WO1994019445A1 - Machine dishwashing composition - Google Patents

Machine dishwashing composition Download PDF

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Publication number
WO1994019445A1
WO1994019445A1 PCT/EP1994/000276 EP9400276W WO9419445A1 WO 1994019445 A1 WO1994019445 A1 WO 1994019445A1 EP 9400276 W EP9400276 W EP 9400276W WO 9419445 A1 WO9419445 A1 WO 9419445A1
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WIPO (PCT)
Prior art keywords
complex
charge
manganese
weight
composition
Prior art date
Application number
PCT/EP1994/000276
Other languages
French (fr)
Inventor
Willem Oldenburg
Jan Hendrik Verkade
Original Assignee
Unilever N.V.
Unilever Plc
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 N.V., Unilever Plc filed Critical Unilever N.V.
Priority to AU60005/94A priority Critical patent/AU6000594A/en
Publication of WO1994019445A1 publication Critical patent/WO1994019445A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • This invention relates to detergent cleaning compositions especially adapted for use in automatic dishwashing machines.
  • compositions comprising chlorine bleach have the disadvantage of silverware-tarnishing at mild alkalinity.
  • a machine dishwashing composition comprising a peroxygen bleach system, preferably also comprising a precursor, said composition combining improved bleaching action with excellent anti-tarnishing properties, especially on low-quality silver plate.
  • Mn manganese, which can individually be in the III or IV oxidation state; each x represents a co ⁇ ordinating or bridging species selected from the group consisting of H 2 0, 0 2 2- o 2 -. OH “ , HO, SH " ;2- >SO, Cl *
  • L is a ligand which is an organic molecule containing a number of nitrogen atoms which co-ordinates via all or some of its nitrogen atoms to the manganese centres;
  • z denotes the charge of the complex and is an integer which can be positive or negative;
  • Y is a monovalent or multivalent counter ion, leading to charge neutrality, which is dependent upon the charge z of the complex; and
  • q z /[charge Y], has excellent anti- tarnishing properties.
  • the present invention concerns the use of a dinuclear manganese complex of the following general formula :
  • a further aspect of the invention provides a non-chlorine machine dishwashing composition
  • a bleach system selected from :
  • composition further comprising a dinuclear manganese complex as defined hereinbefore and hereinafter.
  • the machine dishwashing composition is mildly alkaline, having solution pH below 12, e.g. from 8-12, preferably from 9-12.
  • the solution pH as meant here is the pH as determined from a solution of 3 g/1 of the composition in distilled water.
  • Silver-tarnishing is especially encountered in compositions of mild pH comprising a bleach precursor, particularly TAED.
  • Preferred manganese complexes are those wherein x is either CH 3 COO ⁇ or 0 ⁇ or mixtures thereof, most preferably those wherein the manganese is in the IV oxidation state and x is 0 2 ⁇ .
  • Preferred ligands are those which co-ordinate via three nitrogen atoms to one of the manganese centres, preferably being of a macrocyclic nature. Particularly preferred ligands are :
  • the type of counter ion Y for charge neutrality is not critical for the activity of the complex and can be selected from, for example, any of the following counter ions : chloride; nitrate; methylsulphate; surfactant anions, such as the long-chain alkylsulphates, alkylsulphonates, alkylbenzene sulphonates, tosylate; trifiuoromethyl sulphonate; perchlorate (C10 4 ⁇ ) , BPh 4 ⁇ , and PF 6 ⁇ , though some counter ions are more preferred than others for reasons of product property and safety.
  • the preferred manganese complexes usable in the present invention are :
  • the dinuclear manganese complex may be present in an amount corresponding to an Mn content of from 0.0001 to about 1.0% by weight, preferably from 0.0005 to 0.5% by weight.
  • the peroxygen compound bleaches which can be utilised in the present invention include hydrogen peroxide, hydrogen peroxide-liberating compounds, hydrogen peroxide-generating compounds, as well as the inorganic and organic peroxyacids and water-soluble salts thereof.
  • Hydrogen peroxide sources are well known in the art. They include the alkali metal peroxides and persalt bleaching compounds, such as the alkali metal perborates, percarbonates and perphosphates. Mixtures of two or more of such compounds may also be suitable. Particularly preferred are sodium percarbonate for environmental reasons and sodium perborate and especially sodium perborate monohydrate, because of its excellent storage stability while also dissolving very quickly in aqueous solutions.
  • Organic peroxyacids are those compounds known in the art having normally one or more peroxycarboxy1
  • O / groups (-C-OOH) in their molecular structure e.g. 1,12- diperoxydodecanedioic acid (DPDA) and phthaloylamido peroxycaproic acid (PAP) .
  • DPDA diperoxydodecanedioic acid
  • PAP phthaloylamido peroxycaproic acid
  • An example of an inorganic peroxyacid is potassium monopersulphate.
  • the peroxygen bleach may be present in an amount of from 1 to 40%, preferably from 2 to 20% by weight of the composition.
  • Persalts and peroxyacid may be utilised alone, or in conjunction with a precursor, such as TAED, GTA, CSPC and SNOBS.
  • the precursor is present in amounts up to 10%, preferably up to 6%, more preferably up to 4% by weight of the composition and preferably at least 0.5%, more preferably at least 1%, most preferably at least 1.5% by weight of the composition.
  • compositions of the invention will also normally contain builder material that may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange material and 4) mixtures thereof.
  • Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid, dipicolinic acid, chelidamic acid and their water-soluble salts; the alkali metal salts of ether polycarboxylates, such as carboxymethyloxy succinic acid, oxydisuccinic acid, mellitic acid; ethylene diamine tetraacetic acid, benzene polycarboxylic acid; citric acid; and polyacetal carboxylates as disclosed in US Patents 4,144,226 and 4,146,495.
  • alkali metal polyphosphates such as sodium tripolyphosphate
  • nitrilotriacetic acid dipicolinic acid, chelidamic acid and their water-soluble salts
  • the alkali metal salts of ether polycarboxylates such as carboxymethyloxy succinic acid, oxydisuccinic acid, mellitic acid
  • precipitating builder materials examples include sodium orthophosphate, sodium carbonate and sodium carbonate/ calcite.
  • Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best- known representatives.
  • Other useful materials are, for example, layered silicates, such as SKS®-6 ex Hoechst.
  • compositions of the invention may contain any one of the organic or inorganic builder materials, such as sodium or potassium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate or sodium carbonate/ calcite mixtures, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl alonate, carboxymethyloxy succinate and the water-insoluble crystalline or amorphous alu inosilicate builder materials, or mixtures thereof.
  • the organic or inorganic builder materials such as sodium or potassium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate or sodium carbonate/ calcite mixtures, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl alonate, carboxymethyloxy succinate and the water-insoluble crystalline or amorphous alu inosilicate builder materials, or mixtures thereof.
  • compositions are, however, essentially free of phosphates and will contain, for example, sodium citrate, sodium carbonate, sodium carbonate/calcite, aluminosilicates (zeolites) or mixtures thereof as preferred builder materials.
  • zeolites aluminosilicates
  • the builder material may be present in an amount of from 0-80%, preferably from 5 to 60% by weight.
  • An optional but highly desirable additive ingredient with multi-functional characteristics, particularly in non- phosphate compositions is from 1% to 10%, preferably about 5% by weight of a polymeric material having a molecular weight of from 1,000 to 2,000,000 and which can be a homo- or co-polymer of acrylic acid, maleic acid, or salt or anhydride thereof, vinyl pyrrolidone methyl- or ethyl-, vinyl ethers and other polymerisable vinyl monomers. These polymers are believed to function as co-builders, although under certain conditions they may also function as main builders.
  • the buffering agent is the buffering agent
  • Buffering agents are necessary to adjust and to maintain the alkalinity and pH at the desired level. These are, for example, the alkali metal carbonates, bicarbonates, borates, and silicates. Usually, sodium silicates having Na 2 0:Si0 2 ratios of from about 2:1 to 1:4 are the buffering agents most suitably used in machine dishwashing compositions. A preferred buffering agent is sodium disilicate having Na 2 0:Si0 2 ratio of about 1:1.8 to 1:2.5.
  • the buffering agent may be present from 0-80%, preferably 5-75% by weight of the composition.
  • the cleaning compositions of the invention may, as desired, contain enzyme.
  • Amylolytic enzymes that may be used in the present invention can be those derived from bacteria or fungi. Examples of such enzymes are Sp-95® or Termamyl®, generally presented as granules. Enzyme activities may be of from about 2 to 10 Maltose Units/milligram and can be determined by the method as described by P.Bernfeld in "Method of Enzymology", Volume I (1955), page 149.
  • composition of the invention may also contain proteolytic enzyme.
  • proteolytic enzyme examples are Maxatase®, Alcalase®, Esperase®, Savinase® and Durazym®.
  • Proteolytic activities may be of from about 500 to 1700 Glycine Units/milligram.
  • Enzyme granules containing only minor proportions, e.g. less than 30%, particularly not more than 10% by weight of chloride to substantially nil, are preferably used in the compostion of the invention.
  • these enzymes can each be present in weight percentage amounts of from 0.2 to 5% by weight, such that, for amylolytic enzymes, the final composition will have amylolytic activity of from 10 2 to 10 6 Maltose Units/kg, and, for proteolytic enzymes, the final composition will have proteolytic enzyme activity of from about 10 6 to 10 9 Glycine Units/kg.
  • a small amount of low- to non-foaming nonionic surfactant which includes any alkoxylated nonionic surface-active agent wherein the alkoxy moiety is selected from the group consisting of ethylene oxide, propylene oxide and mixtures thereof, is preferably used to improve the detergency and to suppress excessive foaming due to some protein soil.
  • an excessive proportion of nonionic surfactant should be avoided.
  • nonionic surfactants for use in the invention are the low- to non-foaming ethoxylated straight- chain alcohols of the Plurafac® RA series, supplied by the Eurane Company; of the Lutensol® LF series, supplied by the BASF Company; of the Triton® DF series, supplied by the Rohm & Haas Company, and of the Synperonic® LF series, supplied by the ICI company.
  • compositions of the invention may further contain any of the following additional ingredients.
  • Stabilising and anti- scaling agents, crystal-growth inhibitors and threshold agents are those belonging to the class of phosphonates sold under the tradename "Dequest®", such as ethylene diamine tetra-(methylene phosphonate) , diethylene triamine penta-(methylene phosphonate) and ethylene hydroxy diphosphonate.
  • Dequest® ethylene diamine tetra-(methylene phosphonate)
  • diethylene triamine penta-(methylene phosphonate) ethylene hydroxy diphosphonate.
  • Another suitable class of anti-scaling agents are the low molecular weight polyacrylates, polymaleates and mixtures thereof or the copolymers thereof, having molecular weights of up to about 6000.
  • a further suitable class of anti-scaling agents are polypeptides.
  • Clays such as hectorites and montmorillonites, may be included in the composition of the invention. These assist in reduction of spot formation on glassware, and may be present at from 0.5 to 10% by weight, preferably from 0.5 to 7% by weight. Particularly preferred is the addition of Laponite® clay at about 0.5 to 5% by weight, which is a synthetic hectorite.
  • Laponite® clay is a synthetic hectorite.
  • “Dequest” and “Laponite” are trademarks owned by, respectively, Monsanto and Laporte Industries.
  • a filler may be required to complete the composition, though in compacted powdered compositions it should preferably be avoided.
  • a preferred filler is sodium sulphate.
  • Silver articles were washed 15 times in a Miele 595 SC with the 65°C programme (short and main wash cycles) using water of 8°GH and dosing 6 g egg white per wash. Disclouration degree of silver articles was measured using an Ultrascan spectrophotometer. From the L, A and B readings in the various colours of the spectra, a resulting factor (delta E) is calculated according to CIELAB recommendations (JSDC September 1977, pp. 337-8). The higher the results, the severer the tarnishing. The following compositions were tested:
  • compositions according to the invention have surprisingly good anti-tarnishing properties, particularly on low-quality silver plate.

Abstract

This invention relates to detergent cleaning compositions especially adapted for use in automatic dishwashing machines comprising a bleach system and an anti-tarnishing agent.

Description

MACHINE DIS ASHING COMPOSITION
Field of the Invention
This invention relates to detergent cleaning compositions especially adapted for use in automatic dishwashing machines.
Background and Prior Art
Conventional automatic machine dishwashing compositions are normally phosphate-based, highly alkaline products comprising chlorine bleaching agent and having solution pH generally above 12.0. Though, performance-wise, these conventional products are quite satisfactory, a drawback is their high alkalinity, which has the disadvantage of being aggressive and hazardous.
It has been suggested that this drawback be overcome by formulating a machine dishwashing composition of lower alkalinity. However, compositions comprising chlorine bleach have the disadvantage of silverware-tarnishing at mild alkalinity.
This drawback can be overcome by replacing the chlorine bleach with a peroxygen bleach system. In a further attempt to reduce silverware-tarnishing, chlorine from other sources, such as enzyme capsules, can be removed as described in EP 135 226. Cleaning with such non-chlorine bleach compositions of mild pH that comprise a peroxygen bleach system gives good performance. However, silverware- tarnishing still occurs, especially with low-quality silver. The tarnishing effect is particularly experienced when a bleach precursor is present in the composition.
Consequently, it is an object of the present invention to provide a machine dishwashing composition comprising a peroxygen bleach system, preferably also comprising a precursor, said composition combining improved bleaching action with excellent anti-tarnishing properties, especially on low-quality silver plate.
Description of the Invention Surprisingly, it has now been found that a dinuclear manganese complex of the following general formula :
Figure imgf000004_0001
wherein Mn is manganese, which can individually be in the III or IV oxidation state; each x represents a co¬ ordinating or bridging species selected from the group consisting of H20, 02 2- o2-. OH", HO, SH" ;2- >SO, Cl*
N 3- SCN" N3-, RCOO", NH2 ~ and NR3, with R being H, alkyl or aryl (optionally substituted) ; L is a ligand which is an organic molecule containing a number of nitrogen atoms which co-ordinates via all or some of its nitrogen atoms to the manganese centres; z denotes the charge of the complex and is an integer which can be positive or negative; Y is a monovalent or multivalent counter ion, leading to charge neutrality, which is dependent upon the charge z of the complex; and q = z/[charge Y], has excellent anti- tarnishing properties.
Accordingly, the present invention concerns the use of a dinuclear manganese complex of the following general formula :
Figure imgf000004_0002
wherein Mn is manganese, which can individually be in the III or IV oxidation state; each x represents a co¬ ordinating or bridging species selected from the group consisting of H20, 02 2", 02~, OH", H02 ~, SH", S2~, >S0, Cl", N3~, SCN", N3~, RCOO", NH2 " and NR3, with R being H, alkyl or aryl (optionally substituted) ; L is a ligand which is an organic molecule containing a number of nitrogen atoms which co-ordinates via all or some of its nitrogen atoms to the manganese centres; z denotes the charge of the complex and is an integer which can be positive or negative; Y is a monovalent or multivalent counter ion, leading to charge neutrality, which is dependent upon the charge z of the complex; and q = z/[charge Y], as anti-tarnishing agent in machine dishwashing compositions comprising a peroxygen bleach.
A further aspect of the invention provides a non-chlorine machine dishwashing composition comprising a bleach system selected from :
(i) 2.5 to 19%, preferably from 3 to 17%, more preferably from 5 to 15% by weight of persalt and from 0.5 to 10% by weight of a precursor;
(ii) 2.5 to 6%, preferably from 3% by weight of peroxyacid and from 0 to 10% by weight of precursor; and
(iii) mixtures thereof,
said composition further comprising a dinuclear manganese complex as defined hereinbefore and hereinafter.
Preferably, the machine dishwashing composition is mildly alkaline, having solution pH below 12, e.g. from 8-12, preferably from 9-12. The solution pH as meant here is the pH as determined from a solution of 3 g/1 of the composition in distilled water. Silver-tarnishing is especially encountered in compositions of mild pH comprising a bleach precursor, particularly TAED.
Manganese Complexes
Preferred manganese complexes are those wherein x is either CH3COO~ or 0 ~ or mixtures thereof, most preferably those wherein the manganese is in the IV oxidation state and x is 02~. Preferred ligands are those which co-ordinate via three nitrogen atoms to one of the manganese centres, preferably being of a macrocyclic nature. Particularly preferred ligands are :
(1) l,4,7-trimethyl-l,4,7-triazacyclononane, (Me-TACN), and
(2) 1,2,4,7-tetramethyl-l,4,7-triazacyclononane, (Me-MeTACN) .
The type of counter ion Y for charge neutrality is not critical for the activity of the complex and can be selected from, for example, any of the following counter ions : chloride; nitrate; methylsulphate; surfactant anions, such as the long-chain alkylsulphates, alkylsulphonates, alkylbenzene sulphonates, tosylate; trifiuoromethyl sulphonate; perchlorate (C104~) , BPh4 ~, and PF6~, though some counter ions are more preferred than others for reasons of product property and safety.
Consequently, the preferred manganese complexes usable in the present invention are :
(I) [Me-TACN)MnIV(μ-0)3MnIV(Me-TACN) ]2+(PF6 ")2
(II) [Me-MeTACN)MnIV(μ-0)3MnIV(Me-MeTACN) ]2+(PF6 ")2
(III) [Me-TACN)MnXII(μ-0) (μ-OAc)2MnIi:c(Me-TACN) ]2+(PF6 ")2
(IV) [Me-MeTACN)MnIι:r(μ-0) (μ-0Ac)2MnIι:[ (Me-MeTACN) ]2+(PF6~)2 which are hereinafter also abbreviated as :
(I) [MIV 2(μ-0)3(Me-TACN)2](PF6)2
(II) [MnIV 2(μ-0) 3(Me-MeTACN)2] (PF6)2
(III) [MnIII 2(μ-0) (μ-OAc)2(Me-TACN)2] (PF6)2
(IV) [_-nιττ 2 (μ-0) (μ-OAc)2 (Me-MeTACN)2] (PF6)2
The structure of I is given below :
Figure imgf000007_0001
abbreviated as [Mn ,ιvv 2(μ-0)3(Me-TACN)2] (PF6)2.
The structure of II is given below :
2
Figure imgf000007_0002
abbreviated as [Mn .I-LVV 2(μ-0)3(Me-MeTACN)2] (PF6)2.
It is of note that the manganese complexes used in the present invention are reported in EP-A-0458397 and EP-A-045398 as unusually effective bleach and oxidation catalysts. In the further description of the invention they will also be simply referred to as the "catalyst".
The dinuclear manganese complex may be present in an amount corresponding to an Mn content of from 0.0001 to about 1.0% by weight, preferably from 0.0005 to 0.5% by weight.
Bleach system
The peroxygen compound bleaches which can be utilised in the present invention include hydrogen peroxide, hydrogen peroxide-liberating compounds, hydrogen peroxide-generating compounds, as well as the inorganic and organic peroxyacids and water-soluble salts thereof.
Hydrogen peroxide sources are well known in the art. They include the alkali metal peroxides and persalt bleaching compounds, such as the alkali metal perborates, percarbonates and perphosphates. Mixtures of two or more of such compounds may also be suitable. Particularly preferred are sodium percarbonate for environmental reasons and sodium perborate and especially sodium perborate monohydrate, because of its excellent storage stability while also dissolving very quickly in aqueous solutions.
Organic peroxyacids are those compounds known in the art having normally one or more peroxycarboxy1
O / groups (-C-OOH) in their molecular structure, e.g. 1,12- diperoxydodecanedioic acid (DPDA) and phthaloylamido peroxycaproic acid (PAP) . An example of an inorganic peroxyacid is potassium monopersulphate.
The peroxygen bleach may be present in an amount of from 1 to 40%, preferably from 2 to 20% by weight of the composition. Persalts and peroxyacid may be utilised alone, or in conjunction with a precursor, such as TAED, GTA, CSPC and SNOBS. Preferably, the precursor is present in amounts up to 10%, preferably up to 6%, more preferably up to 4% by weight of the composition and preferably at least 0.5%, more preferably at least 1%, most preferably at least 1.5% by weight of the composition.
Builder material The compositions of the invention will also normally contain builder material that may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange material and 4) mixtures thereof.
Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid, dipicolinic acid, chelidamic acid and their water-soluble salts; the alkali metal salts of ether polycarboxylates, such as carboxymethyloxy succinic acid, oxydisuccinic acid, mellitic acid; ethylene diamine tetraacetic acid, benzene polycarboxylic acid; citric acid; and polyacetal carboxylates as disclosed in US Patents 4,144,226 and 4,146,495.
Examples of precipitating builder materials include sodium orthophosphate, sodium carbonate and sodium carbonate/ calcite.
Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best- known representatives. Other useful materials are, for example, layered silicates, such as SKS®-6 ex Hoechst.
In particular, the compositions of the invention may contain any one of the organic or inorganic builder materials, such as sodium or potassium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate or sodium carbonate/ calcite mixtures, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl alonate, carboxymethyloxy succinate and the water-insoluble crystalline or amorphous alu inosilicate builder materials, or mixtures thereof.
Preferred compositions are, however, essentially free of phosphates and will contain, for example, sodium citrate, sodium carbonate, sodium carbonate/calcite, aluminosilicates (zeolites) or mixtures thereof as preferred builder materials.
The builder material may be present in an amount of from 0-80%, preferably from 5 to 60% by weight.
An optional but highly desirable additive ingredient with multi-functional characteristics, particularly in non- phosphate compositions, is from 1% to 10%, preferably about 5% by weight of a polymeric material having a molecular weight of from 1,000 to 2,000,000 and which can be a homo- or co-polymer of acrylic acid, maleic acid, or salt or anhydride thereof, vinyl pyrrolidone methyl- or ethyl-, vinyl ethers and other polymerisable vinyl monomers. These polymers are believed to function as co-builders, although under certain conditions they may also function as main builders.
The buffering agent
Buffering agents are necessary to adjust and to maintain the alkalinity and pH at the desired level. These are, for example, the alkali metal carbonates, bicarbonates, borates, and silicates. Usually, sodium silicates having Na20:Si02 ratios of from about 2:1 to 1:4 are the buffering agents most suitably used in machine dishwashing compositions. A preferred buffering agent is sodium disilicate having Na20:Si02 ratio of about 1:1.8 to 1:2.5.
The buffering agent may be present from 0-80%, preferably 5-75% by weight of the composition.
Optional ingredients
Though not essential, the cleaning compositions of the invention may, as desired, contain enzyme.
Amylolytic enzymes that may be used in the present invention can be those derived from bacteria or fungi. Examples of such enzymes are Sp-95® or Termamyl®, generally presented as granules. Enzyme activities may be of from about 2 to 10 Maltose Units/milligram and can be determined by the method as described by P.Bernfeld in "Method of Enzymology", Volume I (1955), page 149.
The composition of the invention may also contain proteolytic enzyme. Examples are Maxatase®, Alcalase®, Esperase®, Savinase® and Durazym®. Proteolytic activities may be of from about 500 to 1700 Glycine Units/milligram. Enzyme activity can be determined by the method as described by M.L.Anson in "Journal of General Physiology", Vol. 22 (1938), page 79 (one Anson Unit/g ■= 733 Glycine Units/milligram) .
Enzyme granules containing only minor proportions, e.g. less than 30%, particularly not more than 10% by weight of chloride to substantially nil, are preferably used in the compostion of the invention.
If used, these enzymes can each be present in weight percentage amounts of from 0.2 to 5% by weight, such that, for amylolytic enzymes, the final composition will have amylolytic activity of from 102 to 106 Maltose Units/kg, and, for proteolytic enzymes, the final composition will have proteolytic enzyme activity of from about 106 to 109 Glycine Units/kg.
A small amount of low- to non-foaming nonionic surfactant, which includes any alkoxylated nonionic surface-active agent wherein the alkoxy moiety is selected from the group consisting of ethylene oxide, propylene oxide and mixtures thereof, is preferably used to improve the detergency and to suppress excessive foaming due to some protein soil. However, an excessive proportion of nonionic surfactant should be avoided. Normally, an amount of 0.1 to 7% by weight, preferably from 0.5 to 5% by weight, is quite sufficient.
Examples of suitable nonionic surfactants for use in the invention are the low- to non-foaming ethoxylated straight- chain alcohols of the Plurafac® RA series, supplied by the Eurane Company; of the Lutensol® LF series, supplied by the BASF Company; of the Triton® DF series, supplied by the Rohm & Haas Company, and of the Synperonic® LF series, supplied by the ICI company.
Compositions of the invention may further contain any of the following additional ingredients. Stabilising and anti- scaling agents, crystal-growth inhibitors and threshold agents. Examples of suitable stabilising and anti-scaling compounds are those belonging to the class of phosphonates sold under the tradename "Dequest®", such as ethylene diamine tetra-(methylene phosphonate) , diethylene triamine penta-(methylene phosphonate) and ethylene hydroxy diphosphonate. Another suitable class of anti-scaling agents are the low molecular weight polyacrylates, polymaleates and mixtures thereof or the copolymers thereof, having molecular weights of up to about 6000. A further suitable class of anti-scaling agents are polypeptides. Clays, such as hectorites and montmorillonites, may be included in the composition of the invention. These assist in reduction of spot formation on glassware, and may be present at from 0.5 to 10% by weight, preferably from 0.5 to 7% by weight. Particularly preferred is the addition of Laponite® clay at about 0.5 to 5% by weight, which is a synthetic hectorite. "Dequest" and "Laponite" are trademarks owned by, respectively, Monsanto and Laporte Industries.
Finally, the addition of a filler may be required to complete the composition, though in compacted powdered compositions it should preferably be avoided. A preferred filler is sodium sulphate.
The invention will now be further illustrated by the following Examples.
EXAMPLES
Silver articles were washed 15 times in a Miele 595 SC with the 65°C programme (short and main wash cycles) using water of 8°GH and dosing 6 g egg white per wash. Disclouration degree of silver articles was measured using an Ultrascan spectrophotometer. From the L, A and B readings in the various colours of the spectra, a resulting factor (delta E) is calculated according to CIELAB recommendations (JSDC September 1977, pp. 337-8). The higher the results, the severer the tarnishing. The following compositions were tested:
INGREDIENTS COMPOSITIONS A B 1 2
Citrate Polymer CP5 Polymer PA30 Disilicate 80% Perborate TAED (100%) 3.5 - 3.5 Mn complex 1) - + + Savinase Amylase Nonionic Laponite Perfume
1) Mn complex : Mn ,ι-LvV 2 (μ-0 ) 3 (Me-TACN) 2 ] (PF6) 2 at 10 -"53 Mol/ 1 The following results were obtained
Delta E
Composition Spoon Low quality plate
A 10 16
B 20 36
1 7 2
2 6 3
The results show that compositions according to the invention have surprisingly good anti-tarnishing properties, particularly on low-quality silver plate.

Claims

1. Use of a dinuclear manganese complex of the following general formula:
Figure imgf000016_0001
wherein Mn is manganese, which can individually be in the III or IV oxidation state; each x represents a co¬ ordinating or bridging species selected from the group consisting of H20, 02 2- / o2-, OH", HO,_ SH" -2- >S0, Cl"
N3-, SCN~, N3°-", RC00~, NH2~ and NR3, with R being H, alkyl or aryl (optionally substituted) ; L is a ligand which is an organic molecule containing a number of nitrogen atoms which co-ordinates via all or some of its nitrogen atoms to the manganese centres; z denotes the charge of the complex and is an integer which can be positive or negative; Y is a monovalent or multivalent counter ion, leading to charge neutrality, which is dependent upon the charge z of the complex; and q = z/[charge Y], as anti-tarnishing agent.
2. Use according to Claim 1 wherein the dinuclear manganese complex is present in a composition for mechanical dish washing that comprises bleach precursor.
3. Non-chlorine machine dishwashing composition comprising a bleach system selected from:
(i) 2.5 to 19% by weight of persalt and from 0.5 to 10% by weight of precursor;
(ii) from 2.5 to 6% by weight of peroxyacid and from 0 to 10% by weight of precursor; and (iii) mixtures thereof,
said composition further comprising a dinuclear manganese complex.
4. Composition according to Claim 3, characterised in that the dinuclear manganese complex has the following general formula:
Figure imgf000017_0001
wherein Mn is manganese, which can individually be in the III or IV oxidation state; each x represents a co¬ ordinating or bridging species selected from the group consisting of H20, 02 2^-", 2- OH", H02 ", SH~, S2~, >S0, Cl",
N3-, SCN" N- RCOO", NH2~ and NR3, with R being H, alkyl or aryl (optionally substituted) ; L is a ligand which is an organic molecule containing a number of nitrogen atoms which co-ordinates via all or some of its nitrogen atoms to the manganese centres; z denotes the charge of the complex and is an integer which can be positive or negative; Y is a monovalent or multivalent counter ion, leading to charge neutrality, which is dependent upon the charge z of the complex; and q = z/[charge Y].
5. Composition according to Claims 3-4, characterised in that the dinuclear manganese complex is present in an amount corresponding to a manganese content of from 0.0001 to 1.0% by weight.
PCT/EP1994/000276 1993-02-22 1994-01-28 Machine dishwashing composition WO1994019445A1 (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0672749A1 (en) * 1994-03-17 1995-09-20 The Procter & Gamble Company Bleaching compositions
EP0682105A2 (en) * 1994-04-13 1995-11-15 The Procter & Gamble Company Bleaching compositions
WO1997016520A1 (en) * 1995-10-27 1997-05-09 Henkel Kommanditgesellschaft Auf Aktien Dishwasher detergent
EP0690122A3 (en) * 1994-06-30 1997-11-12 The Procter & Gamble Company Detergent compositions
US6143707A (en) * 1996-03-19 2000-11-07 The Procter & Gamble Company Built automatic dishwashing compositions comprising blooming perfume
US6221824B1 (en) 1999-02-25 2001-04-24 Henkel Kommanditgesellschaft Auf Aktien Process for the production of compounded acetonitrile derivatives
US6225274B1 (en) 1996-11-29 2001-05-01 Henkel Kommandigesellschaft Auf Aktien Acetonitrile derivatives as bleaching activators in detergents
WO2012107187A1 (en) * 2011-02-10 2012-08-16 Clariant International Ltd Use of transition metal complexes as bleach catalysts in washing and cleaning compositions

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EP0458398A2 (en) * 1990-05-21 1991-11-27 Unilever N.V. Bleach activation
EP0509787A2 (en) * 1991-04-17 1992-10-21 Unilever Plc Concentrated detergent powder compositions
EP0522817A1 (en) * 1991-07-11 1993-01-13 Unilever Plc Process for preparing manganese complexes
EP0530870A1 (en) * 1991-08-23 1993-03-10 Unilever N.V. Machine dishwashing composition
EP0544490A1 (en) * 1991-11-26 1993-06-02 Unilever Plc Detergent bleach compositions

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Publication number Priority date Publication date Assignee Title
EP0458398A2 (en) * 1990-05-21 1991-11-27 Unilever N.V. Bleach activation
EP0458397A2 (en) * 1990-05-21 1991-11-27 Unilever N.V. Bleach activation
EP0509787A2 (en) * 1991-04-17 1992-10-21 Unilever Plc Concentrated detergent powder compositions
EP0522817A1 (en) * 1991-07-11 1993-01-13 Unilever Plc Process for preparing manganese complexes
EP0530870A1 (en) * 1991-08-23 1993-03-10 Unilever N.V. Machine dishwashing composition
EP0544490A1 (en) * 1991-11-26 1993-06-02 Unilever Plc Detergent bleach compositions

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0672749A1 (en) * 1994-03-17 1995-09-20 The Procter & Gamble Company Bleaching compositions
EP0682105A2 (en) * 1994-04-13 1995-11-15 The Procter & Gamble Company Bleaching compositions
EP0682105A3 (en) * 1994-04-13 1997-11-05 The Procter & Gamble Company Bleaching compositions
EP0690122A3 (en) * 1994-06-30 1997-11-12 The Procter & Gamble Company Detergent compositions
WO1997016520A1 (en) * 1995-10-27 1997-05-09 Henkel Kommanditgesellschaft Auf Aktien Dishwasher detergent
US6143707A (en) * 1996-03-19 2000-11-07 The Procter & Gamble Company Built automatic dishwashing compositions comprising blooming perfume
US6225274B1 (en) 1996-11-29 2001-05-01 Henkel Kommandigesellschaft Auf Aktien Acetonitrile derivatives as bleaching activators in detergents
US6221824B1 (en) 1999-02-25 2001-04-24 Henkel Kommanditgesellschaft Auf Aktien Process for the production of compounded acetonitrile derivatives
WO2012107187A1 (en) * 2011-02-10 2012-08-16 Clariant International Ltd Use of transition metal complexes as bleach catalysts in washing and cleaning compositions

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