Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • 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
  • C11D3/2017—Monohydric alcohols branched
  • C11D3/202—Monohydric alcohols branched 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. In today's world the consumer becomes more and more conscious of the environment and looks for ways to reduce waste.
• 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 above a certain transition 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. Accordingly, a stable and clear detergent composition that does not show phase separation on increased temperatures (e.g. up to 50°C), remains to be desired.
• increased temperatures e.g. up to 50°C
• EP 160 762 A1 discloses a micro-emulsion sample having surfactant 1 - 40%. It uses paraffin as solvents. 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 Coldgate 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 W097/32967 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
• a lamellar phase detergent composition comprising a surfactant selected from non-ionic and anionic surfactants in a ratio of non-ionic:anionic surfactant between 5:1 and 1 :1 ; having a fat solubilising oil and water, provides an effective solution that removes soils and/or stains of 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 between 5:1 and 1 :1 , 1 -30% by weight of a fat solubilizing oil, having a Hansen solubility parameter (5 H SP) that ranges from 14-22 MPa1/2 (at 25°C), and wherein the Hansen polar component ( ⁇ ) is in the range of 0.5-10 MPa1/2 (at 25°C), the dispersion component ( ⁇ ) is in the range of 3-10 MPa1/2 (at 25°C) and the hydrogen bond component (5D ) is in the range of 13-18 MPa1/2 (at 25°C), and 5-55% by weight of water, and wherein, the fat solubilising oil/(oil+water) fraction ranges from 0.1 to 0.5.
• a surfactant selected from non-ionic and anionic surfactants in a ratio of non-ionic : anionic between 5:1 and 1 :1 ,
• 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), oil (O) and water (W).
• S surfactant
• O oil
• W water
• 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 40 wt% to 90 wt% surfactant.
• Surfactants are included in the formulation for primary cleaning action and are chosen from anionic and non-ionic surfactants.
• Non-ionic and anionic surfactants in a ratio such that the non-ionic : anionic ratio is between 5:1 and 1 :1 , preferably between 3.5:1 and 1 :1 .
• 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 2 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.
• composition comprises not more than 80%, still more preferably not more than
• composition preferably comprises at least 45%, still more preferably at least 50% 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 wt% to 30 wt%.
• the solvent helps solubilise sebum present in sebaceous soil.
• the Hansen Solubility Parameter (HSP, or 5 H SP) 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). While not wishing to be bound by theory, it is believed that the Hansen Solubility Parameter (5 H sp) of sebum is from 15 to 18.5 Mpa 1/2 . In order to be able to dissolve the sebum adequately, it is believed that the 5 H SP of the solvent should not deviate too much from the 5 H sp of the sebum, hence the above ranges.
• 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 (5 H SP) 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).
• 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 HSP is defined as the square root of the sum of the squares of the dispersion, polar and hydrogen bond components:
• the polar component ( ⁇ ⁇ ) 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 ( ⁇ ⁇ ) 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
• the dispersion component (5 D ) is in the range of 13 - 18 MPa (at 25°C), preferably 14 to 17 MPa 1/2 (at 25°C), more preferably 15 - 16 MPa 1 ' 2 (at 25°C).
• This HSP for mixture of solvents are additive according to the respective concentrations of its components.
• 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 include methyl octanoate, ethyl octanoate, propyl dodecanoate and butyl tetradocanoate.
• alkyl esters of fatty acids include methyl octanoate, ethyl octanoate, propyl dodecanoate and butyl tetradocanoate.
• 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:
• 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 28%, more preferably not more than 25%, still more preferably not more than 22%, or even not more than 20% by weight of the composition.
• the composition comprises between 5 and 55% by weight of water, preferably not more than 50%, still more preferably not more than 45%, yet more preferably not more than 40%, even more preferably not more than 35%, or most preferably not more than 30% 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 300 and 10000 mPa.s (25°C and 20s-1 ), more preferably between 500 to 5000, when measured with a TA instrument rheometer CSL-500, with a cone and plate set-up, acylic 4 cm diameter, 2° angle, truncation gap 56 micrometer, in steady flow operation.
• Oil on oil+water fraction is preferably between 300 and 10000 mPa.s (25°C and 20s-1 ), more preferably between 500 to 5000, when measured with a TA instrument rheometer CSL-500, with a cone and plate set-up, acylic 4 cm diameter, 2° angle, truncation gap 56 micrometer, in steady flow operation.
• a lamellar phase detergent composition is preferably stable in ambient temperature throughout the year.
• a lamellar phase liquid detergent composition has a transition temperature beyond which phase separation occurs.
• the transition temperature is preferably higher than the storage / ambient temperature throughout the year.
• the transition temperature for a liquid detergent composition is more than 40 °C.
• compositions of the invention when having a fraction of fat solubilising oil upon the total of fat solubilising oil and water of less than 0.5 the transition temperature is above 40°C.
• the fraction of fat solubilising oil upon the total of fat solubilising oil and water is between 0.1 and 0.5, for the best viscosity preferably between 0.3 and 0.5.
• preferred compositions may also include other ingredients.
• the composition includes a benefit agent.
• the benefit agent may be hydrophobic or hydrophilic.
• the benefit agent may be selected from an electrolyte, a shading dye, a perfume or an optical brightener.
• the composition typically comprises between 1 and 20% by weight of combined other ingredients, preferably at least 2%, or even at least 5%, but preferably not more than 18%, still more preferably not more than 16%, yet more preferably not more than 10% by weight of the composition.
• the composition preferably comprises 0.1 -10% by weight of an electrolyte.
• compositions all concentrations are given by weight based on the total composition. Detailed description of the figure
• 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.
• Viscosity measurement was done using Viscometer both at constant temp (varying shear rate) and at constant shear (varying temperature). Parameters associated with the viscosity measurement are given below:
• 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.
• the reflectance of the fabric swatches was measured at AR460 (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.
• transition temperature i.e. the temperature above which phase separation occurs
• R value (Oil/ (oil+water)) of the composition was calculated at different transition temperature (Temp), keeping viscosity less than l OOOcp.
• composition within the oil/oil+water fraction of between 0.1 and 0.5 has a transition temperature above 40°C, i.e. is not phase separating below 40°C.
• the soiled shirts were cut into two halves. For each shirt, one half was tested with the composition of the invention and the other half with a control sample, both applied directly onto the collar. They were washed in a commercially available top loader washing machine.
• Control is a commercially available liquid detergent (OMO, ex Unilever, Thailand) or Tide liquid (ex P&G, USA).
• the samples were evaluated in pairs by trained panellists on various attributes.
• 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.
• composition according to the invention scores better than OMO on 13 stains, less good on 7 and equal on 2. Specific tests have been done on collar cleaning. Collars soils contain high amounts of sebum and are difficult to clean with commercially available liquid detergent compositions.
• composition according to the invention scores better than OMO on collar cleaning, even after repeated use.

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• 2012
  • 2012-10-30 ES ES12781082.8T patent/ES2617507T3/es active Active
  • 2012-10-30 EP EP12781082.8A patent/EP2782987B1/en not_active Not-in-force
  • 2012-10-30 CN CN201280057117.2A patent/CN103946357B/zh not_active Expired - Fee Related
  • 2012-10-30 IN IN930MUN2014 patent/IN2014MN00930A/en unknown
  • 2012-10-30 WO PCT/EP2012/071480 patent/WO2013075913A1/en not_active Ceased
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• 2014
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