EP0328177B1 - Flüssige Reinigungsmittel - Google Patents

Flüssige Reinigungsmittel Download PDF

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Publication number
EP0328177B1
EP0328177B1 EP89200163A EP89200163A EP0328177B1 EP 0328177 B1 EP0328177 B1 EP 0328177B1 EP 89200163 A EP89200163 A EP 89200163A EP 89200163 A EP89200163 A EP 89200163A EP 0328177 B1 EP0328177 B1 EP 0328177B1
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EP
European Patent Office
Prior art keywords
surfactant
composition according
composition
stabilising
weight
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
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EP89200163A
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English (en)
French (fr)
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EP0328177A3 (en
EP0328177A2 (de
Inventor
David Machin
Johannes Cornelis Van De Pas
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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    • 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

Definitions

  • the present invention is concerned with liquid detergent compositions which contain sufficient detergent active material and sufficient dissolved electrolyte to result in a surfactant structure within the composition.
  • Such compositions are sometimes referred to as 'internally structured' since the structure is due to primary ingredients rather than to secondary additives, such as certain cross-linked polyacrylates, which can be added as 'external structurants' to a composition which would otherwise show no evidence of a structure.
  • Internal structuring is very well known in the art and may be deliberately brought about to endow properties such as consumer preferred flow properties and/or turbid appearance.
  • Many internally structured liquids are also capable of suspending particulate solids such as detergency builders and abrasive particles. Examples of such structured liquids without suspended solids are given in US patent 4 244 840 whilst examples where solid particles are suspended are disclosed in specifications EP-A-160 342; EP-A-38 101; EP-A-104 452 and also in the aforementioned US 4 244 840.
  • a surfactant structuring system in a liquid may be detected by means known to those skilled in the art for example, optical techniques, various rheometrical measurements, x-ray or neutron diffraction, and sometimes, electron microscopy.
  • lamellar dispersion One common type of internal surfactant structure is sometimes referred to as a dispersion of lamellar droplets (lamellar dispersion) These droplets consist of an onion-like configuration of concentric bilayers of surfactant molecules, between which is trapped water or electrolyte solution (aqueous phase). Systems in which such droplets are close-packed provide a very desirable combination of physical stability and solid-suspending properties with useful flow properties.
  • electrolyte means any ionic water soluble material. However, in structured liquids, not all the electrolyte is necessarily dissolved but may be suspended as particles of solid because the total electrolyte concentration of the liquid is higher than the solubility limit of the electrolyte. Mixtures of electrolytes also may be used, with one or more of the electrolytes being in the dissolved aqueous phase and one or more being substantially only in the suspended solid phase. Two or more electrolytes may also be distributed approximately proportionally, between these two phases. In part, this may depend on processing, e.g. the order of addition of components.
  • the term 'salts' includes all organic and inorganic materials which may be included, other than surfactants and water, whether or not they are ionic, and this term encompasses the sub-set of the electrolytes (water soluble materials).
  • 'stabilising surfacants' especially suitable surfactants (hereinafter called 'stabilising surfacants') can be identified using a test of the general kind referred to above, provided that it is framed in a suitable manner, provided that one defines an appropriate threshold for deciding whether a particular surfactant passes the test and provided one also ensures that the composition containing the stabilising surfactant gives a certain result upon centrifugation.
  • the surfactants may be screened for use in novel internally structured detergent liquids.
  • the test herein prescribed for electrolyte tolerance is termed the measurement of salting-out resistance.
  • 200ml is prepared of a 5% by weight aqueous solution of the surfactant in question.
  • Trisodium nitrolotriacetate (NTA) is added at room temperature (ca 25°C) until phase separation, as observed by the onset of cloudiness, occurs.
  • the abbreviation SOR will be used for salting-out resistance.
  • the present invention provides an aqueous liquid detergent composition
  • aqueous liquid detergent composition comprising detergent active material and dissolved electrolyte in amounts sufficient to result in a surfactant structure within said composition, which composition yields substantially no clear liquid active rich layer upon centrifuging at 750G for 20 hours at 25°C
  • the detergent active material comprises a stabilising surfactant, which has an average alkyl chain length greater than 6 carbon atoms, and which has a salting-out resistance (as hereinbefore defined), greater than, or equal to 6.4.
  • the selection of surfactants as described above allows the compositions of the present invention to be capable of greater flexibility in the incorporation of large amounts of salts, especially soluble salts (i.e. electrolytes) and improved possibilities for the incorporation of polymer builders, especially water-soluble builders, which can also act to bring about a desirable viscosity reduction in the product.
  • the incorporation of higher levels of surfactants is advantageous for fatty soil removal.
  • the stabilising surfactant is nonionic in character
  • the ensuing incorporation of high levels of nonionic rather than anionic surfactant is advantageous for the stability of any enzymes present, these in general being more sensitive to anionics than to nonionics.
  • the applicants have observed a trend that the higher the measured SOR, the lower is the concentration of surfactant necessary to achieve a given advantage.
  • compositions to be in accordance with the present invention it is not only necessary for it to contain at least some stabilising surfactant as hereinbefore defined but also for the compositions as a whole to yield substantially no clear liquid active rich layer upon centrifugation at 750G for 20 hours at 25°C.
  • the abbreviation G refers to the value of the earth's normal gravitational force. It should be noted that this requirement excludes compositions which do not demonstrate the advantage provided by compositions of the present invention and also those compositions which are the subject of our co-pending patent application, reference EP-A-328,176 entitled 'Aqueous Detergent Compositions and Methods of Forming Them' filed on the same day as this application.
  • liquid active rich layer means totally or substantially clear to the unaided eye.
  • a liquid layer which is not active rich will contain less than 10% by weight of surfactant (detergent active) material, preferably less than 5%, most preferably less than 2% by weight.
  • the stabilising surfactant may constitute all or part of the detergent active material.
  • the only restriction on the total amount of detergent active and electrolyte is that together they must result in formation of a structuring system.
  • the selection of surfactant types and their proportions, in order to obtain a stable liquid with the required structure will, in the light of the present teaching, now be fully within the capability of those Skilled in the art.
  • an important sub-class of useful compositions is those where the detergent active material comprises one or more conventional or 'primary' surfactants, together with one or more stabilising surfactants.
  • Typical blends useful for fabric washing compositions include those where the primary surfactant(s) comprise nonionic and/or a non-alkoxylated anionic and/or an alkoxylated anionic surfactant.
  • the stabilising surfactant should have an average alkyl chain length greater than 6 carbon atoms, it is usually preferred that the stabilising surfactant have an average alkyl chain length greater than 8 carbon atoms.
  • Some especially preferred classes of stabilising surfactants which may be used alone or in combination are:- alkyl polyalkoxylated phosphates; alkyl polyalkoxylated sulphosuccinates; dialkyl diphenyloxide disulphonates; and alkyl polysaccharides (sometimes called alkyl polyglucosides or polyglycosides).
  • stabilising surfactants for example the alkyl polysaccharides described in European patent specification nos. EP-A-70 074; 70 075; 70 076; 70 077; 75 994; 75 995; 75 996 and 92 355.
  • stabilising surfactants of whatever chemical type which have an SOR greater than 9.0.
  • the total detergent active material may be present at from 2% to 50% by weight of the total composition, especially from 5% to 35% and most preferably from 10% to 30% by weight.
  • these figures will apply both to blends of primary and stabilising surfactants, as well as to the case where the detergent active material consists entirely of stabilising surfactant.
  • the amount of stabilising surfactant material will typically constitute from 0.1% to 45% by weight of the total composition, especially from 0.5% to 30% and most preferably from 1% to 30% by weight.
  • the stabilising surfactant will often constitute from 5% to 90% by weight of the total detergent active material, especially from 7.5% to 90% and most preferably from 10% to 90% by weight.
  • compositions of the present invention should have a rheology and a minimum stability, compatible with most commercial and retail requirements. For this reason, we generally prefer the compositions of the present invention to yield no more than 2% by volume phase separation upon storage at 25°C for 21 days from the time of preparation and to have a viscosity of no greater than 2.5 Pas, preferably 1 Pas at a shear rate of 21 s ⁇ 1.
  • Figure 1 shows a schematic representation of a typical ternary stability diagram for a blend of dodecyl benzene sulphonate (DoBS), a C12 ⁇ 15 fatty alcohol ethoxylated with an average of 7 moles of ethylene oxide, and a stabilising surfactant.
  • DoBS dodecyl benzene sulphonate
  • Locus I illustrates the boundary of compositions which are stable at one electrolyte level (say 10% by weight).
  • the broken lines A, B, C have the following meanings
  • Locus II shows the same boundary at a higher electrolye level (say 12.5% by weight).
  • FIG. 2 represents a system of 23% total surfactant, 10% sodium citrate and 67% water, the surfactants being dodecyl benzene sulphonate, C12 ⁇ 15E7 and the stabilising surfactant C12 ⁇ 13 G3 (see key at end of Example 1).
  • Ternary diagram a) shows the expected additive behavious from the binary systems whilst diagram b) shows the stability area found in practice. N.B. In these diagrams, numbers along the axes denote the fraction of surfactant with respect to the total surfactant in the composition.
  • the detergent active material in general, may comprise one or more surfactants, and whether in the primary or stabilising categories, may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof.
  • suitable nonionic types includes in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.
  • Specific nonionic detergent compounds are alkyl (C6-C18) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phospine oxides and dialkyl sulphoxides.
  • the primary anionic detergent surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols produced for example from tallow or coconut oil, sodium and potassium alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C8-C18) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyl taurine; alkane monos
  • an alkali metal soap of a fatty acid especially a soap of an acid having from 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid, and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palmkernel oil or mixtures thereof.
  • the sodium or potassium soaps of these acids can be used, the potassium soaps being preferred.
  • compositions also contain electrolyte in an amount sufficient to bring about structuring of the detergent active material.
  • the compositions contain from 1% to 60%, especially from 10 to 45% of a salting-out electrolyte.
  • Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646.
  • some salting-in electrolyte (as defined in the latter specification) may also be included, provided if of a kind and in an amount compatible with the other components and the composition is still in accordance with the definition of the invention claimed herein.
  • Some or all of the electrolyte may have detergency builder properties.
  • compositions according to the present invention include detergency builder material, some or all of which may be electrolyte.
  • the builder material is any capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, the suspension of soil removed from the fabric and the dispersion of the fabric softening clay material.
  • Examples of phosphorous-containing inorganic detergency builders when present, include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates.
  • Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates.
  • non-phosphorus-containing inorganic detergency builders when present, include water-insoluble alkali metal carbonates, bicarbinates, silicates and crystalline and amorphous alumino silicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites.
  • organic detergency builders when present, include the alkaline metal, ammonium and substituted ammonium polyacetyl carboxylates and polyhydroxysulphonates. Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilitriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids, citric acid, tartrate di-succinic acid and tartrate mono-succinic acid.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, fabric softeners such as clays, amines and amine oxides, lather depressants, oxygen-releasing bleaching agents such as tricloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases and amylases, germicides and colourants.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids
  • fabric softeners such as clays, amines and amine oxides
  • lather depressants oxygen-releasing bleaching agents such as tricloroisocyanuric acid
  • inorganic salts such as sodium sulphate
  • fluorescent agents such as fluorescent agents, perfumes, enzymes such as proteases and amylases, germicides and colourants.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (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)

Claims (11)

  1. Eine wässerige flüssige Reinigungsmittel-Zusammensetzung, enthaltend detergentaktives Material und gelösten Elektrolyt in Mengen, ausreichend, um eine Surfactant-Struktur innerhalb der Zusammensetzung zu liefern, wobei die Zusammensetzung im wesentlichen keine klare flüssige aktive reiche Schicht beim Zentrifugieren bei 750G während 20 Stunden bei 25°C liefert, worin das detergentaktive Material ein stabilisierendes Surfactant enthält, welches eine durchschnittliche Alkylkettenlänge von größer als 6 C-Atomen aufweist, und welches eine Aussalz-Beständigkeit von größer als oder gleich 6,4 aufweist.
  2. Zusammensetzung nach Anspruch 1, worin das detergentaktive Material auch ein nichtionisches Surfactant und/oder ein nichtalkoxyliertes anionisches Surfactant und/oder ein alkoxyliertes anionisches Surfactant enthält.
  3. Zusammensetzung nach einem der vorhergehenden Ansprüche, worin das stabilisierende Surfactant ausgewählt ist aus:
       Alkyl-polyalkoxylierte-phosphate;
       Alkyl-polyalkoxylierte-sulfosuccinate;
       Dialkyl-diphenyloxid-disulfonate;
       Alkylpolysaccharide;
       und Mischungen derselben.
  4. Zusammensetzung nach einem der vorhergehenden Ansprüche, worin das stabilisierende Surfactant, oder zumindest eines der stabilisierenden Surfactants eine Aussalz-Beständigkeit von größer als oder gleich 9,0 aufweist.
  5. Zusammensetzung nach einem der vorhergehenden Ansprüche, worin das stabilisierende Surfactant eine durchschnittliche Alkylkettenlänge von größer als 8 Kohlenstoffatomen aufweist.
  6. Zusammensetzung nach einem der vorhergehenden Ansprüche, worin das detergentaktive Material von 2 bis 50 Gewichtsprozent der gesamten Zusammensetzung ausmacht.
  7. Zusammensetzung nach einem der vorhergehenden Ansprüche, worin das stabilisierende Surfactant von 0,1 bis 45 Gewichtsprozent der gesamten Zusammensetzung ausmacht.
  8. Zusammensetzung nach einem der vorhergehenden Ansprüche, worin das stabilisierende Surfactant von 5 bis 90 Gewichtsprozent des detergentaktiven Materials ausmacht.
  9. Zusammensetzung nach einem der vorhergehenden Ansprüche, worin die Zusammensetzung von 1 bis 60 Gewichtsprozent eines Aussalz-Elektrolyten enthält, wobei alles oder ein Teil davon den gelösten Elektrolyt ausmacht.
  10. Zusammensetzung nach Anspruch 9, worin der Aussalz-Elektrolyt von 10 bis 45 Gewichtsprozent der gesamten Zusammensetzung ausmacht.
  11. Zusammensetzung nach einem der vorhergehenden Ansprüche, welche nicht mehr als 2 Gewichtsprozent Phasentrennung bei Lagerung bei 25°C während 21 Tagen von dem Zeitpunkt der Herstellung liefert und eine Viskosität von nicht größer als 1 Pas bei einer Scherrate von 21 s⁻¹ aufweist.
EP89200163A 1988-02-10 1989-01-26 Flüssige Reinigungsmittel Expired - Lifetime EP0328177B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8803036 1988-02-10
GB888803036A GB8803036D0 (en) 1988-02-10 1988-02-10 Liquid detergents

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EP0328177A2 EP0328177A2 (de) 1989-08-16
EP0328177A3 EP0328177A3 (en) 1990-07-04
EP0328177B1 true EP0328177B1 (de) 1994-08-03

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EP (1) EP0328177B1 (de)
JP (1) JPH06102795B2 (de)
AU (1) AU606501B2 (de)
BR (1) BR8900560A (de)
CA (1) CA1311398C (de)
DE (1) DE68917167T2 (de)
ES (1) ES2057087T3 (de)
GB (1) GB8803036D0 (de)
ZA (1) ZA891064B (de)

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ZA891064B (en) 1990-10-31
GB8803036D0 (en) 1988-03-09
AU606501B2 (en) 1991-02-07
JPH06102795B2 (ja) 1994-12-14
AU2967589A (en) 1989-08-10
ES2057087T3 (es) 1994-10-16
EP0328177A3 (en) 1990-07-04
CA1311398C (en) 1992-12-15
EP0328177A2 (de) 1989-08-16
JPH01268800A (ja) 1989-10-26
DE68917167D1 (de) 1994-09-08
BR8900560A (pt) 1989-10-10
DE68917167T2 (de) 1994-11-24

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