Abstract:
FORM - 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10 and Rule 13)
IMPROVEMENTS RELATING TO FABRIC CONDITIONERS
HINDUSTAN UNILEVER LIMITED, a company incorporated under
the Indian Companies Act, 1913 and having its registered office
at 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India
The following specification particularly describes the invention and the manner in which it is to be performed
IMPROVEMENTS RELATING TO FABRIC CONDITIONERS
Technical Field
The present invention relates to "superabsorbent" particles and their use to improve the in-wear comfort of fabrics, especially synthetic fabrics, by increasing fabric absorbency.
Background and Prior Art
The comfort of textile articles such as clothes can be compromised during wear as a result of sweating by the wearer. Synthetic fabrics, such as polyester, tend to feel less comfortable than cotton during sweating because they absorb very little moisture. In contrast cotton, which can absorb over 10 % of its weight in moisture, continues to feel dryer to the wearer for longer, even at moderate levels of sweating.
There is a need to improve the in-wear comfort of materials during sweating.
JP03220371A (Kanebo) discloses the coating of the surface of synthetic textile with a resin which contains particles of the silk protein "fibroin". The fabric is tack-free and flexible and has high moisture-permeability. Excellent dry touch and quality is said to be produced at a fibroin content of 10-35 wt %.
JP2000110027A (Mitsubishi) discloses the introduction of a fine clay particle e.g. montmorillonite during the preparation (polymerisation) of thermoplastic polyester, to give a water absorbing polyester. Preferably the clay is swollen with water and water replaced with glycol. Treated fabrics have good spinabiiity, dyeability and softness.
superabsorbent polymeric core and a porous shell, wherein the shell comprises silicone.
According to a third aspect of the invention, there is provided a use of the composition of the second aspect of the invention to increase the moisture absorption of fabric.
According to a fourth aspect of the invention, there is provided a use of the composition of the second aspect of the invention to improve the In-wear comfort of fabric.
According to a fifth aspect of the invention, there is provided a method of treating fabric, comprising contacting fabric with a composition of the second aspect of the invention.
Detailed Description of the Invention
The Superabsorbent Particles
The superabsorbent particles for use in the invention and in the compositions of the invention are capsules (or "encaps"), with a superabsorbent polymeric core and a porous shell. The capsules expand as water is absorbed by the superabsorbent core. The superabsorbent particles of the invention do not feel sticky when they absorb moisture.
The Core
The superabsorbent polymeric core comprises a superabsorbing polymer. Any suitable superabsorbent polymer may be used, including cellulose-based and polyacrylic acid-based polymers. Superabsorbent polymers are polymers that are
capable of absorbing and holding large amounts of water or aqueous solvents by forming aqueous gels.
Suitable superabsorbent polymers include synthetic polymers, in particular acrylic-and methacrylic-acid-based, cross-linked synthetic polymers and copolymers. In the context of this invention, polyacrylic acid superabsorbers refer to acrylic based polymers containing more than 50 % acrylic acid monomer. These known synthetic absorbents are virtually water insoluble. This class of superabsorbent polymers includes crosslinked polyacrylic acid or copolymers, starch grafted polyacrylonitrile hydrolysates, starch and acrylic acid grafted crosslinked polymers as well as hydrolysates of copolymers based on vinylacetate and acrylic esters. In such polymers and copolymers, about 60 to 90 % of all carboxylic groups may be neutralised by alkaline metals. A preferred polyacrylic acid-based polymer is cross-linked poiymethacrylic acid.
Starch-based superabsorbent polymers are also suitabfe, for example starch acrylonitrile graft polymers and gelatinized starch derivatives. Cellulose-based polymers may also be used, for example derivatives of alkyl- or hydroxyalkyl-cellulose, carboxymethylcellulose and polysaccharide-based derivatives. A preferred cellulose-based superabsorbing polymer is Sodium Carboxy Methyl Cellulose (SCMC).
Further suitable polymers as well as crosslinkers are those given in US2005/0013865 at paragraphs [0023] to [0035], and are incorporated herein by reference.
The Shell
The shell prevents sticky feeling when the absorbent material is on the fabric. The shell is hydrophobic in nature and comprises silicone.
The porous shell expands with the core as the core absorbs fluid (such as sweat). This expansion prevents the splitting of the shell and consequent failure of the particle. Suitable silicone based materials are those wherein the silicone is capable of expanding as the core absorbs fluid. A particularly preferred silicone shell is an amidomethicone.
Particle size and average diameter of the capsules can vary from about 10 nanometers to about 1000 microns, preferably from about 100 nanometers to about 100 microns, more preferably from about 200 nanameters to about 40 microns, even more preferably from about 300 nanometers to 15 microns. A particularly preferred range is from about 300 nanometers to 8 microns. The capsule distribution can be narrow, broad or multimodal. Multimodal distributions may be composed of different types of capsule chemistries.
The amount of superabsorbent polymer particles in the compositions of the invention is from 0.01 to 50 wt %, preferably from 0.1 to 15 wt %, more preferably from 4 to 11 wt %, based on the total weight of the composition.
The superabsorbent polymer particles are suitably used in an amount of from 0.1 to 15 wt % by weight of the fabric. When the fabric is cotton, the amount used is preferably from 1 to 15, more preferably from 5 to 15 wt % by weight of the fabric. When the fabric is synthetic, the amount used is preferably from 0.1 to 10, more preferably from 1 to 10 wt % by weight of the fabric.
The preferred superabsorbent polymer particles are Sofcare S-SP manufactured by Kao Corporation. These particles are capsules, which comprise cross-linked polymethacrylic acid (neutralised with Na salt) and which are coated with an expandable silicone.
The Solvent
The compositions of the invention may be non-aqueous. Such compositions may comprise a suitable non-aqueous solvent. Suitable solvents include cyclic siloxanes such as decamethylcyclopentasiloxane (D5) and decamethylcyclohexasiloxane (D6). Further examples include hydrocarbons such as pentane and hexane.
Perfume
The compositions of the invention preferably comprise one or more unconfined perfume, by which is meant a non-encapsulated perfume. Any suitable perfume or mixture of perfumes may be used.
The perfume must be compatible with the carrier oil as described above and must be able to permeate the shell of the capsule. Those with skill in the art will appreciate that the present invention may contain a single ingredient, but it is much more likely that the present invention will comprise at least eight or more fragrance chemicals, more likely to contain twelve or more and often twenty or more fragrance chemicals. The present invention also contemplates the use of complex fragrance formulations containing fifty or more fragrance chemicals, seventy five or more or even a hundred or more fragrance chemicals in a fragrance formulation. Suitable unconfined perfumes for use in the present invention include those disclosed in EP1533364A2 (IFF).
The perfume is preferably present in an amount from 0.01 to 10 % by weight, more preferably from 0.05 to 5 % by weight, even more preferably from 0.1 to 4.0 %, most preferably from 0.2 to 4.0 % by weight, based on the total weight of the composition.
Useful components of the perfume include materials of both natural and synthetic origin. They include single compounds and mixtures. Specific examples of such components may be found in the current literature, e.g., in Fenaroli's Handbook of Flavor Ingredients, 1975, CRC Press; Synthetic Food Adjuncts, 1947 by M. B. Jacobs, edited by Van Nostrand; or Perfume and Flavor Chemicals by S. Arctander 1969, Montclair, N.J. (USA). These substances are well known to the person skilled in the art of perfuming, flavouring, and/or aromatizing consumer products, i.e., of imparting an odour and/or a flavour or taste to a consumer product traditionally perfumed or flavoured, or of modifying the odour and/or taste of said consumer product.
By perfume in this context is not only meant a fully formulated product fragrance, but also selected components of that fragrance, particularly those which are prone to loss, such as the so-called 'top notes'.
Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Examples of well known top-notes include citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. Top notes typically comprise 15-25%wt of a perfume composition and in those embodiments of the invention which contain an increased level of top-notes it is envisaged at that least 20%wt would be present within the encapsulate.
Some or ail of the perfume or pro-fragrance may be encapsulated, typical perfume components which it is advantageous to encapsulate, include those with a relatively low boiling point, preferably those with a boiling point of less than 300, preferably 100-250 Celsius and pro-fragrances which can produce such components.
It is also advantageous to encapsulate perfume components which have a low Clog P (ie. those which will be partitioned into water), preferably with a Clog P of
less than 3.0. These materials, of relatively low boiling point and relatively low Ciog P have been called the "delayed blooming" perfume ingredients and include the following materials:
Allyl Caproate, Amyl Acetate, Amy! Propionate, Anisic Aldehyde, Anisole, Benzaldehyde, Benzyl Acetate, Benzyl Acetone, Benzyl Alcohol, Benzyl Formate, Benzyl Iso Valerate, Benzyl Propionate, Beta Gamma Hexenol, Camphor Gum, Laevo-Carvone, d-Carvone, Cinnamic Alcohol, Cinamyl Formate, Cis-Jasmone, cis-3-Hexenyl Acetate, Cuminic Alcohol, Cyclal C, Dimethyl Benzyl Carbinol, Dimethyl Benzyl Carbinol Acetate, Ethyl Acetate, Ethyl Aceto Acetate, Ethyl Amyl Ketone, Ethyl Benzoate, Ethyl Butyrate, Ethyl Hexyl Ketone, Ethyl Phenyl Acetate, Eucalyptol, Eugenol, Fenchyl Acetate, Flor Acetate (tricyclo Decenyl Acetate), Frutene (tricyclco Decenyl Propionate), Geraniol, Hexenol, Hexenyl Acetate, Hexyl Acetate, Hexyl Formate, Hydratropic Alcohol, Hydroxycitronellal, Indone, Isoamyl Alcohol, Iso Menthone, Isopulegyl Acetate, Isoquinolone, Ligustral, Linalool, Linalool Oxide, Linalyl Formate, Menthone, Menthyl Acetphenone, Methyl Amyl Ketone, Methyl Anthranilate, Methyl Benzoate, Methyl Benyf Acetate, Methyl Eugenol, Methyl Heptenone, Methyl Heptine Carbonate, Methyl Heptyl Ketone, Methyl Hexyl Ketone, Methyl Phenyl Carbinyl Acetate, Methyl Salicylate, Methyl-N-Methyl Anthranilate, Nerol, Octalactone, Octyl Alcohol, p-Cresol, p-Cresol Methyl Ether, p-Methoxy Acetophenone, p-Methyl Acetophenone, Phenoxy Ethanol, Phenyl Acetaldehyde, Phenyl Ethyl Acetate, Phenyl Ethyl Alcohol, Phenyl Ethyl Dimethyl Carbinol, Prenyl Acetate, Propyl Bornate, Pulegone, Rose Oxide, Safrole, 4-Terpinenol, Alpha-Terpinenol, and/or Viridine.
Preferred non-encapsulated perfume ingredients are those hydrophobic perfume components with a ClogP above 3. As used herein, the term "ClogP" means the logarithm to base 10 of the octanol/water partition coefficient (P). The octanol/water partition coefficient of a PRM is the ratio between its equilibrium concentrations in octanol and water. Given that this measure is a ratio of the
equilibrium concentration of a PRM in a non-polar solvent (octanol) with its concentration in a polar solvent (water), ClogP is also a measure of the hydrophobicity of a material-the higher the ClogP value, the more hydrophobic the material. ClogP values can be readily calculated from a program called "CLOGP" which is available from Daylight Chemical Information Systems Inc., Irvine Calif., USA. Octanol/water partition coefficients are described in more detail in U.S. Pat. No. 5,578,563.
Perfume components with a ClogP above 3 comprise: Iso E super, citronellol, Ethyl cinnamate, Bangalol, 2,4,6-Trimethylbenzaldehyde, Hexyl cinnamic aldehyde, 2,6-Dimethyl-2-heptanol, Diisobutylcarbinol, Ethyl salicylate, Phenethyl isobutyrate, Ethyl hexyl ketone, Propyl amyl ketone, Dibutyl ketone, Heptyi methyl ketone, 4,5-Dihydrotoluene, Caprylic aldehyde, Citral, Geranial, Isopropyl benzoate, Cyclohexanepropionic acid, Campholene aldehyde, Caprylic acid, Capryiic alcohol, Cuminaldehyde, 1 -Ethyl-4-nitrobenzene, Heptyi formate, 4-Isopropylphenol, 2-lsopropylphenol, 3-lsopropylphenol, Allyl disulfide, 4-Methyl-1-phenyl-2-pentanone, 2-Propylfuran, Allyl caproate, Styrene, Isoeugenyl methyl ether, Indonaphthene, Diethyl suberate, L-Menthone, Menthone racemic, p-Cresyl isobutyrate, Butyl butyrate, Ethyl hexanoate, Propyl valerate, n-Pentyl propanoate, Hexyl acetate, Methyl heptanoate, trans-3,3,5-Trimethylcyclohexanol, 3,3,5-Trimethylcyclohexanol, Ethyl p-anisate, 2-Ethy[-1-hexanol, Benzyl isobutyrate, 2,5-Dimethylthiophene, Isobutyl 2-butenoate, Caprylnitrile, gamma-Nonalactone, Nerol, trans-Geraniol, 1-Vinylheptanol, Eucalyptol, 4-Terpinenol, Dihydrocarveol, Ethyl 2-methoxybenzoate, Ethyl cyclohexanecarboxylate, 2-Ethylhexanal, Ethyl amyl carbinol, 2-Octanol, 2-Octanol, Ethyl methylphenylglycidate, Diisobutyl ketone, Coumarone, Propyl isovalerate, Isobutyl butanoate, isopentyl propanoate, 2-Ethyibutyl acetate, 6-Methyi-tetrahydroquinoline, Eugenyl methyl ether, Ethyl dihydrocinnamate, 3,5-Dimethoxytoluene, Toluene, Ethyl benzoate, n-Butyrophenone, alpha-Terpineol, Methyl 2-methylbenzoate, Methyl 4-methyibenzoate, Methyl 3, methylbenzoate, sec.Butyl n-butyrate, 1,4-Cineole,
Fenchyl alcohol, Pinanol, cis-2-Pinanol, 2,4, Dimethylacetophenone, Isoeugenol, Safrole, Methyl 2-octynoate, o-Methylanisole, p-Cresyl methyl ether, Ethyl anthranilate, Linalooi, Phenyl butyrate, Ethylene glycol dibutyrate, Diethyl phthalate, Phenyl mercaptan, Cumic alcohol, m-Toluquinoline, 6-Methylquinoline, Lepidine, 2-Ethylbenzaldehyde, 4-Ethylbenzaldehyde, o-Ethylphenol, p-Ethylphenol, m-Ethylphenol, (+)-Pulegone, 2,4-Dimethylbenzaldehyde, Isoxylaldehyde, Ethyl sorbate, Benzyl propionate, 1,3-Dimethylbutyl acetate, Isobutyl isobutanoate, 2,6-Xylenol, 2,4-Xylenol, 2,5-Xylenol, 3,5-Xylenol, Methyl cinnamate, Hexyl methy! ether, Benzyl ethyl ether, Methyl salicylate, Butyl propyl ketone, Ethyl amyl ketone, Hexyl methyl ketone, 2,3-Xylenol, 3,4, Xylenol, Cyclopentadenanolide and Phenyl ethyl 2 phenylacetate 2.
It is commonplace for a plurality of perfume components to be present in a formulation. In the compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components from the list given of delayed blooming perfumes given above and/or the list of perfume components with a ClogP above 3 present in the perfume.
Another group of perfumes with which the present invention can be applied are the so-called 'aromatherapy' materials. These include many components also used in perfumery, including components of essentia! oils such as Clary Sage, Eucalyptus, Geranium, Lavender, Mace Extract, Neroli, Nutmeg, Spearmint, Sweet Violet Leaf and Valerian.
Product Form and Method of Treatment
The compositions of the invention are suitable for domestic use. In the context of this invention, by domestic use is meant use in the home, in launderettes, etc on finished textiles and does not extend to use during the textile manufacturing
process. The composition may be a laundry composition or a fabric treatment composition. For example, the composition may be a fabric softening composition, a detergent composition or a softening in the wash composition.
The method of treatment involves contacting the substrate (fabric) with the composition of the invention.
The treatment of the substrate with the composition of the invention can be made by direct application such as spraying, rubbing, spotting, smearing, etc, preferably spraying.
The amount of superabsorbent particles used in the method of treatment is suitably from 0.1 to 15 wt %, by weight of the fabric. Where the fabric is cotton, the method involves using the superabsorbent polymer particles in an amount of from 5 to 15 wt % by weight of the fabric. Where the fabric is a synthetic fabric, preferably polyester, the method involves using the superabsorbent polymer particles in an amount of from 0.1 to 10 wt % by weight of the fabric.
The treatment may be provided as a spray composition e.g., for domestic (or industrial) application to fabric, for example in a treatment separate from a conventional domestic laundering process. Suitable spray dispensing devices are disclosed in WO 96/15310 (Procter & Gamble).
The compositions of the invention are in liquid form. The composition may be a concentrate to be diluted in a non-aqueous solvent before use. The composition may also be a ready-to-use (in-use) composition. Preferably the composition is provided as a ready to use liquid.
Further Optional Ingredients
The compositions of the invention may contain one or more other ingredients. Such ingredients include dyes, colourants, preservatives (e.g. bactericides), pH buffering agents, perfume carriers, hydrotropes, polyeiectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, peariisers and/or opacifiers.
Method of Manufacture
In a typical method of manufacture, the superabsorbent capsules are added to a solvent. Perfume and other optional adjuncts may be pre- or post-dosed, or added simultaneously.
The superabsorbent capsules and compositions containing them are useful to increase the moisture absorption of fabric and thus reduce the wet fee! caused, for example, by sweating. The superabsorbent particles of the invention are used to improve the in-wear comfort of fabric. The particles are particularly useful in the treatment of synthetic fabric, preferably polyester.
Examples
Embodiments of the invention are now illustrated with reference to the following non-limiting examples. Unless stated otherwise, all proportions are given in weight percent, by weight of the total composition.
Example 1 - Treatment of polyester and cotton with Compositions 1-3 and Control A
Sofcare S-SP was applied to two types of fabric (100 % Knitted Polyester & 100 % Knitted Cotton). Three different concentrations of Sofcare S-SP were applied. A control composition, containing pentane only were also applied to polyester and cotton samples. A pad mangle was used to apply the compositions (Vertical
laboratory padder VFM type ex. Werner Math is AG). Fabric samples were pad applied to 100% pick-up. The fabric samples were then dried in air.
Composition Sofcare S-SP1
(wt % by
weight of
fabric)
1 0.1
2 1.0
3 10.0
A* 0
1 - Sofcare S-SP, ex Kao, 0.166 % active dispersion in pentane A - Control composition
Example 2 - Moisture absorption properties of polyester and cotton treated with Sofcare S-SP
The effect on Sofcare S-SP on moisture absorption of fabrics was assessed as follows.
Moisture absorption was determined using Dynamic Vapour Sorption (DVS) measurements made on a DVS1 (Surface Measurement Systems Limited, UK). The sample weight was measured as a function of humidity, giving a water sorption isotherm.
The sorption isotherms shown below were obtained by taking measurements at several intervals between 0 to 95 % RH (relative humidity) and 95 to 0 % RH. A
measurement was made by holding the textile at a set RH until no further weight change was observed.
All measurements were made at 25°C.
The results are shown in Figure 1 (for cotton) and Figure 2 (for polyester).
It will be seen from Figure 1 and Figure 2 that the use of the superabsorbent particles in accordance with the invention leads to significant increase in the amount of moisture absorbed by the fabrics.
In particular, it will be seen that 1 % Sofcare S-SP on polyester significantly increases the amount of moisture that can be absorbed, i.e. 8.8 % absorption compared with 0.6 % for untreated polyester. A 10 % loading of Sofcare S-SP on polyester gives a greater absorbency than untreated Cotton, i.e. 19.6 % compared with 13.5%.
CLAIMS
1. Use of a superabsorbent particle, comprising a superabsorbent polymeric core and a hydrophobic porous shell in the domestic treatment of fabric, wherein the shell comprises silicone.
2. Use as claimed in claimed 1, to improve the in-wear comfort of fabric.
3. Use as claimed in claim 1 or claim 2 to increase the moisture absorption of fabric.
4. Use as claimed in any preceding claim to reduce the wet feel of fabric.
5. Use as claimed in any preceding claim, wherein the fabric is synthetic.
6. Use as claimed in claim 5, wherein the fabric is polyester.
7. A non-aqueous fabric treatment composition for domestic use, comprising superabsorbent particles and a solvent, wherein the superabsorbent particles comprise a superabsorbent polymeric core and a porous she!}, and wherein the shell comprises silicone.
8. A composition as claimed in claim 7, wherein the silicone is an amidomethicone.
9. A composition as claimed in claim 7 or claim 8, wherein the superabsorbent particles are present in an amount of from 4 to 11 wt %.
10. A composition as claimed in any one of claims 7 to 9, which further comprises a perfume.
11. A composition as claimed in claim 10, wherein the perfume is present in an
amount of from 0.01 to 10 % by weight of the total composition.
12. A composition as claimed in one of claims 7 to 11, wherein the solvent is a
siloxane.
13. Use of a composition as defined in any one of claims 7 to 12 to increase the moisture absorption of fabric.
14. Use of a composition as defined in any one of claims 7 to 12 to improve the in-wear comfort of fabric.
15. Use as claimed in claim 14 to reduce the wet feel of fabric.
16. Use as claimed in any one of claims 13 to 15, wherein the fabric is synthetic, preferably polyester.
17. A method of treating fabric, comprising contacting fabric with a composition as defined in any one of claims 7 to 12.
18. A method as claimed in claim 17, wherein the fabric is cotton.
19. A method as claimed in claim 17, wherein the fabric is a synthetic fabric, preferably polyester.
20. A method as claimed in claim 18, wherein the superabsorbent polymer particles are used in an amount of from 0.1 to 15 wt % by weight of the fabric.
21. A method as claimed in claim 19, wherein the superabsorbent polymer particles are used in an amount of from 5 to 15 wt % by weight of the fabric.
22. A method as claimed in claim 20, wherein the superabsorbent polymer particles are used in an amount of from 0,1 to 10 wt % by weight of the fabric.
23. A method as claimed in any one of claims 18. to 22, wherein the composition is delivered in the form of a spray.
| # | Name | Date |
|---|---|---|
| 1 | 439-mumnp-2011-claims.pdf | 2018-08-10 |
| 1 | 439-MUMNP-2011-FORM 3(12-08-2011).pdf | 2011-08-12 |
| 2 | 439-MUMNP-2011-CORRESPONDENCE(19-6-2012).pdf | 2018-08-10 |
| 2 | 439-MUMNP-2011-FORM 3(10-12-2013).pdf | 2013-12-10 |
| 3 | 439-MUMNP-2011-CORRESPONDENCE(5-9-2011).pdf | 2018-08-10 |
| 3 | 439-MUMNP-2011 -FORM 3(10-11-2014).pdf | 2014-11-10 |
| 4 | 439-mumnp-2011-correspondence.pdf | 2018-08-10 |
| 5 | 439-MUMNP-2011_EXAMREPORT.pdf | 2018-08-10 |
| 5 | 439-mumnp-2011-description(complete).pdf | 2018-08-10 |
| 6 | 439-mumnp-2011-wo international publication report a1.pdf | 2018-08-10 |
| 6 | 439-mumnp-2011-drawing.pdf | 2018-08-10 |
| 7 | 439-mumnp-2011-other documents.pdf | 2018-08-10 |
| 7 | 439-mumnp-2011-form 1.pdf | 2018-08-10 |
| 8 | 439-MUMNP-2011-GENERAL POWER OF ATTORNEY(5-9-2011).pdf | 2018-08-10 |
| 8 | 439-MUMNP-2011-FORM 13(13-2-2012).pdf | 2018-08-10 |
| 9 | 439-MUMNP-2011-FORM 18(19-6-2012).pdf | 2018-08-10 |
| 9 | 439-mumnp-2011-form pct-isa-210.pdf | 2018-08-10 |
| 10 | 439-mumnp-2011-form 2(title lpage).pdf | 2018-08-10 |
| 10 | 439-mumnp-2011-form 5.pdf | 2018-08-10 |
| 11 | 439-mumnp-2011-form 2.pdf | 2018-08-10 |
| 11 | 439-mumnp-2011-form 3.pdf | 2018-08-10 |
| 12 | 439-MUMNP-2011-FORM 3(15-2-2012).pdf | 2018-08-10 |
| 12 | 439-MUMNP-2011-FORM 3(23-1-2013).pdf | 2018-08-10 |
| 13 | 439-MUMNP-2011-FORM 3(21-5-2014).pdf | 2018-08-10 |
| 13 | 439-MUMNP-2011-FORM 3(22-6-2013).pdf | 2018-08-10 |
| 14 | 439-MUMNP-2011-FORM 3(21-5-2014).pdf | 2018-08-10 |
| 14 | 439-MUMNP-2011-FORM 3(22-6-2013).pdf | 2018-08-10 |
| 15 | 439-MUMNP-2011-FORM 3(15-2-2012).pdf | 2018-08-10 |
| 15 | 439-MUMNP-2011-FORM 3(23-1-2013).pdf | 2018-08-10 |
| 16 | 439-mumnp-2011-form 3.pdf | 2018-08-10 |
| 16 | 439-mumnp-2011-form 2.pdf | 2018-08-10 |
| 17 | 439-mumnp-2011-form 5.pdf | 2018-08-10 |
| 17 | 439-mumnp-2011-form 2(title lpage).pdf | 2018-08-10 |
| 18 | 439-MUMNP-2011-FORM 18(19-6-2012).pdf | 2018-08-10 |
| 18 | 439-mumnp-2011-form pct-isa-210.pdf | 2018-08-10 |
| 19 | 439-MUMNP-2011-FORM 13(13-2-2012).pdf | 2018-08-10 |
| 19 | 439-MUMNP-2011-GENERAL POWER OF ATTORNEY(5-9-2011).pdf | 2018-08-10 |
| 20 | 439-mumnp-2011-form 1.pdf | 2018-08-10 |
| 20 | 439-mumnp-2011-other documents.pdf | 2018-08-10 |
| 21 | 439-mumnp-2011-drawing.pdf | 2018-08-10 |
| 21 | 439-mumnp-2011-wo international publication report a1.pdf | 2018-08-10 |
| 22 | 439-mumnp-2011-description(complete).pdf | 2018-08-10 |
| 22 | 439-MUMNP-2011_EXAMREPORT.pdf | 2018-08-10 |
| 23 | 439-mumnp-2011-correspondence.pdf | 2018-08-10 |
| 24 | 439-MUMNP-2011-CORRESPONDENCE(5-9-2011).pdf | 2018-08-10 |
| 24 | 439-MUMNP-2011 -FORM 3(10-11-2014).pdf | 2014-11-10 |
| 25 | 439-MUMNP-2011-FORM 3(10-12-2013).pdf | 2013-12-10 |
| 25 | 439-MUMNP-2011-CORRESPONDENCE(19-6-2012).pdf | 2018-08-10 |
| 26 | 439-MUMNP-2011-FORM 3(12-08-2011).pdf | 2011-08-12 |
| 26 | 439-mumnp-2011-claims.pdf | 2018-08-10 |