EP0883670B1 - Gelförmige maschinengeschirrspülmittel - Google Patents

Gelförmige maschinengeschirrspülmittel Download PDF

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Publication number
EP0883670B1
EP0883670B1 EP97905022A EP97905022A EP0883670B1 EP 0883670 B1 EP0883670 B1 EP 0883670B1 EP 97905022 A EP97905022 A EP 97905022A EP 97905022 A EP97905022 A EP 97905022A EP 0883670 B1 EP0883670 B1 EP 0883670B1
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Prior art keywords
structurant
detergent composition
composition according
builder
acid
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English (en)
French (fr)
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EP0883670A1 (de
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Isaac Israel Secemski
John Richard Nicholson
Bozena Marianna Piatek
Alan Digby Unilever Research TOMLINSON
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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    • 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
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions

Definitions

  • the present invention relates to machine dishwashing gel compositions that have good viscosity and thixotropic profiles and deliver high performance cleaning.
  • Automatic dishwashing detergents for home use have traditionally been in powder or granulate form. More recently, the market-place has seen the advent of liquid forms of automatic dishwashing products. Liquids have advantages over powders in their convenience of dispensing or dosing, their enhanced solubility, absence of lump formation or "caking" during storage, and absence of dustiness associated with the powder form. Since automatic dishwashing machines contain a dispenser cup normally intended for powders, chemists have been challenged in formulating liquid products of appropriate rheological properties.
  • 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.
  • Thixotropic liquids generally maintain high viscosity for storage but revert to lower viscosity under influence of applied shear.
  • Thixotropy is shear thinning behavior that is time dependent in both its decrease in viscosity under applied shear and its regain of viscosity after cessation of shearing.
  • appropriate thixotropic properties ensure that a machine dishwashing composition will be retained in a dispenser cup without leakage yet will be pourable from its bottle.
  • clay structured liquids have a number of disadvantages. Montmorillonite clays, even in the presence of stabilizing agents, are sensitive to ionic strength. They lose their liquid structuring efficiency at the high electrolyte levels normally present in autodish liquid detergents. Clays tend to collapse onto themselves, or flocculate under these conditions. If this collapse occurs to any large extent during prolonged storage, the liquid will lose its physical stability, suffer syneresis and/or settling of solids. Collection of solids at the bottom of the container can lead to the formation of paste-like plugs which are difficult to dispense.
  • Attapulgite clay particles suspended in liquids tend to scatter light. Any large amount of these clay particles will thus impart a muddy dull color to the liquid. Furthermore, clays, being insoluble minerals, can adversely affect glass appearance. Deposition of clay onto the surface of glassware has been known to lead to spotting and filming.
  • polyacrylic acid type polymers have been included as an important component but not necessarily to function as a thickener.
  • the azoles act as a co-structurant, increasing the viscosity of gels structured with cross-linked polycarboxylate structurants.
  • gels with acceptable viscosity profiles can be formulated with azoles that contain lower levels of salt and structurant than would be possible without this molecule.
  • formulating gels with these azole compounds can be complicated since the addition of a triazole molecule like benzotriazole to a gel with acceptable viscosity characteristics can result in an unacceptably thick product, often with a high level of crystal formation, not seen in the absence of the azole compound.
  • Formulation rules leading to acceptable gel properties are defined.
  • these gels exhibit a secondary benefit in delivering acceptable anti-silver tarnishing properties.
  • Azoles have traditionally been used as anticorrosion agents, such as for metal parts such as engine jackets and the like is described in US-A-4,649,025.
  • Aromatic triazoles such as benzotriazole, are particularly known to be effective in preventing silver tarnishing in general.
  • GB-A-1180437 teaches high phosphate systems with surfactant to clean non-ferrous metals; US-A-5,110,494 deals with systems for industrial cleaning of aluminum; US-A-4,518,585 for a sterilizing system for dental and medical equipment; US-A-4,199,483 and US-A-4,321,166 for high surfactant systems for fabrics washing; JO-4359097 and JO-5279700 for a high surfactant system for washing surgical appliances. None of this art is relevant to machine dishwashing.
  • WO-95/01416 describes a combination of a branched paraffin oil and a benzotriazole molecule, along with delaying the release of the oxygen bleach, to reduce silver tarnishing during machine dishwashing
  • EP-A-124,815 describes the value of benzotriazole as a silver protection agent in machine dishwashing.
  • inclusion of aromatic triazoles into machine dishwashing gels is not described in the prior art, especially relating to maintaining good physical stability and viscosity characteristics.
  • the present invention relates to a machine dishwashing gel composition which contains an effective amount of an oxygen bleaching agent, from 10 to 50% by weight of a builder material and from 0.2 to 2.0% by weight of a dual component structuring system consisting of a cross-linked polyacrylate structurant and an azole co-structurant.
  • the components of the dual component structuring system are present in the compositions in an amount calculated on the type and level of the builder material also incorporated in the formulas.
  • the invention relates to the ability of azoles, particularly aromatic triazoles, to act as co-structurants in combination with a cross-linked polycarboxylate structurant, enhancing the viscosity of gels structured with this polymer.
  • the composition has a viscosity and shear-thinning profile consistent with good dispensing via squeezing through an orifice or pouring from a spout as well as retention in the dispensing cup of the dishwashing machine prior to cup opening.
  • a method of processing such a gel formulation is also described.
  • 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 dual component structuring system is preferably composed of a high molecular weight cross-linked polycarboxylate, most preferably a cross-linked polyacrylate, and an aromatic azole, preferably a triazole.
  • the detergent gel compositions of the invention comprise from 10 to 50% by weight of a builder, an effective amount of an oxygen bleaching agent and from 0.2 to 2.0% by weight of a dual component structuring system consisting of a cross-linked polycarboxylate structurant and an azole as described below.
  • Azoles useful as co-structurants in the invention are nitrogen containing heterocylic 5-membered ring compounds which are present in a level of from 0.01% to 0.5% by weight, preferably from 0.01% to 0.2% 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, herein incorporated by reference.
  • 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 structurant of the dual component structuring system 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.
  • the amount of cross-linked polyacrylate present as the structurant is dependent on the type and amount of builder material incorporated in the compositions.
  • the polyacrylate structurant should be present in the amount of 0.5% to 2.0% wt, preferably 0.8% to 1.7% wt.
  • the polyacrylate structurant should be present in an amount of 0.2% to 1.7% wt, preferably 0.5% to 1.5% wt.
  • the total amount of builder material and cross-linked polycarboxylate structurant should fall within a prescribed range which is dependent on the type of builder used and is calculated by the following formula: wt. % of builder x wt. % of structurant
  • the product of the weight percent builder and weight percent structurant should not exceed 60, preferably is 20 to 50, most preferably is 25 to 45.
  • the product of the weight percent builder and weight percent structurant should be less than 40, preferably between 5 and 40, most preferably between 10 and 30.
  • the oxygen bleaching agents of the compositions include organic peroxy acids and diacylperoxides.
  • 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:
  • 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.
  • Preferred oxygen bleaching agents include epsilon-phthalimido-peroxyhexanoic acid, o-carboxybenzaminoperoxyhexanoic acid, and mixtures thereof.
  • the oxygen bleaching agent is present in the composition in an amount from 1 to 20% by weight, preferably 1 to 15% by weight percent, most preferably 2 to 10% by weight.
  • 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 to produce stable capsules in alkaline liquid formulations.
  • the bleaching agent is encapsulated as a core in a paraffin wax material having a melting point from about 40°C to 50°C.
  • the wax coating has a thickness of from 100 to 1500 microns.
  • 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.
  • compositions of this invention contains either organic builders, particularly carboxylates, or inorganic builders, particularly phosphorous containing compounds.
  • phosphorus-containing inorganic builders include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates and polyphosphates, particularly ammonium and alkanol ammonium salts, and phosphonates.
  • Particularly preferred phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates, hexametaphosphates and trimetaphosphates.
  • a phosphate builder When a phosphate builder is incorporated into the formula it is present in an amount of 10% to 50% by wt, most preferably 15 to 35% wt and the product of the weight percent builder and weight percent of cross-linked polycarboxylate structurant should not exceed 40, preferably between 5 and 40, most preferably between about 10 and about 30 as discussed above.
  • Non-phosphorus-containing inorganic builders may be additionally used such as water-soluble alkali metal carbonates, bicarbonates, sesquicarbonates, borates, silicates, layered silicates such as SKS-6 ex Hoechst, metasilicates, phytic acid, borate and crystalline and amorphous aluminosilicates.
  • Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates, including layered silicates and zeolites.
  • Organic detergent builders useful in the present invention including a variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least three (3) carboxylates. Monomeric or polymeric carboxylates are preferred.
  • Such polycarboxylates include polyacrylates, polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate/ polymethacrylate copolymers, acrylate/maleate/vinyl alcohol terpolymers, aminopolycarboxylates and polyacetal carboxylates, and polyaspartates and mixtures thereof.
  • Such carboxylates are described in US-A-4,144,226, US-A-4,146,495 and US-A-4,686,062, herein incorporated by reference.
  • Alkali metal citrates, nitrilotriacetates, oxydisuccinates, polyphosphonates and acrylate/maleate copolymers and acrylate/maleate/vinyl alcohol terpolymers are especially preferred organic builders.
  • detergent builders are meant to illustrate but not limit the types of builders that can be employed 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, and polyhydroxysulfonates.
  • the builder When the builder is comprised primarily of either monomeric or polymeric carboxylates or mixtures thereof the builder should be present in an amount of 10 to 45% wt, most preferably 15 to 40% wt.
  • the product of the weight percent of carboxylate builder and the weight percent of polycarboxylate structurant should be less than 60, preferably 20 to 50, most preferably 25 to 45 as described above.
  • 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, triethylenetetraaminehexaacetates, 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 about 0.1% to about 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 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 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.
  • Useful surfactants include anionic, nonionic, cationic, amphoteric, zwitterionic types and mixtures of these surface active agents. Such surfactants are well known in the detergent art and are described at length in "Surface Active Agents and Detergents", Vol. II, by Schwartz, Perry & Berch, 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.
  • 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.
  • 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.
  • 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® 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.
  • Other preferred nonionic surfactants are linear fatty alcohol alkoxylates with a capped terminal group, as described in U.S. 4,340,766 to 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.
  • 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 and 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 13) carbon atoms;
  • 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 sac
  • Examples of commercially available materials from Henkel Techandit GmbH Aktien of Dusseldorf, Germany include APG® 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® 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® 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 amount of glycoside surfactant, anionic surfactant and/or ethoxylated fatty alcohol surfactant will be from 0.5 to 30% by weight of the composition. Desirably the total amount of surfactant lies in the same range.
  • the preferred range of surfactant is from 0.5 to 20% by weight, more preferably from 0.5 to 10% by weight.
  • An inert filler material which is water-soluble may also be present in cleaning 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 about 2% to about 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 about 10%, preferably 0.5 to 5%.
  • the amount of thickener employed in the compositions is from 0 to 5%, preferably 0.5-3%.
  • 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 about 0.01 to about 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%. Preferred antifoam systems are described in Angevaare et al. 95-158-EDG, herein incorporated by reference.
  • 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., Alcalase®, Savinase® and Esperase® from Novo Industries A/S and Purafect OxP, ex. Genencor), amylases (e.g., Termamyl® and Duramyl® from Novo Industries and Purafect OxAm, ex. Genencor).
  • 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, herein incorporated by reference; 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; soil suspending agents; antiredeposition agents; anti-corrosion agents, such as isocyanuric acid described
  • a number of gel compositions having various levels of builder, polyacrylate and oxygen bleach were prepared as described in Table 1. Half of the samples were prepared with benzotriazole and half were prepared without it. Ingredient % by Weight Sodium citrate/Sokalan CP7 25-35 Carbopol 627 1.0-1.5 Glycerol/borax stabilizer 9.0 Enzymes 1.2 Plurafac LF 403 2.0 Oxygen bleach encapsulates 1.0-2.0 Benzotriazole 0 or 0.05 deionized water to 100%
  • the viscosities (in mPas) of the gels were measured at 1 sec-1 and 20 sec -1 and any negatives regarding physical appearance (presence of crystals, lumpiness) were noted.
  • An acceptable viscosity range for a machine dishwashing gel of this sort is 8,000-18,000 mPas at 1 sec-1 and 1,300-2,000 mPas at 20 sec-1.
  • a formulation region can be defined in which stable gels can be formulated with the correct viscosity profile.
  • the addition of benzotriazole at a level as low as 0.05% dramatically shifts the acceptable formulation region to the area of lower builder and cross-linked polycarboxylate. This is a clear result of the ability of benzotriazole to act as a co-structurant and enhance the viscosity of the gel.
  • Example 1 The gel formulation in Example 1 was modified by replacing the citrate/polycarboxylate builder with potassium tripolyphosphate. Bases, with and without 0.05% BTA, were prepared and the viscosity results are shown in Figure 3 (without benzotriazole) and Figure 4 (with benzotriazole). As with the zero-P systems, benzotriazole acts as a co-structurant in phosphate systems.
  • Example 1 In a different system based on Example 1 with 35% builder and 1.5% Carbopol, glycerol is replaced by sorbitol, the pH is reduced to 6.5 and the encapsulated oxygen bleach system is replaced by unencapsulated N,N'-terephthaloyl-di-6-amino percaproic acid (TPCAP).
  • TPCAP unencapsulated N,N'-terephthaloyl-di-6-amino percaproic acid
  • BTA can deliver anti-tarnish benefits even after solubilization in a gel composition.
  • Example 5 The effect of dissolved BTA on de-staining efficacy of gels was evaluated.
  • the Gels in Example 5 were evaluated for tannin removal on stained tea cups in a standard European machine. BTA had no effect on the tea stain removal.
  • Formulations were prepared according to Example 1 in which BTA was added either separately at the beginning of the processing; separately towards the end of the processing at the point when the surfactant is added just prior to the minor ingredients; or added along with the surfactant after prior dissolution in the surfactant.

Claims (17)

  1. Waschmittelgelzusammensetzung zum maschinellen Geschirrwaschen, umfassend:
    (a) 10 bis 50 Gewichtsprozent eines Buildermaterials;
    (b) eine wirksame Menge eines Sauerstoffbleichmittels;
    (c) 0,2 bis 2,0 Gewichtsprozent eines strukturierenden Zweikomponenten-Systems, bestehend aus einem vernetzten Polyacrylat-Strukturierungsmittel und einem Azol-Costrukturierungsmittel, mit der Maßgabe, dass die Gesamtmenge von dem Builder und dem Strukturierungsmittel 60, wie berechnet durch die Formel: Gewichtsprozent Builder x Gewichtsprozent Polyacrylat-Strukturierungsmittel < 60,
    nicht übersteigt.
  2. Waschmittelzusammensetzung nach Anspruch 1, wobei das Buildermaterial aus der Gruppe eines monomeren Carboxylats, polymeren Carboxylats und Gemischen davon ausgewählt ist.
  3. Waschmittelzusammensetzung nach Anspruch 2, wobei der Builder in einer Menge von 10 bis 45 Gewichtsprozent vorliegt und das Strukturierungsmittel in einer Menge von 0,5 bis 2,0% vorliegt und das Produkt der Gewichtsprozent Builder und Gewichtsprozent Strukturierungsmittel im Bereich von 20 bis 50 liegt.
  4. Waschmittelzusammensetzung nach Anspruch 1, wobei das AzolCostrukturierungsmittel ein Triazolazol ist.
  5. Waschmittelzusammensetzung nach Anspruch 4, wobei das Triazol Benzotriazol ist.
  6. Waschmittelzusammensetzung nach Anspruch 1, wobei das vernetzte Polyacrylat-Strukturierungsmittel ein Salz von Polyacrylsäure mit einem Molekulargewicht von 300000 bis 6 Millionen ist.
  7. Waschmittelzusammensetzung nach Anspruch 1, wobei das Sauerstoffbleichmittel in einer Menge von 1 bis 20 Gewichtsprozent vorliegt.
  8. Waschmittelzusammensetzung nach Anspruch 1, wobei das Sauerstoffbleichmittel aus der Gruppe von organischen Peroxysäuren, Diacylperoxiden und Gemischen davon ausgewählt ist.
  9. Waschmittelzusammensetzung nach Anspruch 8, wobei die organischen Peroxysäuren aus der Gruppe, bestehend aus Peroxybenzoesäure, aliphatischen Monoperoxysäuren, substituierten aliphatischen Monoperoxysäuren und Gemischen davon, ausgewählt sind.
  10. Waschmittelzusammensetzung nach Anspruch 9, wobei die substituierten aliphatischen Monoperoxysäuren aus der Gruppe, bestehend aus ε-Phthalimido-peroxyhexansäure, o-Carboxybenzamidoperoxyhexansäure, N-Nonylamidoperadipinsäure, N-Nonylamidoperbernsteinsäure und Gemischen davon, ausgewählt sind.
  11. Waschmittelzusammensetzung nach Anspruch 8, wobei das Sauerstoffbleichmittel in Wachs eingekapselt ist.
  12. Waschmittelzusammensetzung nach Anspruch 1, wobei die Zusammensetzung weiterhin eine wirksame Menge eines Enzyms umfasst.
  13. Waschmittelzusammensetzung nach Anspruch 1, die weiterhin 0,5 bis 30 Gewichtsprozent eines Tensids umfasst.
  14. Waschmittelzusammensetzung nach Anspruch 1, wobei das Buildermaterial ein wasserlösliches Salz eines Alkalimetallpyrophosphats, eines -orthophosphats, eines -polyphosphats und Gemischen davon ist.
  15. Waschmittelzusammensetzung nach Anspruch 14, wobei der Builder in einer Menge von etwa 10 bis 40 Gewichtsprozent vorliegt, das Polyacrylat-Strukturierungsmittel in einer Menge von 0,2% bis 1,7 Gewichtsprozent vorliegt und das Produkt der Gewichtsprozent Builder und der Gewichtsprozent Strukturierungsmittel im Bereich von etwa 5 bis 40 liegt.
  16. Waschmittelzusammensetzung nach Anspruch 14, wobei das Phosphatsalz aus der Gruppe, bestehend aus Natriumtripolyphosphat, Kaliumtripolyphosphat, -pyrophosphat, -hexametaphosphat, -trimetaphosphaten und Gemischen davon, ausgewählt ist.
  17. Verfahren zum Reinigen von Geschirr in einer Geschirrspülmaschine, umfassend die Schritte:
    a) Zugeben zu einer Waschlauge einer wirksamen Menge einer Waschmittelzusammensetzung, umfassend:
    (i) 10 bis 50 Gewichtsprozent eines Buildermaterials;
    (ii) eine wirksame Menge eines Sauerstoffbleichmittels;
    (iii) 0,2 bis 2,0 Gewichtsprozent eines strukturierenden Zweikomponenten-Systems, bestehend aus einem vernetzten Polyacrylat-Strukturierungsmittel und einem Azol-Costrukturierungsmittel, mit der Maßgabe, dass die Gesamtmenge von dem Builder und dem Strukturierungsmittel 60, wie berechnet durch die Formel: Gewichtsprozent Builder x Gewichtsprozent Strukturierungsmittel ≤ 60,
    nicht übersteigt und
    b) Reinigen des Geschirrs in einer Geschirrspülmaschine.
EP97905022A 1996-02-29 1997-02-13 Gelförmige maschinengeschirrspülmittel Expired - Lifetime EP0883670B1 (de)

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US60883396A 1996-02-29 1996-02-29
US608833 1996-02-29
PCT/EP1997/000687 WO1997031996A1 (en) 1996-02-29 1997-02-13 Machine dishwashing gel compositions

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US6844305B1 (en) 1999-08-27 2005-01-18 The Proctor & Gamble Company Aqueous liquid detergent compositions comprising a polymeric stabilization system

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DE69732339T2 (de) * 1996-12-05 2005-06-09 Unilever N.V. Gelzusammensetzung für Geschirrspülmaschine
US6162055A (en) 1998-02-13 2000-12-19 Britesmile, Inc. Light activated tooth whitening composition and method of using same
DE19854960A1 (de) 1998-11-29 2000-05-31 Clariant Gmbh Maschinengeschirrspülmittel
DE102018212206A1 (de) * 2018-07-23 2020-01-23 Henkel Ag & Co. Kgaa Reinigungsmittel mit Silberschutz

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CA1321115C (en) * 1987-12-30 1993-08-10 Robert Corring Gel detergent compositions
CH679311A5 (de) * 1989-01-07 1992-01-31 Sandoz Ag
CA2171312A1 (en) * 1993-10-14 1995-04-20 Petrus Adrianus J. M. Angevaare Detergent compositions containing silver anti-tarnishing agents

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6844305B1 (en) 1999-08-27 2005-01-18 The Proctor & Gamble Company Aqueous liquid detergent compositions comprising a polymeric stabilization system

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DE69708064D1 (de) 2001-12-13
CZ274798A3 (cs) 1999-03-17
CA2242324A1 (en) 1997-09-04
SK116498A3 (en) 1999-01-11
EP0883670A1 (de) 1998-12-16
WO1997031996A1 (en) 1997-09-04
HUP9900649A2 (hu) 1999-07-28
AU1873297A (en) 1997-09-16
BR9707729A (pt) 1999-07-27

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