multiples incorporant un agent blanchissant
EP0619367A1 (fr) * 1993-04-06 1994-10-12 The Procter & Gamble Company Blocs pour toilettes contenant des enzymes
WO1994026863A1 (fr) * 1993-05-14 1994-11-24 Block Drug Company, Inc. Bloc de nettoyage de toilettes
EP0688857A1 (fr) * 1994-06-24 1995-12-27 The Procter & Gamble Company Compositions de blanchiment à base d'hypochlorite
WO1997047721A1 (fr) * 1996-06-12 1997-12-18 Unilever Plc Perfectionnements relatifs aux blocs nettoyants pour w.-c.

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3166513A (en) * 1963-04-04 1965-01-19 Economics Lab Stable detergent composition
US4249274A (en) * 1979-12-03 1981-02-10 The Procter & Gamble Company Apparatus for sanitizing toilets
US4324677A (en) * 1980-01-12 1982-04-13 Henkel Kommanditgesellschaft Auf Aktien Stable dishwashing agent compositions containing active chlorine
US4861511A (en) * 1987-06-26 1989-08-29 Nalco Chemical Company Toilet bowl cleaner and stain-inhibiting composition
EP0341836A2 (fr) * 1988-04-13 1989-11-15 JEYES GROUP plc Blocs de nettoyage pour cabinets d'aisance
WO1992000369A1 (fr) * 1990-06-26 1992-01-09 The Procter & Gamble Company Produit a nettoyer granulaire pour surfaces multiples incorporant un agent blanchissant
EP0619367A1 (fr) * 1993-04-06 1994-10-12 The Procter & Gamble Company Blocs pour toilettes contenant des enzymes
WO1994026863A1 (fr) * 1993-05-14 1994-11-24 Block Drug Company, Inc. Bloc de nettoyage de toilettes
EP0688857A1 (fr) * 1994-06-24 1995-12-27 The Procter & Gamble Company Compositions de blanchiment à base d'hypochlorite
WO1997047721A1 (fr) * 1996-06-12 1997-12-18 Unilever Plc Perfectionnements relatifs aux blocs nettoyants pour w.-c.

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1621606A1 (fr) * 2004-07-28 2006-02-01 Buck-Chemie GmbH . Agent nettoyant et odorisant pour les toilettes
DE102004036635A1 (de) * 2004-07-28 2006-03-23 Buck-Chemie Gmbh Reinigungs- und Beduftungsmittel für den Toilettenbereich

Also Published As

Publication number Publication date
HUP0101314A2 (hu) 2001-08-28
BR9909499A (pt) 2000-12-12
EP1070114A1 (fr) 2001-01-24
PL343345A1 (en) 2001-08-13
AR018837A1 (es) 2001-12-12
HUP0101314A3 (en) 2002-02-28
CA2320170A1 (fr) 1999-10-21
CZ20003728A3 (cs) 2001-11-14
AU3416699A (en) 1999-11-01

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