Title of Invention	LYOCELL ANTIMICROBIAL FIBER AND A METHOD OF MAKING THEREOF
Abstract	1.An antimicrobial lyocell formulation meant for manufacture of lyocell products comprising : •at least one non-aqueous solvent in the range of about 0.01 to 20% of the mass of the formulation, •at least one water insoluble antimicrobial constituent soluble in said solvent, in the range of about 0.001 to 10% of the mass of the formulation, • at least one water soluble non-cationic surfactant having HLB value in the range of 9 to 40, in the range of 0.001 to 10% of the mass of the formulation, •cellulosic pulp in the range of about 3% to 35% of the mass of the formulation, •N-METHYL-MORPHOLINE-N-OXIDE (NNMO) in the range of about 60 to 80% of the mass of the formulation; and •water in the range of about 0% to 20 % with respect to the mass of the formulation.

Title of Invention

LYOCELL ANTIMICROBIAL FIBER AND A METHOD OF MAKING THEREOF

Abstract

1.An antimicrobial lyocell formulation meant for manufacture of lyocell products comprising : •at least one non-aqueous solvent in the range of about 0.01 to 20% of the mass of the formulation, •at least one water insoluble antimicrobial constituent soluble in said solvent, in the range of about 0.001 to 10% of the mass of the formulation, • at least one water soluble non-cationic surfactant having HLB value in the range of 9 to 40, in the range of 0.001 to 10% of the mass of the formulation, •cellulosic pulp in the range of about 3% to 35% of the mass of the formulation, •N-METHYL-MORPHOLINE-N-OXIDE (NNMO) in the range of about 60 to 80% of the mass of the formulation; and •water in the range of about 0% to 20 % with respect to the mass of the formulation.

Full Text	FORM - 2 THE PATENTS ACT, 1970 (39 OF 1970) AND THE PATENTS RULES, 2003 COMPLETE SPECIFICATION (See section 10; rule 13) A LYOCELL ANTIMICROBIAL FIBER AND A METHOD OF MAKING THEREOF ADITYA BIRLA SCIENCE & TECHNOLOGY CO. LTD. an Indian Company of Aditya Birla Center, 2nd floor, C Wing, S. K. Ahire Marg, Mumbai 400 025, Maharashtra, India THE FOLLOWING SPECIFICATION PARTICULARLY DESCRIBES THE INVENTION AND THE MANNER IN WHICH IT IS TO BE PERFORMED. Field of the invention The present invention relates to textile fibers. Background of the invention The term "fiber" or "textile fiber" means a substance which is capable of being spun into a yarn or made into a fabric by bonding or by interlacing in a variety of methods including weaving, knitting, braiding, felting, twisting, or webbing, and which is the basic structural element of textile products. Fibers are classified on the basis of their length such as short fibers or staple fiber and long fibers or filament fiber. The fibers can also be classified on the basis of their origin such as natural fibers and man-made fibers. The term natural fibers means any fiber that exists as such in the natural state e.g. vegetable fibers or wood fibers. The other type of fibers is obtained from chemical substances. These are called man made fibers. They are polyester, nylon, acrylic (cashmilon) etc. For centuries, mankind has relied upon various plants and animals to provide raw materials for fabrics and clothing. In recent times, the industrialization and scientific advancement has provided several improved materials having far superior properties, particularly suitable for clothing. Lyocell is a manmade fiber derived from cellulose. Though it is related to , viscose is obtained by a solvent spinning technique. The solvent spinning technique, which is simpler and more environmentally sound, since it uses a non¬toxic solvent chemical that can be recycled in the manufacturing process. It is an extremely strong fabric with industrial uses such as in automotive filters, ropes, abrasive materials, bandages and protective suiting material. It is primarily found in the garment industry, particularly in women's clothing. 2 Lyocell fibers are prepared by following process steps: The raw cellulose is dissolved into heated, pressurized vessel filled with an amine oxide solvent. After soaking for a short time in the solvent at high temperature under vacuum to remove excess water, the cellulose forms a clear solution and then it is filtered. The solution is then pumped through spinneret which is pierced with small holes to obtain long strands of fibers. The fibers are then immersed in another dilute solution of amine oxide. This helps to set the fiber strands. Then, they are washed with de-mineralized water. The lyocell fibers are then led to a drying area, where the water is evaporated from it. The strands are led to a finishing area, where the lubricant is applied. The dried, finished fibers are at this stage are called as a tow, which is a large untwisted bundle of continuous length filaments. Tne'bundles ol tow are taken to a crimper, a machine which compresses the fiber, giving it texture and bulk. The crimped fiber is then carded by mechanical carders, which perform an action like combing, to separate and order the strands. The carded strands are cut and baled for shipment to a fabric mill. The amine oxide used to dissolve the cellulose formed set the fiber after spinning is recovered and re-used in the manufacturing process. From the spun or filament yarn, fabric is formed by knitting or weaving operations. Knitted fabrics can be made by using hooked needles to interlock one or more sets of yarns through a set of loops. The loops may be either loosely or closely constructed, depending on the purpose of the fabric. Knitted fabrics can be used for hosiery, underwear, sweaters, slacks, suits, coats, rugs and other home furnishings. Knitting is performed using either weft or warp processes. 3 Some typical preparations that are involved in the weaving operations are warping, slashing or sizing. Sizing agents are added to the yarn by solution or pad/dry techniques. Differences in raw materials, processing chemicals, fiber diameter, post treatments and blend ratios can be manipulated to produce a fiber having customized properties suitable for desired application. It is often desired that the lyocell fabrics possess typical properties such as thermal stability, ability to retain perfumes, antibacterial properties and the like. These properties are essential in several industrial as well as household applications. There has been a considerable interest in developing such materials. In order to impart various desirable properties to the fabric as mentioned above to the fabric, several additives are added. Such additives include antimicrobial agents, deodorizing agents, antistatic agents, perfumes. Besides such specific additives, generic additives for improving overall quality of the fabric, such as sizing agents, additives for increasing yarn softness and pliability are also added. Prior art: US patent 6436419 discloses a process that involves dyeing a polymer with an acid dye to form a dye coated polymer, and attaching an antimicrobial agent like quaternary ammonium salt, thereby making said polymer antimicrobial. A method for producing an antimicrobial effect in biodegradable textile article containing cellulosic material is disclosed in US 20050225002. Lyocell fibers constitute at least 10 % by weight of the textile article. It is reported that in case of use of Lyocell fibers in the textile, the growth of microorganisms is delayed or prevented, respectively, in comparison with other cellulosic fibers such as cotton or viscose fibers. 4 Earlier known processes of incorporating such additives, as reported in the above mentioned patents/applications, mainly involved conventional methods like spraying, solvent spinning the additives on the fabric. However, these methods suffer from several disadvantages which include non-uniform and improper adhesion of additives onto the fiber material, waning and gradual washing out of the additives over a period of time and which further affects the feel and texture of the fabric. There is thus felt a need for a process of incorporating additives to fabric which overcomes these shortcomings. Objects of the Invention It is an object of this invention to provide antimicrobial lyocell fibers, wherein at least one antimicrobial constituent is incorporated into the body of the fiber. Another object of this invention is to provide a process of incorporating antimicrobial constituents into lyocell fibers which ensures uniform distribution of the antimicrobial constituent throughout the fiber length. Yet another object of this invention is to provide antimicrobial lyocell fibers wherein the antimicrobial constituents are retained in the lyocell product over a prolonged period of time. Yet another object of this invention is to provide a process of incorporating antimicrobial constituents to lyocell fibers which does not alter the feel and texture of the fabric. 5 Still another object of this invention is to provide a process of incorporating antimicrobial constituents to lyoceli fibers such that inherent properties of the lyoceli fibers such as fiber strength, linear density, tenacity, heat resistance, dyeability and drying properties are not altered. Definitions: As used in the present specification, the following words and phrases are generally intended to have the meanings as set forth below, except to the extent that the context in which they are used indicates otherwise. "Non-aqueous phase" means a melted mixture in liquid state which is water insoluble. "Aqueous phase" means substance dissolved in water. "Lyoceli Polymer dope" means an intermediate material in the manufacture of lyoceli products that is used for preparation of fibers. "Preform mass" means an intermediate material suitable for making fibers. "NNMO" means N-METHYL-MORPHOLINE-N-OXIDE Summary of the Invention In accordance with this invention there is provided an antimicrobial lyoceli formulation meant for manufacture of lyoceli products comprising: • at least one non-aqueous solvent in the range of about 0.01 to 20% of the mass of the formulation, • at least one water insoluble antimicrobial constituent soluble in said solvent, in the range of about 0.001 to 10% of the mass of the formulation, 6 • at least one water soluble non-cationic surfactant having HLB value in the range of 9 to 40, in the range of 0.001 to 10% of the mass of the formulation, • cellulosic pulp in the range of about 3% to 35% of the mass of the formulation, • N-methyl-morpholine-N-oxide (NNMO) in the range of about 60 to 80% of the mass of the formulation; and • water in the range of about 0% to 20 % with respect to the mass of the formulation. Typically, the antimicrobial constituent is at least one selected from a group consisting of 2-Methyl-4-isothiazolin-3-one, water, Phenoxyethanol Benzoic acid, 4-Hydroxy-methyl ester, Hydroxy-benzoic acid and propyl ester), o-(2-naphthyl) methyl (3-methylphenyl) thiocarbamate, 5-chloro-2-(2,4-dichlorophenoxy)phenol,4,5-dichloro-n-octyl-4-isothiazoline-3-one[DCOIT] 2-n-octyl-4-isothiazolin-3-one, 1-phenoxy propan-2-ol, pentachlorophenol, 5-chloro-2-dichlorophenoxy phenol, clotrimazole, p-chloro-m-xylenol and chloroquinaldol. Typically, the solvent is at least one solvent selected from a group of solvents consisting of C10-C44 alkanes (paraffinic hydrocarbons), polyethylene, polypropylene, polypropylene glycol, polytetramethylene glycol, polypropylene malonate, polyneopentyl glycol sebacate, polypentane glutarate, polyvinyl myristate, polyvinyl stearate, polyvinyl laurate, polyhexadecyl methacrylate, polyoctadecyl methacrylate, polyethylene oxides, polyethylene glycols, Arachidyl alcohol, behenyl alcohol, Selachyl alcohol, chimimyl alcohol, polyesters, di-iso decyl phthalate, benzyl alcohol, C4 -G30 aliphatic alcohols ,C4 -C30 saturated 7 hydrocarbons, C4 -C30 monounsaturated hydrocarbons, natural oils and mineral oil paraffins. Typically, the surfactant is at least one non-cationic surfactant selected from a group of surfactants consisting of alkyl phenol ethoxylates and alkyl alcohol ethoxylates. Typically, the alkyl phenol ethoxylated or alkyl alcohol ethoxylate is at least one selected from a group consisting of Surfonic N-95(Poly (oxy-1, 2-ethanediyl), alpha- (nonyl phenyl)-omega-hydroxyl-glycol ether) ( nonylphenol 9.5-mole ethoxylate) , Surfonic N-120(nonylphenol 12-mole ethoxylate) , Surfonic N-150 (nonylphenol 15-mole ethoxylate), Surfonic N-200 (nonylphenol 20-mole ethoxylate) , Surfonic N-300( nonylphenol 30-mole ethoxylate) , Surfonic N-400 nonylphenol 40-mole ethoxylate, Surfonic LF-7 (Alkyl polyoxyalkylene ether) , Surfonic LF-17 (ethoxylated and propoxylated linear primary 12-14 carbon number alcohol), Igepal CO-630 (nonylphenoxy poly(ethyleneoxy)ethanol,branched), Surfonic DNP-40 , fatty alcohol ether sulfates, alkyl carboxylates, alkyl benzene sulfonates, sulfosuccinates, polyethanoxy ether sulphate esters and polyethanoxy ether phosphate esters. In accordance with one preferred embodiment of the invention, the HLB value of the surfactant is between 16 and 40. In accordance with one aspect of the invention, the antimicrobial constituent, the solvent and the surfactant are processed to form micro-reservoirs which are embe'dded into the body of the formulation. 8 Typically, the average mean size of the micro-reservoir is in the range of 5 nm to 2000 nm. The invention also extends to an antimicrobial lyocell fiber, yarn and fabric manufactured from a formulation in accordance with this invention. In accordance with this invention there is also provided a process for preparation of an antimicrobial lyocell formulation meant for manufacture of lyocell products comprising the following steps: • admixing a water-insoluble antimicrobial constituent with a non¬aqueous solvent followed by heating the resulting admixture to obtain non-aqueous phase ; • dissolving and stirring a surfactant, optionally with a co-surfactant, in water to obtain an aqueous phase; • heating the aqueous-phase; . • mixing the aqueous phase with the non-aqueous phase in the liquid state to form a admixture and homogenizing to obtain a micro-emulsion; • mixing together cellulosic pulp and N-methyl-morpholine-n-oxide (NNMO) solution to form a slurry; • dispersing the micro-emulsion in the slurry to obtain a preform mass wherein the antimicrobial constituent is embedded in evenly dispersed micro-reservoirs; • vaccumising the preform mass to remove water under 7 to 10 mm of Hg and temperature of over 90°C. 9 Brief Description of the accompanying Drawings: The invention will be described in detail with reference to the accompanying drawings. In the accompanying drawing, Figure 1 illustrates the block diagram showing the method steps involved in the process in accordance with this invention. Figure 2 illustrates the cross-sectional view of antimicrobial lyocell fibers prepared in accordance with this invention which shows uniform distribution of micro-reservoirs of antimicrobial constituents entrapped across the length of the fibers. Detailed Description of the Invention A decade of Lyocell technology development has yielded many new opportunities in textile applications due to interesting properties of the solvent spun cellulosic lyocell fibers, especially good mechanical properties and fibrillation resistance. Its versatility and desirable properties provide many advantages, both functional and aesthetic. In terms of performance and properties, lyocell is also friendly to the environment The resulting fiber, lyocell, is both biodegradable and recyclable Lyocell has strength and durability. Lyocell blends well with other fibers including wool, silk, cotton, linen, nylon, and polyester. It successfully takes many finishes, both functional and those designed to achieve different surface effects, and dyes easily. Overall, lyocell is a versatile fiber with many desirable properties. 10 In accordance with this invention there is provided an antimicrobial lyocell formulation meant for manufacture of lyocell products comprising : • at least one non-aqueous solvent in the range of about 0.01 to 20% of the mass of the formulation, • at least one water insoluble antimicrobial constituent soluble in said solvent, in the range of about 0.001 to 10% of the mass of the formulation, • at least one water soluble non-cationic surfactant having HLB value in the range of 9 to 40, in the range of 0.001 to 10% of the mass of the formulation, • cellulosic pulp in the range of about 3% to 35% of the mass of the formulation • N-METHYL-MORPHOLINE-N-OXIDE (NNMO) in the range of about 60 to 80% of the mass of the formulation; and • water in the range of about 0% to 20 % with respect to the mass of the formulation. In accordance with the invention, anti-microbial constituent is typically at least one selected from a group consisting of 2-Methyl-4-isothiazolin-3-one, water, Phenoxyethanol Benzoic acid, 4-Hydroxy-methyl ester, Hydroxy-benzoic acid and propyl ester), o- (2-naphthyl) methyl (3-methylphenyl) thiocarbamate, 5-chloro-2-(2,4-dichlorophenoxy)phenol, 4,5-dichloro-n-octyl-4-isothiazoline-3-one[DCOIT] 2-n-octyl-4-isothiazolin-3-one, 1-phenoxy propan-2-ol, pentachlorophenol, 5-chloro-2-dichlorophenoxy phenol, clotrimazole, p-chloro-m-xylenol and chloroquinaldol. 11 The antimicrobial constituent impart antimicrobial property to the fibers and ultimately to the fabric or garments made from these fibers. In accordance with this invention , only non-aqueous solvent is used which is typically selected from a group of solvents consisting of C10-C44 alkanes (paraffinic hydrocarbons), polyethylene, polypropylene, polypropylene glycol, polytetramethylene glycol, polypropylene malonate, polyneopentyl glycol sebacate, polypentane glutarate, polyvinyl myristate, polyvinyl stearate, polyvinyl laurate, polyhexadecyl methacrylate, polyoctadecyl methacrylate, polyethylene oxides, polyethylene glycols, Arachidyl alcohol, behenyl alcohol, Selachyl alcohol, chimimyl alcohol, polyesters,, di-iso decyl phthalate, benzyl alcohol, C4 -C30 aliphatic alcohols ,C4 -C30 saturated hydrocarbons, C4 -C30 monounsaturated hydrocarbons, natural oils and mineral oil paraffins. Preferably, paraffin wax either alone or in combination with stearyl alcohol is used as the non-aqueous solvent. In accordance with this invention only water soluble non-cationic surfactant/co- surfactant is used. The non-cationic surfactant is selected from a group consisting of alkyl phenoxy ethoxylated non-ionic surfactants and ethoxylated alkyl alcohol surfactants, Polyethylene-block-Poly propylene glycol-block-polyethylene glycol and Ethylenediamine tetrakis(propylene oxide-block-ethylene oxide) tetrol. The alkyl phenol ethoxylated surfactant is at least one selected from a group consisting of Polyoxyethylene(8) isooctylphenyl ether, Nonylphenol polyethylene glycol ether, Polyoxyethylene(9) nonylphenyl ether, Polyoxyethylene(lO) isooctylphenyl ether, Polyoxyethylene(12) nonylphenyl ether, Polyoxyethylene(12) isooctylphenyl ether, Polyoxyethylene(40) nonylphenyl 12 ether, Polyoxyethylene(40) isooctylphenyl ether, Polyoxyethylene(100) nonylphenyl ether, Polyoxyethylene(150) dinonylphenyi ether, Surfonic N-95(Poly (oxy-1, 2-ethanediyl), alpha- (nonyl phenyl)-omega-hydroxyl-glycol ether) ( nonylphenol 9.5-mole ethoxylate) , Surfonic N-95(Poly (oxy-1, 2-ethanediyl), alpha- (nonyl phenyl)-omega-hydroxyl-glycol ether) ( nonylphenol 9.5-mole ethoxylate) , Surfonic N-120(nonylphenol 12-mole ethoxylate) , Surfonic N-150 (nonylphenol 15-mole ethoxylate), Surfonic N-200 (nonylphenol 20-mole ethoxylate) , Surfonic N-300( nonylphenol 30-mole ethoxylate) , Surfonic N-400 nonylphenol 40-mole ethoxylate, Surfonic LF-7 (Alkyl polyoxyalkylene ether) , Surfonic LF-17 (ethoxylated and propoxylated linear primary 12-14 carbon number alcohol), Igepal CO-630 (nonylphenoxy poly(ethyleneoxy)ethanol,branched), Surfonic DNP-40, fatty alcohol ether sulfates, alkyl carboxylates, alkyl benzene sulfonates, sulfosuccinates, polyethanoxy ether sulphate esters and polyethanoxy ether phosphate esters. The non-ionic or anionic surfactant is selected such that the lipophilic portion of the non-ionic or anionic surfactant is compatible with the antimicrobial constituent and the surfactant forms oil in water microemulsion. Surfactants with HLB values within the range of 9 to 40 are used. Preferably, non-ionic or anionic surfactants with HLB values more than 13 are used. In accordance with one preferred embodiment of the invention, the HLB value of the surfactant is between 16 and 40. In accordance with one aspect of the invention, the antimicrobial constituent, the solvent and the surfactant are processed to form micro-reservoirs which are embedded into the body of the formulation. The antimicrobial lyocell contains 13 uniformly dispersed micro-reservoirs throughout the body of the fibers. The micro-reservoirs are discrete, nano-sized structures without any definite geometrical shape. Typically, the average mean size of the micro-reservoir is in the range of 5 nm to 2000 nm. The invention also extends to an antimicrobial lyocell fiber, yarn and fabric manufactured from a formulation in accordance with this invention. In accordance with this invention there is also provided a process for preparation of an antimicrobial lyocell formulation meant for manufacture of lyocell products comprising the following steps : • admixing a water-insoluble antimicrobial constituent with a non¬aqueous solvent followed by heating the resulting mixture to obtain a liquid non-aqueous phase; • dissolving and stirring a surfactant, optionally with a co-surfactant, in water to obtain an aqueous phase; • heating the aqueous-phase; • mixing the aqueous phase with the non-aqueous phase in the liquid state to form a admixture and homogenizing to obtain a micro-emulsion; • mixing together cellulosic pulp and N-METHYL-MORPHOLINE-N-OXIDE (NNMO) solution to form a slurry; 14 • dispersing the micro-emulsion in the slurry to obtain a preform mass wherein the antimicrobial constituent is embedded in evenly dispersed micro-reservoirs; • vaccumising the preform mass to remove water under 7 to 10 mm of Hg and temperature of over 90°C to obtain the formulation. Before arriving at the optimum concentration of the surfactant to be used, cloud point of the aqueous phase is determined. Furthermore, alkalinity of the aqueous phase matches with that of the viscous polymer dope thereby avoiding any drastic change in the alkalinity during the emulsification and homogenization step. Typically, the melted non-aqueous phase containing antimicrobial constituent in a non-aqueous solvent along with aqueous phase containing surfactants is emulsified using high speed mixers, such as Ultraturrex or a mechanical emulsifier; a colloid mill; a high pressure homogenizer and an ultrasonic emulsifier to form a microemulsion. The micro-emulsion may contain further additional antimicrobial constituents, if desired. It is important that the non-aqueous phase is maintained in liquid state throughout the mixing process. The aqueous phase therefore is typically heated upto a particular temperature to ensure that the temperature of the resulting emulsion is above the melting point of the non-aqueous solvent. If this does not happen, the resulting emulsion will break down. The active ingredients are released from the micro-reservoir into the lyocell matrix. The structure of micro-reservoir, lyocell and surrounding conditions determine the release rate of the antimicrobial constituent. The molecules of the volatile antimicrobial constituents migrate from micro-reservoirs to the 15 surrounding primarily by diffusion. The antimicrobial constituent is released from the matrix in a controlled release manner. Conventional method for manufacture of lyocell involves following major steps : Step 1. Creating a solvent solution from wood pulp The wood pulp is obtained from a variety of sources, such as wood chips or even large rolls of paper that have been finely shredded, is the basic starting material for manufacture of lyocell fibers. In case of manufacture of lyocell no further chemical treatment of the wood pulp is needed thereby making the process environment friendly. The wood pulp solution is produced in a straight solvation process by dissolving wood pulp at high temperatures and pressure in a recyclable non-toxic organic solvent solution of amine oxide, particularly N-methylmorpholine N-oxide,(N-METHYL-MORPHOLINE-N-OXIDE (NNMO)). Lyocell is manufactured by a "closed loop" spinning process which conserves energy and water. Step 2 Spinning lyocell fiber from the solvent solution Before being formed into fibers, the lyocell polymer dope, is in a thick liquid state. In the spinning process this liquid is forced through a spinneret, which resembles a large shower head. The clear, viscous resultant solution is filtered and extruded into an aqueous bath of dilute amine oxide, and coagulated into fiber form. 16 Step 3. Washing lyocell fiber to remove solvents The fiber is then washed before it is dried and twisted or spun into yarns, which are woven or knitted into fabrics and garments. Step 4. Drying fiber and producing yarns When the filament dries or solidifies, it forms what is called a continuous filament fiber. Many continuous filaments of specific thicknesses collected in a large bundle called a "tow". A tow may contain over a million continuous filaments. The tow bundle is then crimped, is then mechanically cut into staple fibers, usually ranging in length from 1 to 6-1/2 inches, depending how they are to be used. Strands of continuous filament fibers are then twisted together to form a continuous filament yarn, which is then woven or knit into fabric. Step 5, Finishing producing lyocell fabric The fabric is treated with an enzyme that attacks cellulose fibers. Home laundry detergents containing such enzymes are also used for treatment of the fabric for better finishing purposes. This enzyme dissolves the split-end hairs from the fiber surface. The fiber is then washed and agitated again. The resulting fabric is similar in texture and drape to sueded silk or sueded rayon found in fashion apparel. Fabrics processed this way can usually be machine washed and line dried successfully. Alternatively, the filaments so obtained further blended using standard equipment. The blended fibers are laid in to a web using standard equipment followed by Consolidation of the web to obtain Non-woven Lyocell Fabric. 17 The lyocell product made from the formulation in accordance with this invention contains uniformly dispersed micro-reservoirs throughout the mass which is shown in Fig. 2. The antimicrobial constituent enriched lyocell fabrics as prepared in the above examples can be tested for antimicrobial activity by various test procedures which include antimicrobial assays used to determine or confirm the effectiveness of treatments applied to medical devices, medical and commercial textiles, and other products. Test methods for measuring the antimicrobial activity include ASTM, AATCC, and other modified methods. Testing includes antibacterial and antifungal activity, with both qualitative and quantitative assays available. AATCC 100 is a qualitative test for antibacterial activity. Test lyocell fiber/fabric specimens are placed into contact with a nutrient agar which has been streaked with a microbe such as Staphylococcus aureus, Escherichia coli bacterial culture. Samples are inoculated with Staphylococcus and evaluated for percent reduction of the bacteria over selected contact periods of 1 - 24 hours. Turnaround Time is usually 5 days. The specimens are then incubated at a temperature 37 °C for a period of time of 24 hours. After the 24 hour incubation period, the samples are visually checked for the growth of bacteria. The AATCC 147, Part III protocol provides a qualitative test for antifungal activity. Lyocell fiber/ fabric specimens are subjected to the growth of a common fungus, Aspergillus niger, on Sabouraud Dextrose agar. Prewet specimens are 18 inoculated and incubated at 28 C for seven days. Specimens are then assessea ror growth of the fungus. ASTM E2180-01 test method is used for testing inhibitory mold activity of the lyocell product (fiber /fabric) prepared in accordance with this invention. The antimicrobial lyocell fibers contain the entrapped antimicrobial constituent in releasable form. Microscopic examination of the micro-reservoirs in the lyocell fibers is shown in Fig 2. The resultant lyocell fabric containing antimicrobial constituent are tested. Linear Density (Denier) of the lyocell Fibers is determined by using standard ASTM Test Method (D 1577). The denier of the standard lyocell fiber (lyocell fiber without any antimicrobial constituents) and anti-microbial enriched lyocell fiber remains the same. Thus addition of antimicrobial constituents does not change the linear density of the lyocell fibers. Tensile strength and Young's modulus of lyocell fiber sample is tested on an Instron tensile testing machine as per the ASTM CI557-03 procedure at ambient temperature. Visual appearance of the antimicrobial enriched fiber is evaluated by methods as prescribed in AATCC 124. As far as parameters like % Loss in Dry Tenacity and % loss in dry elongation are concerned, these remain the same in the antimicrobial enriched lyocell fiber and the standard fiber. Incorporation of antimicrobial constituent in accordance with this invention does not affect the visual appearance of the fiber. 19 Feel of the fiber: The antimicrobial enriched lyocell fiber as prepared in accordance with this invention offers the same feel effect as is observed in case of plain lyocell fiber without any antimicrobial constituent (Also referred as standard). Another important concern in textile industry is dye-ability of the fabric, which is tested by comparing the dyeability of the antimicrobial constituent enriched fabric and the standard lyocell fabric. Dyeability of the antimicrobial enriched lyocell fibers as prepared in accordance with this invention remains the same as that of the standard lyocell fiber. The invention will now be described with the help of the following non-limiting examples. Examples Example 1 Example 1 A- Preparation of micro emulsion Stearyl alcohol (225 gms) was heated until it melts and (50gm) of 2-Methyl-4- isothiazolin-3-one, water, phenoxyethanol Benzoic acid, 4-Hydroxy-methyl ester, Hydroxy-benzoic acid and propyl ester was admixed to form a molten mixture (275gm). Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was dissolved and stirred in water (525 ml) to obtain (553 gm)of aqueous phase. The aqueous phase (553 gm) and the mixture (275 gm) were homogenized in a high speed mixer (Ultraturrex) to obtain a micro-emulsion (828 gm ). Example 1 B- Preparation fiber and fabric 20 1000 gm of cellulosic pulp and 12670 gm of 50% NNMO solution were mixed to form a slurry (13670gm).The micro-emulsion as prepared in Example 1A was evenly dispersed in the slurry to obtain a preform mass (14500 gm). The homogenized preform mass was vaccumisied to remove water under 10 mm of Hg and at temperature 110 °C ,was further spun in a spin bath of dilute amine oxide, and coagulated into fiber form. The fiber was then washed before it was dried and spun into a fabric. The lyocell fiber thus obtained contained micro-reservoirs having the entrapped releasable antimicrobial constituents. Although the micro reservoirs did not have any specific shape or size, they were found to be uniformly distributed throughout the body of the fiber. Example 2 Example 2A- Preparation of micro emulsion Myristyl alcohol (225 gms) was heated until it melts and (60gm) of 2-Methyl-4- isothiazolin-3-one, water, phenoxyethanol Benzoic acid, 4-Hydroxy-methyl ester, Hydroxy-benzoic acid and propyl ester was admixed to form a molten mixture (275gm). Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was dissolved and stirred in water (525 ml) to obtain (553 gm)of aqueous phase. The aqueous phase (553 gm) and the mixture (275 gm) were homogenized in a high speed mixer (Ultraturrex) to obtain a micro-emulsion (828 gm ). Example 2 B Preparation of fiber 21 990 gm of cellulosic pulp and 12540 gm of 50% NNMO solution were mixed to form a slurry (13530gm).The micro-emulsion as prepared in Example 2A was evenly dispersed in the slurry to obtain a preform mass (14360 gm) and was spun into fiber as described in example 1. Example 3 Example3 A Preparation of antimicrobial formulation Polyvinyl laurate (200 gms) and cetyl alcohol ( 25 gm) was heated until it melts and (lOOgm) of 2-Methyl-4-isothiazolin-3-one, water, phenoxyethanol Benzoic acid, 4-Hydroxy-methyl ester, Hydroxy-benzoic acid and propyl ester was admixed to form a molten mixture (325gm). Surfonio N-400 nonylphenol 40-mole ehhoxylate (surfactant) (28 gm ) was dissolved and stirred in water (525 ml) to obtain (553 gm)of aqueous phase. The aqueous phase (553 gm) and the mixture (325 gm) were homogenized in a high speed mixer (Ultraturrex) to obtain a micro-emulsion (878 gm). Example 3 B- Preparation of fiber 922 gm of cellulosic pulp and 11680 gm of 50% NNMO solution were mixed to form a slurry (12600 gm).The micro-emulsion as prepared in Example 3A was evenly dispersed in the slurry to obtain a preform mass (13478 gm) and was spun into fiber as described in example 1. Example 4 Example 4 A Preparation of antimicrobial formulation 22 Polyvinyl laurate (250 gms) and cetyl alcohol (25 gm) was heated until it melts and (50 gm) of chloroquinaldol was admixed to form a molten mixture (325gm). Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was dissolved and stirred in water (525 ml) to obtain (553 gm)of aqueous phase. The aqueous phase (553 gm) and the mixture (325 gm) were homogenized in a high speed mixer (Ultraturrex) to obtain a micro-emulsion (878 gm). Example 4 B- Preparation fiber and fabric 1400 gm of cellulosic pulp and 17730 gm of 50% NNMO solution were mixed to form a slurry (19130gm).The micro-emulsion as prepared in Example 4A was evenly dispersed in the slurry to obtain a preform mass (20010 gm) and was spun into fiber as described in example 1. Example 5 Example 5 A Preparation of antimicrobial formulation Polypropylene glycol (100 gm) and paraffin wax (175 gm) were heated until it melts and (50 gm) of chloroquinaldol was admixed to form a molten mixture (325gm). Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was dissolved and stirred in water (525 ml) to obtain (553 gm)of aqueous phase. The aqueous phase (553 gm) and the mixture (325 gm) were homogenized in a high speed mixer (Ultraturrex) to obtain a micro-emulsion (878 gm). Example 5 B- Preparation fiber and fabric 1200 gm of cellulosic pulp and 15200 gm of 50% NNMO solution were mixed to form a slurry (16400 gm).The micro-emulsion as prepared in Example 5A was 23 evenly dispersed in the slurry to obtain a preform mass (17280 gm) and was spun into fiber as described in example 1. Example 6 Example 6 A Preparation of antimicrobial formulation Stearyl alcohol (200gm) and polyethylene(HDPE) (lOOgm) were melted together to form a molten liquid. To this o- (2-naphthyl) methyl (3-methylphenyl) thiocarbamate (Tolnaftate) (200gm) to form a molten mixture (500gm). Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was dissolved and stirred in water (525 ml) to obtain (553 gm)of aqueous phase. The aqueous phase (553 gm) and the mixture (500 gm) were homogenized in a high speed mixer (Ultraturrex) to obtain a micro-emulsion (1053 gm). Example 6 B- Preparation fiber and fabric 947 gm of cellulosic pulp and 12000 gm of 50% NNMO solution were mixed to form a slurry (12947gm).The micro-emulsion as prepared in Example 6A was evenly dispersed in the slurry to obtain a preform mass (13995 gm) and was spun into fiber as described in example 1. Example 7 Example 7 A Preparation of antimicrobial formulation Polyvinyl stearate (150 gm) and paraffin wax (lOOgm) were melted together to form a molten liquid. To this 5-chloro-2-(2,4-dichlorophenoxy)phenol (Triclosan) (150 gm) was added to form a molten mixture (400 gm). 24 Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was dissolved and stirred in water (525 ml) to obtain (553 gm)of aqueous phase. The aqueous phase (553 gm) and the mixture (400 gm) were homogenized in a high speed mixer (Ultraturrex) to obtain a micro-emulsion (953 gm). Example 7 B- Preparation fiber and fabric 1047 gm of cellulosic pulp and 13260 gm of 50% NNMO solution were mixed to form a slurry (14310 gm).The micro-emulsion as prepared in Example 7A was evenly dispersed in the slurry to obtain a preform mass (15260 gm) and was spun into fiber as described in example 1. Example 8 Example 8 A Preparation of antimicrobial formulation Polypentane glutarate (300 gm) was melted to form a molten liquid. To this (lOOgm) 5-chloro-2-(2,4-dichlorophenoxy)phenol (Triclosan) was added to form a mixture (400 gm). Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was dissolved and stirred in water (525 ml) to obtain (553 gm)of aqueous phase. The aqueous phase (553 gm) and the mixture (400 gm) were homogenized in a high speed mixer (Ultraturrex) to obtain a micro-emulsion (953 gm). Example 8 B 1547 gm of cellulosic pulp and 19590 gm of 50% NNMO solution were mixed to form a slurry (21140gm).The micro-emulsion as prepared in Example 8A was 25 evenly dispersed in the slurry to obtain a preform mass (22090 gm) and was spun into fiber as described in example 1. Example 9 Example 9 A Preparation of antimicrobial formulation Stearyl alcohol ( 250 gm) and paraffin wax (200 gm) were melted together to form a molten liquid. To this (50gm) 4,5-dichloro-n-octyl-4-isothiazoline-3- one[DCOIT] was added to form a mixture (500 gm). Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was dissolved and stirred in water (525 ml) to obtain (553 gm) of aqueous phase. The aqueous phase (553 gm) and the mixture (500 gm) were homogenized in a high speed mixer (Ultraturrex) to obtain a micro-emulsion (1053 gm). Example 9 B 1147 gm of cellulosic pulp and 14530 gm of 50% NNMO solution were mixed to form a slurry (15680gm).The micro-emulsion as prepared in Example 8A was evenly dispersed in the slurry to obtain a preform mass (16730 gm) and was spun into fiber as described in example 1. Example 10 Example 10 A Preparation of micro emulsion Stearyl alcohol (150 gm) and polyvinyl laurate (150gm) were melted together to form a molten liquid. To this molten liquid, (200gm) of 2-Methyl-4-isothiazolin-3-one, water, Phenoxyethanol Benzoic acid, 4-Hydroxy-methyl ester, Hydroxy-benzoic acid and propyl ester) was added to form a mixture (500gm). 26 Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was dissolved and stirred in water (525 ml) to obtain (553 gm) of aqueous phase. The aqueous phase (553 gm) and the mixture (500 gm) were homogenized in a high speed mixer (Ultraturrex) to obtain a micro-emulsion (1053 gm). Example 10 B 1347 gm of cellulosic pulp and 17060 gm of 50% NNMO solution were mixed to form a slurry (18410gm).The micro-emulsion as prepared in Example 10 A was evenly dispersed in the slurry to obtain a preform mass (19460 gm) and was spun into fiber as described in example 1. Testing procedures: The antimicrobial lyocell products as prepared in the above examples (1 to 10) were tested by using following test procedures: 1) Linear Density (Denier) of the lyocell Fibers was determined by using standard ASTM Test Method (D 1577). The denier of the standard lyocell fiber (without any antimicrobial constituents) and anti-microbial lyocell fibers as prepared in accordance with example IB was found to be uniform(1.5 denier) irrespective of the type and quantity of the antimicrobial constituent. 2) Tensile strength and Young's modulus of lyocell fiber samples were tested on an Instron tensile testing machine as per the ASTM C1557-03 procedure at ambient temperature. 3) Emulsion stability: The stability of micro-emulsions as prepared in the above examples, was evaluated by keeping the same under observation in measuring cylinders for 3 days. During this period no phase separation was observed. 27 4) Feel of the fabric: The lyocell fabrics as prepared in the above examples and standard fabric (lyocell fabric without antimicrobial constituents), were randomly given to twenty subjects and they were asked to evaluate the texture and feel of the fiber. The test fiber material was interchanged several times amongst the human subjects. Collective results as submitted by the human subjects confirmed that nobody could distinguish between the antimicrobial lyocell fabrics prepared in accordance with the Examples provided above and the standard fabric. 5) Dyeability: The antimicrobial lyocell fabrics as prepared in the above examples and the standard fabric as described above were dyed uniformly with reactive dyes. No noticeable difference as to the Dyeability of the two respective lyocell fabrics, with and without antimicrobial constituent was reported. 6) Visual appearance of the antimicrobial lyocell fiber was evaluated by methods as prescribed in AATCC 124. As far as parameters like % Loss in Dry Tenacity and % loss in dry elongation are concerned, these remained the same( fiber and the standard fiber 7) Testing of antimicrobial constituent enriched fiber/fabrics The antimicrobial constituent enriched lyocell fabrics as prepared in the above examples were tested for antimicrobial activity by various test procedures which included antimicrobial assays used to determine or confirm the effectiveness of treatments applied to medical devices, medical and commercial textiles, and other products. 28 Minimum sample requirements 9 square inches or 6 inches long, per test AATCC 100 (Part I) is a qualitative test for antibacterial activity. Test lyocell fiber/fabric specimens were placed into contact with a nutrient agar which had been streaked with either Staphylococcus aureus or Escherichia coli bacterial culture. Samples are inoculated with Staphylococcus and evaluated for percent reduction of the bacteria over selected contact periods of 1 - 24 hours. Turnaround Time is usually 5 days. The specimens were then incubated at a temperature 37 °C for a period of time of 24 hours. After the 24 hour incubation period, the samples were visually checked for the growth of bacteria. The AATCC 147/100, Part III protocol provides a qualitative test for antifungal activity. Lyocell fiber/ fabric specimens were subjected to the growth of a common fungus, Aspergillus niger, on Sabouraud Dextrose agar. Prewet specimens were inoculated and incubated at 28 C for seven days. Specimens were then assessed for growth of the fungus. ASTM E2180-01 test method was used for testing inhibitory mold activity of the lyocell product (fiber /fabric) prepared in accordance with this invention. All the specimen lyocell fiber and fabrics as obtained in examples 1 to 10 were tested for antimicrobial activity by following the above mentioned test protocols. The results of the above mentioned test protocols are provided in the following tables: 'Percentage kill of bacteria' is as per AATCC 100 test method and 'test results' are as per AATCC 147, showing if any growth of said bacteria was observed. 29 Table 1 Antimicrobial Activity of Lyocell Fibers Sr. No- % kill of bacteria Test results Example 1 Microbe tested : S. aureus 99.8 Not observed Example 2 Microbe tested : S. aureus 100 Not observed Example 3 Microbe tested : E. coli 100 Not observed Example 4 Microbe tested : S. aureus 100 Not observed Example 5 Microbe tested : S Aureus 100 Not observed Example 7 Microbe tested : S. aureus 100 Not observed Example 8 Microbe tested : S Aureus 100 Not observed Example 9 Microbe tested : S. aureus 100 Not observed Example 10 Microbe tested : S. aureus 100 Not observed Table 2 Antimicrobial Activity of Lyocell fabric Sr. No. % kill of bacteria Test results Example 1 Microbe tested : S. aureus 99.8 Not observed Example 2 Microbe tested : S. aureus 100 Not observed Example 3 Microbe tested : S Aureus . 100 Not observed Example 4 Microbe tested : E Coli 100 Not observed Example 5 Microbe tested : E Coli 100 Not observed Example 7 Microbe tested : E Coli 100 Not observed Example 8 Microbe tested : E. coli 100 Not observed Example 9 Microbe tested : S. aureus 100 Not observed Example 10 Microbe tested : S. aureus 100 Not observed 30 The lyocell fiber and fabric lyocell fabric specimens obtained in examples 4, 5 and 6 contained antifungal agent and their antifungal activity was determined by AATCC 147 part III and in case of the all the specimens no fungal growth was observed meaning that all the specimen exhibited excellent antifungal activity. Furthermore, inhibitory mould activity of these specimen was tested by ASTM E 2180-01 test protocol and good inhibitory activity against Aspergillus niger was recorded. The test fabrics made from these fibers thus exhibited significant antimicrobial activity both towards bacteria and fungi. While considerable emphasis has been placed herein on the specific steps of the preferred embodiment, it will be appreciated that many alterations can be made and that many modifications can be made in the preferred embodiment without departing from the principles of the invention. These and other changes in the preferred embodiment as well as other embodiments of the invention will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the invention and not as a limitation. 31 Claim: 1. An antimicrobial lyocell formulation meant for manufacture of lyocell products comprising : • at least one non-aqueous solvent in the range of about 0.01 to 20% of the mass of the formulation, • at least one water insoluble antimicrobial constituent soluble in said solvent, in the range of about 0.001 to 10% of the mass of the formulation, • at least one water soluble non-cationic surfactant having HLB value in the range of 9 to 40, in the range of 0.001 to 10% of the mass of the formulation, • cellulosic pulp in the range of about 3% to 35% of the mass of the formulation, • N-METHYL-MORPHOLINE-N-OXIDE (NNMO) in the range of about 60 to 80% of the mass of the formulation; and • water in the range of about 0% to 20 % with respect to the mass of the formulation. 2. A formulation as claimed in claim 1, wherein the antimicrobial constituent is at least one selected from a group consisting of 2-Methyl-4- isothiazolin-3-one, Phenoxyethanol Benzoic acid, 4-Hydroxy-methyl ester, Hydroxy-benzoic acid and propyl ester), o- (2-naphthyl) methyl (3- methylphenyl) thiocarbamate, 5-chloro~2-(2,4-dichlorophenoxy)phenol, 4,5-dichloro-n-octyl-4-isothiazoline-3-one[DCOIT], 2-n-octyl-4- isothiazolin-3-one, 1-phenoxy propan-2-ol, pentachlorophenol, 5-chloro- 32 2-dichlorophenoxy phenol, clotrimazole, p-chloro-m-xylenol and chloroquinaldol. 3. A formulation as claimed in claim 1, wherein the solvent is at least one solvent selected from a group of solvents consisting of C10-C44 alkanes (paraffmic hydrocarbons), polyethylene, polypropylene, polypropylene glycol, polytetramethylene glycol, polypropylene malonate, polyneopentyl glycol sebacate, polypentane glutarate, polyvinyl myristate, polyvinyl stearate, polyvinyl laurate, polyhexadecyl methacrylate, polyoctadecyl methacrylate, polyethylene oxides, polyethylene glycols, Arachidyl alcohol, behenyl alcohol, Selachyl alcohol, chimimyl alcohol, polyesters, di-iso decyl phthalate, benzyl alcohol, C4 -C30 aliphatic alcohols ,C4 -C30 saturated hydrocarbons, C4 -C30 monounsaturated hydrocarbons, natural oils and mineral oil paraffins. 4. A formulation as claimed in claim 1, wherein the surfactant is at least one surfactant selected from a group of non-ionic or anionic surfactants consisting of alkyl phenol ethoxylated surfactants, alkyl alcohol ethoxylated surfactants, Polyethylene-block-Poly propylene glycol-block-polyethylene glycol and Ethylenediamine tetrakis(propylene oxide-block-ethylene oxide) tetrol. 5. A formulation as claimed in claim 8, wherein the alkyl phenoxy like ethoxylated non-ionic or anionic surfactant with HLB > 9 is at least one selected from a group consisting of Polyoxyethylene(8) isooctylphenyl ether, Nonylphenol polyethylene glycol ether, Polyoxyethylene(9) 33 nonylphenyl ether, Polyoxyethylene(lO) isooctylphenyl ether, Polyoxyethylene(12) nonylphenyl ether, Polyoxyethylene(12) isooctylphenyl ether, Polyoxyethylene(40) nonylphenyl ether, Polyoxyethylene(40) isooctylphenyl ether, Polyoxyethylene( 100) nonylphenyl ether, Polyoxyethylene(150) dinonylphenyl ether, Surfonic N-95(Poly (oxy-1, 2-ethanediyl), alpha- (nonyl phenyl)-omega-hydroxyl-glycol ether) ( nonylphenol 9.5-mole ethoxylate) , Surfonic N-120(nonylphenol 12-mole ethoxylate), Surfonic N-150 (nonylphenol 15-mole ethoxylate), Surfonic N-200 (nonylphenol 20-mole ethoxylate) , Surfonic N-300( nonylphenol 30-mole ethoxylate) , Surfonic N-400 nonylphenol 40-mole ethoxylate, Igepal CO-630 (nonylphenoxy poly(ethyleneoxy) ethanol,branched), Surfonic DNP-40, fatty alcohol ether sulfates, alkyl carboxylates, alkyl benzene sulfonates, sulfosuccinates, polyethanoxy ether sulphate esters and polyethanoxy ether phosphate esters. 6. A formulation as claimed in claim 8, wherein the alkyl alcohol surfactant with HLB > 9 is at least one selected from a group consisting of Polyoxyethylene(lO) stearyl ether, Polyoxyethylene (10) oleyl ether, Polyoxyethylene(lO) cetyl ether, Polyoxyethylene(20) stearyl ether , Polyoxyethylene(20) oleyl ether, Polyoxyethylene(23) lauryl ether, Polyoxyethylene(lOO) stearyl ether, Polyoxyethylene(20) cetyl ether, Ceto Stearyl alcohol ethoxylates and modified alcohol ethoxylates, Surfonic LF-7 (Alkyl polyoxyalkylene ether) and Surfonic LF-17 (ethoxylated and propoxylated linear primary 12-14 carbon number alcohol). 34 7. A formulation as claimed in claim 1, wherein the preferred HLB value of the surfactant is between 16 and 40. 8. A formulation as claimed in claim 1, wherein the average mean size of the micro-reservoir is in the range of 5 nm to 2000 nm. 9. An antimicrobial lyocell fiber manufactured from a formulation as claimed in claim 1. 10.An antimicrobial lyocell yarn manufactured from a formulation as claimed in claim 1. 11.An antimicrobial lyocell fabric manufactured from a formulation as claimed in claim 1. 12. A process of preparation of an antimicrobial lyocell formulation meant for manufacture of lyocell products comprising the following steps : • admixing a water-insoluble antimicrobial constituent with a non¬aqueous solvent followed by heating the resulting mixture to obtain a liquid non-aqueous phase ; • dissolving and stirring a surfactant, optionally with a co-surfactant, in water to obtain an aqueous phase; • heating the aqueous-phase; • mixing the aqueous phase with the non-aqueous phase in the liquid state to form a admixture and homogenizing to obtain a micro-emulsion; 35 • mixing together cellulosic pulp and N-METHYL-MORPHOLINE-N-OXIDE (NNMO) solution to form a slurry; • dispersing the micro-emulsion in the slurry to obtain a preform mass wherein the antimicrobial constituent is embedded in evenly dispersed micro-reservoirs; • vaccumising the preform mass to remove water under 7 to 10 mm of Hg and temperature of over 90 C to obtain the formulation. Dated this 3rd day of July, 2008. Mohan Dewan of R. K. Dewan and Co. Applicants' Patent Attorney 36

Full Text

FORM - 2
THE PATENTS ACT, 1970
(39 OF 1970)
AND
THE PATENTS RULES, 2003
COMPLETE SPECIFICATION
(See section 10; rule 13)

A LYOCELL ANTIMICROBIAL FIBER AND A METHOD OF MAKING
THEREOF
ADITYA BIRLA SCIENCE & TECHNOLOGY CO. LTD.
an Indian Company of Aditya Birla Center, 2nd floor, C Wing, S. K. Ahire Marg, Mumbai 400 025,
Maharashtra, India
THE FOLLOWING SPECIFICATION PARTICULARLY DESCRIBES THE INVENTION AND THE MANNER IN WHICH IT IS TO BE PERFORMED.

Field of the invention
The present invention relates to textile fibers.
Background of the invention
The term "fiber" or "textile fiber" means a substance which is capable of being spun into a yarn or made into a fabric by bonding or by interlacing in a variety of methods including weaving, knitting, braiding, felting, twisting, or webbing, and which is the basic structural element of textile products.
Fibers are classified on the basis of their length such as short fibers or staple fiber and long fibers or filament fiber. The fibers can also be classified on the basis of their origin such as natural fibers and man-made fibers. The term natural fibers means any fiber that exists as such in the natural state e.g. vegetable fibers or wood fibers. The other type of fibers is obtained from chemical substances. These are called man made fibers. They are polyester, nylon, acrylic (cashmilon) etc. For centuries, mankind has relied upon various plants and animals to provide raw materials for fabrics and clothing. In recent times, the industrialization and scientific advancement has provided several improved materials having far superior properties, particularly suitable for clothing.
Lyocell is a manmade fiber derived from cellulose. Though it is related to , viscose is obtained by a solvent spinning technique. The solvent spinning technique, which is simpler and more environmentally sound, since it uses a non¬toxic solvent chemical that can be recycled in the manufacturing process. It is an extremely strong fabric with industrial uses such as in automotive filters, ropes, abrasive materials, bandages and protective suiting material. It is primarily found in the garment industry, particularly in women's clothing.
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Lyocell fibers are prepared by following process steps:
The raw cellulose is dissolved into heated, pressurized vessel filled with an amine
oxide solvent.
After soaking for a short time in the solvent at high temperature under vacuum to
remove excess water, the cellulose forms a clear solution and then it is filtered.
The solution is then pumped through spinneret which is pierced with small holes
to obtain long strands of fibers. The fibers are then immersed in another dilute
solution of amine oxide. This helps to set the fiber strands. Then, they are washed
with de-mineralized water.
The lyocell fibers are then led to a drying area, where the water is evaporated
from it. The strands are led to a finishing area, where the lubricant is applied.
The dried, finished fibers are at this stage are called as a tow, which is a large
untwisted bundle of continuous length filaments. Tne'bundles ol tow are taken to
a crimper, a machine which compresses the fiber, giving it texture and bulk. The
crimped fiber is then carded by mechanical carders, which perform an action like
combing, to separate and order the strands. The carded strands are cut and baled
for shipment to a fabric mill.
The amine oxide used to dissolve the cellulose formed set the fiber after spinning is
recovered and re-used in the manufacturing process.
From the spun or filament yarn, fabric is formed by knitting or weaving operations. Knitted fabrics can be made by using hooked needles to interlock one or more sets of yarns through a set of loops. The loops may be either loosely or closely constructed, depending on the purpose of the fabric. Knitted fabrics can be used for hosiery, underwear, sweaters, slacks, suits, coats, rugs and other home furnishings. Knitting is performed using either weft or warp processes.
3

Some typical preparations that are involved in the weaving operations are warping, slashing or sizing. Sizing agents are added to the yarn by solution or pad/dry techniques. Differences in raw materials, processing chemicals, fiber diameter, post treatments and blend ratios can be manipulated to produce a fiber having customized properties suitable for desired application. It is often desired that the lyocell fabrics possess typical properties such as thermal stability, ability to retain perfumes, antibacterial properties and the like. These properties are essential in several industrial as well as household applications. There has been a considerable interest in developing such materials. In order to impart various desirable properties to the fabric as mentioned above to the fabric, several additives are added. Such additives include antimicrobial agents, deodorizing agents, antistatic agents, perfumes. Besides such specific additives, generic additives for improving overall quality of the fabric, such as sizing agents, additives for increasing yarn softness and pliability are also added.
Prior art:
US patent 6436419 discloses a process that involves dyeing a polymer with an acid dye to form a dye coated polymer, and attaching an antimicrobial agent like quaternary ammonium salt, thereby making said polymer antimicrobial.
A method for producing an antimicrobial effect in biodegradable textile article containing cellulosic material is disclosed in US 20050225002. Lyocell fibers constitute at least 10 % by weight of the textile article. It is reported that in case of use of Lyocell fibers in the textile, the growth of microorganisms is delayed or prevented, respectively, in comparison with other cellulosic fibers such as cotton or viscose fibers.
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Earlier known processes of incorporating such additives, as reported in the above mentioned patents/applications, mainly involved conventional methods like spraying, solvent spinning the additives on the fabric. However, these methods suffer from several disadvantages which include non-uniform and improper adhesion of additives onto the fiber material, waning and gradual washing out of the additives over a period of time and which further affects the feel and texture of the fabric.
There is thus felt a need for a process of incorporating additives to fabric which overcomes these shortcomings.
Objects of the Invention
It is an object of this invention to provide antimicrobial lyocell fibers, wherein at least one antimicrobial constituent is incorporated into the body of the fiber.
Another object of this invention is to provide a process of incorporating antimicrobial constituents into lyocell fibers which ensures uniform distribution of the antimicrobial constituent throughout the fiber length.
Yet another object of this invention is to provide antimicrobial lyocell fibers wherein the antimicrobial constituents are retained in the lyocell product over a prolonged period of time.
Yet another object of this invention is to provide a process of incorporating antimicrobial constituents to lyocell fibers which does not alter the feel and texture of the fabric.
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Still another object of this invention is to provide a process of incorporating antimicrobial constituents to lyoceli fibers such that inherent properties of the lyoceli fibers such as fiber strength, linear density, tenacity, heat resistance, dyeability and drying properties are not altered.
Definitions:
As used in the present specification, the following words and phrases are generally intended to have the meanings as set forth below, except to the extent that the context in which they are used indicates otherwise.
"Non-aqueous phase" means a melted mixture in liquid state which is water
insoluble.
"Aqueous phase" means substance dissolved in water.
"Lyoceli Polymer dope" means an intermediate material in the manufacture of
lyoceli products that is used for preparation of fibers.
"Preform mass" means an intermediate material suitable for making fibers.
"NNMO" means N-METHYL-MORPHOLINE-N-OXIDE
Summary of the Invention
In accordance with this invention there is provided an antimicrobial lyoceli formulation meant for manufacture of lyoceli products comprising:
• at least one non-aqueous solvent in the range of about 0.01 to 20% of the mass of the formulation,
• at least one water insoluble antimicrobial constituent soluble in said solvent, in the range of about 0.001 to 10% of the mass of the formulation,
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• at least one water soluble non-cationic surfactant having HLB value in the range of 9 to 40, in the range of 0.001 to 10% of the mass of the formulation,
• cellulosic pulp in the range of about 3% to 35% of the mass of the formulation,
• N-methyl-morpholine-N-oxide (NNMO) in the range of about 60 to 80% of the mass of the formulation; and
• water in the range of about 0% to 20 % with respect to the mass of the formulation.
Typically, the antimicrobial constituent is at least one selected from a group consisting of 2-Methyl-4-isothiazolin-3-one, water, Phenoxyethanol Benzoic acid, 4-Hydroxy-methyl ester, Hydroxy-benzoic acid and propyl ester), o-(2-naphthyl) methyl (3-methylphenyl) thiocarbamate, 5-chloro-2-(2,4-dichlorophenoxy)phenol,4,5-dichloro-n-octyl-4-isothiazoline-3-one[DCOIT] 2-n-octyl-4-isothiazolin-3-one, 1-phenoxy propan-2-ol, pentachlorophenol, 5-chloro-2-dichlorophenoxy phenol, clotrimazole, p-chloro-m-xylenol and chloroquinaldol.
Typically, the solvent is at least one solvent selected from a group of solvents consisting of C10-C44 alkanes (paraffinic hydrocarbons), polyethylene, polypropylene, polypropylene glycol, polytetramethylene glycol, polypropylene malonate, polyneopentyl glycol sebacate, polypentane glutarate, polyvinyl myristate, polyvinyl stearate, polyvinyl laurate, polyhexadecyl methacrylate, polyoctadecyl methacrylate, polyethylene oxides, polyethylene glycols, Arachidyl alcohol, behenyl alcohol, Selachyl alcohol, chimimyl alcohol, polyesters, di-iso decyl phthalate, benzyl alcohol, C4 -G30 aliphatic alcohols ,C4 -C30 saturated
7

hydrocarbons, C4 -C30 monounsaturated hydrocarbons, natural oils and mineral oil paraffins.
Typically, the surfactant is at least one non-cationic surfactant selected from a group of surfactants consisting of alkyl phenol ethoxylates and alkyl alcohol ethoxylates.
Typically, the alkyl phenol ethoxylated or alkyl alcohol ethoxylate is at least one
selected from a group consisting of Surfonic N-95(Poly (oxy-1, 2-ethanediyl),
alpha- (nonyl phenyl)-omega-hydroxyl-glycol ether) ( nonylphenol 9.5-mole
ethoxylate) , Surfonic N-120(nonylphenol 12-mole ethoxylate) , Surfonic N-150
(nonylphenol 15-mole ethoxylate), Surfonic N-200 (nonylphenol 20-mole
ethoxylate) , Surfonic N-300( nonylphenol 30-mole ethoxylate) , Surfonic N-400
nonylphenol 40-mole ethoxylate, Surfonic LF-7 (Alkyl polyoxyalkylene ether) ,
Surfonic LF-17 (ethoxylated and propoxylated linear primary 12-14 carbon
number alcohol), Igepal CO-630 (nonylphenoxy
poly(ethyleneoxy)ethanol,branched), Surfonic DNP-40 , fatty alcohol ether
sulfates, alkyl carboxylates, alkyl benzene sulfonates, sulfosuccinates, polyethanoxy ether sulphate esters and polyethanoxy ether phosphate esters.
In accordance with one preferred embodiment of the invention, the HLB value of
the surfactant is between 16 and 40.
In accordance with one aspect of the invention, the antimicrobial constituent, the solvent and the surfactant are processed to form micro-reservoirs which are embe'dded into the body of the formulation.
8

Typically, the average mean size of the micro-reservoir is in the range of 5 nm to 2000 nm.
The invention also extends to an antimicrobial lyocell fiber, yarn and fabric manufactured from a formulation in accordance with this invention.
In accordance with this invention there is also provided a process for preparation of an antimicrobial lyocell formulation meant for manufacture of lyocell products comprising the following steps:
• admixing a water-insoluble antimicrobial constituent with a non¬aqueous solvent followed by heating the resulting admixture to obtain non-aqueous phase ;
• dissolving and stirring a surfactant, optionally with a co-surfactant, in water to obtain an aqueous phase;
• heating the aqueous-phase; .
• mixing the aqueous phase with the non-aqueous phase in the liquid state to form a admixture and homogenizing to obtain a micro-emulsion;
• mixing together cellulosic pulp and N-methyl-morpholine-n-oxide (NNMO) solution to form a slurry;
• dispersing the micro-emulsion in the slurry to obtain a preform mass wherein the antimicrobial constituent is embedded in evenly dispersed micro-reservoirs;
• vaccumising the preform mass to remove water under 7 to 10 mm of Hg and temperature of over 90°C.
9

Brief Description of the accompanying Drawings:
The invention will be described in detail with reference to the accompanying drawings.
In the accompanying drawing, Figure 1 illustrates the block diagram showing the method steps involved in the process in accordance with this invention.
Figure 2 illustrates the cross-sectional view of antimicrobial lyocell fibers prepared in accordance with this invention which shows uniform distribution of micro-reservoirs of antimicrobial constituents entrapped across the length of the fibers.
Detailed Description of the Invention
A decade of Lyocell technology development has yielded many new opportunities in textile applications due to interesting properties of the solvent spun cellulosic lyocell fibers, especially good mechanical properties and fibrillation resistance. Its versatility and desirable properties provide many advantages, both functional and aesthetic. In terms of performance and properties, lyocell is also friendly to the environment The resulting fiber, lyocell, is both biodegradable and recyclable Lyocell has strength and durability. Lyocell blends well with other fibers including wool, silk, cotton, linen, nylon, and polyester. It successfully takes many finishes, both functional and those designed to achieve different surface effects, and dyes easily. Overall, lyocell is a versatile fiber with many desirable properties.
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In accordance with this invention there is provided an antimicrobial lyocell formulation meant for manufacture of lyocell products comprising :
• at least one non-aqueous solvent in the range of about 0.01 to 20% of the mass of the formulation,
• at least one water insoluble antimicrobial constituent soluble in said solvent, in the range of about 0.001 to 10% of the mass of the formulation,
• at least one water soluble non-cationic surfactant having HLB value in the range of 9 to 40, in the range of 0.001 to 10% of the mass of the formulation,
• cellulosic pulp in the range of about 3% to 35% of the mass of the formulation
• N-METHYL-MORPHOLINE-N-OXIDE (NNMO) in the range of about 60 to 80% of the mass of the formulation; and
• water in the range of about 0% to 20 % with respect to the mass of the formulation.
In accordance with the invention, anti-microbial constituent is typically at least one selected from a group consisting of 2-Methyl-4-isothiazolin-3-one, water, Phenoxyethanol Benzoic acid, 4-Hydroxy-methyl ester, Hydroxy-benzoic acid and propyl ester), o- (2-naphthyl) methyl (3-methylphenyl) thiocarbamate, 5-chloro-2-(2,4-dichlorophenoxy)phenol, 4,5-dichloro-n-octyl-4-isothiazoline-3-one[DCOIT] 2-n-octyl-4-isothiazolin-3-one, 1-phenoxy propan-2-ol, pentachlorophenol, 5-chloro-2-dichlorophenoxy phenol, clotrimazole, p-chloro-m-xylenol and chloroquinaldol.
11

The antimicrobial constituent impart antimicrobial property to the fibers and ultimately to the fabric or garments made from these fibers.
In accordance with this invention , only non-aqueous solvent is used which is typically selected from a group of solvents consisting of C10-C44 alkanes (paraffinic hydrocarbons), polyethylene, polypropylene, polypropylene glycol, polytetramethylene glycol, polypropylene malonate, polyneopentyl glycol sebacate, polypentane glutarate, polyvinyl myristate, polyvinyl stearate, polyvinyl laurate, polyhexadecyl methacrylate, polyoctadecyl methacrylate, polyethylene oxides, polyethylene glycols, Arachidyl alcohol, behenyl alcohol, Selachyl alcohol, chimimyl alcohol, polyesters,, di-iso decyl phthalate, benzyl alcohol, C4 -C30 aliphatic alcohols ,C4 -C30 saturated hydrocarbons, C4 -C30 monounsaturated hydrocarbons, natural oils and mineral oil paraffins.
Preferably, paraffin wax either alone or in combination with stearyl alcohol is used as the non-aqueous solvent.
In accordance with this invention only water soluble non-cationic surfactant/co-
surfactant is used. The non-cationic surfactant is selected from a group consisting
of alkyl phenoxy ethoxylated non-ionic surfactants and ethoxylated alkyl alcohol
surfactants, Polyethylene-block-Poly propylene glycol-block-polyethylene glycol
and Ethylenediamine tetrakis(propylene oxide-block-ethylene oxide) tetrol. The
alkyl phenol ethoxylated surfactant is at least one selected from a group
consisting of Polyoxyethylene(8) isooctylphenyl ether, Nonylphenol polyethylene
glycol ether, Polyoxyethylene(9) nonylphenyl ether, Polyoxyethylene(lO)
isooctylphenyl ether, Polyoxyethylene(12) nonylphenyl ether,
Polyoxyethylene(12) isooctylphenyl ether, Polyoxyethylene(40) nonylphenyl
12

ether, Polyoxyethylene(40) isooctylphenyl ether, Polyoxyethylene(100) nonylphenyl ether, Polyoxyethylene(150) dinonylphenyi ether, Surfonic N-95(Poly (oxy-1, 2-ethanediyl), alpha- (nonyl phenyl)-omega-hydroxyl-glycol ether) ( nonylphenol 9.5-mole ethoxylate) , Surfonic N-95(Poly (oxy-1, 2-ethanediyl), alpha- (nonyl phenyl)-omega-hydroxyl-glycol ether) ( nonylphenol 9.5-mole ethoxylate) , Surfonic N-120(nonylphenol 12-mole ethoxylate) , Surfonic N-150 (nonylphenol 15-mole ethoxylate), Surfonic N-200 (nonylphenol 20-mole ethoxylate) , Surfonic N-300( nonylphenol 30-mole ethoxylate) , Surfonic N-400 nonylphenol 40-mole ethoxylate, Surfonic LF-7 (Alkyl polyoxyalkylene ether) , Surfonic LF-17 (ethoxylated and propoxylated linear primary 12-14 carbon number alcohol), Igepal CO-630 (nonylphenoxy poly(ethyleneoxy)ethanol,branched), Surfonic DNP-40, fatty alcohol ether sulfates, alkyl carboxylates, alkyl benzene sulfonates, sulfosuccinates, polyethanoxy ether sulphate esters and polyethanoxy ether phosphate esters.
The non-ionic or anionic surfactant is selected such that the lipophilic portion of the non-ionic or anionic surfactant is compatible with the antimicrobial constituent and the surfactant forms oil in water microemulsion. Surfactants with HLB values within the range of 9 to 40 are used. Preferably, non-ionic or anionic surfactants with HLB values more than 13 are used.
In accordance with one preferred embodiment of the invention, the HLB value of the surfactant is between 16 and 40.
In accordance with one aspect of the invention, the antimicrobial constituent, the solvent and the surfactant are processed to form micro-reservoirs which are embedded into the body of the formulation. The antimicrobial lyocell contains
13

uniformly dispersed micro-reservoirs throughout the body of the fibers. The micro-reservoirs are discrete, nano-sized structures without any definite geometrical shape.
Typically, the average mean size of the micro-reservoir is in the range of 5 nm to 2000 nm.
The invention also extends to an antimicrobial lyocell fiber, yarn and fabric manufactured from a formulation in accordance with this invention.
In accordance with this invention there is also provided a process for preparation of an antimicrobial lyocell formulation meant for manufacture of lyocell products comprising the following steps :
• admixing a water-insoluble antimicrobial constituent with a non¬aqueous solvent followed by heating the resulting mixture to obtain a liquid non-aqueous phase;
• dissolving and stirring a surfactant, optionally with a co-surfactant, in water to obtain an aqueous phase;
• heating the aqueous-phase;
• mixing the aqueous phase with the non-aqueous phase in the liquid state to form a admixture and homogenizing to obtain a micro-emulsion;
• mixing together cellulosic pulp and N-METHYL-MORPHOLINE-N-OXIDE (NNMO) solution to form a slurry;
14

• dispersing the micro-emulsion in the slurry to obtain a preform mass wherein the antimicrobial constituent is embedded in evenly dispersed micro-reservoirs;
• vaccumising the preform mass to remove water under 7 to 10 mm of Hg and temperature of over 90°C to obtain the formulation.
Before arriving at the optimum concentration of the surfactant to be used, cloud point of the aqueous phase is determined. Furthermore, alkalinity of the aqueous phase matches with that of the viscous polymer dope thereby avoiding any drastic change in the alkalinity during the emulsification and homogenization step. Typically, the melted non-aqueous phase containing antimicrobial constituent in a non-aqueous solvent along with aqueous phase containing surfactants is emulsified using high speed mixers, such as Ultraturrex or a mechanical emulsifier; a colloid mill; a high pressure homogenizer and an ultrasonic emulsifier to form a microemulsion. The micro-emulsion may contain further additional antimicrobial constituents, if desired.
It is important that the non-aqueous phase is maintained in liquid state throughout the mixing process. The aqueous phase therefore is typically heated upto a particular temperature to ensure that the temperature of the resulting emulsion is above the melting point of the non-aqueous solvent. If this does not happen, the resulting emulsion will break down.
The active ingredients are released from the micro-reservoir into the lyocell matrix. The structure of micro-reservoir, lyocell and surrounding conditions determine the release rate of the antimicrobial constituent. The molecules of the volatile antimicrobial constituents migrate from micro-reservoirs to the
15

surrounding primarily by diffusion. The antimicrobial constituent is released from the matrix in a controlled release manner.
Conventional method for manufacture of lyocell involves following major steps :
Step 1. Creating a solvent solution from wood pulp
The wood pulp is obtained from a variety of sources, such as wood chips or even large rolls of paper that have been finely shredded, is the basic starting material for manufacture of lyocell fibers. In case of manufacture of lyocell no further chemical treatment of the wood pulp is needed thereby making the process environment friendly.
The wood pulp solution is produced in a straight solvation process by dissolving wood pulp at high temperatures and pressure in a recyclable non-toxic organic solvent solution of amine oxide, particularly N-methylmorpholine N-oxide,(N-METHYL-MORPHOLINE-N-OXIDE (NNMO)).
Lyocell is manufactured by a "closed loop" spinning process which conserves
energy and water.
Step 2 Spinning lyocell fiber from the solvent solution
Before being formed into fibers, the lyocell polymer dope, is in a thick liquid state. In the spinning process this liquid is forced through a spinneret, which resembles a large shower head.
The clear, viscous resultant solution is filtered and extruded into an aqueous bath of dilute amine oxide, and coagulated into fiber form.
16

Step 3. Washing lyocell fiber to remove solvents
The fiber is then washed before it is dried and twisted or spun into yarns, which are woven or knitted into fabrics and garments.
Step 4. Drying fiber and producing yarns
When the filament dries or solidifies, it forms what is called a continuous filament fiber. Many continuous filaments of specific thicknesses collected in a large bundle called a "tow". A tow may contain over a million continuous filaments. The tow bundle is then crimped, is then mechanically cut into staple fibers, usually ranging in length from 1 to 6-1/2 inches, depending how they are to be used.
Strands of continuous filament fibers are then twisted together to form a continuous filament yarn, which is then woven or knit into fabric.
Step 5, Finishing producing lyocell fabric
The fabric is treated with an enzyme that attacks cellulose fibers. Home laundry detergents containing such enzymes are also used for treatment of the fabric for better finishing purposes. This enzyme dissolves the split-end hairs from the fiber surface. The fiber is then washed and agitated again. The resulting fabric is similar in texture and drape to sueded silk or sueded rayon found in fashion apparel. Fabrics processed this way can usually be machine washed and line dried successfully.
Alternatively, the filaments so obtained further blended using standard equipment. The blended fibers are laid in to a web using standard equipment followed by Consolidation of the web to obtain Non-woven Lyocell Fabric.
17

The lyocell product made from the formulation in accordance with this invention contains uniformly dispersed micro-reservoirs throughout the mass which is shown in Fig. 2.
The antimicrobial constituent enriched lyocell fabrics as prepared in the above examples can be tested for antimicrobial activity by various test procedures which include antimicrobial assays used to determine or confirm the effectiveness of treatments applied to medical devices, medical and commercial textiles, and other products. Test methods for measuring the antimicrobial activity include ASTM, AATCC, and other modified methods. Testing includes antibacterial and antifungal activity, with both qualitative and quantitative assays available.
AATCC 100 is a qualitative test for antibacterial activity.
Test lyocell fiber/fabric specimens are placed into contact with a nutrient agar which has been streaked with a microbe such as Staphylococcus aureus, Escherichia coli bacterial culture. Samples are inoculated with Staphylococcus and evaluated for percent reduction of the bacteria over selected contact periods of 1 - 24 hours. Turnaround Time is usually 5 days. The specimens are then incubated at a temperature 37 °C for a period of time of 24 hours. After the 24 hour incubation period, the samples are visually checked for the growth of bacteria.
The AATCC 147, Part III protocol provides a qualitative test for antifungal activity. Lyocell fiber/ fabric specimens are subjected to the growth of a common fungus, Aspergillus niger, on Sabouraud Dextrose agar. Prewet specimens are
18

inoculated and incubated at 28 C for seven days. Specimens are then assessea ror growth of the fungus.
ASTM E2180-01 test method is used for testing inhibitory mold activity of the lyocell product (fiber /fabric) prepared in accordance with this invention.
The antimicrobial lyocell fibers contain the entrapped antimicrobial constituent in releasable form. Microscopic examination of the micro-reservoirs in the lyocell fibers is shown in Fig 2.
The resultant lyocell fabric containing antimicrobial constituent are tested. Linear Density (Denier) of the lyocell Fibers is determined by using standard ASTM Test Method (D 1577). The denier of the standard lyocell fiber (lyocell fiber without any antimicrobial constituents) and anti-microbial enriched lyocell fiber remains the same. Thus addition of antimicrobial constituents does not change the linear density of the lyocell fibers.
Tensile strength and Young's modulus of lyocell fiber sample is tested on an Instron tensile testing machine as per the ASTM CI557-03 procedure at ambient temperature.
Visual appearance of the antimicrobial enriched fiber is evaluated by methods as prescribed in AATCC 124. As far as parameters like % Loss in Dry Tenacity and % loss in dry elongation are concerned, these remain the same in the antimicrobial enriched lyocell fiber and the standard fiber. Incorporation of antimicrobial constituent in accordance with this invention does not affect the visual appearance of the fiber.
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Feel of the fiber: The antimicrobial enriched lyocell fiber as prepared in accordance with this invention offers the same feel effect as is observed in case of plain lyocell fiber without any antimicrobial constituent (Also referred as standard).
Another important concern in textile industry is dye-ability of the fabric, which is tested by comparing the dyeability of the antimicrobial constituent enriched fabric and the standard lyocell fabric. Dyeability of the antimicrobial enriched lyocell fibers as prepared in accordance with this invention remains the same as that of the standard lyocell fiber.
The invention will now be described with the help of the following non-limiting examples.
Examples Example 1
Example 1 A- Preparation of micro emulsion
Stearyl alcohol (225 gms) was heated until it melts and (50gm) of 2-Methyl-4-
isothiazolin-3-one, water, phenoxyethanol Benzoic acid, 4-Hydroxy-methyl ester,
Hydroxy-benzoic acid and propyl ester was admixed to form a molten mixture
(275gm).
Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was
dissolved and stirred in water (525 ml) to obtain (553 gm)of aqueous phase.
The aqueous phase (553 gm) and the mixture (275 gm) were homogenized in a
high speed mixer (Ultraturrex) to obtain a micro-emulsion (828 gm ).
Example 1 B- Preparation fiber and fabric
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1000 gm of cellulosic pulp and 12670 gm of 50% NNMO solution were mixed to form a slurry (13670gm).The micro-emulsion as prepared in Example 1A was evenly dispersed in the slurry to obtain a preform mass (14500 gm). The homogenized preform mass was vaccumisied to remove water under 10 mm of Hg and at temperature 110 °C ,was further spun in a spin bath of dilute amine oxide, and coagulated into fiber form. The fiber was then washed before it was dried and spun into a fabric.
The lyocell fiber thus obtained contained micro-reservoirs having the entrapped releasable antimicrobial constituents. Although the micro reservoirs did not have any specific shape or size, they were found to be uniformly distributed throughout the body of the fiber.
Example 2
Example 2A- Preparation of micro emulsion
Myristyl alcohol (225 gms) was heated until it melts and (60gm) of 2-Methyl-4-
isothiazolin-3-one, water, phenoxyethanol Benzoic acid, 4-Hydroxy-methyl ester,
Hydroxy-benzoic acid and propyl ester was admixed to form a molten mixture
(275gm).
Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was
dissolved and stirred in water (525 ml) to obtain (553 gm)of aqueous phase.
The aqueous phase (553 gm) and the mixture (275 gm) were homogenized in a
high speed mixer (Ultraturrex) to obtain a micro-emulsion (828 gm ).
Example 2 B Preparation of fiber
21

990 gm of cellulosic pulp and 12540 gm of 50% NNMO solution were mixed to form a slurry (13530gm).The micro-emulsion as prepared in Example 2A was evenly dispersed in the slurry to obtain a preform mass (14360 gm) and was spun into fiber as described in example 1.
Example 3
Example3 A
Preparation of antimicrobial formulation
Polyvinyl laurate (200 gms) and cetyl alcohol ( 25 gm) was heated until it melts
and (lOOgm) of 2-Methyl-4-isothiazolin-3-one, water, phenoxyethanol Benzoic
acid, 4-Hydroxy-methyl ester, Hydroxy-benzoic acid and propyl ester was
admixed to form a molten mixture (325gm).
Surfonio N-400 nonylphenol 40-mole ehhoxylate (surfactant) (28 gm ) was
dissolved and stirred in water (525 ml) to obtain (553 gm)of aqueous phase.
The aqueous phase (553 gm) and the mixture (325 gm) were homogenized in a
high speed mixer (Ultraturrex) to obtain a micro-emulsion (878 gm).
Example 3 B- Preparation of fiber
922 gm of cellulosic pulp and 11680 gm of 50% NNMO solution were mixed to form a slurry (12600 gm).The micro-emulsion as prepared in Example 3A was evenly dispersed in the slurry to obtain a preform mass (13478 gm) and was spun into fiber as described in example 1.
Example 4
Example 4 A
Preparation of antimicrobial formulation
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Polyvinyl laurate (250 gms) and cetyl alcohol (25 gm) was heated until it melts and (50 gm) of chloroquinaldol was admixed to form a molten mixture (325gm). Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was dissolved and stirred in water (525 ml) to obtain (553 gm)of aqueous phase. The aqueous phase (553 gm) and the mixture (325 gm) were homogenized in a high speed mixer (Ultraturrex) to obtain a micro-emulsion (878 gm).
Example 4 B- Preparation fiber and fabric
1400 gm of cellulosic pulp and 17730 gm of 50% NNMO solution were mixed to form a slurry (19130gm).The micro-emulsion as prepared in Example 4A was evenly dispersed in the slurry to obtain a preform mass (20010 gm) and was spun into fiber as described in example 1.
Example 5
Example 5 A
Preparation of antimicrobial formulation
Polypropylene glycol (100 gm) and paraffin wax (175 gm) were heated until it
melts and (50 gm) of chloroquinaldol was admixed to form a molten mixture
(325gm).
Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was
dissolved and stirred in water (525 ml) to obtain (553 gm)of aqueous phase.
The aqueous phase (553 gm) and the mixture (325 gm) were homogenized in a
high speed mixer (Ultraturrex) to obtain a micro-emulsion (878 gm).
Example 5 B- Preparation fiber and fabric
1200 gm of cellulosic pulp and 15200 gm of 50% NNMO solution were mixed to
form a slurry (16400 gm).The micro-emulsion as prepared in Example 5A was
23

evenly dispersed in the slurry to obtain a preform mass (17280 gm) and was spun into fiber as described in example 1.
Example 6
Example 6 A
Preparation of antimicrobial formulation
Stearyl alcohol (200gm) and polyethylene(HDPE) (lOOgm) were melted together
to form a molten liquid. To this o- (2-naphthyl) methyl (3-methylphenyl)
thiocarbamate (Tolnaftate) (200gm) to form a molten mixture (500gm).
Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was
dissolved and stirred in water (525 ml) to obtain (553 gm)of aqueous phase.
The aqueous phase (553 gm) and the mixture (500 gm) were homogenized in a
high speed mixer (Ultraturrex) to obtain a micro-emulsion (1053 gm).
Example 6 B- Preparation fiber and fabric
947 gm of cellulosic pulp and 12000 gm of 50% NNMO solution were mixed to form a slurry (12947gm).The micro-emulsion as prepared in Example 6A was evenly dispersed in the slurry to obtain a preform mass (13995 gm) and was spun into fiber as described in example 1.
Example 7
Example 7 A
Preparation of antimicrobial formulation
Polyvinyl stearate (150 gm) and paraffin wax (lOOgm) were melted together to
form a molten liquid. To this 5-chloro-2-(2,4-dichlorophenoxy)phenol (Triclosan)
(150 gm) was added to form a molten mixture (400 gm).
24

Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was dissolved and stirred in water (525 ml) to obtain (553 gm)of aqueous phase. The aqueous phase (553 gm) and the mixture (400 gm) were homogenized in a high speed mixer (Ultraturrex) to obtain a micro-emulsion (953 gm).
Example 7 B- Preparation fiber and fabric
1047 gm of cellulosic pulp and 13260 gm of 50% NNMO solution were mixed to form a slurry (14310 gm).The micro-emulsion as prepared in Example 7A was evenly dispersed in the slurry to obtain a preform mass (15260 gm) and was spun into fiber as described in example 1.
Example 8
Example 8 A
Preparation of antimicrobial formulation
Polypentane glutarate (300 gm) was melted to form a molten liquid. To this
(lOOgm) 5-chloro-2-(2,4-dichlorophenoxy)phenol (Triclosan) was added to form
a mixture (400 gm).
Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was
dissolved and stirred in water (525 ml) to obtain (553 gm)of aqueous phase.
The aqueous phase (553 gm) and the mixture (400 gm) were homogenized in a
high speed mixer (Ultraturrex) to obtain a micro-emulsion (953 gm).
Example 8 B
1547 gm of cellulosic pulp and 19590 gm of 50% NNMO solution were mixed to
form a slurry (21140gm).The micro-emulsion as prepared in Example 8A was
25

evenly dispersed in the slurry to obtain a preform mass (22090 gm) and was spun into fiber as described in example 1.
Example 9
Example 9 A
Preparation of antimicrobial formulation
Stearyl alcohol ( 250 gm) and paraffin wax (200 gm) were melted together to
form a molten liquid. To this (50gm) 4,5-dichloro-n-octyl-4-isothiazoline-3-
one[DCOIT] was added to form a mixture (500 gm).
Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was
dissolved and stirred in water (525 ml) to obtain (553 gm) of aqueous phase.
The aqueous phase (553 gm) and the mixture (500 gm) were homogenized in a
high speed mixer (Ultraturrex) to obtain a micro-emulsion (1053 gm).
Example 9 B
1147 gm of cellulosic pulp and 14530 gm of 50% NNMO solution were mixed to form a slurry (15680gm).The micro-emulsion as prepared in Example 8A was evenly dispersed in the slurry to obtain a preform mass (16730 gm) and was spun into fiber as described in example 1.
Example 10
Example 10 A
Preparation of micro emulsion
Stearyl alcohol (150 gm) and polyvinyl laurate (150gm) were melted together to form a molten liquid. To this molten liquid, (200gm) of 2-Methyl-4-isothiazolin-3-one, water, Phenoxyethanol Benzoic acid, 4-Hydroxy-methyl ester, Hydroxy-benzoic acid and propyl ester) was added to form a mixture (500gm).
26

Surfonic N-400 nonylphenol 40-mole ethoxylate (surfactant) (28 gm ) was dissolved and stirred in water (525 ml) to obtain (553 gm) of aqueous phase. The aqueous phase (553 gm) and the mixture (500 gm) were homogenized in a high speed mixer (Ultraturrex) to obtain a micro-emulsion (1053 gm).
Example 10 B
1347 gm of cellulosic pulp and 17060 gm of 50% NNMO solution were mixed to form a slurry (18410gm).The micro-emulsion as prepared in Example 10 A was evenly dispersed in the slurry to obtain a preform mass (19460 gm) and was spun into fiber as described in example 1.
Testing procedures:
The antimicrobial lyocell products as prepared in the above examples (1 to 10) were tested by using following test procedures:
1) Linear Density (Denier) of the lyocell Fibers was determined by using
standard ASTM Test Method (D 1577).
The denier of the standard lyocell fiber (without any antimicrobial constituents) and anti-microbial lyocell fibers as prepared in accordance with example IB was found to be uniform(1.5 denier) irrespective of the type and quantity of the antimicrobial constituent.
2) Tensile strength and Young's modulus of lyocell fiber samples were tested on an Instron tensile testing machine as per the ASTM C1557-03 procedure at ambient temperature.
3) Emulsion stability: The stability of micro-emulsions as prepared in the above examples, was evaluated by keeping the same under observation in measuring cylinders for 3 days. During this period no phase separation was observed.
27

4) Feel of the fabric: The lyocell fabrics as prepared in the above examples and
standard fabric (lyocell fabric without antimicrobial constituents), were
randomly given to twenty subjects and they were asked to evaluate the
texture and feel of the fiber. The test fiber material was interchanged several
times amongst the human subjects. Collective results as submitted by the
human subjects confirmed that nobody could distinguish between the
antimicrobial lyocell fabrics prepared in accordance with the Examples
provided above and the standard fabric.
5) Dyeability: The antimicrobial lyocell fabrics as prepared in the above
examples and the standard fabric as described above were dyed uniformly
with reactive dyes. No noticeable difference as to the Dyeability of the two
respective lyocell fabrics, with and without antimicrobial constituent was
reported.
6) Visual appearance of the antimicrobial lyocell fiber was evaluated by
methods as prescribed in AATCC 124. As far as parameters like % Loss in
Dry Tenacity and % loss in dry elongation are concerned, these remained the
same( fiber and the standard fiber
7) Testing of antimicrobial constituent enriched fiber/fabrics
The antimicrobial constituent enriched lyocell fabrics as prepared in the above examples were tested for antimicrobial activity by various test procedures which included antimicrobial assays used to determine or confirm the effectiveness of treatments applied to medical devices, medical and commercial textiles, and other
products.
28

Minimum sample requirements 9 square inches or 6 inches long, per test AATCC 100 (Part I) is a qualitative test for antibacterial activity. Test lyocell fiber/fabric specimens were placed into contact with a nutrient agar which had been streaked with either Staphylococcus aureus or Escherichia coli bacterial culture. Samples are inoculated with Staphylococcus and evaluated for percent reduction of the bacteria over selected contact periods of 1 - 24 hours. Turnaround Time is usually 5 days. The specimens were then incubated at a temperature 37 °C for a period of time of 24 hours. After the 24 hour incubation period, the samples were visually checked for the growth of bacteria.
The AATCC 147/100, Part III protocol provides a qualitative test for antifungal
activity. Lyocell fiber/ fabric specimens were subjected to the growth of a
common fungus, Aspergillus niger, on Sabouraud Dextrose agar. Prewet
specimens were inoculated and incubated at 28 C for seven days. Specimens
were then assessed for growth of the fungus.
ASTM E2180-01 test method was used for testing inhibitory mold activity of the lyocell product (fiber /fabric) prepared in accordance with this invention.
All the specimen lyocell fiber and fabrics as obtained in examples 1 to 10 were
tested for antimicrobial activity by following the above mentioned test protocols.
The results of the above mentioned test protocols are provided in the following
tables:
'Percentage kill of bacteria' is as per AATCC 100 test method and 'test results'
are as per AATCC 147, showing if any growth of said bacteria was observed.
29

Table 1
Antimicrobial Activity of Lyocell Fibers
Sr. No- % kill of bacteria Test results
Example 1
Microbe tested : S. aureus 99.8 Not observed
Example 2
Microbe tested : S. aureus 100 Not observed
Example 3
Microbe tested : E. coli 100 Not observed
Example 4
Microbe tested : S. aureus 100 Not observed
Example 5
Microbe tested : S Aureus 100 Not observed
Example 7
Microbe tested : S. aureus 100 Not observed
Example 8
Microbe tested : S Aureus 100 Not observed
Example 9
Microbe tested : S. aureus 100 Not observed
Example 10
Microbe tested : S. aureus 100 Not observed
Table 2
Antimicrobial Activity of Lyocell fabric
Sr. No. % kill of bacteria Test results
Example 1
Microbe tested : S. aureus 99.8 Not observed
Example 2
Microbe tested : S. aureus 100 Not observed
Example 3
Microbe tested : S Aureus . 100 Not observed
Example 4
Microbe tested : E Coli 100 Not observed
Example 5
Microbe tested : E Coli 100 Not observed
Example 7
Microbe tested : E Coli 100 Not observed
Example 8
Microbe tested : E. coli 100 Not observed
Example 9
Microbe tested : S. aureus 100 Not observed
Example 10
Microbe tested : S. aureus 100 Not observed
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The lyocell fiber and fabric lyocell fabric specimens obtained in examples 4, 5 and 6 contained antifungal agent and their antifungal activity was determined by AATCC 147 part III and in case of the all the specimens no fungal growth was observed meaning that all the specimen exhibited excellent antifungal activity. Furthermore, inhibitory mould activity of these specimen was tested by ASTM E 2180-01 test protocol and good inhibitory activity against Aspergillus niger was recorded.
The test fabrics made from these fibers thus exhibited significant antimicrobial activity both towards bacteria and fungi.
While considerable emphasis has been placed herein on the specific steps of the preferred embodiment, it will be appreciated that many alterations can be made and that many modifications can be made in the preferred embodiment without departing from the principles of the invention. These and other changes in the preferred embodiment as well as other embodiments of the invention will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the invention and not as a limitation.
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Claim:
1. An antimicrobial lyocell formulation meant for manufacture of lyocell
products comprising :
• at least one non-aqueous solvent in the range of about 0.01 to 20% of the mass of the formulation,
• at least one water insoluble antimicrobial constituent soluble in said solvent, in the range of about 0.001 to 10% of the mass of the formulation,
• at least one water soluble non-cationic surfactant having HLB value in the range of 9 to 40, in the range of 0.001 to 10% of the mass of the formulation,
• cellulosic pulp in the range of about 3% to 35% of the mass of the formulation,
• N-METHYL-MORPHOLINE-N-OXIDE (NNMO) in the range of about 60 to 80% of the mass of the formulation; and
• water in the range of about 0% to 20 % with respect to the mass of the formulation.
2. A formulation as claimed in claim 1, wherein the antimicrobial
constituent is at least one selected from a group consisting of 2-Methyl-4-
isothiazolin-3-one, Phenoxyethanol Benzoic acid, 4-Hydroxy-methyl
ester, Hydroxy-benzoic acid and propyl ester), o- (2-naphthyl) methyl (3-
methylphenyl) thiocarbamate, 5-chloro~2-(2,4-dichlorophenoxy)phenol,
4,5-dichloro-n-octyl-4-isothiazoline-3-one[DCOIT], 2-n-octyl-4-
isothiazolin-3-one, 1-phenoxy propan-2-ol, pentachlorophenol, 5-chloro-
32

2-dichlorophenoxy phenol, clotrimazole, p-chloro-m-xylenol and chloroquinaldol.
3. A formulation as claimed in claim 1, wherein the solvent is at least one solvent selected from a group of solvents consisting of C10-C44 alkanes (paraffmic hydrocarbons), polyethylene, polypropylene, polypropylene glycol, polytetramethylene glycol, polypropylene malonate, polyneopentyl glycol sebacate, polypentane glutarate, polyvinyl myristate, polyvinyl stearate, polyvinyl laurate, polyhexadecyl methacrylate, polyoctadecyl methacrylate, polyethylene oxides, polyethylene glycols, Arachidyl alcohol, behenyl alcohol, Selachyl alcohol, chimimyl alcohol, polyesters, di-iso decyl phthalate, benzyl alcohol, C4 -C30 aliphatic alcohols ,C4 -C30 saturated hydrocarbons, C4 -C30 monounsaturated hydrocarbons, natural oils and mineral oil paraffins.
4. A formulation as claimed in claim 1, wherein the surfactant is at least one surfactant selected from a group of non-ionic or anionic surfactants consisting of alkyl phenol ethoxylated surfactants, alkyl alcohol ethoxylated surfactants, Polyethylene-block-Poly propylene glycol-block-polyethylene glycol and Ethylenediamine tetrakis(propylene oxide-block-ethylene oxide) tetrol.
5. A formulation as claimed in claim 8, wherein the alkyl phenoxy like ethoxylated non-ionic or anionic surfactant with HLB > 9 is at least one selected from a group consisting of Polyoxyethylene(8) isooctylphenyl ether, Nonylphenol polyethylene glycol ether, Polyoxyethylene(9)
33

nonylphenyl ether, Polyoxyethylene(lO) isooctylphenyl ether, Polyoxyethylene(12) nonylphenyl ether, Polyoxyethylene(12) isooctylphenyl ether, Polyoxyethylene(40) nonylphenyl ether, Polyoxyethylene(40) isooctylphenyl ether, Polyoxyethylene( 100) nonylphenyl ether, Polyoxyethylene(150) dinonylphenyl ether, Surfonic N-95(Poly (oxy-1, 2-ethanediyl), alpha- (nonyl phenyl)-omega-hydroxyl-glycol ether) ( nonylphenol 9.5-mole ethoxylate) , Surfonic N-120(nonylphenol 12-mole ethoxylate), Surfonic N-150 (nonylphenol 15-mole ethoxylate), Surfonic N-200 (nonylphenol 20-mole ethoxylate) , Surfonic N-300( nonylphenol 30-mole ethoxylate) , Surfonic N-400 nonylphenol 40-mole ethoxylate, Igepal CO-630 (nonylphenoxy poly(ethyleneoxy) ethanol,branched), Surfonic DNP-40, fatty alcohol ether sulfates, alkyl carboxylates, alkyl benzene sulfonates, sulfosuccinates, polyethanoxy ether sulphate esters and polyethanoxy ether phosphate esters.
6. A formulation as claimed in claim 8, wherein the alkyl alcohol surfactant with HLB > 9 is at least one selected from a group consisting of Polyoxyethylene(lO) stearyl ether, Polyoxyethylene (10) oleyl ether, Polyoxyethylene(lO) cetyl ether, Polyoxyethylene(20) stearyl ether , Polyoxyethylene(20) oleyl ether, Polyoxyethylene(23) lauryl ether, Polyoxyethylene(lOO) stearyl ether, Polyoxyethylene(20) cetyl ether, Ceto Stearyl alcohol ethoxylates and modified alcohol ethoxylates, Surfonic LF-7 (Alkyl polyoxyalkylene ether) and Surfonic LF-17 (ethoxylated and propoxylated linear primary 12-14 carbon number alcohol).
34

7. A formulation as claimed in claim 1, wherein the preferred HLB value of the surfactant is between 16 and 40.
8. A formulation as claimed in claim 1, wherein the average mean size of the micro-reservoir is in the range of 5 nm to 2000 nm.
9. An antimicrobial lyocell fiber manufactured from a formulation as
claimed in claim 1.
10.An antimicrobial lyocell yarn manufactured from a formulation as claimed in claim 1.
11.An antimicrobial lyocell fabric manufactured from a formulation as claimed in claim 1.
12. A process of preparation of an antimicrobial lyocell formulation meant for manufacture of lyocell products comprising the following steps :
• admixing a water-insoluble antimicrobial constituent with a non¬aqueous solvent followed by heating the resulting mixture to obtain a liquid non-aqueous phase ;
• dissolving and stirring a surfactant, optionally with a co-surfactant, in water to obtain an aqueous phase;
• heating the aqueous-phase;
• mixing the aqueous phase with the non-aqueous phase in the liquid state to form a admixture and homogenizing to obtain a micro-emulsion;
35

• mixing together cellulosic pulp and N-METHYL-MORPHOLINE-N-OXIDE (NNMO) solution to form a slurry;
• dispersing the micro-emulsion in the slurry to obtain a preform mass wherein the antimicrobial constituent is embedded in evenly dispersed micro-reservoirs;
• vaccumising the preform mass to remove water under 7 to 10 mm of Hg and temperature of over 90 C to obtain the formulation.
Dated this 3rd day of July, 2008.
Mohan Dewan
of R. K. Dewan and Co.
Applicants' Patent Attorney
36

Documents:

1391-MUM-2008-ANNEXURE TO FORM 3(26-9-2012).pdf

1391-MUM-2008-CLAIMS(AMENDED)-(26-9-2012).pdf

1391-MUM-2008-CLAIMS(AMENDED)-(27-3-2014).pdf

1391-mum-2008-claims.doc

1391-mum-2008-claims.pdf

1391-MUM-2008-CORRESPONDENCE(13-04-2010).pdf

1391-mum-2008-correspondence(18-7-2008).pdf

1391-MUM-2008-CORRESPONDENCE(24-7-2009).pdf

1391-mum-2008-correspondence.pdf

1391-mum-2008-description(complete).doc

1391-mum-2008-description(complete).pdf

1391-mum-2008-drawing.pdf

1391-MUM-2008-EP DOCUMENT(26-9-2012).pdf

1391-mum-2008-form 1(18-7-2008).pdf

1391-MUM-2008-FORM 1(27-3-2014).pdf

1391-mum-2008-form 1.pdf

1391-MUM-2008-FORM 18(24-7-2009).pdf

1391-mum-2008-form 2(title page)-(3-7-2008).pdf

1391-mum-2008-form 2(title page).pdf

1391-mum-2008-form 2.doc

1391-mum-2008-form 2.pdf

1391-MUM-2008-FORM 26(26-9-2012).pdf

1391-MUM-2008-FORM 26(27-3-2014).pdf

1391-MUM-2008-FORM 3(13-04-2010).pdf

1391-mum-2008-form 3(3-7-2008).pdf

1391-mum-2008-form 3.pdf

1391-MUM-2008-MARKED COPY(26-9-2012).pdf

1391-MUM-2008-MARKED COPY(27-3-2014).pdf

1391-MUM-2008-PETITION UNDER RULE 137(27-3-2014).pdf

1391-MUM-2008-REPLY TO EXAMINATION REPORT(26-9-2012).pdf

1391-MUM-2008-REPLY TO HEARING(27-3-2014).pdf

1391-MUM-2008-SPECIFICATION(AMENDED)-(26-9-2012).pdf

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Patent Number

260003

Indian Patent Application Number

1391/MUM/2008

PG Journal Number

14/2014

Publication Date

04-Apr-2014

Grant Date

31-Mar-2014

Date of Filing

03-Jul-2008

Name of Patentee

ADITYA BIRLA SCIENCE & TECHNOLOGY CO. LTD

Applicant Address

ADITYA BIRLA CENTRE, 2ND FLOOR, C WING, S.K. AHIRE MARG, MUMBAI,

Inventors:

#	Inventor's Name	Inventor's Address
1	LODHA PREETI	ADITYA BIRLA CENTRE, 2ND FLOOR, C WING, S.K. AHIRE MARG, MUMBAI-400 025,
2	KAPOOR BIR	ADITYA BIRLA CENTRE, 2ND FLOOR, C WING, S.K. AHIRE MARG, MUMBAI-400 025,
3	MAHAJAN TUSHAR	ADITYA BIRLA CENTRE, 2ND FLOOR, C WING, S.K. AHIRE MARG, MUMBAI-400 025,

PCT International Classification Number

C08K5/01

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA