EP0700428B2 - Compositions detergentes - Google Patents

Compositions detergentes Download PDF

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Publication number
EP0700428B2
EP0700428B2 EP94915115A EP94915115A EP0700428B2 EP 0700428 B2 EP0700428 B2 EP 0700428B2 EP 94915115 A EP94915115 A EP 94915115A EP 94915115 A EP94915115 A EP 94915115A EP 0700428 B2 EP0700428 B2 EP 0700428B2
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EP
European Patent Office
Prior art keywords
zeolite
compositions
nonionic surfactant
surfactant
ratio
Prior art date
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EP94915115A
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German (de)
English (en)
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EP0700428B1 (fr
EP0700428A1 (fr
Inventor
Jelles Vincent Boskamp
Mark Phillip Houghton
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Priority claimed from GB939310823A external-priority patent/GB9310823D0/en
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0700428A1 publication Critical patent/EP0700428A1/fr
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds

Definitions

  • the present invention is concerned with high-performance particulate laundry detergent compositions of high bulk density.
  • EP 544 492A (Unilever), published on 2 June 1993, discloses and claims particulate detergent compositions having a bulk density of at least 650 g/l, preferably at least 700 g/l and advantageously at least 800 g/l.
  • the compositions contain 20-60 wt% of zeolite builder and 15-50 wt% of a high-performanco surfactant system rich in nonionic surfactant: 60-100 wt% of ethoxylated nonionic surfactant having a relatively low average degree of ethoxylation ( ⁇ 6.5EO), and optionally 0-40 wt% of primary alcohol sulphate. It will be seen that the ratio of primary alcohol, sulphate to nonionic surfactant cannot exceed 0.67:1.
  • the zeolite builder is preferably zeolite P having a silicon to aluminium ratio not exceeding 1.33 (zeolite MAP) as described and claimed in EP 384 070A (Unilever). This material has exceptionally good carrying capacity for liquid detergent ingredients, as described and claimed in EP 521 635A (Unilever).
  • zeolite MAP When used at relatively high levels the zeolite MAP enables high concentrations of the mobile surfactant system to be carried without loss of powder flow properties, and the zeolite also acts as a highly efficient builder, with a greater calcium binding capacity than that of conventional zeolite 4A.
  • the relatively high levels of the insoluble zeolite A24 may, under certain wash conditions, lead to deposition of insoluble residues on the wash load; but reduction of the zeolite level would reduce both liquid carrying capacity and building capacity, causing a deterioration in detergency as well as in powder properties.
  • any loss of building capacity resulting in the use of a lower level of zeolite may be made good by the inclusion of a soluble organic builder such as sodium citrate.
  • the average degree of ethorylation of the nonionic surfactant need not be 6.5 or less, as specified in EP 544 492A (Unilever) referred to above, but may be as high as 8 without significant loss of detergency.
  • compositions of EP 544 492A (Unilever) are intended primarily for use in automatic washing machines, especially the front-loading drum-type washing machines used in Europe.
  • compositions of the present invention having a higher ratio of anionic surfactant to nonionic surfactant, and thus a higher potential for foaming in the absence of a foam controller, are also useful for washing fabrics by hand. These compositions have been found to have advantageous foam profiles when compared with conventional handwash formulations.
  • JP 02 049 099A discloses particulate fabric washing detergent compositions of high bulk density containing alkyl sulphate (25-45 wt%), ethoxylated alcohol nonionic surfactant (1-10 wt%), soap and zeolite.
  • the amount of noniontc surfactant is low, and the ratio of alkyl sulphate to nonionic surfactant high (typically from 5:1 to 12:1), but a comparative Example, said to be disadvantageous because of poor anticaking and rinsing properties, contains alkyl sulphate and nonionic surfactant in a ratio of 2.08:1.
  • WO-A-94 13771 discloses a granulated washing and cleaning agent with high surfactant content in which the ratio of anionic alkyl sulphate surfactant to nonionic surfactant is in the range 10:1 to 1: 2.5.
  • the builder may comprise zeolite but zeolite MAP is not mentioned.
  • the present invention accordingly provides a particulate detergent composition having a bulk density of at least 700 g/l, comprising:
  • the particulate detergent composition of the invention has a bulk density of at least 700 g/l.
  • the surfactant level is preferably from 15 to 30 wt%, while for handwashing formulations the surfactant level is preferably from 25 to 35 wt%.
  • the surfactant system consists essentially of primary alcohol sulphate (PAS) and ethoxylated alcohol nonionic surfactant, in a ratio of from 0.68:1 to 2:1. Preferably the ratio ranges from 1:1 to 2:1.
  • the surfactant system thus consists essentially of more than 40 wt% of PAS and less than 60 wt% of nonionic surfactant, preferably from 40.5 to 66.7 wt% of PAS and from 33.3 to 59.5 wt% of ethoxylated nonionic surfactant.
  • the nonionic surfactant has an average degree of ethoxylation within the range of from 3 to 8.
  • a mixture of two or more nonionic surfactants may be used, provided that the aggregate average degree of ethoxylation is within the stated range.
  • the nonionic surfactant may, as in EP 544 492A (Unilever) mentioned above, have an average degree of ethoxylation not exceeding 6.5, especially from 4 to 6, and more especially from 4 to 5.5.
  • the present invention allows greater formulation flexibility using a wider range of nonionic surfactants.
  • nonionic surfactant may if desired have an average degree of ethoxylation anywhere within the range of from 3 to 8, advantageously from 5 to 8.
  • the nonionic surfactant may advantageously have a hydrophilic/lipophilic balance (HLB) of 10.0 or more.
  • HLB hydrophilic/lipophilic balance
  • the ethoxylated alcohol is preferably primary, but in principle secondary alcohol ethoxylates could be used.
  • the alcohol may be straight-chain or branched-chain. Suitable alcohols are vegetable-derived, for example, coconut. Both Ziegler and oxo synthetic alcohols may be used, Ziegler alcohols being preferred.
  • the amount of nonionic surfactant present in the compositions of the invention is preferably within the range of from 6 to 12 wt%.
  • the primary alcohol sulphate (PAS) that is present in the compositions of the invention may have a chain length in the range of C 8 to C 18 , preferably C 12 to C 16 , with a mean value preferably in the C 12-15 range. Especially preferred is PAS consisting wholly or predominantly of C 12 and C 14 material.
  • the PAS may be straight-chain or branched-chain.
  • Vegetable-derived PAS especially PAS from coconut oil (cocoPAS)
  • cocoPAS coco oil
  • Use of branched-chain PAS as described and claimed in EP 439 316A (Unilever) is also within the scope of the invention.
  • the PAS is normally present in the form of the sodium or potassium salt, the sodium salt being generally preferred.
  • the amount of PAS present in the compositions of the present invention is preferably within the range of from 10 to 30 wt%.
  • the amount of zeolite builder in the compositions of the invention is from 10 to 35 wt%. These percentages are based on the (notional) anhydrous material, rather than the hydrated material actually used.
  • formulations intended for machine washing will contain from 10 to 35 wt%, the range of 15 to 30 wt% being especially preferred.
  • compositions having higher levels of zeolite are also within the scope of the invention, and are of especial interest for handwashing formulations.
  • the zeolite builder incorporated in the compositions of the invention is zeolite MAP as described and claimed in EP 384 070A (Unilever).
  • Zeolite MAP is defined as an alkali metal aluminosilleate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably not exceeding 1.15, and more preferably not exceeding 1.07.
  • the calcium binding capacity of zeolite MAP is generally at least 150 mg CaO/g (anhydrous).
  • zeolite MAP has two advantages quite independent of its greater building efficacy: it enables higher total surfactant levels, and more mobile surfactant systems, to be used without loss of powder flow properties; and it gives improved bleach stability.
  • Preferred zeolite MAP for use in the present invention is especially finely divided and has a d 50 (as defined below) within the range of from 0.1 to 5.0 ⁇ m, more preferably from 0.4 to 2.0 ⁇ m and most preferably from 0.4 to 1.0 ⁇ m.
  • the quantity “d 50 " indicates that 50 wt% of the particles have a diameter smaller than that figure, and there are corresponding quantities "d 60 ", "d 90 " etc.
  • Especially preferred materials have a d 90 below 3 ⁇ m as well as a d 50 below 1 ⁇ m.
  • compositions of the invention may advantageously comprise up to 30 wt%, suitably from 5 to 30 wt% and preferably from 10 to 25 wt%, of a soluble organic builder.
  • Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
  • polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates
  • monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates,
  • Especially preferred supplementary builders for use in conjunction with zeolite include citric acid salts, more especially sodium citrate, suitably used in amounts of from 5 to 30 wt%, preferably from 10 to 25 wt%.
  • citric acid salts more especially sodium citrate
  • polycarboxylate polymers more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15.wt%, especially from 1 to 10 wt%, of the detergent composition; the combination of zeolite MAP with polymeric builders is described and claimed in EP 502 675A (Unilever).
  • supplementary organic builders allows formulation with a lower level of zeolite, thus reducing the level of insoluble material present, without loss of calcium binding capacity.
  • Builders are preferably present in alkali metal salt, especially sodium salt, form.
  • compositions of the invention that are intended for heavy duty use will generally contain a bleach system.
  • the bleach system preferably comprises an inorganic or organic peroxy bleach compound capable of yielding hydrogen peroxide in aqueous solution.
  • Peroxy bleach compounds suitable for use in the compositions of the invention include organic peroxides such as urea peroxide, and inorganic persalts, such as the alkali metal perborates, perearbonates, perphosphates, persilicates and persulphates. Mixtures of two of more such compounds may also be suitable.
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and, most preferably, sodium percarbonate.
  • sodium percarbonate having a protective coating against destabilisation by moisture Especially preferred is 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).
  • 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 peroxycathonic acid precursors.
  • An especially preferred bleach precursor suitable for use in the present invention is N,N,N',N'-tetracetyl ethylenediamine (TAED).
  • a bleach stabiliser may also be present.
  • Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA) and the polyphosphonates such as Dequest (Trade Mark), EDTMP.
  • An especially preferred bleach system comprises a peroxy bleach compound (preferably sodium percarbonate optionally together with a bleach activator), and a transition metal bleach catalyst as described and claimed in EP 458 397A, EP 458 398A and EP 509 787A (Unilever).
  • a peroxy bleach compound preferably sodium percarbonate optionally together with a bleach activator
  • a transition metal bleach catalyst as described and claimed in EP 458 397A, EP 458 398A and EP 509 787A (Unilever).
  • compositions containing relatively large amounts of bleach ingredients will generally contain correspondingly smaller amounts of surfactant, builder and other ingredients than will similar light-duty bleach-free formulations.
  • the preferred amounts of surfactant and zeolite for such formulations will therefore generally be towards the lower ends of the ranges claimed in the present invention, while the preferred amounts for handwash or light-duty (non-bleaching) machine wash formulations will be higher.
  • compositions of the invention may contain alkali metal, preferably sodium, carbonate, in order to increase detergency and ease processing.
  • Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%.
  • compositions containing little or no sodium carbonate are also within the scope of the invention.
  • Powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleale polymer, or sodium silicate.
  • a powder structurant for example, a fatty acid (or fatty acid soap), a sugar, an acrylate or acrylate/maleale polymer, or sodium silicate.
  • One preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt%.
  • detergent compositions of the invention include sodium silicate; antiredeposition agents such as cellulosic polymers; fluorescers; inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; proteolytic and lipolytic enzymes; dyes; coloured speckles; perfumes; foam controllers; and fabric softening compounds. This list is not intended to be exhaustive.
  • the particulate detergent compositions of the invention may be prepared by any method suitable for the production of powders of high bulk density, ie at least 700 g/litre, preferably at least 800 g/litre.
  • Such powders may be prepared either by post-tower densification of spray-dried powder, or by wholly non-tower methods such as dry mixing and granulation; in both cases a high-speed mixer/granulator may advantageously be used.
  • Powder flow values are expressed In terms of the dynamic flow rate in ml/s, measured by means of the following procedure.
  • the apparatus used consists of a cylindrical glass tube having an intemal diameter of 35 mm and a length of 600 mm.
  • the tube is securely clamped in a position such that its longitudinal axis is vertical. Its lower end is terminated by means of a smooth cone of polyvinyl chloride having an internal angle of 15° and a lower outlet orifice.
  • a first beam sensor is positioned 150 mm above the outlet, and a second beam sensor is positioned 250 mm above the first sensor.
  • the outlet orifice is temporarily closed, for example, by covering with a piece of card, and powder is poured through a funnel into the top of the cylinder until the powder level is about 10 cm higher than the upper sensor; a spacer between the funnel and the tube ensures that filling is uniform.
  • the outlet is then opened and the time t (seconds) taken for the powder level to fall from the upper sensor to the lower sensor is measured electronically.
  • the averaging and calculation are carried out electronically and a direct read-out of the DFR value obtained.
  • compositions of the invention generally exhibit dynamic flow rates in excess of 130 ml/s.
  • Detergent powders having bulk densities above 700 g/l were prepared by a non-tower process to the following formulations: A 1 2 CocoPAS 6.79 14.63 14.64 Nonionic 7EO 6.69 4.10 7.33 Nonionic 3EO 8.49 3.23 - Soap 2.25 Zeolite MAP 36.47 23.48 24.46 Sodium carbonate 1.19 2.57 2.57 SCMC 0.68 0.53 0.54 Moisture and salts 6.13 5.02 5.13 68.70 53.57 54.66 Sodium citrate - 15.13 14.04 Antifoam, fluorescer 3.00 3.00 3.00 Silicate 3.67 3.67 Percarbonate 16.85 16.85 16.85 TAED 3.75 3.75 3.75 Mn catalyst 1.27 1.27 1.27 EDTMP 0.37 0.37 0.37 Enzymes 1.75 1.75 1.75 Perfume 0.65 0.65 100.00 100.00 100.00 Bulk density. (g/l) 781 727 775 Dynamic flow rate (ml/s) 142 134 148
  • compositions 1 and 2 according to the invention had a 2:1 ratio of PAS to noniontc surfactant, while Comparative Example A had a ratio of PAS to nonionic surfactant of 0.44:1.
  • Comparative Example B was a commercially available high bulk density powder having a surfactant system consisting of alkylbenzene sulphonate and nonionlc surfactant.
  • test methodology was as follows. A 100 g dose of powder was placed in a flexible delivery device of the type supplied with Lever's Persil (Trade Mark) Micro System powder in the UK: a spherical container of flexible plastics material having a diameter of approximately 4 cm and a top opening of diameter approximately 3 cm.
  • the delivery device was placed inside a black cotton pillowcase having dimensions of 30 cm by 60 cm, taking care to keep it upright, and the pillowcase was then closed by means of a zip fastener.
  • the pillowcase containing the (upright) delivery device was then placed on top of a 3.5 kg dry cotton washload in the drum of the washing machine.
  • the machine was operated on the "heavy duty cycle" at a wash temperature of 40°C, using water of 15° French hardness and an inlet temperature of 20°C.
  • the pillowcase was removed, opened and tumed inside out, and the level of powder residues on its inside surfaces determined by visual assessment using a scoring system of 1 to 5: a score of 3 corresponds to a residue of approximately 75 wt% of the powder, while 0 indicates no residue.
  • a panel of five assessors was used to judge each pillowcase and allot a score. With each powder the wash process was carried out ten times and the scores were averaged over the ten repeats.
  • compositions of the invention may be used in the traditional manner without the need for a delivery device.
  • compositions containing a 1:1 ratio of PAS to nonionic surfactant were prepared, to the following formulations: 3 4 CocoPAS 10.99 10.97 Nonionic 7EO 6.14 11.00 Nonionic 3EO 4.84 Zeolite MAP 28.99 28.26 Sodium carbonate 1.93 1.92 SCMC 0.58 0.57 Moisture and salts 5.03 4.95 58.49 57.67 Sodium citrate 10.21 11.03 Antifoam, fluorescer 3.00 3.00 Silicate 3.67 3.67 Prcarbonate 16.85 16.85 TAED 3.75 3.75 Mn catalyst 1.27 1.27 EDTMP 0.37 0.37 Enzymes 1.75 1.75 Perfume 0.65 0.65 100.00 100.00 Bulk density (g/litre) 840 817 Dynamic flow rate (ml/s) 152 146
  • a tergotomeler test was also carried out to compare the detergencies of the compositions of the invention (Examples 1 to 4) with those of Comparative Example A having a lower PAS to nonionic surfactant ratio.
  • the tergotometer tests were carried out in 15° (French) hard water at a product concentration of 4.8 g/litre.
  • the temperature and time conditions were as follows: initially 20°C, warming up to 60°C at 2°/minute, then remaining at 60°C for a 20-minute wash.
  • the agitation rate throughout was 120 oscillations/minute.
  • Detergent compositions intended for washing fabrics by hand were prepared to the following formulations: 10 11 12 13 14 CocoPAS 13.15 19.12 24.04 21.85 20.49 Nonionic 7EO 7.35 5.36 6.74 6.13 5.75 Nonionic 3EO 5.79 4.22 5.31 4.83 4.53 Zeolite MAP 34.69 30.69 38.58 35.07 32.88 Sodium carbonate 2.31 3.35 4.22 3.83 3.59 SCMC 0.69 0.69 0.87 0.79 0.74 Moisture, salts 6.02 6.56 8.25 7.50 7.03 Sodium citrate 4.38 4.38 - - - Fluorescer - - 0.15 0.15 - Silicate 5.00 5.00 10.00 6.00 7.60 Percarbonate 14.00 14.00 - - - TAED 4.00 4.00 - - - Mn catalyst - - - - - EDTMP 0.37 0.37 - - - Enzymes 1.75 1.75 1.20 1.20 1.75 Perfume 0.50 0.50 0.65 0.65 0.65 Sodium
  • foam heights at a product dosage of 3 g/l in 250 ml of 10° (French) hard water in a 1-litre measuring cylinder (diameter 6 cm) at 20°C was determined. The cylinder was inverted twice before reading the foam height. The results were as follows: Composition Foam height (cm) initial after 10 minutes B 12 8 10 14 9 11 17 11 12 18 12 13 17.5 12 14 18 13
  • compositions of the invention generated more foam than the control.
  • Compositions 11 to 14 having a PAS to nonionic surfactant ratio of 2:1 were especially good, but Composition 10 having the lower ratio of 1:1 was also better than the control.
  • a handwash was performed in 10 litres of 18° (French) hard water in a bowl at 40°C.
  • the product dosage was 3 g/l, and the washload consisted of 1.5 kg of light cotton shirts.
  • Five agitations of the load were carried out in 20 seconds.
  • the wash liquor was then drained away, a further 5 litres of water (10°C) added, the load was agitated for 20 seconds, the foam was assessed, and then the rinse water was drained away.
  • the rinse operation was repeated until only a tew bubbles were left behind on the rim of the bowl.
  • compositions of the invention were better than the control, Compositions 10 and 11 giving especially good results.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Inorganic Chemistry (AREA)
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Claims (7)

  1. Composition détergente particulaire ayant une densité apparente d'au moins 700 g/l, comprenant :
    (a) de 15 à 35 % en poids d'un système tensioactif consistant essentiellement en :
    (i) un alkylsulfate primaire en C8 - C18, et
    (ii) un tensioactif non ionique éthoxylé qui est un alcool primaire en C8 - C18 ayant un degré moyen d'éthoxylation dans la gamme de 3 à 8,
    le rapport de (i) à (ii) étant dans la gamme de 0,68 :1 à 2 :1 ;
    (b) de 10 à 35 % en poids (base anhydre) de zéolite P ayant un rapport silicium : magnésium n'excédant pas 1,33 (zéolite PAM) ;
    (c) facultativement, de 0 à 30 % en poids d'adjuvant organique hydrosoluble ;
    (d) facultativement, d'autres ingrédients détergents jusqu'à 100 % en poids.
  2. Composition détergente selon la revendication 1, dans laquelle le rapport de (a) (i) à (a) (ii) est dans la gamme de 1 :1 à 2 :1.
  3. Composition détergente selon la revendication 1, contenant de 10 à 30 % en poids de l'alcool sulfate primaire (a) (i).
  4. Composition détergente selon la revendication 1, contenant de 6 à 12 % en poids du tensioactif non ionique (a) (ii).
  5. Composition détergente selon la revendication 1, dans laquelle le tensioactif non ionique (a) (ii) a un degré moyen d'éthoxylation dans la gamme de 6 à 8.
  6. Composition détergente selon la revendication 1, comprenant de 5 à 30 % en poids d'adjuvant organique soluble (d).
  7. Composition détergente selon la revendication 6, dans laquelle l'adjuvant organique soluble (d) comprend un sel hydrosoluble de l'acide citrique.
EP94915115A 1993-05-26 1994-04-26 Compositions detergentes Expired - Lifetime EP0700428B2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB9310823 1993-05-26
GB939310823A GB9310823D0 (en) 1993-05-26 1993-05-26 Detergent compositions
GB9313857 1993-07-05
GB939313857A GB9313857D0 (en) 1993-05-26 1993-07-05 Detergent compositions
PCT/EP1994/001291 WO1994028109A1 (fr) 1993-05-26 1994-04-26 Compositions detergentes

Publications (3)

Publication Number Publication Date
EP0700428A1 EP0700428A1 (fr) 1996-03-13
EP0700428B1 EP0700428B1 (fr) 1998-08-26
EP0700428B2 true EP0700428B2 (fr) 2006-07-05

Family

ID=26302948

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94915115A Expired - Lifetime EP0700428B2 (fr) 1993-05-26 1994-04-26 Compositions detergentes

Country Status (11)

Country Link
EP (1) EP0700428B2 (fr)
JP (1) JPH08511291A (fr)
AU (1) AU6648494A (fr)
CZ (1) CZ310095A3 (fr)
DE (1) DE69412822T3 (fr)
ES (1) ES2121604T5 (fr)
GB (1) GB9324127D0 (fr)
HU (1) HUT74020A (fr)
PL (1) PL311748A1 (fr)
SK (1) SK144595A3 (fr)
WO (1) WO1994028109A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CZ285027B6 (cs) * 1992-08-25 1999-05-12 Unilever N.V. Průhledný kapalný vodný čistící prostředek
WO1995014767A1 (fr) * 1993-11-24 1995-06-01 Unilever Plc Compositions detergentes
GB9324129D0 (en) * 1993-11-24 1994-01-12 Unilever Plc Detergent compositions and process for preparing them
DE19526483A1 (de) * 1995-07-20 1997-01-23 Henkel Kgaa Tensidabmischungen mit verbesserter Löslichkeit von Aniontensiden auf Basis langkettiger Alkylsulfatsalze auch bei niederen Flottentemperaturen
MY133398A (en) * 1999-07-09 2007-11-30 Colgate Palmolive Co Fabric cleaning composition containing zeolite
US6204239B1 (en) * 1999-11-24 2001-03-20 Colgate-Palmolive, Inc. Fabric cleaning composition containing zeolite
US8778386B2 (en) 2005-12-13 2014-07-15 Kimberly-Clark Worldwide, Inc. Anti-microbial substrates with peroxide treatment

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0384070A2 (fr) † 1988-11-03 1990-08-29 Unilever Plc Zéolite P, son procédé de préparation et son utilisation dans les compositions détergentes
EP0460925A2 (fr) † 1990-06-06 1991-12-11 Unilever Plc Compositions détergentes
EP0544492A1 (fr) † 1991-11-26 1993-06-02 Unilever Plc Compositions détergents sous forme particulaire

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2662221B2 (ja) * 1987-07-15 1997-10-08 花王株式会社 高密度粒状濃縮洗剤組成物
JP2547444B2 (ja) * 1988-05-12 1996-10-23 旭電化工業株式会社 濃縮高比重衣料用粉末洗剤
EP0448297A1 (fr) * 1990-03-19 1991-09-25 Unilever Plc Compositions détergentes
ES2083560T3 (es) * 1991-04-12 1996-04-16 Procter & Gamble Composicion detergente compacta que contiene polivinilpirrolidona.
EP0508034B1 (fr) * 1991-04-12 1996-02-28 The Procter & Gamble Company Composition détergente contenant des polyvinylpyrrolidones
EP0550086B1 (fr) * 1991-12-31 1998-03-11 Unilever N.V. Procédé pour la fabrication d'une composition détergente granuleuse
DE4242185A1 (de) * 1992-12-15 1994-06-16 Henkel Kgaa Granulare Wasch- und Reinigungsmittel mit hohem Tensidgehalt

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0384070A2 (fr) † 1988-11-03 1990-08-29 Unilever Plc Zéolite P, son procédé de préparation et son utilisation dans les compositions détergentes
EP0460925A2 (fr) † 1990-06-06 1991-12-11 Unilever Plc Compositions détergentes
EP0544492A1 (fr) † 1991-11-26 1993-06-02 Unilever Plc Compositions détergents sous forme particulaire

Also Published As

Publication number Publication date
DE69412822D1 (de) 1998-10-01
DE69412822T2 (de) 1999-01-14
WO1994028109A1 (fr) 1994-12-08
ES2121604T5 (es) 2007-03-16
CZ310095A3 (en) 1996-05-15
GB9324127D0 (en) 1994-01-12
PL311748A1 (en) 1996-03-18
EP0700428B1 (fr) 1998-08-26
HUT74020A (en) 1996-10-28
ES2121604T3 (es) 1998-12-01
AU6648494A (en) 1994-12-20
DE69412822T3 (de) 2006-11-09
JPH08511291A (ja) 1996-11-26
EP0700428A1 (fr) 1996-03-13
HU9503373D0 (en) 1996-01-29
SK144595A3 (en) 1996-04-03

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