Classifications

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

Definitions

• the invention relates to activation of bleaches employing peroxy compounds including hydrogen peroxide or hydrogen peroxide adducts, which liberate hydrogen peroxide in aqueous solution, and peroxy acids (or precursors thereof); to compounds that activate or catalyse peroxy compounds; to bleach compositions, including detergent bleach compositions, which contain a catalyst for peroxy compounds; and to processes for bleaching and/or washing substrates using the aforementioned types of compositions.
• peroxy compounds including hydrogen peroxide or hydrogen peroxide adducts, which liberate hydrogen peroxide in aqueous solution, and peroxy acids (or precursors thereof); to compounds that activate or catalyse peroxy compounds; to bleach compositions, including detergent bleach compositions, which contain a catalyst for peroxy compounds; and to processes for bleaching and/or washing substrates using the aforementioned types of compositions.
• the present invention is concerned with the novel use of iron compounds as catalysts for the bleach activation of peroxy compounds.
• Peroxide bleaching agents for use in laundering have been known for many years. Such agents are effective in removing stains, such as tea, fruit, and wine stains, from clothing at or near boiling temperatures. The efficacy of peroxide bleaching agents drops off sharply at temperatures below 60°C.
• dye transfer is a well-known problem in the art and has been addressed in various ways.
• an improved dye transfer inhibition has been obtained by using Fe-porphyrin and Fe-phthalocyanine complexes (see EP-A-537,381, EP-A-553,607, EP-A-538,228).
• these new iron compounds exhibit remarkable dye transfer inhibition properties, and, alternatively, oxidation of organic substrates such as olefins, alcohols and unactivated hydrocarbons.
• the present invention provides a bleach and oxidation catalyst comprising an Fe-complex having formula (A): [LFeX n ] z Y q or precursors thereof, in which
• the present invention provides a bleaching composition
• a peroxy compound bleach preferably selected from hydrogen peroxide, hydrogen peroxide-liberating or -generating compounds, peroxyacids and their salts, and mixtures thereof, optionally together with peroxyacid bleach precursors, and a catalyst according to the present invention.
• the Fe-complex catalyst of the invention may be used in a bleaching system comprising a peroxy compound or a precursor thereof, and may be suitable for use in the washing and bleaching of substrates including laundry, dishwashing and hard surface cleaning.
• the Fe-complex catalyst of the invention may be used for bleaching in the textile, paper and woodpulp industries, as well as in waste water treatment.
• an advantage of the Fe-complex catalysts according to the present invention is that they exhibit a remarkably high oxidation activity in alkaline aqueous media in the presence of peroxy compounds.
• a second advantage of the new Fe-complex catalysts of the invention is that they show good bleaching activity at a broader pH range (generally pH 6-11) than those observed for the previously disclosed iron complexes. Their performance was especially improved at pH of around 10. This advantage may be particularly beneficial in view of the current detergent formulations that employ rather alkaline conditions, as well as the tendency to shift the pH during fabric washing from alkaline (typically, a pH of 10) to more neutral values. Furthermore, this advantage may be beneficial when using the present iron complex catalyst in machine dishwash formulations.
• catalysts of the invention have a relatively low molecular weight and, consequently, are very weight-effective.
• Precursors of the active Fe-complex catalysts of the invention can be any iron coordination complex, which, under fabric washing conditions, is transformed into the active iron complex of general formula (A).
• the precursor of the Fe-complex of the invention can be a mixture of an iron salt, such as Fe(NO 3 ) 3 , and the ligand L.
• the class of ligands is that of compounds of general formula (B), in which the substituent group R 1 is selected from C 0 -C 20 alkylaryl, C 0 -C 20 alkylheteroaryl, and C 0 -C 20 alkyl, and in which the substituent groups R 2 , R 3 , R 4 , and R 5 are independently chosen from C 0 -C 5 alkyl substituted with a pyridine ring and R 1 is other than H.
• More preferred ligands are:
• the most preferred ligands are:
• Suitable counter ions are those which give rise to the formation of storage-stable solids.
• the effective level of the Fe-complex catalyst expressed in terms of parts per million (ppm) of iron in an aqueous bleaching solution, will normally range from 0.001 ppm to 100 ppm, preferably from 0.01 ppm to 20 ppm, most preferably from 0.1 ppm to 10 ppm. Higher levels may be desired and applied in industrial bleaching processes, such as textile and paper pulp bleaching. The lower range levels are preferably used in domestic laundry operations.
• the detergent bleach composition is a mixture of the detergent bleach composition
• the bleaching composition of the invention has particular application in detergent formulations, to form a new and improved detergent bleach composition within the purview of the invention comprising a peroxy compound bleach as defined above, the aforesaid Fe-complex catalyst having general formula (A), a surface-active material and a detergency builder.
• the Fe-complex catalyst will be present in the detergent bleach composition of the invention in amounts so as to provide the required level in the wash liquor.
• the Fe-complex catalyst level in the detergent bleach composition corresponds to an iron content of from 0.0005% to 0.5% by weight.
• the Fe content in the formulation is suitably 0.0025 to 0.5%, preferably 0.005 to 0.25% by weight.
• the Fe content in the formulation is suitably 0.0005 to 0.1%, preferably 0.001 to 0.05% by weight.
• Detergent bleach compositions of the invention are effective over a wide pH-range of between 7 and 13, with optimal pH-range lying between 8 and 11.
• the peroxy bleaching compound may be a compound which is 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.
• 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.
• Another suitable hydrogen peroxide generating system is a combination of a C 1 -C 4 alkanol oxidase and a C 1 -C 4 alkanol, especially a combination of methanol oxidase (MOX) and ethanol.
• MOX methanol oxidase
• Alkylhydroxy peroxides are another class of peroxy bleaching compounds. Examples of these materials include cumene hydroperoxide and t-butyl hydroperoxide.
• Organic peroxyacids may also be suitable as the peroxy bleaching compound.
• Such materials normally have the general formula: wherein R is an alkyl- or alkylidene- 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 COOOH 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
• the bleaching composition of the invention can be suitably formulated to contain from 2 to 35% , preferably from 5 to 25% by weight, of the peroxy bleaching agent.
• Peroxyacid bleach precursors are known and amply described in literature, such as in GB-A-836988; GB-A-864,798; GB-A-907,356; GB-A-1,003,310 and GB-A-1,519,351; DE-A-3,337,921; EP-A-0,185,522; EP-A-0,174,132; EP-A-0,120,591; and US-A-1,246,339; US-A-3,332,882; US-A-4,128,494; US-A-4,412,934 and US-A-4,675,393.
• peroxyacid bleach precursors are those of the cationic i.e. quaternary ammonium substituted peroxyacid precursors as disclosed in US-A-4,751,015 and US-A-4,397,757, in EP-A-0,284,292 and EP-A-331,229.
• Examples of peroxyacid bleach precursors of this class are:
• a further special class of bleach precursors is formed by the cationic nitriles as disclosed in EP-A-303,520; EP-A-458,396 and EP-A-464,880.
• any one of these peroxyacid bleach precursors can be used in the present invention, although 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 diamine (TAED); sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3-benzoloxy benzoate; 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphophenyl carbonate chloride (SPCC); trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3,5,5-trimethyl hexanoyl-oxybenzene sulphonate (STHOBS); and the substituted cationic nitriles.
• SBOBS sodium-4-benzoyloxy benzene sulphonate
• TAED N,N,N'N'-te
• the precursors may be used in an amount of up to 12 %, preferably from 2-10 % by weight, of the composition.
• molecular oxygen may be used as the oxidant.
• the surface-active material is the surface-active material
• the detergent bleach composition according to the present invention generally contains a 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.
• 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 (C 8 -C 18 ) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (C 9 -C 10 ) benzene sulphonates, particularly sodium linear secondary alkyl (C 10 -C 15 ) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and ammonium salts of sulphuric acid esters of higher (C 9 -C 18 ) 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 taurine
• 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 condensation products of aliphatic (C 8 -C 18 ) 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 invention.
• the detergent bleach composition of the invention 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.
• 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) 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, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid; and polyacetal carboxylates as disclosed in US-A-4,144,226 and US-A-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
• polyacetal carboxylates as disclosed in US-A-4,144,226 and US-
• 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 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 contain 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, 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 minor amounts of 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.
• the detergent bleach composition 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 phosphonic acid derivatives (i.e.
• Dequest® types fabric softening agents; inorganic salts and alkaline buffering agents, such as sodium sulphate and sodium silicate; 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.
• a hydrogen peroxide source such as sodium perborate 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 O 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.
• N 4 Py.HClO 4 was prepared as follows: To pyridyl ketone oxim (3 g, 15.1 mmol) was added ethanol (15 ml), concentrated ammonia solution (15 mL) and NH 4 OAc (1.21 g, 15.8 mmol). The solution was warmed until reflux. To this solution was added 4.64 g Zn in small portions. After the addition of all Zn, the mixture was refluxed for 1 hour and allowed to cool to ambient temperature. The solution was filtered and water (15 ml) was added. Solid NaOH was added until pH>>10 and the solution was extracted with CH 2 Cl 2 (3 x 20 ml). The organic layers were dried over Na 2 SO 4 and evaporated until dryness.
• the free amine was obtained by precipitating the salt with 2N NaOH and subsequently by extraction with CH 2 Cl 2 .
• To the free amine was added under argon 20 ml of dry tetrahydrofuran freshly distilled from LiAlH 4 The mixture was stirred and cooled to -70 °C by an alcohol / dry ice bath. Now 1 ml of 2.5 N butyllithium solution in hexane was added giving an immediate dark red colour. The mixture was allowed to warm to -20 °C and now 0.1 ml of methyl iodide was added. The temperature was kept to -10 °C for 1 hour.
• Fe(MeN 4 Py)Fe(CH 3 CN)](ClO 4 ) 2 hereinafter referred to as Fe(MeN 4 Py)
• Fe(BzN 4 Py)Fe(CH 3 CN)(ClO 4 ) 2 was prepared as follows:
• UV/Vis acetonitrile [ ⁇ max, nm ( ⁇ , M -1 cm -1 )]: 380 (7400), 458 nm (5500).
• Mass-ESP cone voltage 17V in CH3CN: m/z 256.4 [BzN 4 Py] 2+ ; 612 [BzN 4 PyFeClO 4 ] +
• test cloths Two pieces of test cloth were stirred for 30 minutes in 1 liter of a 8.6x10 -3 mol/l hydrogen peroxide solution in millipore water, containing concentrations of the compounds as indicated in Table 1. After rinsing with demineralised water, the test cloths were dried for 7 minutes in a microwave oven. The reflectance (R 460 *) of the test cloths was measured on a Minolta® CM-3700d spectrophotometer including UV-filter before and after treatment. The difference ( ⁇ R 460 *) between both reflectance values thus obtained gives a measure of the bleaching performance, i.e. higher ⁇ R 460 * values correspond to an improved bleaching performance. conc.
• Fe ⁇ R 460 * (mol/l) (at pH 10) blank - 6.5 Fe(NO 3 ) 3 10x10 -6 6.2 Fe(N 4 Py) 10x10 -6 12.0 Fe(MeN 4 Py) 10x10 -6 15.8 Fe(BzN 4 Py) 10x10 -6 17.3
• Fe(MeN 4 Py) and Fe(BzN 4 Py) refer to the Fe-catalysts prepared according to Examples 1 and 2, and Fe(N 4 Py) to the non-methylated analogue as described in WO-A-9534628.
• the blank and Fe(NO 3 ) 3 experiment were used as control.
• the bleaching activity of the Fe(MeN 4 Py) catalyst prepared according to Example 1 was demonstrated in the presence of a detergent formulation on standard tea-stained (BC-1) cotton test cloths.
• the detergent formulation contained the following ingredients and was dosed (in water) as indicated in Table 2.
• Detergent formulation used for the bleaching experiments with Fe(MeN 4 Py) Ingredient Dosage (g/I) Sodium linear alkylbenzene sulphonate (LAS) 0.60 Sodium triphosphate (STP) 0.36 Sodium carbonate 0.44 Sodium disilicate 0.20 Sodium sulphate 0.67 Sodium perborate monohydrate 0.20 Tetraacetyleneethylene diamine (TAED) 0.06 Fe(MeN 4 Py) ⁇ 0.01 enzymes, fluorescer, SCMC, minors, moisture 0.19
• test cloths After rinsing with demineralised water, the test cloths were dried for 7 minutes in a microwave oven.
• the reflectance (R 460 *) of the test cloths was measured on a Minolta® CM-3700d spectrophotometer including UV-filter before and after treatment.
• the difference ( ⁇ R 460 *) between both reflectance values thus obtained gives a measure of the bleaching performance, i.e. higher ⁇ R 460 * values correspond to an improved bleaching performance.
• the dye oxidation activity of the Fe-catalysts prepared according to Examples 1 and 2 was demonstrated in the presence of hydrogen peroxide on a dye known as Acid Red 88.
• a higher ⁇ A 503 value represent a better dye - bleaching activity.
• Fe(MeN 4 Py) and Fe(BzN 4 Py) in Table 2 refer to the Fe-catalyst prepared according to Examples 1 and 2. The blank and Fe(NO 3 ) 3 experiment were used as controls.
• the oxidation activity of Fe(MeN 4 Py) catalyst was demonstrated in the presence of hydrogen peroxide on a range of organic substrates.
• the experiments were carried out at ambient temperature in acetone.
• the concentration of the Fe catalyst was 7.7x10 -4 M and the ratio catalyst/H 2 O 2 /substrate was 1/100/1000.
• the turnover numbers indicated in Table 4 represent the number of molecules formed per molecule of catalyst as determined after the indicated time of the reaction by using gas chromatography. In a blank experiment or in the presence of Fe(NO 3 ) 3 , essentially no oxidation products could be detected.

Landscapes

• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Priority Applications (1)

Applications Claiming Priority (3)

Publications (3)

Family

ID=8228776

Family Applications (1)

Country Status (7)

Cited By (8)

Families Citing this family (61)

Family Cites Families (8)

• 1998
  • 1998-09-28 CA CA002248476A patent/CA2248476A1/en not_active Abandoned
  • 1998-09-30 EP EP98307975A patent/EP0909809B1/en not_active Expired - Lifetime
  • 1998-09-30 DE DE69827738T patent/DE69827738T2/de not_active Expired - Lifetime
  • 1998-09-30 ES ES98307975T patent/ES2234080T3/es not_active Expired - Lifetime
  • 1998-10-01 AR ARP980104904A patent/AR017280A1/es active IP Right Grant
  • 1998-10-01 BR BR9803859-1A patent/BR9803859A/pt not_active IP Right Cessation
  • 1998-10-01 ZA ZA9808963A patent/ZA988963B/xx unknown

Also Published As

Similar Documents

Legal Events