WO1994003553A1 - Composition de blanchiment peroxy stabilisee a l'acide ethylenediamine-n,n'-disuccinique - Google Patents

Composition de blanchiment peroxy stabilisee a l'acide ethylenediamine-n,n'-disuccinique Download PDF

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Publication number
WO1994003553A1
WO1994003553A1 PCT/US1993/006837 US9306837W WO9403553A1 WO 1994003553 A1 WO1994003553 A1 WO 1994003553A1 US 9306837 W US9306837 W US 9306837W WO 9403553 A1 WO9403553 A1 WO 9403553A1
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Prior art keywords
composition according
weight
bleaching
detergent composition
compositions
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PCT/US1993/006837
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English (en)
Inventor
Gerard Marcel Baillely
Stefano Scialla
Graham Alexander Sorrie
Semih Cem Ersolmaz
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to KR1019950700419A priority Critical patent/KR950703038A/ko
Priority to JP6505354A priority patent/JPH07509523A/ja
Priority to AU47785/93A priority patent/AU666403B2/en
Priority to EP93918280A priority patent/EP0652924A4/en
Publication of WO1994003553A1 publication Critical patent/WO1994003553A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/20—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen
    • 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/3937—Stabilising agents
    • C11D3/394—Organic compounds

Definitions

  • This invention relates to a bleaching composition
  • a bleaching composition comprising an active oxygen- releasing (peroxy) compound and a zero-phosphorus containing stabilizing agent, wherein the stabilizing agents permits a controlled bleaching action when the composition is used as an aqueous solution in a bleaching process.
  • the stabilizing agent also provides for good storage stability of the product.
  • the bleaching composition is also useful as a component of a detergent composition.
  • peroxy compound hydrogen peroxide or any of its addition compounds including inorganic perhydrate salts, such as perborates and percarbonates, or organic peroxyacids.
  • perborate salts are well known as components of detergent compositions for use in, for example, laundry and automatic dishwashing.
  • Hydrogen peroxide is commonly used as a bleaching agent in, for example, textile and paper pulp bleaching processes.
  • the bleach is released in a controlled manner throughout the process.
  • a stabilizing agent to minimize the rapid decomposition of the peroxy compound is well established in the peroxy bleaching art, because, among other things, the oxygen released by such rapid decomposition of the peroxy compound in general has no bleaching action as contrasted with the normal autodecomposition of the peroxy compound which does result in a bleaching action.
  • the rapid decomposition of the peroxy compound may be harmful. For example, cellulosic materials in strongly alkaline peroxy solutions are attacked by the oxygen from the rapid decomposition with the result of loss of strength by the materials.
  • the stabilizing agent should preferably be effective in alkaline solutions and under the relatively high temperature conditions which may be encountered in practice.
  • the stabilizing agent should also be compatible with other components, which may be present in the detergent or peroxy bleaching solutions.
  • Heavy metal ions may catalyse peroxy bleach decomposition.
  • Such heavy metal ions are inevitably present in the wash liquors of laundry and dishwashing processes, being components of many food and/or body soils.
  • Heavy metal ions are also commonly present components of the liquors of wood pulp bleaching processes, the wood pulp tending to pick up these ions from the machinery used to masticate the wood chips and pulp.
  • Heavy metal sequestering or chelating agents have been employed to control the levels of free heavy metal ions in the aqueous peroxy solutions used in bleaching processes, thus acting as bleach stabilizers by preventing the heavy metal ion catalysed decomposition of the peroxy bleaches.
  • EDTA ethylene diamine tetra acetate
  • Organic phosphonate and amino alkylene poly (alkylene phosphonates) chelants are also known as bleach stabilisers being described in, for example, U.S. Patents 3, 860, 391 and 4, 239, 643.
  • the use of phosphonate chelants in paper pulp and textile bleaching processes as well as in detergent compositions is also known.
  • the phosphonate chelants commonly used today in such processes are however, also non-biodegradable.
  • Phosphorus-containing compounds have also been linked to undesirable eutrophication effects in lakes and rivers, and this has, for example, led to a dramatic reduction in the use of phosphorus-containing builder ingredients in detergent compositions.
  • Laundry detergent compositions containing the nil-phosphorus chelant, ethylenediamine-N,N'-disuccinic acid (EDDS) have been disclosed in EP-A- 0267 653. This disclosure teaches that EDDS, when incorporated into such detergent compositions, assists in the removal of food, beverage and certain other organic stains from fabrics during the laundry process. It also teaches that EDDS may be used as a replacement for all or part of the phosphonate chelants currently used in many existing detergent products.
  • EDDS when used as a component of a detergent composition EDDS assists in the removal of greasy stains.
  • the EDDS molecule has two chiral centres. It was disclosed in EP-A-0 267 653 that the biodegradation of EDDS appeared to be optical isomer-specific with the [S,S] isomer degrading most rapidly and extensively.
  • the Applicants have now confirmed the optical isomer-specific nature of the biodegradation of EDDS.
  • the [S,S] isomer is the only fully biodegradable optical isomer, being broken down essentially completely in the residence time of a normal sewage treatment process.
  • EDDS low levels of EDDS at specific EDDS : peroxy compound weight ratios provides excellent in use stabilization of peroxy compounds in aqueous solutions containing certain heavy metal ions. This stabilization is of particular importance at elevated solution temperatures (>60°C). Surprisingly, EDDS provides significantly better bleach stabilization than its chemical isomer EDTA under the same conditions. The Applicants have also found that incorporation of EDDS into a bleaching composition provides for improved storage stability of that composition.
  • EP-A-0 267 653 teaches that the EDDS-containing laundry detergent compositions described therein may also contain as optional ingredients bleaching agents, bleach activators, bleach stabilizers and the like. Peroxy compounds are not disclosed specifically in this document. EP-A-0 267 653 also makes reference to an article by J. Majer, V. Springer and B. Kopecka, published in Chem. Zvesti. 20(6) : 414-422 (1966) (CAS abstract 65 : 11738f).
  • This articles gives stability constants for the complexes of EDDS with the heavy metal ions Fe 3 + , Cu 2 + , Ni 2 + , Co 2 + , Zn 2 + , Pb 2 + and Cd 2 + and compares these to the corresponding stability constants for the complexes with EDTA.
  • the stability constant for the EDDS complex is lower than for the EDTA complex.
  • the stability constants are practically the same. The Applicant's finding that at elevated temperatures EDDS is a better bleach stabilizer than EDTA are therefore even more surprising in the light of the disclosure of this article.
  • a bleaching composition comprising:
  • a peroxy compound selected from hydrogen peroxide and the addition compounds of hydrogen peroxide, organic peroxyacids, and mixtures thereof;
  • the weight ratio of said peroxy compound to said ethylene diamine-N,N'- disuccinic acid preferably lies in the range from 400 : 1 to 20 : 1 , more preferably from 200 : 1 to 40 : 1 , and most preferably from 150 : 1 to 50 : 1.
  • the peroxy compound is preferably present at a level of from 0.5% to 60%, more preferably from 1 % to 40%, most preferably from 2% to 25% by weight of the bleaching composition.
  • the bleaching compositions of the invention may be used in essentially any bleaching process.
  • the bleaching process will employ an aqueous alkaline solution of the bleaching composition, with a preferred pH range for said solution lying in the range from 7.5-12.5, more preferably from 9-12, most preferably from 9.5 to 11.5.
  • the bleaching process will employ a solution of an acidic peroxy compound containing bleach formulation.
  • Such formulations are commonly employed in bleach additive or household/hard surface cleaner applications.
  • Such acidic bleach formulations typically have a pH of from 0.5 to 6, preferably from 1 to 5.
  • a bleaching process in accord with the invention will be carried out, at least in part, at a temperature greater than 60°C.
  • the first essential component of the bleaching compositions of the invention is a peroxy compound.
  • the peroxy compound may be hydrogen peroxide or any of the addition compounds of hydrogen peroxide, or organic peroxyacid, or mixtures thereof.
  • addition compounds of hydrogen peroxide it is meant compounds which are formed by the addition of hydrogen peroxide to a second chemical compound, which may be for example an inorganic salt, urea or organic carboxylate, to provide the addition compound.
  • a second chemical compound which may be for example an inorganic salt, urea or organic carboxylate, to provide the addition compound.
  • the addition compounds of hydrogen peroxide include inorganic perhydrate salts, the compounds hydrogen peroxide forms with organic carboxylates, urea, and compounds in which hydrogen peroxide is clathrated.
  • inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts.
  • the inorganic perhydrate salts are normally the alkali metal salts. Salts in which hydrogen peroxide is clathrated are described in GB-A- 1494953.
  • Sodium percarborate is a preferred inorganic perhydrate for inclusion in granular bleaching compositions in accordance with the invention. This may be incorporated as either the monohydrate of empirical formula NaB ⁇ 2 .
  • the bleaching compositions of the invention may and any compositions into which they may be incorporated may be of essentially any physical form such as solid, including powders, bars and granules, or fluid, including liquids, gels and pastes.
  • the bleaching composition will generally comprise a concentrated solution of the hydrogen peroxide together with the EDDS.
  • the peroxy compound is an inorganic perhydrate salt
  • the bleaching composition will generally be solid, preferably granular in nature.
  • the inorganic perhydrate salt may be included in such a granular composition as the crystalline solid without additional protection.
  • the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.
  • Sodium percarbonate which is a highly preferred perhydrate for inclusion in granular bleaching compositions in accordance with the invention, is an addition compound having a formula corresponding to 2Na2C ⁇ 3.3H2 ⁇ 2, and is available commercially as a crystalline solid.
  • the percarbonate is most preferably incorporated into such compositions in coated form.
  • the most preferred coating material comprises a mixed salt of an alkali metal sulphate and carbonate.
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1 : 200 to 1 : 4, more preferably from 1 : 99 to 1 : 9, and most preferably from 1 : 49 to 1 : 19.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2S ⁇ 4.n.Na2C ⁇ 3 wherein n is form 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
  • Another suitable coating material is sodium silicate of Si ⁇ 2 : Na2 ⁇ ratio from
  • 1.6 : 1 to 3.4 : 1 preferably 2.8 : 1 , applied as an aqueous solution to give a level of from 2% to 10%, (normally from 3% to 5%) of silicate solids by weight of the percarbonate.
  • Magnesium silicate can also be included in the coating.
  • Other suitable coating materials include the alkali and alkaline earth metal sulphates and carbonates.
  • Potassium peroxymonopersulfate is another inorganic perhydrate salt of particular usefulness in the compositions.
  • the corresponding organic peroxyacid, namely peroxymonopersulfuric acid is also useful.
  • the bleaching compositions of the invention will also preferably contain additional bleaching agents more suited to low temperature bleaching. These will include, for example peroxyacid bleach precursor (bleach activator).
  • t e principal advantage of the presence of EDDS in the bleaching compositions of the invention lies in its stabilization of peroxy compounds when used in high temperature ( >60°C) bleaching processes it still acts as an effective chelant at lower solution temperatures.
  • the heavy metal ion chelation provided by EDDS may also stabilize any organic peroxyacid bleach components which are present as active bleaching agents at these lower solution temperatures.
  • EDDS also provides improved storage stability characteristics when incorporated into bleach containing compositions. Such improved storage stability characteristics are particularly observed when the bleach-containing compositions are formulated as alkaline detergent compositions, or as acidic formulations possessing a pH of from 0.5 to 6. The achievement of good storage stability characteristics for acidic bleaching formulations is known to be a particular problem in the art.
  • the peroxyacid bleach precursors probably contain one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides and acylated derivatives of imidazoles and oximes, and examples of useful materials within these classes are disclosed in GB-A-1586789. The most preferred classes are esters such as are disclosed in GB-A-836988, 864,798, 1147871 and 2143231 and imides such as are disclosed in GB-A-855735 & 1246338.
  • Particularly preferred precursor compounds are the N,N,N1 ,N1 tetra acetylated compounds of formula
  • x can be O or an integer between 1 & 6.
  • TAMD tetra acetyl methylene diamine
  • TAED tetra acetyl ethylene diamine
  • TAHD tetraacetyl hexylene diamine
  • peroxyacid bleach activator compounds are the amide substituted compounds of the following general formulae:
  • R is an aryl or alkaryl group with from about 1 to about 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms
  • R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Rl preferably contains from about 6 to 12 carbon atoms.
  • R 2 preferably contains from about 4 to 8 carbon atoms.
  • R may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 .
  • substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R5 is preferably H or methyl.
  • Rl and R ⁇ should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • peroxyacid bleach precursor compounds include sodium nonanoyloxy benzene sulfonate, sodium trimethyl hexanoyloxy benzene sulfonate, sodium acetoxy benzene sulfonate and sodium benzoyloxy benzene sulfonate as disclosed in, for example, EP-A-0341947.
  • the compositions of the invention may contain as the peroxy compound organic peroxyacids of which a particularly preferred class are the amide substituted peroxyacids of general formulae:
  • Rl, R 2 and R ⁇ are as defined previously for the corresponding amide substituted peroxyacid bleach activator compounds.
  • organic peroxyacids include the dicacyl peroxides and dialkyl peroxides. Suitable are diperoxy dodecanedioc acid, diperoxy tetra decanedioc acid, diperoxyhexadecanedioc acid, mono- and diperazelaic acid, mono- and diperbrassylic acid, monoperoxy phthalic acid, perbenzoic acid, and their salts as disclosed in, for example, EP-A-0341 947.
  • the peroxy compound When incorporated as components of liquid, particularly acidic liquid, bleaching compositions the peroxy compound, and in particular any organic peroxyacids, may be dissolved or dispersed or be incorporated as emulsions or suspensions.
  • the bleaching compositions of the invention contain, as the second essential component from 0.05% to 2% by weight of the composition, preferably from 0.05% to 1 % by weight, most preferably from 0.1 % to 0.5% by weight of ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • EDDS compounds are the free acid form and the sodium or magesium salt or complex thereof. Examples of such preferred sodium salts of EDDS include Na3 EDDS. Examples of such preferred magnesium complexes of EDDS include Mg EDDS and Mg2 EDDS.
  • the magnesium complexes are the most preferred for inclusion in granular compositions in accord with the invention. These complexes may be added to the compositions as such, or they may be formed during the process for making the composition by the reaction of an inert magnesium salt such as MgCl2 or MgS ⁇ 4 fth an EDDS compound present as either the free acid, or as another salt or complex. Where the EDDS compound is added in the making process together with the inert magnesium salt it is preferred that the molar ratio of magnesium to EDDS should be greater than 1:1 , preferably greater than 3: 1 , to ensure formation of the desired magnesium complexes.
  • the structure of the acid form of EDDS is as follows.
  • EDDS can be synthesised, for example, from readily available, inexpensive starting material such as maleic anhydride and ethylene diamine as follows.
  • the [S,S] isomer of EDDS can be synthesised from L-aspartic acid and 1 ,2- dibromoethane, as follows.
  • the bleaching compositions of the invention are useful in the bleaching of cellulosic fibrous material.
  • cellulosic fibrous material as used herein has reference to wood, cotton, linen, jute and other materials of a cellulosic nature, and also includes individual fibres, for example wood pulp or cotton fibre, as well as yarns, tows, webs, fabrics (woven or non-woven) and other aggregates of such fibres.
  • the bleaching compositions of the invention are also useful in the belaching of synthetic textiles including polyamides, viscose, rayon, and polyesters.
  • the bleaching compositions of the invention are also useful in cleaning compositions. These cleaning compositions may be used in essentially any washing, laundering or cleaning processes in which bleaching is required. Thus, the cleaning compositions may be used in home or industrial laundering or automatic dishwashing processes, as laundry additive compositions, stain pretreat compositions, carpet and upholstery cleaners, and in any process involving the cleaning of hard surfaces such as bottle washing, dairy cleaning and kitchen and bathroom cleaning processes, including for example toilet bowl cleaning.
  • the bleaching compositions of the invention are used in an aqueous solution.
  • the most preferred peroxy compound for use in such processes is hydrogen peroxide.
  • the pH of the aqueous peroxy solution is often adjusted with inorganic alkali metal basic materials, such as sodium hydroxide, sodium carbonate, sodium silicate and mixtures thereof.
  • the optimum pH lies somewhere between 7.5 to 12.5.
  • the pH is higher than about 12.5 the peroxy-compounds rapidly decompose so that it is difficult to control a proper bleaching rate without undue damage to the fibres.
  • the rate of bleaching in most cases is slow to the extent of being uneconomical for bleaching.
  • silicates especially sodium silicate may be used to provide alkalinity in the peroxy solutions for use in the bleaching of cellulosic fibres its tendency to form as deposits on the fibres being bleached means that its use is preferably kept to a minimum.
  • the peroxy solutions for use in the bleaching of cellulosic fibres and synthetic textiles using the bleaching compositions of the invention contain no sodium silicate.
  • the concentration of the EDDS stabilizing agent in the cellulose fibre or synthetic textile bleaching peroxy solutions can vary depending upon, inter alia, concentration of the peroxy solution, type of peroxy compound used, pH, temperature and the like, and usually for normal concentrations of peroxy solutions and with conventional cellulose fibre/synthetic textile bleaching methods, the EDDS is preferably present in concentrations from 0.0005% to 0.5% by weight with concentrations of from 0.001 % to 0.1 % by weight being especially preferred.
  • the methods for bleaching using the peroxy solutions containing the bleaching compositions of the present invention vary widely, as for example, from using the peroxy solutions at temperatures of from about 70 °C to about 100°C for periods of time from about 30 minutes to about 6-8 hours, as well as continuous bleaching methods which entail the use of the peroxy solutions at normal temperatures, ie., about 25 °C and contacting the cellulose material by saturation, removing the excess moisture and exposing the cellulose material to saturated steam at temperatures form about 100°C to about 135°C, for period of time from a few seconds (about 20) to about 1 hour and even longer in some cases.
  • U.S. Patents 2,839,353, 2,960,383, and 2,983,568 are illustrative of being representative of continuous peroxy bleaching methods.
  • the bleaching compositions of the invention may also be incorporated into compositions for use in essentially any laundering, washing or cleaning processes.
  • Laundry compositions incorporating the bleaching compositions of the invention can be formulated as granular compositions and heavy duty liquid compositions.
  • compositions may in addition comprise in general terms those ingredients commonly found in detergent products which may include organic surfactants, detergent builders, anti-redeposition and soil supsension agents, suds suppressors, enzymes, optical brighteners, photoactivated bleaches, perfumes, filler salts, anti-corrosion agents and colours.
  • Laundry detergent compositions may also comprise fabric softening and antistatic agents.
  • a wide range of surfactants can be used in the detergent compositions.
  • a list of suitable cationic surfactants is given in U.S. P. 4,259,217 issued to Murphy on March 31 , 1981.
  • Mixtures of anionic surfactants are suitable herein, particularly blends of sulphate, sulphonate and/or carboxylate surfactants.
  • Mixtures of sulphonate and sulphate surfactants are normally employed in a sulphonate to sulphate weight ratio of from 5:1 to 1:2, preferably from 3:1 to 2:3, more preferably from 3:1 to 1:1.
  • Preferred sulphonates include alkyl benzene sulphonates having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a C12-C18 fatty source, preferably from a C16-C18 fatty source.
  • the cation is an alkali metal, preferably sodium.
  • Preferred sulphate surfactants in such sulphonate sulphate mixtures are alkyl sulphates having from 12 to 22, preferably 16 to 18 carbon atoms in the alkyl radical.
  • Another useful surfactant system comprises a mixture of two alkyl sulphate materials whose respective mean chain lengths differ from each other.
  • One such system comprises a mixture of C14-C15 alkyl sulphate and C16-C18 alkyl sulphate in a weight ratio of C14-C15: C16-C18 of from 3:1 to 1 : 1.
  • the alkyl sulphates may also be combined with alkyl ethoxy sulphates having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxy lation of 1 to 6.
  • the cation in each instance is again an alkali metal, preferably sodium.
  • Another highly preferred anionic surfactant system comprises a mixture of a C12-C20 al ⁇ yl sulfate salt with a water soluble Cn_C ⁇ g alkyl ethoxysulfate salt containing an average of from 1 to 7 ethoxy groups per mole wherein the weight ratio of alkyl sulfate to alkyl ethoxysulfate salt lies in the range from 2 : 1 to 19 : 1, more preferably from 3 : 1 to 12 : 1 and most preferably from 3.5 : 1 to 10 : 1.
  • alkyl sulfate salts may be derived from natural or synthetic hydrocarbon sources.
  • Preferred examples of such salts include the substantially branched C14-C15 alkyl sulfate salts, that is where the degree of branching of the C14-
  • C15 alkyl chain is greater than about 20%.
  • Such substantially branched C14- Cj5 alkyl sulfate salts are usually derived from synthetic sources.
  • C16-C20 alkyl sulfate salts which are usually derived from natural sources such as tallow fat and marine oils.
  • the C11-C18 alkyl ethoxysulfate salt comprises a primary alkyl ethoxysulfate which is derived from the condensation product of a Cl 1-C18 alcohol condensed with an average of from one to seven ethylene oxide groups, per mole.
  • Cn_Ci8 alcohol itself can be obtained from natural or synthetic sources.
  • C11-C18 alcohols derived from natural fats, or Ziegler olefin build-up, or OXO synthesis can form suitable sources for the alkyl group.
  • synthetically derived materials include Dobanol 25 (RTM) sold by Shell Chemicals (UK) Ltd which is a blend of Ci2"Cl5 alcohols, Ethyl 24 sold by the Ethyl Corporation, a blend of C13..C15 alcohols in the ratio 67% C13, 33% C15 sold under the trade name Lutensol by BASF GmbH and Synperonic
  • C11-C1 alkyl ethoxysulfate is preferably from 0.5% to 10% more preferably from 0.5% to 5% and most preferably from 1 % to 3% by weight of the composition.
  • anionic surfactants suitable for the purposes of the invention are the alkali metal sarcosinates of formula
  • R-CON (Rl) CH2 COOM wherin R is a C5-C17 linear or branched alkyl or alkenyl group, R is a C ⁇ - C4 alkyl group and M is an alkali metal ion.
  • R is a C5-C17 linear or branched alkyl or alkenyl group
  • R is a C ⁇ - C4 alkyl group
  • M is an alkali metal ion.
  • Preferred examples are the lauroyl, Cocoyl (C12-C14), myristyl and oleyl methyl sarcosinates in the form of their sodium salts.
  • One class of nonionic surfactants useful in the present invention comprises condensates of ethylene oxide with a hydrophobic moiety, providing surfactants having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5.
  • HLB hydrophilic-lipophilic balance
  • the hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water- soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Especially preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing an average of from 3-8 moles of ethylene oxide per mole of alcohol, particularly the C14-C15 primary alcohols containing an average of from 6-8 moles of ethylene oxide per mole of alcohol and the C12-
  • Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula
  • RO (C n H 2 nO)tZ x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 6 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • Another preferred nonionic surfactant is a polyhydroxy fatty acid amide surfactant compound having the structural formula:
  • Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably Cj or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R 2 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C17 alkyl or alkenyl, or mixture thereof: and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxlylated derivative (preferably ethoxylated or propoxylated) thereof.
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of CH2-(CHOH) n -CH2 ⁇ H, -CH(CH2 ⁇ H)-(CHOH) n _ r CH2 ⁇ H, -CH2- (CHOH)2(CHOR')(CHOH)-CH2 ⁇ H, where n is an integer from 3 to 5, inclusive, and R 1 is H or a cyclic or aliphatic monosaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly - CH2-(CHOH) -CH2 ⁇ H.
  • R can be, for example, N-methyl, N-ethyl, N-propyl, N- isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
  • R 2 -CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymalto-triotityl, etc.
  • Preferred compound are N-methyl N-ldeoxyglucityl C14-C18 fatty acid amides.
  • a further class of surfactants are the semi-polar surfactants such as amine oxides.
  • Suitable amine oxides are selected from mono C6-C20. preferably ClO"Cl4 N-alkyl or alkenyl amine oxides and propylene-l,3-diamine dioxides wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxpropyl groups.
  • Cationic surfactants can also be used in the detergent compositions herein and suitable quaternary ammonium surfactants are selected from mono Cs-Cj ⁇ , preferably C10-C14 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Laundry detergent compositions incorporating the bleaching compositions of the invention comprise from 3% to 30% of surfactant but more usually comprise from 5% to 20%, more preferably from 7% to 15% surfactant by weight of the compositions.
  • Machine dishwashing detergent compositions incorporating the bleaching compositions of the invention comprise from 0% to 10% by weight, preferably from 0.5% to 10% by weight, most preferably from 1 % to 5% of surfactant by weight of the compositions.
  • the surfactants may be selected from anionic, cationic, nonionic, amphotonic or zwitterionic surfactants. Most preferably the surfactants are low-foaming.
  • a typical listing of surfactants for inclusion in automatic dishwashing detergent compositions is given in EP-A-0414 549.
  • low-foaming nonionic surfactants especially the water soluble ethoxy lated C ⁇ -Ci ⁇ fatty alcohols and C6-C16 mixed ethoxylated/propoxylated fatty alcohols and mixtures thereof.
  • the ethoxylated fatty alcohols are the C10-C16 ethoxylated fatty alcohols with a degree of ethoxylation of from 5 to 50, most preferably these are the C12-C16 ethoxylated fatty alcohols with a degree of ethoxylation from 8 to 40.
  • the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 16 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.
  • Combinations of surfactant types are preferred, more especially anionic- nonionic and also anionic-nonionic-cationic blends. Particularly preferred combinations are described in GB-A-2040987 and EP-A-0087914. Although the surfactants can be incorporated into the compositions as mixtures, it is preferable to control the point of addition of each surfactant in order to optimise the physical characteristics of the composition and avoid processing problems.
  • a detergent builder system comprising one or more other non- phosphate detergent builders.
  • these can include, but are not restricted to, crystalline layered sodium silicates, carbonates borates, alkali metal aluminosilicates, monomeric polycarboxylates, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms, carbonates, silicates and mixtures of any of the foregoing.
  • Preferred non-phosphate builder salts are the crystalline layered sodium silicates of the general formula
  • NaMSi x ⁇ 2 x + ⁇ .yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE- A-3742043.
  • x in the general formula above has a value of 2, 3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred examples of this formula comprise the o ⁇ -, ⁇ -, If- and 5 " - forms of Na2Si2 ⁇ 5.
  • These materials are available from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is s * - Na2Si2 ⁇ 5, NaSKS-6.
  • the laundry detergent compositions incorporating the bleaching compositions of the present invention preferably comprise crystalline layered sodium silicate at a level of from 1 % to 80% by weight of the composition, more preferably from 5% to 40% and most preferably from 7% to 20% by weight.
  • the crystalline layered sodium silicate material is preferably present as a particulate in intimate admixture with a solid, water-soluble ionisable material.
  • the solid, water-soluble ionisable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof. The primary requirement is that the material should contain at least one functional acidic group of which the pKa should be less than 9, providing a capability for at least partial neutralisation of the hydroxyl ions released by the crystalline layered silicate.
  • the ionisable material need not have a pH ⁇ 7 in solution, or be present in an amount capable of providing hydrogen ions in stoichiometric parity with the hydroxyl ions produced by dissolution of the crystalline silicate.
  • the ionisable material should also have a mean particle size not greater than 300 micrometers and preferably not greater than 100 micrometers. This facilitates uniform distribution of the ionisable material and the crystalline silicate and is believed to enhance localised pH reduction when the particulate dissolves in the wash liquor.
  • Suitable organic acids include ascorbic, citric, glutaric, gluconic, glycolic, malic, maleic, malonic, oxalic, succinic and tartaric acids, 1 hydroxy ethane 1,1-diphosphonic acid (EHDP), amino poly methylene phosphonic acids such as NTMP, EDTMP & DETPMP, and mixtures of any of the foregoing.
  • Suitable acid salts include sodium hydrogen carbonate, sodium hydrogen oxalate, sodium hydrogen sulphate, sodium acid pyrophosphate, sodium acid orthophosphate, sodium hydrogen tartrate or mixtures of any of the foregoing.
  • the particulate mixture of crystalline layered silicate and solid water soluble ionisable material will have a pH of at least 10 (as measured on a 1 % solution in 20°C distilled water) and more usually will have a pH of at least 11 , normally at least 11.5.
  • agglomerates may require the addition of one or more binder agents in order to assist in binding the silicate and ionisable water soluble material so as to produce particulates with acceptable physical characteristics.
  • the binder agents may be present at a level of from 0% to 20% by weight of the composition.
  • the binder agents will be in intimate admixture with the silicate and ionisable water soluble material.
  • Preferred binder agents have a melting point between 30°C-70°C.
  • the binder agents are preferably present in amounts from 1-10% by weight of the composition and most preferably from 2-5% by weight of the composition.
  • Preferred binder agents include the C10-C2O alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole of alcohol and more preferably the C15-C20 primary alcohol ethoxylates containing from 20-100 moles of ethylene oxide per mole of alcohol.
  • binder agents include certain polymeric materials.
  • Polyvinylpyrrolidones with an average molecular weight of from 12,000 to 700,000 and polyethylene glycols with an average weight of from 600 to 10,000 are examples of such polymeric materials.
  • Copolymers of maleic anhydride wit ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constitutin at least 20 mole percent of the polymer are further examples of polymeric materials useful as binder agents. These polymeric materials may be used as such or in combination with solvents such as water, propylene glycol and the above mentioned C10-C2O alcohol ethoxylates containing from 5-100 moles of ethylene oxide per mole.
  • Further examples of binder agents in accord with the invention include the C 10 -C20 mono- and diglycerol ethers and also the C10-C2 fatty acids. Solutions of certain inorganic salts including sodium silicate are also of use for this purpose.
  • Cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acid or their salts are other examples of binder agents in accord with the invention.
  • the particulate can also include other components that are conventional in detergent compositions, provided that these are not incompatible per se and do not interfere with the building function of the crystalline layered silicate.
  • the particulate can include up to 50% by weight of the particulate of an anionic, nonionic, ampholytic or zwitterionic surfactant or a mixture of any of these and certain preferred particulate embodiments incorporate surfactants. Examples of such surfactants are described more fully hereinafter.
  • any surfactant material that is incorporated into the particulate does not introduce a level of free (unbound) moisture that can even partially dissolve the crystalline layered silicate.
  • the surfactant should be solid and should preferably contain no more than about 5% free (unbound) moisture, preferably no more than 2% free moisture and most preferably less than 1 % free moisture.
  • ingredients can also be incorporated in a total amount of up to 50% by weight of the particulate, subject to the same conditions set out above for the inclusion of surfactants.
  • optional ingredients should preferably be solid at normal (ambient) temperatures, and should contain no more than 5% by weight of free (unbound) moisture, preferably less than 1 % .
  • Non-aqueous liquid components can be incorporated in amounts of up to 20% by weight of the particulate provided that the crystalline layered silicate does not have an appreciable solubility in such components. This also applies to normally solid components applied in a molten form to serve as agglomeration/coating agents for the particulate.
  • the particulates can take a variety of physical forms such as extrudates, marumes, agglomerates, flakes or compacted granules.
  • a preferred process for preparing compacted granules comprising crystalline layered silicate and a solid, water-soluble ionisable material has been disclosed in the commonly assigned British Application No. 9108639.7 filed on 23 April 1991 (Attorney's ⁇ Docket No. CM369F).
  • preferred sodium aluminosilicate zeolites have the unit cell formula
  • aluminosilicate materials are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • aluminosilicate ion exchange materials are further characterised by a particle size diameter of from 0.1 to 10 micrometers, preferably from 0.2 to 4 micrometers.
  • particle size diameter herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope or by means of a laser granulometer.
  • the aluminosilicate ion exchange materials are further characterised by their calcium ion exchange capacity, which is at least 200 mg equivalent of CaC ⁇ 3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from 300 mg eq./g to 352 mg eq./g.
  • aluminosilicate ion exchange materials herein are still further characterised by their calcium ion exchange rate which is at least 130 mg equivalent of CaC ⁇ 3/litre/minute/(g/litre) [2 grains Ca + +/ gallon/minute/gram/gallon)] of aluminosilicate (anhydrous basis), and which generally lies within the range of from 130 mg equivalent of CaC ⁇ 3/litre/minute/(gram/litre) [2 grains/gallon/minute/ (gram/gallon)] to
  • Optimum aluminosilicates for builder purposes exhibit a calcium ion exchange rate of at least 260 mg equivalent of CaC03/litre/ minute/ (gram/litre) [4 grains/gallon/minute/(gram/gallon)].
  • Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available and can be naturally occurring materials, but are preferably synthetically derived. A method for producing aluminosilicate ion exchange materials is discussed in US Patent No. 3,985,669.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS, Zeolite MAP and mixtures thereof.
  • the crystalline aluminosilicate ion exchange material is Zeolite A and has the formula
  • Suitable water-soluble monomeric or oligomeric carboxylate builders can be selected from a wide range of compounds but such compounds preferably have a first carboxyl logarithmic acidity /constant (pKj) of less than 9, preferably of between 2 and 8.5, more preferably of between 4 and 7.5.
  • the logarithmic acidity constant is defined by reference to the equilibrium
  • acidity constants are defined at 25 °C and at zero ionic strength.
  • Literature values are taken where possible (see Stability Constants of Metal-Ion Complexes, Special Publication No. 25, The Chemical Society, London): where doubt arises they are determined by potentiometric titration using a glass electrode.
  • the carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Monomeric and oligomeric builders can be selected from acyclic, alicyclic, heterocyclic and aromatic carboxylates having the general formulae
  • Ri represents H,C ⁇ _30 alkyl or alkenyl optionally substituted by hydroxy, carboxy, sulfo or phosphono groups or attached to a polyethylenoxy moiety containing up to 20 ethyleneoxy groups
  • R2 represents H,C ⁇ _4 alkyl, alkenyl or hydroxy alkyl, or alkaryl, sulfo, or phosphono groups
  • X represents a single bond; O; S; SO; SO2; or NRj;
  • Y represents H; carboxy; hydroxy; carboxy methyloxy; or
  • Z represents H; or carboxy; m is an integer from 1 to 10; n is an integer from 3 to 6; p, q are integers from 0 to 6, p + q being from 1 to 6; and wherein, X, Y, and
  • Z each have the same or different representations when repeated in a given molecular formula, and wherein at least one Y or Z in a molecule contain a carboxyl group.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831 ,368, 821 ,369 and 821,370.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1 ,379,241, lactoxysuccinates described in British Patent No. 1 ,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l , l ,3- ⁇ ropane tricarboxylates described in British Patent No. 1,387,447.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1 ,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1 ,1 ,2,3-pr ⁇ pane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 ,398,421 and 1 ,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1 ,439,000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis- tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5- tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates, 1 ,2,3,4,5,6-hexane - hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as components of builder systems of detergent compositions in accordance with the present invention.
  • Suitable water soluble organic salts are the homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB- A- 1,596, 756.
  • Examples of such salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000. These materials are normally used at levels of from 0.5% to 10% by weight more preferably from 0.75% to 8%, most preferably from 1 % to 6% by weight of the composition.
  • the detergent compositions incorporating the bleaching compositions of the present invention will comprise non-phosphate detergent builder compounds at a level of from 1 % to 80% by weight of the compositions, more preferably from 10% to 60% by weight and most preferably from 20% to 50% by weight.
  • sodium aluminosilicate such as Zeolite A will comprise from 20% to 60% by weight of the total amount of builder, a monomeric or oligomeric carboxylate will comprise from 5% to 30% by weight of the total amount of builder and the crystalline layered silicate will comprise from 10% to 65% by weight of the total amount of builder.
  • the builder system preferably also incorporates a combination of auxiliary inorganic and organic builders such as sodium carbonate and maleic anhydride/acrylic acid copolymers in amounts of up to 35 % by weight of the total builder.
  • the detergent compositions may contain optional chelant ingredients.
  • optional chelants may include the organic phosphonates, including amino alkylene poly (alkylene phosphonate), alkali metal ethane 1 -hydroxy diphosphonates, nitrilo tremethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.
  • the phosphonate compounds may be present either in their acid form or as a complex of either an alkali or alkaline metal ion, the molar ratio of said metal ion to said phosphonate compound being at least 1 : 1. Such complexes are described in US-A-4,259,200.
  • the organic phosphonate compounds where present are in the form of their magnesium salt.
  • the level of phosphorus containing chelants in the compositions of the invention is preferably minimised, with their complete exclusion from the compositions being most preferred.
  • Silicates are useful components of automatic dishwashing detergent compositions incorporating the bleaching compositions of the present invention. Suitable silicates include the water soluble sodium silicates with an Si ⁇ 2 : Na2 ⁇ ratio of from 1.0 to 2.8. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an Si ⁇ 2 : Na2 ⁇ ratio of 2.0 is most preferred. Silicates are present in the machine dishwashing detergent compositions at a level of from 5% to 50% by weight of the composition, more preferably from 10% to 40% by weight.
  • soluble silicates serve a variety of purposes in conventional laundry detergent formulations, their presence may be unnecessary in detergent compositions incorporating crystalline layered silicate material. However as the crystalline layered silicate, which forms part of the builder system of the detergent composition, must be added as a dry mix ingredient, soluble silicates may still be useful as structurants in the spray dried granules that normally form part of a laundry detergent composition. This is particularly desirable if the spray dried granule does not incorporate an aluminosilicate builder and would otherwise comprise only organic materials. Suitable silicates are those having an Si ⁇ 2:Na2 ⁇ ratio in the range from 1.6 to 3.4, ratios from 2.0 to 2.8 being preferred.
  • the detergent compositions incorporating the bleaching compositions of the present invention will generally include an inorganic perhydrate salt, normally in the form of the sodium salt. Suitable inorganic perhydrate salts have been described herein before.
  • the bleaching composition will usually be incorporated to give a perhydrate level of from 3% to 40% by weight, more preferably from 5% to 30% by weight and most preferably from 10% to 25% by weight of the detergent composition.
  • the detergent compositions incorporating the bleaching compositions of the present invention will also generally include peroxyacid bleach precursors (bleach activators). Suitable peroxyacid bleach precursors have been described hereinbefore.
  • the peroxyacid bleach precursors are normally incorporated at a level of from 1 % to 20% , more preferably from 1 % to 15%, most preferably from 3% to 10% by weight of the compositions.
  • the detergent compositions may also contain organic peroxyacids at a level of from 1 % to 15% by weight, more preferably from 1 % to 10% by weight of the composition .
  • Anti-redeposition and soil-suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethy cellulose, homo-or co-polymeric polycarboxylic acids or their salts and ployamino compounds.
  • Polymers of this type include the polyacrylates and copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer disclosed in detail in EP-A-137669.
  • Polyamino compounds such as those derived from aspartic acid are disclosed in EP-A-305282, EP-A- 305283 and EP-A-351629. These materials are normally used at levels of from 0.5% to 10% by weight, more preferably from 0.75% to 8%, most preferably from 1 % to 6% by weight of the composition.
  • polyethylene glycols particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 0.20% to 5% more preferably from 0.25% to 2.5% by weight. These polymers and the previously mentioned homo- or co-polymeric polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.
  • Preferred optical brighteners are anionic in character, examples of which are disodium 4,4l-bis-(2-diethanolamino-4-anilino -s- triazin-6- ylamino)stilbene- 2:2 disulphonate, disodium 4,4l-bis-(2-morpholino -4-anilino-2-triazin-6- ylaminostilbene-2:2l-disulphonate,disodium 4, 4l-bis-(2,4-dianilino-s-triazin- 6-ylamino)stilbene-2:2l - disulphonate, monosodium 41.4 H-bis-(2, 4-dianilino- s-triazin-6-ylamino)stilbene-2- sulphonate, disodium 4,4l-bis-(2-anilino-4-(N- methy l-N-2-hydroxyethy lamino)-2-triazin-6-y lamino)stilbene-2 ,21 - dis
  • Soil-release agents useful in detergent compositions are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0272033. A particular preferred polymer in accordance with EP-A-0272033 has the formula
  • Certain polymeric materials such as poly vinyl pyrrolidones, typically of MWt 5000-20000, preferably 10000-15000, also form useful agents in preventing ' the transfer of labile dyestuffs between fabrics during the washing process.
  • Another optional detergent composition ingredient is a suds suppressor, exemplified by silicones, and silica-silicone mixtures.
  • Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms, exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent-impermeable carrier.
  • the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
  • useful silicone suds controlling agents can comprise a mixture of an alkylated siloxane, of the type referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica.
  • a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethyl-silanated) silica having a particle size in the range from 10 nanometers to 20 nanometers and a specific surface area above 50 m 2 /g, intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 1: 1 to about 1:2.
  • a preferred silicone suds controlling agent is disclosed in Bartollota et al. US Patent 3,933,672.
  • Other particularly useful suds suppressors are the self- emulsifying silicone suds suppressors, described in German Patent Application DTOS 2,646,126 published April 28, 1977.
  • An example of such a compound is DC0544, commercially available from Dow Corning, which is a siloxane/glycol copolymer.
  • the suds suppressors described above are normally employed at levels of from 0.001 % to 5% by weight of the composition, preferably from 0.1 % to 3% by weighty
  • the preferred methods of incorporation comprise either application of the suds suppressors in liquid form by spray-on to one or more of the major components of the composition or alternatively the formation of the suds suppressors into separate particulates that can then be mixed with the other solid components of the composition.
  • the incorporation of the suds modifiers as separate particulates also permits the inclusion therein of other suds controlling materials such as C20-C24 fatty acids, microcrystalline waxes and high MWt copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the dispersibility of the matrix. Techniques for forming such suds modifying particulates are disclosed in the previously mentioned Bartolotta et al US Patent No. 3,933,672.
  • Another optional ingredient useful in detergent compositions is one or more enzymes. These may be incorporated at a level of from 0.1 % to 10% , more preferably 0.5% to 5% by weight of the detergent composition.
  • Preferred enzymatic materials include the commercially available amylases, neutral and alkaline proteases, lipases, esterases and cellulases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • Preferred commercially available protease enzymes include those sold under the tradenames Alcalase and Savinase by Novo Industries A/S (Denmark) and Maxatase by International Bio-Synthetics, Inc. (The Netherlands).
  • Preferred amylases include, for example, -amylases obtained from a special strain of B licheniforms, described in more detail in GB-1 ,269,839 (Novo).
  • Preferred commercially available amylases include for example, Rapidase, sold by International Bio-Synthetics Inc, and Termamyl, sold by Novo Industries A/S.
  • An especially preferred lipase enzyme is manufactured and sold by Novo Industries A/S (Denmark) under the trade name Lipolase (Biotechnology Newswatch, 7 March 1988, page 6) and mentioned along with other suitable lipases in EP-A-0258068 (Novo).
  • a further optional ingredient useful in detergent compostions is a corrosion inhibitor C14-C20 fatty acids are preferred examples of such corrosion inhibitors.
  • Fabric softening agents can also be incorporated into laundry detergent compositions. These agents may be inorganic or organic in type. Inorganic softening agents are examplified by the smectite clays disclosed in GB-A- 1 ,400,898. Other suitable inorganic softening systems comprising smectite clays, including hectorite and montmorillonite, are also disclosed in EP-A- 0522206.
  • Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A-1514276 and EP-B-0011340.
  • Levels of smectite clay are normally in the range from 5 % to 15% , more preferably from 8% to 12% by weight, with the material being added as a dry mixed component to the remainder of the formulation.
  • Organic fabric softening agents such as the water-insoluble tertiary amines or dilong chain amide materials are incorporated at levels of from 0.5% to 5% by weight, normally from 1 % to 3 % by weight, whilst the high molecular weight polyethylene oxide materials and the water soluble cationic materials are added at levels of from 0.1 % to 2% , normally from 0.15% to 1.5% by weight.
  • these materials can be added to the aqueous slurry fed to the spray drying tower, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as a molten liquid on to other solid components of the composition.
  • detergent compositions can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation and preferred methods involve combinations of these techniques.
  • a preferred method of making the granular laundry detergent compositions involves a combination of spray drying, agglomeration in a high speed mixer and dry mixing.
  • the bulk density of the granular detergent compositions incorporating the bleaching compositons of the present invention may be in the range of about 450 to 600 g/litre as is typical for conventional laundry detergent compositions.
  • the granular detergent compositions may be concentrated granular detergent compositions that are characterised by a relatively high density in comparison with conventional detergent compositions.
  • Such high density compositions have a bulk density of at least 650 g/litre, more usually at least 700 g/litre and more preferably from 800 g/litre to 1100 g/litre.
  • Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindricl cup disposed below the funnel.
  • the funnel is 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base.
  • the cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
  • the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup.
  • the filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement e.g. a knife, across its upper edge.
  • the filled cup is then weighed and the value obtained for the weight of powder doubled to provide the bulk density in g/litre. Replicate measurements are made as required.
  • Concentrated laundry detergent compositions also normally incorporate at least one multi-ingredient component i.e. they do not comprise compositions formed merely by dry-mixing individual ingredients.
  • Compositions in which each individual ingredient is dry-mixed are generally dusty, slow to dissolve and also tend to cake and develop poor particle flow characteristics in storage.
  • Preferred laundry detergent compositions comprise at lease two particulate multi-ingredient components.
  • the first component comprises at least 15%, conventionally from 25% to 50%, but more preferably no more than 35% by weight of the composition and the second component from 1 % to 50%, more preferably 10% to 40% by weight of the composition.
  • the first component comprises a particulate incorporating an anionic surfactant in an amount of from 0.75% to 40% by weight of the powder and one or more inorganic and/or organic salts in an amount of from 99.25% to 60% by weight of the powder.
  • the particulate can have any suitable form such as granules, flakes, prills, marumes or noodles but is preferably granular.
  • the granules themselves may be agglomerates formed by pan or drum agglomeration or by in-line mixers but are customarily spray dried particles produced by atomising an aqueous slurry of the ingredients in a hot air stream which removes most of the water.
  • the spray dried granules are then subjected to densification steps, e.g. by high speed cutter mixers and/or compacting mills, to increase density before being reagglomerated.
  • densification steps e.g. by high speed cutter mixers and/or compacting mills
  • the first component is described hereinafter as a spray dried powder.
  • Suitable anionic surfactants for the purposes of the first component have been found to be slowly dissolving linear alkyl sulfate salts in which the alkyl group has an average of from 16 to 22 carbon atoms, and linear alkyl carboxylate salts in which the alkyl group has an average of from 16 to 24 carbon atoms.
  • the alkyl groups for both types of surfactant are preferably derived from natural sources such as tallow fat and marine oils.
  • the level of anionic surfactant in the spray dried powder forming the first component is from 0.75% to 40% by weight, more usually 2.5% to 25% preferably from 3% to 20% and most preferably from 5% to 15% by weight.
  • Water-soluble surfactants such as linear alkyl benzene sulphonates or C14-C15 alkyl sulphates can be included or alternatively may be applied subsequently to the spray dried powder by spray on.
  • the other major ingredient of the spray dried powder is one or more inorganic or organic salts that provide the crystalline structure for the granules.
  • the inorganic and/or organic salts may be water-soluble or water-insoluble, the latter type being comprised by the, or the major part of the, water-insoluble builders where these form part of the builder ingredient.
  • Suitable water soluble inorganic salts include the alkali metal carbonates and bicarbonates.
  • Amorphous alkali metal silicates may also be used to provide structure to the spray dried granule provided that aluminosilicate does not form part of the spray dried component.
  • aluminosilicate zeolite forms the, or part of the, builder ingredient, it is preferred that it is not added directly by dry-mixing to the other components, but is incorporated into the multi-ingredient component(s).
  • the first component can also include up to 15% by weight of miscellaneous ingredients such as brighteners, anti-redeposition agents, photoactivated bleaches (such as tetrasulfonated zinc phthalocyanine) and chelants.
  • miscellaneous ingredients such as brighteners, anti-redeposition agents, photoactivated bleaches (such as tetrasulfonated zinc phthalocyanine) and chelants.
  • the first component is a spray dried powder it will normally be dried to a moisture content of from 7% to 11 % by weight, more preferably from 8% to 10% by weight of the spray dried powder.
  • Moisture contents of powders produced by other processes such as agglomeration may be lower and can be in the range 1- 10% by weight.
  • the particle size of the first component is conventional and preferably not more than 5% by weight should be above 1.4mm, while not more than 10% by weight should be less than 0.15 mm in maximum dimension. Preferably at least 60%, and most preferably at least 80%, by weight of the powder lies between 0.7 mm and 0.25 mm in size.
  • the bulk density of the particles from the spray drying tower is conventionally in the range from 540 to 600 g/litre and this is then enhanced by further processing steps such as size reduction in a high speed cutter/mixer followed by compaction. Alternatively, processes other than spray drying may be used to form a high density particulate directly.
  • a second component of a preferred detergent composition is another multi- ingredient particulate containing a water soluble surfactant.
  • surfactants are listed hereinbefore but preferred surfactants are C14-C15 alkyl sulphates, linear C ⁇ ⁇ - C15 alkyl benzene sulphonates and fatty C14-C18 methyl ester sulphonates.
  • the second component may have any suitable physical form, i.e. it may take the form of flakes, prills, marumes, noodles, ribbons, or granules which may be spray-dried or non spray-dried agglomerates.
  • the second component could in theory comprise the water soluble surfactant on its own, in practice at least one organic or inorganic salt is included to facilitate processing. This provides a degree of crystallinity, and hence acceptable flow characteristics, to the particulate and may be any one or more of the organic or inorganic salts present in the first component.
  • the particle size range of the second component should be such as to obviate segregation from the particles of the first component when blended therewith.
  • not more than 5 % by weight should be above 1.4 mm while not more than 10% should be less than 0.15 mm in maximum dimension.
  • the bulk density of the second component will be a function of its mode of preparation.
  • the preferred form of the second component is a mechanically mixed agglomerate which may be made by adding the ingredients dry or with an agglomerating agent to a pan agglomerator, Z blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands and Gebruder Lodige MaschinenbanGmbH, D-4790 Paderborn 1 , Elsenerstrasse 7-9, Postfach 2050 F.R.G.
  • the second component can be given a bulk density in the range from 650 g/litre to 1190 g/litre more preferably from 750 g/litre to 850 g/litre.
  • Preferred laundry detergent compositions include a level of alkali metal carbonate in the second component corresponding to an amount of from 3 % to 15% by weight of the composition, more preferably from 5% to 12% by weight. This will provide a level of carbonate in the second component of from 20% to 40% by weight.
  • a highly preferred ingredient of the second component is also a hydrated water insoluble aluminosilicate ion exchange material of the synthetic zeolite type, described hereinbefore, present at from 10% to 35% by weight of the second component.
  • the amount of water insoluble aluminosilicate material incorporated in this way is from 1 % to 10% by weight of the composition, more preferably from 2% to 8% by weight.
  • the surfactant salt is formed in situ in an inline mixer.
  • the liquid acid form of the surfactant is added to a mixture of particulate anhydrous sodium carbonate and hydrated sodium aluminosilicate in a continuous high speed blender, such as a Lodige C6 mixer, and neutralised to form the surfactant salt whilst maintaining the particulate nature of the mixture.
  • a continuous high speed blender such as a Lodige C6 mixer
  • the surfactant salt is pre-neutralised and added as a viscous paste to the mixture of the other ingredients.
  • the mixer serves merely to agglomerate the ingredients to form the second component.
  • part of the spray dried product comprising the first granular component is diverted and subjected to a low level of nonionic surfactant spray on before being reblended with the remainder.
  • the second granular component is made using the preferred process described above.
  • the first and second components together with a crystalline layered silicate particulate composition, the perhydrate bleach and any peroxy acid bleaeh precursor particles, other dry mix ingredients such as any carboxylate chelating agent, soil-release polymer and enzyme are then fed to a conveyor belt, from which they are transferred to a horizontally rotating drum in which perfume and silicone suds suppressor are sprayed on to the product.
  • a further drum mixing step is employed in which a low (approx. 2% by weight) level of finely divided crystalline material is introduced to increase density and improve granular flow characteristics.
  • Laundry detergent compositions in accordance with the invention can also benefit from delivery systems that provide transient localised high concentrations of product in the drum of an automatic washing machine at the start of the wash cycle, thereby also avoiding problems associated with loss of product in the pipework or sump of the machine.
  • Delivery to the drum can most easily be achieved by incorporation of the composition in a bag or container from which it is rapidly releasable at the start of the wash cycle in response to agitation, a rise in temperature or immersion in the wash water in the drum.
  • the washing machine itself may be adapted to permit direct addition of the composition to the drum e.g. by a dispensing arrangement in the access door.
  • Products comprising a laundry detergent composition enclosed in a bag or container are usually designed in such a way that container integrity is maintained in the dry state to prevent egress of the contents when dry, but are adapted for release of the container contents on exposure to a washing environment, normally on immersion in an aqueous solution.
  • the container will be flexible, such as a bag or pouch.
  • the bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678.
  • it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501 , 0011502, and 0011968.
  • a convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.
  • laminated sheet products can be employed in which a central flexible layer is impregnated and/or coated with a composition and then one or more outer layers are applied to produce a fabric- like aesthetic effect.
  • the layers may be sealed together so as to remain attached during use, or may separate on contact with water to facilitate the release of the coated or impregnated material.
  • An alternative laminate form comprises one layer embossed or deformed to provide a series of pouch-like containers into each of which the detergent components are deposited in measured amounts, with a second layer overlying the first layer and sealed thereto in those areas between the pouch-like containers where the two layers are in contact.
  • the components may be deposited in particulate, paste or molten form and the laminate layers should prevent egress of the contents of the pouch-like containers prior to their addition to water.
  • the layers may separate or may remain attached together on contact with water, the only requirement being that the structure should permit rapid release of the contents of the pouch-like containers into solution.
  • the number of pouch-like containers per unit area of substrate is a matter of choice but will normally vary between 500 and 25,000 per square metre.
  • Suitable materials which can be used for the flexible laminate layers in this aspect of the invention include, among others, sponges, paper and woven and non- woven fabrics.
  • the preferred means of carrying a laundry process is to introduce the composition into the liquid surrounding the fabrics that are in the drum via a reusable dispensing device having walls that are permeable to liquid but impermeable to the solid composition.
  • DETPMP Diethylene triamine penta (methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060
  • Nonionic A C13-C15 ethoxylated/propoxylated fatty alcohol with a degree of ethoxylation of 3.8 and a degree of propoxylation of 4.5 sold under the tradename Plurafac LF404 by BASF GmbH.
  • a similar procedure was used to the test described in Example 1 but adjustments were made to make the test more representative of domestic automatic dishwashing process conditions.
  • a beaker containing 1000 ml water of 17° German Hardness (243 ppm CaC ⁇ 3) was placed in a constant temperature bath initially set at 20°C.
  • To this beaker was added heavy metal ions in the form of inert, soluble inorganic salts to give a heavy metal ion concentration by weight of 1.5 ppm Cu and 0.67 ppm Fe.
  • These levels of Cu and Fe are believed to be typical of the levels which might be found in the wash liquor of a domestic automatic dishwashing machine during a typical wash cycle with a normal wash load.
  • liquid peroxy bleach containing formulations suitable for use as household cleaners or as bleach additives, were prepared in accordance with the invention :
  • Minors include perfume, brightener and dye

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Compositions de blanchiment comprenant un composé peroxy et l'acide éthylènediamine-N,N'-disuccinique ou des sels de ce composé. Les compositions de blanchiment présentent une bonne stabilité de blanchiment dans une solution aqueuse, et sont particulièrement destinées à des procédés de blanchiment effectués au moins en partie à des températures supérieures à 60°C. Les compositions présentent également une bonne stabilité en stockage. Ces compositions peuvent être utilisées pour le blanchiment de matières fibreuses cellulosiques et de textiles synthétiques et peuvent également être utilisés comme constituants de compositions détersives.
PCT/US1993/006837 1992-08-01 1993-07-21 Composition de blanchiment peroxy stabilisee a l'acide ethylenediamine-n,n'-disuccinique WO1994003553A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1019950700419A KR950703038A (ko) 1992-08-01 1993-07-21 에틸렌디아민-n,n′-디석신산으로 안정화시킨 퍼옥시 표백 조성물(peroxy bleaching composition stabilized with ethylenediamine-n,n′-disuccinic acid)
JP6505354A JPH07509523A (ja) 1992-08-01 1993-07-21 エチレンジアミン‐ｎ，ｎ‐ジコハク酸で安定化されたパーオキシ漂白組成物
AU47785/93A AU666403B2 (en) 1992-08-01 1993-07-21 Nonphosphonated dishwashing composition
EP93918280A EP0652924A4 (en) 1992-08-01 1993-07-21 Peroxy bleaching composition stabilized with ethylenediamine-n,n'-disuccinic acid.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9216408.6 1992-08-01
GB929216408A GB9216408D0 (en) 1992-08-01 1992-08-01 Stabilized bleaching compositions

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WO1994003553A1 true WO1994003553A1 (fr) 1994-02-17

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EP (1) EP0652924A4 (fr)
JP (1) JPH07509523A (fr)
KR (1) KR950703038A (fr)
CN (1) CN1084560A (fr)
AU (1) AU666403B2 (fr)
CA (1) CA2141611A1 (fr)
GB (1) GB9216408D0 (fr)
MA (1) MA22947A1 (fr)
MX (1) MX9304665A (fr)
TR (1) TR28150A (fr)
TW (1) TW255911B (fr)
WO (1) WO1994003553A1 (fr)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995025159A1 (fr) * 1994-03-17 1995-09-21 The Procter & Gamble Company Blanchissage ameliore par l'ethylenediamine-n,n'-disuccianate de manganese
WO1996036725A1 (fr) * 1995-05-17 1996-11-21 Ciba Speciality Chemicals Holding Inc. Procede microbiologique de preparation d'acide (s,s)-n,n'-ethylenediaminedisuccinique
EP0760243A1 (fr) 1995-08-31 1997-03-05 The Procter & Gamble Company Utilisation de l'alcool allylique comme agent de réduction de mauvaises odeurs
WO1997030207A1 (fr) * 1996-02-19 1997-08-21 Kemira Chemicals Oy Procede de blanchiment de pate chimique
WO1997030209A1 (fr) * 1996-02-19 1997-08-21 Kemira Chemicals Oy Procede de blanchiment de pate haut rendement
WO1997030210A1 (fr) * 1996-02-19 1997-08-21 Kemira Chemicals Oy Procede de blanchiment de pate haut rendement
WO1997030208A1 (fr) * 1996-02-19 1997-08-21 Kemira Chemicals Oy Procede applicable au traitement de la pate chimique
EP0812348A1 (fr) * 1995-02-28 1997-12-17 The Procter & Gamble Company Pretraitement du linge avec des chelateurs contenant un agent de blanchiment peroxyde pour le fer, le cuivre ou le manganese, pour diminuer la deterioration du tissu
WO1998004775A1 (fr) * 1996-07-26 1998-02-05 Basf Aktiengesellschaft Utilisation d'agents complexants pour le blanchiment de la cellulose et du bois, pour la fabrication du papier et le desencrage de vieux papiers
US5759439A (en) * 1996-06-14 1998-06-02 The Procter & Gamble Company Peroxygen bleaching compositions comprising peroxygen bleach and a fabric protection agent suitable for use as a pretreater for fabrics
US5905065A (en) * 1995-06-27 1999-05-18 The Procter & Gamble Company Carpet cleaning compositions and method for cleaning carpets
US6187055B1 (en) 1996-01-03 2001-02-13 Henkel Kommanditgesellschaft Auf Aktien Washing agents with specific oxidized oligosaccharides
US6245941B1 (en) 1995-04-13 2001-06-12 The Associated Octel Company Limited Reductive alkylation process for the preparation of compounds containing at least two amino groups
EP0772771B2 (fr) † 1994-07-27 2003-12-17 The Dow Chemical Company Determination de la biodegradabilite de derives d'acide aspartique, chelates degradables et leurs utilisations et compositions
WO2005021427A1 (fr) * 2003-08-26 2005-03-10 Henkel Kommanditgesellschaft Auf Aktien Stabilisation de peroxyde d'hydrogene lors de la dissolution de substances alcalinisantes dans des systemes contenant du peroxyde d'hydrogene
EP1811080A1 (fr) * 2006-01-24 2007-07-25 Solvay SA Procédé de blanchiment de pate de papier mecanique
WO2009056893A3 (fr) * 2007-11-02 2009-07-02 Innospec Ltd Procédé de blanchiment de pâte
EP2103676A1 (fr) * 2008-03-18 2009-09-23 The Procter and Gamble Company Composition détergente pour le lavage du linge comprenant un sel de magnésium d'acide diamine-n'n' disuccinique d'éthylène
US8377478B2 (en) 2007-07-26 2013-02-19 Innospec Limited Solid detergent composition
CN103666834A (zh) * 2012-09-07 2014-03-26 杨平 医用织物洗涤剂及其使用方法
CZ309643B6 (cs) * 2021-07-21 2023-06-07 Univerzita Pardubice Hořečnaté sole derivátů asparagové kyseliny a jejich použití jako stabilizátorů peroxidu vodíku

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GB9216410D0 (en) * 1992-08-01 1992-09-16 Procter & Gamble Detergent compositions
US7044985B2 (en) * 1999-12-21 2006-05-16 Clariant Finance (Bvi) Limited Process for pre-treating cellulosic fibers and cellulosic fiber blends
JP4248466B2 (ja) * 2004-09-03 2009-04-02 株式会社島精機製作所 繊維製品の染色方法
EP2417241A4 (fr) * 2009-04-08 2014-10-15 Sunsonix Procédé et appareil destinés à éliminer des substances contaminantes à partir de substrats
US20130209575A1 (en) * 2011-08-29 2013-08-15 E I Du Pont De Nemours And Company Multi-part kit system for the preparation of a disinfectant
CN102363929A (zh) * 2011-11-30 2012-02-29 中冶纸业银河有限公司 一种提高纸浆过氧化氢漂白效率的方法
EP3107987B1 (fr) * 2014-02-20 2018-10-03 Unilever N.V. Compositions de détergent de lave-vaisselle
CN105907483B (zh) * 2016-05-08 2019-01-15 浙江艾卡医学科技有限公司 一种含氧的多功能洗涤剂组合物

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US3686126A (en) * 1969-06-17 1972-08-22 Citrex Sa Bleaching and softening agent
US4075116A (en) * 1975-09-15 1978-02-21 Produits Chimiques Ugine Kuhlmann Mixed persalts stable in detergent compositions
US4378300A (en) * 1981-12-10 1983-03-29 Colgate-Palmolive Company Peroxygen bleaching composition
US4737306A (en) * 1985-07-24 1988-04-12 Kenkel Kommanditgesellschaft Auf Aktien Layered silicates of limited swelling power, a process for their production and their use in detergents and cleaning preparations
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Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995025159A1 (fr) * 1994-03-17 1995-09-21 The Procter & Gamble Company Blanchissage ameliore par l'ethylenediamine-n,n'-disuccianate de manganese
EP0772771B2 (fr) † 1994-07-27 2003-12-17 The Dow Chemical Company Determination de la biodegradabilite de derives d'acide aspartique, chelates degradables et leurs utilisations et compositions
EP0812348A1 (fr) * 1995-02-28 1997-12-17 The Procter & Gamble Company Pretraitement du linge avec des chelateurs contenant un agent de blanchiment peroxyde pour le fer, le cuivre ou le manganese, pour diminuer la deterioration du tissu
EP0812348A4 (fr) * 1995-02-28 2000-04-12 Procter & Gamble Pretraitement du linge avec des chelateurs contenant un agent de blanchiment peroxyde pour le fer, le cuivre ou le manganese, pour diminuer la deterioration du tissu
US6245941B1 (en) 1995-04-13 2001-06-12 The Associated Octel Company Limited Reductive alkylation process for the preparation of compounds containing at least two amino groups
WO1996036725A1 (fr) * 1995-05-17 1996-11-21 Ciba Speciality Chemicals Holding Inc. Procede microbiologique de preparation d'acide (s,s)-n,n'-ethylenediaminedisuccinique
US5905065A (en) * 1995-06-27 1999-05-18 The Procter & Gamble Company Carpet cleaning compositions and method for cleaning carpets
EP0760243A1 (fr) 1995-08-31 1997-03-05 The Procter & Gamble Company Utilisation de l'alcool allylique comme agent de réduction de mauvaises odeurs
US6187055B1 (en) 1996-01-03 2001-02-13 Henkel Kommanditgesellschaft Auf Aktien Washing agents with specific oxidized oligosaccharides
WO1997030208A1 (fr) * 1996-02-19 1997-08-21 Kemira Chemicals Oy Procede applicable au traitement de la pate chimique
WO1997030210A1 (fr) * 1996-02-19 1997-08-21 Kemira Chemicals Oy Procede de blanchiment de pate haut rendement
WO1997030209A1 (fr) * 1996-02-19 1997-08-21 Kemira Chemicals Oy Procede de blanchiment de pate haut rendement
WO1997030207A1 (fr) * 1996-02-19 1997-08-21 Kemira Chemicals Oy Procede de blanchiment de pate chimique
US5759439A (en) * 1996-06-14 1998-06-02 The Procter & Gamble Company Peroxygen bleaching compositions comprising peroxygen bleach and a fabric protection agent suitable for use as a pretreater for fabrics
WO1998004775A1 (fr) * 1996-07-26 1998-02-05 Basf Aktiengesellschaft Utilisation d'agents complexants pour le blanchiment de la cellulose et du bois, pour la fabrication du papier et le desencrage de vieux papiers
WO2005021427A1 (fr) * 2003-08-26 2005-03-10 Henkel Kommanditgesellschaft Auf Aktien Stabilisation de peroxyde d'hydrogene lors de la dissolution de substances alcalinisantes dans des systemes contenant du peroxyde d'hydrogene
EP1811080A1 (fr) * 2006-01-24 2007-07-25 Solvay SA Procédé de blanchiment de pate de papier mecanique
WO2007085579A1 (fr) * 2006-01-24 2007-08-02 Solvay (Société Anonyme) Procédé pour le blanchiment de pâte à papier mécanique
US8377478B2 (en) 2007-07-26 2013-02-19 Innospec Limited Solid detergent composition
US8759397B2 (en) 2007-07-26 2014-06-24 Innospec Limited Detergent composition
WO2009056893A3 (fr) * 2007-11-02 2009-07-02 Innospec Ltd Procédé de blanchiment de pâte
US8906199B2 (en) 2007-11-02 2014-12-09 Innospec Limited Process for bleaching pulp
WO2009117342A1 (fr) * 2008-03-18 2009-09-24 The Procter & Gamble Company Composition de lessive comportant du sel de magnésium d’acide éthylène diamine-n’n’-disuccinique
EP2103676A1 (fr) * 2008-03-18 2009-09-23 The Procter and Gamble Company Composition détergente pour le lavage du linge comprenant un sel de magnésium d'acide diamine-n'n' disuccinique d'éthylène
CN103666834A (zh) * 2012-09-07 2014-03-26 杨平 医用织物洗涤剂及其使用方法
CN103666834B (zh) * 2012-09-07 2015-06-17 杨平 医用织物洗涤剂及其使用方法
CZ309643B6 (cs) * 2021-07-21 2023-06-07 Univerzita Pardubice Hořečnaté sole derivátů asparagové kyseliny a jejich použití jako stabilizátorů peroxidu vodíku

Also Published As

Publication number Publication date
JPH07509523A (ja) 1995-10-19
CA2141611A1 (fr) 1994-02-17
MA22947A1 (fr) 1994-04-01
TR28150A (tr) 1996-02-29
AU4778593A (en) 1994-03-03
AU666403B2 (en) 1996-02-08
KR950703038A (ko) 1995-08-23
CN1084560A (zh) 1994-03-30
MX9304665A (es) 1994-03-31
EP0652924A4 (en) 1995-06-14
TW255911B (fr) 1995-09-01
GB9216408D0 (en) 1992-09-16
EP0652924A1 (fr) 1995-05-17

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