EP1228184B1 - Systemes de tensioactifs structures - Google Patents

Systemes de tensioactifs structures Download PDF

Info

Publication number
EP1228184B1
EP1228184B1 EP00940613A EP00940613A EP1228184B1 EP 1228184 B1 EP1228184 B1 EP 1228184B1 EP 00940613 A EP00940613 A EP 00940613A EP 00940613 A EP00940613 A EP 00940613A EP 1228184 B1 EP1228184 B1 EP 1228184B1
Authority
EP
European Patent Office
Prior art keywords
alkyl
composition
surfactant
weight
deflocculant
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.)
Expired - Lifetime
Application number
EP00940613A
Other languages
German (de)
English (en)
Other versions
EP1228184A1 (fr
Inventor
John Hawkins
Kevan Hatchman
Richard Malcolm Clapperton
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.)
Huntsman International LLC
Original Assignee
Huntsman International LLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from GBGB9914673.0A external-priority patent/GB9914673D0/en
Priority claimed from GBGB9925699.2A external-priority patent/GB9925699D0/en
Application filed by Huntsman International LLC filed Critical Huntsman International LLC
Publication of EP1228184A1 publication Critical patent/EP1228184A1/fr
Application granted granted Critical
Publication of EP1228184B1 publication Critical patent/EP1228184B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • 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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin

Definitions

  • the present invention relates to the formulation of structured surfactant suspending systems. It is particularly relevant to the formulation of laundry detergents especially those used for industrial and institutional cleaning.
  • Suspending solids in liquids presents a problem. If the solids differ in density from the liquid they will tend either to sediment or float. Increasing the viscosity of the liquid can retard, but not prevent such separation, and high viscosities are generally undesirable. Colloidal systems, in which the suspended particles are sufficiently small to experience Brownian motion, e.g. less than 1 micron, may be kinetically stable. However the difficulty or undesirability of comminuting some solids to such sizes, and the impossibility of maintaining many of them at this level in the face of crystal growth or agglomeration, limits the use of colloidal suspensions.
  • One method of suspension which permits even relatively large particles to be stably suspended is structured surfactant.
  • the term covers systems in which a surfactant mesophase, usually a lamellar or G-phase, alone or more usually interspersed with an aqueous phase, provides a yield stress which is sufficient, when the system is at rest, to immobilise any suspended particles, but which is sufficiently low to allow the system to be poured like a normal liquid.
  • Such systems may display very low apparent viscosities when stirred, pumped or poured and yet be capable of maintaining particles, sometimes of millimetre or larger size, indefinitely in suspension.
  • G-phases also known as L ⁇ phases
  • L ⁇ phases can usually be identified by their characteristic textures under the polarising microscope and/or by x-ray diffraction, which is often able to detect evidence of lamellar symmetry. Such evidence may comprise first, second and sometimes third order peaks with d-spacing ( 2 ⁇ Q where Q is the momentum transfer vector) in a simple integral ratio 1:2:3.
  • Other types of symmetry give different ratios, usually non integral.
  • G-phases either at ambient or at some higher temperature when mixed with water in certain specific proportions.
  • G-phases cannot usually be used as structured suspending systems. Useful quantities of solid render them unpourable and smaller amounts tend to sediment.
  • Dispersed lamellar phases are two phase systems in which the surfactant bilayers are arranged as parallel plates to form domains of G-phases which are interspersed with an aqueous phase to form an opaque gel-like system. They are described in EP O 086 614.
  • Spherulitic phases comprise well defined spheroidal bodies, usually referred to in the art as spherulites, in which surfactant bilayers are arranged as concentric shells.
  • the spherulites usually have a diameter in the range 0.1 to 15 microns and are dispersed in an aqueous phase in the manner of a classical emulsion, but interacting to form a structured system.
  • Spherulitic systems are described in more detail in EP O 151 884.
  • a variant on the spherulitic system comprises prolate or rod shaped bodies sometimes referred to as batonets.
  • a third type of structured surfactant system comprises an expanded G-phase. It differs from the other two types of structure system in being essentially a single phase, and from conventional G-phase in having a wider d-spacing. Conventional G-phases have a d-spacing of about 5 to 7 nanometers. Attempts to suspend solids in such phases results in stiff pastes which are either non-pourable, unstable or both. Expanded G-phases with d-spacing between 8 and 20, e.g. 10 to 15 nanometers, form when the electrolyte is added to aqueous surfactants at concentrations just below those required to form a normal G-phase, particularly to surfactants in the M phase.
  • the M phase comprises surfactant molecules arranged to form cylindrical rods of indefinite length. It exhibits hexagonal symmetry and a distinctive texture under the polarising microscope. Typical M phases have so high a viscosity that they appear to be curdy solids. M phases near the lower concentration limit (the L 1 /M phase boundary) may be pourable but have a very high viscosity and often a mucous-like appearance. Such systems tend to form expanded G-phases particularly readily on addition of sufficient electrolyte.
  • Expanded G-phases are described in more detail in EP O 530 708. In the absence of suspended matter they are translucent, unlike dispersed lamellar or spherulitic phases which are necessarily opaque. They are optically anisotropic and have shear dependent viscosity. In this they differ from L 1 phases which are micellar solutions and which include microemulsions. L 1 phases are clear, optically isotropic and substantially Newtonian. They are unstructured and cannot suspend solids. Some L 1 phases exhibit small angle x-ray diffraction spectra which show evidence of hexagonal symmetry. Such phases usually have concentrations near the L 1 /M phase boundary and may form expanded G-phases on addition of electrolyte.
  • Structured surfactants have been applied to the problems of suspending: water insoluble or sparingly soluble builders in laundry detergent; antifoams and enzymes in laundry detergents and other surfactant systems; abrasives in hard surface cleaners; pesticides and oils in agrochemical preparations (EP O 388 239 and EP O 498 231); rock cuttings in drilling muds (EP O 430 602); dyestuffs in dyebath concentrates and printing inks (EP O 472 089); talcs, oils and other cosmetic ingredients in personal care formulations (EP O 530 708).
  • Certain amphiphilic polymers have been found to act as deflocculants of structured surfactants.
  • One type of deflocculant polymer exhibits cteniform (comb-shaped) architecture with a hydrophilic backbone and hydrophobic side chains or vice versa.
  • a typical example is a random copolymer of acrylic acid and a fatty alkyl acrylate.
  • Cteniform deflocculants have been described in a large number of patents, for example WO-A-9106622.
  • a more effective type of deflocculant has surfactant rather than cteniform architecture.
  • Such deflocculants are typically telomers formed by telomerising a hydrophilic monomer with a telogen having a hydrophobic group.
  • Examples of surfactant deflocculants include alkyl thiol polyacrylates and alkyl polyglycosides. Surfactant deflocculants are described in more details in EP O 623 670.
  • EP-A-0 732 394 also describes detergent compositions that make use of deflocculant polymers.
  • a liquid detergent system comprising surfactant, electrolyte, defloculating polymer, a pH jump system comprising sorbitol and boron containing compound, and non ionic polymer is described.
  • a disadvantage of both surfactant and cteniform deflocculants is that the concentration required to deflocculate to optimum viscosity is critical within fairly narrow limits and varies with temperature. Either too little or too much deflocculant causes instability and/or excessive viscosity. As a result the deflocculated systems tend to separate if the temperature varies significantly.
  • An ideal laundry detergent for institutional use would combine: high surfactant levels and in particular high levels of non-ionic surfactant, which has been found particularly effective for removing soil; high alkalinity, to saponify fatty soil; and high levels of builder, which improve the performance of the surfactant by counteracting the effects of calcium in the water.
  • the composition must be homogeneous and pourable and the concentration as high as possible.
  • surfactants with electrolytes at high concentrations to form stable compositions. It has proved particularly difficult to achieve this with non-ionic surfactants which are not capable of forming stable solutions at high alkalinity or in the presence of electrolyte, except at very low concentrations which are too low to be commercially acceptable.
  • water soluble carbohydrates are capable of deflocculating dispersed lamellar or spherulitic structured surfactant systems. They are substantially cheaper than known deflocculants and do not cause excessive foaming. They are generally less sensitive to temperature variations.
  • Our invention provides a structured surfactant composition capable of suspending solids which comprises surfactant, water and, if required, electrolyte in relative proportions adapted to form a flocculated, dispersed lamellar and/or spherulitic structured surfactant system, and, in addition, sufficient of a deflocculant to inhibit the flocculation of said system characterised in that said deflocculant comprises a water-soluble carbohydrate, and wherein the composition further comprises an auxiliary stabiliser which is defined in claim 1.
  • said surfactant consists of a major amount of non-ionic surfactant and optionally a minor amount of anionic and/or amphoteric.
  • Said water is preferably present in a proportion of from 20 to 60%, especially 30 to 50%.
  • Said electrolyte preferably comprises alkali.
  • Said deflocculant preferably comprises at least 10% by weight of the composition of a mono- or preferably di-saccharide.
  • the composition contains an auxiliary stabiliser to prevent or inhibit temperature instability such as bottom separation or phase changes on warming.
  • the stabiliser may comprise (i) an ethoxylated C 8-20 , straight or branched chain alcohol or fatty acid, fatty amine, sorbitan or glycerol ester, alkyl polypropoxy group or alkyl phenyl group and (ii) a water soluble thiocyanate.
  • the number of ethoxy groups may be from 20 to 100, e.g. 30 to 80, preferably 40 to 60.
  • the mole ratio of (i):(ii) may preferably be from 1:100 to 10:1, e.g. 1:50 to 5:1.
  • the total concentration of auxiliary stabiliser may typically be from 5 to 150% molar based on the deflocculant, e.g. 10 to 100%.
  • the concentration of (B) in the composition is preferably from 0.1 to 10%, e.g. 0.5 to 5%, especially 0.8% to 2%.
  • carboxylic acids e.g. gluconic, mannic and ascorbic acids and alginates
  • reduced sugars such as sorbitol, mannitol or inositol and dialdehyde starches.
  • Preferred deflocculants are sorbitol, alginates, soluble starches and mono and di-saccharides.
  • the alginates are preferably alkali metal or ammonium salts e.g. sodium alginate. They are preferably present in concentrations of from 0.05 to 5%, e.g. 0.1 to 2% especially 0.2 to 1%.
  • the mono and di-saccharides and derivatives such as sorbitol are usually required in much higher proportions than polysaccharide deflocculants. Generally concentrations of more than 5% by weight of the composition are required, more usually 10 to 20%, especially 12 to 18%.
  • the di-saccharide is preferably sucrose but may also be, for example, maltose, lactose or cellobiose.
  • Other carbohydrates for use in the invention include glucose, fructose, mannose, ribose, galactose, alldose, talose, gulose, idose, arabinose, xylose, lyxose, erythrose, threose, acrose and rhamiose.
  • the invention provides a detergent composition comprising:-
  • the amount of water is typically greater than 30%, preferably greater than 40%, especially greater than 50% and usually less than 70% based on the total weight of the composition.
  • the surfactant is preferably all non-ionic since in some applications inclusion of anionic surfactant can adversely affect performance. However where anionic surfactant can be tolerated its inclusion has the advantage of enabling higher total concentrations of surfactant to be more easily achieved.
  • wholly non-ionic based formulations contain from 7 to 30%, more typically 10 to 25% by weight surfactant while compositions containing a minor proportion of anionic surfactant may contain up to 50% by weight, e.g. 15 to 40%, especially 20 to 35%.
  • the non-ionic surfactant preferably consists of from 60 to 100% by weight of alkoxylate, preferably ethoxylate or mixed ethoxylate/propoxylate. Typically it comprises alkoxylated C 8-20 , especially C 10-18 natural or synthetic alcohols.
  • the alcohols are typically primary or secondary, straight or branched chain, saturated or unsaturated. Also effective are alkoxylated fatty acids, fatty amines, alkyl phenols, glyceryl mono and dialkyl esters and sorbitan esters.
  • the ethoxylate typically contains an average of from 1 to 10 alkoxy groups depending on the alkyl chain length, to give an HLB of from 10 to 15, preferably 12 to 14.
  • the non-ionic surfactant may comprise a mono- or di- ethanolamide or an amine oxide.
  • the surfactant may optionally contain a minor proportion (i.e. less than 50% based on the total weight of surfactant) of anionic surfactant such as soap and/or alkyl benzene sulphonate.
  • anionic surfactant such as soap and/or alkyl benzene sulphonate.
  • Other anionic surfactants which may be used include alkyl ether sulphates, alkyl sulphates, olefin sulphonates, paraffin sulphonates and alkyl phosphates.
  • the builder is preferably sodium tripolyphosphate, but may alternatively be or comprise sodium or potassium pyrophosphate, sodium or potassium citrate, sodium or potassium carbonate or a zeolite.
  • Other builders include EDTA, nitrilotriacetate, phosphonates and poly electrolytes such as polyacrylates or polymaleates.
  • the builder is present in amounts greater than 10% by weight based on the total weight of the composition, preferably more than 15%. Levels of builder may be above 20%, any excess over the solubility in the system being present as suspended particles. Builder concentrations do not normally exceed 50% by weight and are usually less than 40%, e.g. less than 30%.
  • the composition contains a total of at least 7% by weight of dissolved surfactant desolubilising salts and bases. This includes any dissolved portion of the builder and any alkali required to provide the free alkalinity.
  • the dissolved salts and bases preferably constitute from 10 to 40%, e.g. 15 to 30% by weight of the composition, and sufficient to form a multiphase system in which an aqueous phase is interspersible with a surfactant or surfactant mesophase.
  • the total free alkali should be sufficient to neutralise at least an equal volume of 0.5 normal HCl.
  • the free alkalinity if from 0.7 to 2 normal, e.g. 0.8 to 1.5.
  • the alkyl polyglycoside is preferably a polyglucoside and typically has an average degree of polymerisation between 1.3 and 10, more usually 1.5 to 3.
  • the alkyl polyglycoside is generally added in an amount sufficient to provide an interspersion of the aqueous phase with the surfactant phase at 25°C, which does not separate within 1 month. This may typically require from 0.5 to 10, more usually 1 to 5%, e.g. 2 to 4.5% by weight based on the weight of the composition.
  • the amount is preferably adjusted to obtain a spherulitic composition comprising surfactant vesicles, usually having a multilamellar or G-phase structure, dispersed in an aqueous phase.
  • compositions of the invention contain an auxiliary stabiliser which helps to extend the range of temperature within which the composition is stable. This is particularly desirable where storage at relatively high temperatures, e.g. 40°C, is an important consideration.
  • the auxiliary stabiliser may be an ethoxylated alcohol having an average of 20 to 100, more usually 25 to 75, e.g. 30 to 60 ethylene oxide groups per molecule, together with a thiocyanate especially potassium thiocyanate.
  • the auxiliary stabiliser may be a polycarboxylate having one or more alkyl groups such as C 8-20 alkyl thiol polycarboxylate e.g.
  • polyacrylate or polymaleate or a copolymer of unsaturated carboxylic acid with a C 8-20 alkyl ester of unsaturated carboxylic acid e.g. a copolymer of acrylic acid and/or maleic acid with a minor proportion of a C 8-20 alkyl acrylate and/or alkyl maleate ester.
  • the auxiliary stabiliser may be present in proportions up to 5% by weight, usually 0.01 to 3%, e.g. 0.02 to 2 especially 0.01 to 1. Combinations of two or more auxiliary stabilisers may sometimes be particularly effective.
  • the detergent compositions of the invention preferably also contain the conventional minor detergent ingredients including antifoams such as silicone antifoam, soil suspending agents such as a carboxymethyl cellulose, optical brighteners, stain removers such as enzymes, bleaches including perborate metaborate mixtures, sequestrants such as phosphonates and especially amino phosphonates including aminotrismethylene phosphonate, ethylene diamine tetrakis (methylene phosphonate), diethylene triamine pentakis (methylene phosphonate) and others in the same series, perfumes, colouring, preservatives, corrosion inhibitors, bleach activators such as TAED and/or fabric conditioner.
  • antifoams such as silicone antifoam
  • soil suspending agents such as a carboxymethyl cellulose
  • optical brighteners such as stain removers
  • stain removers such as enzymes
  • bleaches including perborate metaborate mixtures
  • sequestrants such as phosphonates and especially amino phosphon
  • the aforesaid minor ingredients may all be present in conventional amounts and usually constitute a total of less than 5% by weight of the composition, typically less than 1%.
  • the anionic component of the ionic ingredients may typically be sodium, potassium or a mixture of the two. Potassium is preferred where very high solids contents are desired.
  • the above laundry detergent formulation was stable over extended storage periods at ambient, elevated (40°), low (2°) and cycled temperatures and readily pourable.
  • the washing performance was similar to those obtained using either C 12-14 alkyl thiol polyacrylate or alkyl polyglycoside as the deflocculant however use of either of the two latter resulted in excessive foaming, necessitating the addition of an antifoam.
  • the thiol polyacrylate required slightly higher concentrations, and the polyglycoside much higher concentrations, to achieve equivalent viscosity and stability.
  • laundry detergent compositions are stable, pourable, non -flocculated suspensions.
  • Ex 3 Ex 4 C 12-14 alkyl 6 mole ethoxylate 11.5 11.5 C 12-15 branched alkyl 3 mole ethoxylate 1.0 1.0 C 12-14 alkyl polyglucoside (d.p.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Emergency Medicine (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (9)

  1. Composition d'agent tensioactif structuré apte à mettre en suspension des substances solides, qui comprend un agent tensioactif, de l'eau et, s'il le faut, un électrolyte en des proportions relatives propres à former un système d'agent tensioactif structuré, lamellaire et/ou sphérolitique, floculé, dispersé, et, de plus, suffisamment de défloculant pour inhiber la floculation dudit système, dans laquelle ledit défloculant comprend un hydrate de carbone hydrosoluble et dans laquelle la composition comprend en outre un stabilisant auxiliaire qui est un stabilisant auxiliaire qui est un alcool éthoxylé ayant une moyenne de 20 à 100 groupes d'oxyde d'éthylène par molécule, avec un thiocyanate, un polycarboxylate ayant un ou plusieurs groupes alkyles ou un copolymère d'acide carboxylique insaturé avec un ester d'alkyle en C8-20 d'un acide carboxylique insaturé ou qui comprend (i) un alcool ou un acide gras en C8-20 éthoxylé à chaîne linéaire ou ramifiée, une amine grasse, un ester de sorbitane ou de glycérol, un groupe alkyl polypropoxy ou un groupe alkylphényle et (ii) un thiocyanate hydrosoluble.
  2. Composition selon la revendication 1, dans laquelle ledit hydrate de carbone est un alginate présent en une proportion de 0,05% à 5% en poids sur la base du poids de la composition.
  3. Composition selon la revendication 1, dans laquelle ledit hydrate de carbone est un mono ou disaccharide ou un dérivé de celui-ci en une proportion de 10 à 20% en poids sur la base du poids de la composition.
  4. Composition détergente comprenant :
    (A) 20 à 75% d'eau en poids de la composition ;
    (B) Au moins 3%, sur la base du poids de la composition, de préférence 4 à 10%, d'un agent tensioactif comprenant plus de 50%, sur la base du poids total d'agent tensioactif, d'agents tensioactifs non ioniques ayant un équilibre hydrophile-lipophile moyen de 10 à 15 et facultativement une proportion plus petite d'agent tensioactif anionique et/ou amphotère ;
    (C) Au moins 10% en poids, sur la base du poids de la composition, d'adjuvants ;
    (D) Au moins 7%, sur la base du poids de la composition, de sels et bases dissous ne formant pas de micelle qui se dissocient au moins partiellement en ions dans une solution, incluant toute partie dissoute dudit adjuvant ;
    (E) Une alcalinité libre totale d'au moins 0,5 normale ;
    (F) Suffisamment de défloculant pour fournir, conjointement avec les constituants A à E ci-dessus, une composition versable qui ne se sépare pas après 1 mois à 25 °C ;
    (G) un stabilisant auxiliaire qui est un alcool éthoxylé ayant une moyenne de 20 à 100 groupes d'oxyde d'éthylène par molécule, avec un thiocyanate, un polycarboxylate ayant un ou plusieurs groupes alkyles ou un copolymère d'acide carboxylique insaturé avec un ester d'alkyle en C8-20 d'un acide carboxylique insaturé ou qui comprend (i) un alcool ou un acide gras en C8-20 éthoxylé à chaîne linéaire ou ramifiée, une amine grasse, un ester de sorbitane ou de glycérol, un groupe alkyl polypropoxy ou un groupe alkylphényle et (ii) un thiocyanate hydrosoluble ;
    dans laquelle ledit défloculant comprend un hydrate de carbone hydrosoluble.
  5. Composition selon l'une quelconque des revendications 1 à 4, dans laquelle le stabilisant auxiliaire comprend (i) un alcool ou un acide gras en C8-20 éthoxylé à chaîne linéaire ou ramifiée, une amine grasse, un ester de sorbitane ou de glycérol, un groupe alkyl polypropoxy ou un groupe alkylphényle et (ii) un thiocyanate hydrosoluble, et le nombre de groupes éthoxy est de 20 à 100.
  6. Composition selon la revendication 5, dans laquelle le nombre de groupes éthoxy est de 40 à 60.
  7. Composition selon l'une quelconque des revendications 1 à 6, dans laquelle le stabilisant auxiliaire comprend (i) un alcool ou un acide gras en C8-20 éthoxylé à chaîne linéaire ou ramifiée, une amine grasse, un ester de sorbitane ou de glycérol, un groupe alkyl polypropoxy ou un groupe alkylphényle et (ii) un thiocyanate hydrosoluble, et le rapport molaire de (i):(ii) est de 1:100 à 10:1.
  8. Composition selon l'une quelconque des revendications 1 à 4, dans laquelle le stabilisant auxiliaire est un thiol polycarboxylate d'alkyle en C8-20.
  9. Composition selon l'une quelconque des revendications 1 à 4, dans laquelle le stabilisant auxiliaire est un copolymère d'acide acrylique et/ou d'acide maléique avec une proportion mineure d'un acrylate d'alkyle en C8-20 et/ou d'ester maléate d'alkyle.
EP00940613A 1999-06-24 2000-06-22 Systemes de tensioactifs structures Expired - Lifetime EP1228184B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GBGB9914673.0A GB9914673D0 (en) 1999-06-24 1999-06-24 Structured surfactant systems
GB9914673 1999-06-24
GBGB9925699.2A GB9925699D0 (en) 1999-10-30 1999-10-30 Structured surfactant systems
GB9925699 1999-10-30
PCT/GB2000/002447 WO2001000778A1 (fr) 1999-06-24 2000-06-22 Systemes de tensioactifs structures

Publications (2)

Publication Number Publication Date
EP1228184A1 EP1228184A1 (fr) 2002-08-07
EP1228184B1 true EP1228184B1 (fr) 2006-09-27

Family

ID=26315695

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00940613A Expired - Lifetime EP1228184B1 (fr) 1999-06-24 2000-06-22 Systemes de tensioactifs structures

Country Status (8)

Country Link
EP (1) EP1228184B1 (fr)
AT (1) ATE340848T1 (fr)
AU (1) AU778246B2 (fr)
DE (1) DE60030998T2 (fr)
DK (1) DK1228184T3 (fr)
ES (1) ES2272292T3 (fr)
PT (1) PT1228184E (fr)
WO (1) WO2001000778A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU776705B2 (en) * 1999-07-17 2004-09-16 Huntsman International Llc Structured surfactant systems
GB0117676D0 (en) * 2001-07-20 2001-09-12 Huntsman Int Llc Phosphate suspensions
EP1458337B1 (fr) 2001-12-21 2016-05-04 Solvay USA Inc. Compositions de tensioactifs stables pour suspension de composants
BRPI0809314A2 (pt) 2007-03-23 2014-10-14 Rhodia Composições de tensoativo estruturado

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8813978D0 (en) * 1988-06-13 1988-07-20 Unilever Plc Liquid detergents
SK53294A3 (en) * 1993-05-07 1995-04-12 Albright & Wilson Concentrated aqueous mixture containing surface active matter and its use
EP0732394A3 (fr) * 1995-03-13 1999-02-03 Unilever N.V. Compositions détergentes

Also Published As

Publication number Publication date
PT1228184E (pt) 2006-12-29
AU5552500A (en) 2001-01-31
ES2272292T3 (es) 2007-05-01
WO2001000778A1 (fr) 2001-01-04
AU778246B2 (en) 2004-11-25
DE60030998D1 (de) 2006-11-09
DE60030998T2 (de) 2007-05-24
DK1228184T3 (da) 2007-02-12
EP1228184A1 (fr) 2002-08-07
ATE340848T1 (de) 2006-10-15

Similar Documents

Publication Publication Date Title
EP0623670B1 (fr) Compositions tensioactives à base aqueuse
US6090762A (en) Aqueous based surfactant compositions
EP0452106B1 (fr) Composition aqueuse d'un tensio-actif
EP1218483B1 (fr) Systemes de tensioactifs structures
EP1228184B1 (fr) Systemes de tensioactifs structures
AU772925B2 (en) Surfactant emulsions and structured surfactant systems
GB2434586A (en) Structured liquid abrasive composition

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20020124

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17Q First examination report despatched

Effective date: 20040126

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20060927

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060927

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060927

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60030998

Country of ref document: DE

Date of ref document: 20061109

Kind code of ref document: P

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20061031

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20070330

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20070410

Year of fee payment: 8

Ref country code: AT

Payment date: 20070410

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20070412

Year of fee payment: 8

ET Fr: translation filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: MC

Payment date: 20070425

Year of fee payment: 8

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2272292

Country of ref document: ES

Kind code of ref document: T3

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20070509

Year of fee payment: 8

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20070628

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20061228

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20080619

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20080414

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20080630

Year of fee payment: 9

Ref country code: IE

Payment date: 20080424

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20080506

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080630

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

EUG Se: european patent has lapsed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080622

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20090101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080622

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070622

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20060927

REG Reference to a national code

Ref country code: PT

Ref legal event code: MM4A

Free format text: LAPSE DUE TO NON-PAYMENT OF FEES

Effective date: 20091222

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090106

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20090622

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091222

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090622

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090622

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080623

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20090623

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090623

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20120614

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20120619

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20120710

Year of fee payment: 13

BERE Be: lapsed

Owner name: HUNTSMAN INTERNATIONAL LLC

Effective date: 20130630

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20140228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130701

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130622