EP1553162A1 - Stückförmige Toilettenreinigungsmittel - Google Patents

Stückförmige Toilettenreinigungsmittel Download PDF

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Publication number
EP1553162A1
EP1553162A1 EP04078440A EP04078440A EP1553162A1 EP 1553162 A1 EP1553162 A1 EP 1553162A1 EP 04078440 A EP04078440 A EP 04078440A EP 04078440 A EP04078440 A EP 04078440A EP 1553162 A1 EP1553162 A1 EP 1553162A1
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EP
European Patent Office
Prior art keywords
solid phase
phase
gel
block according
recess
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.)
Granted
Application number
EP04078440A
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English (en)
French (fr)
Other versions
EP1553162B2 (de
EP1553162B1 (de
Inventor
Gian Marco Lever Fabergé Italia S.r.l. Contesi
Rocco A. Lever Fabergé Italia S.r.l. Di Benedetto
Vittorio Lever Fabergé Italia S.r.l. Fasoli
Caterina D. Lever Fabergé Italia S.r.l. Fontana
Alice Lever Fabergé Italia S.r.l. Tacconi
Ediz Lever Fabergé Italia S.r.l. Yurtover
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 PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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Publication date
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Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to PL04078440T priority Critical patent/PL1553162T5/pl
Priority to EP04078440A priority patent/EP1553162B2/de
Priority to DE602004005409T priority patent/DE602004005409T3/de
Publication of EP1553162A1 publication Critical patent/EP1553162A1/de
Application granted granted Critical
Publication of EP1553162B1 publication Critical patent/EP1553162B1/de
Publication of EP1553162B2 publication Critical patent/EP1553162B2/de
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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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic 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
    • C11D3/50—Perfumes

Definitions

  • the present invention relates to lavatory blocks.
  • Lavatory blocks are known in the art and are typically configured to provide an automatic and sustained release of active ingredients to the lavatory environment. For example, they may be suspended in a container 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 and releasing active ingredients of the block into the lavatory bowl.
  • lavatory blocks contain a number of active ingredients in order to provide multiple lavatory care benefits such as cleansing, disinfection and fragrancing.
  • Formulating and processing blocks with multiple active ingredients can lead to problems due to the physical and/or chemical incompatibility of such ingredients. For example, it has become commonplace for lavatory blocks to contain a halogen release agent or other bleaching agent. Such materials are powerful chemically reactive species, which are difficult to combine with other oxidation sensitive components (such as perfumes), particularly since blocks are commonly made by extrusion which subjects the ingredients to elevated temperatures and pressures.
  • WO00/23558 describes how it is possible to provide a viable two-part lavatory cleansing block containing bleach and bleach-incompatible substances by extruding two compositions, only one of the compositions containing the bleach, and the other composition containing a component which is incompatible with the bleach, and ensuring that the two compositions do not have a common hydrophobe component. This is said to prevent the migration of the bleach sensitive component.
  • the block parts are co-extruded side-by-side.
  • a problem with such co-extrusion is that it places constraints on the formulation and the physical properties of the constituent block parts. For example, it is difficult to co-extrude parts of significantly different rheologies.
  • lavatory blocks continue to produce lavatory care benefits (such as fragrancing) throughout the useful life of the block, which is typically around 3 to 4 weeks under normal domestic use conditions.
  • lavatory care benefits such as fragrancing
  • a problem with the incorporation of high levels of perfume into blocks formed by an extrusion process is that such incorporation may produce an overplasticised or sticky formulation consistency that is difficult to extrude.
  • perfume materials are normally hydrophobic and high levels may tend to ooze out from the block during manufacture and/or storage.
  • US 5,759,974 describes a WC stick with a relatively high fragrance content in a cast core. This is said to have the advantage of the possibility of incorporating very large quantities of perfume in the core.
  • the stick is manufactured by extruding a hollow shell, cutting the shell to its final length, and placing on a support in such a way that the moulding is closed underneath. The shells are then filled with the molten core material containing the perfume by means of a casting trolley.
  • a problem with this manufacturing method is that it is difficult to scale up and/or operate as a continuous process.
  • WO03/0426 describes how the fragrance life of an in-the-bowl (ITB) toilet article may be extended by placing the perfume in the second chamber of a dual chamber housing so that the perfume is not in the path of the flushing toilet water.
  • the first chamber has an inlet and an outlet opening for water flow and typically contains a cleaning, disinfectant or anti-limescale composition in solid block form which fits into the chamber.
  • a problem with this proposal is that the dual chamber housing is an expensive configuration to manufacture. Also, since the perfume is placed within a gel system which is deposited in the second chamber of the housing, this means that the entire housing will need replacing by the consumer once the perfume is exhausted.
  • the underlying objective of the present invention is to resolve one or more of the problems outlined above.
  • the present invention provides a lavatory cleansing and freshening block, comprising a solid phase and a gel phase, in which the gel phase contains from 2% to 90% by weight perfume (based on the total weight of the gel phase) and is positioned on the surface of the solid phase.
  • the gel phase releases perfume during as well as between the flushes
  • the solid phase of the block according to the invention has a recess moulded on an outer surface in which the gel phase is positioned.
  • the solid phase of the block according to the invention is preferably formed by a process which includes extrusion.
  • a preferred process used to form the solid phase of the block is an extrusion process in which a mixture of the constituent ingredients of the solid phase is extruded into a continuous bar of solid phase which is subsequently cut into pieces of the desired size.
  • the solid phase may be in the form of a single, homogeneous composition, or alternatively may be in the form of one or more layers.
  • a multi-layered solid phase may suitably be produced by extrusion of the layers as complementary shapes which are brought together, or preferably by co-extrusion of the two layers side-by-side into a continuous bar as above.
  • the provision of a multi-layered solid phase is advantageous because it enables incompatible components such as bleach and dye, or bleach and bleach activator, to be segregated by placing them in different layers, thereby enhancing stability and performance of the block.
  • the solid phase of the block preferably has a recess moulded on an outer surface thereof, more preferably a longitudinal surface.
  • the recess extends along the entire length or width of the longitudinal surface of the solid phase of the block as a strip or groove.
  • the recess may be moulded on an outer longitudinal surface of the solid phase of the block by stamping, or preferably by extruding the constituent ingredients of the solid phase through a specially shaped extruder head so that the recess is formed in an outer longitudinal surface of the solid phase as it is extruded.
  • stamping or preferably by extruding the constituent ingredients of the solid phase through a specially shaped extruder head so that the recess is formed in an outer longitudinal surface of the solid phase as it is extruded.
  • the gel phase is positioned in the recess of the solid phase. Preferably it is put into position by injection into the recess. In a more preferred process, the constituent ingredients of the gel phase are heated, mixed and dosed through a nozzle into the recess of the solid phase.
  • the constituent ingredients of the solid phase are extruded through a specially shaped extruder head to form a recess as described above, and the extrudate so formed is mounted to travel upon a belt conveyor which is arranged so that the gel phase may be injected continuously into the recess of the solid phase as it travels along the belt conveyor, for example by dosing the gel phase into the recess through a nozzle as described above. Cooling and cutting of the gel-filled extrudate so formed may then take place to produce the final lavatory block according to the invention. Again this enables continuous operation of the block manufacturing process.
  • Fig 1 depicts an extruded block having a recess moulded along the entire length of a longitudinal surface of the solid phase 1, which is filled with the gel phase 2.
  • Fig. 2 depicts an extruded block having a recess moulded along the entire width of a longitudinal surface of the solid phase 1, which is filled with the gel phase 2.
  • the weight ratio of solid phase to gel phase in the block according to the invention suitably ranges from 40:1 to 5:1, preferably from 30:1 to 5:1, more preferably from 25:1 to 10:1, more preferably from 25:1 to 12.5:1.
  • Suitable substances used to form the solid phase include surfactants, hygiene agents, fillers, whiteners and complexing agents.
  • Surfactants serve to provide a cleansing and foaming effect.
  • the total amount of surfactant, when present, will generally range from 10 to 70wt%, more preferably from 20 to 50wt% (by weight based on the total weight of the solid phase).
  • Anionic surfactants are preferably used. Suitable anionic surfactants include alkali metal or ammonium alkylaryl sulphonates (especially alkyl benzene sulphonates), alkane sulphonates, alkyl sulphates and sarcosinates.
  • the solid phase comprises from 1 to 20wt%, more preferably from 5 to 15wt% of a primary alkyl sulphate (by weight based on the total weight of the solid phase), and from 5 to 40wt%, more preferably from 10 to 35wt%, even more preferably from 15-35% of other anionic surfactants (by weight based on the total weight of the solid phase).
  • Preferred other anionic surfactants are sulphonate anionic surfactants, such as alkyl benzene sulphonates (ABS).
  • Hygiene agents may be used in the solid phase to inhibit germs and keep the lavatory clean.
  • the total amount of such materials, when present, will generally range from 5 to 50wt%, more preferably from 5 to 30wt% (by total weight of hygiene agent based on the total weight of the solid phase).
  • Preferred hygiene agents for use in the block according to the invention are bleaching agents, optionally in combination with one or more bleach activators.
  • Suitable classes of bleaching agent include materials which release active halogen and materials which release active oxygen. Examples from these classes include chlorinated cyanuric acid derivatives such as sodium dichloroisocyanurate; halogenated hydantoins such as 1,3-dichloro-5,5-dimethyl hydantoin , bromochloro-5,5-dimethyl hydantoin and 1,3-dichloro-5-ethyl-5-methyl hydantoin; alkali metal percarbonates such as sodium percarbonate, and alkali metal perborates such as sodium perborate (monohydrate and tetrahydrate). Preferred examples are sodium percarbonate and sodium perborate monohydrate.
  • the solid phase comprises from 5 to 15wt%, more preferably around 10wt% of an oxygen bleach such as alkali metal perborate (by weight based on the total weight of the solid phase), and from 1 to 10wt%, more preferably around 6wt% of a bleach activator such as tetraacetylethylene-diamine (TAED).
  • an oxygen bleach such as alkali metal perborate
  • TAED tetraacetylethylene-diamine
  • the perborate and TAED are segregated into different layers of the solid phase.
  • the solid phase of the block according to the present invention comprises up to 60% by weight of a filler.
  • Preferred levels of filler range from 30 to 50wt% (by total weight filler based on the total weight of the solid phase).
  • Suitable fillers include urea, sodium, magnesium and calcium carbonates, sodium chloride, borax, talc and sodium, magnesium and calcium sulphates.
  • the solid phase comprises from 10 to 25wt% of a sulphate filler, most preferably sodium sulphate (by weight based on the total weight of the solid phase), and from 15 to 35wt% of a carbonate filler, most preferably calcium carbonate (by weight based on the total weight of the solid phase).
  • a sulphate filler most preferably sodium sulphate (by weight based on the total weight of the solid phase)
  • carbonate filler most preferably calcium carbonate (by weight based on the total weight of the solid phase).
  • Whiteners and/or colouring agents may be present in the solid phase of the block according to the present invention, particularly when the solid phase has a multi-layered structure. If present, these materials should be chosen such that they are compatible with any bleaching agent present. Suitable colouring agents include Pigment Blue 15 (CI 74160) and Pyramid S Green TM, ex Minchem. Titanium dioxide is an acceptable whitener. Levels of whiteners and/or colouring agents are typically below 5wt% by total weight based on the total weight of the solid phase.
  • the solid phase may usefully contain complexing agents for water hardness and also for the heavy metal ions often encountered in water such as iron and manganese. Furthermore, the complexing agent may also improve the stability of any bleaching agent in the solid phase.
  • suitable classes of complexing agents are aminopolycarboxylic acids, polyphosphonic acids and their salts, polymeric polycarboxylic acids and their salts, and hydroxypolycarboxylic acids and their salts.
  • Preferred are polyphosphonic acids and salts such as EDTMP (ethylene diamine tetra(methylene phosphonate)), Ca/Na salt.
  • the solid phase comprises from 0.1 to 0.5wt% complexing agent (by weight based on the total weight of the solid phase).
  • the solid phase of the block according to the invention may comprise a processing aid to assist in extrusion.
  • processing aids include oils (including both mineral and silicone oils), esters, alcohol ethoxylates, polybutene and most preferably glycol ethers.
  • the preferred level of glycol ether is up to 4.5wt% (by weight based on the total weight of the solid phase).
  • the solid phase may comprise a perfume wich may also partly or totally perform the function of processing aid.
  • the gel phase contains from 2 to 90% by weight of perfume (based on the total weight of the gel phase) and is positioned in the recess of the solid phase, preferably by injection.
  • the gel phase contains 25-90%, more preferably 40% to 70%, even more preferably 40-60% by weight perfume (based on the total weight of the gel phase).
  • Suitable methods of forming the gel phase include heating, melting and mixing the perfume and gel together in a vessel, or alternatively, heating and melting the gel in a vessel, followed by adding the perfume to the melted gel and then mixing.
  • the perfume may be a single discrete ingredient, but more typically will be a complex blend of volatile liquid (and some solid) ingredients of natural and/or synthetic origin.
  • Suitable gelling agents may be selected by those skilled in the art, and include absorbents, starch based systems, modified celluloses, natural gums and other materials which can form a gel when mixed with the perfume.
  • Preferred gelling agents are those which do not dissolve in water.
  • gelling agents used to form the gel phase in the block according to the invention are polyamide resins.
  • Particularly preferred are ester-terminated polyamide (ETPA) resins, such as are described in US 5,783,657, and tertiary amide-terminated polyamide (ATPA) resins, such as are are described in US 6,268,466. These materials create clear gels in a wide variety of solvents.
  • Suitable resins are available commercially from Arizona Chemicals as UNICLEAR TM and SYLVACLEAR TM gellants. Particularly preferred are UNICLEAR TM 100 and SYLVACLEAR TM A200.
  • a preferred gel phase for use in the block according to the invention may be prepared by warming the gelling agent, preferably a polyamide resin as described above, and the perfume with gentle mixing. At an elevated temperature, typically around 65 to 70 degrees C, the gelling agent and the perfume form a solution or dispersion. The warm liquid mixture may be injected into the recess of the solid phase of the block as described above.
  • the gel phase may include other optional additives as commonly used in the art, including solvents or carriers, inert additives such as pigmented or pearlescent particles for aesthetic purposes, or soluble additives such as colourants.
  • Solvents are not required to form the gel, but may be used to dilute perfume ingredients to a suitable concentration. Hydrophobic solvents are generally preferred for this purpose and well known examples are C1-C4 esters of C8-C20 fatty acids.
  • the gel phase of the blocks according to the invention is preferably insoluble in water and thereby substantially retains its shape and size during the entire lifetime of the block.
  • Blocks according to the invention are preferably arranged in suitable holders such as cage or basket-like containers which can be suspended over the lavatory rim in such a position that they can be reached by the flush water which flows past whenever the lavatory is flushed. They are normally suspended from the inner rim of the lavatory bowl, for example by a hook.
  • suitable holders such as cage or basket-like containers which can be suspended over the lavatory rim in such a position that they can be reached by the flush water which flows past whenever the lavatory is flushed. They are normally suspended from the inner rim of the lavatory bowl, for example by a hook.
  • Lavatory blocks were prepared having a two-layer solid phase with ingredients as shown in the following Tables: Layer A INGREDIENT LEVEL (wt% of total layer) Sodium ABS (1) 21.000 Sodium PAS (2) 7.000 Sodium Perborate Monohydrate 20.000 EDTMP Ca/Na salt (3) 0.204 Calcium Carbonate 19.850 Sodium Sulphate 19.772 Titanium Dioxide 1.000 Colourant (4) 1.000 Glycol Ether (5) 3.750 Minors to 100%
  • Layer B INGREDIENT LEVEL wt% of total layer
  • the solid phase was formed by an extrusion process in which the ingredients of each layer were mixed and co-extruded as a plasticised mass through an extruder head so as to form a continuous bar of the two layers A and B side-by-side.
  • the extruder head was shaped so as to produce a groove of 10 mm width extending along the entire length of one of the outer longitudinal surfaces of the bar, and spanning the two layers A and B.
  • a gel phase was prepared by mixing 50wt% UNICLEARTM 100, ex Arizona Chemical, 49.988wt% perfume (EMPTYSKY 375, ex IFF) and 0.012wt% dye (Sudan Blue, ex BASF) in a mixer heated by a heating jacket to 65 to 70 degrees C and equipped with a pump and nozzle.
  • the hot gel phase was dosed by pumping it through the nozzle so as to inject it into the recess of the solid phase which was mounted to run upon a belt conveyor into the path of the nozzle.
  • the gel-filled bar of solid phase so produced was then cut into 48mm lengths to form the final lavatory blocks.
  • the blocks were tested by placing in a cage suspended over the rim of a lavatory which was contained in a booth measuring 4.35 cubic meters and which was flushed 15 times a day.
  • the perfume intensity of the blocks was evaluated on a scale of 1 to 10 by a panel of 20 subjects.
  • the blocks of the invention gave improved perfume performance over 160 flushes compared to control blocks of equivalent dimensions and solid phase composition, but in which the perfume was distributed throughout the block rather than incorporated into a separate gel phase.
  • the improved perfume performance of the blocks of the invention was observed even with lower overall levels of perfume than in the control blocks (1g vs 1.6g), and was consistent over the life of the block and also in between flushes.

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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)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Bidet-Like Cleaning Device And Other Flush Toilet Accessories (AREA)
  • Cosmetics (AREA)
EP04078440A 2004-01-08 2004-12-17 Stückförmige Toilettenreinigungsmittel Active EP1553162B2 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PL04078440T PL1553162T5 (pl) 2004-01-08 2004-12-17 Toaletowe kostki
EP04078440A EP1553162B2 (de) 2004-01-08 2004-12-17 Stückförmige Toilettenreinigungsmittel
DE602004005409T DE602004005409T3 (de) 2004-01-08 2004-12-17 Stückförmige Toilettenreinigungsmittel

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP04250068 2004-01-08
EP04250068 2004-01-08
EP04078021 2004-11-03
EP04078021 2004-11-03
EP04078440A EP1553162B2 (de) 2004-01-08 2004-12-17 Stückförmige Toilettenreinigungsmittel

Publications (3)

Publication Number Publication Date
EP1553162A1 true EP1553162A1 (de) 2005-07-13
EP1553162B1 EP1553162B1 (de) 2007-03-21
EP1553162B2 EP1553162B2 (de) 2011-04-20

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ID=36712568

Family Applications (1)

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EP04078440A Active EP1553162B2 (de) 2004-01-08 2004-12-17 Stückförmige Toilettenreinigungsmittel

Country Status (6)

Country Link
EP (1) EP1553162B2 (de)
AT (1) ATE357502T1 (de)
DE (1) DE602004005409T3 (de)
ES (1) ES2285350T5 (de)
PL (1) PL1553162T5 (de)
RU (1) RU2377283C2 (de)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008058853A1 (en) * 2006-11-16 2008-05-22 Unilever N.V. Self adhesive hard surface cleaning block
EP2014758A1 (de) 2007-07-13 2009-01-14 Buck-Chemie GmbH Stückförmiges Reinigungsmittel für den Sanitärbereich mit einem Werbeträger
EP2366770A1 (de) 2010-03-05 2011-09-21 Eurvest S.A. Toilettenreinigungsmittel, Toilettenreinigungsvorrichtung aus einem Stückreinigungsmittel und Verfahren zur Herstellung eines Stückreinigungsmittels
DE102010013304A1 (de) 2010-03-29 2011-09-29 Buck- Chemie Gmbh Reinigungs- und Beduftungsmittel für den Sanitärbereich
WO2013172844A1 (en) * 2012-05-17 2013-11-21 Colgate-Palmolive Company Multiphase surfactant fragrance composition
US20140349904A1 (en) * 2011-05-06 2014-11-27 Joachim LEIPOLD Sanitary product in piece form
EP2952570A1 (de) * 2006-06-23 2015-12-09 Reckitt Benckiser LLC Verbesserungen an ausgabevorrichtungen und zusammensetzungen dafür
WO2017025322A1 (de) * 2015-08-07 2017-02-16 Henkel Ag & Co. Kgaa Wc-stein und wc-körbchen
DE102016102949A1 (de) 2016-02-19 2017-08-24 Buck-Chemie Gmbh Reinigungs- und Beduftungsmittel für den Sanitärbereich und Herstellungsverfahren
DE102016110584A1 (de) 2016-06-08 2017-12-14 Buck-Chemie Gmbh Vorrichtung mit Reinigungsmittel für den Toilettenbereich und ein Herstellungsverfahren
EP3628725A1 (de) 2018-09-26 2020-04-01 Buck Service GmbH Reinigungs- und beduftungsmittel für den sanitärbereich und herstellungsverfahren
DE102022203707A1 (de) 2022-04-13 2023-10-19 Henkel Ag & Co. Kgaa Verfahren zur Herstellung einer Waschmittelportionseinheit
DE102022203705A1 (de) 2022-04-13 2023-10-19 Henkel Ag & Co. Kgaa Verfahren zur Herstellung einer Waschmittelportionseinheit
DE102022203711A1 (de) 2022-04-13 2023-10-19 Henkel Ag & Co. Kgaa Verfahren zur Herstellung einer Waschmittelportionseinheit
DE102022203706A1 (de) 2022-04-13 2023-10-19 Henkel Ag & Co. Kgaa Verfahren zur Herstellung einer Waschmittelportionseinheit
DE102022203708A1 (de) 2022-04-13 2023-10-19 Henkel Ag & Co. Kgaa Verfahren zur Herstellung einer Waschmittelportionseinheit

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WO1999027069A1 (en) * 1997-11-26 1999-06-03 The Procter & Gamble Company Detergent tablet
WO1999038950A1 (en) * 1998-01-29 1999-08-05 Reckitt Benckiser France A lavatory cleansing block
WO2000024434A1 (en) 1998-10-22 2000-05-04 Reckitt Benckiser (Uk) Limited Vapour dispensing device
WO2000058434A1 (en) * 1999-03-29 2000-10-05 Unilever Plc Lavatory cleansing compositions
WO2003042462A2 (en) 2001-11-13 2003-05-22 Reckitt Benckiser Inc Improvements relating to toilet bowl cleaning articles
WO2004014438A1 (en) 2003-06-12 2004-02-19 Firmenich Sa Gels for dispensing active volatile materials
EP1418225A1 (de) * 2002-11-08 2004-05-12 Buk-Chemie GmbH Toilettenreinigungs- und Beduftungsmittel
EP1469132A2 (de) 2003-04-15 2004-10-20 The Procter & Gamble Company Unter dem Spülrand eines Toilettenbeckens zu montierende Vorrichtung zur Erzeugung einer Kombination aus permanenter Duftabgabe und eines Duftstosses beim Spülen

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Publication number Priority date Publication date Assignee Title
US5783657A (en) * 1996-10-18 1998-07-21 Union Camp Corporation Ester-terminated polyamides of polymerized fatty acids useful in formulating transparent gels in low polarity liquids
WO1999027069A1 (en) * 1997-11-26 1999-06-03 The Procter & Gamble Company Detergent tablet
WO1999038950A1 (en) * 1998-01-29 1999-08-05 Reckitt Benckiser France A lavatory cleansing block
WO2000024434A1 (en) 1998-10-22 2000-05-04 Reckitt Benckiser (Uk) Limited Vapour dispensing device
WO2000058434A1 (en) * 1999-03-29 2000-10-05 Unilever Plc Lavatory cleansing compositions
WO2003042462A2 (en) 2001-11-13 2003-05-22 Reckitt Benckiser Inc Improvements relating to toilet bowl cleaning articles
EP1418225A1 (de) * 2002-11-08 2004-05-12 Buk-Chemie GmbH Toilettenreinigungs- und Beduftungsmittel
EP1469132A2 (de) 2003-04-15 2004-10-20 The Procter & Gamble Company Unter dem Spülrand eines Toilettenbeckens zu montierende Vorrichtung zur Erzeugung einer Kombination aus permanenter Duftabgabe und eines Duftstosses beim Spülen
WO2004014438A1 (en) 2003-06-12 2004-02-19 Firmenich Sa Gels for dispensing active volatile materials

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EP2952570A1 (de) * 2006-06-23 2015-12-09 Reckitt Benckiser LLC Verbesserungen an ausgabevorrichtungen und zusammensetzungen dafür
AU2007321362B2 (en) * 2006-11-16 2010-09-02 Unilever Global Ip Limited Self adhesive hard surface cleaning block
WO2008058853A1 (en) * 2006-11-16 2008-05-22 Unilever N.V. Self adhesive hard surface cleaning block
EP2014758A1 (de) 2007-07-13 2009-01-14 Buck-Chemie GmbH Stückförmiges Reinigungsmittel für den Sanitärbereich mit einem Werbeträger
DE102007033077A1 (de) 2007-07-13 2009-01-15 Buck- Chemie Gmbh Stückförmiges Reinigungsmittel für den Sanitärbereich mit einem Werbeträger
EP2366770A1 (de) 2010-03-05 2011-09-21 Eurvest S.A. Toilettenreinigungsmittel, Toilettenreinigungsvorrichtung aus einem Stückreinigungsmittel und Verfahren zur Herstellung eines Stückreinigungsmittels
DE102010013304A1 (de) 2010-03-29 2011-09-29 Buck- Chemie Gmbh Reinigungs- und Beduftungsmittel für den Sanitärbereich
EP2374483A2 (de) 2010-03-29 2011-10-12 Buck-Chemie GmbH . Reinigungs- und Beduftungsmittel für den Sanitärbereich
EP2374483B2 (de) † 2010-03-29 2020-06-10 Buck-Chemie GmbH . Reinigungs- und Beduftungsmittel für den Sanitärbereich
US20140349904A1 (en) * 2011-05-06 2014-11-27 Joachim LEIPOLD Sanitary product in piece form
US9187720B2 (en) 2011-05-06 2015-11-17 Buck-Chemie Gmbh Sanitary product in piece form
AU2012380360B2 (en) * 2012-05-17 2015-02-05 Colgate-Palmolive Company Multiphase surfactant fragrance composition
RU2602806C2 (ru) * 2012-05-17 2016-11-20 Колгейт-Палмолив Компани Многофазная композиция, содержащая поверхностно-активное вещество и ароматизирующее вещество
US10975336B2 (en) 2012-05-17 2021-04-13 Colgate-Palmolive Company Aqueous multiphase surfactant fragrance composition
US10106763B2 (en) 2012-05-17 2018-10-23 Colgate-Palmolive Company Multiphase surfactant fragrance composition
WO2013172844A1 (en) * 2012-05-17 2013-11-21 Colgate-Palmolive Company Multiphase surfactant fragrance composition
US10738450B2 (en) 2015-08-07 2020-08-11 Henkel Ag & Co. Kgaa Toilet rim block and rim block cage
CN107922902B (zh) * 2015-08-07 2021-05-14 汉高股份有限及两合公司 马桶边缘清洁块和边缘清洁块笼架
CN107922899A (zh) * 2015-08-07 2018-04-17 汉高股份有限及两合公司 马桶边缘清洁块和边缘清洁块笼架
CN107922902A (zh) * 2015-08-07 2018-04-17 汉高股份有限及两合公司 马桶边缘清洁块和边缘清洁块笼架
WO2017025322A1 (de) * 2015-08-07 2017-02-16 Henkel Ag & Co. Kgaa Wc-stein und wc-körbchen
US10858814B2 (en) 2015-08-07 2020-12-08 Henkel Ag & Co. Kgaa Toilet rim block and rim block cage
AU2016307048B2 (en) * 2015-08-07 2020-04-09 Henkel Ag And Co. Kgaa Toilet rim block and rim block cage
US10829921B2 (en) 2015-08-07 2020-11-10 Henkel Ag & Co. Kgaa Toilet rim block and rim block cage
WO2017025320A1 (de) * 2015-08-07 2017-02-16 Henkel Ag & Co. Kgaa Wc-stein und wc-körbchen
US10781581B2 (en) 2015-08-07 2020-09-22 Henkel Ag & Co. Kgaa Toilet rim block and rim block cage
DE102016102949A1 (de) 2016-02-19 2017-08-24 Buck-Chemie Gmbh Reinigungs- und Beduftungsmittel für den Sanitärbereich und Herstellungsverfahren
WO2017140511A1 (de) 2016-02-19 2017-08-24 Buck-Chemie Gmbh Reinigungs- und beduftungsmittel für den sanitärbereich und herstellungsverfahren
DE102016110584A1 (de) 2016-06-08 2017-12-14 Buck-Chemie Gmbh Vorrichtung mit Reinigungsmittel für den Toilettenbereich und ein Herstellungsverfahren
EP3628725A1 (de) 2018-09-26 2020-04-01 Buck Service GmbH Reinigungs- und beduftungsmittel für den sanitärbereich und herstellungsverfahren
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DE602004005409T2 (de) 2007-07-12
EP1553162B2 (de) 2011-04-20
DE602004005409T3 (de) 2011-08-18
ATE357502T1 (de) 2007-04-15
ES2285350T5 (es) 2011-06-17
PL1553162T3 (pl) 2007-08-31
RU2377283C2 (ru) 2009-12-27
ES2285350T3 (es) 2007-11-16
PL1553162T5 (pl) 2011-07-29
RU2004138756A (ru) 2006-06-10
EP1553162B1 (de) 2007-03-21
DE602004005409D1 (de) 2007-05-03

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