EP0670887A1 - Detergent compositions - Google Patents
Detergent compositionsInfo
- Publication number
- EP0670887A1 EP0670887A1 EP93924768A EP93924768A EP0670887A1 EP 0670887 A1 EP0670887 A1 EP 0670887A1 EP 93924768 A EP93924768 A EP 93924768A EP 93924768 A EP93924768 A EP 93924768A EP 0670887 A1 EP0670887 A1 EP 0670887A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- detergent composition
- surfactant
- average
- nonionic
- chain length
- 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
Links
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
- C11D1/72—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
Definitions
- the present invention relates to particulate detergent compositions containing nonionic surfactants.
- the invention is particularly concerned with particulate detergent compositions having high bulk density, especially those containing alkali metal aluminosilicate builder.
- Nonionic surfactants have beneficial cleaning characteristics when included in detergent formulations, as they are particularly effective in removing hydrophobic soils such as hydrocarbon oils, complex fats and other long-chain unsaturated and saturated glycerides.
- particulate detergent compositions containing nonionic surfactants come in contact with aqueous solutions the nonionic surfactants tend to form viscous phases which impede delivery from the dispenser of an automatic washing machine or from a delivery device, and give poor dispersion and dissolution in the wash liquor.
- Particulate detergent compositions containing short-chain nonionic surfactants are disclosed in GB 1 460 646, GB 1 462 .33, GB 1 462 134, GB 1 485 316 and GB 1 566 326 (Procter & Gamble) ; GB 1 519 433 and FR 2 303 850A
- the present invention accordingly provides a particulate detergent composition having a bulk density of at least 600_ g/1 and comprising a surfactant system comprising a nonionic surfactant, at least one detergency builder and optionally other detergent ingredients, wherein the nonionic surfactant comprises a condensation product of ethylene oxide with an aliphatic alcohol having an average alkyl chain length of less than C 12 and an average degree of ethoxylation not exceeding 8, and the surfactant system is free of ethoxylated nonionic surfactants having an average chain length of C. or above and an average degree of ethoxylation below 7.
- the invention further provides the use of a nonionic " surfactant which is a condensation product of ethylene oxide with an aliphatic alcohol having an average alkyl chain length of less than C 1? and an average degree of ethoxylation not exceeding 8 to improve the delivery into the wash of a particulate detergent composition having a bulk density of at least 600 g/1.
- a nonionic " surfactant which is a condensation product of ethylene oxide with an aliphatic alcohol having an average alkyl chain length of less than C 1? and an average degree of ethoxylation not exceeding 8 to improve the delivery into the wash of a particulate detergent composition having a bulk density of at least 600 g/1.
- the short-chain nonionic surfactant is the short-chain nonionic surfactant
- the detergent compositions of the invention are characterised by a surfactant system containing as an essential ingredient a nonionic surfactant with an average alkyl chain length less than C. and an average degree of ethoxylation not exceeding 8. This component will be referred to hereinafter as the short-chain nonionic surfactant.
- nonionic surfactants are generally mixtures containing a spread of chain lengths around an average value.
- the surfactant system is free of nonionic surfactants which are commercial materials having an average chain length of C. and above and an average degree of ethoxylation below 7.
- compositions of the invention are substantially free of all ethoxylated nonionic surfactants (commercial mixtures) , of any degree of ethoxylation, having an average alkyl chain length of C. or above.
- the short-chain nonionic surfactant is derived from an alcohol of which at least 25% by weight, more preferably at least 50 wt% and most preferably at least 75 wt%, has an alkyl chain length below C._.
- the surfactant system may be substantially free of any nonionic surfactant material having a chain length of C. or above.
- any nonionic surfactant material having a chain length of C. or above.
- the compositions of the invention exhibit excellent detergency performance on a range of soils and also show superior dispersion characteristics.
- Nonionic surfactants having an average alkyl chain length within the range of from C g to C are preferred; more specifically those having an average alkyl chain length within the ranges of from C Q -7 to C 3..3_., and from C. n O to C 3,.3.- . 1_.
- Either primary or secondary alcohol ethoxylates are used, but primary alcohol ethoxylates are generally preferred.
- the average number of ethylene oxide groups per mole of alcohol in the nonionic condensation product is 8 or less, preferably from 2.5 to 8. It may advantageously be 6.5 or less, and most preferably from 2.5 to 6.5.
- Nonionic surfactants derived from alcohols containing some branched-chain material may give some benefits both in detergency and in improved powder delivery amd dissolution.
- the level of free alcohol in the nonionic surfactant is less than 5 wt%, more preferably less than 1 wt%.
- nonionic alcohol ethoxylate surfactants suitable for use in the present invention are given below (* denotes Trade Mark) . Mixtures of these materials may also be used in order to achieve intermediate degrees of ethoxylation.
- Ethoxylates Dobanol 91-2.5 2.5 EO Dobanol 91-5 5 EO Dobanol 91-6 6 EO Dobanol 91 4-6 4-6 EO
- Ethoxylates Lialet 111-4 4 EO Lialet 111-5 5 EO Lialet 111-6 6 EO Lialet 111 4-6 4-6 EO Lialet 111 6.9 6.9 EO Nominal description: C.... alcohol with 50-60% branching
- Nonionic surfactants excluded from the present invention are nonionic surfactants excluded from the present invention.
- any other, longer-chain ethoxylated nonionic surfactants present should not have an average degree of ethoxylation of less than 7.
- Materials having an average chain-length of C or above and an average degree of ethoxylation of 7 or above may, however, be present.
- materials corresponding to those listed above as excluded from the present invention for example, the coconut, Synperonic and Dobanol 23 alcohol ethoxylates, but having higher degrees of ethoxylation, may be present in the compositions of the invention, in addition to the short-chain low-ethoxylated nonionic surfactant which is essential.
- a short-chain material may be used in combination with coconut alcohol 7E0.
- ethoxylated nonionic surfactants of any degree of ethoxylation, having average alkyl chain lengths of C 12 or above are present.
- the total amount of all nonionic detergent-active compounds present in the compositions of the invention is suitably within the range of of from 2 to 50 wt%, preferably from 5 to 30 wt%.
- nonionic surfactants of the class specifically excluded above are absent, other detergent-active materials may be present in the compositions of the invention.
- Detergent-active material present other than the nonionic surfactants may be other anionic (soap or non-soap) , cationic, zwitterionic, amphoteric, or any combination of these.
- Anionic detergent-active compounds may be present in an amount of from 0 to 40 wt%, preferably from 0 to 20 wt%. It is preferred if the ratio of nonionic surfactant to anionic surfactant is within the range of 2:8 to 9:1.
- Synthetic anionic surfactants are well known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C ⁇ ; primary and secondary alkyl sulphates, particularly sodium C. -C 15 primary alcohol sulphates, olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinate; and fatty acid ester sulphonates.
- alkylbenzene sulphonates particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C ⁇
- primary and secondary alkyl sulphates particularly sodium C. -C 15 primary alcohol sulphates, olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinate; and fatty acid ester sulphonates.
- soaps of fatty acids are preferably sodium soaps derived from naturally occurring fatty acids, for example, the fatty acids from coconut oil, beef tallow, sunflower or hardened rapeseed oil.
- the total amount of detergent-active material (surfactant) in the compositions of the invention is suitably from_5_ to 50 wt%.
- surfactant preferably from 15 to 50 wt%.
- compositions may advantageously contain at least 20 wt%, more advantageously at least 25 wt%, of the surfactant system.
- Preferred surfactant systems are described below.
- compositions in accordance with the invention have surfactant systems consisting essentially of short-chain ethoxylated nonionic surfactant as defined above either in combination with primary alcohol sulphate (PAS) , or alone.
- PAS primary alcohol sulphate
- the primary alcohol sulphate (PAS) that may optionally be present, preferably constituting up to 40 wt% of the surfactant system, may have a chain length in the range of C 8 -C 18 , preferably -C lg , with a mean value preferably in the range.
- PAS consisting wholly or predominantly of 12 -C. material.
- mixtures of different chain lengths may be used as described and claimed in EP 342 917A (Unilever) .
- PAS Predominantly or wholly straight-chain PAS is generally preferred; PAS of vegetable origin, and more especially PAS from coconut oil (cocoPAS) is especially preferred.
- cocoPAS PAS from coconut oil
- the PAS is present in the form of the sodium or potassium salt, the sodium salt generally being preferred.
- Surfactant systems of especial interest consist essentially of
- the surfactant system consists essentially of from 65 to 80 wt%, preferably from 65 to 75 wt%, of ethoxylated nonionic surfactant (i) and from 20 to 35 wt%, preferably from 25 to 35 wt%, of the primary alcohol sulphate (ii) .
- ethoxylated nonionic surfactants have been found to give especially good detergency:
- the surfactant system consists essentially of from 80 to 95 wt%, preferably from 85 to 95 wt%, of the ethoxylated nonionic surfactant (i) and from 5 to 20 wt%, preferably from 5 to 15 wt%, of the primary alcohol sulphate (ii) .
- the following ethoxylated nonionic surfactants have been found to give especially good detergency:
- the surfactant system consists essentially of ethoxylated nonionic surfactant (i) alone.
- ethoxylated nonionic surfactants have been found to give especially good detergency: (a) an average alkyl chain length of C -C ⁇ and an average degree of ethoxylation of from 4.5 to 5.5, or
- any short-chain nonionic surfactant of chain length C q to C. and ethoxylation of 2.5 to 6.5 is beneficial.
- the detergent powders of the invention contain one or more detergency builders, suitably in an amount of from 5 to 80 wt%, preferably from 20 to 60 wt%.
- the invention is especially applicable to compositions containing alkali metal aluminosilicates as builders.
- Alkali metal (preferably sodium) aluminosilicates may generally be incorporated in amounts of from 5 to 60% by weight (anhydrous basis) of the composition, preferably from 25 to 55 wt%, and suitably, in a heavy duty detergent composition, from 25 to 48 wt%.
- the alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula:
- the preferred sodium aluminosilicates contain 1.5-3.5 SiO units (in the formula above) . Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 " (Procter & Gamble) . The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof..
- the zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders.
- the zeolite builder incorporated in the compositions of the invention is maximum aluminium zeolite P (zeolite MAP) as
- Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
- zeolite MAP having a silicon to aluminium ratio not exceeding 1.07.
- the calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
- zeolite MAP gives two particular advantages: it is a more effective builder than zeolite 4A, and, quite independently, it enables higher total surfactant levels, and more nonionic-rich surfactant systems, to be incorporated without loss of powder flow properties.
- zeolite MAP as a carrier for liquid detergent ingredients is described and claimed in EP 521 635A (Unilever) .
- Preferred zeolite MAP for use in the present invention is especially finely divided and has a d 5Q (as defined below) within the range of from 0.1 to 5.0 microns, more preferably from 0.4 to 2.0 microns and most preferably from 0.4 to 1.0 microns.
- the quantity “d 50 " indicates that 50 wt% of the particles have a diameter smaller than that figure, and there are corresponding quantities "d g ", "d go “ etc.
- Especially preferred materials have a d go below 3 microns as well as a d5,.0- below 1 micron.
- compositions in accordance with the invention may contain alkali metal, preferably sodium, carbonate, to increase detergency and to ease processing.
- alkali metal preferably sodium, carbonate
- Sodium carbonate may generally be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%, and most suitably from 2 to 13 wt%.
- compositions free of alkali metal carbonate are also within the scope of the invention.
- Especially preferred supplementary builders are polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, especially from 1 to 10 wt%; and monomeric polycarfcoxylates, more especially citric acid and its salts, suitably used in amounts of from 3 to 35 wt%, more preferably from 5 to 30 wt%.
- compositions of the invention preferably do not contain more than 5 wt% of inorganic phosphate builders, and are desirably substantially free of phosphate builders.
- Fully formulated laundry detergent compositions in accordance with the present invention may additionally contain any suitable ingredients normally encountered, for example, inorganic salts such as sodium silicate or sodium sulphate; organic salts such as sodium citrate; antiredeposition aids such as cellulose derivatives and acrylate or acrylate/maleate polymers; fluorescers; bleaches, bleach precursors and bleach stabilisers; proteolytic and lipolytic enzymes; dyes; coloured speckles; perfumes; foam controllers; fabric softening compounds.
- inorganic salts such as sodium silicate or sodium sulphate
- organic salts such as sodium citrate
- antiredeposition aids such as cellulose derivatives and acrylate or acrylate/maleate polymers
- fluorescers bleaches, bleach precursors and bleach stabilisers
- proteolytic and lipolytic enzymes dyes; coloured speckles; perfumes; foam controllers; fabric softening compounds.
- the particulate detergent compositions of the invention may in principle be prepared by any of the available tower (spray-drying) , non-tower (granulation) or combination processes.
- compositions of high bulk density - at least 600 g/1, preferably at least 700 g/1 and more preferably at least 800 g/1 - which may be prepared by granulation and/or densification in a high-speed mixer/granulator.
- the high-speed mixer/granulator also known as a high-speed mixer/densifier, may be a batch machine such as the Fukae (Trade Mark) FS, or a continuous machine such as the
- Lttdige (Trade Mark) Recycler CB30 Lttdige (Trade Mark) Recycler CB30. Suitable processes are described, for example, in EP 340 013A, EP 367 339A, EP 390 251A, EP 420 417A and EP 506 184A (Unilever) .
- One suitable method comprises spray-drying a slurry of compatible heat-insensitive ingredients, including zeolite and any other builders, and at least part of the detergent-active compounds: densifying the resulting base powder in a batch or continuous high-speed mixer/granulator; and then spraying on or postdosing those ingredients, for example, bleach, enzymes, unsuitable for processing via the slurry.
- the spray-drying step can be omitted altogether, a high bulk density base powder being prepared directly from its constituent raw materials, by mixing and granulating in a high-speed mixer/granulator, and then postdosing bleach and other ingredients as in the spray-drying/post-tower densification route.
- the inorganic builders and other inorganic materials are granulated with the surfactants, which act as binders and granulating or agglomerating agents.
- the surfactants which act as binders and granulating or agglomerating agents.
- an anionic surfactant such as PAS
- a mobile surfactant blend as described in EP 265 203A (Unilever) or EP 507 402A (Unilever) may suitably be used. Any optional ingredients as previously mentioned may be incorporated at any suitable stage in the process.
- bleach ingredients (bleaches, bleach precursor, bleach stabilisers) , proteolytic and lipolytic enzymes, coloured speckles, perfumes and foam control granules are most suitably admixed (postdosed) to the dense granular product after it has left the high-speed mixer/granulator.
- the low-ethoxylated short-chain nonionic surfactants with which the present invention is concerned will not normally be included in the base powder but will be admixed with, for example, sprayed onto, the finished base powder.
- Nonionic surfactants of higher ethoxylation may be included in the base powder, post-added, or both.
- Preferably at least a part of any higher-ethoxylated nonionic surfactant is included in the base powder, while either low-ethoxylated surfactant alone or a mixture of higher- and low-ethoxylated nonionic surfactant is post-added.
- Zeolite MAP Zeolite MAP prepared by a method similar to that described in Examples 1 to 3 of EP 384 070A (Unilever) ; Si:Al ratio 1.0-1.07.
- TAED Tetraacetylethylenediamine as 83 wt% granules EDTMP Ethylenediaminetetramethylene- phosphonic acid, calcium salt: Dequest (Trade Mark) 2041 or 2047 ex Monsanto (34 wt% active)
- compositions having a surfactant system consisting of 30 parts of cocoPAS and 70 parts of nonionic surfactant were prepared to the following general formulation:
- Detergencies (removal of radio-labelled triolein soil from polyester) were compared in the tergotometer using a 5 g/1 product concentration, 24° (French) hard water and a wash temperature of 20°C.
- compositions containing surfactant systems consisting of 30 parts cocoPAS, and 70 parts of ethoxylated nonionic surfactant composed of varying proportions of coco 7E0 and Dobanol 91-2.5 (giving various average EO values) as shown in Table 4.
- compositions containing surfactant systems consisting of 10 parts cocoPAS, and 90 parts of ethoxylated nonionic surfactant composed of varying proportions of coco 7EO and Dobanol 91-2.5 as shown in Table 5.
- Detergent base powders having bulk densities of about 800 g/litre were prepared to the following general formulation:
- the powders were prepared by spray-drying a slurry of all the ingredients except the nonionic surfactant, which was subsequently stirred into the powder and fluid bed mixed for 10 minutes at 70 C; the powders were then allowed to weather.
- the nonionic surfactants used were as follows:
- the percentage of the powder dissolved was calculated using a standard conductance procedure. This involved measuring the conductance of the wash liquor at a given time and comparing the reading with that of a liquor containing the -same weight of fully dissolved powder of identical formulation. The results are tabulated in Table 6.
- the surfactants used were as follows:
- This Example demonstrates the benefit of short-chain nonionic surfactant in improving delivery of powder from the dispenser of a front-loading automatic washing machine.
- High-bulk-density (about 800 g/litre) particulate detergent compositions were prepared to the general formulations used in Examples 23 to 25.
- the surfactants used were as follows:
- This Example demonstrates, using three different test methods, the benefit of short-chain nonionic surfactant in improving powder solubility and reducing particulate residues deposited on washed articles.
- the powders had the general formulation given below.
- the base powder was prepared by granulation with in-situ neutralisation in a high-speed mixer/granulator, as described in EP 420 417A and EP 506 184A (Unilever) , and the remaining ingredients were then admixed.
- the finished powders had bulk densities in the 800-900 g/1 range. All had a "fines" (particles smaller than 180 microns) content below 5 wt%.
- a 50_g powder sample was introduced into the cylindrical vessel which was then closed.
- the vessel was attached to the -agitator arm which was then moved down to a position such that the top of the cylindrical vessel was just below the surface of the water. After a 10 second delay, the apparatus was operated for 15 rotation/rest cycles.
- the cylindrical vessel and handle were removed from the water and and the vessel detached from the handle. Surface water was carefully poured off, and any powder residues transferred to a preweighed container and dried for 24 hours at 100°C. _ The weight of dried residue as a percentage of the initial powder weight (50 g) was then calculated.
- This test employed a Siemens Siwamat (Trade Mark) Plus 3700 front-loading automatic washing machine, and the methodology was as follows.
- a 100 g dose of powder was placed in a flexible delivery device of the type supplied with commercially available high bulk density powders, for example, Lever Persil (Trade Mark) Micro System powders 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.
- a flexible delivery device of the type supplied with commercially available high bulk density powders, for example, Lever Persil (Trade Mark) Micro System powders 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 60°C, using water of 15° French hardness and an inlet temperature of 20°C.
- the pillowcase was removed, opened and turned inside out, and the level of powder residues on its inside surfaces determined by visual assessment using a scoring system of 1 to 3: a score of 3 corresponds to a residue of approximately 75 wt% of the powder, while 1 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.
- the nonionic surfactants in these powders were as follows:
- Example 28 Dobanol 91-6T 10.14 6EO
- the dispersion test was carried out as follows. An 0.3 g sample of powder was placed in a small spoon and wetted by holding the spoon horizontally in water at 10°C for 1 minute. The spoon was then removed and surplus water poured off. The spoon with the damp powder was then placed horizontally in a 500 ml beaker of water at 10°C and a stirrer (a magnetic flea set to give a 25 mm vortex) was activated. Turbidity (as indicator of the dispersion of the zeolite) was measured as a function of time.
- the 90% dispersion times were as follows:
- Nonionic surfactant Lorodac 7 6.48 Lorodac 3 8.19
- the nonionic surfactants were as follows:
- the 90% dispersion times were as follows:
- Base powders were prepared by high-speed granulation as in earlier Examples, and the remaining ingredients were postdosed.
- the bulk densities of the powders were above 800 g/litre, and the formulations (in parts by weight) were as follows:
- the tests were carried out using radio-labelled triolein model soil on polyester fabric at 20°C in 500 ml of 24° (calcium only) hard water, at a product concentration of 5 g/litre.
- the powder sample (2.5 g) was placed in a heap on a piece of cotton sheeting
- Detergencies are expressed as percentage removal of the triolein soil, measured after wash times of 6, 10 and 20 minutes. The percentage detergency delivered is defined as follows:
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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)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9224014 | 1992-11-16 | ||
GB929224014A GB9224014D0 (en) | 1992-11-16 | 1992-11-16 | Detergent compositions |
PCT/GB1993/002345 WO1994011487A1 (en) | 1992-11-16 | 1993-11-15 | Detergent compositions |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0670887A1 true EP0670887A1 (en) | 1995-09-13 |
EP0670887B1 EP0670887B1 (en) | 1998-02-04 |
EP0670887B2 EP0670887B2 (en) | 2000-12-27 |
Family
ID=10725171
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93924768A Expired - Lifetime EP0670887B2 (en) | 1992-11-16 | 1993-11-15 | Detergent compositions |
Country Status (14)
Country | Link |
---|---|
EP (1) | EP0670887B2 (en) |
JP (1) | JP2776985B2 (en) |
AU (1) | AU689449B2 (en) |
BR (1) | BR9307457A (en) |
CZ (1) | CZ284655B6 (en) |
DE (1) | DE69316917T3 (en) |
ES (1) | ES2112437T5 (en) |
GB (1) | GB9224014D0 (en) |
HU (1) | HU217238B (en) |
IN (1) | IN179513B (en) |
PL (1) | PL174609B1 (en) |
SK (1) | SK280568B6 (en) |
WO (1) | WO1994011487A1 (en) |
ZA (1) | ZA938507B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2173136A1 (en) * | 1994-03-31 | 1995-10-12 | Peter Robert Garrett | Detergent compositions |
DE4436066A1 (en) * | 1994-10-10 | 1996-04-11 | Henkel Kgaa | fatty substances |
MX9704500A (en) * | 1994-12-16 | 1997-10-31 | Procter & Gamble | Hard surface cleaners comprising highly ethoxylated guerbet alcohols. |
FR2814459B1 (en) | 2000-09-22 | 2002-12-06 | Lafarge Platres | SURFACTANT COMPOSITION FOR PLASTERBOARDS |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2257642A1 (en) * | 1972-11-24 | 1974-06-20 | Basf Ag | BIODEGRADABLE DETERGENTS AND DETERGENTS |
DE2448532A1 (en) * | 1973-10-15 | 1975-04-24 | Procter & Gamble | OIL REMOVAL COMPOSITIONS |
PH14838A (en) * | 1974-03-21 | 1981-12-16 | Procter & Gamble | Detergent composition |
CA1033638A (en) * | 1974-09-11 | 1978-06-27 | The Procter And Gamble Company | Detergent compositions |
US4206070A (en) † | 1975-12-24 | 1980-06-03 | The Procter & Gamble Company | Detergent compositions |
FR2345513A1 (en) * | 1976-03-24 | 1977-10-21 | Rhone Poulenc Ind | TENSIO-ACTIVE COMPOSITION BASED ON NON-IONIC SURFACTANTS |
US4399049A (en) † | 1981-04-08 | 1983-08-16 | The Procter & Gamble Company | Detergent additive compositions |
ES2085273T3 (en) † | 1988-11-02 | 1996-06-01 | Unilever Nv | PROCEDURE FOR PREPARING AN APPARENT HIGH DENSITY GRANULAR DETERGENT COMPOSITION. |
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1992
- 1992-11-16 GB GB929224014A patent/GB9224014D0/en active Pending
-
1993
- 1993-11-15 AU AU54312/94A patent/AU689449B2/en not_active Ceased
- 1993-11-15 BR BR9307457-3A patent/BR9307457A/en not_active IP Right Cessation
- 1993-11-15 HU HU9501434A patent/HU217238B/en not_active IP Right Cessation
- 1993-11-15 WO PCT/GB1993/002345 patent/WO1994011487A1/en active IP Right Grant
- 1993-11-15 DE DE69316917T patent/DE69316917T3/en not_active Expired - Lifetime
- 1993-11-15 ZA ZA938507A patent/ZA938507B/en unknown
- 1993-11-15 ES ES93924768T patent/ES2112437T5/en not_active Expired - Lifetime
- 1993-11-15 SK SK639-95A patent/SK280568B6/en unknown
- 1993-11-15 CZ CZ951051A patent/CZ284655B6/en not_active IP Right Cessation
- 1993-11-15 EP EP93924768A patent/EP0670887B2/en not_active Expired - Lifetime
- 1993-11-15 JP JP6511871A patent/JP2776985B2/en not_active Expired - Lifetime
- 1993-11-15 PL PL93308363A patent/PL174609B1/en unknown
- 1993-11-16 IN IN389BO1993 patent/IN179513B/en unknown
Non-Patent Citations (1)
Title |
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See references of WO9411487A1 * |
Also Published As
Publication number | Publication date |
---|---|
CZ284655B6 (en) | 1999-01-13 |
EP0670887B2 (en) | 2000-12-27 |
SK63995A3 (en) | 1996-04-03 |
AU5431294A (en) | 1994-06-08 |
HU217238B (en) | 1999-12-28 |
ES2112437T5 (en) | 2001-02-16 |
DE69316917D1 (en) | 1998-03-12 |
PL174609B1 (en) | 1998-08-31 |
JP2776985B2 (en) | 1998-07-16 |
PL308363A1 (en) | 1995-07-24 |
JPH08503240A (en) | 1996-04-09 |
HUT72620A (en) | 1996-05-28 |
ES2112437T3 (en) | 1998-04-01 |
DE69316917T3 (en) | 2001-03-29 |
ZA938507B (en) | 1995-05-15 |
BR9307457A (en) | 1999-08-31 |
GB9224014D0 (en) | 1993-01-06 |
DE69316917T2 (en) | 1998-05-28 |
AU689449B2 (en) | 1998-04-02 |
EP0670887B1 (en) | 1998-02-04 |
WO1994011487A1 (en) | 1994-05-26 |
SK280568B6 (en) | 2000-03-13 |
IN179513B (en) | 1997-10-11 |
CZ105195A3 (en) | 1995-11-15 |
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