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
  • C11D3/3907—Organic compounds
  • C11D3/3917—Nitrogen-containing compounds
  • C11D3/3927—Quarternary ammonium compounds
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium compounds

Definitions

• This invention relates to an improved process for bleaching substrates using a peroxyacid bleach compound and to improved bleach compositions comprising a peroxyacid bleach compound.
• substrates used herein includes fibres, textiles and fabrics of both animal and vegetable origins, synthetics and mixtures thereof, such as cottons, cellulosics, wool and other protein fibres, bast fibres, acrylic and other synthetic fibres, fabrics, and textiles.
• organic peroxyacids incorporated as such or in the form of their precursors generating the peroxyacid in situ in bleach formulations are effective bleaches at temperatures significantly below the boil-wash temperatures, e.g. from above 40 to 60°C. Their effect at about 40°C and below, however, is still far from ideal.
• US Patent no. 3,749,674 proposes the use of a quaternary ammonium salt as so-called micelle catalyst for the bleaching reaction of organic peroxyacids containing an additional anionic group capable of forming bi-anionic dimers in solution. Formation of these indispensible transition complexes of the bleaching reaction is said to be facilitated by positively charged micelles formed by the quaternary ammonium salts in solution.
• GB-A-1,557,568 discloses granular laundry compositions comprising an agglomerate of an organic peroxyacid precursor and a quaternary ammonium surfactant.
• the agglomerated quaternary ammonium compound present in the same granular particles together with the peroxyacid precursor is said to reduce the tendency of "pin-point" spotting.
• the quaternary ammonium compounds suitable in the present invention are the mono-long chain type quaternary ammonium compounds having the formula : R1R2R3R4N+X ⁇ wherein R1 is a C8-C18 alkyl, alkenyl or alkaryl group, R2, R3 and R4 are each C1-C3 alkyl groups, wherein the total number of carbon atoms of R1, R2, R3 and R4 is from 15 to 21; and X ⁇ is a counter-ion, including Cl ⁇ , NO3 ⁇ or CH3SO4 ⁇ ; and the poly-long chain type quaternary ammonium compounds having the formula: R.R.R.R.N+.X ⁇ wherein at least two R's are C4-C12 alkyl, alkenyl or alkaryl groups and the remaining R or R's are C1-C12 alkyl, alkenyl or alkaryl groups, wherein the total number of carbon atoms of all four R's is from 12 to 28, preferably from
• Preferred mono-long chain quaternary ammonium compounds are those wherein R1 is an alkyl group having from 12-16 carbon atoms, preferably from 14-16 carbon atoms; R2, R3 and R4 are each methyl or ethyl, preferably methyl; and the carbon atoms of R1, R2, R3 and R4 total 17-19.
• Such compounds are tetradecyl-trimethyl ammonium nitrate; tetradecyl-trimethyl ammonium methosulphate and hexadecyl-trimethyl ammonium chloride.
• Suitable poly-long chain quaternary ammonium compounds are: (C12H25)2.(CH3)2.N+Cl ⁇ (C8H17)3.CH3.N+.NO3 ⁇ (C6H13)4.N+.Cl ⁇ Quaternary ammonium compounds are, of course, known in the art as belonging to the class of cationic surface-active agents. They are referred to in the prior art for use as, among other things, emulsifiers, fabric softeners, antistatics and disinfectants, or for use in a conventional detergent functionality. They have also been used, as claimed in US-A-3,749,674, to improve the bleaching action of monopersulphates and certain types of organic peroxyacids having an extra charged group e.g.
• the present invention is based on the discovery that the bleach performance of the more effective mono-peroxyacid compounds not containing an additional charge can be boosted still to a significant degree with mono- or poly-long chain quaternary ammonium compounds as defined hereinabove already at a level of as low as 1x10 ⁇ 4 Molar (M) in the bleach solution, improving steeply with increasing levels up to about 12x10 ⁇ 4 Molar (M). Below 1x10 ⁇ 4 Molar the effect is too insignificant and above 12x10 ⁇ 4 Molar the effect generally plateaus or decreases quickly.
• Preferred use levels are from 2 to 10x10 ⁇ 4 M, particularly from 5 to 10x10 ⁇ 4 M.
• the pH of the bleaching solution is not critical and improvements of the bleaching and stain-removal effect can be achieved under acid as well as under alkaline conditions, e.g. at pH 4 to about 10.5, though a bleaching pH of from about 7 to about 10 is generally preferred.
• the invention provides in the use of a quaternary ammonium compound having the formula : R1R2R3R4N+X ⁇ wherein R1 is a C8-C18 alkyl, alkenyl or alkaryl group; R2, R3 and R4 are each C1-C3 alkyl groups, wherein the total number of carbon atoms of R1, R2, R3 and R4 is from 15 to 21; and X ⁇ is a counter-ion, including Cl ⁇ , NO3 ⁇ or CH3SO4 ⁇ ; or a quaternary ammonium compound having the formula : R.R.R.R.N+X ⁇ wherein at least two R's are C4-C12 alkyl, alkenyl or alkaryl groups and the remaining R or R's are C1-C12 alkyl, alkenyl or alkaryl groups, wherein the total number of carbon atoms of all four R's is from 12 to 28, preferably from 14 to 26; and X ⁇ is
• the invention provides a process for bleaching substrates by treating the substrate with a bleach solution comprising essentially a peroxyacid bleach compound, characterized in that said bleach solution comprises an organic mono-peroxyacid not containing an additional negative charge and a quaternary ammonium compound having the formula : R1R2R3R4N+X ⁇ wherein R1 is a C8-C10 alkyl, alkenyl or alkaryl group, R2, R3 and R4 are each C1-C3 alkyl groups wherein the total number of carbon atoms of R1, R2, R3 and R4 is from 15 to 21; and X ⁇ is a counter-ion, including Cl ⁇ , NO3 ⁇ or CH3SO4 ⁇ ; or a quaternary ammonium compound having the formula: R.R.R.R.N+.X ⁇ wherein at least two R's are C4-C12 alkyl, alkenyl or alkaryl groups and the remaining R or R's are C1-C12 alky
• Bleaching processes incorporating said low levels of quaternary ammonium compounds can be carried out using the mono-peroxyacid compound at the usual active oxygen concentration in solution of about 0.3x10 ⁇ 3 Molar to about 3x10 ⁇ 3 Molar, preferably from 0.3 to 1.5x10 ⁇ 3 Molar.
• the organic mono-peroxyacid bleach compound as defined above and the quaternary ammonium compound as defined above are present in a molar ratio of peroxyacid bleach compound to quaternary ammonium compound of from about 50:1 to about 1:2.5, preferably from about 25:1 to 1:2.
• compositions comprising the aforesaid mono-peroxyacid compound bleach and the aforesaid quaternary ammonium compound are effective over a wide pH range of between 4 and about 10.5, with optimal pH range lying between 7 and 9.5.
• the peroxyacid bleach compounds utilized in the present invention are the organic mono-peroxyacids and their salts, having no other anionic moiety than the peroxycarboxyl group.
• a suitable class of organic peroxyacids can be represented by compounds of the general formula : wherein R is an alkylene or substituted alkylene group containing 1 to 20 carbon atoms or an arylene group containing from 6 to 8 carbon atoms, n is 0 or 1.
• compounds of this type are peracetic acid, peroxylauric acid, peroxynonanoic acid, peroxybenzoic acid, m-chloroperoxybenzoic acid, and p-nitro-peroxybenzoic acid.
• peroxyacids usable herein are those as described in EP-A-0 325 288 which can be represented by the general formula: wherein X is H, alkyl chain, a halogen or nitro-group in any position of the aromatic ring; R is a straight or branched chain lower C1-C4-alkylene, preferably - CH2 -; and y is between 1 and 12, preferably 3-8.
• a preferred compound within this class is one having the formula: phthaloylamino-peroxycaproic acid.
• Still another class of peroxyacids usable herein is for example the class of fatty peroxyacids and salts thereof having amide moieties in the fatty chain as described in EP-A-0 170 386 and EP-A-0 290,292, of the following general formulae: wherein R1 and R2 are alkyl(ene), aryl(ene) or alkaryl(ene) groups containing from about 1 to about 14 carbon atoms and R5 is H or an alkyl, aryl or alkaryl group containing from about 1 to about 10 carbon atoms.
• Still further classes of organic mono-peroxyacids not containing an additional anionic moiety are known, such as the imidoperoxycarboxylic acids of EP-A-0 366 041.
• Suitable peroxy acid salts for use herein are for example the alkalimetal and magnesium salts thereof.
• the peroxyacid in systems wherein the peroxyacid is formed in situ from its precursor or precursors, can be formed from the combination of an organic peroxyacid precursor and hydrogen peroxide or a persalt of the peroxyhydrate type, e.g. sodium perborate, by perhydrolysis, or from a precursor which generates peroxyacid by hydrolysis.
• peroxyacid precursors will fall within the scope of use in the compositions of the invention. These include, for example, benzoyl peroxide, which is capable of generating peroxybenzoic acid.
• peroxyacid precursors generating peroxyacids by perhydrolysis are disclosed in e.g. US Patent 3,256,198; US Patent 3,272,750; GB Patent 836,988; GB Patent 864,798; US Patent 4,283,301; US Patent 4,486,327; US Patent 4,536,314; US Patent 3,686,127; US Patent 4,397,757; US Patent 4,751,015; and EP-A-0 120 591.
• Preferred peroxyacid precursors include sodium-4-benzoyloxy benzene sulphonate; N,N,N',N'-tetraacetyl ethylene diamine; sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate; and sodium-4-methyl-3-benzoyloxy benzoate, and also those precursors as described in EP-A 0 170 386 and EP-A 0 290 292. These precursors are utilized in the presence of an alkaline source of hydrogen peroxide to generate the corresponding peracids in situ .
• any of the hydrogen peroxide sources known in the art can be utilized together with peracid precursors to generate peracids by a reaction, known as perhydrolysis.
• hydrogen peroxide sources utilizable herein include the alkali metal peroxides, organic peroxides, such as urea peroxide, and the inorganic "persalts" such as the alkali metal perborates, percarbonates, perphosphates and persilicates.
• Preferred compounds for use in the process of the invention are hydrogen peroxide, sodium percarbonate and sodium perborate tetra- or monohydrate.
• the peroxyacid bleach compounds include the peroxyacids or peroxyacid salts per se , as well as the above-described peroxyacid precursor systems generating the peroxyacid bleach in situ , the peroxyacids and salts thereof being preferred.
• the process of the invention is effective at low temperatures, e.g. at 40°C and below, and can be advantageously used in both household practice for the effective bleaching and stain removal from textiles and fabrics, as well as in industrial practice for various purposes whereby the results are substantially improved such as in the following areas:
• compositions of the invention having improved bleaching effect, particularly at the lower temperature region can be used as a true bleaching composition, as a bleach additive to a wash liquor- or for admixing with a cleaning composition.
• the composition will essentially comprise a peroxyacid bleach compound, which may be an organic peroxyacid or a peroxyacid salt or a precursor thereof, as herein before described, and a quaternary ammonium compound as defined hereinbefore.
• a peroxyacid bleach compound which may be an organic peroxyacid or a peroxyacid salt or a precursor thereof, as herein before described, and a quaternary ammonium compound as defined hereinbefore.
• the compositions When admixed to cleaning compositions forming effective low temperature detergent bleach compositions, the compositions are usable for washing and bleaching of textiles, fabrics and fibres at low temperatures.
• the formulation will normally contain, apart from the above essential ingredients, a surface-active material, detergency builders and other known ingredients of such formulations.
• the bleaching composition is incorporated therein in an amount such that, upon use, the detergent bleach composition at a dosage of from 1-6 g/l will have the peroxyacid and the quaternary ammonium compound in the washing and bleaching solution at molar concentrations within the ranges as advantageously described hereinbefore.
• the lower dosage is normally used under US washing conditions, whereas the higher dosage is normal in European washing practice.
• the surface-active material should preferably be non-anionic in nature, since anionic surfactants may neutralize the effect of the cationic quaternary ammonium compound.
• Suitable surface-active agents which can be utilized herein are nonionic, zwitterionic and/or amphoteric in nature, the total level of which may range from 0% up to about 50% by weight, preferably from about 2% to 40% by weight of the composition, most preferably 4 to 25% by weight.
• nonionic surface-active compounds examples 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 6-30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine.
• alkyl polyglycosides long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.
• Amounts 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 nonionic actives.
• the bleaching and cleaning compositions utilizing the bleach composition of the invention will normally also contain a detergency builder.
• 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 polyacetalcarboxylates as disclosed US Patents 4,144,225 and 4,146,495.
• alkali metal polyphosphates such as sodium tripolyphosphate, nitrilotriacetic acid and its water-soluble salts
• polyacetalcarboxylates as disclosed US Patents 4,144,225 and 4,146,495.
• precipitating builder materials examples include sodium orthophosphate, sodium carbonate and long-chain fatty acid soaps.
• 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.
• compositions of the invention may contain any one of the organic or inorganic builder materials, such as sodium or potassium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl malonate, carboxymethyl succinate and the water-insoluble crystalline or amorphous aluminosilicate builder materials, or mixtures thereof.
• the organic or inorganic builder materials such as sodium or potassium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyl malonate, carboxymethyl succinate and the water-insoluble crystalline or amorphous aluminosilicate builder materials, or mixtures thereof.
• These builder materials may be present at a level of, for example, from 5 to 80% by weight, preferably from 10 to 60% by weight.
• a fully formulated bleaching and cleaning composition of the invention can contain any of the conventional additives in the amounts in which such materials are normally employed in fabric-washing detergent compositions.
• these additives include lather boosters, such as alkanolamides, particularly the monoethanolamides 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, fabric-softening agents, inorganic salts such as sodium sulphate, and, usually present in very small amounts, fluorescent agents, perfumes, enzymes such as proteases, cellulases, lipases and amylases, germicides and colorants.
• lather boosters such as alkanolamides, particularly the monoethanolamides derived from palmkernel fatty acids and coconut fatty acids
• the peroxyacid compounds usable in the bleach or bleach and detergent compositions of the invention may be present in an amount of from 0.5-65% by weight of the total composition, preferably from 1-50%, particularly from 1-25% by weight.
• the higher side of the range is usually applied to true bleaching compositions which can be used as such for bleaching fabrics or as a bleach adjunct to detergent compositions.
• the lower side of the range applies to fully formulated heavy duty bleaching detergent compositions.
• the peroxyacid compound is usually present at a level within the range of 0.5-15% by weight, preferably from 1-10% by weight.

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Citations (4)

• 1991
  • 1991-01-16 EP EP19910200071 patent/EP0443640A3/en not_active Ceased
  • 1991-01-18 IN IN21BO1991 patent/IN172454B/en unknown
  • 1991-01-21 AU AU69488/91A patent/AU635381B2/en not_active Ceased
  • 1991-01-23 JP JP3085437A patent/JPH0791779B2/ja not_active Expired - Lifetime

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