EP0726933A1 - Compositions detergentes - Google Patents

Compositions detergentes

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Publication number
EP0726933A1
EP0726933A1 EP95901074A EP95901074A EP0726933A1 EP 0726933 A1 EP0726933 A1 EP 0726933A1 EP 95901074 A EP95901074 A EP 95901074A EP 95901074 A EP95901074 A EP 95901074A EP 0726933 A1 EP0726933 A1 EP 0726933A1
Authority
EP
European Patent Office
Prior art keywords
acid
weight
compositions
alkyl
preferred
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.)
Withdrawn
Application number
EP95901074A
Other languages
German (de)
English (en)
Other versions
EP0726933A4 (fr
Inventor
Fiona S. Macbeath
Alison M. Smith
Jing-Feng You
Gregory Stephen Caravajal
Donna Jean Haeggberg
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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
Priority claimed from GB9418572A external-priority patent/GB2283494A/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0726933A1 publication Critical patent/EP0726933A1/fr
Publication of EP0726933A4 publication Critical patent/EP0726933A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0084—Antioxidants; Free-radical scavengers
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • 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

  • the present invention relates to detergent compositions, adapted for use in machine dishwashing.
  • the compositions exhibit good bleachable stain removal, reduce, ropensity to damage glassware and in a highly preferred execuL n enhanced anti silver-tarnishing properties.
  • compositions designed for use in automatic dishwash; - ⁇ iachines are well known, and a consistent effort has been made by detergent manufacturers to improve the cleaning and/or rinsing efficiency of said compositions on dishes and glassware, as reflected by numerous patent publications.
  • the present invention is concerned with the formulation of a detergent composition useful in machine dishwashing having good stain removal capability, but reduced propensity to tarnish silverware and/or damage glassware.
  • a detergent composition useful in machine dishwashing having good stain removal capability, but reduced propensity to tarnish silverware and/or damage glassware.
  • bleachable soils such as tea and coloured vegetable soils, such as carotenoid soils
  • carotenoid soils is a particular challenge to the formulator of a machine dishwashing detergent composition.
  • the removal of such soils has been enabled by the use of bleach components such as oxygen and chlorine bleaches. Oxygen bleaching species are these days however, largely preferred over chlorine bleaches.
  • a problem encountered with the use of such oxygen bleaches is the tarnishing of any silverware components of the washload.
  • the level of tarnishing observed can range from slight discolouration of the silverware to the formation of a dense black coating on the surface of the silverware.
  • the total level of oxygen bleach in the composition is desirably optimized, and preferably the rate of release of the oxygen bleach is controlled.
  • the rate of release of oxygen bleach is preferably rapid enough to provide satisfactory cleaning, but with minimised tarnishing.
  • the rate of release of any peroxidt >ecies to the wash solution is preferably controlled.
  • compositions containing Mn(II) salts such as MnS ⁇ 4 and MnC in combination with inorganic perhydrate salts and certain bleach activators are disclosed in the aforementioned German Patent Application DE-A- 4,128,672.
  • Mn(II) salts such as MnS ⁇ 4 and MnC in combination with inorganic perhydrate salts and certain bleach activators
  • DE-A-4, 128,672 teaching is provided in DE-A-4, 128,672 that w... .e Mn(II) salts are used as activators for peroxv compounds there is no protection of the silver.
  • European Patent Applications EP-A-0082563, EP-A-127,910, EP-A- 141 ,470, EP-A-145,090 and EP-A-145,091 in the name of Unilever disclose detergent compositions for use in fabric washing containing various Mn(II) compounds. The combination of these various Mn(II) compounds with N-acylated lactam, perbenzoic acid, perbenzoic acid derivative or cationic peroxyacid precursors is not specifically disclosed. Problems specific to the art field of machine dishwashing, in particular the tarnishing of silverware, are not addressed.
  • EP-A-0 530 870 in the name of Unilever discloses machine dishwashing compositions containing a dinuclear manganese complex in which the manganese is in the III or IV oxidation state. No recognition is provided in this document of the utility of Mn (II) salts in reducing silver tarnishing.
  • a detergent composition adapted for use in a machine diswashing method containing a water soluble alkali metal silicate at a level (measured as Si ⁇ 2) of from 1 % to 11 % by weight wherein said composition has a pH measured as a 1 % solution in distilled water at 20°C of from 9.0 to 11.5.
  • the detergent composition additionally contains a crystal growth inhibitor component.
  • the detergent composition contains
  • an oxygen-releasing bleach system comprising a hydrogen peroxide source and a peroxyacid bleach precursor compound preferably selected from the group consisting of
  • n is from 0 to about 8, preferably from 0 to about 2, and R is H, an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbons, or a substituted phenyl group containing from about 6 to about 18 carbon atoms;
  • said oxygen-releasing bleaching system is incorporated such that the level of available oxygen measured according to the method herein is from 0.3% to 2.5% , preferably 0.5% to 1.7% by weight.
  • the rate of release of said available oxygen is such that the available oxygen is completely released from the composition in a time interval of from 3.5 minutes to 10.0 minutes, using the test protocol described in the present description.
  • the bleaching composition contains no additional corrosion inhibitor component, particularly no benzotriazole.
  • the Mn(II) compound is an Mn(II) salt or complex with an organic ligand, which may itself have heavy metal ion sequestering or ; ferably crystal growth inhibiting properties.
  • compositions herein are adapted for use in a machine dishwashing method. Such compositions are formulated to enable the removal of, typically food based, soils and stains from soiled tableware under the conditions present in a machine dishwasher. Typically the compositions are low foaming, preferably containing only low levels of low-foaming surfactants.
  • the present compositions contain a water soluble alkali metal silicate.
  • Preferred are the water soluble sodium silicates with an Si ⁇ 2- Na2 ⁇ ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being preferred, and 2.0 ratio being most preferred.
  • the alkali metal silicate may be in the form of either the anhydrous salt or a hydrated salt.
  • Sodium silicate with an Si ⁇ 2- Na2 ⁇ ratio of 2.0 is the most preferred silicate.
  • the alkali metal silicate is present in the detergent compositions in accord with the invention at a level (measured as Si ⁇ 2) of from 1 % to 11 % , preferably from 5% to 10%, most preferably from 6% to 9% by weight.
  • compositions have a pH measured as a 1 % solution in distilled water of from 9.0 to 11.5, preferably from 9.5 to 11.0, most preferably from 9.7 to 10.8.
  • the detergent compositions preferably contain a crystal growth inhibitor component, preferably an organodiphosphonic acid component, incorporated preferably at a level of from 0.01 % to 5% , more preferably from 0.1 % to 1 % by weight of the compositions.
  • organo diphosphonic acid it is meant herein an organo diphosphonic acid which does not contain nitrogen as part of its c. emical structure. This definition he ore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion sequestrant components.
  • the organo diphosphonic acid is preferably a C1-C4 diphosphonic acid, m ⁇ referab « a C2 diphosphonic acid, such as ethylene diphosp z acid, or most preferably eth?"5 1 -hydroxy- 1 ,1- diphosphc;.-c acid (HEDP) and may be pr .nt in partially or fully ionized form, particularly as a salt or complex.
  • compositions most preferably contain an oxygen-releasing bleach system and an Mn(II) compound.
  • the level of available oxygen is preferably controlled.
  • the rate of release of available oxygen and of any peroxide bleaching species is also controlled.
  • a highly preferred ture of the invention is an oxygen-releasing bleaching system.
  • the bleaching system comprises a hydrogen peroxide source and a peroxyacid bleach precursor compound.
  • the production of the peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • Suitable sources of hydrogen peroxide include inorganic perhydrate bleaches.
  • the peroxyacid bleach prec ⁇ r ⁇ or is preferably selected from perbenzoic acid precursors, perbenzoic d derivative precursors, N-acylated lactam bleach precursors and cation.,, peroxyacid precursors, or mixtures thereof.
  • Peroxyacid bleach precursors perbenzoic acid precursors, perbenzoic d derivative precursors, N-acylated lactam bleach precursors and cation.,, peroxyacid precursors, or mixtures thereof.
  • the peroxyacid bleach precursors are preferably incorporated at a level of from 0.5 % to 20% by weight, more preferably from 1 % to 15% by weight, most preferably from 1.5% to 10% by weight of the compositions.
  • N-acylated precursor compounds of the lactam class are disclosed generally in
  • GB-A-855735 Whilst the broadest aspect of the invention contemplates the use of any lactam useful as a peroxyacid precursor, preferred materials comprise the caprolactams and valerolactams.
  • Suitable peroxyacid bleach precursors typically contain one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides and acylated derivatives of imidazoles and oximes, and examples of useful materials within these classes are disclosed in GB-A- 1586789.
  • Suitable esters are disclosed in GB-A-836988, 864798, 1147871 , 2143231 and EP-A-0170386.
  • Useful N-acyl compounds are disclosed in GB-A-855735, 907356 and GB-A-1246338.
  • Preferred precursor compounds of the imide type include the N-,N,N1N tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 , 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
  • TAED Tetraacetyl ethylene diamine
  • Suitable imidazoles include N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group-containing peroxyacid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • Another preferred class of peroxyacid bleach activator compounds are the amide substituted compounds of the following general formulae:
  • R is an alkyl group with from 1 to 14 carbon atoms
  • R ⁇ is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group
  • Rl preferably contains from 6 to 12 carbon atoms.
  • R ⁇ preferably contains from 4 to 8 carbon atoms.
  • Rl may be straight chain or branched alkyl containing branching, substitution, or both and may be sourced from either SV ⁇ -z sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2.
  • substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R$ is preferably H or methyl.
  • Rl and R ⁇ should not contain more than 18 carbon atoms in total.
  • L may be selected from any of the leaving groups described hereinbefore for the analogues having Ri as an aryl or alkaryl group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • Suitable N-acylated lactam precursors have the formula:
  • n is from 0 to about 8, preferably from 0 to 2
  • R is H, an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbons, or a substituted phenyl group containing from 6 to 18 carbon atoms
  • Suitable caprolactam bleach precursors are of the formula:
  • R is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms, most preferably R is phenyl.
  • Suitable valero lactams have the formula:
  • Rl is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from 1 to 12 carbon atoms, preferably from 6 to 12 carbon atoms.
  • Rl is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.
  • the most preferred materials are those which are normally solid at ⁇ 30°C, particularly the phenyl derivatives, i.e. benzoyl valerolactam, benzoyl caprolactam and their substituted benzoyl analogues such as chloro, amino alkyl, alkyl, aryl and alkoxy derivatives.
  • Precursor compounds wherein Ri comprises from 1 to 6 carbon atoms provide hydrophilic bleaching species which are particularly efficient for bleaching beverage stains.
  • Mixtures of 'hydrophobic' and 'hydrophilic' caprolactams and valero lactams, typic? y at weight ratios of 1 :5 to 5: 1 , preferably 1 : 1 can be used herein for mixed stain removal benefits.
  • caprolactam and valerolactam precursors include benzoyl caprolactam, nonanoyl capro-lactam, benzoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl caprolactam, 3,5,5- trimethylhexanoyl valerolactam, octanoyl caprolactam, octanoyl valerolactam, decanoyl caprolactam, decanoyl valerolactam, undecenoyl caprolactam, undecenoyl valerolactam, (6- octanamidocaproyl)oxybenzene-sulfonate, (6- nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)- oxybenzenesulfonate, and mixtures thereof.
  • Examples of highly preferred substituted benzoyl lactams include methylbenzoyl caprolactam, methylbenzoyl valerolactam, ethylbenzoyl caprolactam, ethylbenzoyl valerolactam, propylbenzoyl caprolactam, propylbenzoyl valerolactam, isopropylbenzoyl caprolactam, isopropylbenzoyl valerolactam, butylbenzoyl caprolactam, butylbenzoyl valerolactam, tert-butylbenzoyl caprolactam, tert-butylbenzoyl valerolactam, pentylbenzoyl caprolactam, p r.tylbenzoyl valerolactam, hexylbenzoyl caprolactam, hexylbenzoyl valerolactam, ethoxybenzoyl caprolactam, e
  • any perbenzoic acid precursors are suitable herein, including those of the N-acylated lactam class, which are preferred.
  • O-acylated perbenzoic acid precursor compounds include benzoyl oxybenzene sulfonate and monobenzoyltetraacetyl glucose benzoyl peroxide.
  • Preferred perbenzoic acid precursor-compounds of the imide type include N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas.
  • Preferred perbenzoic acid precursors include the benzoyl diacyl peroxides and benzoyl tetraacyl peroxides.
  • perbenzoic acid precursor compounds are the amide substituted compounds of the following general formulae:
  • R is an aryl group with from 1 to 14 carbon atoms
  • R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Rl preferably contains from 6 to 12 carbon atoms.
  • R2 preferably contains from 4 to 8 carbon atoms.
  • R* may be aryl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R ⁇ .
  • substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • Rl and R ⁇ should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type ar? described in EP-A-0170386.
  • the L group must be sufficiently reactive for the reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • These characteristics are generally paralleled by the pKa of the conjugate acid of the leaving group, although exceptions to this convention aro known. Ordinarily, leaving groups that exhibit such behaviour are those in which their conjugate acid has a pKa in the range of from 4 to 13, preferably from 6 to 11 and most preferably from 8 to 11.
  • Preferred bleach precursors are thos ⁇ e " ⁇ wherein R 1 , R and R 5 are as defined for the amide substituted compounds and L is selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms
  • R is an alkyl chain containing from 1 to 8 carbon atoms
  • R is H or R
  • Y is H or a solubilizing group.
  • the preferred solubilizing groups are -SO3 - M + , -CO2 M 4- , -SO ⁇ ' M 4- , -N + (R 3 ) X " and 0 ⁇ -N(R 3 ) 3 and most preferably -S0 3 ' M + and -CO ⁇ ' M wherein R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
  • bleach activators with a leaving group that does not contain a solubilizing groups should be well dispersed in the bleaching solution in order to assist in their dissolution.
  • perbenzoic acid precursors include:
  • Preformed peracids including:
  • ie perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the perbenzoic group is substituted by essentia ' "y any functional group including alkyl groups.
  • Cationic peroxyacid precursor compounds are also suitable herein.
  • cationic peroxyacid precursors are formed by substituting the peroxyacid part with an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammonium group.
  • Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751 ,015; 4,988,451 ; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5, 106,528; U.K. 1 ,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N- acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • a preferred cationically substituted benzoyl oxybenzene sulfonate is the 4- (trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
  • a preferred cationically substituted alkyl oxybenzene sulfonate is the methyl ammonium derivative of 2,3,3-tri-methyl hexanoyloxybenzene sulfonate.
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam:
  • Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.
  • Betaine ester trimethyl ammonium meta chloro xylenol is also preferred:
  • compositions in accord with the invention include a hydrogen peroxide source.
  • Suitable hydrogen peroxide sources include the inorganic perhydrate salts.
  • the inorganic perhydrate salts are normally incorporated in the form of the sodium salt at a level of from 1 % to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5% to 25% by weight of the compositions.
  • inorganic perhydrate salts include perborate, percarbonate, perphosphat , persulfate and persilicate salts.
  • the inorganic perhydrate salts are normally the alkali metal salts.
  • the inorganic perhydrate salt may be included as the crystalline solid without additional protection.
  • the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.
  • Sodium perborate can be in the form of the monohydrate of nominal formula NaB ⁇ 2H2 ⁇ 2 or the tetrahydrate NaB ⁇ 2H2 ⁇ 2-3H2 ⁇ .
  • Sodium percarbonate which is a preferred perhydrate for inclusion in compositions in accordance with the invention, is an addition compound having a formula typically corresponding to 2Na2C ⁇ 3.3H2 ⁇ 2, and is available commercially as a crystalline solid.
  • the percarbonate is most preferably incorporated into such compositions in a coated form which provides in product stability.
  • a suitable coating material providing in product stability comprises mixed salt of a water soluble alkali metal sulphate and carbonate.
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1 : 200 to 1 : 4, more preferably from 1 : 99 to 1 : 9, and most preferably from 1 : 49 to 1 : 19.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2S ⁇ 4.n.Na2C ⁇ 3 wherein n is form 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
  • coatings which contain silicate (alone or with borate salts or boric acids or other inorganics), waxes, oils, fatty soaps can also be used advantageously within the present invention.
  • Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.
  • compositions may also contain organic peroxyacids, typically at a level of from 1 % to 15 % by weight, more preferably from 1 % to 10% by weight of the composition.
  • organic peroxyacids typically at a level of from 1 % to 15 % by weight, more preferably from 1 % to 10% by weight of the composition.
  • R is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • R- preferably contains from 6 to 12 r ⁇ rbon atoms.
  • R 2 preferably contains from 4 to 8 carbon atoms.
  • R* may . straight cha 1 or branched alkyl, substituted aryl or alkylaryl containing brancning, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 .
  • substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical subst' t groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • Rl 5 should not contain more than 18 carbon atoms in total. Amide ⁇ ituted organic peroxyacid compounds of this type are described in -_. -A-0170386.
  • organic r - oxyacids include diperoxydodecanedioc acid, diperoxytetra di anedioc acid, diperoxyhexadecanedioc acid, mono- and diperazelaic acid, mono- and diperbrassylic acid, monoperoxy pht c acid and its magnesium salt, perbenzoic acid, and their salts as diseased in, for example, EP-A-0341 947.
  • the level of available oxygen in the present compositions should preferab y-b carefully controlled; the level of available oxygen should hence preferabl be in the range from 0.3 % to 2.5 % , preferably from 0.5 % to 1.7%, more preferably from 0.6% to 1.5 % , most preferably from 0.7% to 1.2% , measured according to the method described hereunder.
  • the rate of release of available oxygen is preferably also controlled; the rate of release of available oxygen from the compositions herein preferably should be such that, when using the method described hereinafter, the available oxygen is not completely released from the composition until after 3.5 minutes, preferably the available oxygen is released in a time interval of from 3.5 minutes to 10.0 minutes, more preferably from 4.0 minutes to 9.0 minutes, most preferably from 5.0 minutes to 8.5 minutes.
  • a beaker of water (typically 2L) is placed on a stirrer Hotplate, and the stirrer speed is selected to ensure that the product is evenly dispersed through the solution.
  • the detergent composition typically 8g of product which has been sampled down from a bulk supply using a Pascal sampler
  • the detergent composition is added and simultaneously a stop clock is started.
  • the temperature control should be adjusted so as to maintain a constant temperature of 20°C throughout the experiment.
  • the level of AvO, measured in units of % available oxygen by weight, for the sample at each time interval corresponds to the amount of titre according to the following equation
  • AvO level is plotted versus time to determine the maximum level of AvO, and the rate of release of AvO
  • the rate of release of any organic peroxyacid species is also preferably controlled.
  • the kinetics of release to a wash solution are preferably such that in the T50 test method herein described the time to achieve a concentration that is 50% of the ultimate concentration of the peroxyacid bleach is from 180 seconds to 480 seconds, more preferably from 200 seconds to 400 seconds, most preferably from 240 seconds to 360 seconds.
  • controlled release kinetics or organic peroxyacid herein are defined with respect to a 'TA test method' which measures the time to achieve A% of the ultimate concentration/level of the organic peroxyacid when a composition containing the organic peroxyacid is dissolved according to the standard conditions now set out.
  • the standard conditions involve a 1 litre glass beaker filled with 1000 ml of distilled water at 20°C, to which lOg of composition is added. The contents of the beaker are agitated using a magnetic stirrer set at 100 ⁇ m. The ultimate concentration/level is taken to be the concentration/level maximum level of organic peroxyacid attained after addition of the composition to the water-filled beaker.
  • Suitable analytical methods are chosen to enable a reliable determination of the incidental, and ultimate in solution concentrations of the organic peroxyacid, subsequent to the addition of the composition to the water in the beaker.
  • Such analytical methods can include those involving a continuous monitoring of the level of concentration of the component, including for example photometric and conductrimetric methods.
  • methods involving removing titres from the solution at set time intervals, stopping the dissolution process by an appropriate means such as by rapidly reducing the temperature of the titre, and then determining the concentration of the component in the titre by any means such as chemical titrimetric methods, can be employed.
  • Suitable graphical methods including curve fitting methods, can be employed, where appropriate, to enable calculation of the TA value from raw analytical results.
  • the particular analytical method selected for determining the concentration of the organic peroxyacid component will depend on the nature of that component, and of the nature of the composition containing that component.
  • Controlled rate of release - means
  • a means may be provided for controlling the rate of release of oxygen bleacl o the wash solution.
  • Means for controlling the rate of release of the bleach may provide for controlled release of peroxide species to the wash solution.
  • Such means could, for example, include controlling the release of any inorganic perhydrate salt, acting as a hydrogen peroxide source, to the wash solution.
  • Suitable controlled release means can include coating any suitable component with a coating designed to provide the controlled release.
  • the coating may therefore, for example, comprise a poorly water soluble material, or be a coating of sufficient thicknes: that the kinetics of dissolution of the thick coating provide the controlled rate of release.
  • the coating material may be applied using various methods. Any coating material is typically present at a weight ratio of coating material to bleach of from 1 :99 .o 1:2, preferably from 1 :49 to 1 :9.
  • Suitable coating materials include triglycerides (e.g. partially) hydrogenated vegetable oil, soy bean oil, cotton seed oil) mono or diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and any mixtures thereof.
  • suitable coating materials can comprise the alkali and alkaline earth metal sulphates, silicates and carbonates, including calcium carbonate an silicas.
  • a preferred coating material particularly for an inorganic perhydrate salt bleach source is sodium silicate of S.O2 : Na2 ⁇ ratio from 1.6 : 1 to 3.4 : 1 , preferably 2.2: 1 to 2.8: 1 , applied as an aqueous solution to give a level of from 2% to 10% , (normally from 3 % to 5 %) of silicate solids by weight of the inorganic perhydrate salt.
  • Magnesium silicate can also be included in the coating.
  • Suitable binders include the C10-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole of alcohol and more preferably the C15-C20 primary alcohol ethoxylates containing from 20 - 100 moles of ethylene oxide per mole of alcohol.
  • binders include certain polymeric materials.
  • Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols (PEG) with an average molecular weight of from 600 to 5 x 10 6 preferably 1000 to 400,000 most preferably 1000 to 10,000 are examples of such polymeric materials.
  • Copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the polymer are further examples of polymeric materials useful as binder agents.
  • polymeric materials may be used as such or in combination with solvents such as water, propylene glycol and the above mentioned C10-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole.
  • solvents such as water, propylene glycol and the above mentioned C10-C20 alcohol ethoxylates containing from 5 - 100 moles of ethylene oxide per mole.
  • binders include the C10- C20 mono- and diglycerol ethers and also the C10-C20 f att y acids.
  • Cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts are other examples of binders suitable for use herein.
  • One method for applying the coating material involves agglomeration.
  • Preferred agglomeration processes include the use of any of the organic binder materials described hereinabove. Any conventional agglomerator/mixer may be used including, but not limited to pan, rotary drum and vertical blender types. Molten coating compositions may also be applied either by being poured onto, or spray atomized onto a moving bed of bleaching agent.
  • Suitable means of providing the required controlled release include mechanical means for altering the physical characteristics of the bleach to control its solubility and rate of release. Suitable protocols could include compaction, mechanical injection, manual injection, and adjustment the solubility of the bleach compound by selection of particle size of any particulate component.
  • particle size Whilst the choice of particle size will depend both on the composition of the particulate component, and the desire to meet the desired controlled release kinetics, it is desirable that the particle size should be more than 500 micrometers, preferably having an average particle diameter of from 800 to 1200 micrometers.
  • Additional protocols for providing the mean-, of controlled release include the suitable choice of any other components of the detergent composition matrix such that when the composition is introduced to the wash solution the ionic strength environment therein provided enables the required controlled release kinetics to be achieved.
  • the compositions most preferably contain an Mn(II) compound to inhibit the tarnishing of silverware.
  • the Mn(II) compound is preferably inco ⁇ orated at a level of from 0.005 % t_. 5 % by weight, more preferably from 0.01 % to 1 % , most preferably from 0.02% to 0.4% by weight of t ⁇ e compositions.
  • the Mn(II) compound is incorporated at a 1' . ?1 to provide from 0.1 ppm to 250 ppm, more preferably from 0.5 ppm to 30 ppm, most preferably from 1 ppm to 20 ppm by weight of Mn(II) ions in any bleaching solution.
  • the Mn (II) compound may be an inorganic salt in anhydrous, or any hydrated forms. Suitable salts include manganese sulphate, manganese carbonate, manganese phosphate, manganese nitrate, manganese acetate and manganese chloride.
  • the Mn(II) compound may be a salt or complex of an organic fatty acid such as manganese acetate or manganese stearate.
  • the Mn(II) compound may be a salt or complex of an organic ligand.
  • any salts/complexes are water soluble.
  • the organic ligand is a heavy metal ion sequestrant.
  • the organic ligand is a crystal growth inhibitor component.
  • heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper. ___
  • Suitable heavy metal ion sequestrants include organic amniophosphonates, such as the amino alkylene poly (alkylene phosphonates), and nitrilo trimethylene phosphonates.
  • Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) and hexamethylene diamine tetra (methylene phosphonate).
  • Suitable heavy metal ion sequestrants include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid, and the partially or fully ionized forms thereof.
  • Ethylenediamine disuccinic acid is preferred, most preferably in the form of its S,S isomer.
  • Suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A- 399, 133.
  • iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein.
  • EP-A-476,257 describes suitable amino based heavy metal ion sequestrants.
  • EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein.
  • EP-A-528,859 describes a suitable alkyl imino etic acid sequestrant. Dipicolinic acid and 2-phosphonobutane- 1 ,2,4-mcarboxylic acid are also suitable.
  • Glycinamide-N,N'-disuccinic acid (GADS) is also suitable.
  • the organic ligand may be a crystal growth inhibitor component, particularly an organo diphosphonic acid component as described hereinbefore.
  • compositions of the invention may comprise additional ingredients, which are often quite desirable ones.
  • compositions of the present invention may contain as a highly preferred component a water-soluble builder compound, typically present at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.
  • Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from ea. i other by not more that two carbon atoms, carbonates, bicarbonates, borates, phosphates, and mixtures of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and p -formance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1 ,379,241, lactoxysuccinates described in British Patent No. 1 ,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l , l ,3-propane tricarboxylates described in British Patent No. 1 ,387,447.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1 ,261 ,829, 1 ,1 ,2,2-ethane tetracarboxylates, 1 , 1 ,3,3-propane tetracarboxylates and 1 ,1 ,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1 ,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1 ,439,000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane- cis,cis ⁇ s-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5- tetrahydrofuran - cis - dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates, 1 ,2,3,4,5,6-hexane - hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1 ,425,343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
  • Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions can also be used but are not preferred at wash conditions less that about 50°C, especially less than about 40°C.
  • carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Pattnt Application No. 2,321 ,001 published on November 15, 1973.
  • water-soluble phosphate builders are the alkali me al tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21 , and salts of phytic acid.
  • Partially soluble or insoluble builder compound Partially soluble or insoluble builder compound
  • compositions of the present invention may contain a partially soluble or insoluble builder compound, typically present at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.
  • Examples of partially water soluble builders include the crystalline layered silicates.
  • Examples of largely water insoluble builders include the sodium aluminosilicates.
  • Crystalline layered sodium silicates have the general formula
  • x in the general formula above has a value of 2, 3 or 4 and is preferably 2.
  • the most preferred material is 5-Na2Si2 ⁇ 5, available from Hoechst AG as NaSKS-6.
  • the crystalline layered sodium silicate material is preferably present in granular detergent compositions as a particulate in intimate admixture with a solid, water-soluble ionisable material.
  • the solid, water-soluble ionisable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(Al ⁇ 2) z (Si ⁇ 2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28% , more preferably from 18% to 22% water in bound form.
  • the aluminosilicate ion exchange materials can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeoilte MAP, Zeolite HS and mixtures thereof. Zeolite A has the formula
  • Zeolite X has the formula Na 8 6 KAI ⁇ 2)86(Si ⁇ 2)l06l. 2 ?6 H 2 0.
  • a highly preferred component of the compositions of the invention is a surfactant system comprising surfactant selected from anionic, cationic, nonionic ampholytic and zwitterionic surfactants and mixtures thereof.
  • the surfactant system comprises low foaming surfactant, which is typically nonionic in character.
  • the surfactant system is typically present at a level of from 0.2% to 30% by weight, more preferably from 0.5% to 10% by weight, most preferably Jrom 1 % to 5% by weight of the compositions.
  • Sulphonate and sulphate surfactants are useful herein.
  • Sulphonates include alkyl benzene sulphonates having from 5 to 15 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid testers in which the fatty acid is derived from a C6-C18 fatty source.
  • Preferred sulphate surfactants are alkyl sulphates having from o to 16, preferably 6 to 10 carbon atoms in the alkyl radical.
  • Useful surfactant system comprises a mixture of two alkyl sulphate materials whose respective mean chain lengths differ from each other.
  • the cation in each instance is again an alkali metal, preferably sodium.
  • the alkyl sulfate salts may be derived from natural or synthetic hydrocarbon sources.
  • the C6-C16 alkyl ethoxysulfate salt comprises a primary alkyl ethoxysulfate which is derived from the condensation product of a C - C ⁇ 6 alcohol condensed with an average of from one to seven ethylene xide groups, per mole.
  • Preferred ar the C6-C10 alkyl ethoxysulfate salts with an average of from one to five ethoxy groups per mole.
  • anionic surfactants suitable for the pu ⁇ oses of the invention are the alkali metal sarcosinates of formula
  • R-CON (R 1 ) CH2 COOM wherein R is a C5- 7 linear or branched alkyl or alkenyl group, Ri is a C1-C4 alkyl group and M is an alkali metal ion.
  • R is a C5- 7 linear or branched alkyl or alkenyl group
  • Ri is a C1-C4 alkyl group
  • M is an alkali metal ion.
  • Preferred examples are the lauroyl, Cocoyl (C 12-C 14), myristyl and oleyl methyl sarcosinates in the form of their sodium salts.
  • alkyl ester sulfonate surfactants which include linear esters of C3-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society, " 52 (1975), pp. 323-329.
  • Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
  • the preferred alkyl ester sulfonate surfactants have the structural formula:
  • R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof
  • R 4 is a Cj-C ⁇ hydrocarbyl, preferably an alkyl, or combination thereof
  • M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
  • Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine.
  • R ⁇ is C10-C16 alkyl
  • R ⁇ is methyl, ethyl or isopropyl.
  • the methyl ester sulfonates wherein R 3 is C10-C16 alkyl.
  • One preferred class of low foaming nonionic surfactants useful in the present invention comprises the water soluble ethoxylated C6-C16 fatty alcohols and C6-C16 mixed ethoxylated/propoxylated fatty alcohols and mixtures thereof.
  • the ethoxylated fatty alcohols are the C10- Ci6 ethoxylated fatty alcohols with a degree of ethoxylation of from 3jo__ 50, most preferably these are the C12-C16 ethoxylated fatty alcohols with " a degree of ethoxylation from 3 to 40.
  • the mixed ethoxylated/propoxyiated fatty alcohols have an alkyl chain length of from 10 to 16 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.
  • C6-C16 alcohol itself can be obtained from natural or synthetic sources.
  • C6-C16 alcohols derived from natural fats, or Ziegler olefin build-up, or OXO synthesis can form suitable sources for the alkyl group.
  • synthetically derived materials include Dobanol 25 (RTM) sold by Shf Chemicals (UK) Ltd wh h is a blend of C12-C15 alcohols, Ethyl 24 id by the Ethyl Corporati-. ..
  • Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula
  • Z is a moiety derived from glucose
  • R is a saturated hydrophobic alkyl group that contains from 6 to 16 carbon atoms preferably from 6 to 14 carbon atoms
  • t is from 0 to 10 and n is 2 or 3
  • x is from 1.1 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 0094118.
  • Another preferred nonic.ic surfactant is a polyh ⁇ xy fatty acid amide surfactant compound having the structural formula:
  • R 2 — Cl — N I Z ⁇ z T
  • Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably C ⁇ or C2 alkyl, most preferably C ⁇ alkyl (ie.
  • R 2 is a C5-C15 hydrocarbyl, preferably straight chain C5- 3 alkyl or alkenyl, more preferably straight chain C5-C1 1 alkyl or alkenyl, most preferably straight chain C5-C9 alkyl or alkenyl, or mixture thereof: and Z is a polyhydroxyhydrocarbyl having linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxlylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of -CH2-(CHOH) n -CH2 ⁇ H, -CH(CH2 ⁇ H)-(CHOH) n _ ⁇ - CH2OH, -CH2-(CHOH)2(CHOR')(CHOH)-CH2 ⁇ H, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly - CH2-(CHOH)4-CH2 ⁇ H.
  • Rl can be, for example, N-methyl, N-ethyl, N-propyl, N- isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
  • R 2 -CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, or tallowamide.
  • Z can be l-deoxyglucityl, 2-deoxyfrucittyl, 1-deoxymaltityl, 1- deoxylactityl, 1-deoxygalactityl or 1-deoxymannityl, or 1-deoxymalto- triotityl.
  • Preferred compounds are N-methyl N-ldeoxyglucityl C14-C18 fatty acid amides.
  • a further class of surfactants are the semi-polar surfactants such as amine oxides.
  • Suitable amine oxides are selected from mono C6-C20. preferably C($-C ⁇ Q N-alkyl or alkenyl amine oxides and propylene- 1 ,3- diamine dioxides wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxpropyl groups.
  • Cationic surfactants can also be used in the detergent compositions herein and suitable quaternary ammonium surfactants are selected from mono C6"Cl6. preferably C -Cio N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • compositions may contain narrowly defined levels of a heavy metal ion sequestrant which is not in the form of a Mn(II) compound, such levels being in the range 0.005% to 3%, preferably 0.01 to 1 %, most preferably 0.05% to 0.8%, by weigh, of the total composition.
  • Heavy metal ion sequestrants which are acidic in nature, having for example phosphonic acid or carboxylic acid functionalities, may be present either in their acid form or as a complex/salt with a suitable non Mn(II) counter cation such as an alkali 0 saline metal ion, ammonium, or substituted ammonium ion, or any mi? cs thereof.
  • a suitable non Mn(II) counter cation such as an alkali 0 saline metal ion, ammonium, or substituted ammonium ion, or any mi? cs thereof.
  • the molar ratio of said counter cation to the heavy metal ion sequestrant is preferably at least 1 :1.
  • the heavy metal ion sequestrant may be any of those desc.ibed as suitable heavy metal ion sequestrant-type organic ligands in the Mn(II) compounds section of this description.
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • Preferred EDDS compounds are the free acid form and t a , sodium or magnesium salt or complex thereof.
  • Examples of such preferred sodium salts of EDDS include Na2EDDS and Na3EDDS.
  • Examples of such preferred magnesium complexes of EDDS include MgEDDS and Mg2EDDS.
  • the heavy metal ion sequestrant herein can consist of a mixture of the above described species.
  • Chlorine bleaches include the alkali metal hypochlorites and chlorinated cyanuric acid salts.
  • the use of chlorine bleaches in the composition of the invention is optional and preferably minimized, and more preferably the present compositions contain no chlorine bleach.
  • Another optional ingredient useful in the compositions is one or more additional enzymes.
  • Preferred additional enzymatic materials include the commercially available upases, amylases, neutral and alkaline proteases, esterases, cellulases pectinases, lactases and peroxidases conventionally inco ⁇ orated into detergent compositio: .
  • Suitable enzymes are discussed in US Patents 3,519,570 and 3,533, 139.
  • protease enzymes include those sold under the tradenames lcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes.
  • Protease enzyme may be inco ⁇ orated into the compositions in accordance with the invention at 2 level of from 0.0001 % to 4% active enzyme by weight of the composition.
  • Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B licheniformis, described i more detail in GB- 1,269,839 (Novo).
  • Preferred commercial ⁇ available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S.
  • Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001 % to 2% active enzyme by weight of the composition.
  • Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001 % to 2% by weight, preferably 0.001 % to 1 % by weight, most preferably from 0.001 % to 0.5% by weight of the compositions.
  • the lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein.
  • a preferred lipase is derived from Pseudomonas pseudoalcaligenes. which is described in Granted European Patent, EP-B-0218272.
  • Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza. as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.
  • Preferred enzyme-containing compositions herein may comprise from about 0.001 % to about 10% , preferably from about 0.005% to about 8%, most preferably from about 0.01 % to about 6% , by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme.
  • Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, and mixtures thereof.
  • Such stabilizing systems can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.
  • compositions herein may further comprise from 0 to about 10% , preferably from about 0.01 % to about 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions.
  • chlorine bleach scavengers While chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme during washing is usually large; accordingly, enzyme stability in-use can be problematic.
  • Suitable chlorine scavenger anions are widely available, and are illustrated by salts containing ammonium cations or sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
  • Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), anc mixtures thereof can likewise be used.
  • EDTA ethylenediaminetetracetic acid
  • MEA monoethanolamine
  • scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide sue as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, forme re, lactate, malate, ⁇ rtrate, salicylate, etc. and mixtures thereof can be used if desired.
  • Organic polymeric compounds are particularly preferred componentj of the compositions in accord with the invention.
  • organic polymeric compound it is meant essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents. jn detergent compositions.
  • Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0. . 7 o to 30% , preferably from 0.5% to 15%, most preferably from 1 % to 10% by weight of the compositions.
  • organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carb- - atoms.
  • Polymers of the latter type are disclosed in GB-A- 1 ,5: 756.
  • salts are polyacrylates of molecular weight 2000-10000 and their copolymers with any suitable other monomer units including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixtures thereof.
  • Preferred are the copolymers of acrylic acid and maleic anhydride having a molecular weight of from 20,000 to 100,000.
  • Preferred commercially available acrylic acid containing polymers having a molecular weight below 15,000 include those sold under the tradename Sokalan PA30, PA20, PA 15, PA 10 and Sokalan CP10 by BASF GmbH, and those sold under the tradename Acusol 45N by Rohm and Haas.
  • Preferred acrylic acid containing copolymers include those which contain as monomer units: a) from 90% to 10% , preferably from 80% to 20% by weight acrylic acid or its salts and b) from 10% to 90% , preferably from 20% to 80% by weight of a substituted acrylic monomer or its salts having the general formula -[CR2-CR ⁇ (CO-0-R3)J- wherein at least one of the substituents R ⁇ , R2 or R3, preferably R ⁇ or R2 is a 1 to 4 carbon alkyl or hydro xyalkyl group, R ⁇ or R2 can be a hydrogen and R3 can be a hydrogen or alkali metal salt.
  • R ⁇ is methyl
  • R2 is hydrogen (i.e. a methacrylic acid monomer).
  • the most preferred copolymer of this type has a molecular weight-of 3500 and contains 60% to 80% by weight of acrylic acid and 40% to 20% by weight of methacrylic acid.
  • suitable polyacrylate/modified polyacrylate copolymers include those copolymers of unsaturated aliphatic carboxylic acids disclosed in U.S. Patents No.s 4,530,766, and 5,084,535 which have a molecular weight of less than 15,000.
  • Suitable organic polymeric compounds include the copolymers of acrylamide and acrylate having a molecular weight of from 3,000 to 100,000, and the acrylate/fumarate copolymers having a molecular weight of from 2,000 to 80,000.
  • the polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
  • organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose.
  • organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.
  • compositions of the invention may contain a lime soap dispersant compound, which has a lime soap dispersing power (LSDP), as defined hereinafter of no more than 8, preferably no more than 7, most preferably no more than 6.
  • LSDP lime soap dispersing power
  • the lime soap dispersant compound is preferably present at a level of from 0.1 % to 40% by weight, more preferably 1 % to 20% by weight, most preferably from 2% to 10% by weight of the compositions.
  • a lime soap dispersant is a material that prevents the precipitation of alkali metal, ammonium or amine salts of fatty acids by calcium or magnesium ions.
  • a numerical measure of the effectiveness of a lime soap dispersant is given by the lime soap dispersing power (LSDP) which is determined using the lime soap dispersion test as described in an article by H.C. Borghetty and CA. Bergman, J. Am. Oil. Chem. Soc, volume 27, pages 88-90, (1950).
  • This lime soap dispersion test method is widely used by practitioners in this art field being referred to , for example, in the following review articles; W.N. Linfield, Surfactant Science Series, Volume 7, p3; W.N. Linfield, Tenside Surf. Det.
  • Surfactants having good lime soap dispersant capability will include certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated alcohols.
  • Polymeric lime soap dispersants suitable for use herein are described in the article by M.K. Nagarajan and W.F. Masler, to be found in Cosmetics and Toiletries, Volume 104, pages 71-73, (1989).
  • Examples of such polymeric lime soap dispersants include certain water-soluble salts of copolymers of acrylic acid, methacrylic acid or mixtures thereof, and an acrylamide or substituted acrylamide, where such polymers typically have a molecular weight of from 5,000 to 20,000.
  • compositions of the invention when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01 % to 15% , preferably from 0.05% to 10% , most preferably from 0.1 % to 5% by weight of the composition.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds, 2-alkyl and alcanol antifoam compounds.
  • antifoam compound any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.
  • Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound includirg a silicone component.
  • Such silicone antifoam compounds also typically contain a silica component.
  • Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.
  • Suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. Th monocarboxylic fatty acids, and salts thereof, for use as suds suppre: typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • Suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acio triglycerides), fatty acid esters of monovalent alcohols, aliphatic C 18-C40 ke ones (e.g. stearone) N- alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
  • high molecular weight fatty esters e.g. fatty acio triglycerides
  • fatty acid esters of monovalent alcohols e.g. fatty acid esters of monovalent alcohols
  • Copolymers of ethylene oxide and propylene oxide are also suitable antifoam compounds for use herein.
  • Suitable 2-alky-alcanols antifoam compounds for use herein have been described in DE 40 21 265.
  • the 2-alkyl-alcanols suitable for use herein consist of a C6 to C i6 alkyl chain carrying a terminal hydroxy group, and said alkyl chain is substituted in the a position by a C ⁇ to C[ Q alkyl chain. Mixtures of 2-alkyl-alcanols can be used ⁇ n the compositions according to the present invention.
  • a preferred suds suppressing system comprises
  • antifoam compound preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination
  • silica at a level of from 1 % to 50% , preferably 5% to 25% by weight of the silicone/silica antifoam compound;
  • silica/silicone antifoam compound is inco ⁇ orated at a level of from 5% to 50% , preferably 10% to 40% by weight;
  • a dispersant compound most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1 : 1.1 , at a level of from 0.5% to 10% , preferably 1 % to 10% by weight;
  • a particularly preferred silicone glycol rake copolymer of this type is DC0544, commercially available from DOW Corning under the tradename DC0544;
  • an inert carrier fluid compound most preferably comprising a C ⁇ - Cj8 ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70% , by weight;
  • a preferred particulate suds suppressor system useful herein comprises a mixture of an alkylated siloxane of the type hereinabove disclosed and solid silica.
  • the solid silica can be a fumed silica, ajirecipitated silica or a silica, made by the gel formation technique.
  • the silica particles suitable have an average particle size of from 0.1 to 50 micrometers, preferably from 1 to 20 micrometers and a surface area of at least 50m 2 /g. These silica particles can be ⁇ ndered hydrophobic by treating them with dialkylsilyl groups and/or groups either bonded directly onto the silica or by means of a silicone resin. It is preferred to employ a silica the particles of which have been rendered hydrophobic with dimethyl and/or trimethyl silyl groups.
  • a preferred particulate antifoam compound for inclusion in the detergent compositions in accordance with the invention suitably contain an amount of silica such that the weight ratio of silica to silicone lies u. the range from 1 : 100 to 3: 10, preferably from 1 :50 tc 1 :7.
  • Another suitable particulate suds suppressing system is represented by a hydrophobic silanated (most preferably trimethyl-silanated) silica having a particle size in the range from 10 nanometers to 20 nanometers and a specific surface area above 50m 2 /g, intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 1 : 1 o about 1 :2.
  • a hydrophobic silanated (most preferably trimethyl-silanated) silica having a particle size in the range from 10 nanometers to 20 nanometers and a specific surface area above 50m 2 /g, intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 1 : 1 o about 1 :2.
  • a highly preferred particulate suds suppressing system is described in EP- A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85 °C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms.
  • EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45 °C to 80°C.
  • An exemplary particulate suds suppressing system for use herein is a particulate agglomerate component, made by an agglomeration process, comprising in combination
  • agglomerate binder compound (iii) from 5 % to 30% , preferably from 10% to 20% by weight of the component of agglomerate binder compound, where herein such compound can be any compound, or mixtures thereof typically employed as binders for agglomerates, most preferably said agglomerate binder compound comprises a ethoxylated alcohol with a degree of ethoxylation of from 50 to 100; and
  • compositions herein may also comprise from 0.01 % to 10 % , preferably from 0.05% to 0.5 % by weight of polymeric dye transfer ⁇ ⁇ inhibiting agents.
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
  • compositions may contain, but preferably do not contain, additional corrosion inhibitor inhibitors such as benzotriazole and paraffin.
  • compositions of the invention can be formulated in any desirable form such as powders, granulates, pastes, liquids, gels and tablets, granular forms being preferred.
  • the bulk density of the granular detergent compositions in accordance with the present invention is typically of at least 650 g/litre, more usually at least 700 g/litre and more preferably from 800 g/litre to 1200 g/litre.
  • Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrial cup disposed below the funnek
  • the funnel is 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base.
  • the cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
  • the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup.
  • the filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement e.g. a knife, across its upper edge.
  • the filled cup is then weighed and the value obtained for the weight of powder doubled to provide the bulk density in g/litre ⁇ Z Replicate measurements are made as required.
  • the particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5% of particles are greater than 1.4mm in diameter and not more than 5 % of particles are less than 0.15mm in diameter.
  • the liquid should be thixotropic (ie; exhibit high viscosity when subjected to low stress and lower viscosity when subjected to high stress), or at least have very high viscosity, for example, of from 1 ,000 to 10,000,000 centipoise.
  • a viscosity control agent or a thixotropic agent to provide a suitable liquid product form.
  • Suitable thixotropic or viscosity control agents include methyl cellulose, carboxymethylcellulose, starch, polyvinyl, pyrrolidone, gelatin, colloidal silica, and natural or synthetic clay minerals.
  • Pasty compositions in accordance with the invention generally have viscosities of about 5,000 centipoise and up to several hundred million centipoise.
  • a small amount of a solvent or solubilizing agent or of a gel-forming agent can be included. Most commonly, water is used in this context and forms the continuous phase of a concentrated dispersion. Certain nonionic surfactants at high levels form a gel in the presence of small amount of water and other solvents. Such gelled compositions also envisaged in the present invention.
  • Any suitable methods for washing or cleaning soiled tableware, including soiled glassware and silverware, are envisaged including machine dishwashing methods.
  • a preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware, silverware and cutlery and mixtures thereof, with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine dishwashing composition in accord with the inevntion.
  • an effective amount of the machine dishwashing composition it is meant from 8g to 60g of product dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine dishwashing methods.
  • the abbreviated component identifications have th° following meanings:
  • Nonionic C 13-C15 mixed ethoxylated/propoxyiated fatt alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 sold under the tradename Plurafac LF404 by BASF Gmbh (low foaming)
  • Percarbonate Anhydrous sodium percarbonate bleach of empirical formula 2Na2C ⁇ 3.3H2 ⁇ 2 coated with a mixed salt of formula Na2S ⁇ 4.n.Na2C ⁇ 3 where n is 0.29 and where the weight ratio of percarbonate to mixed salt is 39: 1
  • Paraffin Paraffin oil sold under the tradename Winog 70 by Wintershall.
  • Protease Proteolytic enzyme sold under the tradename Savinase by Novo Industries A/S (approx 2% enzyme activity).
  • Alcalase Proteolytic enzyme sold by Novo Industries A/S under the tradename Alcalase 2T (approximately 2% enzyme activity)
  • Amylase Amylolytic enzyme sold under the tradename Termamyl 60T by Novo Industries A/S (approx 0.9% enzyme activity)
  • Lipase Lipolytic enzyme sold under the tradename Lipolase by Novo Industries A/S (approx 2% enzyme activity) DETPMP Diethyler - triamine penta (methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060
  • composition A is a prior art composition
  • compositions B to F are in accord with the invention.
  • compositions B and C of Example I were compared for glasscare performance, to a ference composition (composition A of Example I).
  • I ne testing involved complete immersion of s. clear glass beakers in a 1 % product solution of each of compositions A to C at 65 °C for 168 hours. This test is believed to be representative of the conditions which would be experienced in 504 complete 20 minute wash cycles in a machine dishwasher. Performance was graded by 4 expert panellists through visual inspection according to a scale of from 2 to 10 where:
  • Results were as follows : (average of the 4 gradings from the panellists)
  • composition A Composition B Composition B
  • the following base machine dishwashing detergent compositions were prepared (parts by weight).
  • Example I base composition A of Example I was compared for anti-silver tarnishing performance to reference compositions G and H containing 0.13 % MnS04 and 0.13 % Mn(II)EDDS respectively.
  • the testing involved machine testing, using a Bosch Siemens dishwasher, 20g product dosage, 65 °C economy cycles, and 14 cycles.
  • Silver tarnishing performance was graded by 4 expert pan e llists through visual inspection according to the following scale :
  • Results were as follows : (average of the 4 gradings from the panellists)
  • Composition A Composition B Compositic"; C
  • Composition A also showed a satisfactory glasscare profile in accord with the invention.

Abstract

La composition détergente destinée à être utilisée dans les lave-vaisselle réduit la tendance à la dégradation des verres. Cette composition détergente contient du silicate de sodium à un niveau (mesure de SiO2) compris entre 1 % et 11 % en poids, ladite composition ayant un pH mesuré en solution à 1 % d'eau distillée à 20 °C compris entre 9,0 et 11,5. De préférence, la composition contient un inhibiteur de croissance des cristaux. Lorsque la composition contient un système de blanchiment à libération d'oxygène, elle contient aussi un composé Mn(II) afin de réduire la propension au ternissement de l'argent.
EP95901074A 1993-11-03 1994-10-28 Compositions detergentes Withdrawn EP0726933A4 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US14722293A 1993-11-03 1993-11-03
US147222 1993-11-03
GB9418572A GB2283494A (en) 1993-11-03 1994-09-15 Machine dishwashing
GB9418572 1994-09-15
PCT/US1994/012405 WO1995012652A1 (fr) 1993-11-03 1994-10-28 Compositions detergentes

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EP0726933A1 true EP0726933A1 (fr) 1996-08-21
EP0726933A4 EP0726933A4 (fr) 1997-01-22

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TR199700936T1 (xx) * 1995-03-11 1998-02-21 The Procter & Gamble Company Hidrojen peroksit kayna�� ve proteaz enzimini i�eren deterjan bile�imi.
GB9513990D0 (en) * 1995-07-08 1995-09-06 Procter & Gamble Detergent compositions
DE19860670A1 (de) * 1998-12-29 2000-08-10 Benckiser Nv Wasserlösliches Glas als Korrosionsschutz in einer Geschirrspülmaschine
US8114344B1 (en) 2010-12-21 2012-02-14 Ecolab Usa Inc. Corrosion inhibition of hypochlorite solutions using sugar acids and Ca
US8557178B2 (en) 2010-12-21 2013-10-15 Ecolab Usa Inc. Corrosion inhibition of hypochlorite solutions in saturated wipes
US8603392B2 (en) 2010-12-21 2013-12-10 Ecolab Usa Inc. Electrolyzed water system
EP2890771A1 (fr) * 2012-08-28 2015-07-08 Henkel AG&Co. KGAA Produit pour laver la vaisselle contenant un alkyléthersulfate
WO2014158490A1 (fr) 2013-03-14 2014-10-02 Ecolab Usa Inc. Détergent contenant des enzymes et composition de prétrempage et procédés d'utilisation

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EP0145090A2 (fr) * 1983-12-06 1985-06-19 Unilever N.V. Compositions détergentes et de blanchiment
EP0518719A1 (fr) * 1991-05-31 1992-12-16 Colgate-Palmolive Company Composition liquide non aqueuse contenant des enzymes pour le lavage automatique de la vaisselle

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BE792851A (fr) * 1971-12-17 1973-06-15 Henkel & Cie Gmbh Agents de lavage, de rincage et de nettoyage
GR76237B (fr) * 1981-08-08 1984-08-04 Procter & Gamble
IS1740B (is) * 1982-02-05 1999-12-31 Albright & Wilson Uk Limited Samsetning á hreinsivökva
US4623357A (en) * 1985-04-02 1986-11-18 Lever Brothers Company Bleach compositions

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Publication number Priority date Publication date Assignee Title
EP0145090A2 (fr) * 1983-12-06 1985-06-19 Unilever N.V. Compositions détergentes et de blanchiment
EP0518719A1 (fr) * 1991-05-31 1992-12-16 Colgate-Palmolive Company Composition liquide non aqueuse contenant des enzymes pour le lavage automatique de la vaisselle

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Title
See also references of WO9512652A1 *

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WO1995012652A1 (fr) 1995-05-11

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