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WO1996006157A1 - Composition detergente de blanchiment - Google Patents

Composition detergente de blanchiment Download PDF

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Publication number
WO1996006157A1
WO1996006157A1 PCT/EP1995/003308 EP9503308W WO9606157A1 WO 1996006157 A1 WO1996006157 A1 WO 1996006157A1 EP 9503308 W EP9503308 W EP 9503308W WO 9606157 A1 WO9606157 A1 WO 9606157A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
aryl
weight
bleach
optionally substituted
Prior art date
Application number
PCT/EP1995/003308
Other languages
English (en)
Inventor
Anna Leonarda M. Van Asperen
Joseph Reinoldus Maria Holterhues
Johann Bernhard Warnaar
Thomas WEYHERMÜLLER
Karl Wieghardt
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 AU33866/95A priority Critical patent/AU3386695A/en
Publication of WO1996006157A1 publication Critical patent/WO1996006157A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—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 concentrated detergent powder compositions. More particularly, the invention relates to improved, concentrated and highly concentrated, also called super-concentrated, heavy duty laundry detergent bleach powder compositions.
  • detergent powder composition refers to particulate detergent compositions consisting of granules or particles or mixtures thereof, of a size which, as a whole, will have the appearance of a powdered composition.
  • highly concentrated deter- gent powder compositions having a bulk density of at least 650 g/1 to even above 750 g/1 have been commercialised.
  • Non-functional ingredients are ingredients not really essential to the washing performance; an example of such ingredient is sodium sulphate.
  • Minimizing the amount of air in the product and packet can be achieved by densifying and shaping the particles so as to reduce the specific volume of the product, i.e. increasing the bulk density.
  • Essential ingredients in the formulation of modern heavy duty detergent compositions are bleaching agents for the removal of bleachable stains.
  • the bleach system as generally used in concentrated and highly concentrated detergent powder formulations consists of a mixture of a peroxygen bleach compound, e.g. sodium perborate mono- or tetrahydrate, particularly the monohydrate, or sodium percarbonate, and a peroxyacid bleach precursor, e.g. tetraacetylethylene dia ine (TAED) .
  • a peroxygen bleach compound e.g. sodium perborate mono- or tetrahydrate, particularly the monohydrate, or sodium percarbonate
  • TAED tetraacetylethylene dia ine
  • the required level of sodium perborate or other peroxygen compound in such compositions will be from about 10 to 25% by weight, and the peroxyacid bleach precursor, e.g. TAED, is generally present at a level of from 2 to 10% by weight, making up to a total level of bleach system of from about 12 to 35% by weight of the composition.
  • the peroxyacid bleach precursor e.g. TAED
  • EP-A-509,787 discloses a concentrated detergent powder formulation comprising a surfactant, a detergency builder, a peroxygen bleach compound, and additionally a triazacyclononane-based manganese complex bleach catalyst.
  • a surfactant e.g., a surfactant for reacting with the peroxygen compound forming the corresponding peroxyacid
  • a peroxygen bleach compound e.g., a peroxygen bleach compound
  • a triazacyclononane-based manganese complex bleach catalyst e.g., the bleach catalysts disclosed by EP-A-509,787 work differently and are effec ⁇ tive already in very small amounts.
  • R 5 and R 6 are each independently selected from H, NR 8 and OR 9 , alkyl, aryl, optionally substituted and R 7 , R 8 and R 9 are each independently selected from H, alkyl, aryl, both optionally substituted.
  • the present invention relates to a concentrated detergent powder composition having a bulk density of above 600 g/1, comprising: (a) from 10 to 50% by weight of a surface active material;
  • bleach catalyst characterised in that said bleach catalyst is a dinuclear manganese complex having the formula:
  • Mn is manganese which can individually be in the III or IV oxidation state
  • X 2 , X 2 and X 3 each independently represent a coordinating or bridging species selected from the group consisting of H 2 0, 0 2 2" , O 2 ", OH “ , H0 2 ⁇ , SH “ , S 2" , >S0, Cl “ , N 3 ⁇ , SCN “ , RCOO “ , RSO “ 3 , RB0 2 2- , NH 2 " and NR 3 , with R being H, alkyl, aryl, both optionally substituted, R'COO " where R' is alkyl, aryl, both optionally substituted; L is a ligand which is an organic molecule containing at least three nitrogen atoms which coordinates via all or some of the nitrogen atoms to the manganese centres; z denotes the charge of the complex and is an integer which can be positive or negative;
  • the bleach catalyst comprises two ligands having the formula:
  • R 1 and R 2 are each independently selected from H, alkyl, aryl, both optionally substituted;
  • R 3 is independently selected from hydrogen, alkyl, aryl both optionally substituted, with the proviso that a bridging unit R 4 is formed by one R 3 unit from each ligand where R 4 is the group C n R 5 R 6 -(D) p -C m R 5 R 6 where p is zero or one;
  • D is selected from a heteroatom or a heteroatom containing group, such as oxygen and NR 7 , or is part of an aromatic or saturated homonuclear or heteronuclear ring; n is an integer from 1 to 4; m is an integer from 1 to 4; with the proviso that n + m ⁇ 4;
  • R 5 and R 6 are each independently selected from H, NR 8 and OR 9 , alkyl, aryl, optionally substituted and R 7 , R 8 and R 9 are each independently selected from H, alkyl, aryl, both optionally substituted.
  • the present invention is not concerned with these con ⁇ centration and densifying production methods per se.
  • the concentrated powder compositions of the invention can be obtained on the basis of any of the densifying and compac ⁇ ting methods known in the art; in such processes the bleach component including the catalyst is normally dry-mixed with the densified powder as one of the last steps of the manufacturing process.
  • the invention is of particular advantage to concentrated detergent powder compositions having a bulk density within the range of from 650 g/1 to about 1200 g/1, preferably from 750 g/1 to 1000 g/1.
  • the bleach catalyst is the bleach catalyst
  • the manganese complexes which may be included in the deter- gent bleach composition of the present invention are reported in EP-A-544,490. These complexes were found to be not only unusually effective but also remarkably storage stable bleach and oxidation catalysts. In the further description of the invention they will also be referred to as the "bleach catalyst”" or simply "catalyst”.
  • the concentration of the bleach catalyst in the detergent bleach composition of the invention is from 0.004 to 1.0%, preferably from 0.008 to 0.5% by weight.
  • Suitable ligands in their simplest form which may be present in the bleach catalysts are:
  • Tris(Triazol-l-yl)methane (iii) Tris(pyridin-2-yl)borate; Tris(triazol-1-yl)borate;
  • ligands which may be optionally substituted on the amine N-atom and/or the CH 2 carbon atom and/or the aromatic ring, are all connected to another ligand by a bridging unit as mentioned in the definition of the invention. Bleach catalysts containing thus connected ligands with different chemical structure, are within the scope of the invention.
  • ligand is especially preferred: l,2-bis(4,7-dimethyl-l,4,7-triaza-l-cyclonoyl) ethane (Et-bridged(Me 2 TACN) 2 ) .
  • 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; sulphate; nitrate; methylsulphate; surfac- tant-anions, such as the long-chain alkylsulphates, alkyl- sulphonates, alkylbenzenesulphonates, tosylate; trifluor- methylsulphonate; perchlorate (C10 4 ⁇ ) , BF 4 " and PF 6 " , though some counter-ions are more preferred than others for reasons of product property and safety.
  • the most preferred manganese complex as used in the present invention is:
  • the level of peroxy bleaching agents in the detergent bleach compositions of the invention is in the range of from 5 to 35%, preferably from 10 to 25% by weight.
  • peroxy bleaching agents may be compounds which are capable of yielding hydrogen peroxide in aqueous solution.
  • Hydrogen peroxide sources are well known in the art. They include the alkali metal peroxides, organic peroxides such as urea peroxide, and inorganic persalts, such as the alkali metal perborates, percarbonates, perphosphates persilicates and persulphates. Mixtures of two or more such compounds may also be suitable. Particularly preferred are sodium perborate tetrahydrate and, especially, sodium perborate monohydrate. Sodium perborate monohydrate is preferred because of its high active oxygen content. Sodium percarbonate may also be preferred for environmental reasons.
  • Alkylhydroxy peroxides are another class of peroxy bleaching agents. Examples of these materials include cu ene hydroperoxide and t-butyl hydroperoxide.
  • Organic peroxyacids may also be suitable as the peroxy bleaching agent.
  • Such materials normally have the general formula:
  • R is an alkylene or substituted alkylene group containing from 1 to about 20 carbon atoms, optionally having an internal amide linkage; or a pheylene or substituted phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an imido-aro atic or non-aromatic group, a C00H or
  • Typical onoperoxy acids useful herein include, for example:
  • aliphatic, substituted aliphatic and arylalkyl monoperoxyacids e.g. peroxylauric acid, peroxys- tearic acid and N,N-phthaloylaminoperoxy caproic acid (PAP) ; and (iii) 6-octylamino-6-oxo-peroxyhexanoic acid.
  • diperoxyacids useful herein include, for example: (iv) 1, 12-diperoxydodecanedioic acid (DPDA) ; (v) 1,9-diperoxyazelaic acid;
  • diperoxybrassilic acid diperoxysebasic acid and diperoxyisophthalic acid
  • diperoxybrassilic acid diperoxysebasic acid and diperoxyisophthalic acid
  • diperoxyisophthalic acid diperoxyisophthalic acid
  • 2-decyldiperoxybutane-l,4-diotic acid 2-decyldiperoxybutane-l,4-diotic acid
  • 4, 4 '-sulphonylbisperoxybenzoic acid 4, 4 '-sulphonylbisperoxybenzoic acid.
  • inorganic peroxyacid compounds are suitable, such as for example potassium monopersulphate (MPS) . If organic or inorganic peroxyacids are used as the peroxygen compound, the amount thereof will normally be within the range of about 2-10 % by weight, preferably from 4-8 % by weight.
  • MPS potassium monopersulphate
  • All these peroxide compounds may be utilized alone or in conjunction with a peroxyacid bleach precursor and/or an organic bleach catalyst not containing a transition metal.
  • Peroxyacid bleach precursors are known and amply described in literature, such as in the British Patents 836988; 864,798; 907,356; 1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522; EP-A-0174132; EP-A-0120591; and US Patents 1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.
  • peroxyacid bleach precursors are that of the cationic i.e. quaternary ammonium substituted peroxyacid precursors as disclosed in US Patent 4,751,015 and 4,397,757, in EP-A0284292 and EP-A-331,229.
  • peroxyacid bleach precursors of this class are: 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphonphenyl carbonate chloride - (SPCC) ;
  • a further special class of bleach precursors is formed by the cationic nitriles as disclosed in EP-A-303,520 and in European Patent Specification No. 's 458,396 and 464,880.
  • any one of these peroxyacid bleach precursors can be used in the present invention, though some may be more preferred than others.
  • the preferred classes are the esters, including acyl phenol sulphonates and acyl alkyl phenol sulphonates; the acyl-amides; and the quaternary ammonium substituted peroxyacid precursors including the cationic nitriles.
  • Examples of said preferred peroxyacid bleach precursors or activators are sodium-4-benzoyloxy benzene sulphonate (SBOBS) ; N,N,N'N'-tetraacetyl ethylene dia ine (TAED); sodium-l-methyl-2-benzoyloxy benzene-4-sulphonate; sodium- 4-methyl-3-benzoloxy benzoate; SPCC; trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3 ,5,5-trimethyl hexanoyloxyben- zene sulphonate (STHOBS) ; and the substituted cationic nitriles.
  • SBOBS sodium-4-benzoyloxy benzene sulphonate
  • TAED N,N,N'N'-tetraacetyl ethylene dia ine
  • TAED sodium-l-methyl-2
  • the precursors may be used in an amount of up to 12 %, preferably from 2-10 % by weight, of the composition.
  • the composition may also additional ⁇ ly include an organic bleach catalyst of the sulfonimine type, as disclosed in EP-A-453,002 and EP-A-446,982.
  • the detergent bleach compositions of the invention general ⁇ ly contain surface-active material in an amount of from 10 to 50% by weight.
  • Said surface-active material may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof.
  • ac ⁇ tives are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
  • Typical synthetic anionic surface-actives are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher aryl radicals.
  • suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulphates, especially those obtained by sulphating higher (C 8 -C 18 ) alcohols produced, for example, from tallow or coconut oil; sodium and am ⁇ monium alkyl (C 9 -C 10 ) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 -C 15 ) benzene sul ⁇ phonates; sodium alkyl glyceryl ether sulphates, especially those ester of the higher alcohols derived from tallow or coconut oil fatty acid monoglyceride sulphates and sul ⁇ phonates; sodium and ammonium salts of sulphuric acid esters of higher (C 9 -C 18 ) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction products; the reac ⁇ tion products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and ammonium salts of fatty acids
  • nonionic surface-active compounds which may be used, preferably together with the anionic surface-active compounds, include, in particular, the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C 6 -C 22 ) phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule; and the conden ⁇ sation products of aliphatic (C 8 -C 1B ) primary or secondary linear or branched alcohols with ethylene oxide, generally 2-30 EO.
  • alkylene oxides usually ethylene oxide
  • alkyl (C 6 -C 22 ) phenols generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule
  • conden ⁇ sation products of aliphatic (C 8 -C 1B ) primary or secondary linear or branched alcohols with ethylene oxide generally 2-30 EO.
  • nonionic surface-actives include alkyl polyglycosides, sugar esters, long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulphoxides.
  • Amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic actives.
  • the performance of the hereinbefore described bleach catalyst may be dependent upon the active detergent system and the builder system present in the detergent bleach composition of the inven ⁇ tion.
  • the detergent bleach composition of the invention comprises from 10 to 50% by weight of a surface active agent.
  • Said composition will preferably comprise from 1-15 % wt of anionic surfactant and from 10-40 % by weight of nonionic surfactant.
  • the detergent active system is free from C 16 -C 12 fatty acids soaps.
  • the detergent composition of the invention also contains a detergency builder in an amount of from about 15-80 % by weight, preferably from about 10-60 % by weight.
  • Builder materials may be selected from 1) calcium se ⁇ questrant materials, 2) precipitating materials, 3) caladium ion-exchange materials and 4) mixtures thereof.
  • Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid and its water- soluble salts; the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuc- cinic acid, mellitic acid, benzene polycarboxylic acids, 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 and its water- soluble salts the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuc- cinic acid, mellitic acid, benzene polycarboxylic acids, citric acid
  • polyacetal carboxylates as disclosed in US Patents 4,144,226 and
  • precipitating builder materials examples include sodium orthophosphate and sodium carbonate.
  • Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amor ⁇ phous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also know as Zeolite P) , zeolite C, zeolite X, zeolite Y and also the zeolite P type as described in EP-A-0384070.
  • zeolites are the best known representatives, e.g. zeolite A, zeolite B (also know as Zeolite P) , zeolite C, zeolite X, zeolite Y and also the zeolite P type as described in EP-A-0384070.
  • compositions of the invention may con- tain any one of the organic and inorganic builder materials, though, for environmental reasons, phosphate builders are preferably omitted or only used in very small amounts.
  • Typical builders usable in the present invention are, for example, sodium carbonate, calcite/carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, car- boxymethyloxy malonate, carboxymethyloxy succinate and the water-insoluble crystalline or amorphous aluminosilicate builder material, each of which can be used as the main builder, either alone or in admixture with other builders or polymers as co-builder.
  • the composition contains not more than 5% by weight of a carbonate builder, expressed as sodium carbonate, more preferable not more than 2.5 % by weight to substantially nil, if the composition pH lies in the lower alkaline region of up to 10.
  • Enzymes are preferably present in the composition of the invention in an amount ranging from 0.001 to 5% by weight, more preferably from 0.01 to 3% by weight, depending upon their activity.
  • the enzymes are generally incorporated in the form of granules, prills or "marumes".
  • the amount is such that the final detergent product has a proteolytic activity of about 2-20 Anson units per kilogram of final product.
  • the types of enzymes applied in the detergent composition of the invention may be proteolytic, amylolytic, cel- lulolytic, or lipolytic enzymes, or mixtures thereof.
  • Preferred enzymes are proteolytic enzymes.
  • proteolytic enzymes which are suitable for use in the present invention are catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains, in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal or yeast origin. They comprise natural types of enzyme and genetically engineered variants.
  • proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4- 12 are available and can be used in the composition of the invention.
  • suitable proteolytic enzymes are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis, such as the commercially available subtilisins Maxatase , as supplied by Gist- Brocades N.V. Delft, Holland, and Alcalase , as supplied by Novo Industri A/S, Copenhagen, Denmark.
  • protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, and being commercially available, e.g. from Novo Industri A/S under the registered trade names Esperase and Savinase .
  • the preparation of these and analogous enzymes is described in British Patent Specification 1,243,784.
  • suitable proteases are pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, papain, bro elin, carboxypeptidases A and B, aminopeptidase and aspergillopeptidases A and B.
  • the detergent bleach compositions of the invention can contain any of the conventional additives in amounts of which such materials are normally employed in fabric washing detergent com ⁇ positions.
  • these additives include buffers such as carbonates, lather boosters, such as alkanolamides, particularly the monoethanol amides derived from palmkernel fatty acids and coconut fatty acids; lather depressants, such as alkyl phosphates and silicones; anti-redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers; stabilizers, such as phosphonic acid derivatives (i.e. Dequest® types); fabric softening agents; inorganic salts and alkaline buffering agents, such as sodium sulphate, sodium silicate etc. ; and usually in very small amounts, fluorescent agents; per ⁇ fumes; germicides and colourants.
  • buffers such as carbonates
  • lather boosters such as alkanolamides, particularly the monoethanol amides derived from palmkernel
  • the composition contains not more than 5 % by weight of a carbonate buffer, expressed as sodium car ⁇ bonate, more preferable not more than 2.5% by weight to substantially nil, if the composition pH lies in the lower alkaline region of up to 10.
  • a hydrogenperoxide source such as sodium per ⁇ borate or sodium percarbonate
  • transition metal sequestrants such as EDTA and the phosphonic acid derivatives, e.g. ethylene diamine tetra-(methylene phosphonate) -EDTMP- are of special importance, as not only do they improve the stability of the catalyst/H 2 0 2 system and sensitive ingredients, such as enzymes, fluorescent agents, perfumes and the like, but also improve the bleach performance, especially at the higher pH region of above 10, particularly at pH 10.5 and above.
  • detergent bleach compositions comprising a surface-active material, a peroxide bleaching agent, the manganese complex bleach catalyst, a carbonate builder and a transition metal sequestrant, having pH in solution of above 10, especially of 10.5 and above, are within the purview of the present invention.
  • Another optional but highly desirable additive ingredient with multi-functional characteristics in detergent com- positions is from 0.1 % to about 3 % 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 ethylvinyl ethers, and other polymerizable vinyl monomers.
  • polyacrylic acid or plyacrylate polyacrylic acid or plyacrylate; polymaleic acid/acrylic acid copolymer; 70-30 acrylic acid/hydroxyethyl maleate copolymer; 1:1 styrene/maleic acid copolymer; isobutylene/maleic acid and diisobutylene/maleic acid copolymers; methyl- and ethyl- vinylether/maleic acid copolymers; ethylene/maleic acid copolymer; polyvinyl pyrrolidone; and vinyl pyr- rolidone/maleic acid copolymer.
  • the bleaching performance was determined of detergent products which had been stored during 0, 7, 14, and 42 days, using the above conditions.
  • the experiments were carried out at an isothermal temperature of 60°C, whereby Millipore ultra pure water was used at a pH of 10. Furthermore, a dosage of approximately 5 g/1 of the bleaching detergent formulation with catalyst to be tested was applied for each experiment.
  • the test formulation had the following general composition: component parts by weight base composition 62.26 sodium carbonate 4.00 sodium percarbonate 20.50 TAED 9.25
  • 2 tea-stained cotton test cloth (BC-1) were washed in 1 liter millipore ultra pure water at 60°C and containing 5 g/1 of the detergent formulation with catalyst to be tested. During the test the pH was adjusted to 10.0. After 15 minutes, one cloth was removed from the solution, after 30 minutes the second was removed. The cloths are rinsed with tap water for 10 minutes and dried in a tumbler drier for 15 minutes. After rinsing and drying the reflectance at 460 nm was measured. The difference in reflectance between the thus measured value and the (reference) value measured before the washing treatment,i.e. the ⁇ R value, is a measure for the bleach activity.
  • H 2 0 2 -content (in mmol/1 H 2 0 2 ) was deter ⁇ mined after washing periods of 15 respectively 30 minutes, using the following method.
  • 20 ml 4N H 2 S0 4 25 ml of the solution is added (in a 300 ml erlenmeyer flask).
  • 1 ml of the thiosulphate solution equals 1 mmol/1 H 2 0 2 .
  • the invention will now be illustrated by way of the fol ⁇ lowing non-limiting examples.
  • 1,2-dibromoethane (3.25 g) was added to (1) (6.0 g) in 30 ml acetonitrile and the mixture was kept at room temperature for 4 days. The precipitate obtained was fil ⁇ tered, washed with acetonitrile and ether and dried to leave 7.65 g of white icrocrystalline salt (which is: 1,2- bis(tricyclo[5.2.1.0 4 ' 10 ]-1,4,7-trazadecany1)ethane dibromide (2)).
  • Example 1 Comparative Example A Two detergent products having the general composition shown above and including different types of manganese complex catalyst were first stored during several periods ( 0, 7, 14, and 42 days) whereby the conditions as described above were applied. Subsequently, these detergent products were tested using the above described experimental method.
  • the tested products include the following base composition: base composition parts by weight
  • Zeolite A24 (anhydrous) 31.27 light soda ash 2.83
  • Na-PAS C 12 sodium salt of primary alkyl sulphate
  • Nonionic 7EO :C 12 -C 14 ethoxylated alcohol having on average 7 ethylene oxide groups e.g.
  • Nonionic 3EO :C 12 -C 14 ethoxylated alcohol having on average 3 ethylene oxide groups e.g.
  • the reduction in bleaching activity of the product according to the present invention is significantly less than the reduction observed for the product of Example A , when comparing the respec ⁇ tive ⁇ R values found for the products stored for 42 days with those for the products not stored at all.
  • Example A gives much more H 2 0 2 decom ⁇ position than the product of the present invention, after a storage period of up to about 2 weeks. It can also be seen that the H 2 0 2 decomposition resulting from washing with the product of the present invention does not clearly reduce when longer storage periods are applied.

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Abstract

On décrit des compositions détergentes concentrées, en poudre, possédant une masse volumique supérieure à 600 g/l, et comprenant un tensioactif, un adjuvant de détergence, un composé peroxy de blanchiment ainsi qu'un type spécifique de complexe de manganèse binucléaire en tant que catalyseur efficace de blanchiment. Un complexe particulièrement préféré de manganèse binucléaire est le suivant: [Et-ponté(Me2TACN)2)MnIIIMnIV(ν-0)¿2?(ν-OAc)]?2+(PF¿6-)2. On a trouvé que ce catalyseur de blanchiment démontrait une bonne stabilité de stockage dans une composition de poudre détergente concentrée selon l'invention.
PCT/EP1995/003308 1994-08-19 1995-08-18 Composition detergente de blanchiment WO1996006157A1 (fr)

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Application Number Priority Date Filing Date Title
AU33866/95A AU3386695A (en) 1994-08-19 1995-08-18 Detergent bleach composition

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EP94202373 1994-08-19
EP94202373.0 1994-08-19

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WO1996006157A1 true WO1996006157A1 (fr) 1996-02-29

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WO (1) WO1996006157A1 (fr)
ZA (1) ZA956914B (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998054282A1 (fr) * 1997-05-26 1998-12-03 Henkel Kommanditgesellschaft Auf Aktien Systeme de blanchiment
US5866531A (en) * 1994-08-19 1999-02-02 Henkel Kommanditgesellschaft Auf Aktien Process for the production of detergent or cleaning tablets
US6969752B1 (en) 2000-07-21 2005-11-29 Georgia Tech Research Corporation Water soluble/dispersible and easy removable cationic adhesives and coating for paper recycling
US7335629B2 (en) 2001-12-21 2008-02-26 Henkel Kommanditgesellschaft Auf Aktien Support-fixed bleaching catalyst complex compounds suitable as catalysts for peroxygen compounds
DE102009017722A1 (de) 2009-04-11 2010-10-14 Clariant International Limited Bleichmittelgranulate mit Aktivcoating
WO2010115581A1 (fr) 2009-04-11 2010-10-14 Clariant International Ltd Granulés d'agent de blanchiment
DE102012015826A1 (de) 2012-08-09 2014-02-13 Clariant International Ltd. Flüssige tensidhaltige Alkanolamin-freie Zusammensetzungen
DE102013004428A1 (de) 2013-03-15 2014-09-18 Clariant International Ltd. Verfahren zum Waschen und Reinigen von Textilien
DE102013010150A1 (de) 2013-06-15 2014-12-18 Clariant International Ltd. Bleichkatalysatorgranulate
DE102013010549A1 (de) 2013-06-15 2014-12-18 Clariant International Ltd. Bleichmittel-Co-Granulate
EP2857485A1 (fr) 2013-10-07 2015-04-08 WeylChem Switzerland AG Poche à compartiments multiples comprenant des compositions de nettoyage sans alkanolamine, processus de lavage et utilisation de produits de lavage et de nettoyage de textiles et plats
EP2857487A1 (fr) 2013-10-07 2015-04-08 WeylChem Switzerland AG Poche à compartiments multiples comprenant des compositions de nettoyage, processus de lavage et utilisation de produits de lavage et de nettoyage de textiles et plats
EP2857486A1 (fr) 2013-10-07 2015-04-08 WeylChem Switzerland AG Poche à compartiments multiples comprenant des compositions de nettoyage, processus de lavage et utilisation de produits de lavage et de nettoyage de textiles et plats
DE102013019269A1 (de) 2013-11-15 2015-06-03 Weylchem Switzerland Ag Geschirrspülmittel sowie dessen Verwendung
EP3181677A1 (fr) 2015-12-18 2017-06-21 WeylChem Wiesbaden GmbH Catalyseurs de blanchiment à particules fines, son procédé de production et d'utilisation
WO2018210442A1 (fr) 2017-05-17 2018-11-22 Weylchem Wiesbaden Gmbh Granulés enrobés, leur utilisation et produits de lavage et de nettoyage contenant ces granulés
US10144005B2 (en) 2011-09-08 2018-12-04 Richard William Kemp Catalysts

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EP0509787A2 (fr) * 1991-04-17 1992-10-21 Unilever Plc Compositions détergentes concentrées en poudre
EP0544490A1 (fr) * 1991-11-26 1993-06-02 Unilever Plc Compositions détergentes de blanchiment

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EP0509787A2 (fr) * 1991-04-17 1992-10-21 Unilever Plc Compositions détergentes concentrées en poudre
EP0544490A1 (fr) * 1991-11-26 1993-06-02 Unilever Plc Compositions détergentes de blanchiment

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5866531A (en) * 1994-08-19 1999-02-02 Henkel Kommanditgesellschaft Auf Aktien Process for the production of detergent or cleaning tablets
WO1998054282A1 (fr) * 1997-05-26 1998-12-03 Henkel Kommanditgesellschaft Auf Aktien Systeme de blanchiment
US6479450B1 (en) 1997-05-26 2002-11-12 Henkel Kommanditgesellschaft Auf Aktien Bleaching system
US6969752B1 (en) 2000-07-21 2005-11-29 Georgia Tech Research Corporation Water soluble/dispersible and easy removable cationic adhesives and coating for paper recycling
US7335629B2 (en) 2001-12-21 2008-02-26 Henkel Kommanditgesellschaft Auf Aktien Support-fixed bleaching catalyst complex compounds suitable as catalysts for peroxygen compounds
WO2010115582A1 (fr) 2009-04-11 2010-10-14 Clariant International Ltd Granulés d'agent de blanchiment à revêtement actif
WO2010115581A1 (fr) 2009-04-11 2010-10-14 Clariant International Ltd Granulés d'agent de blanchiment
DE102009017724A1 (de) 2009-04-11 2010-10-14 Clariant International Limited Bleichmittelgranulate
US8486881B2 (en) 2009-04-11 2013-07-16 Clariant Finance (Bvi) Limited Bleach granules comprising an active coating
US8883704B2 (en) 2009-04-11 2014-11-11 Clariant International Ltd. Bleach granules
DE102009017722A1 (de) 2009-04-11 2010-10-14 Clariant International Limited Bleichmittelgranulate mit Aktivcoating
US10144005B2 (en) 2011-09-08 2018-12-04 Richard William Kemp Catalysts
US9777249B2 (en) 2012-08-09 2017-10-03 Weylchem Switzerland Ag Liquid surfactant-containing alkanolamine-free compositions
DE102012015826A1 (de) 2012-08-09 2014-02-13 Clariant International Ltd. Flüssige tensidhaltige Alkanolamin-freie Zusammensetzungen
WO2014023427A1 (fr) 2012-08-09 2014-02-13 Clariant International Ltd Compositions liquides contenant des agents tensio-actifs dépourvues d'alcanolamines
DE102013004428A1 (de) 2013-03-15 2014-09-18 Clariant International Ltd. Verfahren zum Waschen und Reinigen von Textilien
DE102013010150A1 (de) 2013-06-15 2014-12-18 Clariant International Ltd. Bleichkatalysatorgranulate
DE102013010549A1 (de) 2013-06-15 2014-12-18 Clariant International Ltd. Bleichmittel-Co-Granulate
EP2857487A1 (fr) 2013-10-07 2015-04-08 WeylChem Switzerland AG Poche à compartiments multiples comprenant des compositions de nettoyage, processus de lavage et utilisation de produits de lavage et de nettoyage de textiles et plats
EP2857486A1 (fr) 2013-10-07 2015-04-08 WeylChem Switzerland AG Poche à compartiments multiples comprenant des compositions de nettoyage, processus de lavage et utilisation de produits de lavage et de nettoyage de textiles et plats
WO2015051901A1 (fr) 2013-10-07 2015-04-16 Weylchem Wiesbaden Gmbh Poche multicompartiment comprenant des compositions de nettoyage sans alcanolamine, procédé de lavage et utilisation pour le lavage et le nettoyage de textiles et d'assiettes
EP2857485A1 (fr) 2013-10-07 2015-04-08 WeylChem Switzerland AG Poche à compartiments multiples comprenant des compositions de nettoyage sans alkanolamine, processus de lavage et utilisation de produits de lavage et de nettoyage de textiles et plats
DE102013019269A1 (de) 2013-11-15 2015-06-03 Weylchem Switzerland Ag Geschirrspülmittel sowie dessen Verwendung
EP3181677A1 (fr) 2015-12-18 2017-06-21 WeylChem Wiesbaden GmbH Catalyseurs de blanchiment à particules fines, son procédé de production et d'utilisation
DE102015016402A1 (de) 2015-12-18 2017-06-22 Weylchem Wiesbaden Gmbh Feinteilige Bleichkatalysatoren, Verfahren zu deren Herstellung und deren Verwendung
WO2018210442A1 (fr) 2017-05-17 2018-11-22 Weylchem Wiesbaden Gmbh Granulés enrobés, leur utilisation et produits de lavage et de nettoyage contenant ces granulés
DE102017004742A1 (de) 2017-05-17 2018-11-22 Weylchem Wiesbaden Gmbh Beschichtete Granulate, deren Verwendung und Wasch- und Reinigungsmittel enthaltend diese
US11268048B2 (en) 2017-05-17 2022-03-08 Weylchem Wiesbaden Gmbh Coated granules, use thereof, and washing and cleaning agents containing same

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