EP1238052A1 - Compositions detergentes - Google Patents

Compositions detergentes

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Publication number
EP1238052A1
EP1238052A1 EP00983141A EP00983141A EP1238052A1 EP 1238052 A1 EP1238052 A1 EP 1238052A1 EP 00983141 A EP00983141 A EP 00983141A EP 00983141 A EP00983141 A EP 00983141A EP 1238052 A1 EP1238052 A1 EP 1238052A1
Authority
EP
European Patent Office
Prior art keywords
detergent
ids
compound
formula
detergent composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00983141A
Other languages
German (de)
English (en)
Other versions
EP1238052B1 (fr
Inventor
Lesley Unilever Research Port Sunlight EBBRELL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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Filing date
Publication date
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Publication of EP1238052A1 publication Critical patent/EP1238052A1/fr
Application granted granted Critical
Publication of EP1238052B1 publication Critical patent/EP1238052B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • 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

Definitions

  • the present invention relates to particulate detergent compositions containing the sequestrant, iminodisuccinate or hydroxyiminodisuccinate .
  • the invention is of especially interest for detergent powders of high bulk density . (so- called "compact" powders) and to tablets of compacted detergent powder.
  • the invention is especially applicable to laundry detergent powders but is also relevant to powders or tablets for mechanical dishwashing.
  • Iminodisuccinate (IDS) and hydroxyiminodisuccinate (HIDS) are known as detergency builders and, in bleaching detergent compositions, as stabilisers for peroxy bleach precursors.
  • US 3 697 453 discloses detergent compositions having a pH of from 9 to 12, containing iminodisuccinate as a detergency builder, used together with detergent surfactant in a weight ratio of 0.25:1 to 10:1.
  • IDS as a detergency builder is also disclosed in EP 757 094A (Bayer) .
  • HIDS is disclosed in US 5 318 726 (Henkel) .
  • EP 509 382A (W R Grace & Co/Hampshire Chemical Corporation) discloses a bleaching detergent composition comprising a bleaching agent and a bleach stabiliser of defined formula which includes IDS.
  • the use of IDS as a bleach stabiliser is also disclosed in WO 97 20907A (Procter & Gamble) .
  • WO 00/34427A discloses and claims non-bleaching laundry detergent compositions containing from 0.05 to
  • the compositions provides improved maintenance and/or restoration of colour fidelity during the wash, especially at low wash pH.
  • the IDS or HIDS is also an effective chlorine scavenger, reducing the in-wash fading of chlorine-sensitive dyes.
  • the incorporation of the IDS or HIDS improves the stain removal performance of the composition.
  • IDS is commercially available in sodium salt form, eg as IDS Na-salt from Bayer.
  • the sodium salt is highly water-soluble and the material is supplied as an aqueous solution (approximate IDS Na-salt content 34%) and as a solid white powder prepared from the solution by spray-drying. If IDS is to be incorporated into an aqueous liquid detergent or into a spray-dried detergent powder via the slurry, the solution form is most conveniently used. However, it is not suitable for the preparation of a powder of high bulk density by a non-tower (non-spray-drying) route because the water content is too high. For such products it is necessary to use IDS in powder form.
  • the powder is extremely hygroscopic and, according to the manufacturer Bayer's recommendation, must be stored in tightly closed containers. If stored in contact with the atmosphere it rapidly takes up water and deliquesces, ie becomes a liquid. The problem is exacerbated in humid atmospheres so that any storage or handling of the material causes major problems with stickiness. When this sticky raw material is incorporated into a detergent powder, poor powder properties result .
  • the resulting Ca/Na or Mg/Na salts or complexes are stable solids which are significantly less hygroscopic than the sodium salt. They can readily be incorporated into particulate detergent compositions and, surprisingly, the resulting compositions show no loss of sequestrant activity as compared with similar compositions containing the sodium salt .
  • GB 2 048 930A discloses bleaching detergent compositions containing an organic phosphonate sequestrant - ethylenediamine tetramethylene phosphonate (EDTMP) or diethylenetriamine pentamethylene phosphonate (DETPMP) present as a complex of a magnesium, calcium, zinc or aluminium ion, the molar ratio of the metal ion to the phosphonate compound being at least 1:1.
  • ETMP organic phosphonate sequestrant - ethylenediamine tetramethylene phosphonate
  • DETPMP diethylenetriamine pentamethylene phosphonate
  • JP 09 110 813A and JP 09 104 897A disclose a builder powder of reduced hygroscopicity based on IDS, in which sodium IDS is compounded with an inorganic metal salt, preferably zeolite, sodium carbonate or sodium silicate .
  • JP 09 100 497A discloses high bulk density detergent powders containing IDS, prepared by granulating together detergent ingredients including an inorganic builder salt, eg zeolite, and sodium IDS or HIDS (3-20 wt% of the final composition) .
  • the hygroscopicity of the IDS is exploited to bind fine zeolite particles and thereby improve flow and reduce stickiness.
  • the present invention provides a particulate detergent composition containing a sequestrant which is a compound of the formula I
  • COOX COOX COOX COOX COOX COOX wherein Y is H or OH, and X is a countercation, the compound being in the form of a complex of a metal ion selected from calcium and magnesium ions, the molar ratio of the metal ion to the compound of the formula I being at least 2:1.
  • the invention further provides a process for the preparation of a particulate detergent composition, which includes the step of mixing and/or granulating a compound of the formula I in powder form with other detergent ingredients, wherein the compound of the formula I is in the form of a complex of a metal ion selected from calcium and magnesium ions, the molar ratio of the metal ion to the compound of the formula I being at least 2:1.
  • the detergent composition of the invention contains a compound of the formula I above as an essential ingredient.
  • Y is H
  • the compound is IDS
  • Y is OH
  • the compound is HIDS.
  • IDS For convenience only IDS will be discussed in the description below, but this should be understood to refer equally to HIDS.
  • IDS is a pentadentate ligand ie it can form complexes with metal ions in which bonds are formed with the nitrogen atom and all four carboxyl groups. Indeed its efficacy as a detergency builder is based on its capacity to form such complexes with calcium and magnesium ions, and its efficacy as a bleach stabiliser and for colour care is based on its capacity for forming such complexes with heavy metal ions such as iron and copper.
  • IDS in the form of a 2:1 or higher complex with calcium or magnesium is substantially less hygroscopic than the sodium salt .
  • the calcium complexes are especially preferred, more especially complexes having a Ca : IDS molar ratio of 2:1 or above, for example, 2:1 or 3:1.
  • the 1:1 complex is also less hygroscopic than the sodium salt, but the benefit is significantly greater with the higher ratio complexes.
  • the 3:1 complex is especially preferred.
  • the magnesium complexes are also useful but the benefit observed is less than with the calcium complexes.
  • the calcium or magnesium complexes may be prepared by reacting the sodium salt, in aqueous solution, with the appropriate amount of a soluble calcium or magnesium salt, preferably calcium or magnesium chloride. The reaction also produces a soluble inorganic sodium salt (eg sodium chloride) .
  • a soluble calcium or magnesium salt preferably calcium or magnesium chloride.
  • the soluble inorganic sodium salt produced as a by-product of the preparation process is removed by using a filtration step.
  • a filtration step where this is possible, a further significant reduction of hygroscopicity has been observed.
  • solubility between the complex and the inorganic salt byproduct, which is highly soluble.
  • the CalDS and CaHIDS 3:1 complexes are especially preferred in this respect because their solubility is sufficiently reduced, compared with that of the sodium salt, to allow sodium chloride to be separated by filtration during their preparation, yet is sufficiently high for these materials to be delivered effectively into the wash liquor.
  • an especially preferred embodiment of the invention involves the use of a CalDS or CaHIDS 3 : 1 complex which has been prepared by a method which includes removal of any inorganic salt by-product.
  • the detergent compositions of the invention contain IDS (or HIDS) as an essential ingredient. This may be present at levels sufficient for detergency building, either alone or in conjunction with another detergency builder, or at the much lower levels appropriate for bleach stabilisation, or for colour care benefits and stain removal in non-bleaching formulations as disclosed in WO 00/34427A (Unilever) .
  • the amount of IDS or HIDS present in the composition may therefore range very widely, for example, from 0.05 to 80 wt%. Suitable ranges are, for example, 5 to 80 wt% if IDS is the sole or principal builder; 1 to 20 wt% if it is present as cobuilder to, for example, zeolite, phosphate or carbonate; 0.5 to 10 wt% for bleach stabilisation; 0.05 to 2.5 wt% for colour care benefits in non-bleaching formulations .
  • compositions of the invention may contain other conventional detergent ingredients as detailed below.
  • a composition in which IDS is present as a cobuilder or a bleach stabiliser may comprise the following:
  • a non-bleaching formulation in which a low level of IDS has been included for colour care benefits may suitably comprise :
  • the detergent composition of the invention is in particulate form.
  • the invention is especially applicable to powders of high bulk density, and to tablets prepared by compacting powder. In these products the use of a hygroscopic material would be especially problematic.
  • the composition of the invention preferably has a bulk density of at least 500 g/1, and preferably from 600 to 1000 g/1, more preferably from 800 to 1000 g/1.
  • the invention is also applicable to powders of lower bulk density.
  • the IDS complex may be in admixture mixed with a spray-dried detergent base powder and optionally other conventional detergent ingredients.
  • compositions of the invention may also be in tablet form.
  • While the invention is primarily applicable to laundry detergent compositions, it is also relevant to mechanical dishwashing detergents, both powders and tablets, containing IDS.
  • the invention is especially applicable to particulate detergent compositions of high bulk density.
  • Such compositions may be prepared by non- tower (non-spray-drying) processes in which particulate raw materials are mixed and/or granulated.
  • to prepare compositions of this type the IDS complex is mixed and/or granulated with other detergent ingredients.
  • the mixing and/or granulation may suitably be carried out in a high-speed mixer/granulator, for example a Fukae (Trade Mark) FSG mixer or a Loedige Recycler (Trade Mark) .
  • a detergent base powder may be prepared by conventional slurry-making and spray- drying processes, and other ingredients in powder form, including the IDS complex in accordance with the present invention, may be admixed (postdosed) to the base powder.
  • IDS in a non-hygroscopic powder form adds further flexibility in the manufacture of detergent powders, and is especially valuable where different products of different bulk densities are manufactured on the same site.
  • Tablets may be prepared by compacting powders containing the IDS complex.
  • compositions of the invention also contain other conventional detergent ingredients.
  • Essential ingredients are surfactants (detergent-active compounds) , and (unless IDS is the sole builder) detergency builders.
  • the detergent compositions will contain, as essential ingredients, one or more detergent active compounds (surfactants) which may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds, and mixtures thereof.
  • surfactants may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds, and mixtures thereof.
  • surfactants may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds, and mixtures thereof.
  • surfactants may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds, and mixtures thereof.
  • suitable detergent active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Ber
  • the preferred detergent active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds .
  • Anionic surfactants are well-known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C ⁇ 5 ; primary and secondary alkylsulphates , particularly C 8 -C ⁇ 5 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • Sodium salts are generally preferred.
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C 8 -C2o aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C ⁇ 5 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkylpolyglycosides , glycerol monoethers, and polyhydroxyamides (glucamide) .
  • Cationic surfactants that may be used include quaternary ammonium salts of the general formula R ⁇ R 2 R 3 RN + X " wherein the R groups are long or short hydrocarbyl chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a solubilising cation (for example, compounds in which Ri is a C 8 _C 2 2 alkyl group, preferably a C 8 -C 10 or C ⁇ 2 -C 14 alkyl group, R 2 is a methyl group, and R 3 and R 4 , which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters) .
  • R groups are long or short hydrocarbyl chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups
  • X is a solubilising cation
  • Ri is a C 8 _C 2 2 alkyl group,
  • Ri represents a C 8 -C ⁇ 0 or C ⁇ 2 -C ⁇ 13
  • R and R 3 represent methyl groups, and R 4 presents a hydroxyethyl group.
  • Amphoteric surfactants for example, amine oxides, and zwitterionic surfactants, for example, betaines, may also be present .
  • the quantity of anionic surfactant is in the range of from 5 to 50% by weight of the total composition. More preferably, the quantity of anionic surfactant is in the range of from 8 to 35% by weight.
  • Nonionic surfactant if present, is preferably used in an amount within the range of from 1 to 20% by weight.
  • the total amount of surfactant present is preferably within the range of from 5 to 60 wt%.
  • compositions may suitably contain from 10 to 80%, preferably from 15 to 70% by weight, of detergency builder.
  • the quantity of builder is in the range of from 15 to 50% by weight.
  • the detergent compositions may contain as builder a crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate (zeolite) .
  • a crystalline aluminosilicate preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate (zeolite) .
  • the zeolite used as a builder may be the commercially available zeolite A (zeolite 4A) now widely used in laundry detergent powders.
  • the zeolite may be maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070B (Unilever) , and commercially available as Doucil (Trade Mark) A24 from Crosfield Chemicals Ltd, UK.
  • Zeolite MAP is defined as an alkali metal aluminosilicate of zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, preferably within the range of from 0.90 to 1.20.
  • zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00.
  • the particle size of the zeolite is not critical. Zeolite A or zeolite MAP of any suitable particle size may be used.
  • phosphate builders especially sodium tripolyphosphate . This may be used in combination with sodium orthophosphate, and/or sodium pyrophosphate .
  • inorganic builders that may be present additionally or alternatively include sodium carbonate, layered silicate, amorphous aluminosilicates .
  • Organic builders that may be present, as well as IDS itself, include polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers; polyaspartates ; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-di- and trisuccinates, carboxymethyloxysuccinates , carboxy-methyloxymalonates , dipicolinates, hydroxyethyliminodiacetates , alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts .
  • polycarboxylate polymers such as polyacrylates and acrylic/maleic copolymers
  • polyaspartates monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-di- and trisuccinates, carboxymethyloxysuccinates , carboxy-methyloxymalonates , dipicolinate
  • IDS and other organic builders may be used in minor amounts as supplements to inorganic builders such as phosphates and zeolites.
  • Especially preferred supplementary organic builders are citrates, suitably used in amounts of from 5 to 30 wt %, preferably from 10 to 25 wt %; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt %, preferably from 1 to 10 wt%.
  • Builders both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
  • Detergent compositions according to the invention may also suitably contain a bleach system.
  • a bleach system This is preferably based on peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
  • Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates , perphosphates, persilicates and persulphates .
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate .
  • sodium percarbonate having a protective coating against destabilisation by moisture Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao) . - 1 (
  • the peroxy bleach compound is suitably present in an amount of from 5 to 35 wt%, preferably from 10 to 25 wt%.
  • the peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures.
  • the bleach precursor is suitably present in an amount of from 1 to 8 wt%, preferably from 2 to 5 wt%.
  • Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors.
  • An especially preferred bleach precursor suitable for use in the present invention is N,N,N',N'- tetracetyl ethylenediamine (TAED) .
  • TAED N,N,N',N'- tetracetyl ethylenediamine
  • the novel quaternary ammonium and phosphonium bleach precursors disclosed in US 4 751 015 and US 4 818 426 (Lever Brothers Company) and EP 402 971A (Unilever) are also of great interest.
  • Especially preferred are peroxycarbonic acid precursors, in particular cholyl-4-sulphophenyl carbonate.
  • peroxybenzoic acid precursors in particular, N,N, N-trimethylammonium toluoyloxy benzene sulphonate; and the cationic bleach precursors disclosed in EP 284 292A and EP 303 520A (Kao) .
  • a bleach stabiliser may also be present.
  • suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark), EDTMP .
  • the detergent compositions may also contain one or more enzymes. Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and upases usable for incorporation in detergent compositions.
  • Preferred proteolytic enzymes are catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.
  • Proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available. Proteases of both high and low isoelectric point are suitable.
  • enzymes that may suitably be present include lipases, amylases, and cellulases including high-activity cellulases such as "Carezyme”) .
  • detergency enzymes are commonly employed in granular form in amounts of from about 0.1 to about 3.0 wt%. However, any suitable physical form of enzyme may be used in any effective amount.
  • Antiredeposition agents for example cellulose esters and ethers, for example sodium carboxymethyl cellulose, may also be present .
  • compositions may also contain soil release polymers, for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene - I S
  • soil release polymers for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene - I S
  • glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) HP22.
  • Especially preferred soil release polymers are the sulphonated non-end-capped polyesters described and claimed in WO 95 32997A (Rhodia Chimie) .
  • ingredients that may be present include solvents, hydrotropes, fluorescers, photobleaches , foam boosters or foam controllers (antifoams) as appropriate, sodium carbonate, sodium bicarbonate, sodium silicate, sodium sulphate, calcium chloride, other inorganic salts, fabric conditioning compounds, and perfumes.
  • An 0.04M aqueous solution of NalDS (ex Bayer) was prepared and the pH adjusted to 12 with 1M NaOH solution.
  • CaCl 2 or MgCl solution was added slowly while stirring to give a final mole ratio of Ca or Mg to IDS of 1:1, 2:1 or 3:1.
  • a white precipitate formed with slow addition of the Ca or Mg salt solution.
  • the Mg:IDS also formed a thicker, more gelatinous precipitate than Ca : IDS .
  • the dry salt was obtained by collecting the total liquor and precipitate and freeze drying.
  • the dry salt was ground up using a mortar and pestle.
  • the dry salt was sieved to obtain a fraction with constant size and therefore constant surface area.
  • the size fraction 355-500 micrometres was selected as being a representative portion of normal detergent powders.
  • Approximately 1 g portions of these sieved Ca : IDS and Mg:IDS powders were weighed out into plastic dishes. These open dishes were stored in a humidity cabinet at 20°C/75% RH, the relative humidity being generated by an atmosphere of saturated NaCl (- 6M) . - 20
  • the dishes were re-weighed periodically over a period of 7 days' storage under these conditions, and the % water uptake was calculated.
  • Example shows the benefit of separating the sodium chloride formed as a by-product .
  • the procedure was generally similar to that of Example 1, but with an added filtration step.
  • a 0.04M solution of NalDS was prepared and the pH adjusted to 12 with 1M NaOH solution. 0.12M CaCl 2 solution was added slowly while stirring, to give a final mole ratio of 3:1 Ca:IDS) . A white precipitate formed with slow addition of the Ca salt solution. After the required amount of Ca salt solution had been added, the pH was re-adjusted back to 12.
  • the slurry obtained was filtered under vacuum through a 542 filter paper fitted to a Buchner funnel . This removed the majority of the NaCl generated during the reaction of NalDS with CaCl 2 . The filter cake was dried in an oven overnight at 120°C.
  • Example 3 1 CaHIDS complexes were prepared by the procedures described in Example 1 (without filtration) and Example 2 (with filtration) .
  • the starting NaHIDS was ex Nippon Shokubai .
  • a particulate detergent composition was prepared by a conventional slurry-making and spray-drying process to the following formulation:
  • each ar was then transferred to open cardboard trays, and stored for a period of 7 days m a controlled temperature/humidity store, (37°C/70% RH) .
  • Compression and caking were measured using an apparatus comprising a graduated open-ended perspex cylinder of height 80 mm and internal diameter 24 mm standing on an aluminium base plate and fitted at its upper end with a plunger having a large flat circular top on which cylindrical weights could be placed.
  • the cylinder was filled with powder to a height of 30 mm, the plunger inserted until just touching the top of the powder, and a 1 kg weight placed on the top of the plunger.
  • the weight was removed after 2 minutes, and the compression of the powder sample (the fall in its level, in mm) was measured using the graduations on the cylinder and recorded.
  • the resulting "cake" of powder was expelled from the lower end of the cylinder, by means of the plunger, onto the base plate. 20g weights were added to the top of the powder cake until the cake disintegrated, and the total weight required to break up the cake (the unconfined compression test score or UCT, in g) was recorded. Higher UCT values were obtained when a higher level of compression was achieved, ie the "powder cakes" were stronger. Increased compression and higher UCT values were also generally linked to increased water uptake.
  • the fabrics used were cotton dyed with Direct Red 80. They were pre-treated with demineralised water containing 0.5 ppm Cu 2+ ions and having the pH adjusted to 6.5 by means of sodium hydroxide. The pretreatment was carried out using tergotometers at 30°C, 90 rpm and a liquor to cloth ratio of 200:1, then the fabrics were line dried.
  • the fabrics were then washed in a wash liquor containing 2.5 g/1 of the detergent composition (as used above), and 0.5 ppm Cu 2+ , in 20/6° Ca/Mg French hard water: the pH was adjusted from 9.9 to 9.5 using dilute sulphuric acid.
  • the washes were carried out in tergotometers at 30°C, 90 rpm and a liquor to cloth ratio of 200:1.
  • the washes were followed by two rinses in 20/6° Ca/Mg French hard water containing 0.05 ppm Cu 2+ at a liquor to cloth ratio of 200:1, and the fabrics were then line dried.
  • the sequestrants where present, were dosed directly into the wash liquor in amounts to give the equivalent of 1.25% (by weight on the detergent composition) of NalDS or NaHIDS. - 30 -
  • Colour changes were monitored by reflectance changes at 620 nm, the standard being the fabrics prior to pretreatment. All values were negative, the ideal being the smallest possible negative value. Colour changes were also recorded as degree or % recovery of copper damaged coloured fabrics, ie as a % of the maximum possible recovery.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

Une composition détergente particulaire contient un séquestrant, de l'iminodisuccinate (IDS) ou de l'hydroxyiminodisuccinate (HIDS), se présentant sous la forme d'un complexe de calcium ou de magnésium, le rapport molaire entre les ions calcium ou magnésium et (H)IDS étant d'au moins 2 :1. Ledit complexe présente une hygroscopie sensiblement inférieure à celle de l'IDS(H) de sodium. Ladite composition est de préférence une composition détergente lessivielle se présentant sous forme de poudre, notamment de poudre compacte ou de pastille.
EP00983141A 1999-12-16 2000-11-13 Compositions detergentes Expired - Lifetime EP1238052B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9929840.8A GB9929840D0 (en) 1999-12-16 1999-12-16 Detergent compositions
GB9929840 1999-12-16
PCT/EP2000/011356 WO2001044428A1 (fr) 1999-12-16 2000-11-13 Compositions detergentes

Publications (2)

Publication Number Publication Date
EP1238052A1 true EP1238052A1 (fr) 2002-09-11
EP1238052B1 EP1238052B1 (fr) 2004-04-07

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EP00983141A Expired - Lifetime EP1238052B1 (fr) 1999-12-16 2000-11-13 Compositions detergentes

Country Status (13)

Country Link
EP (1) EP1238052B1 (fr)
CN (1) CN1229479C (fr)
AT (1) ATE263828T1 (fr)
AU (1) AU760259B2 (fr)
BR (1) BR0016435A (fr)
DE (1) DE60009745T2 (fr)
ES (1) ES2217001T3 (fr)
GB (1) GB9929840D0 (fr)
HU (1) HUP0203587A2 (fr)
PL (1) PL355785A1 (fr)
TR (1) TR200401196T4 (fr)
WO (1) WO2001044428A1 (fr)
ZA (1) ZA200204545B (fr)

Families Citing this family (3)

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Publication number Priority date Publication date Assignee Title
GB0013501D0 (en) * 2000-06-02 2000-07-26 Unilever Plc Detergent compositions
JP2007031594A (ja) 2005-07-27 2007-02-08 Nippon Shokubai Co Ltd ３−ヒドロキシ−２，２′−イミノジコハク酸塩類含有固体組成物及びその製造方法
US9650205B2 (en) 2013-06-14 2017-05-16 S. C. Johnson & Son, Inc. Chelating system for a polymer lined steel container

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4024552A1 (de) * 1990-08-02 1992-02-06 Henkel Kgaa Derivat der aminobernsteinsaeure als komplexierungsmittel
JP3623971B2 (ja) * 1993-02-26 2005-02-23 ライオン株式会社 高嵩密度粒状洗剤組成物
EP0678572A1 (fr) * 1994-04-20 1995-10-25 The Procter & Gamble Company Compositions de poudres détergentes
JPH09279183A (ja) * 1996-04-10 1997-10-28 Kao Corp 高密度粒状洗剤組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0144428A1 *

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CN1229479C (zh) 2005-11-30
DE60009745T2 (de) 2005-04-28
BR0016435A (pt) 2002-10-01
AU2000401A (en) 2001-06-25
PL355785A1 (en) 2004-05-17
ES2217001T3 (es) 2004-11-01
WO2001044428A1 (fr) 2001-06-21
ZA200204545B (en) 2003-08-18
TR200401196T4 (tr) 2004-07-21
AU760259B2 (en) 2003-05-08
GB9929840D0 (en) 2000-02-09
ATE263828T1 (de) 2004-04-15
CN1434855A (zh) 2003-08-06
EP1238052B1 (fr) 2004-04-07
DE60009745D1 (de) 2004-05-13
HUP0203587A2 (hu) 2003-02-28

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