EP2782987B1 - Composition de détergent liquide - Google Patents

Composition de détergent liquide Download PDF

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Publication number
EP2782987B1
EP2782987B1 EP12781082.8A EP12781082A EP2782987B1 EP 2782987 B1 EP2782987 B1 EP 2782987B1 EP 12781082 A EP12781082 A EP 12781082A EP 2782987 B1 EP2782987 B1 EP 2782987B1
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EP
European Patent Office
Prior art keywords
mpa
composition
oil
range
water
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.)
Not-in-force
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EP12781082.8A
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German (de)
English (en)
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EP2782987A1 (fr
Inventor
Deeleep Kumar Rout
Ritesh Kumar Sinha
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Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
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Publication of EP2782987A1 publication Critical patent/EP2782987A1/fr
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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.
  • Detergent transport, packaging and production add to the product carbon footprint.
  • a lot of the cost in processing, transport and packaging is caused by the high amounts of water in the product. Therefore, a concentrated liquid detergent composition is highly desired, as it reduces packaging material (per wash), it reduces the cost of transport and the cost of processing.
  • 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 Cold 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.
  • 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.
  • 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 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 WO97/32967 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.
  • WO 2011/073062 discloses a bi-continuous micro-emulsion detergent composition comprising a short chain non-ionic surfactant, however microemulsions 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.
  • EP-A1-2 361 963 discloses bi-continuous micro-emulsion detergent compositions which comprise a It is an object of the present invention to provide a composition that provides fast dissolution of fatty material based stains and soils.
  • 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 ( ⁇ 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 5-55% by weight of water, and wherein, the fat solubilising oil/(oil+water) fraction ranges from 0.1 to 0.3.
  • 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.
  • the composition comprises not more than 80%, still more preferably not more than 75%, or even not more than 70%, while the 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 ⁇ 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).
  • ⁇ HSP Hansen Solubility Parameter
  • 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).
  • 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 MPa1/2 (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).
  • 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 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 1 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 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.
  • 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 0.3.
  • preferred compositions may also include other ingredients.
  • 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.
  • 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.
  • phase separates and a non transparent emulsion is formed; above C-D and left to A-D, the composition appears highly viscous; right to B-C, the phase separates.
  • 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: Viscometer : TA Instruments, CSL Rheometer. Operating pressure : 4 kg/cm2 Geometry : Cone and Plate, Acrylic 4 cm diameter. 2 Degree angle, gap 56 micron (zero gap correction) Procedure : Steady flow
  • 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 ⁇ 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.
  • 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 1000cp.
  • 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.
  • the control is a commercially available liquid detergent (OMO, ex Unilever, Thailand) or Tide liquid (ex P&G, USA).
  • OMO organic radical detergent
  • Tide liquid ex P&G, USA.
  • Ex 4 0.5 g/L (60 % surfactants)
  • Omo 1.1 g/L (27 % surfactants)
  • Tide Liquid 1 g/L (ca 30 % surfactant)
  • 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.
  • Collars soils contain high amounts of sebum and are difficult to clean with commercially available liquid detergent compositions.
  • Table 8 Collar Cleaning 2 nd Wash 5 th wash 10 th wash 15 th wash 20 th wash Ex 4 16 17 17 19 19 Omo 3 6 4 4 2 Parity 5 1 3 1 3 Confidence level 99% 99% 99% 99.9% 99.9%
  • composition according to the invention scores better than OMO on collar cleaning, even after repeated use.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (6)

  1. Composition de détergent liquide en phase lamellaire comprenant :
    a 40-90 % en masse d'un tensioactif, choisi parmi des tensioactifs non-ioniques et anioniques dans un rapport de non-ionique : anionique de 5:1 à 1:1 ;
    b 1-30 % en masse d'une huile solubilisant une graisse, présentant un paramètre de solubilité Hansen (δHSP) qui est de 14-22 MPa1/2 (à 25°C), et dans laquelle le constituant polaire Hansen (δP) se trouve dans l'intervalle de 0,5-10 MPa1/2 (à 25°C), le constituant de dispersion (δH) se trouve dans l'intervalle de 3-10 MPa1/2 (à 25°C) et le constituant de liaison hydrogène (δD) se trouve dans l'intervalle de 13-18 MPa1/2 (à 25°C) ; et
    c 5-55 % en masse d'eau ; et
    dans laquelle, la fraction huile solubilisant une graisse/(huile+eau) est de 0,1 à 0,3.
  2. Composition selon la revendication 1, dans laquelle ladite huile solubilisant une graisse est choisie parmi des esters alkyliques d'acides gras, des mono, di- ou tri-glycérides d'acides gras et d'alcool gras ayant une longueur de chaine de 8 à 16, de préférence de 10-12 atomes de carbone.
  3. Composition selon la revendication 1, dans laquelle la viscosité de la composition est de 300 à 10 000 mPa.s (à 25°C et 20s-1).
  4. Composition selon la revendication 1, dans laquelle l'huile solubilisant une graisse présente un paramètre de solubilité Hansen (δHSP) qui se trouve dans l'intervalle de 15-18,5 MPa1/2 (à 25°C), et dans laquelle le constituant polaire Hansen (δP) se trouve dans l'intervalle de 1-8 MPa1/2 (à 25°C), le constituant de dispersion (δH) se trouve dans l'intervalle de 3-8 MPa1/2 (à 25°C) et le constituant de liaison hydrogène (δD) se trouve dans l'intervalle de 14-17 MPa1/2 (à 25°C).
  5. Composition selon la revendication 1, dans laquelle ladite composition comprend du parfum.
  6. Composition selon la revendication 1, dans laquelle ladite composition comprend 0,1-10 % en masse d'un électrolyte.
EP12781082.8A 2011-11-25 2012-10-30 Composition de détergent liquide Not-in-force EP2782987B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
IN3328MU2011 2011-11-25
EP12153058 2012-01-30
PCT/EP2012/071480 WO2013075913A1 (fr) 2011-11-25 2012-10-30 Composition de détergent liquide

Publications (2)

Publication Number Publication Date
EP2782987A1 EP2782987A1 (fr) 2014-10-01
EP2782987B1 true EP2782987B1 (fr) 2016-11-30

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EP12781082.8A Not-in-force EP2782987B1 (fr) 2011-11-25 2012-10-30 Composition de détergent liquide

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EP (1) EP2782987B1 (fr)
CN (1) CN103946357B (fr)
BR (1) BR112014011725A2 (fr)
CL (1) CL2014001342A1 (fr)
ES (1) ES2617507T3 (fr)
IN (1) IN2014MN00930A (fr)
WO (1) WO2013075913A1 (fr)
ZA (1) ZA201403729B (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108350391B (zh) * 2015-10-20 2020-09-08 荷兰联合利华有限公司 用于处理基材的组合物和方法
US11098271B2 (en) 2019-06-12 2021-08-24 Henkel IP & Holding GmbH Salt-free structured unit dose systems

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8409054D0 (en) 1984-04-07 1984-05-16 Procter & Gamble Stabilized oil-in-water cleaning microemulsions
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
CA2355059A1 (fr) * 1998-12-16 2000-06-22 Unilever Plc Composition detergente liquide structuree
RU2542993C2 (ru) 2009-12-16 2015-02-27 Юнилевер Н.В. Бинепрерывная микроэмульсионная моющая композиция
EP2361963A1 (fr) * 2010-02-01 2011-08-31 Unilever N.V. Composition de détergent à micro-émulsion bi-continue

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CN103946357B (zh) 2017-03-08
WO2013075913A1 (fr) 2013-05-30
ES2617507T3 (es) 2017-06-19
CL2014001342A1 (es) 2015-01-16
ZA201403729B (en) 2015-11-25
CN103946357A (zh) 2014-07-23
IN2014MN00930A (fr) 2015-04-17
BR112014011725A2 (pt) 2017-05-30
EP2782987A1 (fr) 2014-10-01

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