Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3932—Inorganic compounds or complexes
• • 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
  • C11D3/395—Bleaching agents

Definitions

• This invention relates to detergent bleach compositions. More particularly, it relates to improved detergent bleach compositions, especially but not exclusively adapted for washing and cleaning of fabrics, containing, a surfactant material, a peroxide bleaching agent and a manganese complex as bleach catalyst.
• the manganese complex used in the present invention is a dinuclear manganese complex of the formula: wherein Mn is manganese which can individually be in the III or IV oxidation state; X1, X2 and X3 each independently represent a coordinating or bridging species selected from the group consisting of H2O, O22 ⁇ , O2 ⁇ , OH ⁇ , HO2 ⁇ , SH ⁇ , S2 ⁇ , >SO, Cl ⁇ , N3 ⁇ , SCN ⁇ , RCOO ⁇ , RSO ⁇ 3, NH2 ⁇ and NR3, with R being H, alkyl, aryl, both optionally substituted, or 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; Y is a monovalent or multivalent counter-i
• Preferred manganese-complexes are those wherein X1, X2 and X3 are either CH3COO ⁇ or O2 ⁇ or mixtures thereof and, most preferably, wherein the manganese is in the IV oxidation state and X1, X2 and X3 are O2 ⁇ .
• ligand is of formula wherein t is an integer from 2 to 3; s is an integer from 3 to 4; u is zero or one; R1, R2 and R3 are each independently selected from H, alkyl, aryl, both optionally substituted.
• 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; surfactant-anions, such as the long-chain alkylsulphates, alkylsulphonates, alkylbenzenesulphonates, tosylate; trifluormethylsulphonate; perchlorate (C104 ⁇ ), BPh4 ⁇ and PF6-, though some counter-ions are more preferred than others for reasons of product property and safety.
• manganese complexes as used in the present invention are: (I) [ (Me3TACN)Mn IV ( ⁇ -O)3Mn IV (Me3TACN) ]2+(PF6 ⁇ )2 (II) [ (Me4TACN)Mn IV ( ⁇ -O)3Mn IV (Me4TACN) ]2+ (PF6 ⁇ )2 (III) [ (Me3TACN)Mn III ( ⁇ -O)( ⁇ -OAc)2Mn III (Me3TACN) ]2+ (PF6 ⁇ )2 (IV) [ (Me4TACN)Mn III ( ⁇ -O)( ⁇ -OAc)2Mn III (Me4TACN) ]2+ (PF6 ⁇ )2 (V) [ (Et-bridged(Me2TACN)2)Mn III Mn IV ( ⁇ -O)2( ⁇ -OAc) ]2+ (ClO4 ⁇ )2 which are hereinafter also abbreviated as: (I) [
• the invention now relates to detergent bleaching compositions comprising a surface-active material, a peroxide bleaching agent and the above-described dinuclear manganese-complex as bleach catalyst.
• the peroxide bleaching agents are normally 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.
• the amount thereof in the composition of the invention usually will be within the range of about 5-35% by weight, preferably from 10-25% by weight.
• Alkylhydroxy peroxides are another class of peroxide bleaching agents. Examples of these materials include cumene hydroperoxide and t-butyl hydroperoxide.
• Organic peroxyacids may also be suitable as the peroxide bleaching agent.
• Such materials normally have the general formula: wherein R is an alkylene or substituted alkylene group containing from 1 to about 20 carbon atoms, optionally having an internal amide linkage; or a phenylene or substituted phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an imido-aromatic or non-aromatic group, a COOH or group or a quaternary ammonium group.
• Typical monoperoxy acids useful herein include, for example:
• Typical diperoxyacids useful herein include, for example:
• 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.
• Peroxyacid bleach precursors are known and amply described in literature, such as in the British Patents 836,988; 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 Patents 4,751,015 and 4,397,757, in EP-A-284292 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); N-octyl,N,N-dimethyl-N10-carbophenoxy decyl ammonium chloride - (ODC); 3-(N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate; and N,N,N-trimethyl ammonium toluyloxy benzene sulphonate.
• SPCC 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphonphenyl carbonate chloride -
• ODC N-octyl,N,N-dimethyl-N10-carbophenoxy decyl ammonium chloride -
• a further special class of cationic peroxyacid bleach precursors is formed by the cationic nitriles as disclosed in EP-A-0303520 and in European Patent Specification No.'s 458396 and 464880.
• 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-benzoloxy benzene sulphonate (SBOBS); N,N,N',N'-tetraacetyl ethylene diamine (TAED); sodium-1-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 hexanoyloxybenzene sulphonate (STHOBS); and the substituted cationic nitriles.
• SBOBS sodium-4-benzoloxy benzene sulphonate
• TAED N,N,N',N'-tetraacetyl ethylene diamine
• TAED sodium-1-methyl-2-benzoyloxy benzene-4-sulphon
• the precursors may be used in an amount of about 1-8%, preferably from 2-5% by weight, of the composition.
• Organic bleach catalyst most suitable for being utilized here are the so-called suphonimides as disclosed in EP-A-0,453,003 and EP-A-0,446,982.
• the surface-active material normally used in detergent bleach compositions may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwiterionic, cationic actives and mixtures thereof.
• suitable actives 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 (C8-C18) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (C9-C10) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those esters of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and ammonium salts of sulphuric acid esters of higher (C9-C18) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and ammonium salts of fatty acid amides of methyl
• 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 (C6-C22) phenols, generally 5-25 EO, i.e 5-25 units of ethylene oxides per molecule; the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, generally 2-30 EO, and products may be condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine.
• alkylene oxides usually ethylene oxide
• alkyl (C6-C22) phenols generally 5-25 EO, i.e 5-25 units of ethylene oxides per molecule
• condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide generally 2-30 EO
• products may be condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine.
• nonionic surface-actives include alkyl polyglycosides, sugar esters, long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulphoxides.
• Amount of 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.
• It is therefore an object of the present invention to provide a detergent bleach composition comprising a surface-active material, a peroxide bleaching agent and a dinuclear manganese complex as hereinbefore described having optimal bleaching action.
• nonionic provided it is present in sufficient amounts, compensates the strong negative effect of anionic surfactants by resolubilization of the catalyst.
• the invention provides a detergent bleach composition
• a detergent bleach composition comprising a surface-active material, a peroxide bleaching agent and a dinuclear manganese complex as the bleach catalyst, which composition is characterized in that it comprises from 0-25% by weight of anionic surfactant and from 7.5-55% by weight of nonionic surfactant, the weight ratio of nonionic surfactant to anionic surfactant being at least 0.75 if the composition contains 0-7.5% by weight of a carbonate builder, expressed as sodium carbonate, and at least 2.2 if the composition contains more than 7.5% by weight of carbonate builder.
• composition will comprise from 0-15% by weight of anionic surfactant and from 10-40% by weight of nonionic surfactant.
• the detergent active system is free from C16-C22 fatty acid soaps.
• the detergent bleach composition is an all-nonionic based formulation exempt from any anionic surfactant.
• composition of the invention normally and preferably also contains a detergency builder in an amount of from about 5-80% by weight, preferably from about 10-60% by weight.
• Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixture 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, oxydisuccinic 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
• the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid and polyacetal carboxylates as disclosed in US patents 4,144,226 and 4,146,495.
• 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 amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as Zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P type as described in EP-A-0,384,070.
• zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as Zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P type as described in EP-A-0,384,070.
• compositions of the invention may contain any one of the organic or 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, carboxymethyloxy 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.
• alkalimetal carbonates and phosphates especially sodium carbonate, sodium bicarbonate and sodium triphosphate, also have a negative influence on the catalytic bleach performance of hydroperoxide bleaches, but surprisingly, only to a much lesser extent on the catalytic bleach performance of peroxyacid bleaches.
• the carbonate effect is however pH dependent in that upon increasing the pH to above 10, particularly to 10.5 and above, the negative effect is largely removed.
• 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.
• the detergent compositions of the invention can contain any of the conventional additives in amounts of which such materials are normally employed in fabric washing detergent compositions.
• 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 ethylene diamine tetraacetic acid (EDTA) and the phosphonic acid derivatives (i.e.
• 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
• 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; perfumes; enzymes, such as proteases, cellulases, lipases, amylases and oxidases; germicides and colourants.
• the composition contains not more than 5% by weight of a carbonate buffer, 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.
• 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/H2O2 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.
• detergent bleach compositions comprising a surface-active material, a peroxyacid bleach, such as DPDA, PAP and MPS, the bleach catalyst, and a phosphate builder, preferably sodium triphosphate.
• Another optional but highly desirable additive ingredient with multi-functional characteristics in detergent compositions 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 polyacrylate are polyacrylic acid or polyacrylate; 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 ethylvinylether/maleic acid copolymers; ethylene/maleic acid copolymer; polyvinyl pyrrolidone; and vinyl pyrrolidone/maleic acid copolymer.
• Detergent bleach compositions of the invention when formulated as free-flowing particles, e.g. in powdered or granulated form, can be produced by any of the conventional techniques employed in the manufacture of detergent compositions, for instance by slurry-making, followed by spray-drying to form a detergent base powder to which the heat-sensitive ingredients including the peroxide compound bleach and optionally some other ingredients as desired, and the bleach catalyst, can be added as dry substances.
• the detergent base powder compositions, to which the bleach catalyst is added can itself be made in a variety of other ways, such as the so-called part-part processing, non-tower route processing, dry-mixing, agglomeration, granulation, extrusion, compacting and densifying processes etc., such ways being well known to those skilled in the art and not forming the essential part of the present invention.
• the bleach system in the wash solution was added at a concentration of 2.5 ⁇ mol/1 catalyst and 8.6 mmol/1 PBM, corresponding to 0.03% by weight of catalyst and 14.3% by weight of PBM if a detergent bleach formulation is dosed at 6 g/1.
• Test cloths were immersed for 30 minutes in each of the compositions of the examples. After rinsing with tap water, the cloths were dried in a tumble drier. The reflectance (R 460* .) was measured on a Zeiss Elrephometer before and after treatment. The difference ( ⁇ R 460* .) in the value gives a measure of the effectiveness of the treatment.
• Example 2 shows the effect of nonionic addition on the bleach performance of a formulation containing 9% C18-soap.
• the experiments were carried out under exactly the same conditions as used in Example 1.
• Example 3 shows the effect of nonionic addition on the bleach performance of a formulation containing 9% ABS.
• the experiments were carried out under exactly the same conditions as used in Example II and the results are shown in Table 3.
• Table 3 present - 9% ABS addition - - NI 2) NI 2) wt.% - - 4 8 ⁇ R460* 25.0 16.6 23.9 26.7
• Example 2 shows the effect of increasing amounts of C12-soap on the catalytic bleach performance of a catalyst/PBM bleach system on tea-stained test cloths.
• the experiments were carried out under the same conditions as used in Example I. The results are given in Table 4.
• Table C12-soap(% by weight) 0 9 21 33 74 mmol/1 0 2.4 5.8 9.0 20 ⁇ R460* 25.0 28.6 25.1 23.4 20.2
• This Example shows the effect of Na2CO3 on the bleach performance of a detergent bleach composition of the following nominal formulation: Formulation % by Weight Alkyl benzene sulphonate (ABS) 3.0 C18-soap 1.7 Nonionic (Synperonic A3/A7) 9.8 Zeolite 24.0 Polymer (Sokalan CP5 ex BASF) 4.0 Sodium carboxymethylcellulose 0.6 Sodium perborate monohydrate 14.3 Mn-complex (I) catalyst 0.03
• Example I was repeated except the bleach catalyst used was Mn III Mn IV ( ⁇ -O)2( ⁇ -OAc)(Et-bridged(Me2TACN)2) # and millipore water (ie. demineralised water which was further purified by treatment through a Milli-Q plus water purification system ex Millipore Corporation).
• # - prepared according to a method described by Prof Wieghardt at the 1991 ICBIC Conference in Oxford (UK)
• the level of catalyst corresponds to 0.037% by weight and of PBM to 14.3% by weight if a detergent bleach formulation is dosed at 6g/1.

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• 1992
  • 1992-11-24 EP EP92310719A patent/EP0544490A1/fr not_active Withdrawn
  • 1992-11-24 CA CA002083661A patent/CA2083661A1/fr not_active Abandoned
  • 1992-11-25 CN CN92111815A patent/CN1031647C/zh not_active Expired - Fee Related
  • 1992-11-25 BR BR9204549A patent/BR9204549A/pt not_active Application Discontinuation
  • 1992-11-25 MX MX9206779A patent/MX9206779A/es not_active Application Discontinuation
  • 1992-11-25 AU AU29620/92A patent/AU661522B2/en not_active Ceased
  • 1992-11-26 TR TR01152/92A patent/TR27075A/xx unknown
  • 1992-11-26 JP JP4317228A patent/JPH0768543B2/ja not_active Expired - Lifetime
  • 1992-11-26 KR KR1019920022431A patent/KR960000205B1/ko not_active IP Right Cessation
  • 1992-11-26 ZA ZA928188A patent/ZA928188B/xx unknown
  • 1992-12-04 TW TW081109741A patent/TW234144B/zh active

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