Title of Invention

IMPROVED CLEANING COMPOSITION

Abstract A cleaning composition comprising: i. a non-polar phase comprising one or more liquids such as herein described having an electric dipole moment less than that of water characterized in that at least 10% of the said non-polar phase has an electric dipole moment greater thaft 0.8 debye a polar liquid such as herein described; wherein the non-polar liquids are present at levels above their mutual miscibility limits, such that they form at least two immiscible phases.
Full Text ORIGINAL
FORM -2
THE PATENTS ACT, 1970 (39 of 1970)
COMPLETE SPECIFICATION
(See Section 10)
IMPROVED CLEANING COMPOSITION
HINDUSTAN LEVER LIMITED, a company incorporated under the Indian Companies Act, 1913 and having its registered office at Hindustan Lever House, 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India
The following specification particularly describes the nature of the invention and the manner in which it is to be performed.
GRANTED
29-9-2004

Technical field:
The invention relates to a cleaning/washing composition having a system of at least two liquids, which are present above their mutual miscibility limits, such that the composition is not a single homogenous clear phase.
Background and prior art:
Commercial hard surface cleaning compositions typically comprise, one or more surfactants and a plurality of abrasives dispersed therein. Combinations of these together with electrolytes are generally used to form a structuring system as is well known in the art. Commercial liquid hard surface cleaning compositions typically comprise one or more surfactants dispersed in an aqueous base, with or without additional organic solvents, which are water miscible/soluble, and may contain non-polar liquids which are present as micro-emulsion droplets. The later requires the surfactant concentrations typically above 5 % and additional solvents and such systems are well known in the art. The conventional cleaning compositions for hard surface cleaning are formulated in the form of solids such as powders, granules, pastes and bars, and in the form of fluid formulations such as liquids and gels.
Hard surfaces within household are kitchenware, kitchen floors and platforms, floors, bathrooms etc. and one encounters different types of soil on these surfaces. The soil generally encountered on kitchenware is of two types i.e. the mobile or greasy soil and the tough or difficult to remove soil consisting of dried-

on or cooked-on food. The problem becomes more pronounced when, the soil builds on over a period of time and this requires considerable, effort to clean.
Solvent based compositions are well known for cleaning, difficult to clean, hard-
surfaces. EP 0428816 (P&G, 1988) & EP 0261874 (P&G, 1991) "disclose hard
surface cleaning compositions using different water miscible/soluble solvents and surfactants. These compositions are solvent based cleaning compositions and are different from the current invention in that they do not require two liquids present at a level above their mutual miscibility limit.
US5780407 (Union oil Co., 1998) discloses a non-aqueous cleaning composition which contains essentially at least two different surfactants, which have a significant difference in their HLB values along with a diluent oil and the system is devoid of water or is essentially less than 5%. This differs from the current invention in that the present invention does not necessarily require a surfactant irrespective of the HLB. This is applicable for cleaning crude oil and lifting oil from surfaces and does not teach the cleaning of tough soil or polymerised oil for which a specific two phase system is most effective.
US5080822 (Buckeye, International, Inc., 1992) discloses a stable aqueous degreaser composition in the form of an aqueous solution comprising at least one sparingly water soluble organic solvent, an organic solubilizing coupler required

o completely solubilize said organic solvent and water and being free from foaming surfactants.
Our co-pending application 469/Mum/2000 dated 23/5/200D discloses a process of cleaning fabric using the liquid-liquid interface of at least two immiscible liquid phases with an interfacial tension greater than 5mN/m, under agitation. This refers to specifically machine cleaning of fabric and does not teach cleaning of tough soil from hard surfaces.
Removal of "tough" polymerised oil films is typically done by the abrasives, which are present in dish wash powders and bars. When clear liquids are used for dish washing, the abrasive action required for removing tough solid films, are provided by abrasive implements. However the use of abrasive products or abrasive implements leave visible scratches on the utensils. These vessels are observed to lose their shine due to the use of the above, though they may be clean or free of oily matter. This gradual loss of shine or decay of appearance of utensils is currently accepted by the consumers as a necessary "cost" for having clean utensils. However a product which cleans tough soil films without degrading the appearance of kitchenware or kitchen surfaces remains an elusive goal for dish wash / kitchen cleaning products.
It has now been found that a cleaning composition comprising of at least two liquids, present at levels above their mutual miscibility limits, comprising a polar

and a relatively non-polar liquid, can be formulated to effectively clean the tough or polymerised soil from hard surfaces. The above composition is effective provided the electric dipole moment of a fraction ,the non-polar component is greater than 0.8 debye. The system comprising the liquid phases present above their miscibility limit is superior to pure solvent cleaning or the conventional cleaning compositions in terms of removal of soil.
Dipole moment is property of a molecule and it reflects the extent of separation of charge centers in an electrically neutral molecule (Handbook of chemistry and physics, CRC Press 80th Edition, Ed. David Lide). It is quantitatively expressed as the charge of the dipole times the distance of separation between the dipoles. It is expressed in debye. A dipole formed by a pair of poles with charge equal to 1 electronic charge unit (~ 1.6 * 10~19 Coulombs) separated by a distance of 0.21 A0, has a dipole moment of 1 Debye. Permittivity is the ratio of the reduction of electric field strength by a medium of a substance to that of vacuum. It is a consequence of the molecular dipoles, which align with the applied field, to shield the field from a charged entity placed in it.

Description of the invention:
According to the present invention there is provided a;, cleaning composition

comprising:
i. a non-polar phase comprising one or more liquids having an electric
dipole moment less than that of water wherein at least 10% of the said non-polar phase has an electric dipole moment greater than 0.8 debye;
ii. a polar liquid;
whejrein the non-polar and polar liquids are present at levels above their mutual
miseibility limits, such that they form at least two immiscible phases.
According to the preferred aspect of the present invention there is provided a
cleaning composition comprising:
i. a non-polar phase comprising one or more liquids having an electric
dipole moment less than that of water wherein at least 50% of the said
non-polar phase has an electric dipole moment is in the range 1 to 1.8
debye; ii. a polar liquid such that its interfacial tension with the said non-polar liquid
is not greater than 45 mN/m; wherein the non-polar and polar liquids are present at levels above their mutual miseibility limits, such that they form at least two immiscible phases.


According to a more preferred aspect of the present inveotLonihere,i.s provided a
cleaning composition comprising:
i. a non-polar phase comprising one or more liquids, having; an electric
;;dipole moment less than that of water wherein at least-10% of the said

non-polar phase has an electric dipole moment greater than 0.8 debye; ii. a polar liquid iii. upto 10% by weight surfactant
wherein the non-polar and polar liquids are present at levels above their mutual miscibility limits, such that they form at least two immiscible phases, which is optionally a stable emulsion.
Detailed description of the invention:
It is the essential feature of the composition of present invention that it comprises of at least two liquids, comprising a polar and a relatively non-polar liquid, which are present at levels higher than their mutual miscibility limit, and at least 10% of the non-polar phase has an electric dipole moment greater than 0.8 debye and preferably between 1.0 to 1.8 debye. Mixtures of the non-polar and polar liquids forming the immiscible system exhibit at least one interface and the interfacial tension is preferably less than 45 mN/m.
It may however, be noted that the relative densities of the polar and non-polar liquids do not have a specific bearing on the performance of the system with regard to cleaning efficacy. Although it is not essential to incorporate surfactants,


upto 10% by weight surfactants can form a part of the composition. When
surfactants are present the immiscible phases may form a stable emulsion This
emulsion may appear as a single homogenous system but actually comprises of

a stable dispersion of a non-polar phase and a polar phaase
The Composition:
The two phases comprising of a non-polar phase and a polar phase form the immiscible system of the invention. These can be chosen in general form liquids that can include water, alcohols, esters, ethers, ketones, hydrocarbons, paraffins, aromatic solvents, halogenated solvents, heterocyclics etc.
Non-polar phase:
The "non-polar" phase of the present invention refers to liquids having an electric dipole moment less than that of water. The electric dipole moment of water is 1.85 debye and thus the non-polar phase can comprise liquids having a dipole moment in the range 0 to 1.85 debye. However, at least 10% of the non-polar phase should comprise of liquids with an electric dipole moment greater than 0.8 debye and preferably 1.0 to 1.8 debye.
The liquids for the non-polar phase can be selected from the following that have a carbon chain length greater than 6 may be selected from branched and linear alkanes (chemical formula CnH 2n+2 where n is greater than 6), including but not limited to hexane, heptane, octane, nonane, decane, dodecance, tridecane,

tetradecane, pentadecane etc. and mixtures thereof. Commercially available mixtures of this type include Isopar L (C11-C15 alkanes - ex-Exxon) and DF2000 (ex-Exxon). Branched and linear alkenes with greater than 6 carbon atoms including but not limited to octenes, nonenes, decenes, undecenes', dodecenes etc, with one or more degree of unsaturation and mixtures thereof.
Ethers including fluoroether such as Methoxy nonafluorobutane HFE7100 (ie. C4F9-OCH3) and ethoxy nonafluorobutane HFE-7200 (ie. C4F9-OC2H5), esters, such as Dibutyl phthalate, Dioctyl phthalate and terpenes, such as limonene or mixtures thereof may be used. Halogenated hydrocarbons such as Carbon Tetrachloride may also be used.
Liquids with SiO units greater than 3 may be selected from polydimethyl siloxane oils.; Linear and cyclic siloxanes known as Lx and Dx where x is greater than three are suitable for this technology. Specific examples include Octamethyl cyclbtetrasiloxane(D4) (ex-DowComing), Decamethyl cyclopentasiloxane (D5), Dodecamethylcyclohexasiloxane (D6), Decamethyltetrasiloxane (L4) and do
decamethyl pentasiloxane(L5).

The relatively non-polar liquids that have a dipole moment greater than 0.8 debye unit!:may be selected from chlorinated hydrocarbons such as Dichloroethanes, Dichloroehtylenes, Dichloro ethyl ethers, Dichloromethane, Dichloropropanes,

chloroform as well as other Halocarbons such as dibromomethane Bromochloromethane and Bromoform.
The: non-polar phase with dipole moment greater than 0.8 Debye may also include ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol ethyl ether acetate, ethylene glycol monomethyl ether acetate, ethyl acetate and ethyl formate.
The non-polar phase, with dipole moment greater than 0.8 Debye may also include alcohols which show limited water miscibility such as butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol and all compounds described by the generic form CnH 2n+20 and their isomers.
Polar phase:
The polar phase typically comprises of water and water soluble solvents such as acetone, alkanolamines, water miscible alcohols and ethers etc.
Conventional ingredients:
It is possible to incorporate other conventional detergent ingredients such as surfactants, builders, soil release polymers, hydrotropes, enzymes, bleaches, perfumes etc. into the immiscible liquid system. They may be suitably incorporated into the polar or non-polar phase.

'•*"%..
Detergent actives:
The composition according to the invention will optionally comprise an anionic
surfactant with an alkali or alkaline earth metal or ammonium or alkanblamine'
counter ion or a mixture thereof. Other detergent activesfsuch'as .nonionic,


catidnic, amphoteric or zwitterionic surfactants may also be present However, it is preferred that a detergent active is incorporated in the composition and is upto a maximum concentration of 10% by weight.
Examples of suitable detergent-active compounds are compounds commonly used as surface-active agents given in the well-known textbooks "Surface Active Agents", Volume I by Schwartz and Perry and "Surface Active Agents and Detergents", Volume II by Schwartz, Perry and Berch.
The nature of the invention, its objects and advantages will be more apparent from the ensuing description made with relation to non-limiting exemplary descriptions of the above identified various aspects of the invention.
EXAMPLES
Process for preparing the composition:
i. Composition without surfactant:
50ml of the polar phase was taken in a glass beaker to which 50ml of the non-polar
phase that consisted of a single liquid whose dipole moment was greater than 0.8
debye, as in case of examples 5 (chloroform) and example 7 (Isobutanol), was
added drop wise to the polar phase under constant stirring. However, when the

non-polar phase was made up of two liquids a combination of hexadecane and chloroform in a definite proportion as in example 10 (23.3:26.7) was added drop wise to the polar phase under constant stirring. In this case chloroform that has a dipole moment of 1.04 debye was at a level greater than 10% of the non-polar phase which is a requirement of the invention.
ii. Composition with surfactant:
In example 11, 0.5% by wt. of sodium linear alkyl benzene sulphonate was dissolved in the polar phase to which a combination of hexadecane and chloroform in a; definite proportion (22.8:26.7) was added drop wise to the polar phase under constant stirring. This formed a stable milky white emulsion. In this case chloroform that has a dipole moment of 1.04 debye was at a level greater than 10% of the non-polar phase which is a requirement of the invention.
iii. ,i Comparison formulations:
Compositions with two liquid systems used as controls for comparison of the performance were prepared by the same process described above. Single phase systems are however, are used as such.
Method of depositing the soil and cleaning:
Stainless Steel plates were coated with sunflower oil, which were polymerized in an oven maintained at 180° C for 1 hr. The plates coated with the polymerised oil were soaked in 100ml of the liquid cleaning compositions described in Table 1 and Table 2, for 5 minutes to 60 minutes. The compositions according to the

invention was prepared by the process described above. The plates were gently agitated. The plates were removed after fixed timeJrite'rvais^and^washed under a
.'• ■ . - .. '■■«- ^..
tap of running water for ~ 30 seconds. A comparison of the initial Iqyel of the polymerised soil deposited on the plate was\:cotjipared; by/a quantitative optical
V.
^
.-*?'
technique, with the removal of the soil after cleanioganid washing. The/data was collected in replicates.

Table 1

'. Dipole Mo. D Ex1 Ex 2 Ex 3 Ex 4 Ex 5 Ex 6 Ex 7 Ex 8 Ex 9
Water 1.85 100 50 50 - 50 - 50 - 50
Hexadecane 0 - 50 - 100 - - - - -
Xylene 0.64 - - 50 - - - - - -
Chloroform 1.04 - - - - 50 100 - - -
Isopropanol 1.56 - - - - - - - - 50
Isobutanol 1.64 - - - - - - 50 100 -
Immiscible phases - yes yes - yes - yes - No
% Clean - 5min 0 0 0 0 100 0 50 0 0
% Clean - 60min 0 0 0 0 100 0 100 0 0
The data in table 1 show that when plates soiled with polymerised oil, created in the manner described above, are washed in a polar liquid (water) alone, there is no removal of soil (Ex 1). Similarly when they are washed in equal volumes of water and a non-polar liquid, for e.g. hexadecane (EX 2) or xylene (Ex3) or in a

non-polar system alone (EX 4), where no fraction of the non-polar liquid has a dipole moment above 0.8 debye, there is no removal of soil. However, example 5 shows that if the relatively non-polar phase used has a dipole moment above 0.8 debye and is used along with a polar liquid, complete removal of, the tough soil occurs. The polar liquid in this case is. water, and the two liquids are present above their mutual miscibility limits, as described by this invention. Example 6 however, shows that when the non-polar phase having a dipole moment above 0.8 debye is used without the polar phase, no cleaning occurs. Example 7 shows a composition in accordance with this invention where the relatively non-polar phase such as isobutanol has a dipole moment of 1.64, and is used in combination with a polar liquid above their mutual miscibility limit, complete soil removal is achieved. Example 8 shows that isobutanol without the polar phase, is ineffective. In example 9, although the dipole moment of isopropanol is greater than 0.8 debye, as it is miscible with the polar phase, it does not help in cleaning and. it is an essential requirement of the invention that there are two immiscible phases. It may be noted that in example 5 the relatively non-polar phase is heavier than the polar phase, while in example 7, the polar phase is heavier. This shows that the density of the liquids do not effect cleaning.
The effect of surfactants in the system:
The data shown in this table compares two compositions, both in accordance with the invention, but different in that one contains surfactant (Ex 11) while the other does not (Ex 10). In the example 11 where 0.5% surfactant was added, the

non-polar liqzuid with dipole moment less than 0.8 debye (Hexadecane) was
proportionately reduced.
Table 2

Example 10, prepared according to this invention shows that only a fraction of the non-polar phase needs to have a dipole moment above 0.8 debye for effective cleaning. It can be seen from example 11, that while the presence of surfactant is not essential part of this invention, it is not a deterrent and aids the cleaning process, hence forming a preferred option. It is also evident from table 1 and 2 that if the non-polar phase entirely comprises of a liquid with dipole moment greater than 0.8 debye the rate of cleaning is faster.

We Claim:
1. A cleaning composition comprising:
i. a non-polar phase comprising one or more liquids such as herein described
having an electric dipole moment less than that of water characterized in that at least 10% of the said non-polar phase has an electric dipole moment greater thaft 0.8 debye a polar liquid such as herein described;
wherein the non-polar liquids are present at levels above their mutual miscibility limits, such that they form at least two immiscible phases.
2. A cleaning composition as claimed in claim 1 comprising:
i. a non-polar phase comprising one or more liquids having an electric dipole
moment less than that of water wherein at least 50% of the said non-polar phase has an electric dipole moment in the range 1 to 1.8 debye;
ii. a polar liquid such that its interfacial tension with the said non-polar liquid is not
greater than 45mN/m;
wherein the non-polar and polar liquids are present at levels above their mutual miscibility limits, such that they form at least two immiscible phases.
3. A cleaning composition as claimed in anyone of claims 1 or 2 comprising:
i. a non-polar phase comprising one or more liquids having an electric dipole
moment less than that or water wherein at least 10% of the said non-polar phase has an electric dipole moment greater than 0.8 debye;
ii. a polar liquid;
iii. optionally up to 10% by weight surfactant

wherein the non-polar and polar liquids are present at levels above their mutual miscibility limits, such that they form at least two immiscible phases, which is optionally a stable emulsion.
4. A cleaning composition as claimed in anyone of claims 1 to 3 wherein the said non-polar phase and polar phase form an immiscible system and are selected from liquids comprising water, alcohol, esters, ethers, ketones, hydrocarbons, paraffins, aromatic solvents, halogenated solvents, heterocyclics.
5. A cleaning composition as claimed in anyone of claims 1 to 4 wherein the non-polar phase comprise liquids having a dipole moment in the range 0 to 1.85 debye with at least 10% of the non-polar phase comprising of liquids with an electric dipole moment greater than 0.8 debye and preferably 1.0 to 1.8 debye.
6. A cleaning composition as claimed in anyone of claims 1 to 5 wherein the liquids for the non-polar phase are selected to have a carbon chain length greater than 6 selected from branched and linear alkanes CnH 2n+2 wherein n is greater than 6 preferably, hexane, heptane, octane, nonane,. decane, dodecance, tridecane, tetradecane, pentadecane and mixtures thereof, branched and linear alkenes with greater than 6 carbon atoms preferably octenes, nonenes, decenes, undecenes, dodecenes with one or more degree of unsaturation and mixtures thereof.
7. A cleaning composition as claimed in claim 4 wherein the ethers are selected from fluoroether preferably Methoxy nonafluorobutane and ethoxy nonafluorobutane the esters are selected from Dibutyl phthalate, Dioctyl phthalate and terpenes preferably limonene or mixtures thereof and said hydrocarbons comprise halogenated hydrocarbons preferably carbon tetrachloride.


8. A cleaning composition as claimed in anyone of claims 1 to 7 wherein liquids with SiO units greater than 3 are selected from polydimethyl siloxane oils, linear and cyclic siloxane.
9. A cleaning composition as claimed in anyone of claims 1 to 8 comprising relatively non-polar liquids having dipole moment greater than 0.8 debye selected from chlorinated hydrocarbons preferably Dichloroethanes, Dichloroethylenes, Dichloro ethyl ethers, Dichloromethane, Dichloropropanes, chloroform, other halocarbons preferably disromomethane Bromochloromethane and Bromoform.
10.A cleaning composition as claimed in anyone of claims 1 to 9
comprising non-polar phase with dipole moment greater than 0.8 Debye selected from ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol ethyl ether acetate, ethylene glycol monomethyl ether acetate, ethyl acetate and ethyl formate.
11. A cleaning composition as claimed in anyone of claims 1 to 10 comprising non-polar phase, with dipole moment greater than 0.8 Debye selected from alcohols which s how limited water miscibility preferably butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol and all compounds covered by the generic from CnH 2n+2O and their isomers.
12. A cleaning composition as claimed in anyone of claims 1 to 11 wherein the polar phase comprises of water and water soluble solvents such as acetone, alkanolamines, water miscible alcohols and ethers.
13.A cleaning composition as claimed in anyone of claims 1 to 11 comprising conventional detergent ingredients selected from detergent active, builders, soil release polymers, hydrotropes, enzymes, bleaches and perfumes.


14. A cleaning composition as claimed in anyone of claims 1 to 13 optionally comprising an anionic detergent active with an alkali or alkaline earth metal or ammonium or alkanolamine counter ion or a mixture thereof.
15.A cleaning composition as claimed in anyone of claims 1 to 14 comprising other detergent actives selected from nonionic, cationic, amphoteric or zwitterionic surfactants.
16. A cleaning composition substantially as herein described and illustrated with reference to the accompanying examples
Dated this 15th day of November 2002
Dr.Sanchita Ganguli Of S.MAJUMDAR & CO. Applicant's Agents

Documents:

1111-mum-2001-cancelled pages(29-09-2004).pdf

1111-mum-2001-claims(granted)-(29-09-2004).pdf

1111-mum-2001-claims(granted)-(29-9-2004).doc

1111-mum-2001-correspondence(ipo)-(04-01-2006).pdf

1111-mum-2001-correspondence1(15-11-2002).pdf

1111-mum-2001-correspondence2(31-01-2006).pdf

1111-mum-2001-form 1(22-11-2001).pdf

1111-mum-2001-form 19(23-06-2003).pdf

1111-mum-2001-form 2(granted)-(29-09-2004).pdf

1111-mum-2001-form 2(granted)-(29-9-2004).doc

1111-mum-2001-form 3(15-11-2002).pdf

1111-mum-2001-form 3(22-11-2001).pdf

1111-mum-2001-form 5(15-11-2002).pdf

1111-mum-2001-power of attorney(23-09-2004).pdf


Patent Number 198017
Indian Patent Application Number 1111/MUM/2001
PG Journal Number 42/2008
Publication Date 17-Oct-2008
Grant Date 04-Jan-2006
Date of Filing 22-Nov-2001
Name of Patentee HINDUSTAN LEVER LIMITED
Applicant Address HINDUSTAN LEVER HOUSE, 165/166, BSCKBAY RECLAMATION, MUMBAI-400 020, MAHARASHTRA, INDIA.
Inventors:
# Inventor's Name Inventor's Address
1 CHATTERJEE JAIDEEP 4A, AGRASAR, HLRC CAMPUS, CHAKALA, ANDHERI (EAST), MUMBAI - 400099, MAHARASHTRA, INDIA.
2 BARGAJE VIJAYA MILIND #5, A.V. RESIDENCY, OFF. 80 FT. ROAD, BEHIND TATA INFOTECH, INDIRANAGAR, BANGALORE - 560 066, KARNATAKA, INDIA.
PCT International Classification Number N/A
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA