WO2014016134A1

WO2014016134A1 - Liquid detergent composition

Info

Publication number: WO2014016134A1
Application number: PCT/EP2013/064699
Authority: WO
Inventors: Deeleep Kumar Rout; Ritesh Kumar Sinha; Pintu PAUL
Original assignee: Unilever N.V.; Unilever Plc; Conopco, Inc., D/B/A Unilever
Priority date: 2012-07-26
Filing date: 2013-07-11
Publication date: 2014-01-30
Also published as: CN104487560A; EP2877564A1; BR112015001328A2; CN104487560B; ZA201500321B; EP2877564B1; IN2015MN00103A; ES2594329T3

Abstract

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. Efficient cleaning of fabric articles, especially the removal of soils such as sebum from cuffs and collars, remains to be desired. It is an object of the present invention to provide a composition that provides fast dissolution of fatty material based stains. It has been found that a lamellar phase detergent composition comprising a surfactant selected from non-ionic and anionic in a ratio of non-ionic:anionic between 3:1 and 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 of solid or solidified fatty material; is stable at normal storage and washing conditions and may be delivered as a pourable liquid.

Description

LIQUID DETERGENT COMPOSITION

Field of the invention

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.

Background of the invention

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.

The removal of oily soils and stains from fabrics has been an important area of concern in fabric cleaning and there have been several approaches to solve the problem.

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. Another option is to make the detergent composition in the form of a micro emulsion with an aqueous phase and a solvent. Typical micro-emulsion compositions, however, 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.

Accordingly a stable and clear detergent composition that does not show phase separation on increased temperatures (e.g. up to 60 °C), remains to be desired.

EP 160 762 A1 (The Procter and Gamble Company) 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 (Colgate 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. Our co-pending application 3328/MUM/201 1 describes lamellar phase detergent compositions comprising very high active levels of between 40% and 90% by weight of active material. However, compositions with such high active levels, have little formulation space left for fat solubilising materials such as oils. Hence, 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 201 1/073062 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.

It is an object of the present invention to provide a composition that provides fast dissolution of fatty material based stains and soil.

It is another object of the invention to provide a stable liquid detergent composition with low levels of surfactant. It is still another object of the invention to provide a stable liquid detergent composition that does not irreversibly phase separate upon fluctuation of the temperature.

It is yet another object of the invention to provide a pourable concentrated detergent composition having a low viscosity.

Surprisingly it has been found that 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. Summary of the invention

The present invention provides a liquid detergent composition comprising 10- less than 40% by weight of 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^<€), and wherein the Hansen polar component (· P) is in the range of 0.5-10 MPa1/2 (at 25^<€), the dispersion component (· H) is in the range of 3-10 MPa1 /2 (at 25^qC) 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 to 0.3.

In a second aspect 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.

These and other aspects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. For the avoidance of doubt, any feature of one aspect of the present invention may be utilized in any other aspect of the invention. The word "comprising" is intended to mean "including" but not necessarily "consisting of" or "composed of." In other words, the listed steps or options need not be exhaustive. It is noted that the examples given in the description below are intended to clarify the invention and are not intended to limit the invention to those examples per se. Similarly, all percentages are weight/weight percentages unless otherwise indicated. Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word "about".

Numerical ranges expressed in the format "from x to y" are understood to include x and y. When for a specific feature multiple preferred ranges are described in the format "from x to y", it is understood that all ranges combining the different endpoints are also contemplated. Detailed description of the invention

The present invention provides a liquid detergent composition comprising of a surfactant, a fat solubilising oil and water. Surfactant

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.

HLB values may be calculated, e.g. by Griffin's method (Griffin WC: "Calculation of HLB Values of Non-Ionic Surfactants," Journal of the Society of Cosmetic Chemists 5 (1954): 259), or Davies' group contribution method (Davies JT: "A quantitative kinetic theory of emulsion type, I. Physical chemistry of the emulsifying agent," Gas/Liquid and Liquid/Liquid Interface. Proceedings of the International Congress of Surface Activity (1957): 426-438); or the group calculation method (HLB= 7+· (Hydrophilic group numbers)-* (Lipophilic group numbers)).

For the purpose of the present invention, 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).

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. methyl branched), alkylphenols (preferably from 8 to 20 carbon atoms) in which 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.

These and other surfactants are described in "Surface Active Agents" Vol. I, by Schwartz & Perry, Interscience 1949; "Surface Active Agents" Vol II, by Schwartz, Perry & Berch, Interscience 1958; the current editions of "McCutcheon's Emulsifiers & Detergents" published by the McCutcheon Manufacturing Confectioners Company; in "Tensid-Taschenbuch" H. Stache 2^nd Edition, Carl Hanser Verlag, Munchen & Wien, 1981 ; and in the various patent literature describing various types of liquid detergent compositions, which for the purpose of the invention need no further detailing.

Preferably 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

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 ^/2 (at 25°C), preferably 15 to 20 MPa ^/2 (at 25°C), more preferably from 15 to 18.5 MPa ^/2 (at 25 ^<€).

While not wishing to be bound by theory, it is believed that the Hansen Solubility Parameter (· _HSP) of sebum is from 15 to 18.5 Mpa ^/2. In order to be able to dissolve the sebum adequately, it is believed that the · _HSP of the solvent should not deviate too much from the · _HSP of the sebum, hence the above ranges.

While the Hansen Solubility Parameter for Paraffin oil closely matches that of sebum, 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 ^/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:

(i) the energy from dispersion bonds between molecules (D);

(ii) the energy from dipolar intermolecular force between molecules (P);

(iii) the energy from hydrogen bonds between molecules (H).

Each of the three parameters (i.e., dispersion, polar and hydrogen bonding) represents a different characteristic of solvency, or solvent capability. In combination, 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 (· _P) is in the range of 0.5 - 10 MPa ^/2 (at 25 ^<€), preferably 1 to 8 MPa ^/2 (at 25^<€), more preferably 2 - 6 MPa ^/2 (at 25°C), still more preferably 3 - 5 MPa ^/2 (at 25^<€). The hydrogen bond component (· _H) is in the range of 3 - 10 MPa ^/2 (at 25 ^), preferably 3 to 8 MPa ^/2 (at 25^<€), more preferably 3 - 7 MPa ^/2 (at 25^<€), still more preferably 3 - 6 MPa ^/2 (at 25^<€).

The dispersion component (· _D) is in the range of 13 - 18 MPa ^/2 (at 25°C), preferably 14 to 17 MPa ^/2 (at 25^<€), more preferably 15 - 16 MPa ^/2 (at 25°C).

This HSP for mixture of solvents are additive according to the respective

concentrations of its components.

The 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. Examples of alkyl esters of fatty acids 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.

Examples of fatty alcohol include decanol, dodecanol.

Some examples of alkyl esters and their HSP values are given in the table below:

Table A

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.

Water

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. Viscosity

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. Temperature

The stability of a lamellar phase detergent is affected by the storage temperature. Therefore 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. Fat solubilising oil on Fat solubilising oil + water ratio

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 .

Surfactant to fat solubilising oil ratio

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. Other ingredients

In addition to the essential ingredients, preferred 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.

Method

In another aspect 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.

When washing fabric articles with the composition according to the invention, 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 .

For tough stains the composition according to the invention may also be applied neat onto the fabric article. 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. For tough stains the composition according to the invention may also be applied neat onto a sponge, cloth or brush and used directly onto the surface.

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).

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.

Note the letters A - D on the diagram. The composition for each of these points is shown below.

Table B

Examples

The invention will now be explained with the help of non-limiting examples of preferred embodiments. Methods

Preparation of lamellar gel

Preparation of lamellar gel was done by adding each ingredient in appropriate amount in a plastic container and was mixed by using Silversion™ Mixer. Process conditions are given bellow:

Mixer type Silversion Mixer

RPM 4000

Mixer Blade Diameter 4 cm

Mixer blade type Two Flat blades at 90 degree attached to a SS rod which

was fitted to the Motor.

Mixing time 25 min for a 2 kg batch size.

Temperature 25 °C (Lab temp.)

Materials:

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).

C12E07: Ci₂ 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

NaCI: ex Merck

NaOH: ex Merck

Tinopal CBSX: ex Ciba

Viscosity measurement

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/cm²

Geometry : Cone and Plate, Acrylic 4 cm diameter. 2 Degree angle, gap 52-56 micron ( zero gap correction)

Procedure : Steady flow

Temperature : 25°C

In statistics, 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.

Estimation of Sebum removal:

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.

Reflectance measurement:

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 detection

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.

Example 1 : Performance of the detergent compositions on collar cleaning 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, 201 1 ). The compositions were prepared by the method as described above.

Table 1

1 ) Minors include soil release polymer (NaPAA, 1 %), Soda (0.8%), NaCI (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.

Wash conditions were as follows:

Water hardness : 24fH (Ca⁺⁺:Mg⁺⁺ = 1 :2)

Wash load : -2.5 kg for each wash

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.

Results:

Washing results on consumer fabrics is represented in the table below. Table 2 illustrates superior collar cleaning properties of the detergent compositions (Ex E and Ex F) of the present invention over Omo. Table 2

It can be noted from the above table that 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.

Example 1 a: Performance of the detergent compositions on collar cleaning effect of the solvent

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 1 1 1 1

SLES 5.5 5.5

NaLAS 5.5 5.5

Methyl laurate 5 0

Minors¹' 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 NaCI 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.

Wash conditions were as follows:

Water hardness : 24fH (Ca⁺⁺:Mg⁺⁺ = 1 :2)

Wash load : -2.5 kg for each wash

The samples were evaluated in pairs by trained panellists. Results:

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

It can be noted from the above table that the number of collars cleaned by the detergent composition of the present invention is much higher than the number of collars cleaned by Comp H, without the fat solubilising oil according to the invention.

Example 1 b: Performance of the detergent compositions on collar cleaning effect of the solvent 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

Minors¹' 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 NaCI only

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.

Wash conditions were as follows:

Water harshness : 24fH (Ca⁺⁺:Mg⁺⁺ = 1 :2)

Wash load : -2.5 kg for each wash

The samples were evaluated in pairs by trained panellists. Results:

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

The above table shows that the number of collars cleaned by the detergent

compositions of the present invention is much higher than the number of collars cleaned by Comp T, without the fat solubilising oil according to the invention.

Example 2: Effect of surfactant concentration on the lamellar phase

In this example, 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

NaCI 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 table above shows that when the concentration of the surfactants is outside the scope of the present invention, the liquid detergent composition of the present invention is not in a lamellar phase, but an emulsion, which is not preferred.

Example 3: Effect of the HLB value of the surfactants

In this example the effect of the HLB value of the surfactant is demonstrated. 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.

Table 8

Ingredients (wt%) Comp AA Ex B Ex AB

C12E07 17.6 1 1 4.4

SLES 2.2 5.5 8.8

NaLAS 2.2 5.5 8.8

Methyl laurate 5 5 5

EPEI sokalan HP- 2.5 2.5 2.5

20

NaPAA-2000 0 0 0

NaOH 0.7 0.7 0.7

NaCI 4 4 4

Dequest-2010 1 .69 1 .69 1 .69 CBSX 0.12 0.12 0.12

Perfume 0.5 0.5 0.5

Enzyme 0.75 0.75 0.75

Water QS 62.74 62.74 62.74

Oil /( oil + water) 0.07 0.07 0.07

Surf/Oil 4.4 4.4 4.4

Non-ionic to 4:1 1 :1 1 :4 anionic ratio

HLB 14.1 20.66 27.1

Viscosity@20s^~1 900 CP 700 CP 1 100 CP

Phase Non Lamellar Lamellar Lamellar

It is inferred from the above table that Comp AA is not in a lamellar phase as the HLB value of the surfactants falls outside the claimed value. Stable lamellar phase compositions are obtained at an HLB value according to the present invention.

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 cm² 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.

Synthetic sebum

Component Name Weight % Physical State at 25°C

Laurie acid 7 Solid Oleic acid 7 Liquid

Isostearic acid 3.5 Liquid

Trilaurin 16 Solid

Triolein 24 Liquid

Myristyl Myristate 20.8 Solid

Isostearyl 5.2 Liquid

Isostearate

Squalene 13 Liquid

Cholesterol 3.5 Solid

Washing procedure: An approximate amount of 0.12 g detergent sample was directly applied on each soiled fabric. The swatches and water quantity were maintained in such a way that the product concentration in the solution was 2.3 g/l. The treated swatches were soaked in respective wash solutions for about half an hour at ambient conditions. Washing was carried out in a terg-o-tometer (7243 Es), for 15 minutes at 90 rpm and ambient conditions with L/C = 25. Rinsing was performed at same L/C twice for two minutes. Washed swatches were line dried and later used for estimations of oil/fat removal as well as reflectance measurement.

Results:

Sebum removal and reflectance values (Delta R) for the compared samples are given in the table below. Table 9

Fabric % Sebum removed (within error Delta R ( reflectance within error type of ± 0.5 units) of ± 1.5 units)

Ex S Comp T Ex S Comp T

Cotton 70.8 69.6 17.09 16

Poly 59 43 18.4 13.6 cotton

Poly 27 14.5 15 1 1 .5 ester The results represented in the table above show that the amount of sebum removed by the composition of the present invention (Ex S) is more when compared to the amount of sebum removed by comp T. The table also indicates that the fabrics washed with Ex S shows a better reflectance than Comp T due to a higher amount of sebum removal. A significant difference in the cleaning performances of Ex S and Comp T is noted predominantly in poly cotton and poly ester type fabrics.

Example 4a: Cleaning performance of the detergent compositions on dirty motor oil soiling

In this example, cleaning performance of the detergent composition of Ex S (formulation as in table 5) is demonstrated in comparison to Comp T (comparative composition devoid of a fat solubilising oil) (formulation as in table 5) 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.

Results:

Reflectance values (Delta R) for the compared samples are given in the table below. Table 10

The results in the table above indicates that the reflectance of fabrics washed with the detergent composition of the present invention (Ex S) is higher when compared to the reflectance of fabrics washed with the composition of Comp T.

Example 4b: Cleaning performance of the detergent compositions on WFK fabric

In this example, cleaning performance of the detergent composition of Ex S (formulation as in table 5) is demonstrated in comparison to Comp T (comparative composition devoid of a fat solubilising oil) (formulation as in table 5) on WFK fabric (ex WFK Testgewebe, Germany).

Washing procedure: 10cm^*10cm WFK 10D and 20D from Warwick, UK were used. Water used was 24 °FH (Ca+2:Mg+2::2:1 ) water throughout the experiments.

Direct application wash (D)

A detergent product weighing -0.5 g was directly applied on each of the WFK fabrics, after which the treated fabrics were soaked for 30 min in a conical flax containing 150 ml 24 °fH (Ca²⁺:Mg²⁺ = 2:1 ) water. Subsequently, the conical flax was shaken by hand for 10 seconds. The cleaned fabric was rinsed with 24 °fH water by dipping into it. Washed swatches were line dried and later used for reflectance measurement.

Results:

Reflectance values (Delta R) for the compared samples are given in the table below. Table 1 1

The results in the table above indicate that the reflectance of fabrics washed with the detergent composition of the present invention (Ex S) is better when compared to the reflectance of fabrics washed with the composition of Comp T. A significant difference in the cleaning performances of Ex S and Comp T is noted predominantly in poly cotton type fabrics.

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 SGamble Company, USA) and Omo liquid (ex Unilever, Thailand). Comp U is an unstable comparative example composition formulated without a fat solubilising oil.

Table 12

Ingredients Ex I Ex J Ex K Ex N Ex O Ex Q Ex R Comp U (wt%)

C12E07 8.8 21 21 17 17 17 17 21

SLES 6.6 3.5 3.5 8.5 8.5 8.5 8.5 3.5

NaLAS 6.6 3.5 3.5 8.5 8.5 8.5 8.5 3.5

Methyl 5 7 7 8.5 8.5 5 8.5 0 laurate

EPEI 0 0 3.75 2.5 2.5 2.5 2.5 3.75 sokalan HP- 20

NaPAA-2000 0 0 0 0 0 0 0 0

NaOH 0.7 0.96 0.96 1.2 1.2 1.2 1.2 0.96

NaCI 6 0 0 5 5 5 5 0

Dequest- 1.69 3.39 3.39 1.69 3.39 3.39 0 3.39 2010

CBSX 0.12 0.34 0.34 0.34 0.34 0.34 0.34 0.34

Perfume 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5

Enzyme 0.75 1.8 1.8 1.8 1.8 1.8 1.8 1.8

Water QS 63.24 58.01 54.26 44.47 42.77 46.27 46.16 61.26

Oil /( oil +

water) 0.07 0.11 0.11 0.16 0.16 0.09 0.15 0

Surf/Oil 4.4 4 4 4 4 6.8 4 -

Non-ionic to

anionic ratio 1:1.5 3:1 3:1 1:1 1:1 1:1 1:1 3:1

22.83 15.23 15.23

HLB 3 6 6 20.66 20.66 20.66 20.66 15.236

Viscosity@2 900 900 900 900 900 900 900

OS^"1 CP CP CP CP CP CP CP

Phase Lamel Lamel Lamel Lamel Lamel Lamel Lamel Unstable lar lar lar lar lar lar lar

Washing procedure: 10cm^*10cm standard stain sets from Warwick, UK were used. Water used was 24 °fH (Ca²⁺:Mg²⁺ = 2:1) water throughout the experiments. Direct application wash (D)

For standard stain sets, 35 gm was divided into all stains and applied directly. Then the stains set were put into a washing machine (Samsung top loader or IFB front loader) in 24 FH water. A fabric ballast was also added. Solution wash (B)

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.

Results:

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 0(B) vs Ex Q(B) vs Ex R(B) vs Ex N(B) vs

Ariel gel Ariel gel Ariel gel 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± 1 .24±2.6

3.2

Beef patty dripping -1 .44±0.31 -0.7±0.16 -2±0.78 1 .61 ±1 .41

Red piper/oil -water 0.31 ±0.51 4.7±3.35 0.9±0.66 1 .26±0.35

Dende oil 3.48±1 .2 1 .1 +1 .8 29.7±0.6 0.62±1 .6 The results in the above table shows that in most of the stain sets, the stain removal index is positive indicating that the performance of the compositions of the present invention is better than Ariel gel (positive values are in favour of the compositions of the invention and negative values are in favour of Ariel Gel)

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

The results in the above table shows that on an average the performance of the compositions of the present invention is better than Ariel gel and Comp U (positive values are in favour of the compositions of the invention and negative values are in favour of Ariel Gel or Comp U) 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 l(D) Vs Omo

Yellow rajah curry -22.8±24.3

DMO -18.5±1 1 .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 sunflower oil -0.6+2.7

Garden soil -0.6±3.7

Beef patty dripping -0.5+0.4

Black coffee -0.3+0.4

Choc ice cream prem 0.1 ±0.6

HP Brown sauce 0.2±0.5

Ragu sunflower oil 0.5±0.5

Cocoa Milk 0.6±1 .3

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±2.0

Sebum 1 .8±3.4

Cooking oil + violet dye 2.9±3.2

Indian red Clay 2.9±3.3

Yellow pottery clay 3.3±0.8

Grape Juice 3.4±0.2 Blue poster paint 4.0±1 .6

White tea 4.3±0.2

Hamburger grease + violet dye 4.4±3.0

Face makeup 4.6±2.7

Red pottery clay 5.2±0.8

Chocolate ice cream Economy 6.0±5.5

Blackberry whole fruit 6.8±0.7

Lipstick 7.0±17.2

Black current juice 7.1 ±1 .9

Mechanical grease 7.8±9.2

Black shoe polish 8.0±2.8

Red curry 9.4±13.2

Lard + violet dye 9.8±9.7

Red wine 10.8±6.6

Black tea 12.3±1 .2

Chocolate pudding 12.7±1 1 .3

Gravy instant 23.8±14.6

The results in the above table shows that in most of the stain sets, the stain removal index is positive indicating that the performance of the compositions of the present invention is better than Omo (positive values are in favour of the compositions of the invention and negative values are in favor of Omo)

Example 5: Effect of surfactant to fat solubilising oil ratio on sebum removal

In this example, the effect of surfactant to fat solubilising oil ratio on sebum removal is demonstrated. The example composition of Ex J (formulation as in table 12) is tested for cleaning performance with different ratios of surfactant to fat solubilising oil. Sebum removal of more than 70 % is considered to be good. Table 16

It is inferred from the results of the above table that good sebum removal is obtained at a surfactant to fat solubilising oil ratio according to the invention.

Claims

1 A lamellar phase liquid detergent composition comprising:

a 10-40% by weight of 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;

b 1 .25-16% by weight of a fat solubilizing oil, having a Hansen solubility parameter (· _HSP) that ranges from 14-22 MPa ^/2 (at 25 'Ό), and wherein the Hansen polar component (· _P) is in the range of 0.5-10 MPa ^/2 (at 25°C), the dispersion component (· _H) is in the range of 3-10 MPa ^/2 (at 25 'Ό) and the hydrogen bond component (·_□ ) is in the range of 13-18 MPa ^/2 (at 25°C); and

c 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 to 0.3.

2 A composition according to claim 1 , wherein the said fat solubilising oil is

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.

3 A composition according to claim 1 or 2, wherein the viscosity of the composition is between 50 and 2000 mPa.s (at 25^ and 20s^"1 in a TA instrument rheometer AR-1000, with a cone and plate set-up, acrylic 4 cm diameter, 2° angle, truncation gap 56 micrometer).

4 A composition according to any one of the preceding claims, wherein the fat

solubilising oil on (fat solubilising oil + water) ratio ranges from 0.05 to 0.1 .

5 A composition according to any one of the preceding claims, wherein the

surfactant to fat solubilising oil ratio ranges from 3 to 6.

6 A composition according to any one of the preceding claims, wherein the fat

solubilizing oil has a Hansen solubility parameter (· HSP) that ranges from 15-

18.5 MPa ^/2 (at 25 'Ό), and wherein the Hansen polar component (· P) is in the range of 1 -8 MPa ^/2 (at 25 'Ό), the dispersion component (· H) is in the range of 3- 8 MPa ^/2 (at 25°C) and the hydrogen bond component (· D ) is in the range of 14- 17 MPa ^/2 (at 25°C). A method for washing fabric articles comprising the steps of:

a Dosing between 2-20 ml of the composition according to anyone of the preceding claims per litre of wash or cleaning liquor. A method according to claim 7, wherein the liquor is a wash liquor and wherein fabric articles are added to the wash liquor in liquor:fabric article a ratio of between 2.5:1 and 15:1 . A method according to claim 7, wherein the liquor is a household cleaning liquor.