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EP0273775A2 - Geschützte optische Aufheller - Google Patents

Geschützte optische Aufheller Download PDF

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Publication number
EP0273775A2
EP0273775A2 EP87311536A EP87311536A EP0273775A2 EP 0273775 A2 EP0273775 A2 EP 0273775A2 EP 87311536 A EP87311536 A EP 87311536A EP 87311536 A EP87311536 A EP 87311536A EP 0273775 A2 EP0273775 A2 EP 0273775A2
Authority
EP
European Patent Office
Prior art keywords
protected
liquid
sodium
compound
detergent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP87311536A
Other languages
English (en)
French (fr)
Other versions
EP0273775A3 (de
Inventor
Edward Tunstall Messenger
Anthony Martin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay Solutions UK Ltd
Original Assignee
Albright and Wilson Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB868631101A external-priority patent/GB8631101D0/en
Priority claimed from GB878723616A external-priority patent/GB8723616D0/en
Application filed by Albright and Wilson Ltd filed Critical Albright and Wilson Ltd
Publication of EP0273775A2 publication Critical patent/EP0273775A2/de
Publication of EP0273775A3 publication Critical patent/EP0273775A3/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0063—Photo- activating 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • 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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • 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
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay

Definitions

  • the present invention relates to protected detergent additives, including optical brighteners, bleaches and other fabric whitening agents, perfumes and dyes, which are suitable for use in liquid laundry detergents.
  • Optical brighteners, blueing agents, peroxygenated and chlorinated bleaches, and photoactivated bleaches have long been known as ingredients of detergent formulations, and are referred to collectively herein as fabric whitening agents.
  • Optical brightening agents are fluorescent dyes which increase the brightness of laundered fabrics by absorbing ultraviolet light and reradiating the energy as visible light. Blueing agents are blue dyes which counteract the tendency of fabrics to yellow after repeated washing and chemical bleaches react chemically with stains, e.g. oxidising them to colourless products.
  • O.B.A will be used for convenience to include not only the conventional fluorescent optical brightening agents to which it properly applies, but also any other minor additive to a liquid detergent which is capable, on application to fabric, of altering the appearance thereof relative to the clean untreated fabric, and in particular to include chemical bleaches, photoactivated bleaches, blueing agents, perfumes and dyes.
  • Liquid laundry detergents are increasingly replacing the more traditional powders in the marketplace, due to certain advantages in handling and use.
  • liquid detergents are popular because they can be used for "prespotting" - that is application of the undiluted liquid directly to a localised stain prior to laundering.
  • Our invention provides a novel composition which offers a means of incorporating O.B.A.s into liquid detergents and which substantially ameliorates or avoids many of the foregoing difficulties. In particular it helps reduce or prevent any localised discolouration due to excessive adsorption of O.B.A. from the undiluted heavy duty liquid on prespotting, and any incompatibility between the O.B.A. and the liquid detergent or other O.B.A.s present therein, but enables the O.B.A. to perform effectively when applied to the main wash.
  • our invention therefore provides a protected O.B.A. system suitable for use in a liquid cleaning composition, said system comprising at least one O.B.A. dispersed in or coated with a hydrophobic protective substance, which is insoluble in concentrated liquid detergent but dispersible therein as particles or droplets, and which is sufficiently fluid or friable at wash temperature to be disrupted under cleaning conditions.
  • our invention provides a protected O.B.A. system for use in a liquid cleaning composition consisting essentially of granules comprising at least one O.B.A. encapsulated within a hydrophobic protective substance which is not soluble in the liquid cleaning composition and which is fluid or friable at normal wash temperatures.
  • our invention provides a protected O.B.A. system for use in liquid detergent compositions consisting essentially of a dispersion of O.B.A. in a hydrophobic liquid which is insoluble in liquid detergent.
  • our invention provides a method of protecting O.B.A. which comprises dispersing an O.B.A. in a hydrophobic protective substance which is insoluble in concentrated liquid detergent at room temperature, and fluid or friable at 60°C.
  • our invention provides a liquid cleaning composition having dispersed therein particles or droplets of a protected O.B.A. system of our invention as hereinbefore described.
  • references herein to solubility in a medium refer to both dissolution in an aqueous or other continuous solvent phase of the medium and solubilisation in micelles or any other discontinuous surfactant phase dispersed in the medium.
  • the hydrophobic material is preferably a hydrophobic liquid polymer.
  • the polymer may be an organo polysiloxane oil, e.g. a poly di(alkyl)siloxane, wherein the alkyl group has preferably from 1 to 4 carbon atoms, especially a poly di(methyl) siloxane.
  • hydrophobic liquids which have been stabilised by suspending therein hydrophobic solid particles. Examples include the silicone compositions which have been proposed for use as antifoam in liquid detergents which comprise hydrophobic silicone oil and hydrophobic silica, e.g. a finely divided silica with a silicone at least partly bonded to the surface of the silica particles.
  • a hydroxy functional organosiloxane may be condensed with the hydroxy groups of the silica surface.
  • examples of such compositions include those sold under the Registered Trade Marks "WACKER” Antifoam S132,”BEVALOID” 4237, "UNION CARBIDE” Y1206, or DIAMOND SHAMROCK'S”NOPCO” 8315.
  • the silicone antifoam may be diluted with an unmodified silicone oil such as a poly dimethyl siloxane.
  • the viscosity of the silicone may be increased by addition of finely divided silica, e.g. fumed silica such asDegussa's "AEROSIL" 200 (RTM).
  • the hydrophobic material may be a high molecular weight hydrocarbon, e.g. petroleum bright stock or a so-called petroleum jelly, a high molecular weight alcohol, e.g. more than 28 carbon atoms or a high molecular weight fluocarbon or a hydrophobic phosphate ester such as a mono- and/or di- fatty alkyl phosphate ester or a salt thereof, especially a sodium or calcium salt or a trialkyl or triaryl phosphate.
  • Hydrophobic fluid materials may be further stabilised by inclusion of hydrophobic solid particles, e.g. those formed by condensing silica with silicone as described above or with a fatty alcohol.
  • the hydrophobic material may be a solid or waxy material at ambient temperature, which has a softening or preferably melting point below normal wash temperature, e.g. below 60°C, preferably below 50°C, more usually 40°C, often below 30°C.
  • Such solid materials provide products which are particularly suitable for use in powder as well as liquid detergents.
  • our hydrophobic material has a viscosity greater than 0.05 Pascal seconds at normal storage temperature (e.g. room temperature) preferably greater than 0.2, more preferably greater than 0.5 and most preferably greater than 0.8 Pascal seconds.
  • the viscosity should be greater than 1 Pascal second e.g. greater than 2 Pascal seconds, especially greater than 10 Pascal seconds.
  • the viscosity should be less than 200 Pascal seconds, most preferably less than 100 Pascal seconds, e.g. less than 60 Pascal seconds and especially less than 40 Pascal seconds, at the temperature of use. Fluid materials having a viscosity between 1 and 50 Pascal seconds at ambient temperature are especially suitable.
  • the O.B.A. may be any fluorescent dye capable of increasing the proportion of light reflected from fabric at visible wavelengths such as suphonated aromatic dyes including any of those hitherto recommended or proposed for use in detergents.
  • O.B.A.s which may be used in the present invention include : ethoxylated 1, 2-(benzimidazolyl) ethylene; 2-­styrylnaphth[1,2d-]oxazole; 1,2-bis(5 ⁇ methyl-2-benzoxazolyl) ethylene; disodium-4,4 ⁇ -bis(6-methylethanolamine-3-anilino-1,3,5-­triazin-2 ⁇ -yl)-2,2 ⁇ -stilbene sulphonate; N-(2-hydroxyethyl-4,4 ⁇ -bis (benzimidazolyl)stilbene; tetrasodium 4,4 ⁇ -bis [4 ⁇ -bis(2 ⁇ -­hydroxymethyl)-amino-6 ⁇ (3 ⁇ -sulphophenyl) amino-1 ⁇ , 3 ⁇ , 5 ⁇ -triazin-2 ⁇ -­yl amino]-2,2 ⁇ -stilbenedisulphonate; disodium-4-(6 ⁇ -­sulphonaphtho[1 ⁇
  • O.B.A.s which may be used according to our invention include blueing agents, dyes, colourants, perfumes, peroxy bleaches and photoactive bleaches.
  • examples include sodium peroxide or, preferably, peroxy carboxylic acids such as peroxy acetic, peroxy benzoic and peroxy fatty acids and especially C 6-20 alkyl di peroxy dioic acids (e.g. diperoxy dodecane dioic acid).
  • Chlorinated bleaches, such as sodium hypochlorite and photoactivated bleaches may also be protected according to the invention as may perfumes.
  • the protected system may additionally comprise stabilisers, activators or synergists for the O.B.A.
  • peroxy bleaches may be stabilised by the presence of phosphonate salts such as dimerised acetodiphosphonate salts or amino tris (methylene­phosphonate), ethylenediamine tetrakis (methylenephosphonate) or diethylenetriamine pentakis (methylenephosphonate).
  • the O.B.A. may be present in the hydrophobic material in the form of dispersed droplets of a solution of O.B.A. in a solvent, e.g. in water or a lower, preferably water miscible, mono-, di- or polyhydric alcohol such as propylene glycol, where the O.B.A. is water-soluble.
  • a solvent e.g. in water or a lower, preferably water miscible, mono-, di- or polyhydric alcohol such as propylene glycol, where the O.B.A. is water-soluble.
  • O.B.A. may be present in the form of suspended solid particles.
  • the O.B.A. may also be present in a water soluble granule or marume.
  • a soluble crystalline carbohydrate such as sucrose or a salt such as sodium chloride, sodium carbonate or sodium sulphate may be granulated or marumerised with the O.B.A. and the product dispersed in, or coated with, silicone or a hydrocarbon, such as petroleum jelly or other hydrophobic agent.
  • the O.B.A. may be incorporated in an inert oil by dispersion by simple stirring. Where the hydrophobic material is solid at room temperature it may first be melted before dispersing the 0.B.A. and subsequently cooled to room temperature. Optionally the dispersion may be spray cooled to provide a particulate product.
  • the proportion of O.B.A. in a liquid protected system may be determined by the desired viscosity of the system, where it is desired to handle or store the latter as a liquid. Higher proportions tend to provide higher viscosities, but are less prone to sedimentation of the dispersed O.B.A. However, we do not exclude the use of sedimenting systems provided that the O.B.A. can be easily redispersed by stirring before the system is added to the detergent composition.
  • the particle size and proportion of the O.B.A. in liquid protected systems are chosen to provide an overall viscosity of the protected system greater than 0.1 Pascal seconds, typically greater than 0.5 Pascal seconds especially greater than 1 Pascal second more preferably greater than 2 Pascal seconds, e.g. greater than 3 Pascal seconds and optionally greater than 10 Pascal seconds, under the conditions of storage and less than 200 Pascal seconds, more preferably less than 100 Pascal seconds, e.g. less than 70 Pascal seconds under the conditions of use.
  • Systems having a viscosity in the range of 2 to 60 Pascal seconds at ambient temperature are generally preferred.
  • the solution preferably contains 1 to 90% by weight of O.B.A., e.g. 2 to 80%, typically 5 to 60%, and its dispersion in the oil typically contains 1-80, more usually 5-70, preferably 10-60, more preferably 15-50, e.g. 20-40 or 30-50% by weight of O.B.A. solution, the percentages being expressed by weight of the total protected system.
  • Suspensions of solid O.B.A. in the protective material typically contain 1 to 90, more usually 5 to 80, preferably 20-60, e.g. 30-50 or 20-30% by weight of solid, based on the total weight of suspension.
  • the proportion of O.B.A. in the protected system may depend on whether the hydrophobic substance is required to perform any useful function in its own right, e.g. as antifoam. Where a low foaming composition is required the O.B.A. and antifoam may conveniently be in the same relative proportions as those which are required in the final composition. Alternatively a more concentrated suspension of O.B.A. may be prepared and diluted with more antifoam prior to use, or added to the composition simultaneously with or separately from the additional antifoam.
  • the concentration of the latter may be the maximum which is consistent with a manageable product.
  • the particle size of the dispersed O.B.A. in the protected system can vary within wide limits.
  • the dispersed O.B.A. may have a particle size in the range 1 ⁇ to 2mm, preferably 5 ⁇ to1mm, e.g. 10 ⁇ -700 ⁇ .
  • the protected system is generally readily dispersed in the liquid detergent by simple stirring.
  • the system may be dispersed as particles or droplets of from 2 ⁇ to 2.5mm diameter,more usually 5u-500 ⁇ , preferably 10 ⁇ -100 ⁇ , where a dispersed solution is used as the protected system.
  • the preferred particle size of the system in the liquid detergent is 500 ⁇ to 1mm.
  • Dispersants and emulsifiers may be used as required but are not usually preferred.
  • the composition is added to a liquid detergent which comprises an aqueous phase, surfactant, sufficient electrolyte dissolved in the aqueous phase to form with the surfactant, a structure capable of supporting suspended particles, and a protected O.B.A. system of our invention, suspended in the detergent composition.
  • a liquid detergent which comprises an aqueous phase, surfactant, sufficient electrolyte dissolved in the aqueous phase to form with the surfactant, a structure capable of supporting suspended particles, and a protected O.B.A. system of our invention, suspended in the detergent composition.
  • the composition contains an effective amount of a detergent builder.
  • Suitable builders include condensed phosphates, especially sodium tripolyphosphate or, less preferably, potassium pyrophosphate or sodium tetraphosphate, sodium carbonate, sodium silicate, sodium orthophosphate, sodium citrate, sodium nitrilotriacetate, a phosphonate such as sodium ethylenediamine tetramethylene phosphonate, sodium aceto diphosphonate or sodium aminotris (methylene phosphonate), sodium ethylenediamine tetracetate or a zeolite.
  • Other less preferred builders include potassium or lithium analogues of the above sodium salts.
  • the proportion of builder is typically from about 5% to about 40% by weight of the liquid detergent composition, usually 10% to 35%, preferaby 15%-30%, more preferably 18% to 28%, most preferably 20 to 27%.
  • Mixtures of two or more builders are often employed, e.g. sodium tripolyphosphate with sodium silicate and/or sodium carbonate, or with zeolite; or sodium nitrilotriacetate with sodium citrate.
  • the builder is at least partly present as solid particles suspended in the composition.
  • liquid detergent compositions according to the aforesaid GB 2,123,846 or GB 2,153,380.
  • the invention is also applicable to the preparation of unbuilt surfactant compositions or compositions in which all the builder is present in solution.
  • the surfactant may be an anionic, nonionic, cationic, amphoteric, zwitterionic and/or semi polar surfactant which may typically be present in concentrations of from 2 to 35% by weight of the composition, preferably 5 to 30%, more usually 7 to 25%, e.g. 10 to 20%.
  • the composition contains an alkyl benzene sulphonate together with one or more other surfactants such as an alkyl polyoxyalkylene sulphate and/or a non-ionic surfactant.
  • the latter may typically be an alkanolamide or a polyoxyalkylated alcohol.
  • anionic surfactants include alkyl sulphate, alkane sulphonates, olefin sulphonate, fatty ester sulphonates, soaps, alkyl sulphosuccinates, alkyl sulphosuccinamates, taurides, isethionates and polyoxyalkylene derivates of the aforesaid categories of anionic surfactant.
  • the surfactant for use herein has an alkyl group with an average of from 8 to 22, preferably 10 to 20, e.g. 12 to 18 carbon atoms.
  • Alkyl groups are preferably primary and straight chain, however we do not exclude branched chain or secondary alkyl groups. In the case of alcohol based non-ionics the branched chain are sometimes preferred.
  • the surfactant may be wholly or predominantly non-ionic, e.g. a polyoxyalkylated alcohol alone or in admixture with a polyoxyalkylene glycol.
  • non-ionic surfactants which may be used include polyoxyalkylated derivatives of carboxylic acids, glycerol, sorbitan, alkylphenols, alkylolamides or amine oxides.
  • polyoxyalkylene groups are preferably to polyoxyethylene groups, or less preferably to polyoxypropylene or mixed oxyethylene oxypropylene copolymeric or block copolymeric groups or to such groups with one or more glyceryl groups.
  • the polyoxyalkylene groups have from 1 to 30, more usuallly 2 to 20, e.g. 5 to 15, alkyleneoxy units.
  • Cationic surfactants for use according to our invention include quaternised alkyl amines, amido amines and imidazolines.
  • Amphoteric surfactants include betaines and sulphobetaines.
  • any surfactant referred to in GB 1,123,846, or in "Surface Active Agents and Detergents" by Schwartz, Perry and Berch, may be used.
  • the pH of the liquid detergent composition is alkaline, e.g. about 7.5, especially 7.5 to 12 typically 8 to 11,e.g. 9 to 10.5.
  • the liquid detergent composition contains dissolved electrolyte.
  • This may comprise a dissolved portion of the builder and/or any other salt, inorganic or organic, which is not itself a surfactant and which salts out the surfactants present from solution (including micellar solution). Examples include sodium chloride, sodium nitrate, sodium bromide, sodium iodide, sodium borate, sodium formate, or sodium acetate, or corresponding potassium salts.
  • the electrolyte is a salt which is required to perform a useful function in the wash liquor.
  • the electrolyte is preferably sufficient to form a spherulitic or lamellar surfactant structure interspersed with an aqueous electrolyte solution.
  • the electrolyte may comprise sodium sulphate in minor concentrations, but electrolyte mixtures containing concentrations of sodium sulphate of about 3% or over, based on the total weight of the detergent composition, are preferably not used because they may give rise to undesirably large crystals of sodium sulphate of more than 1mm in length, e.g. up to 5cm, or even longer.
  • the detergent composition may contain any of the usual minor ingredients such as soil suspending agents (e.g. carboxymethyl cellulose), enzymes, perfumes and bentonite clays.
  • soil suspending agents e.g. carboxymethyl cellulose
  • enzymes e.g. carboxymethyl cellulose
  • perfumes e.g., perfumes and bentonite clays.
  • liquid detergents are those containing long chain, e.g. C 10-14 linear alkyl benzene sulphonates in an amount of 5-12%, long chain alkyl ether sulphates, e.g. with 1-5 ethyleneoxy units in amount of 0-3%, fatty acid alkanolamides, e.g. iethanolamides in amount of 1-5%, mixtures of mono and di long chain alkyl phosphates in amount of 0-3%, e.g. 0.1-1%, sodium tripolyphosphate (preferably pre-hydrated with from 0.5 to 5% by weight of water) in an amount of 14-30%, e.g. 14-18% or 20-30% and optionally sodium carbonate in an amount of up to 10%, e.g.
  • long chain alkyl ether sulphates e.g. with 1-5 ethyleneoxy units in amount of 0-3%
  • fatty acid alkanolamides e.g. iethanolamides in amount of 1-5%
  • the liquid detergent may have a pH of 6 to 13, preferably 7 to 12, more usually 8 to 11, e.g. 9 to 10.5.
  • compositions of the invention may typically contain 0.01 to 10%, e.g. 0.05-0.5% by weight of the protected O.B.A. system.
  • a particular advantage of the present invention is that it assists in the formulation of stable detergents by inhibiting possible interactions between the O.B.A. and any other component of the detergent which may be chemically incompatible therewith.
  • the hydrophobic substance may protect peroxide bleaches from hydrolysis in an alkaline aqueous liquid detergent, or prevent interaction between bleaches and dyes in the composition.
  • the compositions of our invention may advantageously be added to solid, powder detergents as well as to liquid detergents, in order to inhibit interactions between the O.B.A.'s and other components of the powder cleaning compositions. Powder cleaning compositions containing protected O.B.A.'s as hereinbefore described constitute a further aspect of this invention
  • O.B.A. dispersed in silicone antifoam, polyvinyl alcohol or viscous hydrocarbon may be incorporated into a powder laundry detergent.
  • powders may contain surfactant (usually in total amounts of from 5 to 30% by wt.), builder, a solid filler and optionally a bleach.
  • the surfactant comprises a sodium alkyl (preferably C 12-14 linear) benzene sulphonate in amounts of from 2 to 20%, preferably 5 to 15%, by weight of the total composition and optionally a sodium alkyl (e.g. C 12-18 ) polyoxyethylene (e.g. 2 to 10% mole) sulphate and/or a non-ionic surfactant such as an alkanolamide, e.g. coconut, mono- or di- ethanolamide and/or a polyethoxylated fatty alcohol.
  • a non-ionic surfactant such as an alkanolamide, e.g. coconut, mono- or di- ethanolamide and/or
  • the builder is typically sodium tripolyphosphate although zeolites, sodium carbonate, sodium silicates, sodium citrate, sodium nitrilotriacetate and mixtures thereof may be present as well as or in place of sodium tripolyphosphate.
  • the total amount of builder is usually between 10 and 40% by weight of the total powder, e.g. 20 to 30%.
  • the filler is typically sodium sulphate which may typically be present in a proportion of from 0 to 60% usually 20 to 50% of the total composition in order to ensure a free flowing powder.
  • the powder preferably contains at least two protected O.B.A. systems including a fluorescent brightening agent and a bleach.
  • the bleach is normally a peroxy compound especially a perborate, percarbonate or peroxycarboxylic acid.
  • the powder also usually contains the usual minor ingredients such as soil suspending agent (typically sodium carboxymethyl cellulose), enzymes and perfume and optionally colouring.
  • soil suspending agent typically sodium carboxymethyl cellulose
  • enzymes typically sodium carboxymethyl cellulose
  • perfume optionally colouring.
  • Protected O.B.A. systems according to our invention may be added to machine dishwashing powders, scouring creams and other hard surface cleaners, carpet shampoos, degreasing compositions, oven cleaners, dishwashing liquids, soap powders, laundry pre-soak compositions and other cleaning preparations.
  • Dishwashing powders according to our invention may typically comprise a substantial proportion, e.g. 20 to 60%, preferably 30 to 50%, of an alkali such as a sodium carbonate and a minor proportion, e.g. 1 to 5%, of surfactant preferably a non-ionic surfactant such as an alkoxylated alcohol, together, optionally but preferably, with a builder such as sodium tripolyphosphate in proportions of up to about 45% by weight of the composition, e.g. 20 to 35%, an alkaline silicate such as sodium metasilicate and an alkaline buffer such as borax.
  • the protected O.B.A. preferably comprises a bleach such as chlorinated trisodium phosphate in a proportion of from 0.1 to 5%, preferably 0.5 to 3%, e.g. 1 to 2%.
  • Liquid dishwashing compositions of our invention typically comprise highly soluble builders such as potassium pyrophosphate, and/or potassium silicate in a total concentration of 10 to 30% by weight, surfactants, preferably non-ionic in concentrations of 0.2 to 5% by weight and hydrotropes such as sodium xylene sulphonate, sodium toluene sulphonate or sodium benzene sulphonate in concentrations of 1 to 10% by weight.
  • highly soluble builders such as potassium pyrophosphate, and/or potassium silicate in a total concentration of 10 to 30% by weight
  • surfactants preferably non-ionic in concentrations of 0.2 to 5% by weight
  • hydrotropes such as sodium xylene sulphonate, sodium toluene sulphonate or sodium benzene sulphonate in concentrations of 1 to 10% by weight.
  • Hard surface cleaners of our invention may typically comprise 1 to 10%, surfactant, typically non-ionic or anionic/nonionic mixtures, 1 to 10% hydrotrope and 2 to 10% soluble builder such as potassium pyrophosphate.
  • Hard surface cleaners may also optionally comprise abrasives such as silica, or calcium carbonate as arragonite or calcite suspended in a structural liquid.
  • Carpet shampoos according to our invention may according to our invention comprise relatively high concentrations, e.g. 5 to 20% by weight, of high foaming surfactants such as mixtures of anionic surfactants (e.g. alkyl sulphates) with foaming agents (e.g. alkanolamides).
  • high foaming surfactants such as mixtures of anionic surfactants (e.g. alkyl sulphates) with foaming agents (e.g. alkanolamides).
  • Oven cleaners according to our invention may be of the caustic type comprising, e.g. 4 to 12% of alkalis such as sodium hydroxide, and typically a high foaming anionic surfactant such as a sodium alkyl ether sulphate, or else of the solvent based type containing e.g. 10 to 30% of a water miscible organic solvent such as a lower mon- di- or polyhdric alcohol or other alcohol, e.g. propylene glycol, and typically a non ionic surfactant, together preferably with a builder such as sodium tripolyphosphate.
  • a builder such as sodium tripolyphosphate.
  • Protected O.B.A. systems shall be deemed fluid or friable under wash conditions if they release O.B.A. into contact with any fabric present when agitated in a washing machine in a wash liquor containing the relevant cleaning composition at a total solids concentration of 0.5% and at 60°C.
  • the O.B.A. a 4,4 ⁇ -distyryl biphenyl compound sold by Ciba Geigy under the registered trade mark "TINOPAL" CBS-X, was ground in a ball mill with a polymethyl siloxane oil containing fumed silica currently sold by Wacker under the trade designation S132 in a proportion of one part O.B.A. to four of silicone oil.
  • a liquid detergent formulation was prepared having the following composition by weight. Sodium linear C 12-14 alkyl benzene sulphonate 6% Sodium linear C 12-18 alkyl 3-mole ethoxy sulphate 2% Coconut diethanolamide 1.5% Sodium tripolyphosphate 25% Sodium carboxymethyl cellulose 0.1% Sodium salt of a mixed mono/bis C 16-18 alkyl ethylenediamine tetrakis (methylene phosphonate) ester sold by Albright & Wilson Limited under the registered trade mark "BRIQUEST" 543-S 0.5% Perfume 0.3%
  • the liquid was divided into three portions. To one was added 0.05% by weight of the unprotected O.B.A., to the second one was added 0.25% by weight of the O.B.A./silicone oil and the third was retained as a control. Each of the first two samples was thoroughly mixed with the added O.B.A., and 2gm drops of the three detergents samples were applied to separate areas of a blue-dyed linen cloth and rubbed gently with a finger to form spots of equal area. After 1 minute the fabric was laundered in a washing machine without further addition of detergent. After rinsing and drying the cloth was inspected under U.V.light and the excess absorption of O.B.A. compared to the untreated cloth measured by visually estimating the intensity of whitening.
  • the sample containing silicone protected O.B.A. When added directly to a washing machine as a main wash detergent, the sample containing silicone protected O.B.A. performs similarly to the sample containing the unprotected O.B.A.
  • Example 3 10% by weight of a mixture of sodium sulphate and diperoxydodecyldicarboxylic acid (DPDDA) in n a weight ratio of 88:1 was suspended in the liquid detergent formulation of Example 1 to provide comparative Example B.
  • the second portion of the same mixture was first mixed with an equal weight of silicone oil (Wacker S132) to provide Example 2 and a third portion was first mixed with 80%, based on the weight of solid mixture, of "BEVALOID" 4237 silicone oil to provide Example 3.
  • High sulphate compositions such as comparative Example B notoriously give rise to the formation of large needle-shaped crystals of sodium sulphate on standing.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Glass Compositions (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Materials For Medical Uses (AREA)
EP87311536A 1986-12-31 1987-12-31 Geschützte optische Aufheller Withdrawn EP0273775A3 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB868631101A GB8631101D0 (en) 1986-12-31 1986-12-31 Protected optical brighteners
GB8631101 1986-12-31
GB8723616 1987-10-08
GB878723616A GB8723616D0 (en) 1987-10-08 1987-10-08 Protected optical brighteners

Publications (2)

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EP0273775A2 true EP0273775A2 (de) 1988-07-06
EP0273775A3 EP0273775A3 (de) 1989-04-26

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EP87311536A Withdrawn EP0273775A3 (de) 1986-12-31 1987-12-31 Geschützte optische Aufheller

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EP (1) EP0273775A3 (de)
JP (1) JPH0196296A (de)
AU (1) AU8318487A (de)
BR (1) BR8707185A (de)
DK (1) DK690187A (de)
FI (1) FI875790L (de)
GB (1) GB2200377A (de)
NO (1) NO875493L (de)
PT (1) PT86485B (de)

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0333270A2 (de) * 1988-03-14 1989-09-20 The Procter & Gamble Company Photoaktivatorfarbstoffzusammensetzung für Reinigungsmittel
US5073295A (en) * 1987-12-29 1991-12-17 Ciba-Geigy Corporation Encapsulated fluorescent whitening agent, photoativator or anti-microbial agent
EP0583512A1 (de) * 1992-08-18 1994-02-23 The Procter & Gamble Company Reinigungsmittelzusätze
US5434069A (en) * 1993-11-12 1995-07-18 Lever Brothers Company, Division Of Conopco, Inc. Capsule comprising oil surrounding hydrophobic or hydrophilic active and polymeric shell surrounding oil
US5441660A (en) * 1993-11-12 1995-08-15 Lever Brothers Company Compositions comprising capsule comprising oil surrounding hydrophobic or hydrophilic active and polymeric shell surrounding oil
EP0675194A1 (de) * 1994-03-28 1995-10-04 The Procter & Gamble Company Reinigungszusätze in strukturierten Flüssigkeiten
WO1998023720A1 (en) * 1996-11-26 1998-06-04 The Procter & Gamble Company Laundry detergent compositions containing a combination of surfactants and optical brighteners
DE19855346A1 (de) * 1998-12-01 2000-06-08 Henkel Kgaa Peroxidhaltige Zubereitungen mit stabilisierten optischen Aufhellern
DE19855329A1 (de) * 1998-12-01 2000-06-08 Henkel Kgaa Aktivchlorhaltige Zubereitungen mit stabilisierten optischen Aufhellern
EP1033433A2 (de) * 1998-11-11 2000-09-06 Gomes, Jaime Isidoro Naylor Rocha Verfahren zum Schützen von Farbstoffen auf Textilien vor dem Angriff von Bleichmitteln wie Wasserstoffperoxid, Perborate und Percarbonate
WO2001025389A1 (en) * 1999-10-04 2001-04-12 Unilever N.V. Detergent composition comprising fragrance particle
EP1111034A1 (de) * 1999-12-22 2001-06-27 The Procter & Gamble Company Wasch- und Reinigungsmittel und/oder Gewebebehandlungszusammensetzungen
US6420333B1 (en) 2001-08-28 2002-07-16 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Manufacture of capsules for incorporation into detergent and personal care compositions
US6730651B2 (en) 2001-08-28 2004-05-04 Unilever Home & Personal Care Usa Division Of Conopco. Inc. Concentrated stock of capsules for detergent or personal care compositions
DE10313455A1 (de) * 2003-03-25 2004-10-14 Henkel Kgaa Wasch- und Reinigungsmittel
US6878680B2 (en) 2002-05-02 2005-04-12 Procter & Gamble Detergent compositions and components thereof
US6927201B2 (en) 2001-08-28 2005-08-09 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Capsules for incorporation into detergent or personal care compositions
US7211273B2 (en) 2001-08-28 2007-05-01 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent or personal care composition with oil capsules
US8871807B2 (en) 2008-03-28 2014-10-28 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US9242879B2 (en) 2012-03-30 2016-01-26 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US9288992B2 (en) 2013-03-05 2016-03-22 Ecolab USA, Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US9585397B2 (en) 2013-03-05 2017-03-07 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US9676711B2 (en) 2008-03-28 2017-06-13 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9902627B2 (en) 2011-12-20 2018-02-27 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US12096768B2 (en) 2019-08-07 2024-09-24 Ecolab Usa Inc. Polymeric and solid-supported chelators for stabilization of peracid-containing compositions
US12203056B2 (en) 2008-03-28 2025-01-21 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents

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ES2281002T3 (es) * 2003-08-06 2007-09-16 Ciba Specialty Chemicals Holding Inc. Composiciones para formar tonalidades.
US7977299B2 (en) * 2004-08-18 2011-07-12 Ecolab Usa Inc. Treated oxidizing agent, detergent composition containing a treated oxidizing agent, and methods for producing
AU2009230713C1 (en) 2008-03-28 2018-08-02 Ecolab Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
EP2310483B1 (de) 2008-07-07 2016-03-16 Basf Se Enzymzusammensetzung mit enzymhaltigen polymerpartikeln

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EP0238216A1 (de) * 1986-02-20 1987-09-23 Albright & Wilson Limited Geschützte Enzymsysteme
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EP0206718A2 (de) * 1984-01-27 1986-12-30 The Clorox Company Verfahren und Zusammensetzung zum Bleichen und optischen Aufhellen
US4708816A (en) * 1984-01-27 1987-11-24 The Clorox Company Bleach composition containing controlled density capsules
EP0238216A1 (de) * 1986-02-20 1987-09-23 Albright & Wilson Limited Geschützte Enzymsysteme

Cited By (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5073295A (en) * 1987-12-29 1991-12-17 Ciba-Geigy Corporation Encapsulated fluorescent whitening agent, photoativator or anti-microbial agent
EP0333270A2 (de) * 1988-03-14 1989-09-20 The Procter & Gamble Company Photoaktivatorfarbstoffzusammensetzung für Reinigungsmittel
EP0333270A3 (en) * 1988-03-14 1990-06-27 The Procter & Gamble Company Photoactivator dye composition for detergent use
AU605682B2 (en) * 1988-03-14 1991-01-17 Danochemo A/S Encapsulated photoactivator dyes for detergent use
EP0583512A1 (de) * 1992-08-18 1994-02-23 The Procter & Gamble Company Reinigungsmittelzusätze
TR27709A (tr) * 1992-08-18 1995-06-22 Procter & Gamble Hidrofil deterjan aktif bilesiklerini iceren deterjan ilave maddeleri.
US5434069A (en) * 1993-11-12 1995-07-18 Lever Brothers Company, Division Of Conopco, Inc. Capsule comprising oil surrounding hydrophobic or hydrophilic active and polymeric shell surrounding oil
US5441660A (en) * 1993-11-12 1995-08-15 Lever Brothers Company Compositions comprising capsule comprising oil surrounding hydrophobic or hydrophilic active and polymeric shell surrounding oil
EP0675194A1 (de) * 1994-03-28 1995-10-04 The Procter & Gamble Company Reinigungszusätze in strukturierten Flüssigkeiten
WO1998023720A1 (en) * 1996-11-26 1998-06-04 The Procter & Gamble Company Laundry detergent compositions containing a combination of surfactants and optical brighteners
EP1033433A2 (de) * 1998-11-11 2000-09-06 Gomes, Jaime Isidoro Naylor Rocha Verfahren zum Schützen von Farbstoffen auf Textilien vor dem Angriff von Bleichmitteln wie Wasserstoffperoxid, Perborate und Percarbonate
EP1033433A3 (de) * 1998-11-11 2000-10-25 Gomes, Jaime Isidoro Naylor Rocha Verfahren zum Schützen von Farbstoffen auf Textilien vor dem Angriff von Bleichmitteln wie Wasserstoffperoxid, Perborate und Percarbonate
DE19855346A1 (de) * 1998-12-01 2000-06-08 Henkel Kgaa Peroxidhaltige Zubereitungen mit stabilisierten optischen Aufhellern
DE19855329A1 (de) * 1998-12-01 2000-06-08 Henkel Kgaa Aktivchlorhaltige Zubereitungen mit stabilisierten optischen Aufhellern
WO2001025389A1 (en) * 1999-10-04 2001-04-12 Unilever N.V. Detergent composition comprising fragrance particle
US6362159B1 (en) 1999-10-04 2002-03-26 Unilever Home & Personal Care Usa Domestic care product
CN1328365C (zh) * 1999-12-22 2007-07-25 宝洁公司 洗衣、清洗和/或织物护理组合物
WO2001046374A1 (en) * 1999-12-22 2001-06-28 The Procter & Gamble Company Laundry and cleaning and/or fabric care compositions
EP1111034A1 (de) * 1999-12-22 2001-06-27 The Procter & Gamble Company Wasch- und Reinigungsmittel und/oder Gewebebehandlungszusammensetzungen
US7601681B2 (en) 1999-12-22 2009-10-13 The Procter & Gamble Company Laundry and cleaning and/or fabric care composition
US6420333B1 (en) 2001-08-28 2002-07-16 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Manufacture of capsules for incorporation into detergent and personal care compositions
US6730651B2 (en) 2001-08-28 2004-05-04 Unilever Home & Personal Care Usa Division Of Conopco. Inc. Concentrated stock of capsules for detergent or personal care compositions
US6927201B2 (en) 2001-08-28 2005-08-09 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Capsules for incorporation into detergent or personal care compositions
US7211273B2 (en) 2001-08-28 2007-05-01 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent or personal care composition with oil capsules
US6878680B2 (en) 2002-05-02 2005-04-12 Procter & Gamble Detergent compositions and components thereof
DE10313455A1 (de) * 2003-03-25 2004-10-14 Henkel Kgaa Wasch- und Reinigungsmittel
US12203056B2 (en) 2008-03-28 2025-01-21 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US10077415B2 (en) 2008-03-28 2018-09-18 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US11827867B2 (en) 2008-03-28 2023-11-28 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9540598B2 (en) 2008-03-28 2017-01-10 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US11015151B2 (en) 2008-03-28 2021-05-25 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9676711B2 (en) 2008-03-28 2017-06-13 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US8871807B2 (en) 2008-03-28 2014-10-28 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US10017720B2 (en) 2008-03-28 2018-07-10 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US10669512B2 (en) 2008-03-28 2020-06-02 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US10323218B2 (en) 2008-03-28 2019-06-18 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9902627B2 (en) 2011-12-20 2018-02-27 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9926214B2 (en) 2012-03-30 2018-03-27 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10023484B2 (en) 2012-03-30 2018-07-17 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10017403B2 (en) 2012-03-30 2018-07-10 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing enzymes for treatment of drilling fluids, frac fluids, flowback water and disposal water
US9242879B2 (en) 2012-03-30 2016-01-26 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US11180385B2 (en) 2012-10-05 2021-11-23 Ecolab USA, Inc. Stable percarboxylic acid compositions and uses thereof
US11939241B2 (en) 2012-10-05 2024-03-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US10893674B2 (en) 2013-03-05 2021-01-19 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US9585397B2 (en) 2013-03-05 2017-03-07 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US11206826B2 (en) 2013-03-05 2021-12-28 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US9288992B2 (en) 2013-03-05 2016-03-22 Ecolab USA, Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US12096768B2 (en) 2019-08-07 2024-09-24 Ecolab Usa Inc. Polymeric and solid-supported chelators for stabilization of peracid-containing compositions

Also Published As

Publication number Publication date
NO875493L (no) 1988-07-01
DK690187A (da) 1988-07-01
PT86485B (pt) 1990-11-20
AU8318487A (en) 1988-07-07
FI875790A0 (fi) 1987-12-31
DK690187D0 (da) 1987-12-29
BR8707185A (pt) 1988-08-09
GB2200377A (en) 1988-08-03
PT86485A (en) 1988-01-01
GB8730348D0 (en) 1988-02-03
JPH0196296A (ja) 1989-04-14
NO875493D0 (no) 1987-12-30
FI875790L (fi) 1988-07-01
EP0273775A3 (de) 1989-04-26

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