FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
&
THE PATENTS RULES, 2003
COMPLETE SPECIFICATION
[See section 10 and rule 13]
1. TITLE OF THE INVENTION:
IMPROVED POLYMER PRODUCT WITH SUSTAINED RELEASE
INSECTICIDAL COMPOSITIONS
2. APPLICANT:
NAME ADITYA BIRLA SCIENCE AND TECHNOLOGY COMPANY
LIMITED
NATIONALITY AN INDIAN COMPANY
ADDRESS ADITYA BIRLA CENTRE, S.K. AHIREMARG,
WORLI, MUMBAI- 400030
The following specification particularly describes the invention and the manner in which it is to be performed.

IMPROVED POLYMER PRODUCT WITH SUSTAINED RELEASE INSECTICIDAL COMPOSITIONS
FIELD OF INVENTION
[0001] The present invention is directed to a polymer product. More particularly the
present invention is directed to an improved polymer product with sustained release
insecticidal compositions. A process for preparing the improved polymer product is also
disclosed.
BACKGROUND OF INVENTION
[0002] Polymer products having active compounds are desired for various applications. Various methods have been employed in the art to include such active compounds in a polymer. For example, the polymer product may be surface-treated with the active compounds and a surface finish may be applied to the polymer product to enable binding of the active compounds. Other techniques of applying active compounds include microencapsulating the active compounds and including them in the polymer product during preparation of the polymer product. The challenge however has been in retention of these active compounds. In surface treated polymer products the active compounds are generally lost upon subsequent treatments such as washing, bleaching, etc.. In the microencapsulation technique though the active compounds are retained in the fibre for a relatively longer period of time. However once the active compounds are discharged out of the encapsulant it may not be possible to replenish the microcapsules with the active compounds. [0003] Therefore, it is desirable to have a polymer product including active compounds that may be retained in the polymer product for a longer period of time than the products known in the art. A process for making such a polymer product is also desirable. It is also

desirable that the polymer product may be regenerated with the active compounds once the effectiveness of the active compounds reduces below the necessary values. [0004] Thus, there is a need for animproved and cost-effective polymer product that can retain the insecticide over an increased number of washes. There is also a need for an improved formulation and a process that may be used in making the polymer product.
SUMMARY OF INVENTION
[0005] In one embodiment, is provided a polymer product. The polymer product includes an active arrester and an active compound. The active compound is selected from the group consisting of a volatile insecticide and an antimicrobial. The wash durability of the polymer product is in a range of from about 30 percent to about 95 percent over 10 washes. [0006] In another embodiment, is provided a polymer product. The polymer product includes an active arrester and an active compound. The active compound is selected from the group consisting of a volatile insecticide and an antimicrobial. The wash durability of the polymer product is in a range of from about 20 percent to about 85 percent over 20 washes. [0007] In yet another embodiment, is provided a polymer product. The polymer product includes an active arrester and an active compound. The active compound is selected from the group consisting of a volatile insecticide and an antimicrobial. The wash durability of the polymer product is in a range of from about 10 percent to about 75 percent over 30 washes. [0008] In yet another embodiment, a formulation is provided. The formulation includes an active compound, an active arrestor, a swelling agent, and a surface active agent. The active compound includes a volatile insecticide or an antimicrobial. The formulation is a sustained release insecticidal composition used in the preparation of a polymer product disclosed herein.

[0009] In still yet another embodiment a process for making the polymer product is
provided. The process includes a first step of preparing a formulation. The formulation
comprises an active compound, an active arrestor, a swelling agent, and a surface active
agent. The active compound comprises a volatile insecticide or an antimicrobial. In a second
step a reservoir polymer is contacted with the formulation at a temperature in a range of from
about 40 degrees Celsius to about 90 degrees Celsius. The resultant polymer product formed
includes the active arrester and the active compound.
[0010] In still yet another embodiment, is provided a process for regenerating a polymer
product. The process comprises a first step of contacting a reservoir polymer with a
formulation at a temperature in a range of from about 40 degrees Celsius to about 90 degrees
Celsius to form a polymer product. The polymer product comprises an active arrester and an
active compound. The formulation comprises an active compound, an active arrestor, a
swelling agent, and a surface active agent. The active compound comprises a volatile
insecticide or an antimicrobial. The polymer product may then be washed multiple times to
provide a polymer product substantially free of active compound. In a further step, the
polymer product substantially free of active compound is re-contacted with the formulation to
provide a regenerated polymer product comprising the active arrester and the active
compound.
[0011] By employing the above disclosed technique an improved, efficient, and cost
effective polymer productwith an increased retention of the active compound may be made
possible.
DETAILED DESCRIPTION
[0012] Embodiments of the invention as disclosed herein provide a value added and
improved polymer product containing at least one attribute imparting agent. The polymer
product disclosed herein includes a sustained release insecticidal formulation that may result

in prolonged retention of the attributing imparting agent, i.e., the insecticide in the polymer product. The resultant polymer product has an increased wash durability of the insecticide that is introduced in a polymer to form the polymer product.
[0013] Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as "about" is not limited to the precise value specified. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. The singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise.
[0014] As used herein, the phrase "sustained release" refers to the release of active volatile compound such that an effective amount of active compound is released over an extended duration and over a number of washes of the improved polymer product. [0015] Accordingly in one embodiment is provided, a polymer product. The polymer product includes an active arrester, and an active compound comprising a volatile insecticide, an antimicrobial, or a combination thereof. In one embodiment, the polymer product may have a wash durability in a range of from about 30 percent to about 95 percent over 10 washes. In one embodiment, the polymer product may have a wash durability in a range of from about 20 percent to about 85 percent over 20 washes. In one embodiment, the polymer product may have a wash durability in a range of from about 10 percent to about 75 percent over 30 washes. As used herein the phrase "active arrester" refers to a chemical compound that may be capable of increasing the retention power of the active compound in the polymer product. Use of the active arrestor renders the formulation to function as a sustained release composition, thus increasing the retention power of the active compound in the polymer product. Suitable examples of the active arrester include but are not limited to piperonyl

butoxide, diethyl phthalate, and propyl gallate. In one embodiment, the active arrester is present in an amount in a range of from about 0.02 weight percent to about 15 weight percent based on the total weight of the polymer product. In another embodiment, the active arrester is present in an amount in a range of from about 0.1 weight percent to about 12 weight percent based on the total weight of the polymer product. In yet another embodiment, the active arrester is present in an amount in a range of from about 0.5 weight percent to about 10 weight percent based on the total weight of the polymer product.
[0016] The active compound used in the formulation functions as an insect repellent. In one embodiment, the active compound is a volatile insecticide. The volatile insecticide may include a volatile pyrethroid. Suitable examples of pyrethroid include but are not limited to transfluthrin, allethrin, bifenthrin, cyfluthrin, cypermethrin, cyphenothrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, imiprothrin, lambda-cyhalothrin, metofluthrin, permethrin, prallethrin, resmethrin, silafluofen, sumithrin, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, N,N-Diethyl-meta-toluamide (DEET), neem oil, citronella oil, geraniol oil, lemon grass oil, pine tree oil, lemon eucalyptus oil, lemon grass oil, catnip oil, and jatamansi Valeriana.
[0017] In one embodiment, the active compound may include an antimicrobial. Suitable examples of antimicrobials include but are not limited to 2-Methyl-4-isothiazolin-3-one, water, Phenoxyethanol benzoic acid, 4-Hydroxy-methyl ester, Hydroxy-benzoic acid 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.
[0018] In one embodiment, the active compound is present in an amount in a range of from about 0.1 weight percent to about 15 weight percent based on the total weight of the

polymer product. In another embodiment, the active compound is present in an amount in a range of from about 0.5 weight percent to about 12 weight percent based on the total weight of the polymer product. In yet another embodiment, the active compound is present in an amount in a range of from about 1.0 weight percent to about 10 weight percent based on the total weight of the polymer product.
[0019] In one embodiment, is provided a formulation. The formulation includes an insecticidal formulation that may be employed to form the polymer product described herein. The formulation includes an active compound, an active arrester, a surface active agent, and a swelling agent.
[0020] In one embodiment, the active compound is present in an amount in a range of from about 0.1 weight percent to about 15 weight percent based on the total weight of the formulation. In another embodiment, the active compound is present in an amount in a range of from about 0.5 weight percent to about 12 weight percent based on the total weight of the formulation. In yet another embodiment, the active compound is present in an amount in a range of from about 1.0 weight percent to about 10 weight percent based on the total weight of the formulation. In one embodiment, the active arrester is present in an amount in a range of from about 0.02 weight percent to about 15 weight percent based on the total weight of the formulation. In another embodiment, the active arrester is present in an amount in a range of from about 0.1 weight percent to about 12 weight percent based on the total weight of the formulation. In yet another embodiment, the active arrester is present in an amount in a range of from about 0.5 weight percent to about 10 weight percent based on the total weight of the formulation.
[0021] A surface active agent is a substance which lowers the surface tension of the medium in which it is dissolved, and/or the interfacial tension with other phases, and, accordingly, is positively adsorbed at the liquid/vapour and/or at other interfaces. The term

surface active agent is also applied correctly to sparingly soluble substances, which lower the surface tension of a liquid by spreading spontaneously over its surface. [0022] In various embodiments, the surface active agents include but are not limited to anionic surface active agent, cationic surface active agent, zwitterionic surface active agent with sulphate, sulphonate, carbonate, and its alkaline and alkaline earth metal salts as head group and hydrocarbon(hydrogen) tail having about 8 to 18 carbon atoms. Suitable examples of the surface active agents include but are not limited to at least one non-ionic or anionic surfactant active agent selected from a group consisting of alkyl phenoxy ethoxylated non-ionic surface active agent and ethoxylated alkyl alcohol surface active agent, polyethylene-block-poly propylene glycol-block-polyethylene glycol and ethylenediamine tetrakis(propylene oxide-block-ethylene oxide) tetrol.
[0023] In one embodiment, the surface active agent is present in an amount in a range of from about 0.02 weight percent to about 15 weight percent based on the total weight of the formulation. In another embodiment, the surface active agent is present in an amount in a range of from about 0.1 weight percent to about 12 weight percent based on the total weight of the formulation. In yet another embodiment, the surface active agent is present in an amount in a range of from about 0.5 weight percent to about 10 weight percent based on the total weight of the formulation.
[0024] Suitable examples of swelling agents include but are not limited to water. In various embodiments, the swelling agent is used in an amount based on the amount of the active arrestor, the volatile insecticide, and the surface active agent present in the formulation. For example, if the weight of the formulation, is 100 grams, and the amount of the active arrestor is 0.2 grams, the surface active agent is 10 grams, the amount of volatile insecticide is 2 grams then the amount of swelling agent is ^7.8 grams.

[0025] In one embodiment, the formulation may be made by a process known to one skilled in the art. The process employed should be such that the resultant formulation should include all the ingredients in the appropriate proportion, and the process parameters like time, temperature, stirring speed, etc., used may ensure that all the ingredients are combined to form the desired formulation.
[0026] In one embodiment, is provided a process for making a polymer product. The process includes a first step of preparing a formulation, wherein the formulation comprises, an active compound, an active arrestor, a surface active agent, and a swelling agent. In a second step, the formulation is contacted with a reservoir polymer at a specified temperature to form the polymer product described herein.
[0027] As mentioned herein the term "contacting" may refer to treating the reservoir polymer with the formulation by soaking the reservoir polymer in the formulation. In one embodiment, the reservoir polymer may be soaked in the formulation for a sufficient period to achieve about 90 percent intake of the formulation from a soaking bath into the reservoir polymer. In one embodiment, the reservoir polymer may be contacted with the formulation for a period of about I hour to about 10 hours to ensure sufficient intake (of about 90 percent) of the formulation.
[0028] In one embodiment, the temperature at which the contacting is carried out is in a range of from about 40 degrees Celsius to about 90 degrees Celsius. In another embodiment, the temperature is in a range of from about 45 degrees Celsius to about 85 degrees Celsius. In yet another embodiment, the temperature is in a range of from about 50 degrees Celsius to about 80 degrees Celsius.
[0029] The reservoir polymer may be prepared by employing the process described in Patent Application Number WO/2010/041270, titled "A PROCESS FOR CHARGING A POLYMERIC PRODUCT WITH ATTRIBUTE IMPARTING AGENT(S)", having a

common assignee as the disclosure made herein, which is incorporated herein in its entirety by reference.
[0030] In one embodiment, when the wash durability of the polymer product decreases over a number of washes, the reservoir polymer that remains behind may be again treated with the formulation disclosed herein and the polymer product may be regenerated.
EXAMPLES
Table I

Sr. No. Raw Material Brand Name Source Chemical Name
I Active compound Transfluthrin Shogun Organics (1 R,3S}-3-{2,2,-dichlorovinyl)-2,2-dimethyl-
1-cyclopropanecarboxylic acid 92,3,5,6-
tetrafluorophenvlo)methYl ester
2 Active arrester Piperonyl butoxidc Venus lmpex 5-[2-(2-butoxyetnoxy)ethoxynictyl]-6-propyl-l,3-benzodioxole
3 Surface active agent (ionic) Auxiwet Auxichem Sodium dodecyl benzene sulfonate
4 Swelling agent water Distilled water —
5 Non-polar organic reservoir Paraffin wax Any standard supplier Merck Standard Wax with a melting point of about 60±2 degrees Centigrade
6 Non-ionic surface active agent Hydol 20 Unitop Chemicals Polyoxyethylene AlkyI Ether
Example 1: Preparation of a reservoir polymer:
Step A: Preparation of a reservoir formulation:
[0031] An emulsion was prepared by adding paraffin wax, a non-polar organic reservoir
10 grams to a non-ionic surface active agent, such as Hydol 20, 4 grams (with a hydrophile-
lipophile balance (HLB) of 15) and water 20 grams, at a temperature of about 70 degrees
Celsius. The emulsion was prepared using a high pressure homogenizer at 600 bars for a
double pass. The resultant emulsion was found to be stable,
[0032] 25 grams of the emulsion was added to 2200 grams of 9 percent cellulose in
xanthate form polymer dope under stirring at about 1500 rotations per minute over a period
of about 15 minutes. This corresponds to about 2.2 weight percent to about 6 weight percent

of paraffin wax based on the total weight of 9 percent cellulose polymer dope (viscose). The amount of ingredients added to form the formulation are provided in Table 2.
TABLE 2

Example No. Amount of Emulsion Percentage of paraffin present in emulsion Polymer Dope
1 25 5 9 percent cellulose in xanthate form (viscose)
Step B: Preparation of a reservoir polymer:
[0033] The formulation prepared in Step A of Example 1 was then spun through a spinneret 80 micron having 90 holes and a spinning rate of about 3 to about 10 milliliters pre minute into a spin bath containing sulphuric acid 147 grams per litre, sodium sulphate (Na2SO4, 365 grams per liter), and alum /zinc sulphate (9 grams per litre); and at a temperature of about 49 degrees Celsius. The first godet speed was maintained at about 25 to 28 meters per minute and the second godet speed was maintained at about 42 to 47 meters per minute. The regenerated polymer collected from the second godet was washed as discussed herein below. In a first step, the polymer was washed in 18 grams per litre sulphuric acid solution at 90 degrees Celsius for 15 minutes followed by a wash using running tap water. In a second step the polymer was washed in 0.2 grams per litre sodium hydroxide solution at 85 degrees Celsius for 15 minutes followed by a wash with running tap water. In a third step the fibre was washed in 4.0 grams per litre sodium hypochlorite solution at 45 degrees Celsius for 15 minutes and then again washed with running tap water. The washed polymer was then finally dried in an oven at 90 degrees Celsius for 2 hours to yield a reservoir polymer.
Example 2: Preparation of improved polymer product containing a volatile insecticide. [0034] A formulation was made by mixing 0.05 weight percent of an active compound, 0.05 weight percent of a surface active agent, 0.05 weight percent of an active arrester, and

99.85 weight percent water (all weight percent was based on the total weight of the formulation) at about 70 degrees Celsius. 10 grams of reservoir polymer, prepared as described in Example 1, was contacted with the formulation at about 70 degrees Celsius for about 2 hours in a DG wash. The resultant improved polymer product was analysed to determine the retention of the active compound and wash durability of the improved polymer product. Retention of the active compound was measured by extraction of the active compound in soxhlet apparatus for 3 hours and analysed using high pressure liquid chromatography (HPLC). The retention of the active compound was studied by anlaysing the wash durability for 10, 20, and 30 washes. The washes were carried out using 2 grams per litre detergent in Digiwash by Paramount Instruments, New Delhi (Model: digiWASH I NXTM) at a temperature of about 70 degrees Celsius for about 30 minutes. The results of wash durability of improved polymer prepared in Example 2 is provided in Table 3.
Example 3: Preparation of improved polymer product containing a volatile insecticide, using blend of cellulose with the reservoir polymer prepared in Example 1.
[0035] A formulation was made by mixing 0.05 weight percent of an active compound, 0.05 weight percent of a surface active agent, 0.05 weight percent of an active arrester, and 99.85 weight percent water (all weight percent was based on the total weight of the formulation) at about 70 degrees Celsius. 10 grams of 60:40 cotton/viscose reservoir polymer(a blend of 60 weight percent cotton is prepared with 40 weight percent of reservoir polymer prepared in Example 1 using methods known in the art), was contacted with the formulation at about 70 degrees Celsius for about 2 hours in a DG wash. The resultant improved polymer product was analysed to determine the retention of the active compound and wash durability of the improved polymer product. Retention of the active compound was measured by extraction of the active compound in soxhlet apparatus for 3 hours and analysed

using high pressure liquid chromatography (HPLC). The retention of the active compound was studied by analysing the wash durability for 10, 20, and 30 washes. The washes were carried out using 2 grams per litre detergent in Digiwash by Paramount instruments, New Delhi (Model: digiWASH 1 NXTM) at a temperature of about 70 degrees Celsius for about 30 minutes. The results of wash durability of improved polymer prepared in Example 3 is provided in Table 3.
Example 4: Preparation of improved polymer product containing a volatile insecticide, using blend of polyester with the reservoir polymer prepared in Example 1.
[0036] A formulation was made by mixing 0.05 weight percent of an active compound, 0.05 weight percent of a surface active agent, 0.05 weight percent of an active arrester, and 99.85 weight percent water (all weight percent was based on the total weight of the formulation) at about 70 degrees Celsius. 10 grams of 65:35 polyester/viscose reservoir polymer (a blend of 65 weight percent polyester is prepared with 35 weight percent of reservoir polymer prepared in Example 1 using methods known in the art), was contacted with the formulation at about 70 degrees Celsius for about 2 hours in a DG wash. The resultant improved polymer product was analysed to determine the retention of the active compound and wash durability of the improved polymer product. Retention of the active compound was measured by extraction of the active compound in soxhlet apparatus for 3 hours and analysed using high pressure liquid chromatography (HPLC). The retention of the active compound was studied by analysing the wash durability for 10, 20, and 30 washes. The washes were carried out using 2 grams per litre detergent in Digiwash by Paramount Instruments, New Delhi (Model: digiWASH I NXTM) at a temperature of about 70 degrees Celsius for about 30 minutes. The results of wash durability of improved polymer prepared in Example 4 is provided in Table 3.

Table 3:

Sr. No. EXAMPLE Wash durability in percentage after number of Washes

0 10 20 30
1 2 86 86 67.36 39.53
2 3 56.6 65.3 55.47 36
3 4 60.6 52.14 34.98 19.14
[0037] One skilled in the art will appreciate that the washes were carried out using a detergent having a higher pH in the range of about 10 to about 13 as used to test the wash durability of the polymer products prepared in Examples 2 to 4. The temperature used for testing is also higher at about 70 degrees Celsius. The wash durability may be higher if the detergents used have a lower pH, are less harsh, and if lower temperatures are employed. Once the amount of the active volatile compound in the reservoir polymer is depleted due to the washes to a level below its effectiveness, the reservoir polymer may be re-contacted with the formulation comprising the active volatile compound to provide a regenerated form of the improved polymer product containing a volatile insecticide.
[0038] The foregoing embodiments meet the overall objectives of this disclosure as summarized above. However, it will be clearly understood by those skilled in the art that the foregoing description has been made in terms only of the most preferred specific embodiments. Therefore, many other changes and modifications clearly and easily can be made that are also useful improvements and definitely outside the existing art without departing from the scope of the present disclosure, indeed which remain within its very broad overall scope, and which disclosure is to be defined over the existing art by the appended claims.

We Claim:
1. A polymer product comprising:
an active arrester;
an active compound comprising a volatile insecticide or an antimicrobial; wherein the wash durability of the polymer product is in a range of from about 30 percent to about 95 percent over 10 washes.
2. The polymer product of Claim 1, wherein the volatile insecticide comprises a volatile pyrethroid insecticide.
3. The polymer product of Claim 1, wherein the active arrestor is selected from the group consisting of piperonyl butoxide, diethyl phthalate, and propyl gallate.
4. A polymer product comprising:
an active arrester; and
an active compound comprising a volatile insecticide or an antimicrobial; wherein the wash durability of the polymer product is in a range of from about 20 percent to about 85 percent over 20 washes.
5. A polymer product comprising:
an active arrester;and
an active compound comprising a volatile insecticide or an antimicrobial; wherein the wash durability of the polymer product is in a range of from about 10 percent to about 75 percent over 30 washes.
6. A formulation comprising:

an active compound comprising a volatile insecticide or an antimicrobial; an active arrestor; a swelling agent; and a surface active agent;
wherein said formulation is a sustained release insecticidal composition used in the preparation of a polymer product.
7. A process for making a polymer product comprising:
preparing a formulation, wherein the formulation comprises, an active compound, an active arrestor, a swelling agent, and a surface active agent, wherein the active compound comprises a volatile insecticide or an antimicrobial;
contactinga reservoir polymer with the formulation at a temperature in a range of from about 40 degrees Celsius to about 90 degrees Celsius; and
forming a polymer product comprising an active arresterand an active compound.
8. The polymer product of Claim 7, wherein the volatile insecticide comprises a volatile pyrethroid insecticide.
9. The polymer product of Claim 7, wherein the active arrestor is selected from the group consisting of piperonyl butoxide, diethyl phthalate, and propyl gallate.
10. A process of regenerating a polymer product comprising:
contacting a reservoir polymer with a formulation at a temperature in a range of from about 40 degrees Celsius to about 90 degrees Celsius to form a polymer product comprising an active arrester and an active compound; wherein the formulation comprises an active compound, an active arrestor, a swelling agent, and a surface active agent, wherein the active compound comprises a volatile insecticide or an antimicrobial;

washing the polymer product multiple number of times to provide a polymer product substantially free of active compound; and
re-contacting the polymer product free of active compound with the formulation at a temperature in a range of from about 40 degrees Celsius to about 90 degrees Celsius to form a regenerated polymer product comprising the active arrester and the active compound.