(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2017/177211 Al 12 October 2017 (12.10.2017) P O P C T
(51) International Patent Classification: (71) Applicant: BATTELLE MEMORIAL INSTITUTE A 25/28 (2006.01) A OIN 53/00 (2006.01) [US/US]; 505 King Avenue, Columbus, Ohio 43201 -2696 A0 25/04 (2006.01) A01P 7/04 (2006.01) (US). (21) International Application Number: (72) Inventors: LALGUDI, Ramanathan S.; Battelle Memori PCT/US20 17/026727 al Institutue, 505 King Avenue, Columbus, Ohio 43201- 2696 (US). SHQAU, Krenar; Battelle Memorial Institute, (22) International Filing Date: 505 King Avenue, Columbus, Ohio 43201-2696 (US). 8 April 2017 (08.04.2017) (74) Agent: PRIOR, Patricia L.; GREER, BURNS & CRAIN, (25) Filing Language: English LTD., 300 South Wacker Drive, Suit 2500, Chicago, (26) Publication Language: English Illinois 60606 (US). (30) Priority Data: (81) Designated States (unless otherwise indicated, for every 62/3 19,907 8 April 2016 (08.04.2016) kind of national protection available): AE, AG, AL, AM, 62/335,987 13 May 2016 (13.05.2016) AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DJ, DK, DM,
[Continued on nextpage]
(54) Title: ENCAPSULATION COMPOSITIONS (57) Abstract: An encapsulation composition is described. The composition comprises a plurality of capsules, each capsule com prising an amphiphilic material encapsulating a pyrethroid. The encapsulated pyrethroid has a release rate less than the release rate of the unencapsulated pyrethroid. Coated fabric products are also described.
o o w o 2017/177211 A i 1 I II «III ill III I 1 1 I I III I I I I l I I I I I
DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, GT, HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KH, TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, KN, KP, KR, KW, KZ, LA, LC, LK, LR, LS, LU, LY, TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, NG, NI, NO, NZ, OM, PA, PE, PG, PH, PL, PT, QA, RO, LU, LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, RS, RU, RW, SA, SC, SD, SE, SG, SK, SL, SM, ST, SV, SI, SK, SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, GN, GQ, GW, KM, ML, MR, NE, SN, TD, TG). VN, ZA, ZM, ZW. Published: (84) Designated States (unless otherwise indicated, for every — with international search report (Art. 21(3)) kind of regional protection available): ARIPO (BW, GH, ENCAPSULATION COMPOSITIONS
This application claims priority to U.S. Provisional Application No. 62/335,987 which was filed May 13, 2016, and U.S. Provisional Application No. 62/3 19,907 which was filed April 8, 2016, and the contents of which are hereby incorporated by reference in their entirety.
STATEMENT OF GOVERNMENT RIGHTS This invention was made with government support under Contract Number W81XWH-14-C-0005 awarded by the US Army Medical Research and Materiel Command. The government has certain rights in the invention.
BACKGROUND OF THE INVENTION This invention relates in general to encapsulation materials and methods, and in particular to pyrethroids encapsulated by amphiphilic materials. The practice of protecting pyrethroids from an incompatible environment by encapsulation is well known. Encapsulation may be employed for a variety of reasons, including protecting pyrethroids from oxidation, preventing volatile losses, preventing chemical reaction or improving the handling characteristics of pyrethroids. The protective coating or shell is ruptured at the time of desired action of the ingredient. The rupturing of the protective shell is typically brought about through the application of chemical or physical stimuli such as pressure, shear, melting, response solvent action, enzyme attack, chemical reaction or physical disintegration. A number of companies have worked on improvements in encapsulation materials, including Revolymer Limited (U.K.) as disclosed in their published international patent applications WO 2009/050203, WO 201 1/064555, WO 2012/140442 and WO 2014/140550 Al; and Novozymes A/S (Denmark) as disclosed in WO 2016/ 023685. There is still a need for further improvements in encapsulation materials, particularly in regards to the releasable encapsulation of pyrethroids. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart of one embodiment of the encapsulation of a pyrethroid with a copolymer. Figure 2 is a schematic representation of a pyrethroid being encapsulated in polymer micelles. Figure 3 is a graph of the particle size distribution of an encapsulation composition according to the invention, which is made as described in Example 2 . Figure 4 is a graph of the particle size distribution of another embodiment of a encapsulation composition according to the invention, which is made as described in Example 3 . Figure 5 is a graph of the particle size distribution of a further embodiment of a encapsulation composition according to the invention, which is made as described in Example 4 . Figure 6 is a bar graph showing the results of a micellar disintegration study.
DESCRIPTION OF THE INVENTION The present invention relates to an encapsulation composition comprising a plurality of capsules, each capsule comprising an amphiphilic material encapsulating a pyrethroid. The pyrethroid has a release rate less than a release rate of the unencapsulated pyrethroid. In a particular embodiment, the encapsulating materials have well- balanced hydrophilic and hydrophobic chemical moieties that are useful for encapsulating pyrethroid. The addition of materials with well-balanced hydrophilic and hydrophobic moieties to a pyrethroid results in the encapsulation of the pyrethroid via association of the amphiphilic materials onto the pyrethroid. The association of the material onto the pyrethroid may be driven by one or a combination of noncovalent forces such as dipole, hydrogen bonding, van der Waals, electrostatic, cation-pi electron interaction, or hydrophobic effects. The amphiphilic material is a material composed of hydrophilic and hydrophobic portions or parts, which in certain embodiments are hydrophilic and hydrophobic sections or blocks. In certain embodiments involving block copolymers or surfactants useful for forming micelles, the amphiphilic material has a hydrophilic- lipophilic balance (HLB) within a range of from about 1 to about 20, or from about 11 to about 20, or from about 14 to about 18. The hydrophilic portion anchors the encapsulated pyrethroid, and the hydrophobic portion forms a shell wall of the capsule. In certain embodiments, the amphiphilic material is a polymer, and more particularly, a copolymer such as a graft copolymer or a block copolymer. In some non-limiting examples, the amphiphilic material may be included in one or more of the following classes of materials: a graft copolymer, a modified N,N,N',N'-Tetrakis(2-hydroxypropyl)ethylenediamine, a cationic nanoparticle, a diblock or triblock copolymer, an ionic or nonionic surfactant, a low surface energy silica, a Guerbet ester, or a poly(stearyl methacrylate -co- acrylic acid). For example, the amphiphilic material may be one or more of the following: a non-ionic graft copolymer, such as poly(lauiylmethacrylate)-g- polyethylene oxide (PLMA-g-PEG) (50:50, 75:25) or hydrophobically modified starch; a material prepared by modification of N,N,N',N'-Tetrakis(2- hydroxypropyl)ethylenediamine with trimethyl silyl chloride, with epoxy, or with a fluorinated epoxy mixture of poly(dimethyl siloxane)-amine (PDMS-amine) with fluoro trichlorosilane 1% siloxane/N-alkyl emulsion; a material prepared by modification of epoxy functional terminated polyethylene oxide, with amine functional terminated poly(dimethyl siloxane) (PDMS-PEO-PDMS) a cationic nanoparticle, such as a cationic nanoparticle prepared as described in the US patent 9,000,203 by a sol-gel condensation of 3-aminopropyl trimethoxy silane and tridecafluoro-l,l,2,2-tetrahydrooctyl triethoxysilane. a cationic nanoparticle, such as a cationic nanoparticle prepared as described in the US patent 9,000,203 by a sol-gel condensation of 3- aminopropyl trimethoxy silane and a non-bioaccumulating fluorosilane such as trimethoxy(3,3,3-trifluoropropyl)silane
a non-ionic triblock polymer obtained by reacting monomethoxy terminated poly ethylene oxide with heptadecane dicarboxylic acid methyl ester such
a non-ionic triblock polymer obtained by reacting monohydroxyl terminated poly ethylene oxide with heptadecane dicarboxylic acid such as C19 di- PEG a heptadecane carboxylic acid ester salts such as C19 di-acid salts with, Na+, K+, or Ca 2+ ions; a tert-octyl phenol derivative of sulfonated dichloro diphenyl sulfone, such as
or a nonyl phenol derivative of sulfonated dichloro diphenyl sulfone, or a poly(dimethyl siloxane) derivative of sulfonated dichloro diphenyl sulfone;
a low surface energy nonionic surfactant, such as isostearic acid- g-PEG; a low surface energy graft copolymer, such as isostearic acid PEG triblock ester or isostearic acid-ester- co - PEG - methacrylate; a low surface energy silica, such as isostearic acid ester silica; a Guerbet ester, such as a highly branched tri-isostearic acid citrate ester; a poly(stearyl methacrylate co acrylic acid), such as poly(stearyl methacrylate) - co- acrylic acid (PSMA - co- AA) 80:20; a poly(stearyl methacrylate co Ν,Ν '-dimethylamino ethyl methacrylate, NN-DMEA), such as poly(stearyl methacrylate) - co- NN- DMEA (PSMA - co-PNNDMEA) 50:50; a non-ionic diblock copolymer prepared by reacting mono hydroxy polyethylene oxide with 1-bromo octadecane; a nonionic triblock copolymer prepared by reacting di hydroxy polyethylene oxide with 1-bromo octadecane; a non-ionic diblock copolymer prepared by reacting mono hydroxy polyethylene oxide with linolenic acid; or a non-ionic diblock copolymer prepared by reacting mono hydroxy polyethylene oxide with linoleic acid.
By cationic non-bio accumulating fluoropolymer, we mean a fluoropolymer with less than a 6 fluorocarbon chain. By low surface energy, we mean the surface energy is less than about 20 dynes/cm. The encapsulated pyrethroid can be liquid, or solid, or combinations thereof. Some non-limiting examples of pyrethroids are allethrin, permethrin, transfluthrin, tefluthrin, metofluthrin, fenfluthrin, kadethrin, neopynamins, prallethrin, vapothrin, esbiothrin, dichlovos, deltamethrin, and cypermethrin. The pyrethroid may be encapsulated by the amphiphilic material by any suitable method. Some encapsulation techniques include, but are not limited to, dispersion, suspension, emulsification, and coating via conventional and electrostatic spray. When the pyrethroid is a solid or a liquid, it can be mixed in a solution of the amphiphilic material. The amphiphilic material forms a coating around the solid or liquid particles. In some cases, the pyrethroid can be dissolved in a solvent (such as water, methanol, ethanol, isopropyl alcohol, hexane, nonane, dodecane, toluene, xylene, N-methyl-2-pyrrolidone, dimethyl formamide, and dimethyl acetamide) before being mixed into the solution of amphiphilic material. The solvent used to dissolve the amphiphilic material should be immiscible with the solvent used to dissolve the active ingredient. For example, if the pyrethroid to be encapsulated is soluble in an organic solvent (e.g., transfluthrin), then water is used to dissolve the amphiphilic material, and organic solvent to dissolve the pyrethroid. Solid or liquid pyrethroids should be sparingly soluble in the liquid used for the solution of the amphiphilic material. By sparingly soluble, we mean the solubility of the solute is less than about 3 g in 100 ml of the liquid. The capsules can be nanocapsules and/or microcapsules. The capsules are typically in the range of about 10 nm to about 500 µ , or about 0.1 µηι to about 100 µηι , or about 1 µ to about 50 µι ι. In some embodiments, the capsules are stable at alkaline pH. In addition to the amphiphilic material, an additional surfactant (or co- surfactant) can be added to the mixture. Examples of co-surfactants include, but are not limited to, Sodium dodecyl sulfate, Sodium dodecylbenzenesulfonate, Sodium laureth sulfate, Sodium lauroyl sarcosinate, Sodium myreth sulfate, Sodium nonanoyloxybenzenesulfonate, Sodium stearate, Sulfolipid, Benzalkonium chloride, Benzyldodecyldimethylammonium bromide, Cetylpyridinium chloride, Dimethyldioctadecylammonium bromide, Dodecyltrimethylammonium bromide, Hexadecylpyridinium chloride, Tridodecylmethylammonium chloride Figure 1 is a flow chart of the encapsulation of a pyrethroid with an amphiphilic material. In step 100, the pyrethroid, such as TAED, is suspended in a solvent, such as hexane. In step 105, amphiphilic material is added. In step 110, in some cases, the amphiphilic material forms micelles. In step 115, if micelles are formed, the micelles are deposited onto the pyrethroid with the amphiphilic material. Otherwise, the amphiphilic material encapsulates the pyrethroid without forming micelles. The product can then be isolated in step 120. In certain embodiments, the amphiphilic material is an amphiphilic polymer capable of forming a micelle around the pyrethroid when the capsule is dispersed in a liquid. Micelles form only when the concentration of the polymer is greater than the critical micelle concentration (CMC). In certain embodiments, capsules have a CMC within a range of from about 0.0001 wt% to about 50 wt%. In addition, micelles only form when the temperature is above the critical micelle temperature (CMT) (also known as the cloud point or Krafft temperature). The CMT depends on a number of factors including the molecular weight of the polymer, the ratio of the hydrophobic portion to the hydrophilic portion, and functionality of the hydrophilic moiety. In general, the higher the amount of the hydrophobic portion, the higher the critical micelle temperature. In general, block copolymers having a number average molecular weight less than 100,000 kD will form micelles. Examples of amphiphilic polymers forming micelles include, but are not limited to, PEO-PPO-PEO, PEO-PPO, PDMS- PEO-PDMS, PDMS-PEO, C19-diPEG, diblock copolymer prepared by reacting mono hydroxy polyethylene oxide with 1-bromo octadecane, nonionic triblock copolymer prepared by reacting di hydroxy polyethylene oxide with 1-bromo octadecane, C19 dicarboxylic acid salts, tert-octyl phenol derivative of sulfonated dichloro diphenyl sulfone, nonyl phenol derivative of sulfonated dichloro diphenyl sulfone, and poly(dimethyl siloxane) derivative of sulfonated dichloro diphenyl sulfone. Figure 2 is a schematic representation of the encapsulation of a pyrethroid in amphiphilic micelles. As shown, in the first step 200, an amphiphilic material 205 is dispersed in a solvent, such as water. The amphiphilic material 205 has a hydrophilic segment 210 and a hydrophobic segment 215. The hydrophobic segment 215 of the amphiphilic material is adsorbed onto the pyrethroid 220. Above the CMC and CMT of the amphiphilic material 205 as shown in the second step 225, the amphiphilic material 205 forms micelles 230 around the pyrethroid 220. The pyrethroid 220 is encapsulated inside a hydrophobic core of the micelle 230 formed by the hydrophobic segment 215 of the amphiphilic material 205. The hydrophilic segment 210 of the amphiphilic material 205 extends radially outward and forms the shell of the micelle 230. Figure 6 illustrates the disintegration of micelles by dilution with water in graphical form. The amphiphilic material was a non-ionic diblock copolymer prepared by reacting mono hydroxy polyethylene oxide with 1-bromo octadecane. When the copolymer was dissolved in water at a concentration of 0.01 wt%, the surface tension of the water was 37.5 dynes/cm (bar 1). When the copolymer was dissolved in water at a concentration of 0.0035 wt% and exposed to 9.5 pH aqueous solution, the surface tension of the water was 38.1 dynes/cm (bar 2). When the copolymer was dissolved in water at a concentration of 0.0035 wt% the surface tension of the water was 42.1 dynes/cm (bar 3). When the copolymer was dissolved in water at a concentration of 0.006 wt% and exposed to 9.5 pH aqueous solution, the surface tension of the water was 54.1 dynes/cm (bar 4). For reference purposes, the surface tension of water is 70 dynes/cm. When more water was added to the micelles, the surface tension increased and approached the value of water, which suggests that the non-ionic diblock copolymer prepared by reacting mono hydroxy polyethylene oxide with 1-bromo octadecane disintegrates on dilution. When the pyrethroid is transfluthrin, a preferred amphiphilic material is PEO-PPO-PEO. The encapsulated product is coated on a fabric. The coating can be accomplished using any suitable coating process including, but not limited to, immersion, spraying, knife coating, direct roll coating, pad-dry coating, calender coating, hot melt extrusion coating, foam finishing, and gravure printing. The fabric can be derived from polymeric fibers such as polyester, polyamide, polyester amide, polyimide, poly ester imide, polybenzimidazole, polybenzoxazole, polythiazole, polydimethyl siloxane-polyether amide copolymer, and the blends thereof. The fibers can be derived from natural materials such as cotton, soybeans, corn, sorghum, sugarcane, coconut, animal proteins and sea weed. One or more additional ingredients useful for formulating the product can be included. Additional ingredients include, but are not limited to, thickening agents (e.g., polyvinyl alcohol, poly vinyl pyrrolidone, and carboxyl methyl cellulose), and co-solvents (e.g., glycerol, and 1,2-propylene glycol). The release rate of active ingredient from the encapsulation composition of the present invention was determined by gravimetric analysis. A fabric (lsq.inch) was coated with the encapsulation composition and dried at room temperature to remove excess water and toluene. The coated fabric was kept under a controlled atmosphere (70 degree F and 68% relative humidity), and its weight was monitored and recorded as a function of time. The release rate was calculated using the following equation:
K = _ At Where, K is the release rate, Am is difference in mass and At is the difference in time.
EXAMPLES
Example 1 Screening of Amphiphilic Materials for Encapsulation: In the first step, the amphiphilic material is dissolved in water. The amphiphilic materials were commercially available products (Pluronic®) from BASF, asn shown below. In the second step, the pyrethroid, transfluthrin, was dissolved in a large amount in toluene. In the third step, the mixture obtained from second step was added to the mixture obtained from first step to form the pyrethroid encapsulated in the amphiphilic material. The release rate of the pyrethroid from the capsules is controlled by a number of factors. One is the amount of amphiphilic material used in step 1. Higher amounts of amphiphilic material in step 1result in decreased release rates of the pyrethroid. The release rate of the pyrethroid from the capsules is further controlled by the CMC of the amphiphilic material used in step 1. The higher the CMC of the amphiphilic material in step 1, the lower the release rate of the pyrethroid. The release rate of the pyrethroid from the capsules is further controlled by the ratio of organic solvents to the pyrethroid in step 2 . The higher the ratio of organic solvents to the pyrethroid in step 2, the lower the release rate of the pyrethroid.
Example 2 In the first step, an aqueous solution of 5.6 wt% poly(ethylene oxide) — block—poly(propylene oxide) —block—poly(ethylene oxide) (PEO-PPO-PEO) (Pluronic® L64 (BASF)) was prepared by mixing 23.7 g of the block co-polymer in 400 g water. The solution was mixed for 3 hr using a magnetic stirrer at 300 rpm.
In the second step, 11.3 g of transfluthrin (TF) was dissolved in 15.8 g of toluene. In the third step, the mixture obtained from the second step was added to the mixture obtained from the first step at room temperature to form the pyrethroid encapsulated in the amphiphilic material.
The product obtained from third step was characterized for particle size using dynamic-light-scattering (DLS, Master sizer 2000, Malvern). Formation of 3 µ ι droplet size with uniform drop-size-distribution was observed, as shown in Figure 3 . The release rate of the transfluthrin as determined by the gravimetric method was found to be <0.2 mg/day.
Example 3 In the first step, an aqueous solution of 5.7 wt% poly(ethylene oxide) — block—poly(propylene oxide) —block—poly(ethylene oxide) (PEO-PPO-PEO) (Pluronic® L64 (BASF)) was prepared by mixing 24. 1 g of the block co-polymer in 400 g water. The solution was mixed for 3 hr using a magnetic stirrer at 300 rpm. In the second step, 13.48 g of transfluthrin (TF) was dissolved in 74.8 g of toluene. In the third step, the mixture obtained from the second step was added to the mixture obtained from the first step at room temperature to form the pyrethroid encapsulated in the amphiphilic material. The product obtained from third step was characterized for particle size using dynamic-light-scattering (DLS, Master sizer 2000, Malvern). Formation of 3 µ ι droplet size with uniform drop-size-distribution was observed, as shown in Figure 4 . The release rate of the transfluthrin as determined by the gravimetric method was found to be <0.4 mg/day.
Example 4 In the first step, an aqueous solution of 7.1 wt% poly(ethylene oxide) — block—poly(propylene oxide) —block—poly(ethylene oxide) (PEO-PPO-PEO) (Pluronic® L64 (BASF)) was prepared by mixing 30.8 g of the block co-polymer in 400 g water. The solution was mixed for 3 hr using a magnetic stirrer at 300 rpm. In the second step, 18.48 g of transfluthrin (TF) was dissolved in 289.8 g of toluene. In the third step, the mixture obtained from the second step is added to the mixture obtained from the first step at room temperature to form the pyrethroid encapsulated in the amphiphilic material. The product obtained from third step, was characterized for particle size using dynamic-light-scattering (DLS, Master sizer 2000, Malvern). Formation of 3 µ ι droplet size with uniform drop-size-distribution was observed, as shown in Figure
5 . The release rate of the transfluthrin as determined by the gravimetric method was found to be <0.6 mg/day. By about, we mean within 10% of the value, or within 5%, or within 1%. While at least one exemplary embodiment has been presented in the foregoing detailed description of the invention, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment of the invention. It being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the invention as set forth in the appended claims. CLAIMS
1. An encapsulated composition comprising: a plurality of capsules each comprising an amphiphilic material encapsulating a pyrethroid, the encapsulated pyrethroid having a release rate less than a release rate of unencapsulated pyrethroid.
2 . The composition of claim 1 wherein the pyrethroid is at least one of allethrin, permethrin, transfluthrin, tefluthrin, metofluthrin, fenfluthrin, kadethrin, neopynamins, prallethrin, vapothrin, esbiothrin, dichlovos, deltamethrin, and cypermethrin.
3 . The composition of any one of claims 1-2 wherein the amphiphilic material is a polymer.
4 . The composition of claim 3 wherein the polymer is a copolymer.
5. The composition of any one of claims 1-4 wherein the amphiphilic material is a graft copolymer, a modified N,N,N',N'-Tetrakis(2- hydroxypropyl)ethylenediamine, a cationic nanoparticle, a diblock or triblock copolymer, an ionic or nonionic surfactant, a low surface energy silica, a Guerbet ester, or a poly(stearyl methacrylate -co- acrylic acid).
6 . The composition of any one of claims 1-5 wherein the amphiphilic material has hydrophilic and hydrophobic portions, and wherein the hydrophilic portion anchors the encapsulated substance and the hydrophobic portion forms a shell wall of the capsule.
7 . The composition of any one of claims 1-6 wherein the amphiphilic material has a hydrophilic-lipophilic balance within a range of from about 1 to about 20. 8. The composition of any one of claims 1-7 wherein the capsules are stable at alkaline pH.
9 . The composition of any one of claims 1-2 and 5-8 wherein the amphiphilic material is at least one of a diblock colpolymer, a triblock copolymer, and a nonionic surfactant, and wherein the amphiphilic polymer is capable of forming a micelle around the pyrethroid when the capsule is dispersed in a liquid.
10. The composition of any one of claims 1-3 and 5-9 wherein the amphiphilic material is an amphiphilic polymer and wherein the amphiphilic polymer is capable of forming a micelle around the pyrethroid when the capsule is dispersed in a liquid.
11. The composition of any one of claims 9-10 wherein the capsules have a critical micelle concentration within a range of from about 0.0001 wt% to about 50 wt%.
12. The composition of any one of claims 9-1 1 wherein the pyrethroid is transfluthrin.
13. The composition of any one of claim 9-12 wherein the amphiphilic material is a poly(ethylene oxide) — poly(propylene oxide) — poly(ethylene oxide) triblock copolymer.
14. A product comprising: the composition of any one of claims 1-13 coated on a fabric.
15. The product of claim 14 further comprising one or more additional ingredients useful for formulating the product.
A . CLASSIFICATION O F SUBJECT MATTER INV. A01N25/28 A01N25/04 A01N53/00 A01P7/04 ADD.
According to International Patent Classification (IPC) or to both national classification and IPC
B . FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) A01N
Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched
Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)
EPO-Internal , CHEM ABS Data
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X| Further documents are listed in the continuation of Box C . See patent family annex.
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Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.
WO 03/051116 Al (MARS INC [US] ; GIMENO 1-15 MIGUEL [AT] ; GIMENO BARBARA [AT] ) 26 June 2003 (2003-06-26) page 4 , 1 . 18-33 ; Exampl e s 1-4, c l aims 1-40
W0 2015/127051 Al ( FMC CORP [US] ) 1-12 27 August 2015 (2015-08-27) page 6 , 1 .5-32 , page 7 , 1 . 1-25 ; exampl e 1 ; c l aims 1-44
W0 2013/105107 A2 (SAHAH DI EPAK [IN] ) 1-13 18 July 2013 (2013-07-18) page 3 , 1 . 24-26; page 5 , 1 . 9-36; page 6 , 1 . 1-24; page 15 , 1 . 13-15 , 30-37 ; exampl e 1 ; Tabl e 1 ( LI , L2 , L4tabl e 3 , ( L4, L24, L57 , L16) ; c l aims 1-8, 10-13 , 15 , 16, 18, 20, 24-29 . Patent document Publication Patent family Publication cited in search report date member(s) date
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US 2002136773 Al 26-09-2002 AT 309858 T 15-12-2005 AU 7420801 A 17-12-2001 AU 2001274208 B2 17-03-2005 B R 0111465 A 01-07-2003 CN 1446120 A 01-10-2003 DE 60115033 Dl 22-12-2005 DE 60115033 T2 01-06-2006 DK 1292386 T3 27-03-2006 EP 1292386 A2 19-03-2003 ES 2248340 T3 16-03-2006 P 2004502519 A 29-01-2004 KR 20030034085 A 01-05-2003 MX PA02011951 A 14-07-2003 NO 20025827 A 03-02-2003 NZ 522785 A 28-05-2004 PL 359225 Al 23-08-2004 T W 587956 B 21-05-2004 US 2002136773 Al 26-09-2002 WO 0194001 A2 13-12-2001
US 5849264 A 15-12-1998 A R 003849 Al 09-09-1998 AU 709344 B2 26-08-1999 B R 9610904 A 13-07-1999 CA 2234103 Al 17-04-1997 CN 1202797 A 23-12-1998 DE 69626835 Dl 24-04-2003 DE 69626835 T2 20-11-2003 EP 0855858 Al 05-08-1998 ES 2195012 T3 01-12-2003 GB 2306327 A 07-05-1997 HK 1011260 Al 19-05-2000 NZ 319074 A 23-12-1998 US 5849264 A 15-12-1998 WO 9713409 Al 17-04-1997 ZA 9608544 B 19-05-1997
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