EP2877564B1 - Flüssige reinigungsmittelzusammensetzung - Google Patents

Flüssige reinigungsmittelzusammensetzung Download PDF

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Publication number
EP2877564B1
EP2877564B1 EP13735295.1A EP13735295A EP2877564B1 EP 2877564 B1 EP2877564 B1 EP 2877564B1 EP 13735295 A EP13735295 A EP 13735295A EP 2877564 B1 EP2877564 B1 EP 2877564B1
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EP
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Prior art keywords
oil
mpa
fat
composition
surfactant
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EP13735295.1A
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English (en)
French (fr)
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EP2877564A1 (de
Inventor
Deeleep Kumar Rout
Ritesh Kumar Sinha
Pintu PAUL
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/201—Monohydric alcohols linear
    • C11D3/2013—Monohydric alcohols linear fatty or with at least 8 carbon atoms in the alkyl chain
    • 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
    • C11D3/2093—Esters; Carbonates

Definitions

  • the present invention is in the field of stable detergent compositions; in particular liquid crystal ternary lamellar phase detergent compositions, for use in laundry and/or household cleaning amongst others.
  • Liquid detergent compositions are widely known in the art and are widely favoured by modern day consumers. Such liquid detergent compositions are principally used in fabric cleaning and household care applications. Present day consumer's are looking for stable, non-phase separating and moderately viscous liquids for fabric cleaning and household care applications.
  • Liquid detergent compositions generally comprise a surfactant active and a solvent. They may further comprise perfume, bleach, thickeners, fluorescers, and other common detergent ingredients. Such compositions are often structured, e.g. to control the viscosity of the liquid or to improve stability and prevent phase separation or to be able to incorporate ingredients that are water insoluble.
  • Lamellar phase cleaning compositions as a vehicle for delivering typically surfactant blends to a cleaning location provide a solution to that has proved useful to a large extent.
  • a lamellar phase system consist of a surfactant bilayer packed with hydrophobic (water-rejecting) alkyl tails inwardly directed and polar hydrophilic (water-attracting) head groups on the outside surfaces.
  • the lamellar phase can be obtained at a certain range of temperature and can, under certain conditions, it is known to the skilled person that lamellar phases possess very high capacity to solubilise oil and fats.
  • micro-emulsion compositions do not provide desired soil removal when challenged with cleaning of tough soils and mixtures of oily and particulate soils.
  • EP 637 629 A1 (Colgate Palmolive) discloses a stable, clear, all-purpose microemulsion cleaner with surfactants 1- 20 %. Under low temperature and high temperature conditions, often encountered while shipping product or storing product in a warehouse, microemulsions exhibiting stability in a fairly narrow temperature range tend to become unstable. As a result, the microemulsion phase separates and the effectiveness of the composition for removing soil is decreased. In addition, when such a phase separation occurs, it may take a considerable amount of time for the microemulsion to reform. In general, cleaning operations until a composition forms a microemulsion in order to obtain optimum cleaning benefits.
  • EP 160 762 A1 discloses a micro-emulsion sample comprising 1-40%w of surfactant. It uses paraffin as solvent. Paraffin is not considered an effective solvent for sebum and polymerized fats majorly found in cuffs and collars. Also, paraffin has a reduced rate of biodegradability. Biodegradation refers to the ability of a material to be broken down by the action of bacteria and other living organisms. Most of the detergents containing paraffin have slow biodegradation and hence they may cause pollution.
  • WO 97/32967 A1 Cold Palmolive discloses a liquid crystal detergent composition, and micro emulsions with 2-66% surfactants. However, it is found that the cleaning performance of the compositions of WO 97/32967 leaves to be desired, especially for fatty stains, such as sebum. This is thought to be caused by the lack of fat solubilising materials in the composition.
  • compositions with such high active levels have little formulation space left for fat solubilising materials such as oils.
  • efficient cleaning of fabric articles especially the removal of soils such as sebum from cuffs and collars, remains to be desired.
  • a further co-pending application WO 2011/073062 discloses a bi-continuous micro-emulsion detergent composition comprising a short chain non-ionic surfactant, however micro-emulsions are typically less viscous and less temperature stable and therefore not appreciated by modern day consumers. To provide a temperature stable thickened detergent composition remains to be desired.
  • a lamellar phase detergent composition comprising a surfactant selected from non-ionic and anionic surfactants in a ratio of non-ionic:anionic surfactant from 3:1 to 1:4 and having HLB value of not less than 15, a fat solubilising oil and water provides an effective solution that removes soils and/or stains containing solid or solidified fatty material; is stable at normal storage and washing conditions and may be delivered as a pourable liquid.
  • the present invention provides a liquid detergent composition
  • a surfactant selected from non-ionic and anionic surfactants in a ratio of non-ionic : anionic surfactant from 3:1 to 1:4 and having HLB value(Davies Scale) of not less than 15, 1.25-16% by weight of a fat solubilizing oil, having a Hansen solubility parameter (• HSP) that ranges from 14-22 MPa1/2 (at 25°C), and wherein the Hansen polar component (• P) is in the range of 0.5-10 MPa1/2 (at 25°C), the dispersion component (• H) is in the range of 3-10 MPa1/2 (at 25 °C) and the hydrogen bond component (• D) is in the range of 13-18 MPa1/2 (at 25°C); and water upto 100%; and wherein, the surfactant to fat solubilising oil ratio ranges from 2.5 to 8 and the fat solubilising oil on (fat solubilising oil + water) ratio ranges from 0.03
  • the invention provides a method for washing fabric articles comprising the steps of dosing between 2-20 ml of the composition according to the invention per litre of wash or cleaning liquor.
  • the present invention provides a liquid detergent composition
  • a liquid detergent composition comprising of a surfactant, a fat solubilising oil and water.
  • the detergent compositions according to the invention include 10 wt% to less than 40 wt% surfactant.
  • Surfactants are included in the formulation for primary cleaning action and are chosen from anionic and non-ionic surfactants.
  • the non-ionic and anionic surfactants are in a ratio such that the non-ionic : anionic surfactant ratio is from 3:1 to 1:4, preferably from 2:1 to 1:2.
  • the surfactant system according to the invention is defined by an HLB value.
  • HLB value defines the hydrophilic to lipophilic balance of the surfactant system.
  • the HLB system predicts the optimum emulsion stability when the HLB value of the surfactant system matches the required HLB of the oil/water system.
  • the required HLB is the value at which enhanced emulsion stability will be attained.
  • a stable lamellar phase detergent composition is obtained when the HLB value of the mixed surfactant system is not less than 15.
  • Anionic surfactants are well known in the art and are primarily important for soil removal. These include, but not limited to, carboxylates (soaps), such as Sodium laurate and Sodium myristate, dicarboxylates, sulphates, e.g. Sodium dodecyl sulphate (SDS) and sulphonates, e.g. Sodium salts of linear alkyl benzene sulphonates, more preferably, Sodium lauryl ether sulphate (SLES), preferably having 1 to 9 ethylene oxide groups; and Linear Alkylbenzene Sulfonate (LAS).
  • carboxylates such as Sodium laurate and Sodium myristate
  • dicarboxylates e.g. Sodium dodecyl sulphate (SDS)
  • SDS Sodium dodecyl sulphate
  • SLES Sodium lauryl ether sulphate
  • LAS Linear Alkylbenzen
  • Non-ionic surfactants are also well-known in the art and are known for oil removal from soiled fabric.
  • the preferred non-ionic surfactant is alkoxylated fatty alcohol, which typically comprises from 1 to 100 ethoxy and/or propoxy groups, more preferably 1-12 ethoxy or propoxy groups.
  • Other non-ionic surfactants include mono- or di-alkanolamide groups in chemical combination with an organic hydrophobic group derived from, for example, fatty alcohols with from 8 to 16 carbon atoms (optionally branched, e.g.
  • alkylphenols preferably from 8 to 20 carbon atoms
  • the alkyl group contains from about 6 to about 12 carbon atoms
  • dialkylphenols in which each alkyl group contains from 6 to 12 carbon atoms
  • primary, secondary or tertiary aliphatic alcohols or alkyl-capped derivatives thereof
  • monocarboxylic acids having from 8 to about 24 carbon atoms in the alkyl group and polyoxypropylenes.
  • Alkyl poly glucosides are also considered in the context of the present invention.
  • the composition comprises not more than 35%, still more preferably not more than 30%, or even not more than 25%, while the composition preferably comprises at least 15%, still more preferably at least 20% by weight of the composition of total surfactant.
  • the fat solubilising solvent is the fat solubilising solvent
  • the composition includes a fat solubilising solvent at 1.25 wt% to 16 wt%.
  • the solvent helps solubilise sebum present in sebaceous soil.
  • the Hansen Solubility Parameter (HSP, or • HSP ) of the solvent is from 14 to 22 MPa 1/2 (at 25°C), preferably 15 to 20 MPa 1/2 (at 25°C), more preferably from 15 to 18.5 MPa 1/2 (at 25°C).
  • the Hansen Solubility Parameter (• HSP ) of sebum is from 15 to 18.5 Mpa 1/2 .
  • the • HSP of the solvent should not deviate too much from the • HSP of the sebum, hence the above ranges.
  • Paraffin oil is not preferred, because the P and H values do not closely match that of sebum. This means that the polarity and hydrogen bonding of paraffin oil is less than optimal.
  • Hansen Solubility Parameters were developed by Charles Hansen as a way of predicting if one material will dissolve in another to form a solution. The parameters are based on the idea that like dissolves like where one molecule is defined as being 'like' another if it bonds to itself in a similar way. Specifically, each molecule is given three Hansen parameters, each generally measured in MPa 1/2 .
  • the solubility parameter has been defined as the square root of the cohesive energy density and describes the attractive strength between molecules of the material. Hansen assumed that the cohesive energy arises from the dispersive, permanent dipole-dipole interactions and hydrogen bonding forces.
  • the basis of the Hansen solubility parameter (• HSP ) is that the total energy of vaporisation of a liquid consists of several individual parts. Hansen has defined three types of contributions to the energy of vaporisation, namely: dispersive (D), polar (P) and hydrogen bonding (H). The three parameters are:
  • Each of the three parameters represents a different characteristic of solvency, or solvent capability.
  • the three parameters are a measure of the overall strength and selectivity of a solvent.
  • the total Hansen solubility parameter which is the square root of the sum of the squares of the three parameters mentioned previously, provides a more general description of the solvency of the solvents.
  • the polar component (• P ) is in the range of 0.5 - 10 MPa 1/2 (at 25°C), preferably 1 to 8 MPa 1/2 (at 25°C), more preferably 2 - 6 MPa 1/2 (at 25°C), still more preferably 3 - 5 MPa 1/2 (at 25°C).
  • the hydrogen bond component (• H) is in the range of 3 - 10 MPa 1/2 (at 25°C), preferably 3 to 8 MPa 1/2 (at 25°C), more preferably 3 - 7 MPa 1/2 (at 25°C), still more preferably 3 - 6 MPa 1/2 (at 25°C).
  • the dispersion component (• D ) is in the range of 13 - 18 MPa 1/2 (at 25°C), preferably 14 to 17 MPa 1/2 (at 25 °C), more preferably 15 - 16 MPa 1/2 (at 25°C).
  • Hansen Solubility Parameter may either be calculated or predicted using the methods disclosed in " Hansen Solubility Parameters: a User's Handbook", by Charles M. Hansen, CRC Press, Boca Raton, 2000 . Hansen Solubility Parameters of any solvent may also be calculated by "Molecular Modelling Pro” software, version 5.1.9 (ChemSW, Fairfield CA, www.chemsw.com) or Hansen Solubility from Dynacomp Software.
  • Preferred fat solubilising solvents are oils selected from alkyl esters of fatty acids, mono, di- or tri-glycerides of fatty acids and fatty alcohol having a chain length 8 to 16, preferably 10-12 carbon atoms.
  • alkyl esters of fatty acids examples include methyl octanoate, ethyl octanoate, propyl dodecanoate and butyl tetradocanoate.
  • Examples of mono, di- and tri-glycerides of fatty acids include glycerol trioleate, glycerol tri-iso-myristate, glycerol mono caproate, glycerol dioleate, and glycerol tricaprylate.
  • fatty alcohol examples include decanol, dodecanol.
  • alkyl esters and their HSP values are given in the table below: Table A fat solubilizers • D MPa 1/2 • P MPa 1/2 • H MPa 1/2 Total SP MPa 1/2 Methyl octanoate 15.9 4.4 6.1 17.9 Ethyl octanoate 15.9 4.3 5.8 17.7 Methyl dodecanoate 16.2 3.5 5.1 17.3 Ethyl dodecanoate 16.2 3.5 5.3 17.2 Butyl oleate 16.3 3.7 4.2 16.7 Ethyl caproate 15.5 3.2 5.9 17.4 Ethyl oleate 14.5 3.8 3.7 16.8 Isopropyl palmitate 14.3 3.9 3.7 17.2
  • the fat solubilising oil is typically present in the composition in a concentration of at least 3%, more preferably at least 5%, even more preferably at least 8% or still more preferably at least 10%, while the composition typically comprises not more than 15%, more preferably not more than 13%by weight of the composition.
  • the composition further comprises water adding upto a 100% by weight of the total composition, preferably between 44 and 88%,more preferably not more than 80%, still more preferably not more than 75%, yet more preferably not more than 70%, even more preferably not more than 65%, or most preferably not more than 60% by weight of the composition.
  • the composition is preferably somewhat viscous. Consumers typically do not associate water thin compositions with high active (i.e. concentrated) detergent compositions. However, the viscosity should not be so high that the liquid is no longer pourable.
  • Viscosity describes a fluid's internal resistance to flow and may be thought of as a measure of fluid friction. Simply put, the less viscous the fluid is, the greater its ease of movement (fluidity).
  • the Viscosity of the compositions according to the invention is preferably between 50 and 2000 mPa.s (25°C and 20s -1 ), more preferably between 100 to 1000, when measured with a TA instrument rheometer AR-1000, with a cone and plate set-up, acrylic/steel 4 cm diameter, 2° angle, truncation gap 52-56 micrometer, in steady flow operation.
  • a lamellar phase detergent composition is preferably stable in ambient temperature throughout the year.
  • the lamellar phase detergent composition of the present invention is typically stable at a temperature range of between 0 and 60°C. When the composition is allowed to freeze too deep or repeatedly, an irreversible phase separation may be observed. On the other hand, when the temperature goes above 60°C, a reversible phase separation may be observed.
  • the lamellar phase detergent composition is found to be the stable when having a fat solubilising oil upon the total fat solubilising oil and water ratio ranging from 0.03 to 0.3, preferably from 0.05 to 0.1.
  • the lamellar phase detergent composition is found to be stable when having a surfactant to fat solubilising oil ratio ranging from 2.5 to 8, preferably from 3 to 6.
  • compositions may also include optional ingredients selected from an enzyme, preferably mannanases and savinases, a sequestrant, preferably a phosphonic acid sequestrant, a soil suspending agent, an electrolyte, a shading dye, a perfume or a fluorescer.
  • an enzyme preferably mannanases and savinases
  • a sequestrant preferably a phosphonic acid sequestrant
  • a soil suspending agent preferably an electrolyte
  • a shading dye preferably a perfume or a fluorescer.
  • the invention provides a method for washing fabric articles comprising the steps of dosing between 2-20 ml of the composition according to the invention per litre of wash or cleaning liquor; preferably between 4 and 12 ml of the composition per liter of wash or cleaning liquor.
  • the fabric articles are ideally added to the wash liquor in liquor:fabric article ratio of between 2.5:1 and 15:1, for hand wash or front loading washing machines the ratio is preferably 4:1 to 8:1; while for top load machines the ratio is typically 6:1 to 12:1.
  • composition according to the invention may also be applied neat onto the fabric article.
  • composition When washing household surfaces the composition may be diluted in a bucket for cleaning floors and other surfaces or put into a trigger spray dispenser for direct application onto a surface.
  • composition according to the invention may also be applied neat onto a sponge, cloth or brush and used directly onto the surface.
  • a ternary diagram of the detergent composition is represented in the Figure ( Figure 1 ) in form of a triangle, where each of the three apexes represents a component of the composition, such as surfactant (S), fat solubilising oil (O) and water (W).
  • S surfactant
  • O fat solubilising oil
  • W water
  • a point plotted at the top of the vertical line nearest S indicates 100% S.
  • a horizontal bar at the bottom of the line (farthest from S) represents 0% of S.
  • Point O is at the lower right apex of the triangle.
  • Point W is at the lower left apex of the triangle.
  • SLES Sodium lauryl ether sulphate: - Texapon N70 LS-J (SLES 3EO) (ex Cognis), - Galaxy LES 70 2EO
  • NaLAS Sodium Linear alkylbenzene sulphonate (Las acid ex Rhodia, neutralised with NaOH by Unilever India).
  • C12EO7 C 12 fatty alcohol having 7 moles of ethylene oxide per mole of alcohol
  • EPEI Sokalan-HP20 (ex BASF)
  • NaPAA Sodium Polyacrylic acid (ex Dow chemicals)
  • Dequest ex Thermphos NaCl: ex Merck NaOH: ex Merck Tinopal CBSX: ex Ciba
  • Viscosity measurement was done using Viscometer both at constant temperature (varying shear rate) and at constant shear (varying temperature). Parameters associated with the viscosity measurement are given below: Viscometer : TA Instruments, CSL Rheometer. Operating pressure : 4 kg/cm 2 Geometry : Cone and Plate, Acrylic 4 cm diameter. 2 Degree angle, gap 52-56 micron (zero gap correction) Procedure : Steady flow Temperature : 25 °C
  • Z-value indicates how many standard deviations an observation or datum is above or below the mean. It is a dimensionless quantity derived by subtracting the population mean from an individual raw score and then dividing the difference by the population standard deviation.
  • Sebum removal was estimated by Iodine value method, wherein the sebum remaining on the washed fabric swatches were directly estimated by measuring the Iodine value of the sebum.
  • the reflectance of the fabric swatches was measured at • R460 (values at 460 nanometer, UV excluded and included) using a Macbeth 7100 color eye reflectometer. SAV aperture and SAV lens were used for the measurement. Reflectance measurements were carried out on new fabric pieces and after wash. 'SRI' is defined as soil removal index. This is mostly used for colored stains. A positive delta SRI means a better soil removal.
  • Lamellar phase in the present invention is detected through a microscope using polarized light or by x- ray diffraction.
  • Lamellar phase can be seen as "the Maltese crosses” when viewed through a microscope using polarized light and as having a spacing of 1:1/2;1/3 between bilayers when detected through small angle x-ray diffraction.
  • This example demonstrates the improved collar soil cleaning exhibited on consumer fabrics in comparison to products already available.
  • compositions The following compositions were compared with commercially available liquid washing detergent (Omo, ex Unilever Thailand, 2011). The compositions were prepared by the method as described above. Table 1 Ingredients (wt%) Ex E Ex F C12EO7 11 8.8 SLES 5.5 6.6 NaLAS 5.5 6.6 Methyl laurate 5 5 Minors 1) 8.86 8.86 Water QS 64.14 64.14 Oil /( oil + water) 0.07 0.07 Surf/Oil 4.4 4.4 Non-ionic to anionic ratio 1:1 1:1.5 HLB 20.66 22.833 Viscosity@20s -1 700 cP 700 cP Phase Lamellar Lamellar 1) Minors include soil release polymer (NaPAA, 1%), Soda (0.8%), NaCl (4%), Sequestrant (Dequest-2010, 1.69%), Fluorescer (Tinopal CBSX, 0.12%), Perfume (0.5%) and Enzyme (0.75%)
  • Soiling procedure 20 shirts (10 cotton and 10 polycotton) were given to a test panel to generate soil and the soiled shirts were cleaned the following day.
  • washing procedure The soiled shirts were cut into two halves. For each shirt, one half was tested with the example composition of the present invention and the other half with a control sample, which is a product available in the market. They were washed in commercially available washing machines as direct wash. In direct wash, 35 ml of the formulation was divided among 20 half collars and directly applied onto the collar.
  • the samples were evaluated in pairs by trained panellists.
  • the panellists compared one half of the shirt washed with the example composition with the other half of the shirt washed with the control, to check if the result was in favour of the composition of the invention, the control or was equal.
  • Table 2 illustrates superior collar cleaning properties of the detergent compositions (Ex E and Ex F) of the present invention over Omo. Table 2 Number of collars in favor Ex E Ex F Invention 14 10 Omo 5 8 Parity 1 2
  • the detergent compositions of the present invention have a better cleaning performance on collars than Omo.
  • the number of collars cleaned by the detergent compositions of the present invention is higher than the number of collars cleaned by Omo.
  • This example demonstrates the improved collar soil cleaning exhibited on consumer fabrics in comparison to a composition (Comp H) outside the scope of the present invention which is devoid of a fat solubilising oil.
  • compositions The following compositions were compared with each other to demonstrate the superior collar cleaning properties of the composition of the present invention (Ex G) having a non-ionic to anionic surfactant ratio of 1:1.
  • the compositions were prepared by the method as described above.
  • Table 3 Ingredients (wt%) Ex G Comp H C12E07 11 11 SLES 5.5 5.5 NaLAS 5.5 5.5 Methyl laurate 5 0 Minors 1) 0.1 0.1 Water QS 72.9 77.9 Oil /( oil + water) 0.06 0.00 Surf/Oil 4.4 - Non-ionic to anionic ratio 1:1 1:1 HLB 20.66 20.66 Viscosity@20s -1 700 cP - Phase Lamellar Micelles 1) Minors include NaCl only
  • Soiling procedure 20 shirts (10 cotton and 10 polycotton) were given to a test panel to generate soil and the soiled shirts were cleaned the following day.
  • washing procedure The soiled shirts were cut into two halves. For each shirt, one half was tested with the example composition of the present invention and the other half with a control sample, which is a comparative example. They were washed in commercially available washing machines as direct wash. In direct wash, 35 ml of the formulation was divided among 20 half collars and directly applied onto the collar.
  • the samples were evaluated in pairs by trained panellists.
  • Table 4 illustrates superior collar cleaning properties of the detergent compositions of the present invention over comparative example Comp H.
  • the detergent compositions of the present invention have a better cleaning performance on collars than comparative example Comp H.
  • Table 4 Number of collars in favour Ex G Invention 10 Parity 5 Comp H 5 (Only surfactant and electrolyte)
  • This example demonstrates the improved collar soil cleaning exhibited on consumer fabrics in comparison to a composition (Comp T) outside the scope of the present invention which is devoid of a fat solubilising oil.
  • compositions The following compositions were compared with each other to demonstrate the superior collar cleaning properties of the composition of the present invention (Ex S) having a non-ionic to anionic surfactant ratio of 3:1.
  • the compositions were prepared by the method as described above.
  • Table 5 Ingredients (wt%) Ex S Comp T C12E07 21 21 SLES 3.5 3.5 NaLAS 3.5 3.5 Methyl laurate 7 0 Minors 1) 0.1 0.1 Water QS 64.9 71.9 Oil /( oil + water) 0.10 0.00 Surf/Oil 4.0 - Non-ionic to anionic ratio 3:1 3:1 HLB 15.236 15.236 Viscosity@20S -1 900 cP >10000 cP Phase Lamellar Hexagonal 1) Minors include NaCl only
  • Soiling procedure 20 shirts (10 cotton and 10 polycotton) were given to a test panel to generate soil and the soiled shirts were cleaned the following day.
  • washing procedure The soiled shirts were cut into two halves. For each shirt, one half was tested with the example composition of the present invention and the other half with a control sample, which is a comparative example. They were washed in commercially available washing machines as solution wash.
  • the samples were evaluated in pairs by trained panellists.
  • Table 6 illustrates superior collar cleaning properties of the detergent compositions of the present invention over comparative example Comp T.
  • the detergent compositions of the present invention have a better cleaning performance on collars than Comp T.
  • Table 6 Number of collars in favour Ex S Invention 10 Parity 6 Comp T 4 (Only surfactant and electrolyte)
  • comparative compositions were formulated with only the surfactants in a concentration outside the scope of the present invention.
  • the compositions were prepared by the method as described above.
  • the comparative compositions were the following: Table 7 Ingredients (wt%) Comp X Comp AG C12E07 5 3.75 SLES 2 1.875 NaLAS 2 1.875 Methyl laurate 5 1.875 EPEI sokalan HP-20 2.5 2.5 NaPAA-2000 0 0 NaOH 0.35 0.7 NaCl 2 4 Dequest-2010 0.85 1.69 CBSX 0.06 0.12 Perfume 0.25 0.5 Enzyme 0.38 0.75 Water QS 79.62 80.365 Oil /( oil + water) 0.06 0.02 Surf/Oil 1.8 4 Non-ionic to anionic ratio 1.25:1 1:1 HLB 19.45 20.66 Viscosity@20s -1 - - Phase Emulsion Emulsion
  • the liquid detergent composition of the present invention is not in a lamellar phase, but an emulsion, which is not preferred.
  • compositions The following compositions were compared with each other to demonstrate the effect of the HLB value of the surfactants.
  • Ex B and Ex AB are compositions according to the present invention and Comp AA is a comparative example composition having an HLB value below 15.
  • the compositions were prepared by the method as described above.
  • Example 4 Cleaning performance of the detergent compositions on sebum and carbon soot soiling
  • This example illustrates the cleaning performance of the detergent composition of Ex S (formulation as in table 5) in comparison to Comp T (comparative composition devoid of a fat solubilising oil) (formulation as in table 5) on sebum and carbon soot soiling.
  • Soiling procedure Synthetic sebum (composition see table below) was mixed with carbon soot in the ratio of 10000:1 by weight, melted at 50°C and sonicated for 45 minutes at 50 °C. An amount of 0.2 ml of this mixture was loaded on to preheated (50 °C - 60 °C) desized cotton, polycotton and polyester fabrics of area 100 cm 2 weighing about 1.7 g (approximately 10 wt.% of the fabric weight). These soiled swatches were stored in the freezer (-5 °C) prior to use and used when required.
  • Sebum removal and reflectance values (Delta R) for the compared samples are given in the table below.
  • Table 9 Fabric type % Sebum removed (within error of ⁇ 0.5 units) Delta R (reflectance within error of ⁇ 1.5 units) Ex S Comp T Ex S Comp T Cotton 70.8 69.6 17.09 16 Poly cotton 59 43 18.4 13.6 Poly ester 27 14.5 15 11.5
  • Example 4a Cleaning performance of the detergent compositions on dirty motor oil soiling
  • Soiling procedure For dirty motor oil (DMO) preparation, commercially available engine oil and waste diesel oil of a generator were mixed in a ratio of 1:1 by weight and sonicated for 15 minutes at room temperature. 0.2 ml of this DMO was applied on each swatch and kept it as such for 4 days at room temperature (27°C to 30°C). These soiled swatches were stored in the freezer prior to use and used when required.
  • DMO dirty motor oil
  • Example 4b Cleaning performance of the detergent compositions on WFK fabric
  • Example 4c Cleaning performance of the detergent compositions on standard stain sets
  • This example shows the cleaning performance of the compositions of the present invention against Ariel gel or Comparative compositions on standard stain sets in solution wash application or direct wash.
  • compositions The following compositions were used for the comparative study. The compositions were prepared by the method as described above. The commercially available liquid washing detergents used in comparison were Ariel gel actilift (The Procter &Gamble Company, USA) and Omo liquid (ex Unilever, Thailand). Comp U is an unstable comparative example composition formulated without a fat solubilising oil.
  • a detergent product weighing 35 g was directly dispensed into a washing machine (Samsung top loader or IFB front loader), followed by the standard stain sets. Along with the standard stain sets, fabric ballast was also added.
  • Stain removal indices (Delta SRI) for the compared samples on various stains are given in the tables below.
  • Table 13 indicates the stain removal indices of example compositions Ex O, Q, R and N of the present invention against Ariel gel.
  • Table 13 Stain/formulation/SRI Ex O(B) vs Ariel gel Ex Q(B) vs Ariel gel Ex R(B) vs Ariel gel Ex N(B) vs Ariel gel Ragu/sunflower 1.47 ⁇ 0.35 4.55 ⁇ 0.72 0.84 ⁇ 0.44 0.66 ⁇ 0.46 Tomato ketchup 0.78 ⁇ 1.1 -0.8 ⁇ 2.2 0.4 ⁇ 0.97 0.65 ⁇ 1.27 Face make up-2 3.515 ⁇ 0.76 2.1 ⁇ 0.3 10.5 ⁇ 1.66 -1 ⁇ 1.09 Green curry 2.1 ⁇ 0.33 3.5 ⁇ 0.9 2.1 ⁇ 0.88 0.9 ⁇ 1.25 Mechanical grease 8.01 ⁇ 3.07 -2.13 ⁇ 4.57 8.7 ⁇ 2.4 1.45 ⁇ 5.4 Sebum 3.7 ⁇ 2 7 ⁇ 2.7 2.8 ⁇ 3.3 6.3 ⁇ 1.65 Hamburger grease 4.3 ⁇ 2.9 0.15 ⁇ 5.87 0.44 ⁇ 3.2 1.24 ⁇ 2.6 Beef patty dripping
  • Table 14 indicates the stain removal indices of example compositions Ex J and K of the present invention against Ariel gel and also Ex K against comparative example composition U.
  • Table 14 Stain Delta SRI J(B) vs Ariel gel Delta SRI K(D) vs Ariel gel Delta SRI U(D) vs K(D) Tomato + sunflower oil 2.78 ⁇ 2.2 -8 ⁇ 1 -8.0 ⁇ 1.3
  • Rimmel lipstic coral in gold -2.2 ⁇ 2.6 30 ⁇ 5 -8.3 ⁇ 7.4 Kiwi black shoe polish 3.5 ⁇ 2.7 14 ⁇ 3 14.3 ⁇ 1.7 Yellow curry razah 5 ⁇ 0.63 3 ⁇ 1 -0.2 ⁇ 2.0 Red curry- osman 4.5 ⁇ 0.77 1 ⁇ 1 -2.1 ⁇ 2.3
  • Face makeup 1 1.2 ⁇ 1.65 2 ⁇ 1 -0.1 ⁇ 0.7 Lard violet dye -4.3 ⁇ 0.68 -3 ⁇ 3 5.6 ⁇ 2.5
  • Table 15 indicates the stain removal indices of example compositions Ex I of the present invention against Omo.
  • Table 15 Stain set complete Delta SRI I(D) Vs Omo Yellow rajah curry -22.8 ⁇ 24.3 DMO -18.5 ⁇ 11.2 Lard+ Violet dye -10.3 ⁇ 8.9
  • Fountain ink -8.5 ⁇ 0.8 Dende oil unheated -8.5 ⁇ 2.8 Face make up 2 -3.0 ⁇ 1.0
  • Tomato ketchup 0.8 ⁇ 0.7 Green curry + tinned coconut cream 0.8 ⁇ 0.6 Red Pepper/oil/water 1.2 ⁇ 1.0 Rubbed grass 1.3 ⁇ 0.4 Blood 1.4 ⁇ 0.9 Pureed carrot HIP 1.5 ⁇ 1.5 Fruiji chocolate milk shake 1.5 ⁇ 2.3
  • Gravy Vlarr 1.6 ⁇

Landscapes

  • 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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (9)

  1. Laminarphasige, flüssige Reinigungsmittelzusammensetzung, umfassend:
    a 10 bis 40 Gewichts-% eines Tensids, ausgewählt unter nicht-ionischen und anionischen Tensiden in einem Verhältnis von nicht-ionischem Tensid : anionischem Tensid von 3:1 bis 1:4 und mit einem HLB-Wert (Davies-Skala) von nicht weniger als 15,
    b 1,25 bis 16 Gewichts-% eines Fett löslichmachenden Öls mit einem Hansen-Löslichkeitsparameter (*HSP), der zwischen 14 und 22 MPa1/2 (bei 25°C) schwankt, und wobei die Hansen-Polarkomponente (*p) in dem Bereich von 0,5 bis 10 MPa1/2 (bei 25°C) liegt, die Dispersionskomponente (*H) in dem Bereich von 3 bis 10 MPa1/2 (bei 25°C) und die Wasserstoffbrückenkomponente (*D) in dem Bereich von 13 bis 18 MPa1/2 (bei 25°C) liegt und
    c bis zu 100% Wasser und
    wobei das Verhältnis des Tensids zu dem Fett löslichmachenden Öl zwischen 2,5 und 8 und das Verhältnis von Fett löslichmachendem Öl zu (Fett löslichmachendes Öl + Wasser) zwischen 0,03 und 0,3 schwankt.
  2. Zusammensetzung gemäß Anspruch 1, wobei das Fett löslich machende Öl unter Alkylestern von Fettsäuren, Mono-, Di- oder Tri-Glyceriden von Fettsäuren und Fettalkohol einer Kettenlänge von 8 bis 16, vorzugsweise 10 bis 12 Kohlenstoffatomen, ausgewählt ist.
  3. Zusammensetzung gemäß Anspruch 1 oder 2, worin die Viskosität der Zusammensetzung zwischen 50 und 2000 mPa.s (bei 25°C und 20 s-1 in einem TA-Instrument-Rheometer AR-1000, mit einem Kegel- und Platten-Aufbau, Acryl 4 cm Durchmesser, 2° Winkel, Truncationsspalt 56 Mikrometer) liegt.
  4. Zusammensetzung gemäß irgendeinem der vorhergehenden Ansprüche, wobei das Verhältnis von Fett löslichmachendem Öl zu (Fett löslichmachendem Öl + Wasser) zwischen 0,05 und 0,1 schwankt.
  5. Zusammensetzung gemäß irgendeinem der vorhergehenden Ansprüche, wobei das Verhältnis des Tensids zu dem Fett löslichmachenden Öl zwischen 3 und 6 schwankt.
  6. Zusammensetzung gemäß irgendeinem der vorhergehenden Ansprüche, wobei das Fett löslichmachende Öl einen Hansen-Löslichkeitsparameter (*HSP) aufweist, der zwischen 15 und 18,5 MPa1/2 (bei 25°C) schwankt und wobei die Hansen-Polarkomponente (*P) in dem Bereich von 1 bis 8 MPa1/2 (bei 25°C) liegt, die Dispersionskomponente (*H) in dem Bereich von 3 bis 8 MPa1/2 (bei 25°C) liegt und die Wasserstoffbrückenkomponente (*D) in dem Bereich von 14 bis 17 MPa1/2 (bei 25°C) liegt.
  7. Verfahren zum Waschen von Textilien, umfassend die Schritte:
    a Zudosieren von 2 bis 20 ml der Zusammensetzung gemäß irgendeinem der vorhergehenden Ansprüche pro Liter Wasch- und Reinigungsflotte.
  8. Verfahren gemäß Anspruch 7, wobei die Flotte eine Waschflotte ist und wobei die Textilien zu der Waschflotte in einem Verhältnis von Flotte : Textilien von 2,5:1 bis 15:1 gegeben werden.
  9. Verfahren gemäß Anspruch 7, wobei die Flotte eine Haushaltsreinigungsflotte darstellt.
EP13735295.1A 2012-07-26 2013-07-11 Flüssige reinigungsmittelzusammensetzung Not-in-force EP2877564B1 (de)

Priority Applications (1)

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Applications Claiming Priority (3)

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EP12177959 2012-07-26
PCT/EP2013/064699 WO2014016134A1 (en) 2012-07-26 2013-07-11 Liquid detergent composition
EP13735295.1A EP2877564B1 (de) 2012-07-26 2013-07-11 Flüssige reinigungsmittelzusammensetzung

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EP2877564A1 EP2877564A1 (de) 2015-06-03
EP2877564B1 true EP2877564B1 (de) 2016-06-29

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IN (1) IN2015MN00103A (de)
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DE102020007520A1 (de) 2020-12-09 2022-06-09 Ovidiu Dicoi Modifizierte strukturierte, fließfähige Wasch- und Reinigungsmittel

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TR201906872T4 (tr) * 2015-10-20 2019-05-21 Unilever Nv Substratların işleme tabi tutulması için bir bileşim ve usul.
US9796948B2 (en) 2016-01-13 2017-10-24 The Procter & Gamble Company Laundry detergent compositions comprising renewable components
CN112654695B (zh) * 2018-09-05 2022-09-27 联合利华知识产权控股有限公司 可发泡清洁组合物
DE102021132672A1 (de) * 2021-12-10 2023-06-15 Werner & Mertz Gmbh Verwendung einer Zusammensetzung und Zusammensetzung zum Vorbehandeln von Verschmutzungen an textilen Flächengebilden sowie Verfahren zum Entfernen von Verschmutzungen

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US5707957A (en) 1989-09-22 1998-01-13 Colgate-Palmolive Co. Liquid crystal compositions
NZ264113A (en) 1993-08-04 1996-06-25 Colgate Palmolive Co Liquid crystal or microemulsion liquid cleaners containing esterified polyethoxyether nonionic surfactant, anionic surfactant, cosurfactant, optionally a fatty acid, and water-insoluble hydrocarbon or perfume
DE4418487C2 (de) * 1994-05-27 1999-08-05 Gunter Dipl Chem Dr Feile Verfahren zur Herstellung einer Naßreinigungsmittelkombination nach dem Baukasten-System
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DE19527596A1 (de) * 1995-07-28 1997-01-30 Henkel Kgaa Wäßrige Tensidmischung
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Publication number Priority date Publication date Assignee Title
DE102020007520A1 (de) 2020-12-09 2022-06-09 Ovidiu Dicoi Modifizierte strukturierte, fließfähige Wasch- und Reinigungsmittel

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CN104487560A (zh) 2015-04-01
BR112015001328A2 (pt) 2018-05-22
EP2877564A1 (de) 2015-06-03
CN104487560B (zh) 2017-08-01
ZA201500321B (en) 2017-09-27
WO2014016134A1 (en) 2014-01-30
IN2015MN00103A (de) 2015-10-16
ES2594329T3 (es) 2016-12-19

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