WO2000036064A1 - Bleaching compositions based on air oxidation of aromatic aldehydes at specific ph range - Google Patents

Bleaching compositions based on air oxidation of aromatic aldehydes at specific ph range Download PDF

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Publication number
WO2000036064A1
WO2000036064A1 PCT/EP1999/008580 EP9908580W WO0036064A1 WO 2000036064 A1 WO2000036064 A1 WO 2000036064A1 EP 9908580 W EP9908580 W EP 9908580W WO 0036064 A1 WO0036064 A1 WO 0036064A1
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Prior art keywords
bleaching
composition according
air
aldehyde
aromatic aldehyde
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PCT/EP1999/008580
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French (fr)
Inventor
Uday Shanker Racherla
Robert Charles Vermeer
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Unilever Plc
Unilever Nv
Hindustan Lever Limited
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Priority to AU13818/00A priority Critical patent/AU1381800A/en
Publication of WO2000036064A1 publication Critical patent/WO2000036064A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/10Preparations for permanently dyeing the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/11Encapsulated compositions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/22Peroxides; Oxygen; Ozone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/69Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing fluorine
    • A61K8/70Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing fluorine containing perfluoro groups, e.g. perfluoroethers
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q11/00Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
    • A61Q11/02Preparations for deodorising, bleaching or disinfecting dentures
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2072Aldehydes-ketones
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/24Organic compounds containing halogen
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/24Organic compounds containing halogen
    • C11D3/245Organic compounds containing halogen containing fluorine

Definitions

  • This invention concerns compositions and processes for bleaching substrates directly with air.
  • Oxygen bleaches are well known for their ability to remove stains from substrates.
  • the substrate is subjected to hydrogen peroxide or substances which can generate hydroperoxyl radicals.
  • the latter may be inorganic or organic peroxides.
  • these systems must be activated.
  • a method of activation is to employ wash temperatures of 60°C or higher. Unfortunately, these high temperatures often lead to inefficient cleaning. They can also cause premature damage to the substrate.
  • a preferred approach to generating hydroperoxyl bleach radicals is the use of inorganic peroxides coupled with organic precursor compounds. These systems are employed for many commercial laundry powders. European systems are based on tetraacetyl ethylenediamine (TAED) as the organic precursor coupled with sodium perborate or sodium percarbonate. Well known in the United States are laundry bleach products based on sodium nanonyloxybenzenesulphonate (SNOBS) as the organic precursor coupled with sodium perborate. Precursor systems are generally effective yet they still exhibit several disadvantages. For example, organic precursors are moderately sophisticated molecules requiring multi-step manufacturing processes resulting in high capital costs.
  • TAED tetraacetyl ethylenediamine
  • SNOBS sodium nanonyloxybenzenesulphonate
  • precursor systems have large formulation space requirements; a significant percent of a laundry powder must be devoted to the bleach components leaving less room for other active ingredients and complicating development of concentrated powders.
  • precursor systems do not bleach very efficiently in countries where consumers have wash habits entailing low dosage, short wash times, cold temperatures and low wash liquor to cloth ratios.
  • WO 97/38074 reports use of molecular oxygen (air) for oxidizing stain from fabrics. It was discovered that fabrics can be bleached by bubbling air through an aqueous solution containing an aldehyde.
  • a broad range of aliphatic, aromatic and heterocyclic aldehydes were reported to be useful, particularly para-substituted aldehydes such as 4-methyl-, 4-ethyl- and 4-isopropyl benzaldehyde. It was also necessary in these systems to employ a radical initiator.
  • a broad range of initiators were disclosed including N-hydroxysuccinimide, various peroxides and transition metal coordination complexes.
  • the pH range of operability was broadly disclosed as being from 4 to 12, but preferably in the range of 7 to 10 with most experiments being performed at pH 7. While this disclosure appears to be a step-change in bleach chemistry, it is clear that more work is required to reveal the optimum system.
  • Another object of the present invention is to provide a bleaching system which is cost-effective and environmentally friendly.
  • the present invention provides a bleaching composition which includes:
  • a method for bleaching stains from substrates is provided by treating the substrates with air and an aromatic aldehyde in an aqueous system at pH between 8 and 10.
  • An essential feature of the present invention is a C -C 20 aromatic aldehyde.
  • aromatic aldehydes selected from those having a calculated logP ranging from about 2 to about 3.
  • logP is the mathematical log value of the partition coefficient for solubility of the aldehyde between water and 1 - octanol. It is a property of a two-phase system in which 1-octanol and water are in equilibrium, at a fixed temperature, and an organic substance is distributed between these phases. LogP is best defined as the equilibrium distribution or the ratio of an organic substance in the 1-octanol phase to that in the water phase. In general, logP tends to be small for polar hydrophilic substances and large for nonpolar hydrophobic substances.
  • logP provides a measure of the hydrophilic vs. hydrophobic nature (HLB balance) of a compound, which is an important consideration in assessing solubility.
  • HLB balance hydrophilic vs. hydrophobic nature
  • Examples of specific aromatic aldehydes which are particularly effective include: 2-methylbenzaldehyde. 3-methylbenzaldehyde. 4-methylbenzaldehyde. 2- chlorobenzaldehyde, 2.3-dimethylbenzaldehyde. 2,4-dimethylbenzaldehyde, 2,5- dimethylbenzaldehyde, 3,6-dimethylbenzaldehyde, 3.4-dimethylbenzaldehyde. 3.5- dimethylbenzaldehyde, 4,5-dimethylbenzaldehyde, 4.6-dimethylbenzaldehyde. 5.6- dimethylbenzaldehyde. 2-ethylbenzaldehyde, 2-trifluoromethylbenzaldehyde.
  • aromatic aldehyde encompasses substituted aromatic rings.
  • substituted groups are alkyl (particularly methyl and ethyl), trifluoromethyl. carboxy, phospho, sulpho, chloro, bromo, fluoro, cyano, alkoxy. nitro, amino, quaternary ammonium, hydroxyalkyl and combinations thereof.
  • substituent must allow the aldehyde to fall within the acceptable calculated logP value of about 2 to about 3 and other criteria previously specified for optimum bleaching performance.
  • the aromatic aldehyde should be added in an amount effective for stain removal. Amounts of the aromatic aldehyde may range from about 0.01 to about 80%, preferably from about 0.1 to about 50%, more preferably from about 0.5 to about 20%, optimally from about 1 to about 5% by weight of the bleaching composition. Optionally present may be a promoter for allowing molecular oxygen of the air to combine with the aromatic aldehyde.
  • promoters examples include di C 2 -C 2 o peroxides (such as t-butylperoxy acetate, di-t-butylperoxide, cumene peroxide and urea peroxide), inorganic peroxides (such as potassium peroxydisulphate and calcium peroxide), C -C 20 azides (such as azo-bis-isobutyronitrile and sodium azide) and C 4 -C 20 imides.
  • Other promoters include transition metals whether in complexed or uncomplexed form. Suitable metals include manganese, iron, cobalt, molybdenum, tungsten and titanium. Most preferred are iron and cobalt.
  • the most preferred promoter is that of an aromatic imide of the general structure:
  • A is CX q and X is selected from the group consisting of hydrogen, C 1 -C 5 alkyl, a heteroatom substituent and mixtures thereof, where q is independently 1 or 2;
  • R is a moiety, which if hydrocarbyl may have from 1 to 7 carbon atoms, and is selected from the group consisting of hydrogen, alkyl, cycloalkyl. aryl, alkoxy, hydroxy, acyloxy, halo, carboxy, amino, quaternary amino, sulpho, phospho, cyano radicals and mixtures thereof; m and n may independently range from 0 to 4. Particularly preferred substituents are methyl, ethyl, isopropyl.
  • Amounts of the promoter when present may range from about 0.001 to about 65%, preferably from about 0.01 to about 7%, more preferably from about 0.1 to about 1% by weight of the bleaching composition.
  • the weight ratio of aldehyde to promoter may range from about lxl0 8 :l to about 1 :2, preferably from about lxl0 6 :l to about 1 :1, most preferably from about 1000:1 to about 10:1.
  • Bleach systems of the present invention may be employed for a wide variety of purposes. These include cleaning hard surfaces, food utensils, kitchenware, floors, bathtubs, hair, carpets, dentures and fabrics. Most especially the systems are useful in the cleaning of laundry and kitchenware.
  • the aldehyde and imide of the present invention may usually be combined with surface-active materials, detergency builders and other known ingredients of detergent formulations.
  • the surface-active material i.e. surfactants or cleansing agents
  • anionic. nonionic. amphoteric. zwitterionic. cationic actives and mixtures thereof 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.
  • the total level of the surface-active material may range up to 50% by weight, preferably being from 0.5 to 40% by weight of the composition, most preferably 4 to 25%.
  • 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.
  • suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulphates, especially those obtained by sulphating higher (C 8 -Cj 8 ) alcohols produced for example from tallow or coconut oil; sodium and ammonium alkyl (C 8 -C 2 o) benzene sulphonates, sodium alkyl glyceryl ether sulphates, especially those ethers 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 (C 9 -C ⁇ 8 ) 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 neutralized with sodium hydroxide; sodium and ammonium salts of fatty acid amides of methyl taurine; sarcosinate salts; alkan
  • the preferred anionic detergent compounds are sodium (C11-C1 5 ) alkylbenzene sulphonates. sodium (Ci 6 -C ⁇ 8 ) alkyl sulphates and sodium (C
  • 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 oxide per molecule; the condensation products of aliphatic (C 8 -Cj 8 ) primary or secondary linear or branched alcohols with ethylene oxide, generally 2-30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine.
  • alkylene oxides usually ethylene oxide
  • alkyl (C 6 -C 22 ) phenols generally 5-25 EO, i.e. 5-25 units of ethylene oxide per molecule
  • condensation products of aliphatic (C 8 -Cj 8 ) primary or secondary linear or branched alcohols with ethylene oxide generally 2-30 EO
  • nonionic surface-actives include alkyl polyglucosides, long chain tertiary amine oxides, and fatty amido polyols such as alkyl methyl glucamides and alkyl lactobionamides.
  • Amphoteric or zwitterionic surface-active compounds such as alkylamidopropyl betaines can also be used in the compositions of the invention. 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.
  • Soaps may also be incorporated into the compositions of the invention, preferably at a level of less than 30% by weight. They are particularly useful at low levels in binary (soap/anionic) or ternary mixtures together with nonionic or mixed synthetic anionic and nonionic compounds. Soaps which are used are preferably the sodium, or less desirably potassium, salts of saturated or unsaturated C ⁇ o-C 24 fatty acids or mixtures thereof. The amount of such soaps can be varied between 0.5 and 25% by weight, with lower amounts of 0.5 to 5% being generally sufficient for lather control. Amounts of soap between 2 and 20%, especially between 5 and 15. are used to give a beneficial effect on detergency. This is particularly valuable in compositions used in hard water where the soap acts as a supplementary builder.
  • anionic surfactants such as linear alkylbenzene sulphonate
  • a hydrotrope or phase regulant such as alkali metal benzene sulphonate, toluene sulphonate and ethyl benzene sulphonate thereby improving the bleaching effect.
  • the detergent compositions 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.
  • compositions of the invention may contain any one of the organic or inorganic builder materials, such as sodium, potassium, lithium or magnesium salts of tripolyphosphate, pyrophosphate. orthophosphate. carbonate, nitrilotriacetic acid, citrate, carboxymethylmalonate, carboxymethyloxysuccinate, tartrate mono- and di- succinate, oxydisuccinate, bicarbonate, tetraborate, tetraboratedecahydrate, crystalline or amorphous aluminosilicates and mixtures thereof.
  • Most preferred among the builders are the salts of carbonate, sesquicarbonate, bicarbonate and borate as well as zeolite and mixtures thereof.
  • Polycarboxylic homo- and co-polymers may also be included as builders and to function as powder structurants or processing aids. Particularly preferred are polyacrylic acid (available under the trademark Acrysol from the Rohm and Haas Company) and acrylic-maleic acid copolymers (available under the trademark Sokalan from the BASF Corporation) and alkali metal or other salts thereof. These builder materials may be present at a level of from about 1 to 80% by weight, preferably from about 10 to 60% by weight.
  • the initial amount of aldehyde should range anywhere from about 0.1 to about 30 mmol/liter, preferably from about 1 to about 15 mmol/liter of the aqueous wash liquor.
  • the N-hydroxy imide can range anywhere from about 0.001 to about 10 mmol/liter, preferably from about 0.01 to about 2 mmol/liter.
  • Surfactant when present in the wash water may range from about 0.05 to about 1.0 grams/liter, preferably from about 0.15 to about 0.25 grams/liter.
  • the builder amount may range from about 0.1 to about 3.0 grams/liter.
  • the aldehydes of the present invention are sensitive to certain detergent ingredients as well as to air; they can be protected by encapsulation or some other suitable protective barrier.
  • Methods of encapsulation are described in U.S. Patents 5,385,959, U.S. Patent 5.441.660 and U.S. Patent 5,434,069.
  • Examples of preferred encapsulation polymers include, but are not limited to, polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone, carrageenan, guar gum. xanthan gum and celluloses.
  • the bleaching compositions of the invention may contain any of the conventional additives in the amounts in which such materials are normally employed in cleaning compositions.
  • these additives include dye transfer inhibition agents such as polyamine N-oxide polymers, metallo phthalocyanines, and polymers based on N-vinylpyrrolidone and N- vinylimidazole, lather boosters such as alkanolamides, particularly the monoethanolamides derived from palmkerael fatty acids and coconut fatty acids, lather- depressants such as alkyl phosphates and silicones, anti-redeposition agents such as sodium carboxymethylcellulose and alkyl or substituted alkylcellulose ethers, stabilizers such as ethylene diamine tetraacetic acid and phosphonic acid derivatives (Dequest®), fabric softening agents, inorganic salts such as sodium sulphate, and, usually present in very small amounts, fluorescent agents, perfumes, enzymes such as proteases, cellulases, lipa
  • dye transfer inhibition agents
  • the aldehydes in combination with the imide may be useful for removing stains both in consumer type products and for industrial applications.
  • consumer products incorporating this invention are laundry detergents, laundry bleaches, hard surface cleaners, toilet bowl cleaners, automatic dishwashing compositions and even denture cleansers.
  • Stained consumer products benefiting from treatment with compositions of this invention may include clothes and other fabrics; household fixtures and appliances such as sinks, toilet bowls and oven ranges; tableware such as drinking glasses, dishes, cookware and utensils; and dentures.
  • Hair colorants may also be formulated with the bleach composition of this invention.
  • the bleaching system of this invention may also be applied to industrial uses such as for the bleaching of wood pulp.
  • the system of the present invention may be delivered in a variety of product forms including powders, on sheets or other substrates, in pouches, in tablets, in aqueous liquids, or in nonaqueous liquids such as liquid nonionic detergents, aerosol, gel, cream or granular form.
  • the reflectance of 4 stained swatches (4 per pot) were measured before and after washing using a Gardner reflectometer (Model #2000) set at 460*nm (*UV filter).
  • the change in reflectance ( ⁇ R) was determined by taking the difference of the swatch before and after each washing.
  • the standard deviation ( ⁇ ) and ⁇ R ave was assigned to each experimental group.
  • Rj Initial reflectance of stained swatch before washing.
  • ⁇ R ave Represents the average bleaching by the aldehyde system.
  • Tables IV-V report the stain removal of tea (BC-1) and strawberry stain (CS-18) in a buffered system at pH 8.
  • Tables VI-VII examine the tea and strawberry stained cloth bleaching, respectively at pH 10. Wash conditions were identical to those reported under Example 1 with the exception that p- methylbenzaldehyde was employed as the model aldehyde.
  • the following formulation illustrates a disinfectant cleaning composition which may include the bleaching system of the present invention.
  • the following formulation illustrates an automatic dishwashing composition which may include the bleaching system of the present invention.
  • the following formulation illustrates an abrasive cleaning composition which may include the bleaching system of the present invention.
  • the following formulation illustrates a hard-surface detergent cleaning composition which may include the bleaching system of the present invention.
  • the following formulation illustrates an oven cleaning composition which may include the bleaching system of the present invention.
  • the following formulation illustrates a denbare cleaning composition which may include the bleaching system of the present invention.
  • the following formulation illustrates a hair lightening composition for dying hair blonde which may include the bleaching system of the present invention.

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Abstract

A bleach composition and a method for bleaching stains is provided, the composition including a C7-C20 aromatic aldehyde and the composition having a pH when dispersed in water ranging from 8 to 10. Air is employed as source of oxygen which combines with the aldehyde to form the bleach active species. Peroxides, inorganic persalts and bleach precursors are unnecessary elements for the bleach systems of this invention.

Description

BLEACHING COMPOSITIONS BASED ON AIR OXIDATION OF AROMATIC ALDEHYDES AT SPECIFIC PH RANGE
This invention concerns compositions and processes for bleaching substrates directly with air.
Oxygen bleaches are well known for their ability to remove stains from substrates. Traditionally the substrate is subjected to hydrogen peroxide or substances which can generate hydroperoxyl radicals. The latter may be inorganic or organic peroxides. Generally these systems must be activated. A method of activation is to employ wash temperatures of 60°C or higher. Unfortunately, these high temperatures often lead to inefficient cleaning. They can also cause premature damage to the substrate.
A preferred approach to generating hydroperoxyl bleach radicals is the use of inorganic peroxides coupled with organic precursor compounds. These systems are employed for many commercial laundry powders. European systems are based on tetraacetyl ethylenediamine (TAED) as the organic precursor coupled with sodium perborate or sodium percarbonate. Well known in the United States are laundry bleach products based on sodium nanonyloxybenzenesulphonate (SNOBS) as the organic precursor coupled with sodium perborate. Precursor systems are generally effective yet they still exhibit several disadvantages. For example, organic precursors are moderately sophisticated molecules requiring multi-step manufacturing processes resulting in high capital costs. Secondly, precursor systems have large formulation space requirements; a significant percent of a laundry powder must be devoted to the bleach components leaving less room for other active ingredients and complicating development of concentrated powders. Moreover, precursor systems do not bleach very efficiently in countries where consumers have wash habits entailing low dosage, short wash times, cold temperatures and low wash liquor to cloth ratios.
A long cherished dream has been to use air directly as the oxygen source. Air would avoid costly synthesized organic precursors. Unfortunately, air is kinetically inert towards bleaching substrates due to the spin barrier restriction and exhibits no bleaching ability. Recently some progress has been made in this area.
WO 97/38074 reports use of molecular oxygen (air) for oxidizing stain from fabrics. It was discovered that fabrics can be bleached by bubbling air through an aqueous solution containing an aldehyde. A broad range of aliphatic, aromatic and heterocyclic aldehydes were reported to be useful, particularly para-substituted aldehydes such as 4-methyl-, 4-ethyl- and 4-isopropyl benzaldehyde. It was also necessary in these systems to employ a radical initiator. A broad range of initiators were disclosed including N-hydroxysuccinimide, various peroxides and transition metal coordination complexes. Moreover, the pH range of operability was broadly disclosed as being from 4 to 12, but preferably in the range of 7 to 10 with most experiments being performed at pH 7. While this disclosure appears to be a step-change in bleach chemistry, it is clear that more work is required to reveal the optimum system.
Accordingly, it is an object of the present invention to provide an optimum bleaching system with improved stain removal efficacy based on air or molecular oxygen.
Another object of the present invention is to provide a bleaching system which is cost-effective and environmentally friendly.
Still another object of the present invention is to provide a bleaching system based on air that is operable under harsh water conditions which includes relatively low temperatures, short contact times and low dosage requirements. Yet another object of the present invention is to provide an improved hygiene or antimicrobial benefit coupled with reduction in dye transfer damage.
These and other objects of the present invention will become more readily apparent from the following summary and detailed description.
Accordingly, the present invention provides a bleaching composition which includes:
(i) a C7-C20 aromatic aldehyde for stain removal; and (ii) air as a primary source of oxygen atoms to combine with the aldehyde, wherein the composition when placed in water has a pH ranging from 8 to 10.
Furthermore, a method for bleaching stains from substrates is provided by treating the substrates with air and an aromatic aldehyde in an aqueous system at pH between 8 and 10.
Now it has been discovered that stains can be removed simply by air oxidation through the intermediacy of a C -C20 aromatic aldehyde in an aqueous wash system wherein pH is limited to the range of 8 to 10, preferably between 8 and 9 and optimally between 8 and 8.5.
An essential feature of the present invention is a C -C20 aromatic aldehyde. Particularly advantageous are aromatic aldehydes selected from those having a calculated logP ranging from about 2 to about 3. The term logP is the mathematical log value of the partition coefficient for solubility of the aldehyde between water and 1 - octanol. It is a property of a two-phase system in which 1-octanol and water are in equilibrium, at a fixed temperature, and an organic substance is distributed between these phases. LogP is best defined as the equilibrium distribution or the ratio of an organic substance in the 1-octanol phase to that in the water phase. In general, logP tends to be small for polar hydrophilic substances and large for nonpolar hydrophobic substances. Thus logP provides a measure of the hydrophilic vs. hydrophobic nature (HLB balance) of a compound, which is an important consideration in assessing solubility. We have found that aldehydes outside the calculated logP range of about 2 to 3 do not bleach and are ineffective. Even more advantageous are aromatic aldehydes that are liquids and have a total carbon content from 7 to 15, preferably from 7 to 10, and optimally from 8 to 9 carbon atoms.
Examples of specific aromatic aldehydes which are particularly effective include: 2-methylbenzaldehyde. 3-methylbenzaldehyde. 4-methylbenzaldehyde. 2- chlorobenzaldehyde, 2.3-dimethylbenzaldehyde. 2,4-dimethylbenzaldehyde, 2,5- dimethylbenzaldehyde, 3,6-dimethylbenzaldehyde, 3.4-dimethylbenzaldehyde. 3.5- dimethylbenzaldehyde, 4,5-dimethylbenzaldehyde, 4.6-dimethylbenzaldehyde. 5.6- dimethylbenzaldehyde. 2-ethylbenzaldehyde, 2-trifluoromethylbenzaldehyde. 4- ethylbenzaldehyde. 3-ethylbenzaldehyde. 2,3.4-trimethylbenzaldehyde. 2.3,5- trimethylbenzaldehyde, 2.3,6-trimethylbenzaldehyde, 2,4,5-trimethylbenzaldehyde. 2,4,6-trimethylbenzaldehyde. 2.5,6-trimethylbenzaldehyde, 3,4.5- trimethylbenzaldehyde, 3 ,4.6-trimethylbenzaldehyde, 3 ,5 ,6-trimethylbenzaldehyde, 4,5,6-trimethylbenzaldehyde and the like.
For purposes of this invention it is to be understood that the term aromatic aldehyde encompasses substituted aromatic rings. Illustrative but not limiting examples of substituted groups are alkyl (particularly methyl and ethyl), trifluoromethyl. carboxy, phospho, sulpho, chloro, bromo, fluoro, cyano, alkoxy. nitro, amino, quaternary ammonium, hydroxyalkyl and combinations thereof. Of course, the choice of substituent must allow the aldehyde to fall within the acceptable calculated logP value of about 2 to about 3 and other criteria previously specified for optimum bleaching performance.
The aromatic aldehyde should be added in an amount effective for stain removal. Amounts of the aromatic aldehyde may range from about 0.01 to about 80%, preferably from about 0.1 to about 50%, more preferably from about 0.5 to about 20%, optimally from about 1 to about 5% by weight of the bleaching composition. Optionally present may be a promoter for allowing molecular oxygen of the air to combine with the aromatic aldehyde. Examples of these promoters include di C2-C2o peroxides (such as t-butylperoxy acetate, di-t-butylperoxide, cumene peroxide and urea peroxide), inorganic peroxides (such as potassium peroxydisulphate and calcium peroxide), C -C20 azides (such as azo-bis-isobutyronitrile and sodium azide) and C4-C20 imides. Other promoters include transition metals whether in complexed or uncomplexed form. Suitable metals include manganese, iron, cobalt, molybdenum, tungsten and titanium. Most preferred are iron and cobalt.
When present, the most preferred promoter is that of an aromatic imide of the general structure:
Figure imgf000007_0001
wherein
A is CXq and X is selected from the group consisting of hydrogen, C1-C5 alkyl, a heteroatom substituent and mixtures thereof, where q is independently 1 or 2;
R is a moiety, which if hydrocarbyl may have from 1 to 7 carbon atoms, and is selected from the group consisting of hydrogen, alkyl, cycloalkyl. aryl, alkoxy, hydroxy, acyloxy, halo, carboxy, amino, quaternary amino, sulpho, phospho, cyano radicals and mixtures thereof; m and n may independently range from 0 to 4. Particularly preferred substituents are methyl, ethyl, isopropyl. chloro, trifluoromethyl, methoxy, acetyl and cyclic groups, the latter being exemplified by pyridyl, naphthyl, phenyl, furanyl and indolyl radicals. Most preferred is the unsubstituted generic structure where m and n are both 0; this material is known as N-hydroxyphthalimide (NHPI). Examples of other potentially useful stuctures are outlined below.
Figure imgf000008_0001
Figure imgf000008_0002
Amounts of the promoter when present may range from about 0.001 to about 65%, preferably from about 0.01 to about 7%, more preferably from about 0.1 to about 1% by weight of the bleaching composition. The weight ratio of aldehyde to promoter may range from about lxl08:l to about 1 :2, preferably from about lxl06:l to about 1 :1, most preferably from about 1000:1 to about 10:1. Bleach systems of the present invention may be employed for a wide variety of purposes. These include cleaning hard surfaces, food utensils, kitchenware, floors, bathtubs, hair, carpets, dentures and fabrics. Most especially the systems are useful in the cleaning of laundry and kitchenware. When intended for such purpose, the aldehyde and imide of the present invention may usually be combined with surface-active materials, detergency builders and other known ingredients of detergent formulations.
The surface-active material (i.e. surfactants or cleansing agents) may be naturally derived, or synthetic material selected from anionic. nonionic. amphoteric. zwitterionic. cationic actives and mixtures thereof. Many 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. The total level of the surface-active material may range up to 50% by weight, preferably being from 0.5 to 40% by weight of the composition, most preferably 4 to 25%.
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.
Examples of suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulphates, especially those obtained by sulphating higher (C8-Cj8) alcohols produced for example from tallow or coconut oil; sodium and ammonium alkyl (C8-C2o) benzene sulphonates, sodium alkyl glyceryl ether sulphates, especially those ethers 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-Cι8) 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 neutralized with sodium hydroxide; sodium and ammonium salts of fatty acid amides of methyl taurine; sarcosinate salts; alkane monosulphonates such as those derived by reacting alpha-olefins (C8-C20) with sodium bisulphite and those derived by reacting paraffins with SO2 and Cl2 and then hydrolyzing with a base to produce a random sulphonate; sodium and ammonium C7-Cι2 dialkyl sulphosuccinates; and olefin sulphonates, which term is used to describe the material made by reacting olefins, particularly Cι0-C o alpha-olefins, with SO3 and then neutralizing and hydrolyzing the reaction product, sulphated or sulphonated alkyl polyglucosides. sulphated alkyl methyl glucamides. sulphated lactobionamides and combinations thereof. The preferred anionic detergent compounds are sodium (C11-C15) alkylbenzene sulphonates. sodium (Ci6-Cι8) alkyl sulphates and sodium (C|6-Cι8) alkyl ether sulphates.
Examples of suitable 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 oxide per molecule; the condensation products of aliphatic (C8-Cj8) primary or secondary linear or branched alcohols with ethylene oxide, generally 2-30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine. Other so-called nonionic surface-actives include alkyl polyglucosides, long chain tertiary amine oxides, and fatty amido polyols such as alkyl methyl glucamides and alkyl lactobionamides.
Amphoteric or zwitterionic surface-active compounds such as alkylamidopropyl betaines can also be used in the compositions of the invention. 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.
Soaps may also be incorporated into the compositions of the invention, preferably at a level of less than 30% by weight. They are particularly useful at low levels in binary (soap/anionic) or ternary mixtures together with nonionic or mixed synthetic anionic and nonionic compounds. Soaps which are used are preferably the sodium, or less desirably potassium, salts of saturated or unsaturated Cιo-C24 fatty acids or mixtures thereof. The amount of such soaps can be varied between 0.5 and 25% by weight, with lower amounts of 0.5 to 5% being generally sufficient for lather control. Amounts of soap between 2 and 20%, especially between 5 and 15. are used to give a beneficial effect on detergency. This is particularly valuable in compositions used in hard water where the soap acts as a supplementary builder.
In systems where anionic surfactants such as linear alkylbenzene sulphonate are employed, it may be desirable to include a hydrotrope or phase regulant such as alkali metal benzene sulphonate, toluene sulphonate and ethyl benzene sulphonate thereby improving the bleaching effect.
The detergent compositions 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.
In particular, the compositions of the invention may contain any one of the organic or inorganic builder materials, such as sodium, potassium, lithium or magnesium salts of tripolyphosphate, pyrophosphate. orthophosphate. carbonate, nitrilotriacetic acid, citrate, carboxymethylmalonate, carboxymethyloxysuccinate, tartrate mono- and di- succinate, oxydisuccinate, bicarbonate, tetraborate, tetraboratedecahydrate, crystalline or amorphous aluminosilicates and mixtures thereof. Most preferred among the builders are the salts of carbonate, sesquicarbonate, bicarbonate and borate as well as zeolite and mixtures thereof.
Polycarboxylic homo- and co-polymers may also be included as builders and to function as powder structurants or processing aids. Particularly preferred are polyacrylic acid (available under the trademark Acrysol from the Rohm and Haas Company) and acrylic-maleic acid copolymers (available under the trademark Sokalan from the BASF Corporation) and alkali metal or other salts thereof. These builder materials may be present at a level of from about 1 to 80% by weight, preferably from about 10 to 60% by weight.
Upon dispersal in a wash water, the initial amount of aldehyde should range anywhere from about 0.1 to about 30 mmol/liter, preferably from about 1 to about 15 mmol/liter of the aqueous wash liquor. The N-hydroxy imide can range anywhere from about 0.001 to about 10 mmol/liter, preferably from about 0.01 to about 2 mmol/liter. Surfactant when present in the wash water may range from about 0.05 to about 1.0 grams/liter, preferably from about 0.15 to about 0.25 grams/liter. When present, the builder amount may range from about 0.1 to about 3.0 grams/liter.
Often the aldehydes of the present invention are sensitive to certain detergent ingredients as well as to air; they can be protected by encapsulation or some other suitable protective barrier. Methods of encapsulation are described in U.S. Patents 5,385,959, U.S. Patent 5.441.660 and U.S. Patent 5,434,069. Examples of preferred encapsulation polymers include, but are not limited to, polyvinyl alcohol, polyacrylamide, polyvinyl pyrrolidone, carrageenan, guar gum. xanthan gum and celluloses.
Apart from the components already mentioned, the bleaching compositions of the invention may contain any of the conventional additives in the amounts in which such materials are normally employed in cleaning compositions. Examples of these additives include dye transfer inhibition agents such as polyamine N-oxide polymers, metallo phthalocyanines, and polymers based on N-vinylpyrrolidone and N- vinylimidazole, lather boosters such as alkanolamides, particularly the monoethanolamides derived from palmkerael fatty acids and coconut fatty acids, lather- depressants such as alkyl phosphates and silicones, anti-redeposition agents such as sodium carboxymethylcellulose and alkyl or substituted alkylcellulose ethers, stabilizers such as ethylene diamine tetraacetic acid and phosphonic acid derivatives (Dequest®), 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.
The aldehydes in combination with the imide may be useful for removing stains both in consumer type products and for industrial applications. Among consumer products incorporating this invention are laundry detergents, laundry bleaches, hard surface cleaners, toilet bowl cleaners, automatic dishwashing compositions and even denture cleansers. Stained consumer products benefiting from treatment with compositions of this invention may include clothes and other fabrics; household fixtures and appliances such as sinks, toilet bowls and oven ranges; tableware such as drinking glasses, dishes, cookware and utensils; and dentures. Hair colorants may also be formulated with the bleach composition of this invention. The bleaching system of this invention may also be applied to industrial uses such as for the bleaching of wood pulp.
The system of the present invention may be delivered in a variety of product forms including powders, on sheets or other substrates, in pouches, in tablets, in aqueous liquids, or in nonaqueous liquids such as liquid nonionic detergents, aerosol, gel, cream or granular form.
The following examples will more fully illustrate the embodiments of this invention. All parts, percentages and proportions referred to herein and in the appended claims are by weight unless otherwise illustrated.
EXAMPLES
EXAMPLE 1
A general outline of the essential steps in our experimental protocol are shown below.
An Outline of the Essential Protocol Steps
a) Measure the initial reflectance of the swatches (Rj). b) Saturate the wash solution with air. c) Wash, rinse and dry the swatches. d) Measure the final reflectance of the swatches (Rf).
All work was conducted in a Tergotometer with 2L stainless steel pots. The swatches were dried flat on a rack in a Kenmore dryer. Each experiment was performed once with 2 replicate pots containing the same aldehyde (average of 2 values), except for the exceptional bleaching aldehydes, which were repeated 3 times with 2 replicate pots containing the same aldehyde (average of 6 values). The conditions utilized were as follows:
Conditions for Saturating the Wash Solution with Air
Figure imgf000015_0001
Each Tergotometer Pot was filled with 1 liter of milli-Q-water containing the carbonate buffer solution which was saturated for 15 minutes with air under agitation at 25°C. Tea stained (BC-1) swatches were washed for 30 minutes in the presence of aldehyde, air and NHPI at pH=8 or 10 (25°C). The corresponding controls (buffer alone) were performed simultaneously. All swatches were rinsed twice for 3 minutes with agitation at 25°C and dried flat on a rack in a Kenmore with soft heat for 30 minutes. Bleaching Evaluation
To quantify the degree of stain removal, the reflectance of 4 stained swatches (4 per pot) were measured before and after washing using a Gardner reflectometer (Model #2000) set at 460*nm (*UV filter). The change in reflectance (ΔR) was determined by taking the difference of the swatch before and after each washing. The standard deviation (σ) and ΔΔRave was assigned to each experimental group.
ΔR = Rf - R,
Rj = Initial reflectance of stained swatch before washing.
Rf = Final reflectance of stained swatch after washing.
ΔRaldehyde system + control " ΔR control = ΔΔR 2-3 X ΔΔRave
ΔΔRave = Represents the average bleaching by the aldehyde system.
Statistics
Standard Deviation (σ) = [ ∑n aj - aa)2/N-I ]° 5 aj = actual ΔR aa = mean ΔR ∑n = sum (aj-aa)2 per measurement N = number of measurements = 8
The following table lists aldehydes for which the logP was calculated and (for most) the bleach activity on a tea stain was reported.
TABLE I
Figure imgf000017_0001
Figure imgf000018_0001
TABLE II
Figure imgf000019_0001
Figure imgf000020_0001
TABLE III
The Calculated LogP (3.10-5.69) and ΔΔR for Group III Aldehvdes
Figure imgf000020_0002
Figure imgf000021_0001
* = Exceptional Bleaching Aldehyde
It is evident from the Tables I-III that only certain aldehydes, and most especially only those aromatic aldehydes in Table II having a logP between about 2 to about 3 provide an exceptional bleaching benefit. The aldehydes of Table II are all liquids and have a total carbon content from about 7 to 10 carbon atoms.
EXAMPLE 2
A series of experiments were conducted to evaluate the effect of pH. buffering and building on bleaching. Tables IV-V report the stain removal of tea (BC-1) and strawberry stain (CS-18) in a buffered system at pH 8. Tables VI-VII examine the tea and strawberry stained cloth bleaching, respectively at pH 10. Wash conditions were identical to those reported under Example 1 with the exception that p- methylbenzaldehyde was employed as the model aldehyde.
TABLE IV
Bleaching Tea Stains by Air and 4-Methylbenzaldehyde with N-Hydroxyphthalimide at pH 8
Figure imgf000022_0001
Carbonate, Borate, Citrate or Phosphate = ΔR for buffer NHPI = Δ (ΔR) for N-hydroxyphthalimide p-MBA = Δ(ΔR) for -methylbenzaldehyde
/7-MBA+NHPI = Δ(ΔR) for/?-methylbenzaldehyde + N-hydroxyphthalimide
* = Statistically significant bleaching over buffer alone (σave - 0.3) TABLE V
Bleaching Strawberry Stains by Air and 4-Methylbenzaldehyde with N-Hydroxyphthalimide at pH 8
Figure imgf000023_0001
Carbonate, Borate, Citrate or Phosphate = ΔR for buffer NHPI = Δ (ΔR) for N-hydroxyphthalimide /7-MB A = Δ(ΔR) for ^-methylbenzaldehyde
/?-MBA+NHPI = Δ(ΔR) for/?-methylbenzaldehyde + N-hydroxyphthalimide
* = = Statistically significant bleaching over buffer alone (σave = 0.5) TABLE VI
Bleaching Tea Stains by Air and 4-Methylbenzaldehvde with N-Hvdroxyphthalimide at pH 10
Figure imgf000024_0001
Carbonate, Borate, Citrate or Phosphate = ΔR for buffer NHPI = Δ (ΔR) for N-hydroxyphthalimide p-MBA = Δ(ΔR) for ^-methylbenzaldehyde jp-MBA+NHPI = Δ(ΔR) for / methylbenzaldehyde + N-hydroxyphthalimide
* = Statistically significant bleaching over buffer alone (σave = 0.4) TABLE VII
Bleaching Strawberry Stains by Air and 4-Methylbenzaldehyde with N-Hydroxyphthalimide at pH 10
Figure imgf000025_0001
Carbonate, Borate, Citrate or Phosphate = ΔR for buffer NHPI = Δ (ΔR) for N-hydroxyphthalimide p-MBA = Δ(ΔR) for/ nethylbenzaldehyde jP-MBA+NHPI = Δ(ΔR) for/?-methylbenzaldehyde + N-hydroxyphthalimide
Statistically significant bleaching over buffer alone (σave = 0.6) Comparison of tea stain removal values in Tables IV and VI reveals activity across the pH range from 8 to 10. However, optimum results are found around pH 8 with decreasing deficiency as the pH arrives at 10. A similar comparison on strawberry stained cloth is found in Tables V and VII. Bleaching of strawberry stain was found to be much better at pH 8 although there was activity across the whole pH range 8-10.
EXAMPLE 3
The following formulations are suitable for the cleaning of fabrics.
TABLE VIII
Figure imgf000026_0001
EXAMPLE 4
The following formulation illustrates a disinfectant cleaning composition which may include the bleaching system of the present invention.
Figure imgf000027_0001
EXAMPLE 5
The following formulation illustrates an automatic dishwashing composition which may include the bleaching system of the present invention.
Figure imgf000027_0002
EXAMPLE 6
The following formulation illustrates an abrasive cleaning composition which may include the bleaching system of the present invention.
Figure imgf000028_0001
EXAMPLE 7
The following formulation illustrates a hard-surface detergent cleaning composition which may include the bleaching system of the present invention.
Figure imgf000028_0002
EXAMPLE 8
The following formulation illustrates an oven cleaning composition which may include the bleaching system of the present invention.
Figure imgf000029_0001
EXAMPLE 9
The following formulation illustrates a denbare cleaning composition which may include the bleaching system of the present invention.
Figure imgf000029_0002
EXAMPLE 10
The following formulation illustrates a hair lightening composition for dying hair blonde which may include the bleaching system of the present invention.
Figure imgf000030_0001
The foregoing description and examples illustrate selected embodiments of the present invention. In light thereof variations and modifications will be suggested to one skilled in the art, all of which are within the spirit and purview of this invention.

Claims

CLAIMS:
1. A bleaching composition comprising:
(i) a C7-C 0 aromatic aldehyde for stain removal; and (ii) air as a primary source of oxygen atoms to combine with the aldehyde, wherein the composition when placed in water has a pH ranging from 8 to 10.
2. A composition according to claim 1 wherein the aromatic aldehyde is a liquid and contains from 7 to 10 carbon atoms.
3. A composition according to claim 1 or claim 2 wherein the aromatic aldehyde is selected from the group consisting of 2-methylbenzaldehyde, 3 -methylbenzaldehyde. 4-methylbenzaldehyde, 2-chlorobenzaldehyde, 3-trifluoromethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 3.5-dimethylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 2-trifluoromethylbenzaldehyde. 2-ethylbenzaldehyde,
3-ethylbenzaldehyde, 4-ethylbenzaldehyde, 2,4,6-trimethylbenzaldehyde and mixtures thereof.
4. A composition according to any preceding claim further comprising from about 1 to about 80% of a detergent builder.
5. A composition according to any preceding claim further comprising from about 0.5 to about 50% of a surfactant.
6. A composition according to any preceding claim further comprising an effective amount for cleaning of an enzyme selected from the group consisting of proteases, cellulases, lipases, amylases, peroxidases and mixtures thereof.
7. A composition according to any preceding claim in a form selected from the group consisting of a powder, sheet, pouch, tablet, aqueous liquid, nonaqueous liquid, aerosol, gel, cream and granular form.
8. A composition according to any preceding claim wherein the aromatic aldehyde is present in an amount from about 0.01 to about 80% by weight.
9. A composition according to any preceding claim wherein the pH ranges from 8 to 9.
10. A composition according to claim 9 wherein the pH ranges from 8 to 8.5.
1 1. A method for bleaching a stained substrate, the method comprising contacting the stain substrate in an aqueous medium in air with a C -C 0 aromatic aldehyde, the aqueous medium having a pH maintained between 8 and 10.
12. A method according to claim 1 1 comprising contacting the stained substrate in an aqueous medium in air with a C -C 0 aromatic aldehyde, a surfactant to clean the substrate and the aqueous medium having pH ranging between 8 and 10.
13. A method according to claim 1 1 or claim 12 wherein the pH is maintained between 8 and 9.
14. A method according to claim 13 wherein the pH is maintained between 8 and 8.5.
15. A method according to any of claims 1 1 to 14 wherein the substrate is selected from the group consisting of fabrics, household fixtures and kitchenware.
16. A method according to any of claims 1 1 to 14 wherein the substrate is a denture.
PCT/EP1999/008580 1998-12-16 1999-11-09 Bleaching compositions based on air oxidation of aromatic aldehydes at specific ph range WO2000036064A1 (en)

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Cited By (2)

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GB2388375A (en) * 2002-05-11 2003-11-12 Reckitt Benckiser Nv Process for removing stains from plastics substrates
JP2022509417A (en) * 2018-10-31 2022-01-20 ジボダン エス エー Alkoxybenzaldehyde derivatives and their precursors

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Publication number Priority date Publication date Assignee Title
GB2388375A (en) * 2002-05-11 2003-11-12 Reckitt Benckiser Nv Process for removing stains from plastics substrates
JP2022509417A (en) * 2018-10-31 2022-01-20 ジボダン エス エー Alkoxybenzaldehyde derivatives and their precursors

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