Title of Invention	"SUSPENSION CONCENTRATE FORMULATION CONTAINING PYRIMETHANIL"
Abstract	The invention provides an aqueous SC formulation comprising: a) 50 to 80 % w/v pyrimethanil; b) 0.2 to 5 % w/v of a polyoxyethylene-polyoxypropylene block copolymer surfactant; and c) 0.2 to 5 % w/v of a naphthalene formaldehyde condensate surfactant. We have found that formulations according to the invention surprisingly do not solidify when milled during manufacture and also exhibit a low propensity to crystallise when stored for prolonged periods.

Title of Invention

"SUSPENSION CONCENTRATE FORMULATION CONTAINING PYRIMETHANIL"

Abstract

The invention provides an aqueous SC formulation comprising: a) 50 to 80 % w/v pyrimethanil; b) 0.2 to 5 % w/v of a polyoxyethylene-polyoxypropylene block copolymer surfactant; and c) 0.2 to 5 % w/v of a naphthalene formaldehyde condensate surfactant. We have found that formulations according to the invention surprisingly do not solidify when milled during manufacture and also exhibit a low propensity to crystallise when stored for prolonged periods.

Full Text	SUSPENSION CONCENTRATE FORMULATION CONTAINING PYRIMETHANIL This invention relates to liquid formulations of pyrimethanil and methods for their preparation. In particular, the invention relates to suspension concentrate (SC) formulations that contain high proportions of solid pyrimethanil. Commercial SC formulations comprising the fungicide pyrimethanil include Mythos® and Scala®. Typically these formulations contain not more than 40% w/v pyrimethanil. Increasing the amount of pyrimethanil in these formulations above 40% would be advantageous, since it would reduce the cost of transporting a given amount of active ingredient. These savings would be particularly significant where pyrimethanil is transported to remote places where distribution is difficult, such as to tropical zones. However, increasing the concentration of pyrimethanil in these formulation leads to milling problems during manufacture and crystallisation during storage. It is therefore an object of the invention to devise an SC formulation system containing concentrations of pyrimethanil significantly greater than 40% without experiencing the abovementioned problems. According to a first aspect, the invention provides an aqueous SC formulation comprising a) 50 to 80% w/v pyrimethanil, preferably 60 to 80% w/v; b) 0.2 to 5% w/v of a polyoxyethylene-polyoxypropylene block copolymer surfactant, preferably 0.3 to 1.5 %; and c) 0.2 to 5% w/v of a napthalene formaldehyde condensate surfactant, preferably 0.3 to 1.5%. We have found that formulations according to the invention surprisingly do not solidify when milled during manufacture and also exhibit a low propensity to crystallise when stored for prolonged periods. Throughout this specification, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising" will be understood to imply the inclusion of a stated integer or group of integers, but not the exclusion of any other integer or group of integers including method steps. Preferably component b) has a molecular weight of 6000 to 14 000, especially 9000 to 13000. Further, component b) contains 20 to 80% w/w of polyoxyethylene, especially 40 to 80%. In particular, the molecular weight of component b) is nominally 12000 and the amount of polyoxyethylene is nominally 70% w/w. Preferably component c) is a salt, particularly the sodium salt. Preferably the formulation also comprises a dispersant, such as a polymethyl methacrylate-polyethylene glycol graft copolymer, preferably having a molecular weight of 20000 to 30000, in amounts of 1 to 10% w/v, preferably 3 to 8%. A particularly preferred SC formulation comprises a) approximately 60% w/v pyrimethanil, b) approximately 0.5% w/v of an ethenylenoxy-propyleneoxy block copolymer surfactant, c) approximately 1% w/v of sodium naphthalene formaldehyde condensate surfactant, d) approximately 5% w/v polymethyl methacrylate-polyethylene glycol graft copolymer, e) approximately 6% w/v propylene glycol and f) approximately 37.5% w/v water. Our invention is illustrated, by way of example only, with reference to the following. Examples A number of formulations of differing composition were prepared. Table 1 shows the components and their concentrations in w/v. In most cases the components are given as their trade name. Their chemical composition and major function are as follows. Atlox 4894 is polyoxyethylene alkyl ether (NPE-free); acts as a dispersant and wetter. Atlox 4913 is polymethyl methacrylate-polyethylene glycol graft copolymer; acts as a dispersant. Atlox 5406B is a blend of anionic and nonionic surfactants; acts as a dispersant and wetter. Morwet D425 is sodium naphtalene formaldehyde condensate; acts as a dispersant and viscosity modifier. Synperonic PE F127 is a polyoxyethylene-polyoxypropylene block copolymer; acts as a dispersant and wetter. Lauropal X1003 is an ethoxylated alcohol; acts as a wetter. Polyfon H is sodium lignosulphonate; acts as a dispersant. Tegopren 5840 is a copolymer consisting of polymethyl siloxanes and polyoxyethylene-polyoxypropylene segments; acts as a wetter. Reax 85A is sodium lignosulphonate; acts as a dispersant. Surfynol 104-E is tetramethyl decynediol and ethylene glycol; acts mainly as a wetter. Surfynol 420 is polyoxyethylene (1.3 moles) tetramethyl decynediol; acts as a wetter. Arylan SBC25 is sodium dodecylbenzene sulphonate; acts as a wetter. Witconol NS 500 LQ is a nonionic surfactant blend; acts as a dispersant. Synperonic 91/6 is polyoxyethylene (6 moles) synthetic primary C9/C11 alcohol; acts as a wetter. Emcol CC9E is polypropylene glycol (9 moles) diethylmonium chloride; acts as a dispersant and viscosity modifier. Aerosol OT/ S is dioctyl sodium sulfosuccinate; acts as a wetter. Each formulation was prepared as follows. Method All components (except aqueous Kelzan pregel) are dispersed using a high speed mixer. The dispersion is passed through a bead mill under such conditions to achieve the desired particle size distribution and viscosity. Aqueous Kelzan pregel is added to the milled suspension. Formulations 1 and 2 are formulations of the invention. The remaining formulations are by way of comparison. Each formulation was analysed in terms of milling performance and extent of crystallisation after 2 weeks storage at 54 °C. The results are as follows Milling performance Formulations 3 to 6, 13 to 18, 20 and 24 solidified during milling. Formulations 1, 2, 7 to 12, 19, 21, 22 and 23 exhibited no milling problems. Extent of crystallisation after storage at 54 °C Formulations 7 to 12, 19, 21, 22 and 23 exhibited crystal growth after 2 weeks at 54°C, this was particularly marked with 11, 19, 21 and 23. Formulation 2 showed very slight crystallisation. Formulation 1 showed no crystal growth.(Table Removed) Claims 1 An aqueous SC formulation comprising a) 50 to 80% w/v pyrimethanil, b) 0.2 to 5% w/v of a polyoxyethylene-polyoxypropylene block copolymer surfactant, and c) 0.2 to 5% w/v of a napthalene formaldehyde condensate surfactant. 2 A formulation according to claim 1 wherein component b) has a molecular weight of 6000 to 14 000. 3 A formulation according to claim 1 wherein component b) has a molecular weight of 9000 to 13000. 4 A formulation according to claim 1 wherein component b) contains 20 to 80% w/w of polyoxyethylene. 5 A formulation according to claim 1 wherein component b) contains 40 to 80% w/w of polyoxyethylene. 6 A formulation according to claim 1 wherein the molecular weight of component b) is nominally 12000 and the amount of polyoxyethylene is nominally 70% w/w. 7 A formulation according to any preceding claim wherein component c) is a salt. 8 A formulation according to any preceding claim which also comprises a polymethyl methacrylate-polyethylene glycol graft copolymer dispersant. 9 A formulation according to claim 8 wherein the dispersant has a molecular weight of 20000 to 30000, in amounts of 1 to 10% w/v. 10 A formulation comprising a) approximately 60% w/v pyrirnethanil, b) approximately 0.5% w/v of an ethenylenoxy-propyleneoxy block co-polymer surfactant, c) approximately 1% w/v of sodium naphthalene formaldehyde condensate surfactant, d) approximately 5% w/v polymethyl methacrylate- polyethylene glycol graft copolymer, e) approximately 6% w/v propylene glycol and f) approximately 37.5% w/v water.

Full Text

SUSPENSION CONCENTRATE FORMULATION CONTAINING PYRIMETHANIL
This invention relates to liquid formulations of pyrimethanil and methods for their preparation. In particular, the invention relates to suspension concentrate (SC) formulations that contain high proportions of solid pyrimethanil.
Commercial SC formulations comprising the fungicide pyrimethanil include Mythos® and Scala®. Typically these formulations contain not more than 40% w/v pyrimethanil. Increasing the amount of pyrimethanil in these formulations above 40% would be advantageous, since it would reduce the cost of transporting a given amount of active ingredient. These savings would be particularly significant where pyrimethanil is transported to remote places where distribution is difficult, such as to tropical zones. However, increasing the concentration of pyrimethanil in these formulation leads to milling problems during manufacture and crystallisation during storage.
It is therefore an object of the invention to devise an SC formulation system containing concentrations of pyrimethanil significantly greater than 40% without experiencing the abovementioned problems.
According to a first aspect, the invention provides an aqueous SC formulation comprising a) 50 to 80% w/v pyrimethanil, preferably 60 to 80% w/v; b) 0.2 to 5% w/v of a polyoxyethylene-polyoxypropylene block copolymer surfactant, preferably 0.3 to 1.5 %; and c) 0.2 to 5% w/v of a napthalene formaldehyde condensate surfactant, preferably 0.3 to 1.5%.
We have found that formulations according to the invention surprisingly do not solidify when milled during manufacture and also exhibit a low propensity to crystallise when stored for prolonged periods.
Throughout this specification, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising" will be understood to imply the inclusion of a stated integer or group of integers, but not the exclusion of any other integer or group of integers including method steps.
Preferably component b) has a molecular weight of 6000 to 14 000, especially 9000 to 13000. Further, component b) contains 20 to 80% w/w of polyoxyethylene, especially

40 to 80%. In particular, the molecular weight of component b) is nominally 12000 and the amount of polyoxyethylene is nominally 70% w/w.
Preferably component c) is a salt, particularly the sodium salt.
Preferably the formulation also comprises a dispersant, such as a polymethyl methacrylate-polyethylene glycol graft copolymer, preferably having a molecular weight of 20000 to 30000, in amounts of 1 to 10% w/v, preferably 3 to 8%.
A particularly preferred SC formulation comprises a) approximately 60% w/v pyrimethanil, b) approximately 0.5% w/v of an ethenylenoxy-propyleneoxy block copolymer surfactant, c) approximately 1% w/v of sodium naphthalene formaldehyde condensate surfactant, d) approximately 5% w/v polymethyl methacrylate-polyethylene glycol graft copolymer, e) approximately 6% w/v propylene glycol and f) approximately 37.5% w/v water.
Our invention is illustrated, by way of example only, with reference to the following.
Examples
A number of formulations of differing composition were prepared. Table 1 shows the components and their concentrations in w/v. In most cases the components are given as their trade name. Their chemical composition and major function are as follows.
Atlox 4894 is polyoxyethylene alkyl ether (NPE-free); acts as a dispersant and wetter.
Atlox 4913 is polymethyl methacrylate-polyethylene glycol graft copolymer; acts as a
dispersant.
Atlox 5406B is a blend of anionic and nonionic surfactants; acts as a dispersant and
wetter.
Morwet D425 is sodium naphtalene formaldehyde condensate; acts as a dispersant
and viscosity modifier.
Synperonic PE F127 is a polyoxyethylene-polyoxypropylene block copolymer; acts as
a dispersant and wetter.
Lauropal X1003 is an ethoxylated alcohol; acts as a wetter.
Polyfon H is sodium lignosulphonate; acts as a dispersant.
Tegopren 5840 is a copolymer consisting of polymethyl siloxanes and
polyoxyethylene-polyoxypropylene segments; acts as a wetter.

Reax 85A is sodium lignosulphonate; acts as a dispersant.
Surfynol 104-E is tetramethyl decynediol and ethylene glycol; acts mainly as a wetter.
Surfynol 420 is polyoxyethylene (1.3 moles) tetramethyl decynediol; acts as a wetter.
Arylan SBC25 is sodium dodecylbenzene sulphonate; acts as a wetter.
Witconol NS 500 LQ is a nonionic surfactant blend; acts as a dispersant.
Synperonic 91/6 is polyoxyethylene (6 moles) synthetic primary C9/C11 alcohol; acts as
a wetter.
Emcol CC9E is polypropylene glycol (9 moles) diethylmonium chloride; acts as a
dispersant and viscosity modifier.
Aerosol OT/ S is dioctyl sodium sulfosuccinate; acts as a wetter.
Each formulation was prepared as follows.
Method
All components (except aqueous Kelzan pregel) are dispersed using a high speed mixer. The dispersion is passed through a bead mill under such conditions to achieve the desired particle size distribution and viscosity. Aqueous Kelzan pregel is added to the milled suspension.
Formulations 1 and 2 are formulations of the invention. The remaining formulations are by way of comparison. Each formulation was analysed in terms of milling performance and extent of crystallisation after 2 weeks storage at 54 °C. The results are as follows
Milling performance
Formulations 3 to 6, 13 to 18, 20 and 24 solidified during milling.
Formulations 1, 2, 7 to 12, 19, 21, 22 and 23 exhibited no milling problems.
Extent of crystallisation after storage at 54 °C
Formulations 7 to 12, 19, 21, 22 and 23 exhibited crystal growth after 2 weeks at 54°C,
this was particularly marked with 11, 19, 21 and 23.
Formulation 2 showed very slight crystallisation.
Formulation 1 showed no crystal growth.(Table Removed)

Claims
1 An aqueous SC formulation comprising a) 50 to 80% w/v pyrimethanil, b) 0.2 to
5% w/v of a polyoxyethylene-polyoxypropylene block copolymer surfactant, and
c) 0.2 to 5% w/v of a napthalene formaldehyde condensate surfactant.
2 A formulation according to claim 1 wherein component b) has a molecular
weight of 6000 to 14 000.
3 A formulation according to claim 1 wherein component b) has a molecular
weight of 9000 to 13000.
4 A formulation according to claim 1 wherein component b) contains 20 to 80%
w/w of polyoxyethylene.
5 A formulation according to claim 1 wherein component b) contains 40 to 80%
w/w of polyoxyethylene.
6 A formulation according to claim 1 wherein the molecular weight of component
b) is nominally 12000 and the amount of polyoxyethylene is nominally 70% w/w.
7 A formulation according to any preceding claim wherein component c) is a salt.
8 A formulation according to any preceding claim which also comprises a
polymethyl methacrylate-polyethylene glycol graft copolymer dispersant.
9 A formulation according to claim 8 wherein the dispersant has a molecular
weight of 20000 to 30000, in amounts of 1 to 10% w/v.
10 A formulation comprising a) approximately 60% w/v pyrirnethanil, b)
approximately 0.5% w/v of an ethenylenoxy-propyleneoxy block co-polymer
surfactant, c) approximately 1% w/v of sodium naphthalene formaldehyde
condensate surfactant, d) approximately 5% w/v polymethyl methacrylate-
polyethylene glycol graft copolymer, e) approximately 6% w/v propylene glycol
and f) approximately 37.5% w/v water.

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Patent Number

269565

Indian Patent Application Number

IN/PCT/2001/00185/DEL

PG Journal Number

44/2015

Publication Date

30-Oct-2015

Grant Date

28-Oct-2015

Date of Filing

05-Mar-2001

Name of Patentee

BAYER CROPSCIENCE GMBH

Applicant Address

BRUNINGSTRASSE 50, 65929 FRANKFURT AM MAIN, GERMANY.

Inventors:

#	Inventor's Name	Inventor's Address
1	GALIA DIMITROVA	AGREVO UK LTD., CHESTERFORD PARK, SAFFRON WALDEN, ESSEX CB10 1XL U.K.

PCT International Classification Number

A61K

PCT International Application Number

PCT/GB99/02624

PCT International Filing date

1999-08-09

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	9817354.5	1998-08-11	U.K.