EP1290131B1 - Reinigungsmittel für harte oberflächen - Google Patents

Reinigungsmittel für harte oberflächen Download PDF

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Publication number
EP1290131B1
EP1290131B1 EP01964957A EP01964957A EP1290131B1 EP 1290131 B1 EP1290131 B1 EP 1290131B1 EP 01964957 A EP01964957 A EP 01964957A EP 01964957 A EP01964957 A EP 01964957A EP 1290131 B1 EP1290131 B1 EP 1290131B1
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EP
European Patent Office
Prior art keywords
composition
perfume
toilet
weight
surfactant
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.)
Expired - Lifetime
Application number
EP01964957A
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English (en)
French (fr)
Other versions
EP1290131A2 (de
Inventor
Matthew J. Unilever Research Port Sunlight LEACH
Franca Lever Faberge Italia S.p.A. MARIANINI
Frank Lever Faberge Italia S.p.A VAN DER SCHEUR
Adriano Lever Faberge Italia S.p.A. VIOLANTE
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
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Unilever PLC
Unilever NV
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Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Priority to EP01964957A priority Critical patent/EP1290131B1/de
Publication of EP1290131A2 publication Critical patent/EP1290131A2/de
Application granted granted Critical
Publication of EP1290131B1 publication Critical patent/EP1290131B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • 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
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes

Definitions

  • the invention relates to hard surface cleaning compositions.
  • the invention relates to liquid toilet cleaning compositions for use with dosing devices for toilets.
  • the invention also relates to a toilet cleaning system comprising a toilet cleaning composition and a delivery device.
  • Cleaning compositions for toilets and particularly those which are dosed via a dosing device into the flush water of a toilet, have specific requirements as regards cleaning and deodorising.
  • dosing devices deliver a small dose of product with each flush it is generally necessary to incorporate a high level of perfume into the composition to ensure that each dose delivers a sufficient level of perfume.
  • the incompatibility between oxidising agents, particularly peroxidising agents and perfumes has generally made it difficult to combine the two components into a single phase, physically stable composition.
  • conventional oxidising agents the use of high levels of perfume usually results in separation of the composition into two layers of differing density. In order to obtain perfume and hygiene agent delivered from such a separated composition, a highly complex dosing device would be required.
  • WO 96/27714 describes an in-cistern toilet cleaner and a number of compositions for use therewith. While some of the compositions include the use of the hypohalite oxidising agent, potassium dichlorocyanuric acid, none disclose the use of the perfume with this, or any, oxidising agent. Likewise, US 4,212,089 discloses a cleaning composition for an in-cistern dosing device comprising 1% perfume and 99% of a sanitising composition in which peroxidising agents are absent.
  • EP 0 596 493 teaches the use of a fragrance solubilised by surfactant to mask the irritating odour of peracetic acid.
  • EP 0 784 091 selects specific fragrance components for use with oxidising agents, in particular persulphate salts, solubilised by surfactants. Although the text mentions up to 5% by weight of perfume, the examples are limited to 0.5% by weight of the fragrance components.
  • US 6,010,993 discloses aqueous liquids formed from peroxyacids or peroxides, selected antimicrobial essential oils and surfactants, with examples limited to 3% by weight of essential oils.
  • EP 0 905 227 discloses stable anhydrous liquids comprising peracid, solvent and surfactant with perfume.
  • an aqueous liquid hard surface cleaning composition comprising:
  • ester peracid oxidising agents can be incorporated into hard surface cleaning composition along with significant amounts of perfume.
  • the resulting aqueous compositions can be made in a single phase form, are stable to phase separation and do not suffer from the irritating odour associated with peracetic acid. This is particularly advantageous for toilet cleaning applications, where the perfume is needed to mask malodour in the environment rather than malodour inherently present in the cleaning composition.
  • Suitable ester peracid oxidising agents have the general formula: Wherein R represents an alkyl group having from 1 to 4 carbon atoms and X is from 1 to 4. Typically, when R has 3 or 4 carbon atoms, the alkyl group may be branched or linear. Thus the alkyl group may be n- or isopropyl, or n-, iso- or tertiary butyl. Ideally R is a methyl group and typically the value of X is 2, 3 or 4. In a preferred embodiment of the invention the composition comprises a mixture of ester peracids where X is 2, 3 or 4, thus a mixture, for example, of the monoesters of peradipic, perglutaric and persuccinic acids.
  • the ester peracids may exist as equilibrium mixtures in aqueous solution in which the ester peracid is in equilibrium with water, hydrogen peroxide and the non-peroxidised acid. In such cases the equilibrium obeys the following general equation in the presence of strong acid: RCO 2 (CH 2 ) x COOH + H 2 O 2 ⁇ RCO 2 (CH 2 ) x CO 3 H + H 2 O
  • R represents a hydrogen or an organic radical.
  • ester peracid oxidising agents have been found to be particularly suitable for compositions which in use will be substantially diluted such as for example in-cistern and toilet-rim mounted toilet cleaning systems. Generally in such uses, between 0.05 and 5 mls of composition will be dosed into a toilet flush water and the resulting dilution requires a strong oxidising agent.
  • the ester peracid is present in an amount of at least 0.1%, preferably at least 0.3%, more preferably at least 0.5%, more preferably at least 0.7%, most preferably at least 1.0% by weight of ester peracid to composition.
  • compositions according to the invention include at least 2% perfume, however it has been found that greater amounts of perfume can be supported within the compositions which is a great advantage for certain toilet cleaners which need to carry a lot of perfume due to the extreme dilution of the product in the flush water.
  • the compositions of the invention typically include up to 10%, suitably between 2 and 8% and preferably between 3 and 6% perfume by weight.
  • Suitable perfumes for use in toilet cleaning compositions are those which are chemically stable in the presence of oxidising agents. As discussed in WO 99/57233, this may be determined by screening perfume components to identify those which display stability in the presence of oxidising agents. Such routes are disclosed in WO 92/08780 and EP 299 561.
  • EP 299 561 provides a method for assessing the chemical stability of perfume components in the presence of peracid.
  • Suitable perfumes would be blended from the chemically stable components by those skilled in the art.
  • the pH of the composition will be suitably between 1 and 3, preferably between 1 and 2. At higher pH's the ester peracid oxidising becomes less stable and loses its activity. Further, as the pH of the composition drops below 1 the ability of the perfume to solubilise in the composition lessens with a resultant decrease in perfume stability in the composition.
  • the perfume chosen for the invention will, be those that are reasonably stable at pH's between 1 and 3, and especially between 1 and 2.
  • the composition will include an anionic surfactant.
  • Suitable anionic surfactants include the sulphonate hydrotropes.
  • Preferred surfactants are secondary alkane sulphonates such as HOSTAPUR 30 from Clariant or DOWFAX from Dow Chemicals. It is also possible to use alkylarylsulphonates such as salts, particularly alkali metal salts, of toluene, cumene or xylene sulphonate.
  • the preferred anionic surfactant is sodium cumenesulphonate.
  • a suitable material is ELTESOL SC 40TM (ex. Albright and Wilson). Typical levels of anionic surfactant range from 1 to 40 wt% on product.
  • compositions according to the invention additionally comprise nonionic surfactant.
  • Suitable nonionic surfactants include alkoxylated alcohols, preferably ethoxylated alcohols.
  • Suitable nonionic detergent active compounds can be broadly described as compounds produced by the condensation of alkylene oxide groups, which are hydrophilic in nature, with an ,organic hydrophobic compound which may be aliphatic or alkyl aromatic in nature.
  • the length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • the preferred alkoxylated alcohols are selected from the group comprising ethoxylated alcohols of the general formula: R 1 -(OCH 2 CH 2 ) m -OH wherein R 1 is straight or branched, C 8 to C 18 alkyl or hydroxyalkyl and m is, on average, 1-14.
  • Ethoxylated alcohols suitable for use in the present invention include LIAL 111.10EO [TM] available in the marketplace from DAC. Typical levels of nonionic surfactant in products according to the present invention range from 0-15wt%. A particularly suitable non-ionic is Neodol 91-5TM from Shell.
  • Stabilisers can be suitably employed to improve the storage stability of solutions according to the invention, and are particularly useful when the compositions according to the invention include compounds known to cause decomposition such as transition ion metals.
  • Suitable chelating agents are often aminocarboxylic acids or salts thereof such as EDTA or DPTA and/or carboxylic acid substituted N-containing heterocyclics such as 8-hydroxyquinoline or picolinic or dipicolinic acid, and organopolyphosphates including hydroxyethylidinediphosphonic acid, and alkyleneaminomethylene phosphonic acids such as ethylene diaminotetramethylene phosphonic acid and cyclohexane-1,2-diaminotetramethylene phosphonic acid.
  • the amount of chelant in the solution is preferably greater than 0.25%.
  • xanthan gums are suitable thickeners.
  • Preferred xanthan gums are the KelzanTM series (available from Kelco Corp). Typical levels of xanthan gum range from 0.05-1wt%.
  • Metal ion sequestrants such as ethylene diamine tetraacetates, amino-poly phosphonates (such as those in the DEQUESTTM range ex. Monsanto) and phosphates and a wide variety of other poly-functional organic acids and salts, can also optionally be employed.
  • Preferred metal ion complexing agents are selected from dipicolinic acid, ethylene diamine tetra acetic acid (EDTA) and its salts, hydroxy-ethylidene diphosphonic acid (Dequest 2010), ethylenediaminetetra(methylene phosphonic acid) (Dequest 2040), diethylenetriamine-penta(methylene phosphonic acid) (Dequest 2060).
  • minor components also include those typically found in cleaning compositions and are selected from opacifiers, colours and fluorescers.
  • the invention also relates to the use of a composition according to the invention in a toilet in-cistern dosing device.
  • in-cistern dosing device refers to dosing devices having a chamber for liquid toilet cleaning compositions and a dosing arrangement which delivers a defined dose of the composition into the flush water in the toilet cistern in response to the flushing of the toilet. Many such devices are known from the prior art.
  • US 4,212,089 describes such a device having a chamber for cleaning composition connected to a siphon tube via a u-tube, the arrangement being such that when the toilet cistern is evacuated the downward movement of the water in the cistern exerts a negative pressure in the siphon which pulls a dose of product from the reservoir.
  • Similar devices are described in US 3,953,902 and PCT/GB98/0349.
  • in-cistern dosing device comprises an inverted container having a discharge spout contained within a sleeve wherein discharge of product is automatically controlled by alternate compression and decompression of air within the sleeve arising from rising and falling of the cistern water.
  • in-cistern dosing devices the device is adapted to be mounted within the toilet cistern, however the term "in-cistern" in this specification should be taken to include devices which are located outside a toilet cistern but which deliver the dose of active agent into the water in the cistern.
  • the invention further relates to the use of a composition according to the invention in toilet-rim dosing devices.
  • the term "toilet-rim dosing device” as used in this specification means dosing devices for liquid compositions which hang from the rim of a toilet.
  • Such a device is disclosed in European patent application EP-A-0,538,957 and comprises a unit having a bottle containing a cleansing and odorising liquid for suspension from the rim of a toilet bowl.
  • the cleansing and odorising liquid seeps from the bottle onto a porous mass when the unit has been suspended in the toilet bowl.
  • the flush water flows over the porous mass and dispenses the active agent around the toilet bowl.
  • European patent application EP-A-0,785,315 relates to a modification of the unit disclosed in European patent application EP-A-0,538,957.
  • the unit includes at least one liquid passage and one air supply opening communicating with the discharge opening of the bottle so that the liquid pressure of the active agent on the porous mass is substantially equal and independent of the liquid level in the bottle.
  • the invention also relates to the combination of the above type of toilet dosing devices, i.e. those which upon flushing delivers a dose of product into the toilet flush water, and a toilet cleaning composition according to the invention.
  • the dosing device delivers a dose of cleaning composition which is less than 5 mls, preferably between 0.05 and 2mls and most preferably between 0.1 and 2mls.
  • a product containing monomethylglutaric peracid was prepared as follows. 11.0 grams of monomethylglutaric acid (ex. Aldrich Chemicals) was dissolved in 60.4 grams of demineralised water and 28.6 grams of a 35 weight % solution of hydrogen peroxide (ex. Degussa). The pH of the solution was adjusted to 1.1 with concentrated sulphuric acid and left to stand at ambient temperature. After 4 weeks, the concentration of peracid was 0.3% by weight of the mixture. Other components of the mixture were unreacted monomethylglutaric acid, glutaric acid, hydrogen peroxide and methanol. Diperoxyglutaric acid was also present in trace amounts in the mixture. Product analysis was carried out using high pressure liquid phase chromatography combined with ultra violet and mass spectrometry detection.
  • formulations according to the invention were made using the product mixture, sodium secondary alkane sulphonate (ex. Clariant under the trade name SAS 30 comprising 30% surfactant), alcohol ethoxylate (ex. Shell; Neodol 98-1) and various levels of perfume (ex Quest; LB0146D).
  • the perfume comprises bornyl acetate, limonene, camphene, alpha pinene, diphenyl oxide, eucalyptol, dipropylene glycol, borneol and p-cymene.
  • the perfume was soluble in all three formulations, which were homogeneous, colourless and fully transparent.

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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)

Claims (10)

  1. Wässrige flüssige Einphasen-Reinigungszusammensetzung für harte Oberflächen, umfassend:
    mindestens 0,1 Gew. % Esterpersäure-Oxidationsmittel;
    mindestens 2 Gew. % Duftstoff;
    und bis zu 40 Gew. % Tensid.
  2. Zusammensetzung nach Anspruch 1, in der das Esterpersäure-Oxidationsmittel eine Esterpersäure mit der allgemeinen Formel:
    Figure 00150001
    ist, in der R eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen darstellt und X für 1 bis 4 steht.
  3. Zusammensetzung nach Anspruch 1 oder 2, umfassend ein oder mehrere Tenside, die aus der Gruppe von nichtionischen Tensiden und anionischen Tensiden ausgewählt sind.
  4. Zusammensetzung nach Anspruch 3, in der das nichtionische Tensid ein ethoxylierter Alkohol ist.
  5. Zusammensetzung nach Anspruch 3 oder 4, in der das anionische Tensid ein sekundäres Alkansulfonat ist.
  6. Zusammensetzung nach irgendeinem vorangehenden Anspruch mit 2 bis 8 Gew. % Duftstoff.
  7. Zusammensetzung nach Anspruch 6, die 3 bis 6 Gew. % Duftstoff umfasst.
  8. Zusammensetzung nach irgendeinem vorangehenden Anspruch, die mindestens 1 Gew. % Tensid umfasst.
  9. Zusammensetzung nach irgendeinem vorangehenden Anspruch mit einem pH zwischen 1 und 3 und bevorzugter zwischen 1,5 und 3 und am bevorzugtesten von etwa 2,5.
  10. Kombination einer Toilettendosierungsvorrichtung der Art, die beim Spülen dem Toilettenspülwasser eine Produktdosis zuführt, und einer Toilettenreinigungszusammensetzung nach irgendeinem der Ansprüche 1 bis 9.
EP01964957A 2000-06-08 2001-05-31 Reinigungsmittel für harte oberflächen Expired - Lifetime EP1290131B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP01964957A EP1290131B1 (de) 2000-06-08 2001-05-31 Reinigungsmittel für harte oberflächen

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP00304885 2000-06-08
EP00304885 2000-06-08
EP01964957A EP1290131B1 (de) 2000-06-08 2001-05-31 Reinigungsmittel für harte oberflächen
PCT/EP2001/006296 WO2001094520A2 (en) 2000-06-08 2001-05-31 Hard surface cleaning compositions

Publications (2)

Publication Number Publication Date
EP1290131A2 EP1290131A2 (de) 2003-03-12
EP1290131B1 true EP1290131B1 (de) 2003-12-03

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EP01964957A Expired - Lifetime EP1290131B1 (de) 2000-06-08 2001-05-31 Reinigungsmittel für harte oberflächen

Country Status (9)

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EP (1) EP1290131B1 (de)
AR (1) AR028688A1 (de)
AT (1) ATE255629T1 (de)
AU (1) AU2001285730A1 (de)
DE (1) DE60101387T2 (de)
HU (1) HUP0300968A3 (de)
PL (1) PL194358B1 (de)
TR (1) TR200302295T4 (de)
WO (1) WO2001094520A2 (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1473355A1 (de) 2003-04-29 2004-11-03 The Procter & Gamble Company Verfahren zur erhöhung der Hydrophobizität einer Toilettenbeckenoberfläche
US20080032912A1 (en) 2006-08-04 2008-02-07 Takasago International Corporation Use of fragrance compositions for the prevention of the development of indole base malodours from fecal and urine based soils
EP2110118B1 (de) 2008-04-15 2014-11-19 Takasago International Corporation Zusammensetzung zur Verringerung von schlechten Gerüchen und Verwendungen dafür
DE102010055742A1 (de) * 2010-12-22 2012-06-28 Clariant International Ltd. Zusammensetzungen enthaltend sekundäres Paraffinsulfonat und Alkoholalkoxylat
JP7048317B2 (ja) 2015-02-24 2022-04-05 高砂香料工業株式会社 増強香料組成物
ES2961747T3 (es) 2016-02-24 2024-03-13 Takasago Perfumery Co Ltd Producto de lavandería
US20190054200A1 (en) 2016-02-24 2019-02-21 Takasago International Corporation Household product delivering warming and/or tingling sensations
EP3219332A3 (de) 2016-02-24 2018-01-10 Takasago International Corporation Haushaltsproduktabgabe-kühlungsempfindungen

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8716219D0 (en) * 1987-07-09 1987-08-12 Unilever Plc Perfume compositions
DD292477B5 (de) * 1990-03-05 1994-12-08 Fit Chemische Produkte Gmbh Parfuemierte, mit Riechstoffen versehene, fluessige Wasch-, Geschirrspuel-und Reinigungsmittel
US5248434A (en) * 1992-04-20 1993-09-28 The Proctor & Gamble Company Liquid or gel bleaching composition containing amidoperoxyacid bleach and perfume
JP3197371B2 (ja) * 1992-11-04 2001-08-13 稲畑香料株式会社 芳香を有する過酢酸系殺菌剤組成物及び漂白剤組成物
GB9412051D0 (en) * 1994-06-16 1994-08-03 Solvay Interox Ltd Novel peroxygen compounds
US6055679A (en) * 1995-03-03 2000-05-02 S. C. Johnson & Son, Inc. Passive lavatory cleanser dispensing system
EP0784091A1 (de) * 1996-01-12 1997-07-16 The Procter & Gamble Company Stabile parfümierte Bleichmittelzusammensetzung
US6010993A (en) * 1996-02-23 2000-01-04 The Procter & Gamble Company Disinfecting compositions
EP0905227A1 (de) * 1997-09-30 1999-03-31 The Procter & Gamble Company Persäure enthaltende wasserfreie Zusammensetzungen
EP1001012A1 (de) * 1998-11-10 2000-05-17 The Procter & Gamble Company Desinfektions- und Reinigungszusammensetzungen
EP1072673A3 (de) * 1999-07-20 2001-03-21 The Procter & Gamble Company Riechstoffkompositionen

Also Published As

Publication number Publication date
HUP0300968A2 (hu) 2003-08-28
WO2001094520A3 (en) 2002-03-07
DE60101387D1 (de) 2004-01-15
PL194358B1 (pl) 2007-05-31
EP1290131A2 (de) 2003-03-12
PL360251A1 (en) 2004-09-06
AU2001285730A1 (en) 2001-12-17
AR028688A1 (es) 2003-05-21
ATE255629T1 (de) 2003-12-15
HUP0300968A3 (en) 2006-06-28
TR200302295T4 (tr) 2004-01-21
DE60101387T2 (de) 2004-06-09
WO2001094520A2 (en) 2001-12-13

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