EP0961823B1 - Liberation a ph controle de constituants detergents - Google Patents

Liberation a ph controle de constituants detergents Download PDF

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Publication number
EP0961823B1
EP0961823B1 EP98905366A EP98905366A EP0961823B1 EP 0961823 B1 EP0961823 B1 EP 0961823B1 EP 98905366 A EP98905366 A EP 98905366A EP 98905366 A EP98905366 A EP 98905366A EP 0961823 B1 EP0961823 B1 EP 0961823B1
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EP
European Patent Office
Prior art keywords
coated
acid
agent
weight
detergent composition
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EP98905366A
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German (de)
English (en)
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EP0961823A1 (fr
Inventor
Thomas Gassenmeier
Jürgen MILLHOFF
Thomas Müller-Kirschbaum
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • 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
    • C11D3/0047—Other compounding ingredients characterised by their effect pH regulated 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • 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
    • C11D3/3942—Inorganic per-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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the invention relates to coated solid detergent components and detergent compositions, containing these coated components. Specifically affects the Invention detergent compositions that delay one of their ingredients and Dispense controlled to the wash liquor, controlling the release via the pH the washing liquor takes place.
  • the bleach destroys excess enzyme and so does that To prevent remaining on the laundry (odor formation), the first way is usually chosen.
  • Another advantage that results from the coating of the bleach particles is the increased Storage stability, since uncoated bleaching agents stick to longer storage moist air can be hydrolyzed quickly and so the detergent compositions Lose washing power.
  • Detergent and bleaching compositions comprising a source of hydrogen peroxide and a Contain peroxyacid bleach precursors (bleach activator) and one in the wash liquor Provide initial pH in alkaline (pH 10-11), as well as the delayed release of Acid in the wash liquor in order to achieve a reduced pH in the liquor described in the prior art and for example in the European Patent applications EP-A-0 290 081 (Unilever) and EP-A-0 396 287 (Clorox) published.
  • WO94 / 15010 discloses coating TAED with water-soluble acidic polymers, the coating being in the form of a melt, by spraying or can be applied in the form of solutions and dispersions, and also describes the simultaneous use of percarbonate, which is preferably also coated.
  • the sour Polymer has a solubility of at least 5 g / l at 20 ° C.
  • EP-A-0 651 053 (Procter & Gamble) describes detergent compositions containing a alkali metal percarbonate coated with alkali metal sulfate and carbonate, a bleach activator and contain a sustained release (coated) acidifying agent so that the pH of the wash liquor (1% solution at 20 ° C) is initially 9.5 to 13 while it after complete release of the acidifying agent is 7 to 9.3.
  • the time to complete release of the acidifying agent is in the range of 30 seconds up to 10 minutes. Only when a pH threshold is undershot is the coating on the Percarbonate attacked and dissolved, so that the bleaching effect occurs.
  • FR-A-2 180 864 discloses ⁇ a washing and cleaning agent which, among others Ingredients has a coated pH regulator and coated enzymes, so that the pH regulator can set the optimal pH value for the enzyme.
  • the release pH regulator and enzyme occur simultaneously or with a short time delay.
  • the invention is based on the object of developing a system which is pH-controlled Release of detergent ingredients, especially bleach, allows and the release takes place in an alkaline medium.
  • the invention accordingly relates to a washing method for washing textiles Fabrics using a solid, particulate detergent composition, wherein the pH of the wash liquor after dissolving the agent is below 8 and as it progresses the washing process by dissolving a coated alkalizing agent to values rises above 8.5, which is a release of a specially coated ingredient and a enable a delayed effect of this ingredient.
  • an alkalizing agent is used Bleach, preferably sodium percarbonate, used while as special coated ingredient a bleach activator, preferably tetraacetylethylenediamine (TAED), is used.
  • TAED tetraacetylethylenediamine
  • the pH in the wash liquor when adding the Detergent composition comparatively low, i.e. it is below 8.
  • Subsequently solves the bleaching agent coating slowly builds up and increases alkaline bleach free, which increases the pH of the wash liquor. exceeds the pH of the liquor has a value of approx. 8.5, the coating of the Dissolve bleach activator and thereby releases the bleach activator.
  • a temporal Delay now starts the full bleaching effect in the wash liquor.
  • the detergent composition is through the Coating of both the bleach and the bleach activator have excellent storage stability and shows no loss in bleaching activity even in humid air.
  • Sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important as coated bleaching agents (component a) which supply H 2 O 2 in water.
  • Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and salts and salts of peracids which provide H 2 O 2 , such as perbenzoic acid, peroxophthalic acid, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • the content of the agents in the coated bleaching agents is 1 to 40% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.
  • the coating materials for the bleaching agent particles are water-soluble Substances in question that slowly dissolve in the wash liquor, not one abrupt release of the coated bleach and lead to their dissolving properties have no strong pH dependence. In addition, fabrics are preferred, which in turn are used for Do not change the pH of the wash liquor.
  • Preferred as covering materials Fatty alcohols, which can optionally be mixed with other coating materials. exemplary a mixture of fatty alcohols and aluminum stearate should be mentioned here.
  • magnesium sulfate and sodium hexaphosphate (BE 857 017, Solvay Interox), dihydrogen phosphate or pyrophosphate (EP 024201, Clorox), phosphonic acids (EP 295 384, Degussa), sodium metaborate and silicate (DE 28 10 379, Degussa), water glass and sodium polyphosphate (DE 27 12 138, Degussa), Sodium sulfate, sodium carbonate and silicate (DE 26 22 610, Solvay Interox), or sodium bicarbonate (DE 24 17 572, Solvay Interox), borax and magnesium sulfate (DE 33 21 082, Kao), Boric acid (DE 28 00 916 Solvay-Interox), but also some organic components such as Fat derivatives, paraffins and waxes (EP 030 759, Solvay Interox, melting temperature of the compounds between 25 and 90 ° C
  • the coating materials can be applied from the melt or from solutions or dispersions take place, the solvent or emulsifier being removed by evaporation application as a fine powder, for example by electrostatic techniques possible, although this method leads to irregular and poorly adhering coatings leads.
  • the casing materials can be placed on the in agitators, mixers and granulators Bleach particles are applied. However, application of the wrapping materials is preferred in a fluidized bed, with a simultaneous size classification of the particles can. Under certain circumstances the wrapping materials should turn into sticky products lead, it can be useful to additionally coat the bleach particles with fine particles To apply substances ("powdering"). All fine particles come as powdering agents Substances in question, but also other detergent ingredients such as builder substances can be used.
  • Preferred additional pudding agents are zeolites, silicates, polymeric polycarboxylates, carbonates, citrates, starch, etc. are used. Also a part of the acidifying agent can be used for powdering.
  • coated bleach activators can be compounds that under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted Perbenzoic acid result, are used. Substances containing O- and / or N-acyl groups are suitable the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups.
  • Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or.
  • TAED Tetraacetylethylenediamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • acylated glycolurils in particular Tetraacetylglycoluril (TAGU)
  • iso-NOBS carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol or their in the European patent application EP 0 525 239 (Ausimont SPA) (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated Glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/006
  • the bleach activator is coated with polymeric acids, which only change at pH values resolve above 8.5. At pH values below 8, the coated Bleach activator particles in aqueous solution are stirred for hours without being in solution go.
  • polymeric acids which are particularly suitable for coating Called polyacrylates, which are dependent on the required solubilities from the pH value on the one hand and good processability on the other.
  • Other polymeric acids that can be used as coating materials are copolymers from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid and mesaconic acid with an unsaturated monocarboxylic acid such as acrylic acid or ⁇ -alkyl substituted Acrylic acids.
  • the coating of the bleach activators can basically be done in the same way as that Bleaching agents are coated.
  • a method is preferred in which the polymeric Acids are applied to the bleach activators via a dispersion.
  • the wrapping materials for both the bleach and the bleach activator are in such quantities used that an optimal interaction of the individual components and thus a precisely controlled release is made possible. Depending on the period, within whose release should not take place and depending on the size of the coated particles you will measure the amount of wrapping material. Use preferred embodiments less than 20% by weight of shell material, based on the mass of the coated particles, in particular less than 10% by weight of wrapping materials are preferred.
  • the acidifying agent used as the third component is used in amounts of 0.1 to 40 preferably from 1 to 25% by weight, based on the finished composition.
  • an acidifying agent all water-soluble substances can be used, which are suitable, the pH value to lower an aqueous solution below 8. In interaction with the In this way, other components of the agents according to the invention have a starting pH reached, which is slowly increased as the washing process progresses (release of the Bleach), which eventually releases the pH at 8.5 in the wash liquor Bleach activator and thus leads to the onset of the bleaching effect.
  • Preferred acidifying agents are inorganic and organic acids, for example the solid mono-, oligo- and polycarboxylic acids such as citric, tartaric and succinic acid, Polycarboxylic acids such as polyacrylic acid, but also acids such as malonic acid, adipic acid, maleic acid, Fumaric acid, oxalic acid, boric acid or amidosulfonic acid and mixtures of the mentioned acids.
  • Acidic salts such as hydrogen sulfates or carbonates can also be used as acidifying agents are used, again in turn only on compliance with the pH conditions must be respected.
  • Acidifiers are a quick way to get a wash liquor with a pH below 8 to be chosen so that they dissolve quickly and the pH quickly to the desired values bring.
  • a coating that would cause a release delay is for the acidifiers unsuitable for the purposes of the present invention.
  • the requirement for the acidifying agent (s) is to be met make sure that they are not volatile.
  • solid acidifiers are which have a low tendency to sublimation and a high melting point with a good one Agree on water solubility, clearly preferred.
  • Liquid or pasty acidifying agents can only in minor amounts below 5 wt .-% of the total composition packaging measures must be taken when they are used to ensure the storage stability even with increased air humidity.
  • liquid and volatile acids or those that cannot be handled in powder detergents, such as hydrochloric acid, Nitrate or sulfuric acid are therefore automatically forbidden the selection of the acidifying agent (s) also ensure that the resulting Washing liquor does not harm textiles or human skin.
  • the agents according to the invention contain, in addition to the coated components and uncoated Excipients that have a pH-controlled release of the coated ingredients enable other common ingredients for detergents, especially anionic and non-ionic surfactants, builder substances and other auxiliary substances such as soil repellents, Foam inhibitors, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filling salts as well as colors and fragrances, opacifiers or pearlescent agents.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C 12-18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the Receives sulfonation products.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization:
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of the hydrogenated coconut , Palm kernel or tallow fatty acids are suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are in the Manufactured by esterification of a monoglycerin with 1 to 3 moles of fatty acid or the transesterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained.
  • preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 up to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, Lauric acid, palmitic acid, stearic acid or behenic acid.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12-18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10-20 oxo alcohols and those half esters secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 16-18 alk (en) yl sulfates are particularly preferred for reasons of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use C 16 -C 18 -alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably C 12-18 fatty alkyl sulfates or mixtures of C 12-14 fatty alkyl sulfates or C 12-18 fatty alkyl sulfates with C 16-18 fatty alkyl sulfates and in particular C 12-16 fatty alkyl sulfates with C 16-18 fatty alkyl sulfates.
  • not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 18 fatty alcohol radicals or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • Soaps are particularly suitable as further anionic surfactants.
  • Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • those soap mixtures are preferred which are composed of 50 to .100% by weight of saturated C 12-24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available.
  • the anionic surfactants are preferably in the form of their sodium or Potassium salts, especially in the form of the sodium salts.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants either as the sole nonionic surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably described in the international patent application WO-A-90/13533 (Henkel) can be prepared.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this rest.
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy or N-aryloxy-substituted compounds can then, for example, according to the Teaching of international application WO-A-95/07331 (Procter & Gamble) by implementation with fatty acid methyl esters in the presence of an alkoxide as catalyst in the desired Polyhydroxy fatty acid amides are transferred.
  • the detergent granules can also contain builder substances and other ingredients of detergents.
  • builders and cobuilder substances can be used as builders in the Detergent compositions. These include in particular zeolites, Citrates and polymeric polycarboxylates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • M sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the sodium salts of orthophosphates, pyrophosphates are particularly suitable and especially the tripolyphosphates.
  • Their salary is generally not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished Medium.
  • tripolyphosphates in particular are already in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances to a synergistic improvement of the secondary washing ability to lead.
  • Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
  • DE dextrose equivalent
  • cobuilders are, preferably, oxydisuccinates and other derivatives of disuccinates Ethylenediamine.
  • glycerol disuccinates and glycerol trisuccinates such as those found in the United States Patents US 4,524,009, US 4,639,325 (both Staley), in European Patent application EP-A-0 150 930 (Staley) and Japanese patent application JP 93/339896 can be described.
  • Suitable amounts are those containing zeolite and / or formulations containing silicate at 3 to 15% by weight.
  • detergents can contain a large number of compounds are used, for example foam inhibitors, phosphonates, Enzymes and optical brighteners called.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • the salts of polyphosphonic acids are preferably the neutral sodium salts for example 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylene diamine tetramethylene phosphonate in amounts from 0.1 to 1.5% by weight.
  • enzyme mixtures for example from protease and amylase or protease and lipase or protease and Cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, Lipase and cellulase, but especially cellulase-containing mixtures of particular Interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
  • Crystalline tetraacetylethylenediamine (TAED) was 5: 1 with a 32% Polyacrylate dispersion mixed, granulated and dried at 45 ° C. That way Granules obtained show a high stability and can be in a pH neutral to weakly acidic The surfactant solution should be stirred for several hours without going into solution. In alkaline Solution (pH> 8.5) the granules disintegrate in 1 to 2 minutes.
  • a bleach and enzyme-free detergent composition comprising surfactants, builders and auxiliaries (for composition, see Table 1) was mixed with the coated bleach particles, the coated bleach activator particles and with crystalline citric acid in the amounts given in Table 2.
  • Ingredients of the detergent composition (% by weight). Soap 5.42 Sodium C 12-14 alkyl benzene sulfonate 22.67 Sodium C 14-16 fatty alcohol sulfate 4.59 C 12-18 fatty alcohol-5 EO 0.81 sodium 4.55 Zeolite A 29.86 sodium silicate 8.00 Acrylic acid-maleic acid copolymer 16.16 opt.
  • detergent composition 59.5% by weight coated bleach (Na percarbonate) 23.3% by weight coated bleach activator (TAED) 7% by weight Citric acid monohydrate 10.2% by weight

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  • Wood Science & Technology (AREA)
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  • Detergent Compositions (AREA)

Claims (8)

  1. Procédé de lavage pour le lavage de tissus textiles, utilisant une composition de détergent solide, sous forme particulaire, dans lequel la valeur du pH du jus de lavage se situe lors d'une addition de la composition de détergent, en dessous de 8 et en poursuivant le processus de lavage, par mise en solution d'un agent d'alcalinisation revêtu, monte à des valeurs supérieures à 8,5 qui rendent possibles une libération d'un ingrédient revêtu d'un acide polymère et une action retardée dans le temps de cet ingrédient.
  2. Procédé de lavage selon la revendication 1,
    caractérisé en ce que
    l'agent d'alcalinisation revêtu, est un agent de blanchiment dont la solution aqueuse présente une réaction alcaline, et est de préférence du percarbonate de sodium.
  3. Procédé de lavage selon l'une des revendications 1 à 2,
    caractérisé en ce que
    l'ingrédient spécialement revêtu est un activateur de blanchiment, de préférence la tétra-acétyléthylène diamine (TAED).
  4. Composition détergente solide, sous forme particulaire contenant :
    a) de 1 à 40 % en poids d'un agent de blanchiment revêtu, dont la solution aqueuse présente une réaction alcaline ;
    b) de 0,5 à 15 % en poids d'un activateur de blanchiment ;
    c) de 0,1 à 40 % en poids d'un agent d'acidification,
    caractérisée en ce que
    l'agent de blanchiment est revêtu d'un matériau d'enveloppe qui se dissout lentement dans l'eau, indépendamment de la valeur du pH, l'activateur de blanchiment est revêtu d'un acide polymère et on utilise l'agent d'acidification sans revêtement.
  5. Composition détergente selon la revendication 4,
    caractérisée en ce qu'
    elle renferme comme matériau d'enveloppe pour l'agent de blanchiment, des alcools gras de préférence en mélange avec d'autres matériaux d'enveloppe.
  6. Composition détergente selon l'une des revendications 4 à 5,
    caractérisée en ce qu'
    elle renferme comme agent de blanchiment du percarbonate de sodium.
  7. Composition détergente selon l'une des revendications 4 à 6,
    caractérisée en ce qu'
    elle renferme comme activateur de blanchiment, de la tétraacétyl éthylène diamine (TAED).
  8. Composition détergente selon l'une des revendications 4 à 7,
    caractérisée en ce qu'
    elle contient comme agent d'acidification, des acides polycarboxyliques.
EP98905366A 1997-02-07 1998-01-29 Liberation a ph controle de constituants detergents Expired - Lifetime EP0961823B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19704634 1997-02-07
DE19704634A DE19704634A1 (de) 1997-02-07 1997-02-07 pH-gesteuerte Freisetzung von Waschmittelkomponenten
PCT/EP1998/000474 WO1998035009A1 (fr) 1997-02-07 1998-01-29 Liberation a ph controle de constituants detergents

Publications (2)

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EP0961823A1 EP0961823A1 (fr) 1999-12-08
EP0961823B1 true EP0961823B1 (fr) 2002-10-30

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US (2) US6225276B1 (fr)
EP (1) EP0961823B1 (fr)
JP (1) JP4130998B2 (fr)
AT (1) ATE226978T1 (fr)
DE (2) DE19704634A1 (fr)
ES (1) ES2187004T3 (fr)
WO (1) WO1998035009A1 (fr)

Families Citing this family (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19957038A1 (de) * 1999-11-26 2001-05-31 Henkel Kgaa Wasch- und Reinigungsmittel
EP1113069A1 (fr) * 1999-12-28 2001-07-04 Reckitt Benckiser N.V. Liquide péroxide compositions contenant particules en suspension
US20030186065A1 (en) * 2002-03-27 2003-10-02 Jun Hou Polymeric acid protective coatings for LCD glass
US6896928B2 (en) * 2002-06-07 2005-05-24 Corning Incorporated Two-layer protective coating system for LCD glass
WO2004094313A1 (fr) * 2003-04-24 2004-11-04 Lion Corporation Particule a surface traitee de compose inorganique hydrosoluble, son procede de production, et composition detergente particulaire
US20050065054A1 (en) * 2003-05-30 2005-03-24 Manske Scott D. Detergent formulations containing alkaline peroxide salts and organic acids
US7682403B2 (en) * 2004-01-09 2010-03-23 Ecolab Inc. Method for treating laundry
US20060019854A1 (en) * 2004-07-21 2006-01-26 Johnsondiversey. Inc. Paper mill cleaner with taed
EP1912659A4 (fr) * 2005-08-05 2012-09-19 Hemostasis Llc Composition antimicrobienne et systeme correspondant
US20080087390A1 (en) * 2006-10-11 2008-04-17 Fort James Corporation Multi-step pulp bleaching
EP2045319B8 (fr) * 2007-09-19 2016-02-24 Dalli-Werke GmbH & Co. KG Composition de détergent revêtu et processus de fabrication
GB0805908D0 (en) * 2008-04-01 2008-05-07 Reckitt Benckiser Inc Laundry treatment compositions
DE102008050415A1 (de) 2008-10-04 2010-04-08 Bayer Technology Services Gmbh Freisetzungs-System zur kontrollierbaren Freisetzung einer Substanz
GB0918914D0 (en) 2009-10-28 2009-12-16 Revolymer Ltd Composite
US8845860B2 (en) 2010-09-16 2014-09-30 Georgia-Pacific Consumer Products Lp High brightness pulps from lignin rich waste papers
GB201019628D0 (en) * 2010-11-19 2010-12-29 Reckitt Benckiser Nv Dyed coated bleach materials
US8846107B2 (en) 2010-12-29 2014-09-30 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
WO2012090123A2 (fr) 2010-12-29 2012-07-05 Ecolab Usa Inc. Génération d'acides peroxycarboxyliques à un ph alcalin et leur utilisation en tant qu'agents de blanchiment de textiles et antimicrobiens
GB201106391D0 (en) 2011-04-15 2011-06-01 Reckitt & Colman Overseas Novel composite
GB201106377D0 (en) 2011-04-15 2011-06-01 Reckitt & Colman Overseas Novel composite
GB201106408D0 (en) 2011-04-15 2011-06-01 Revolymer Ltd Novel composite
GB201106409D0 (en) 2011-04-15 2011-06-01 Revolymer Ltd Novel composite
AU2012244292B2 (en) 2011-11-04 2015-03-05 Bissell Inc. Enzyme cleaning composition and method of use
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
CN104254496B (zh) 2012-03-30 2016-10-26 艺康美国股份有限公司 过乙酸/过氧化氢和过氧化物还原剂用于处理钻井液、压裂液、回流水和排放水的用途
JP6129319B2 (ja) * 2012-09-14 2017-05-17 シムライズ アーゲー 香気物質としての不飽和ラクトン
US8822719B1 (en) 2013-03-05 2014-09-02 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US20140256811A1 (en) 2013-03-05 2014-09-11 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
DE102013004428A1 (de) * 2013-03-15 2014-09-18 Clariant International Ltd. Verfahren zum Waschen und Reinigen von Textilien
US9701931B2 (en) 2013-09-30 2017-07-11 Chemlink Laboratories, Llc Environmentally preferred antimicrobial compositions
DE102016223472A1 (de) * 2016-11-25 2018-05-30 Henkel Ag & Co. Kgaa Mehrkammer-Portionsbeutel mit Bleichaktivator/Komplexbildner-Compound
CA3067095C (fr) 2017-06-22 2023-02-14 Ecolab Usa Inc. Blanchiment a l'aide d'acide peroxyformique et d'un catalyseur a l'oxygene
JP7209690B2 (ja) * 2017-07-31 2023-01-20 ダウ グローバル テクノロジーズ エルエルシー カプセル化方法
JP7330943B2 (ja) * 2017-07-31 2023-08-22 ダウ グローバル テクノロジーズ エルエルシー 洗剤添加剤

Family Cites Families (74)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL211065A (fr) 1955-10-03
LU66925A1 (fr) 1973-01-29 1974-09-25
GB1370626A (en) * 1971-01-27 1974-10-16 Laporte Industries Ltd Coated peroxygen compounds
DE2318930A1 (de) 1972-04-17 1973-10-31 Procter & Gamble Enzym enthaltende detergenzgemische
GB1398876A (en) 1972-07-27 1975-06-25 Interox Chemicals Ltd Coated peroxygen compounds
DE2402392C2 (de) 1973-01-29 1982-09-02 Interox, Bruxelles Stabilisierte teilchenförmige Peroxyverbindungen, Verfahren zu deren Herstellung und ihre Verwendung
FR2215384A1 (en) 1973-01-29 1974-08-23 Interox Stabilization of alkali metal per-salts - by coating with vinyl chloride/ethylene copolymers
FR2226460B1 (fr) 1973-04-20 1976-12-17 Interox
LU72575A1 (fr) 1975-05-23 1977-02-10
CH609795A5 (fr) 1976-04-30 1979-03-15 Gretag Ag
LU75466A1 (fr) 1976-07-27 1978-02-08
DE2810379C3 (de) 1978-03-10 1980-12-11 Degussa Ag, 6000 Frankfurt Verfahren zur Herstellung von stabilisiertem Natriumpercarbonat
DE2712138A1 (de) 1977-03-19 1978-09-21 Degussa Natriumpercarbonat-partikel
LU76548A1 (fr) 1977-01-10 1978-09-18
US4120812A (en) 1977-06-17 1978-10-17 Fmc Corporation Polyethylene glycol-stabilized peroxygens
US4131562A (en) 1977-06-17 1978-12-26 Fmc Corporation Stabilized particulate peroxygen compounds
US4428914A (en) 1977-12-23 1984-01-31 Interox Process for making sodium percarbonate granules
DE2916416A1 (de) 1979-04-23 1980-11-06 Karl Hans Dr Heinlein Pulverfoermiges wasch- oder vorwaschmittel
US4260508A (en) 1979-08-15 1981-04-07 The Clorox Company Stabilized alkali metal percarbonate powder bleach
FR2471222A1 (fr) 1979-12-12 1981-06-19 Interox Procede pour la stabilisation de particules contenant des composes peroxygenes et compositions de blanchiment contenant des particules stabilisees selon ce procede
DE3321082C2 (de) 1982-06-10 1996-08-22 Kao Corp Bleich-Reinigungsmittel
JPS58217599A (ja) 1982-06-10 1983-12-17 花王株式会社 漂白洗浄剤組成物
JPS58217598A (ja) 1982-06-10 1983-12-17 日本油脂株式会社 洗剤組成物
US4524009A (en) 1984-01-31 1985-06-18 A. E. Staley Manufacturing Company Detergent builder
CA1238917A (fr) 1984-01-31 1988-07-05 Vivian B. Valenty Adjuvant pour detergent
DE3413571A1 (de) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
DE3417184A1 (de) 1984-05-09 1985-11-14 Technoplast B.V., Monster Sicherungsverschluss
US4639325A (en) 1984-10-24 1987-01-27 A. E. Staley Manufacturing Company Detergent builder
FR2597473B1 (fr) 1986-01-30 1988-08-12 Roquette Freres Procede d'oxydation de di-, tri-, oligo- et polysaccharides en acides polyhydroxycarboxyliques, catalyseur mis en oeuvre et produits ainsi obtenus.
GB8710690D0 (en) 1987-05-06 1987-06-10 Unilever Plc Detergent bleach composition
DE3720277A1 (de) 1987-06-19 1988-12-29 Degussa Verfahren zur verminderung der neigung zum zusammenbacken von teilchenfoermigen aktivsauerstoffverbindungen
WO1990008171A1 (fr) 1989-01-10 1990-07-26 Teijin Limited Film en polyester aromatique et production de ce film
GB8902909D0 (en) * 1989-02-09 1989-03-30 Unilever Plc Coating process
DE3914131A1 (de) 1989-04-28 1990-10-31 Henkel Kgaa Verwendung von calcinierten hydrotalciten als katalysatoren fuer die ethoxylierung bzw. propoxylierung von fettsaeureestern
EP0396287A3 (fr) 1989-05-04 1991-10-02 The Clorox Company Méthode et produit pour accroítre le blanchiment avec formation in situ de peracide
ATE124960T1 (de) 1989-11-10 1995-07-15 Tno Verfahren zur herstellung von polydicarboxysacchariden.
US5000869A (en) 1990-02-14 1991-03-19 Safe Aid Products, Inc. Novel polymer coated bleaching composition
IT1249883B (it) 1990-08-13 1995-03-30 Ferruzzi Ricerca & Tec Agenti sequestranti del calcio a base di carboidrati ossidati e loro impiego come builder per detergenti
IT1245063B (it) 1991-04-12 1994-09-13 Ferruzzi Ricerca & Tec Procedimento per l'ossidazione di carboidrati
US5423997A (en) * 1991-05-31 1995-06-13 Colgate Palmolive Co. Spray dried powdered automatic dishwashing composition containing enzymes
EP0525239B1 (fr) 1991-07-31 1997-07-09 AUSIMONT S.p.A. Procédé pour augmenter l'efficacité de blanchiment d'un persel inorganique
US5458801A (en) * 1991-09-27 1995-10-17 Kao Corporation Process for producing granular bleach activator composition and granular bleach activator composition
DE4134914A1 (de) 1991-10-23 1993-04-29 Henkel Kgaa Wasch- und reinigungsmittel mit ausgewaehlten builder-systemen
EP0542496B1 (fr) 1991-11-14 1998-05-20 The Procter & Gamble Company Amidon oxydé à C6/C2-C3 utilisé comme ingrédient pour détergent
JPH05339896A (ja) 1992-06-03 1993-12-21 Arakawa Chem Ind Co Ltd 紙用サイズ剤および紙サイジング方法
WO1994015010A1 (fr) * 1992-12-22 1994-07-07 The Procter & Gamble Company Composition de precurseurs de peroxyacide enrobes, servant d'agents de blanchiment
ATE182617T1 (de) 1993-05-20 1999-08-15 Procter & Gamble Bleichmittelzusammensetzungen enthaltend n- acylcaprolactam aktivatoren
AU6833394A (en) 1993-05-20 1994-12-20 Procter & Gamble Company, The Bleaching compounds comprising n-acyl caprolactam for use in hand-wash or other low-water cleaning systems
DE69412092T2 (de) 1993-05-20 1999-04-01 Procter & Gamble Bleichmittel, welche einen substituierten benzoyl caprolactam bleichaktivator enthalten
DE4317519A1 (de) 1993-05-26 1994-12-01 Henkel Kgaa Herstellung von Polycarboxylaten auf Polysaccharid-Basis
US5405413A (en) 1993-06-24 1995-04-11 The Procter & Gamble Co. Bleaching compounds comprising acyl valerolactam bleach activators
NL194919C (nl) 1993-09-07 2003-07-04 Tno Werkwijze voor het oxideren van koolhydraten.
WO1995007331A1 (fr) 1993-09-09 1995-03-16 The Procter & Gamble Company Detergents liquides comportant des tensioactifs d'amides d'acides gras n-alcoxy ou n-aryloxy polyhydroxy
EP0651053A1 (fr) * 1993-11-03 1995-05-03 The Procter & Gamble Company Composition détergente pour le linge
US5716923A (en) * 1993-11-03 1998-02-10 The Proctor & Gamble Company Laundry detergent containing a coated percarbonate and an acidification agent to provide delayed lowered pH
NL9301905A (nl) 1993-11-04 1995-06-01 Inst Voor Agrotech Onderzoek Werkwijze voor het oxideren van koolhydraten.
DE4338922A1 (de) 1993-11-15 1995-05-18 Degussa Aktivatoren für anorganische Persauerstoffverbindungen
GB9323634D0 (en) * 1993-11-16 1994-01-05 Warwick Int Ltd Bleach activator compositions
ES2133710T3 (es) 1993-11-25 1999-09-16 Warwick Int Group Composiciones blanqueantes.
US5534196A (en) 1993-12-23 1996-07-09 The Procter & Gamble Co. Process for making lactam bleach activator containing particles
DE4400024A1 (de) 1994-01-03 1995-07-06 Henkel Kgaa Silikatische Builder und ihre Verwendung in Wasch- und Reinigungsmitteln sowie Mehrstoffgemische für den Einsatz auf diesem Sachgebiet
DE4402051A1 (de) 1994-01-25 1995-07-27 Henkel Kgaa Gerüststoff für Wasch- oder Reinigungsmittel
DE4402851A1 (de) 1994-01-31 1995-08-03 Henkel Kgaa Wirbelschicht-Oxidationsverfahren zur Herstellung von Polycarboxylaten auf Polysaccharid-Basis
GB9407532D0 (en) * 1994-04-13 1994-06-08 Procter & Gamble Detergent compositions
GB9407534D0 (en) 1994-04-13 1994-06-08 Procter & Gamble Detergent compositions
GB9407299D0 (en) 1994-04-13 1994-06-08 Procter & Gamble Detergent compositions
GB9407535D0 (en) * 1994-04-13 1994-06-08 Procter & Gamble Detergent compositions
GB9407279D0 (en) 1994-04-13 1994-06-08 Procter & Gamble Detergent compositions
GB9407533D0 (en) 1994-04-13 1994-06-08 Procter & Gamble Detergent compositions
GB9407276D0 (en) 1994-04-13 1994-06-08 Procter & Gamble Detergent compositions
GB9407628D0 (en) 1994-04-13 1994-06-08 Procter & Gamble Detergent compositions
GB9419091D0 (en) 1994-09-22 1994-11-09 Cerestar Holding Bv Process for decreasing the build up of inorganic incrustations on textiles and detergent composition used in such process
DE4443177A1 (de) 1994-12-05 1996-06-13 Henkel Kgaa Aktivatormischungen für anorganische Perverbindungen
AU4877296A (en) * 1995-02-18 1996-09-11 Albright & Wilson Uk Limited Enzyme detergents

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DE19704634A1 (de) 1998-08-27
ES2187004T3 (es) 2003-05-16
US20010012826A1 (en) 2001-08-09
JP2001510501A (ja) 2001-07-31
US6225276B1 (en) 2001-05-01
DE59806112D1 (de) 2002-12-05
WO1998035009A1 (fr) 1998-08-13
US6407052B2 (en) 2002-06-18
JP4130998B2 (ja) 2008-08-13
EP0961823A1 (fr) 1999-12-08
ATE226978T1 (de) 2002-11-15

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