Abstract: N/A
3 times) a-ionone 366 Increase HS (>3 times) 15 Table 5; Perfume that Could Change "Note" on Dilution in Surfactant Containing Product 20 Fragrance Component PBI Dilution Behavior 2-heptanone -153 Decrease HS Menthone -71.4 Decrease HS Isoeugenol 58 Increase HS (>3 times) Tetrahydrolinalool 202 Increase HS (>3 times) Linalool 240 Increase HS (>3 times) WO 03/072078 PCT/EP03/01692 - Example 5 , It is also possible to take advantage of the technology of the invention to provide the introduction of a smell during 5 dilution of the surfactant-containing product. This can be achieved by formulating a fragrance ingredient into the product at a concentration just below the odor threshold. Therefore this component will not be perceived by the consumer in the original product, but as dilution occurs, if 10 the PBI is large enough to supply a concentration of that component into the headspace above the product to exceed the odor threshold, the fragrance molecule will now be perceived upon use. 15 This concept can be used to provide a product that is essentially " fragrance-free", but produces a light fragrance, with product dilution. This concept can also be utilized to , change fragrance note, but providing a new smell upon product dilution to combine with the other perfume molecules 20 to produce a new overall perfume mixture with use. Example 6 As suggested by the theoretical predictions, formulation 25 factors also play a role in controlling the fragrance burst from the surfactant containing product in use. Two very important factors are the surfactant concentration in the original product, and the CMC of the surfactant mixture used in the formulation. 30 WO 03/072078 PCT/EP03/01692 The effect of surfactant concentration can be predicted from the theoretical predictions in Example 1. The charts in Figure 5 show the result of two different perfumes with PBI of ~700 and ~12 with varying surfactant concentration 5 (surfactant CMC = 0.005 wt/wt). As the graphs indicate, with a lower surfactant concentration in the original formulation, the initial fragrance concentration above the product will be higher (e.g., because fewer fragrance molecules are in surfactant micelles), and maximum fragrance 10 burst can be reached with fewer dilutions. This is especially important, because the actual amount of dilution that typically occurs during product use is variable, depending on the type'of product and the consumer's habits. If the fragrance burst occurs with minimal dilution, the 15 effect is more likely to be noticed by the product user. The other distinct advantage of products with low surfactant levels is that the absolute amount of fragrance available during the fragrance burst is greater, therefore the 20 consumer will experience more fragrance during product use. Example 7 Experiments performed on actual perfumes in products with 25 different surfactant concentrations are shown in Figure 6. Limonene (PBI=12.2) was tested in shower liquids containing sodium laurate at 5, 10, 15 and 20 wt.%; gamma-methyl ionone and menthone were tested in sodium laurate at 5, 10 and 15 wt.% (Figure 6) . As noted in the theoretical.calculation 30 in Example 6, the maximum fragrance burst is reached with fewer dilutions in the 5% soap product, and the overall WO 03/072078 PCT/EP03/01692 amount of fragrance available during the burst is also greater for the 5% product. Thus, as seen, lower surfactant concentration is highly 5 beneficial. Example 8 t As noted in Examples 2. and 6, another variable that affects 10 the fragrance burst properties of a formulation is the critical micellization concentration (CMC) of the surfactant system. The CMC is actually used to calculate the PBI for various fragrance molecules. As the CMC of the surfactant system is decreased,the PBI values for different fragrance 15 molecules also decreases as shown in Table 6. Therefore in products with surfactant systems with low CMC values, the expected extent of the fragrance burst for different fragrances will be less. WO 03/072078 PCT/EP03/01692 - Table 6: Fragrance Burst Potential in Surfactants with Different CMC's 5 Fragrance PBI CMC=0.005 Burst PBI CMC=0.0025 Burst PBI CMC=0.001 Burst Benzyl Acetate -819 No -1694 No -4319 No Hexanal -109 No -268 No -599 No Methyl Benzoate -13 i No -32 No -89 No 2-Octanone -5 No -178 No -697 No Isoeugenol 58 Yes 21 Yes -90 No Hexyl Acetate 86 Yes -119 No -188 No Napthalene 107 Yes 78 Yes -10 No 2-Nonanone 194 Yes -94 No -190 No Linanool 24,0' Yes 147 Yes -133 No Limonene 1.2 Yes 9 Yes 1 No a-Ionone 1692; Yes 1261 Yes -30 No a-Pinene 20 Yes 19 Yes 16 Yes Tetrahydrolinolool 202 Yes 183 Yes 127 Yes Dihydromyrcenol 307 Yes 267 Yes 145 Yes Ethyl Undecylenate 624' Yes 557 Yes 357 Yes Decanal 942 Yes 916 Yes 847 Yes Methyl linolenate 771304 Yes 771283 Yes 771222 Yes As expected, the lower the CMC of the surfactant systems, the lower the fragrance burst potential. Also, since the 10 CMC is lower and the maximum burst is found around the CMC, as one moves to products with lower CMC's, the consumer will have to dilute the product more to actually experience higher fragrance concentrations. WO 03/072078 PCT/EP03/01692 Example 9 . Limonene and gamma-Methyl Ionone were tested in two different shower liquid samples. One product was formulated 5 with 5% sodium laurate (CMC = 0.005 wt/wt) and the second with 5% sodium laureth sulfate (CMC = 0.0011 wt/wt) (Figure 8). These results validate the theoretical results in Figure 7. The product with the lower CMC gives a lower overall fragrance burst, and more dilutions are required to 10 reach the maximum burst potential. Example 10 A typical fully formulated perfume used in a commercial 15 product, e.g., personalm wash formulation, usually is a multi-component composition in which the properties of each perfume component can vary dramatically. A typical perfume mixture in a 5 wt.% sodium laurate formulation was tested for its "perfume burst" behaviour upon dilution. The PBI 20 values of the componerits in this perfume mixture vary from a large negative number (e.g., benzyl acetate, PBI = -819; PEA, PBI = -200 in sodium laurate solution) to a large positive number (e.g., gamma-methyl-ionone, PBI = 1,677 in sodium laurate solution). The dilution behaviour of each 25 component in this perfume mixture is shown in Figure 9 (the graph represents a normalized GC measurement so the amount of burst of each molecule is clearly indicated). In this perfume mixture of twelve components, the dilution 30 behaviour of each component is different. Each component has a unique dilution curve (GC headspace vs. dilution WO 03/072078 PCT/EP03/01692 i factor) governed by the factors (hydrophobicity, volatility, etc) discussed previously. For instance, for those perfumes with a negative PBI (e.g., benzyl acetate), the perfume headspaces decrease upon dilution. For those perfumes with 5 a moderate positive PBI (e.g., limonene, PBI = 12; p-cymene = 12.2 in sodium laurate solution), the perfume headspaces increases 1-2 times upon dilution. For those fragrance components with a very large positive PBI (e.g., gamma-methyl-ionone), the "perfume burst" can be as high as seven 10 times. The results shown in Figure 9 indicated that in a fully formulated perfume, in terms of dilution behaviour, the performance of each component is mostly determined by its own individual physical properties. 15 Example 11 Trained sensory panel analyses were carried out to validate the "perfume burst" phenomena. A group of 20 to 30 expert sensory panellists were asked to rate the intensity of the 20 fragrance over formulations and anchor their scores to a perfume standard supplied for each test. Formulations containing a single perfume (gamma-methyl-ionone) and multi-component perfume were studied in two separate panels. The multi-component perfume contains four perfumes of equal 25 weight percentage, menthone, tetra-hydro-linalool, a-ionone, y-methyl-ionone, that will all "burst" in a sodium laurate product, but will not "burst" (e.g., menthone, a-ionone) or will give a moderate "burst" (e.g., tetra-hydro-linaiooi, y-methyl-ionone) in an SLES product with dilution. 30 WO 03/072078 PCT/EP03/01692 Each sample was tested in duplicate and the sample information and the panel study results are shown in Tables 7 and 8, and Figures 10 and 11. As shown in Tables 7 and 8, perfumes at two different initial concentrations were tested 5 in the sodium laurate solution. The scores shown in Figures 10 and 11 are the panel averages for each sample. The results of the panel analyses indicate that as expected, both the single perfume and the perfume mixture (Figure 10 10 and 11) in a sodium laurate product (a surfactant of high CMC, CMC = 0.5 wt.%), have higher sensory scores for the 10 times diluted solution compared to the original undiluted formulations. In the :SLES formulations (a surfactant of relatively low CMC, CMC = 0.1 wt.%), both single perfume and 15 perfume mixture (Figure'10 and 11) have lower sensory scores for the 10 times diluted solution compared to the original undiluted product. These results are consistent with the discussion and data presented in Example 8, which indicate that a surfactant of low CMC lowers the PBI of the perfume 20 and can greatly reduce the expected "perfume burst" upon dilution. The panel studies indicate that this "perfume burst" upon dilution can be perceived quite easily by the human nose if 25 the formulation is designed according to the rules listed in this specification. WO 03/072078 PCT/EP03/01692 Table 7: Sample Information of the Single Perfume (y-methyl-ionone) System for Panel Study Sample Name Information 1 0.0649 wt.% y-methyl-ionone in 4.5 wt.% sodium laurate 2 10 times dilution of 0.064 9 wt.% y-methyl-ionone in 4.5 wt.% sodium laurate 3 0.2193 wt.%. y-methyl-ionone in 4.5 wt.% sodium laurate 4 10 times dilution of 0.2193 wt.% y-methyl-ionone in 4.5 wt.% sodium laurate 5 0.2200 wt.% y-methyl-ionone in 4.5 wt.% SLES 6 10 times dilution of 0.2200 wt.% y-methyl-ionone in 4.5 wt.% SLES Table 8: Sample Information of the Multi-Component Perfume (menthone, tetra-hydro-linalool, a-ionone, y-methyl-ionone) System for Panel Study 10 Sample Name Information 7 0.2404 wt.% perfume mixture in 5 wt.% sodium laurate 8 10 times dilution of 0.2404 wt.% perfume mixture in 5 wt.% sodium laurate 9 0.6022 wt.% perfume mixture in 5 wt.% sodium laurate 10 10 times dilution of 0.6022 wt.% perfume mixture in 5 wt.% sodium laurate 11 0.2433 wt.% perfume mixture in 5 wt.% SLES 12 10 times dilution of 0.2433 wt.% perfume mixture in 5 wt.% SLES Example 12 15 There are any number of surfactant containing formulations that should provide a "perfume burst" in use. These include WO 03/072078 PCT/EP03/01692 personal wash products (i.e. shower gels, soap bars), shampoos, household cleaners, light duty detergents, fabric washing products, etc. All of these products undergo some dilution with use which could potentially cause release of 5 fragrance molecules from the surfactant micelles and provide a *burst" of fragrance intensity. As explained in the previous examples, the CMC of the surfactant mixture, the amount of surfactant in the product and the perfume ingredients used in the fragrance formulation all contribute 10 to the type and intensity of the "perfume burst" during product use. The following formulations are just a few examples of products that would be, expected to provide a "fragrance 15 burst" or change in fragrance note, assuming the perfume was properly designed (i.e. a fragrance containing a fraction of components with high PBI values). Table 9 Formulation Ingredients (%) Form. #1 Form. #2 Form. #3 Form. #4 Form. #5 Form. #6 Form. #7 Form. #8 Sodium Laurate 10 5 8 4 4 5 TEA Laurate 5 5 Sodium Laureth Sulfonate 2 4 8 Sodium Lauryl Sulfate 8 Alkylpoly Glucoside 7 Nonionic Polymeric Surfactant Containing Mixture of Alkylene Oxides 2 5 Caprylamido Propylbetaine 1 1 2 1 Sodium Cocoylisethionate 10 Laurie Acid 3 2 2 3 Amine Oxide 1 Xanthan Gum 1 0.8 Jaguar S13 (Cationic Polymer) 0.4 Polyacrylates (e.g., Structuring Agent) 0.6 0.6 Polymer JR (Cationic Polymer) 0.3 Triclosan 0.5 Trichlorocarbanilide 0.5 Propylene Glycol 10 Glycerine: 30 Vitamin E 0.05 Perfume 1 1 1.3. 1 1 1.2 0.8 1 Water To 100 To 100 To 100 To 100 To 100 To 100 To 100 To 100 O H o WO 03/072078 PCT/EP03/01692 As noted, these are examples of the many formulations in which the perfume burst concept can be used. Example 13 5 The deposition of the fragrance components onto a surface (e.g., skin) upon dilution of a surfactant containing product is also closely related to the thermodynamic characteristics of theperfume (e.g.,- oil/water partition coefficient, O, and 10 volatility constant, K) and the formulation (e.g., the surfactant CMC). For a perfume-containing composition that has a high PBI, the perfume headspace will increase upon dilution due to the increase of the perfume concentration in the continuous phase caused by surfactant demicellization. 15 This increase in perfume concentration in the continuous phase will also favor the deposition of the perfume onto the surface that the product comes into contact with due to the enhanced chemical potential of the perfume in the continuous phase 20 which is in direct 'contact with the surface. Since perfume deposition is directly correlated with perfume burst, the PBI can also be used to predict fragrance delivery to a substrate during product use. Therefore, for a certain perfume, the surfactant systems which facilitate perfume burst upon 25 dilution can also enhance the deposition of perfume onto the surface in contact, compared to the surfactant systems which less favor the burst. The deposition of a Type 2 perfume which-typically have high 30 PBI values was tested in two surfactant systems with different CMCs (sodium laurate, CMC=0.5 wt. %, and SLES, WO 03/072078 PCT/EP03/01692 CMC=0.1 wt. %) on a synthetic skin substrate (e.g., Vitro-Skin®) . The recovery of the perfume, which is the ratio of the amount of perfume extracted after deposition to that originally dosed onto the surface, is used to reflect the 5 deposition efficiency of the perfume. The results of the recovery of y-methyl-ionone are plotted vs. the dilution factor for both sodium laurate and SLES surfactant systems (Figure 12). 10 The recovery of y-methyl-ionone from the skin washed with the undiluted sodium laurate and SLES surfactant systems (the surfactant concentration in both systems is 5%) is not significantly different. Upon dilution, the recovery of the perfume is enhancedin both surfactant systems, however, the 15 sodium laurate surfactant system, which has a higher PBI due to the higher CMC of the surfactant, provides a much higher deposition efficiency upon dilution than the SLES surfactant system. These results correlate as expected with the perfume burst results. 20 Example 14 The deposition of a multi-component "burst" perfume composed of perfumes with relatively high PBI's (i.e. high oil/water 25 partition coefficient (O) and low volatility constant (K) ) was tested on vitro-skin from sodium laurate surfactant system (high CMC) and SLES surfactant system (low CMC). The results were plotted in Figure 13. It was found that the recoveries of the perfumes from this mixture after 30 deposition from the undiluted sodium laurate and SLES surfactant systems (the surfactant concentration in both WO 03/072078 PCT/EP03/01692 systems is 5%) are very similar. An enhanced recovery of the perfume in both diluted surfactant systems (sodium laurate and SLES) is observed compared with that of the perfume in the undiluted surfactant systems. However, after 5 10 times dilution, the perfume recoveries were higher in sodium laurate surfactant system than that in SLES. These results again correlate with the perfume burst measurements, indicating that the BBI can be a useful tool for predicting fragrance deposition from surfactant containing products. WE CLAIM 1. Compositions yielding a maximum fragrance burst of one or more of the fragrance components of at least 20%, relative to an undiluted product, wherein said composition is defined by perfume burst index PBI: 4>-1.4/CMC PBI = K wherein . <|> = oil/water partition coefficient of a selected perfume or perfume components in a mixture; CMC=critical micellization concentration (wt./wt.) of selected surfactant system or mixture of surfactant system in diluent or continuous phase; K=volatility constant of selected perfume from said continuous phase or diluent (atmospheres); wherein said perfume or at least one component of said perfume mixture and wherein said surfactant system or said mixture of surfactant systems are selected such that variables are calculated to provide a PBI that is greater than about 3; wherein by maximum fragrance burst of at least 20% is meant that the perfume concentration in the headspace above said fragrance or fragrance components increases at least 20% relative to the perfume concentration in the headspace of an undiluted product comprising the same fragrance or fragrance components measured as the composition comprising said fragrance or fragrance components is diluted below the critical micelle concentration (CMC) of the fragrance, surfactant and water system. 2. A composition according to claim 1, wherein said perfume is a type 2 perfume selected to have an oil/water partition coefficient greater than about 500 and volatility constant of less than about 20. A composition according to claim 2, wherein said perfume is selected from the group consisting of allyl cyclohexane propionate, ambrettolide, Ambrox DL (dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,l-b]furan), amyl benzoate, amyl cinnamate, amyl cinnamic aldehyde, amyl salicylate, anethol, aurantiol, benzophenone, benzyl butyrate, benzyl iso-valerate, benzyl salicylate, cadinene, campylcyclohexal, cedrol, cedryl acetate, cinnamyl cinnamate, citronellyl acetate, citronellyl isobutyrate, citronellyl propionate, cuminic aldehyde, cyclohexylsalicylate, cyclamen aldehyde, cyclomyral, dihydro isojamonate, diphenyl methane, diphenyl oxide, dodecanal, dodecalactone, ethylene brassylate, ethylmethyl phenylglycidate, ethyl undecylenate, exaltolide, Galoxilide.™-(l,3,4,6,7,8-hexhydro,4,6,6,7,8,8-hexamethyl-cyclopenta-.gamma.-2-benzopyr an), geranyl acetate, geranyl isobutyrate, hexadecanolide, hexenyl salicylate, hexyl cinnamic aldehyde, hexyl salicylate, a.-ionone, P-ionone, y-ionone, a.-irone, isobutyl benzoate, isobutyl quinoline, Iso E Super.™. (7-acettl,l,2,3,4,5,6,7,8-octahydro,l,l,6,7-tetramethyl napthalene), cis-jasmine, lilial, linalyl benzoate, 20 methoxy naphthaline, methyl cinnamate, methyl eugenol, .gamma.-methylionone, methyl linolate, methyl linolenate, musk indanone, musk ketone, musk tibetine, myristicin, neryl acetate, .8-nonalactone, .gamma.-nonalactone, patchouli alcohol, phantolide, phenylethyl benzoate, phenylethylphenylacetate, phenyl heptanol, phenyl hexanol, a-santalol, thibetolide, tonalid, . 8 -undecalactone, y-undecalactone, vertenex, vetiveryl acetate, yara-yara, ylangene, and mixtures thereof. A composition according to claim 1, wherein said perfume is a type 3 perfume selected to have a partition coefficient of greater than about 500 and volatility constant of about 20 to about 1000. A composition according to claim 4, wherein said perfume is selected from the group consisting of allo-ocimene, allyl caproate, allyl heptoate, anisole, camphene, carvacrol, carvone, citral, citronellal, citronellol, citronellyl nitrile, coumarin, cyclohexyl ethylacetate, p-cymene, decanal, dihydromyrcenol, dihydromyrcenyl acetate, dimethyl octanol, ethyllinalool, ethylhexyl ketone, eucalyptol, fenchyl acetate, geraniol, gernyl formate, hexenyl isobutyrate, hexyl acetate, hexyl neopentanoate, heptanal, isobornyl acetate, isoeugenol, isomenthone, isononyl acetate, isononyl alcohol, isomenthol, isopulegol, limonene, linalool, linalyl acetate, menthyl acetate, methyl chavicol, methyl octyl acetaldehyde, myrcene, napthalene, nerol, neral, nonanal, 2-nonanone, nonyl acetate, octanol, octanal, . a-pinene, p-pinene, rose oxide, a-terpinene, y-terpinene, a-terpinenol, terpinolene, terpinyl acetate, tetrahydrolinalool, tetrahydromyrcenol, undecenal, veratrol, verdox, and mixtures thereof. 6. A composition according to claim 1 yielding maximum fragrance burst of at least 25%. 7. A composition according to claim 1, wherein said surfactant or mixture of surfactant system has CMC greater than about 0.0001 wt. to wt.,. 8. A composition according to claim 1, wherein surfactant systems contain surfactants selected from the group consisting of sodium lauryl ether sulfate, sodium laurate, potassium laurate, sodium oleate, potassium oleate, triethanolamine laurate, alkylpolyglucosides, sodium lauryl sulfate, caprylamidopropyl betaine, sodiumcocoylisethionate and mixtures thereof. 9. A composition according to claim 8, wherein the diluent or continuous phase in which said surfactant systems or surfactant system mixtures is found additionally comprises CMC modifying ingredients selected from the group consisting of urea; glycerine; C1-C12 straight-chained or branched alcohols or diols; water soluble polymers selected from polyvinylpyrolidone, polyvinylalcohol, polyethyleneglycol, polypropyleneglycol; multivalent electrolytes selected from magnesium, calcium and aluminum salts; sugars selected from dextrose, glucose, maltose, galactose, sucrose and mixtures thereof. A process for selecting a composition yielding a maximum fragrance burst of one or more of the fragrance components of at least 20%, when it is diluted, wherein said composition is defined by perfume burst index PBI: 0-1.4/CMC PBI = K wherein (j)=oil/water partition coefficient of a selected perfume or perfume components in a mixture; CMC=critical micellization concentration (wt./wt.) of selected surfactant systems or mixture of surfactant systems in diluent or continuous phase; K=volatility constant of selected perfume from said continuous phase or diluent (atmospheres); wherein said process comprises selecting a first perfume or at least one component of a first perfume mixture and selecting a first surfactant system or mixture of surfactant systems such that the above-noted variables are calculated to provide a PBI that is greater than about 3; wherein by maximum fragrance burst of at least 20% is meant that the perfume concentration in the headspace above said fragrance or fragrance components increases at least 20%, when it is diluted, relative to the perfume concentration in the headspace of a second composition, differing in perfume properties, surfactant concentration and/or CMC of a surfactant system with a PBI less than that of the first composition, both compositions measured as the compositions comprising said fragrance or fragrance components are diluted below the critical micelle concentration (CMC) of the fragrance, surfactant and water system. A method for changing fragrance note in a composition subsequent to dilution by (1) selection a fragrance with mixture perfume components wherein one or more of the perfume components have a PBI of greater than 3 and one or more components have a PBI of less than 3; and (2) assuring the selection of fragrance components such that the components desired in a new fragrance have a PBI greater than 3. 12. A method for introducing a fragrance to a composition subsequent to dilution by ensuring desired fragrance or fragrance components have a PBI of greater than about 3 so that, upon dilution, the concentration of desired fragrance components in a vapour phase exceeds an odour threshold of the desired components. 13. A process according to claim 10 for providing enhanced deposition of one or more fragrance components on to surfaces on which the composition comes into contact. Dated this 16th day of August 2004. Abhishek Sen OfS.Majumdar&Co. Applicant's Agent
| # | Name | Date |
|---|---|---|
| 1 | 00450-mumnp-2004-form-pct-isa-210 (16-08-2004).pdf | 2004-08-16 |
| 1 | 206544-FORM 27-2010.pdf | 2024-03-04 |
| 2 | 206544-FORM 27-2013.pdf | 2024-03-01 |
| 2 | 00450-mumnp-2004-form-pct-ipea-409 (16-08-2004).pdf | 2004-08-16 |
| 3 | 450-MUMNP-2004-CORRESPONDENCE(8-2-2012).pdf | 2018-08-09 |
| 3 | 00450-mumnp-2004-form 5(16-08-2004).pdf | 2004-08-16 |
| 4 | 450-MUMNP-2004-CORRESPONDENCE(RENEWAL PAYMENT LETTER)-(6-2-2012).pdf | 2018-08-09 |
| 4 | 00450-mumnp-2004-form 3(16-08-2004).pdf | 2004-08-16 |
| 5 | abstract1.jpg | 2018-08-09 |
| 5 | 00450-mumnp-2004-form 1a(16-08-2004).pdf | 2004-08-16 |
| 6 | 00450-mumnp-2004-drawing(16-08-2004).pdf | 2004-08-16 |
| 6 | 00450-mumnp-2004-correspondence 2(05-02-2007).pdf | 2007-02-05 |
| 7 | 00450-mumnp-2004-form 19(12-10-2004).pdf | 2004-10-12 |
| 7 | 00450-mumnp-2004-correspondence(ipo)-(03-01-2007).pdf | 2007-01-03 |
| 8 | 00450-mumnp-2004-correspondence 1(12-10-2004).pdf | 2004-10-12 |
| 9 | 00450-mumnp-2004-power of attorney (13-03-2006).pdf | 2006-03-13 |
| 10 | 00450-mumnp-2004-cancelled page(16-10-2006).pdf | 2006-10-16 |
| 10 | 00450-mumnp-2004-form 2(granted)-(16-10-2006).pdf | 2006-10-16 |
| 11 | 00450-mumnp-2004-claim(granted)-(16-10-2006).pdf | 2006-10-16 |
| 12 | 00450-mumnp-2004-cancelled page(16-10-2006).pdf | 2006-10-16 |
| 12 | 00450-mumnp-2004-form 2(granted)-(16-10-2006).pdf | 2006-10-16 |
| 13 | 00450-mumnp-2004-power of attorney (13-03-2006).pdf | 2006-03-13 |
| 14 | 00450-mumnp-2004-correspondence 1(12-10-2004).pdf | 2004-10-12 |
| 15 | 00450-mumnp-2004-correspondence(ipo)-(03-01-2007).pdf | 2007-01-03 |
| 15 | 00450-mumnp-2004-form 19(12-10-2004).pdf | 2004-10-12 |
| 16 | 00450-mumnp-2004-correspondence 2(05-02-2007).pdf | 2007-02-05 |
| 16 | 00450-mumnp-2004-drawing(16-08-2004).pdf | 2004-08-16 |
| 17 | 00450-mumnp-2004-form 1a(16-08-2004).pdf | 2004-08-16 |
| 17 | abstract1.jpg | 2018-08-09 |
| 18 | 00450-mumnp-2004-form 3(16-08-2004).pdf | 2004-08-16 |
| 18 | 450-MUMNP-2004-CORRESPONDENCE(RENEWAL PAYMENT LETTER)-(6-2-2012).pdf | 2018-08-09 |
| 19 | 450-MUMNP-2004-CORRESPONDENCE(8-2-2012).pdf | 2018-08-09 |
| 19 | 00450-mumnp-2004-form 5(16-08-2004).pdf | 2004-08-16 |
| 20 | 206544-FORM 27-2013.pdf | 2024-03-01 |
| 20 | 00450-mumnp-2004-form-pct-ipea-409 (16-08-2004).pdf | 2004-08-16 |
| 21 | 206544-FORM 27-2010.pdf | 2024-03-04 |
| 21 | 00450-mumnp-2004-form-pct-isa-210 (16-08-2004).pdf | 2004-08-16 |