USOO920463OB2 (12) United States Patent (10) Patent No.: US 9.204,630 B2 Shirley et al. (45) Date of Patent: Dec. 8, 2015 (54) CAPSULE FORMULATION (58) Field of Classification Search CPC ... A01N 2300/00: A01N 43/90: A01N 47/02: (75) Inventors: Ian Malcolm Shirley, Bracknell (GB); A01N 25/22: A01N 25/28 Tanya Wright, Basel (CH); Robert See application file for complete search history. Michael Perrin, Bracknell (GB); Patrick Mulqueen, Bracknell (GB); Anne Waller, Bracknell (GB); Andy (56) References Cited Pierce, Bracknell (GB) U.S. PATENT DOCUMENTS (73) Assignee: Syngenta Participations AG, Basel 4,440,756 A * 4/1984 Herve et al. ................... 514,521 (CH) 6,395,776 B1* 5/2002 Losel et al. ................... 514,531 2002/003730.6 A1* 3/2002 Van Koppenhagen et al. ............................. 424/408 (*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 2004/O198704 A1* 10, 2004 Shuster et al. ... 514/151 U.S.C. 154(b) by 1634 days. 2004/0235898 A1* 11/2004 Klein et al. ................... 514,318 (21) Appl. No.: 11/817,068 FOREIGN PATENT DOCUMENTS CN 1386419 A 12/2002 (22) PCT Filed: Feb. 23, 2006 CN 149 1552 A 4/2004 DE 4009 141 A1 9, 1990 (86). PCT No.: PCT/EP2006/OO1657 DE 19503157 A1 8, 1995 EP O761096 A 3, 1997 S371 (c)(1), WO 89,04170 A 5, 1989 (2), (4) Date: Aug. 19, 2008 WO OO/O5951. A 2, 2000 (87) PCT Pub. No.: WO2006/089747 OTHER PUBLICATIONS PCT Pub. Date: Aug. 31, 2006 Anonymous, “Pyrethrinoids Stabilized by Non-azo—dyes'. Research Disclosure No. 22221, Oct. 1982, XPO02408404, whole (65) Prior Publication Data document. US 2008/0306O26A1 Dec. 11, 2008 * cited by examiner (30) Foreign Application Priority Data Feb. 24, 2005 (EP) ..................................... O5004OO6 Primary Examiner — Kyle Purdy (74) Attorney, Agent, or Firm — Brian D. McAlhaney (51) Int. Cl. AOIN 25/00 (2006.01) AOIN 47/34 (2006.01) (57) ABSTRACT AOIN 53/00 (2006.01) An encapsulated composition of (a) a pesticide at least active AOIN 47/12 (2006.01) via ingestion that is photolabile, and (b) at least one photo AOIN 47/40 (2006.01) protectant, wherein the encapsulating polymeric barrier is AOIN 25/22 (2006.01) base triggerable is disclosed. A method for controlling dam AOIN 25/28 (2006.01) age of a material by a pest by the use of Such encapsulated AOIN 43/90 (2006.01) compositions is likewise disclosed. The composition as dis AOIN 47/02 (2006.01) closed gives protection for beneficial arthropods and reduces (52) U.S. Cl. workers exposure. CPC ................ A0IN 25/22 (2013.01); A0IN 25/28 (2013.01); A0IN 43/90 (2013.01); A0IN 47/02 (2013.01) 17 Claims, 1 Drawing Sheet U.S. Patent Dec. 8, 2015 US 9.204,630 B2 Figure 1 - PhotoStability of emamectin benzoate Coencapsulated With photoprotectants PHOTO STABLITY OF ERAWECTN BENZOATE COENCAPSULATED WITH PHOTOPROTECTANTS EAFTER 5 HRS RRADATION AFTER 24 HRS RRADATION 100.0 90.0 8.O 7).O 60. 50. 4D.O. 30.0 2O.O O.O. O.O - I EXAMPLE3 EXAMPLE EXAMPLE9 EXAMPLEB EXAMPLE5 EXAMPLE 11 EXAMPLE 10 Figure 2 - Photostability of emamectin benzoate Coencapsulated with photoprotectants PHOTOSABILITY OF EAIAWECTN BENZOATE COENCAPSULATED AITH PHOTOPROTECTANTS EAFTER 5 HRS RRADATION AFTER 24 HRS RRADATION 1O) 9 8O 70 SO 5 AO 3O 20 10 EXAMPE3 EXAMPLE21 EXAMPLE 19 EXAMPLE 2.0 EXAMPLE 22 EXAMPLE 24 EXAMPLE 23 US 9,204,630 B2 1. 2 CAPSULE FORMULATION 9,10-dihydro-9,10-dioxo-4-(phenylamino)-2-anthrace nesulfonate, 1-amino-2-methyl-9,10-anthracenedione; This application is a 371 of International Application No. 1,4-bis(1-methylethyl)aminol-9,10-anthracenedione: PCT/EP2006/001657 filed Feb. 23, 2006, which claims pri 1,4-bis(4-methylphenyl)aminol-9,10-anthracenedi ority to EP 05004006.2 filed Feb. 24, 2005, the contents of 5 one: 1-hydroxy-4-(4-methylphenyl)aminol-9,10-an which are incorporated herein by reference. thracenedione; monosodium 4-hydroxy-3-(2-hydroxy The present invention relates to a method for improving the 1-naphthalenyl)aZo-benzenesulfonate; monosodium delivery of a pesticide to its target site, where the pesticide is 4-(2-hydroxy-1-naphthalenyl)azo-3-methyl-benzene at least active via ingestion and is photolabile, and encapsu Sulfonate; 4-(4-nitrophenyl)azol-N-phenyl-benze lated compositions for Such a method. 10 namine: 4-4-(phenylazo)-1-naphthalenylaZo-phe There is a need for effective ways of controlling the dam nol; 3-ethylA-(4-nitrophenyl)aZophenylamino age of materials. Such as plants and construction materials, by pests. Many such pests have alkaline conditions in the gut. propanenitrile, 4-(4-nitrophenyl)aZo-benzenamine; Additionally many pesticides including insecticides active monosodium 3-hydroxy-4-(1-hydroxy-2-naphthale via ingestion are photolabile and suffer loss of efficacy in 15 nyl)azol-7-nitro-1-naphthalenesulfonate: 1-2,5-dim sunlight. Furthermore, it is desirable to improve selectivity of ethyl-4-(2-methylphenol)aZophenylaZo-2-naphtha said insecticides to beneficial insects and minimize operator lenol; 1-4-(dimethylphenyl)azodimethylphenyl exposure during use. aZo-2-naphthalenol; 1-(ortho-tolylazo)-2-naphthol; Capsule technologies have been in existence for a number tetrasodium 4-amino-5-hydroxy-3,6-bis(4-2-(sulfooxy) of years (see, for example, GB1513614, CA2133779, WO00/ ethylsulfonylphenylazol-2.7-naphthalenedisulfonate; 05951, U.S. Pat. No. 6,485,736, and U.S. Pat. No. 5,846,554). 1-4-(phenyl)azo)phenylaZo-2-naphthalenol; 1-3-me By capsule we mean a composition in which one Substance is thyl-4-(3-methylphenol)aZophenylazol-2-naphthalenol; embedded in another substance. Microcapsules for use in the 2,3-dihydro-2,2-dimethyl-6-4-(phenylazo)-1-naphthale present invention may vary from 0.5 to 1000 micrometers, nylaZo-1H-perimidine; 1-(phenylazo)-2-naphthalenol; preferably from 0.5 to 100 micrometers, and particularly 25 1-2-methyl-4-(2-methylphenol)aZophenylazol-2-naph preferably from 1 to 40 micrometers. thalenol; 1.3(2H)-dione, 2-(3-hydroxy-2-quinolinyl)-1H-in Base-triggerable capsule technology has also been dis dene: 2-(1,3-dihydro-3-oxo-2H-indol-2-ylidene)-1,2-dihy closed for pesticides (see, for example, WO00/05951). dro-3H-indole-3-one; disodium 2-(1,3-dihydro-3-oxo-5- Further, the use of a photoprotectant in capsules to inhibit sulfo-2H-indol-2-ylidene)-2,3-dihydro-3-oxo-1H-indole-5- the photodegradation of an insecticide has been disclosed in 30 sulfonate; mixture of 1-(phenylazo)-2-naphthalenol with 1,4- WO96/33611, where the capsule contained particulate sus bis(1-methylethyl)aminol-9,10-anthracenedione; mixture pensions selected from titanium dioxide, zinc oxide and mix of 1-(phenylazo)-2-naphthalenol with 1,4-bis(1-methyl tures thereof. ethyl)aminol-9,10-anthracenedione and 1-2-methyl-4-(2- By photoprotectant, we mean a compound or combination methylphenol)aZolphenylazol-2-naphthalenol; benzoa of compounds that reduce the chemical degradation of a 35 phenoxazin-7-ium, 5-amino-9-(diethylamino)-, Sulfate; pesticide that is induced by light, typically between the wave N-4--(diethylamino)phenyl(2,4-disulfophenyl)methyl lengths of 200 nm to 800 nm. Such degradation is typically ene-2,5-cyclohexadien-1-ylidene-N-ethyl-ethanaminium, termed photoinstability or photodegradation and said pesti inner salt, sodium salt; N-4-4-(dimethylamino)phenylA cide is deemed to be photolabile, photounstable or photosen (phenylamino)-1-napthalenylmethylene-2,5-cyclohexa sitive. 40 dien-1-ylidene-N-methyl-methanaminium chloride; N-4- It has now been found that certain compositions containing 4-(dimethylamino)phenyl 4-(ethylamino)-1-napthalenyl a pesticide that is both at least active via ingestion and pho methylene-2,5-cyclohexadien-1-ylidene-N-methyl tolabile provide unexpected control of pests that have alkaline methanaminium chloride; 4,5,6,7-tetrachloro-3',6'- conditions in the gut. dihydroxy-2',4',5'7"-tetraiodospiro isobenzofuran-1 (3H), 9'- The term "ingestion' is understood to refer to the con 45 9HXanthen-3-one disodium salt; 2-(3,4- Sumption by a pest of an agronomic or non-agronomic mate dihydroxyphenyl)-3,5,7-trihydroxy-4H-1-benzopyran-4- rial (e.g. plant, bait, foodstuff or other phagostimulatory one; N,N',N',N'-tetrakis(4,6-bis(butyl-(N-methyl)-2.2.6,6- material) treated with a pesticide. Then the uptake of the said tetramethylpiperidin-4-yl)amino)triazin-2-yl)-4,7- pesticide into said pest principally occurs via the gut. diazadecane-1,10-diamine; poly 6-(1,1,3,3- Accordingly, in a first aspect, the present invention pro 50 tetramethylbutyl)amino-1,3,5-triazine-2-4-diy12.2.6,6- vides a method for controlling damage of a material by a pest, tetramethyl-4-piperidinyl)imino-1,6-hexanediyl (2.2.6.6- which comprises applying to the material a composition com etramethyl-4-piperidinyl)imino); mixture of esters of 2.2.6. prising a capsule, which comprises: 6-tetra-methyl-4-piperidinol with higher fatty acids (mainly (a) a pesticide at least active via ingestion and that is Stearic and palmitic acids); propanedioic acid, (4-methoxy photolabile, and 55 phenyl)-methylene-, bis(1.2.2.6,6-pentamethyl-4-piperidi (b) at least one photoprotectant compound selected from nyl)ester; bis(2.2.6,6-tetramethyl-4-piperidyl) sebaceate; bis all-trans-(all-E)-1,1'-(3,7,12,16-tetramethyl-1,3,5,7,9. (1.2.2.6,6-pentamethyl-4-piperidinyl)ester; polymer of N,N'- 11,13,15, 17-octadecanonaene-1,18-diyl)bis 2.6,6-tri bis(2.2.6.6-tetramethyl-4-piperidinyl)-1,6-hexanediamine methylcyclohexene; 2-ethylhexyl-p-methoxycin with 2,4,6-trichloro-1,3,5-triazine reaction products with namate; 1,3-bis-2'-cyano-3',3-diphenylacryloyl)oxy 60 3-bromo-1-propene, N-butyl-1-butanamine