EP0846757B1 - Composition gélifiée pour lave-vaisselle - Google Patents

Composition gélifiée pour lave-vaisselle Download PDF

Info

Publication number
EP0846757B1
EP0846757B1 EP19970203470 EP97203470A EP0846757B1 EP 0846757 B1 EP0846757 B1 EP 0846757B1 EP 19970203470 EP19970203470 EP 19970203470 EP 97203470 A EP97203470 A EP 97203470A EP 0846757 B1 EP0846757 B1 EP 0846757B1
Authority
EP
European Patent Office
Prior art keywords
composition according
detergent composition
group
acid
builder
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
EP19970203470
Other languages
German (de)
English (en)
Other versions
EP0846757A3 (fr
EP0846757A2 (fr
Inventor
John Richard Nicholson
Bozena Marianna Piatek
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 NV
Original Assignee
Unilever NV
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 NV filed Critical Unilever NV
Publication of EP0846757A2 publication Critical patent/EP0846757A2/fr
Publication of EP0846757A3 publication Critical patent/EP0846757A3/fr
Application granted granted Critical
Publication of EP0846757B1 publication Critical patent/EP0846757B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • 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
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • C11D3/394—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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions

Definitions

  • the present invention relates to machine dishwashing gel compositions that deliver high performance cleaning and that do not discolor in storage.
  • the composition must be a uniform mixture to deliver an optimum combination of active ingredients to the wash with each dose.
  • the liquid must possess physical stability against syneresis or physical separation of its active components during storage.
  • a liquid product must be compatible with automatic dishwashing equipment presently available to the consumer.
  • Home dishwashers are fitted with a closed cup to house detergent through several cycles preliminary to the wash cycle. Cups in these machines do not seal tightly and do not adequately retain liquids of low viscosity. Excessive leakage leads to underdosing in the wash cycle. Performance may be adversely affected. Consequently, any liquid product must possess high viscosity to be effectively retained in the cup and avoid leakage during cycles preceding that of the main wash.
  • a low viscosity is desirable for easy dispensing of product from its bottle.
  • Formulations that contain oxygen bleach systems can lead to problems of tarnishing of silverware in the wash. Therefore, tarnish inhibitors such as benzotriazole and its derivatives are generally incorporated into machine dishwashing formulations containing oxygen bleaches in order to mitigate this negative effect. Again, tarnish inhibitors are more easily incorporated into a powder or a tablet product form than into a gel.
  • the detergent builder is preferably either a monomeric carboxylate, a polymeric carboxylate or a mixture thereof, or a mixture of phosphate salts (e.g. a tripolyphosphate or pyrophosphate).
  • the oxygen bleach system is preferably a peracid or a peracid precursor with a source of hydrogen peroxide.
  • the structuring system is preferably a high molecular weight cross-linked polycarboxylate, most preferably a cross-linked polyacrylate.
  • the silver anti-tarnish agent is an aromatic azole, preferably a triazole.
  • an effective amount of an inorganic stabilizing compound such as titanium dioxide prevents discoloration of machine dishwashing gel products as described herein.
  • the combination of oxygen bleach and anti-tarnish agent can result in the generation of a highly colored species.
  • the inorganic compound either prevents the formation of this highly colored species, or limits its concentration to levels that do not result in discoloration of the gel.
  • the inorganic compound is present in an amount of from 0.0001 to 5 wt. % preferably 0.001 to 3 wt. %, most preferably 0.01 to 1 wt. %.
  • the gel compositions of the invention further comprise 10 to 50 wt. % of a builder, an effective amount of an oxygen bleach and an azole as described below.
  • Azoles useful as silver anti-tarnishing agents in the invention are nitrogen containing heterocylic 5-membered ring compounds which are present in a level of from 0.01% to 2.0% by weight, preferably from 0.01% to 0.5% by weight, most preferably from 0.02% to 0.1% by weight.
  • Such azoles include triazoles, pyrazoles, imidazoles, isoxazoles, oxazoles, isothiazoles, thiazoles and mixtures thereof as disclosed in US-A-2,618,608, US-A-2,742,369 and US-A-2,941,953.
  • the triazoles which can be employed in the composition of this invention are water-soluble 1,2,3-triazoles such as 1,2,3-triazole itself or a substituted 1,2,3-triazole where the substitution takes place in either the 4 or 5 position (or both) of the triazole ring as shown here by the structural formula:
  • Suitable triazoles include benzotriazole; tolyltriazole; 4-phenyl-1,2,3-triazole; 1,2-naphthotriazole and 4-nitrobenzotriazole; and the like, especially preferred is benzotriazole.
  • pyrazoles which can be used in the composition of this invention include water-soluble pyrazoles such as pyrazole itself or a substituted pyrazole where the substitution takes place in the 3,4 or 5 position (or several of these positions) of the pyrazole ring as shown by the structural formula:
  • Suitable pyrazoles include pyrazole; 3,5-dimethyl pyrazole; 6-nitroindazole, 4-benzyl pyrazole; 4,5-dimethyl pyrazole; and 3-allyl pyrazole; and the like.
  • Imidazoles which can be used in the composition of this invention include water-soluble imidazoles such as imidazole itself or a substituted imidazole where the substitution takes place in the 2,4 or 5 position (or several of these positions) of the imidazole ring as shown here by the structural formula:
  • Suitable imidazoles which can be employed in the composition of this invention include imidazole; adenine; guanine; benzimidazole; 5-methyl benzimidazole; 2-phenyl imidazole; 2-benzyl imidazole; 4-allyl imidazole; 4-(betahydroxy ethyl)-imidazole; purine; 4-methyl imidazole; xanthine; hypoxanthine; 2-methyl imidazole; and the like.
  • Isoxazoles which can be employed in the composition of this invention include water-soluble isoxazoles such as isoxazole itself or a substituted isoxazole where the substitution takes place in the 3,4 or 5 position (or several of these positions) of the isoxazole ring as shown here by the structural formula:
  • Suitable isoxazoles include isoxazole; 3-mercaptoisoxazole; 3-mercaptobenzisoxazole; benzisoxazole; and the like.
  • Suitable oxazoles include oxazole; 2-mercaptaxazole; 2-mercaptobenzoxazole; and the like.
  • the isothiazoles which can be employed in the compositions of this invention include water-soluble isothiazoles such as isothiazol itself or a substituted isothiazole where the substitution takes place in the 3, 4 or 5 position (or several of these positions) of the isothiazole ring as shown here by the structural formula:
  • Suitable isothiazoles include isothiazole; 3-mercaptoisothiazole; benzoisothiazole and the like.
  • Suitable thiazoles include thiazole; 2-mercaptothiazole; 2-mercaptobenzothiazole; benzothiazole and the like.
  • the constituents substituted in the azole rings can be alkyl, aryl, aralkyl, alkylol, and alkenyl radicals so long as the substituted azole is water soluble.
  • substituted members typically have from 1 to about 12 carbon atoms.
  • 1,3 N-azoles which are useful include those azoles described in US-A-5,480,576 and US-A-5,468,410, herein incorporated by reference.
  • the 1,3 azole compounds have a formula: wherein X is C-R 3 or X is nitrogen provided Y is also nitrogen, Y is nitrogen or C-R 2 , and R 1 , R 2 and R 3 are each independently a hydrogen, an amine, an amido, a straight or branched alkyl chain having from 1 to 20 carbon atoms, an amino or carboxylic containing chain, an alkoxy, an aklylthio, a hydroxy, a hydroxyalkyl and an alkenyl, or R 1 and R 2 taken together form a substituted or unsubstituted aryl; and salts corresponding thereto.
  • the purine compounds have a formula: wherein X is nitrogen or C-R 3 and Y is nitrogen or C-R 4 and R 1 , R 2 , R 3 and R 4 are each independently a hydrogen, an oxygen, a hydroxy, an alkoxy, an amine, a straight or branched alkyl chain having 1 to 20 carbon atoms, an amido, an amidoaklyl, an alkylthio, an alkenyl or a hydroxalkyl.
  • Preferred azoles are the triazoles, particularly benzotriazole and the 1,3-N azoles, including the purines described above. Most preferred are the triazoles, especially benzotriazole.
  • the oxygen bleaching agents of the compositions include organic peroxy acids diacylperoxides, or mixtures thereof, inorganic peroxygen compounds and peracid precursors.
  • Typical monoperoxy acids useful herein include alkyl peroxy acids and aryl peroxy acids such as:
  • Typical diperoxy acids useful herein include alkyl diperoxy acids and aryl diperoxy acids, such as:
  • Preferred peracid bleaching agents include epsilon-phthalimido-peroxyhexanoic acid, o-carboxybenzaminoperoxyhexanoic acid, and mixtures thereof. Also those peracids having a low solubility in water, such as N,N 1 -terephthaloyl-di(6-aminopercaproic acid).
  • a typical diacylperoxide useful herein includes dibenzoylperoxide.
  • Inorganic peroxygen compounds are also suitable for the present invention.
  • these materials useful in the invention are salts of monopersulfate, perborate monohydrate, perborate tetrahydrate, and percarbonate.
  • Suitable peroxygen peracid precursors for peroxy bleach compounds have been amply described in the literature, including GB Nos. 836,988; 855,735; 907,356; 907;358; 907,950; 1,003,310 and 1,246,339; US-A-3,332,882 and US-A-4,128,494.
  • Typical examples of precursors are polyacylated alkylene diamines, such as N,N,N 1 ,N 1 -tetraacetylethylene diamine (TAED) and N,N,N 1 ,N 1 -tetraacetylmethylene diamine (TAMD); acylated glycolurils, such as tetraacetylglycoluril (TAGU); triacetylcyanurate, sodium sulfophenyl ethyl carbonic acid ester, sodium acetyloxybenene sulfonate (SABS), sodium nonanoyloxy benzene sulfonate (SNOBS) and choline sulfophenyl carbonate.
  • SABS sodium acetyloxybenene sulfonate
  • SNOBS sodium nonanoyloxy benzene sulfonate
  • choline sulfophenyl carbonate choline sulfophen
  • Peroxybenzoic acid precursors are known in the art, e.g., as described in GB-A-836,988. Examples of suitable precursors are phenylbenzoate; phenyl p-nitrobenzoate; o-nitrophenyl benzoate; o-carboxyphenyl benzoate; p-bromophenylbenzoate; sodium or potassium benzoyloxy benzene-sulfonate; and benzoic anhydride.
  • Preferred peroxygen bleach precursors are sodium p-benzoyloxybenzene sulfonate, N,N,N 1 ,N 1 -tetraacetylethylene diamine, sodium nonanoyloxybenzene sulfonate and choline sulfophenyl carbonate.
  • the oxygen bleaching agent is suitably present in the composition in an amount of from 1 to 20 weight percent, preferably 1 to 15 weight percent, most preferably 2 to 10 weight percent.
  • the organic peroxy acid is present in the compositon in an amount such that the level of organic peroxy acid in the wash solution is 1 ppm to 100 ppm AvOx, most preferably 5 ppm to 30 ppm AvOx.
  • the oxygen bleaching agent may be incorporated directly into the formulation or may be encapsulated by any number of encapsulation techniques known in the art.
  • a preferred encapsulation method is described in US-A-5,200,236.
  • the bleaching agent is encapsulated as a core in a paraffin wax material having a melting point from 40°C to 50°C.
  • the wax coating has a thickness of from 100 to 1500 microns.
  • detergent builders are meant to illustrate but not limit the types of builders that can be employed in the present invention.
  • compositions of this invention can contain all manner of detergent builders commonly taught for use in machine dishwashing or other cleaning compositions.
  • the builders can include any of the conventional inorganic and organic water-soluble builder salts, or mixtures thereof and may comprise 1 to 75%, and preferably, from 5 to 70%, more preferably from 10 to 45% by weight of the cleaning composition.
  • phosphorus-containing inorganic builders when present, include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates and polyphosphates.
  • specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates.
  • non-phosphorus-containing inorganic builders when present, include water-soluble alkali metal carbonates, bicarbonates, sesquicarbonates, borates, silicates, including layered silicates usch as SKS-6 ex. Hoechst, metasilicates, and crystalline and amorphous aluminosilicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites.
  • Organic detergent builders can also be used in the present invention.
  • organic builders include alkali metal citrates, succinates, malonates, fatty acid sulfonates, fatty acid carboxylates, nitrilotriacetates, phytates, phosphonates, alkanehydroxyphosphonates, oxydisuccinates, alkyl and alkenyl disuccinates, oxydiacetates, carboxymethyloxy succinates, ethylenediamine tetraacetates, tartrate monosuccinates, tartrate disuccinates, tartrate monoacetates, tartrate diacetates, oxidized starches, oxidized heteropolymeric polysaccharides, polyhydroxysulfonates, polycarboxylates such as polyacrylates, polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/ polymethacrylate copolymers, acrylate/maleate/vinyl alcohol terpolymers, aminopol
  • Alkali metal citrates, nitrilotriacetates, oxydisuccinates, polyphosphonates, acrylate/maleate copolymers and acrylate/maleate/vinyl alcohol terpolymers are especially preferred organic builders. When present they are preferably available from 5% to 70% of the total weight of the detergent compositions.
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese co-chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraamine-hexaacetates, diethylenetriaminepentaacetates, ethylenediamine disuccinate, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates), nitrilotris (methylenephosphonates) and diethylenetriaminepentakis (methylenephosphonates).
  • these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. (See US-A-3,812,044).
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
  • these chelating agents will generally comprise from 0.1% to 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from 0.1% to 3.0% by weight of such composition.
  • Scale formation on dishes and machine parts is an important problem that needs to be resolved or at least mitigated in formulating a machine warewashing product, especially in the case of low-phosphate (e.g. less than the equivalent of 20% by weight, particularly 10% by weight of sodium triphosphate) and phosphate-free machine warewashing compositions, particularly zero-P machine warewashing compositions.
  • low-phosphate e.g. less than the equivalent of 20% by weight, particularly 10% by weight of sodium triphosphate
  • phosphate-free machine warewashing compositions particularly zero-P machine warewashing compositions.
  • co-builders such as polyacrylic acids or polyacrylates (PAA), acrylate/maleate copolymers, polyaspartates, ethylenediamine disuccinate and the various organic polyphosphonates, e.g. Dequest series, may be incorporated in one or more system components.
  • PAA polyacrylic acids or polyacrylates
  • PAA polyacrylates
  • polyaspartates polyaspartates
  • ethylenediamine disuccinate e.g. Dequest series
  • the block co-polymers of formula (I) as defined in published PCT patent specification WO 94/17170 may also be used.
  • the amount of anti-scalant may be in the range of from 0.5 to 10, preferably from 0.5 to 5, and more preferably from 1 to 5% by weight.
  • a surfactant may be included in the first layer including anionic, nonionic, cationic, amphoteric, zwitteronic surfactants and mixtures of these surface active agents.
  • Such surfactants are well known in the detergent arts and are described at length in "Surface Active Agents and Detergents", Vol. 2 by Schwartz, Perry and Birch, Interscience Publishers, Inc., 1959, herein incorporated by reference.
  • Preferred surfactants are one or a mixture of:
  • Anionic synthetic detergents can be broadly described as surface active compounds with one or more negatively charged functional groups.
  • An important class of anionic compounds are the water-soluble salts, particularly the alkali metal salts, of organic sulfur reaction products having in their molecular structure an alkyl radical containing from about 6 to 24 carbon atoms and a radical selected from the group consisting of sulfonic and sulfuric acid ester radicals.
  • R 1 OSO 3 M where R 1 is a primary alkyl group of 8 to 18 carbon atoms and M is a solubilizing cation.
  • the alkyl group R 1 may have a mixture of chain lengths. It is preferred that at least two thirds of the R 1 alkyl groups have a chain length of 8 to 14 carbon atoms. This will be the case if R 1 is coconut alkyl, for example.
  • the solubilizing cation may be a range of cations which are in general monovalent and confer water solubility. Alkali metal, notably sodium, is especially envisaged. Other possibilities are ammonium and substituted ammonium ions, such as trialkanolammonium or trialkylammonium.
  • R 1 O(CH 2 CH 2 O) n SO 3 M
  • R 1 is a primary alkyl group of 8 to 18 carbon atoms
  • n has an average value in the range from 1 to 6 and M is a solubilizing cation.
  • the alkyl group R 1 may have a mixture of chain lengths. It is preferred that at least two thirds of the R 1 alkyl groups have a chain length of 8 to 14 carbon atoms. This will be the case if R 1 is coconut alkyl, for example.
  • n has an average value of 2 to 5.
  • R 2 CH (SO 3 M) CO 2 R 3 where R 2 is an alkyl group of 6 to 16 atoms, R 3 is an alkyl group of 1 to 4 carbon atoms and M is a solubilizing cation.
  • the group R 2 may have a mixture of chain lengths. Preferably at least two thirds of these groups have 6 to 12 carbon atoms. This will be the case when the moiety R 2 CH(-)CO 2 (-) is derived from a coconut source, for instance. It is preferred that R 3 is a straight chain alkyl, notably methyl or ethyl.
  • R 4 ArSO 3 M where R 4 is an alkyl group of 8 to 18 carbon atoms, Ar is a benzene ring ( C 6 H 4 ) and M is a solubilizing cation.
  • the group R 4 may be a mixture of chain lengths. Straight chains of 11 to 14 carbon atoms are preferred.
  • Organic phosphate based anionic surfactants include organic phosphate esters such as complex mono- or diester phosphates of hydroxyl- terminated alkoxide condensates, or salts thereof. Included in the organic phosphate esters are phosphate ester derivatives of polyoxyalkylated alkylaryl phosphate esters, of ethoxylated linear alcohols and ethoxylates of phenol. Also included are nonionic alkoxylates having a sodium alkylenecarboxylate moiety linked to a terminal hydroxyl group of the nonionic through an ether bond. Counterions to the salts of all the foregoing may be those of alkali metal, alkaline earth metal, ammonium, alkanolammonium and alkylammonium types.
  • Paraffin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, in the alkyl moiety. These surfactants are commercially available at Hostapur SAS from Hoechst Celanese .
  • Olefin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms.
  • U.S. Patent No. 3,332,880 contains a description of suitable olefin sulfonates.
  • Particularly preferred anionic surfactants are the fatty acid ester sulfonates with formula: R 2 CH(SO 3 M)CO 2 R 3 where the moiety R 2 CH(-)CO 2 (-) is derived from a coconut source and R 3 is either methyl or ethyl; primary alkyl sulfates with the formula: R 1 OSO 3 M wherein R 1 is a primary alkyl group of 10 to 18 carbon atoms and M is a sodium cation; and paraffin sulfonates, preferably with 12 to 16 carbon atoms to the alkyl moiety.
  • Nonionic surfactants can be broadly defined as surface active compounds with one or more uncharged hydrophilic substituents.
  • a major class of nonionic surfactants are those compounds produced by the condensation of alkylene oxide groups with an organic hydrophobic material 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.
  • Illustrative, but not limiting examples, of various suitable nonionic surfactant types are:
  • Ethoxylated fatty alcohols may be used alone or in admixture with anionic surfactants, especially the preferred surfactants above.
  • the average chain lengths of the alkyl group R 5 in the general formula: R 5 O(CH 2 CH 2 O) n H is from 6 to 20 carbon atoms.
  • the group R 5 may have chain lengths in a range from 9 to 18 carbon atoms.
  • the average value of n should be at least 2.
  • the numbers of ethylene oxide residues may be a statistical distribution around the average value. However, as is known, the distribution can be affected by the manufacturing process or altered by fractionation after ethoxylation.
  • Particularly preferred ethoxylated fatty alcohols have a group R 5 which has 9 to 18 carbon atoms while n is from 2 to 8.
  • nonionic surfactants having a formula: wherein R 6 is a linear alkyl hydrocarbon radical having an average of 6 to 18 carbon atoms, R 7 and R 8 are each linear alkyl hydrocarbons of about 1 to about 4 carbon atoms, x is an integer of from 1 to 6, y is an integer of from 4 to 20 and z is an integer from 4 to 25.
  • One preferred nonionic surfactant of the above formula is Poly-Tergent SLF-18 7 a registered trademark of the Olin Corporation, New Haven, Conn. having a composition of the above formula where R 6 is a C 6 -C 10 linear alkyl mixture, R 7 and R 8 are methyl, x averages 3, y averages 12 and z averages 16.
  • R 9 is a linear, aliphatic hydrocarbon radical having from about 4 to about 18 carbon atoms including mixtures thereof; and R 10 is a linear, aliphatic hydrocarbon radical having from about 2 to about 26 carbon atoms including mixtures thereof; j is an integer having a value of from 1 to about 3; k is an integer having a value from 5 to about 30; and z is an integer having a value of from 1 to about 3. Most preferred are compositons in which j is 1, k is from about 10 to about 20 and l is 1. These surfactants are described in WO 94/22800. Other preferred nonionic surfactants are linear fatty alcohol alkoxylates with a capped terminal group, as described in US-A-4,340,766. Particularly preferred is Plurafac LF403 ex. BASF.
  • R 11 is a C 6 -C 24 linear or branched alkyl hydrocarbon radical and q is a number from 2 to 50; more preferably R 11 is a C 8 -C 18 linear alkyl mixture and q is a number from 2 to 15.
  • polyoxyethylene or polyoxypropylene condensates of alkyl phenols whether linear- or branched-chain and unsaturated or saturated,containing from about 6 to 12 carbon atoms and incorporating from about 2 to about 25 moles of ethylene oxide and/or propylene oxide.
  • the preferred polyoxyethylene derivatives are of sorbitan monolaurate, sorbitan trilaurate, sorbitan monopalmitate, sorbitan tripalmitate, sorbitan monostearate, sorbitan monoisostearate, sorbitan tripalmitate, sorbital tristearate, sorbitan monooleate, and sorbitan trioleate.
  • the polyoxyethylene chains may contain between about 4 and 30 ethylene oxide units, preferably about 10 to 20.
  • the sorbitan ester derivatives contain 1, 2 or 3 polyoxyethylene chains dependent upon whether they are mono-, di- or tri-acid esters.
  • polyoxyethylene-polyoxypropylene block copolymers having formula: HO(CH 2 CH 2 O) a (CH(CH 3 ) CH 2 O) b (CH 2 CH 2 O) c H or HO(CH(CH 3 )CH 2 O) d (CH 2 CH 2 O) e (CH(CH 3 )CH 2 O) f H wherein a, b, c, d, e and f are integers from 1 to 350 reflecting the respective polyethylene oxide and polypropylene oxide blocks of said polymer.
  • the polyoxyethylene component of the block polymer constitutes at least about 10% of the block polymer.
  • the material preferably has a molecular weight of between about 1,000 and 15,000, more preferably from about 1,500 to about 6,000. These materials are well-known in the art. They are available under the trademark "Pluronic” and "Pluronic R", a product of BASF Corporation.
  • Amine oxides having formula: R 12 R 13 R 14 N O wherein R 12 , R 13 and R 14 are saturated aliphatic radicals or substituted saturated aliphatic radicals.
  • Preferable amine oxides are those wherein R 12 is an alkyl chain of about 10 to about 20 carbon atoms and R 13 and R 14 are methyl or ethyl groups or both R 12 and R 13 are alkyl chains of about 6 to about 14 carbon atoms and R 14 is a methyl or ethyl group.
  • Amphoteric synthetic detergents can be broadly described as derivatives of aliphatic tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contain from about 8 to about 18 carbons and one contains an anionic water-solubilizing group, i.e., carboxy, sulpho, sulphato, phosphato or phosphono.
  • an anionic water-solubilizing group i.e., carboxy, sulpho, sulphato, phosphato or phosphono.
  • Examples of compounds falling within this definition are sodium 3-dodecylamino propionate and sodium 2-dodecylamino propane sulfonate.
  • Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium and sulphonium compounds in which the aliphatic radical may be straight chained or branched, and wherein one of the aliphatic substituents contains from about 8 to about 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulpho, sulphato, phosphato or phosphono. These compounds are frequently referred to as betaines. Besides alkyl betaines, alkyl amino and alkyl amido betaines are encompassed within this invention.
  • R 15 O(R 16 O) n (Z 1 ) p
  • R 15 is a monovalent organic radical (e.g., a monovalent saturated aliphatic, unsaturated aliphatic or aromatic radical such as alkyl, hydroxyalkyl, alkenyl, hydroxyalkenyl, aryl, alkylaryl, hydroxyalkylaryl, arylalkyl, alkenylaryl, arylalkenyl, etc.) containing from about 6 to about 30 (preferably from about 8 to 18 and more preferably from about 9 to about.
  • a monovalent organic radical e.g., a monovalent saturated aliphatic, unsaturated aliphatic or aromatic radical such as alkyl, hydroxyalkyl, alkenyl, hydroxyalkenyl, aryl, alkylaryl, hydroxyalkylaryl, arylalkyl, alkenylaryl, arylalkenyl, etc.
  • R 16 is a divalent hydrocarbon radical containing from 2 to about 4 carbon atoms such as ethylene, propylene or butylene (most preferably the unit ( R 16 O ) n represents repeating units of ethylene oxide, propylene oxide and/or random or block combinations thereof); n is a number having an average value of from 0 to about 12; Z 1 represents a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms (most preferably a glucose unit); and p is a number having an average value of from 0.5 to about 10 preferably from about 0.5 to about 5 .
  • Examples of commercially available materials from Henkel Techandit GmbH Aktien of Dusseldorf, Germany include APG 7 300, 325 and 350 with R 15 being C 9 -C 11 , n is 0 and p is 1.3, 1.6 and 1.8-2.2 respectively; APG 7 500 and 550 with R 15 is C 12 -C 13 , n is 0 and p is 1.3 and 1.8-2.2, respectively; and APG 7 600 with R 15 being C 12 -C 14 , n is 0 and p is 1.3.
  • esters of glucose are contemplated especially, it is envisaged that corresponding materials based on other reducing sugars, such as galactose and mannose are also suitable.
  • the preferred range of surfactant is from 0.5 to 30 % by wt., more preferably from 0.5 to 15% by wt of the composition.
  • An inert filler material which is water-soluble may also be present in the machine dishwashing compositions. This material should not precipitate calcium or magnesium ions at the filler use level. Suitable for this purpose are organic or inorganic compounds.
  • Organic fillers include sucrose esters and urea.
  • Representative inorganic fillers include sodium sulfate, sodium chloride and potassium chloride.
  • a preferred filler is sodium sulfate. Its concentration may range from 0% to 20%, preferably from 2% to 10% by weight of the cleaning composition.
  • Thickeners are often desirable for liquid cleaning compositions.
  • Thixotropic thickeners such as smectite clays including montmorillonite (bentonite), hectorite, saponite, and the like may be used to impart viscosity to liquid cleaning compositions.
  • Silica, silica gel, and aluminosilicate may also be used as thickeners.
  • Use of clay thickeners for machine dishwashing compositions is disclosed for example in US-A-4,431,559; US-A-4,511,487; US-A-4,740,327; US-A-4,752,409.
  • Commercially available synthetic smectite clays include Laponite supplied by Laporte Industries.
  • bentonite clays include Korthix H and VWH ex Combustion Engineering, Inc.; Polargel T ex American Colloid Co.; and Gelwhite clays (particularly Gelwhite GP and H) ex English China Clay Co.
  • Polargel T is preferred as imparting a more intense white appearance to the composition than other clays.
  • the amount of clay thickener employed in the compositions is from 0.1 to 10%, preferably 0.5 to 5%.
  • the amount of thickener employed in the compositions is from 0 to 5%, preferably 0.5-3%.
  • agent useful in the gel composition of the invention is a cross-linked polycarboxylate, preferably a polyacrylate acrylic acid polymer.
  • Particularly preferred are salts of polyacrylic acid of molecular weight of from 300,000 up to 6 million and higher which are cross-linked.
  • Acrylic acid polymers that are cross-linked manufactured by, for example, B.F. Goodrich and sold under the trade name "Carbopol” or by 3V Inc. and sold under the tradename Polygel DA have been found to be effective for production of the inventive formulas.
  • stabilizers such as long-chain calcium and sodium soaps and C 12 to C 18 sulfates are detailed in US-A-3,956,158 and US-A-4,271,030 and the use of other metal salts of long-chain soaps is detailed in US-A-4,752,409.
  • Other stabilizers include Laponite and metal oxides and their salts as described in US-A-4,933,101.
  • the amount of stabilizer which may be used in the liquid cleaning compositions is from 0.01 to 5% by weight of the composition, preferably 0.01-2%. Such stabilizers are optional in gel formulations.
  • Stabilizers which are found especially suitable for gels include trivalent metal ions at 0.01-4% of the compositions, Laponite and/or water-soluble structuring chelants at 0.01-5%. These stabilizers are more fully described in US-A-5,141,664.
  • the formulations of the cleaning composition comprising surfactant may further include a defoamer.
  • Suitable defoamers include mono-and distearyl acid phosphate, silicone oil and mineral oil. Even if the cleaning composition has only defoaming surfactant, the defoamer assists to minimize foam which food soils can generate.
  • the compositions may include 0.02 to 2% by weight of defoamer, or preferably 0.05-1.0%.
  • Enzymes capable of facilitating the removal of soils from a substrate may also be present in an amount of up to about 10% by wt., preferably 1 to about 5 wt. %.
  • Such enzymes include proteases (e.g., Alcalase7, Savinase7 and Esperase7 from Novo Industries A/S and Purafect OxP, ex. Genencor), amylases (e.g., Termamyl7 and Duramyl7 from Novo Industries and Purafect OxAm, ex. Genencor) and lipases (e.g. Lipolase7 from Novo Industries).
  • bleach scavengers including but not limited to sodium bisulfite, sodium perborate, reducing sugars, and short chain alcohols; solvents and hydrotropes such as ethanol, isopropanol and xylene sulfonates; enzyme stabilizing agents; soil suspending agents; antiredeposition agents; anti-corrosion agents, such as isocyanuric acid described in US-A-5,374,369; ingredients to enhance decor care such as certain aluminum salts described in U.S. Serial No. 08/444,502 and 08/444,503; and anti-foaming agents such as those described in U.S. Serial No. 08/540,285 and 08/539,923; colorants; perfumes; and other functional additives.
  • bleach scavengers including but not limited to sodium bisulfite, sodium perborate, reducing sugars, and short chain alcohols; solvents and hydrotropes such as ethanol, isopropanol and xylene sulfonates; enzyme stabilizing agents
  • the following inventive gel composition was prepared: Ingredient Sample A % by Weight Citrate 30.0 Sokalan CP7 5.0 TiO 2 0.1 Sulfite 0.1 Carbopol 627 1.5 Glycerol 6.0 Sodium Tetraborate 3.0 Enzymes 1.2 Plurafac LF 403 2.0 PAP 4.0 BTA 0.05 NaOH 0.8 Water to 100%
  • the composition contains the peracid, phthalimidoperhexanoic acid (PAP), encapsulated in wax and the pH of the gel is 8.5.
  • PAP phthalimidoperhexanoic acid
  • BTA was incorporated via pre-dissolution in the Plurafac nonionic surfactant.
  • the TiO 2 (0.1%) was incorporated into the base liquid.
  • a second composition (B) was also prepared except the TiO 2 was not incorporated. These two formulations were stored at ambient temperature and at 45°C for at least 14 weeks.
  • Sample A After 14 weeks storage at ambient temperature Sample A, within the scope of the invention, showed no visible change from its original white color. Sample (B), however, showed a considerable degree of yellow discoloration within the gel.
  • the melting point of the wax used to coat the PAP peracid lies in the range 42-46°C. Therefore, storage at a temperature of 45°C represents an extreme test condition designed to cause early melting of the wax coating and full release of the peracid into the gel. After two days the gel of Sample (B) was very intensely yellow-colored. In contrast, there was a barely perceptible color change observed in Sample (A), containing the TiO 2 .
  • the following inventive Sample (C) was prepared. Ingredient % by Weight-Sample C Water to 100 Carbopol 627 1.5 Sodium Citrate 30.0 Sorbitol 6.0 Borax 3.0 Sokalan CP-7 5.0 Plurafac LF 403 2.0 Suspended TPCAP 1.7 BTA 0.05 TiO 2 0.1
  • a second Sample D was prepared, which was identical to Sample C except for the fact that TiO 2 was not incorporated into the base liquid. These two formulations were stored at 40°C as described in Example 1.

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)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (16)

  1. Composition de gel détergent pour machine à laver la vaisselle comprenant :
    (a) 1 à 75 % en poids d'un matériau adjuvant ;
    (b) une quantité efficace d'un agent de blanchiment oxygéné ;
    (c) 0,01 à 2% en poids d'un composé azole ; et
    (d) 0,0001 à 5% en poids d'un composé inorganique stabilisant choisi dans le groupe constitué du dioxyde de titane.
  2. Composition de détergent selon la revendication 1, dans laquelle le matériau adjuvant est un composé organique choisi dans le groupe constitué par un carboxylate monomère, un carboxylate polymère et leur mélange.
  3. Composition de détergent selon la revendication 2, dans laquelle l'adjuvant est présent dans une quantité de 10 à 45% en poids.
  4. Composition de détergent selon la revendication 1, dans laquelle l'azole est un azole triazole.
  5. Composition de détergent selon la revendication 4, dans laquelle le triazole est du benzotriazole.
  6. Composition de détergent selon la revendication 1, dans laquelle l'agent de blanchiment oxygéné est présent dans une quantité de 1 à 20% en poids.
  7. Composition de détergent selon la revendication 1, dans laquelle l'agent de blanchiment oxygéné est choisi dans le groupe des acides peroxycarboxyliques organiques, des diacylperoxydes et de leur mélange.
  8. Composition de détergent selon la revendication 7, dans laquelle les acides peroxycarboxyliques organiques sont choisis dans le groupe constitué par l'acide peroxybenzoïque, les acides monoperoxycarboxyliques aliphatiques et les acides monoperoxycarboxyliques substitués et leur mélange.
  9. Composition de détergent selon la revendication 8, dans laquelle les acides monoperoxycarboxyliques aliphatiques substitués sont choisis dans le groupe constitué par l'acide epsilon-phtalimidoperoxyhexanoïque, l'acide o-carboxybenzamidoperoxyhexanoïque, l'acide N-nonylamidoperadipique, l'acide N-nonylamidopersuccinique et leur mélange.
  10. Composition de détergent selon la revendication 7, dans laquelle l'agent de blanchiment oxygéné est de la cire capsulée.
  11. Composition de détergent selon la revendication 1, dans laquelle la composition comprend en outre une quantité efficace d'un enzyme.
  12. Composition de détergent selon la revendication 1, comprenant en outre 0,5 à 30% en poids d'un surfactant.
  13. Composition de détergent selon la revendication 1, dans laquelle le matériau adjuvant est un adjuvant inorganique.
  14. Composition de détergent selon la revendication 13, dans laquelle l'adjuvant inorganique est un composé contenant du phosphore choisi dans le groupe constitué par les pyrophosphates, les orthophosphates, les polyphosphates de métaux alcalins et leur mélange.
  15. Composition de détergent selon la revendication 13, dans laquelle l'adjuvant inorganique est un adjuvant ne contenant pas du phosphore choisi dans le groupe constitué par les carbonates, les bicarbonates, les sesquicarbonates, les borates, les silicates, les métasilicates, les aluminosilicates cristallins, les aluminosilicates amorphes de métaux alcalins et leur mélange.
  16. Procédé de lavage de vaisselle dans une machine à laver la vaisselle comprenant les étapes consistant à :
    1. appliquer une composition de produit vaisselle sur la vaisselle dans un lave-vaisselle, ladite composition comprenant :
    (a) 1 à 75% en poids d'un matériau adjuvant,
    (b) une quantité efficace d'un agent de blanchiment oxygéné.
    (c) 0,01 à 2,0% en poids d'un composé azole, et
    (d) 0,001 à 5% en poids d'un composé inorganique stabilisant choisi dans le groupe constitué du dioxyde de titane, et
    2. laver essentiellement la vaisselle dans le lave-vaisselle.
EP19970203470 1996-12-05 1997-11-11 Composition gélifiée pour lave-vaisselle Expired - Lifetime EP0846757B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US76085096A 1996-12-05 1996-12-05
US760850 1996-12-05

Publications (3)

Publication Number Publication Date
EP0846757A2 EP0846757A2 (fr) 1998-06-10
EP0846757A3 EP0846757A3 (fr) 1999-11-24
EP0846757B1 true EP0846757B1 (fr) 2005-01-26

Family

ID=25060356

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19970203470 Expired - Lifetime EP0846757B1 (fr) 1996-12-05 1997-11-11 Composition gélifiée pour lave-vaisselle

Country Status (3)

Country Link
EP (1) EP0846757B1 (fr)
CA (1) CA2221955A1 (fr)
DE (1) DE69732339T2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7674761B2 (en) 2001-03-16 2010-03-09 Unilever Home & Personal Care, Division Of Conopco, Inc. Water soluble sachet with a dishwashing enhancing particle

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6162055A (en) 1998-02-13 2000-12-19 Britesmile, Inc. Light activated tooth whitening composition and method of using same
EP0987314A1 (fr) * 1998-09-16 2000-03-22 The Procter & Gamble Company Compositions de blanchiment
US6534463B1 (en) 1998-09-16 2003-03-18 The Procter & Gamble Company Bleaching compositions
ATE340850T1 (de) 2000-11-27 2006-10-15 Procter & Gamble Geschirrspülverfahren
US8283300B2 (en) 2000-11-27 2012-10-09 The Procter & Gamble Company Detergent products, methods and manufacture
US7125828B2 (en) 2000-11-27 2006-10-24 The Procter & Gamble Company Detergent products, methods and manufacture
US8940676B2 (en) 2000-11-27 2015-01-27 The Procter & Gamble Company Detergent products, methods and manufacture
WO2002042400A2 (fr) 2000-11-27 2002-05-30 The Procter & Gamble Company Procede de lavage de vaisselle
US7541325B2 (en) * 2001-01-11 2009-06-02 Joker Ag Agent for removing solid particles
US6475977B1 (en) * 2001-03-16 2002-11-05 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Water soluble sachet with a dishwasher composition
US6863897B2 (en) * 2002-03-22 2005-03-08 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Stabilization of resorcinol derivatives in cosmetic compositions
EP3181675B2 (fr) 2015-12-17 2022-12-07 The Procter & Gamble Company Composition de détergent de lave-vaisselle automatique
GB201903318D0 (en) * 2019-03-11 2019-04-24 Reckitt Benckiser Finish Bv Product
WO2021170637A1 (fr) * 2020-02-28 2021-09-02 Basf Se Composition de lavage de vaisselle automatique comprenant au moins un composé à base d'imidazole

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5094771A (en) * 1991-05-07 1992-03-10 Colgate-Palmolive Co. Nonaqueous liquid automatic dishwasher detergent composition
AU7812494A (en) * 1993-10-14 1995-05-04 Unilever Plc Detergent compositions containing silver anti-tarnishing agents
JPH07305094A (ja) * 1994-05-10 1995-11-21 Kao Corp 液体漂白剤組成物
HUP9900649A3 (en) * 1996-02-29 2002-04-29 Unilever Nv Machine dishwashing gel compositions and method for cleaning dishes in dishwashing machine

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7674761B2 (en) 2001-03-16 2010-03-09 Unilever Home & Personal Care, Division Of Conopco, Inc. Water soluble sachet with a dishwashing enhancing particle

Also Published As

Publication number Publication date
EP0846757A3 (fr) 1999-11-24
DE69732339D1 (de) 2005-03-03
CA2221955A1 (fr) 1998-06-05
EP0846757A2 (fr) 1998-06-10
DE69732339T2 (de) 2005-06-09

Similar Documents

Publication Publication Date Title
US5741767A (en) Peracid based dishwashing detergent composition
US5374369A (en) Silver anti-tarnishing detergent composition
US5837663A (en) Machine dishwashing tablets containing a peracid
EP0723577B1 (fr) Compositions detergentes contenant des agents empechant le ternissement de l'argent
EP0846757B1 (fr) Composition gélifiée pour lave-vaisselle
US5698506A (en) Automatic dishwashing compositions containing aluminum salts
US5624892A (en) Process for incorporating aluminum salts into an automatic dishwashing composition
US5480576A (en) 1,3-N azole containing detergent compositions
AU727942B2 (en) Anti-foam system for automatic dishwashing compositions
EP0816481B1 (fr) Granulés peracides contenant l'acide citrique de monohydrate pour l'amélioration de la vitesse de dissolution
US5468410A (en) Purine class compounds in detergent compositions
US5783539A (en) Process for incorporating aluminum salts into an automatic dishwashing composition
EP0876457B1 (fr) Systeme anti-mousse base sur des polymeres d'hydrocarbure et des solides particulaires hydrophobes
EP0883670B1 (fr) Composition de gel detergent pour machine a laver la vaisselle
EP0826024A1 (fr) Compositions contenant des sels d'aluminium pour le lavage automatique de la vaisselle
CA2236881C (fr) Composition detergente de lavage de la vaisselle a base de peracide

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE DE FR IT NL

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

RIC1 Information provided on ipc code assigned before grant

Free format text: 6C 11D 17/00 A, 6C 11D 3/39 B, 6C 11D 3/28 B, 6C 11D 3/12 B, 6C 11D 7/32 B

17P Request for examination filed

Effective date: 20000204

AKX Designation fees paid

Free format text: BE DE FR IT NL

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER PLC

Owner name: UNILEVER N.V.

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNILEVER N.V.

17Q First examination report despatched

Effective date: 20020920

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR IT NL

REF Corresponds to:

Ref document number: 69732339

Country of ref document: DE

Date of ref document: 20050303

Kind code of ref document: P

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20051016

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20051117

Year of fee payment: 9

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20051208

Year of fee payment: 9

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20060102

Year of fee payment: 9

26N No opposition filed

Effective date: 20051027

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061130

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20061130

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070601

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070601

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20070601

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20070731

BERE Be: lapsed

Owner name: *UNILEVER N.V.

Effective date: 20061130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20061130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20071111