Betydningen af svampemidlernes formulering samt ... · PDF fileplays a key role in the field the performance and the market success 06/09/ 2012 Dr. Murat Mertoglu ... boscalid 250

Formulation Technology Dr. Murat Mertoglu Denmark, September 6, 2012

Outline

Definition of formulation

Formulation types

Requirement of formulations

Delivery of actives to target vs. formulation

Exercise: lets chose a formulation type

Future trends: more sustainable formulations

Summary

2 06/09/ 2012 Dr. Murat Mertoglu (BASF SE)

What Does the Term “Formulation” Mean?

Definition: Formulation is the process of converting

an active ingredient (or technical-

material) into an applicable product.

Cheese

Cake

Flat

Cake

You cannot get a good product only by using good active ingredients, formulation also plays a key role in the success of a product on the field!


Formulation Technology

Codes of Plant Protection Products

Code Description

EC Emulsifiable concentrate

SL Soluble concentrate

DC Dispersible concentrate

SC Suspension concentrate

SE Suspoemulsion

FS Flowable concentrate for seed treatment

OD Dispersion in oil

EW Emulsion, oil in water

ME Microemulsion

CS Capsule suspension

WG Water dispersible granule

WP Wettable powder

International coding

http://www.croplife.org

Search for:

„Technical Monograph No2“

63 codes

(+ 29 abandoned)


Choice of Formulation Type

biological efficacy

– systemic, and/or contact

intrinsic physical and chemical properties

– liquid/ solid, melting point, solubility, stability, volatile, etc....)

type application (herbicide, insecticide, fungicide)

type of crop (cereals, specialty crop…)

regulatory

– eye tox, tank mix additive, smell, drift

packaging ( 5 lt, 10, 50 lt, 1000 lt)

plays a key role in the field the performance and the market success


Simple Classification


Simple Classification


Liquid Formulation

dilute

in water

X 400

EC (ME) emulsion

DC a.i. particles

< 150 nm

SL a.i.

dissolved


Liquid Formulation

a.i.+ solvent

solvent a.i. crystal

water

dilute

in water

X 400


Typical additives for continuous phase water

SC, SE, EW

─ dispersing agent,

─ antifreeze,

─ thickener,

─ bactericide,

─ antifoaming agent

─emulsifier

─solvent,

─adjuvants (to improve spreading,

uptake, retention),

─crystallization inhibitors,

─stabilizers (buffer, antioxidant, etc..)

10 Dr. Murat Mertoglu (BASF SE) 06/09/ 2012

+ +

+

+

+ -

- - - -

- - -

+ + + +

+

+ +

+

+

+ -

- - - -

- -

- +

+ + +

+

+

+ + +

+ +

+

- -

-

- - -

- +

+ + +

+ +

+

-

- -

- - -

-

a) steric b) electrostatic c) electrostatic + steric

stabilization

Confidential 11

12x weeks

at 40°C

12x weeks

at 40°C

Particle size

distribution d90 (µm)

without

d90 (µm)

with 2%

initial 3.4 3.3

after 12 weeks 10.3 5.0

CH2

O

OH

*

CH3

CH2

CH2

CH

*

RO

O

CH3

CH3

n

n

n

boscalid 250 g/l

antifreeze 70 g/l

dispersing agent a 20 g/l

dispersing agent b 30 g/l

antifoam 5 g/l

thickener 2 g/l

bactericide 2 g/l

inhibitor 2 g/l

water add 1 lt

no crystal growth with polymer, and so no nozzle blockage

Typical additives for continuous phase water

Inhibitor polymer

Typical additives for continuous phase solvent

EC, DC, OD,

─ solvent

─ emulsifier

─ dispersing agent,

─ thickener

─ adjuvants (to improve spreading, uptake, retention),


+ +

+

+

+ -

- - - -

- - -

+ + + +

+

+ +

+

+

+ -

- - - -

- -

- +

+ + +

+

+

+ + +

+ +

+

- -

-

- - -

- +

+ + +

+ +

+

-

- -

- - -

-

a) steric b) electrostatic c) electrostatic + steric

stabilization

Requirements for Liquid Formulations

Active loading 100g- 500 g /lt (in general)

Viscosity < 200 mPa/s

Chemical stability:

– maximum 5 % a.i. Decomposition allowed

– For 2 years and 8 weeks at 40°C

Physical stability

– at ambient temperature for 2- 3 years

– at 0°C to 40 °C for several day

30 µm 30 µm

Crystal

growth

30 µm

Flocculation Concentate

30 µm

Coalescence Phase

separation

X


Dry (solid) Formulations

spontaneous

dispersibility

is requested!

Limited number additives technology intensive

Low cost of goods Relatively higher production cost !


Delivery Properties

Structure of particles Absorption

Penetration

Retention or Anti-bouncing Spraying

Uptake

Fixation

Static surface tension

Evaporation / Adhesion

Wetting

Dynamic surface tension

Distribution

Contact angle

Spreading

An effective active and a stable formulation are not alone enough!


the smaller are the size of droplets, the larger is the drift problem!

Drift Reduction

Spraying (Atomization)


Retention (Deposition)

R Rioboo et al. (2001). Outcomes from a drop impact on solid surfaces. At. Sprays 11:155–65

Retention

sprayed pesticide droplets must remain on the plant!


Retention Improvement via Formulation

Epoxiconazole (SC) Epox.(SC) + Metco (EC) Epox. + Metco. (EC)

Source de

lumière

Générateur de

gouttelettes

Support

d’échantillon

Caméra: 250.000

prises/seconde

0

100

200

300

400

500

WaterSC (1) EC(1+2)

Sp

ray R

ete

nti

on

%


1s 10s 60s

Contact Angle


Spreading

spreading is particularly important for contact fungicides

Water SC

Sp

read

ing

SE


2000 : 1 5000 : 1

better contact with leave surface: good for uptake & rain fastness

Adhesion REM Pictures Structure of particles


waxy layer and the cuticle barrier for active ingredient uptake

Cuticle Epicuticular wax

Barriers for Uptake of A.I.

Transverse section of a wheat leaf

Epicuticular waxes

Cuticle with

embedded waxes

Epidermal cells

“on leaf”

“in waxy layer”

“in leaf” (uptake)

Epidermal cell

Absorption


Through the Barrier

after M. Riederer, Würzburg

a.i. diffusion path without adjuvant a.i. diffusion path with adjuvant

Special adjuvants and/or solvents opens channels in crystalline wax layer

Uptake depends:

on plant type

intrinsic mobility of active

used solvents and/or adjuvants (non ionic surfactants: fatty

alcohol alkoxylated)

Absorption


0 2 4 6 10 12 14 18 20 days 16 8

septoria tritici

No efficacy with fungicides Curative action Preventative action

spore-germination infection mycelial growth sporulation pycnidia

green leaf tissue chlorosis dry lesion + pycnidia

conazole

carboxamide

Superficial

hyphal

growth

Penetration

Sub-

epidermal

runner

hyphae

Latent

myce-

lium

Necro-

trophic

myce-

lium

Spore

germination

Pycnidium

formation

Cirrhus

production &

spore extrusino

It could be used effectively within 12 days after an infection to save the plants!

Formulation Development Exercise!


Actives: boscalid + epoxiconazole + pyraclostrobin

Chose formulation type, but consider requirements & intrinsic

properties!

– uptake of epoxiconazole & pyraclostrobin: apply molecularly

dissolved form + adjuvant

– spreading of boscalid on the surface

– boscalid is not soluble in registered solvents

– pyraclostrobin has low melting point

– pyraclostrobin & boscalid: not compatible with adjuvants;

crystallization

– rain fastness



1stactive (a.i.)

solvent

2ndactive (a.i.)

water EC solution of

a.i in solvent

EW emulsion of

dissolved a.i in water

ME micro -

emulsion

SC dispersed a.i.

(crystalline in water

SE combination

of SC + EW

OD dispersion of

crystalline a.i in solvent

SL solution of

active in water



Formulation Development Exercise

Pseudo= OD+ EC

Pseudo OD fulfills all requirements for maximum biological efficacy!

EC solution of

a.i in solvent

+

OD dispersion of


=

water

OD

dilution

OD dispersion of


1stactive (a.i.)

solvent

2nd (a.i.)+Solvent

Boscalid

conazole

+ strobin.

OD


Formulation Development Ex.

OD vs. Tank Mix (SC + SE)

Uptake

OD provided improved uptake of epoxiconazole and pyraclostrobin


91

9

63

37

66

34

0

20

40

60

80

100

wash uptake

%

Boscalid (SC) + Pyrac.&Epoxi. (SE)

boscalid epoxiconazole pyraclostrobin

90

10 21

79

52 48

0

20

40

60

80

100

wash uptake

%

OD

boscalid epoxiconazole pyraclostrobin

Improved spreading for boscalid : better spreader in formulation


Spreading

Spreading ~ 120 % Spreading > 1000%


Rain Fastness

Via quantitative Determination of A.I. Uptake

new methods: quantitative determination of un-labeled a.i.s.

Analysis with LC-MS-MS

Drying Time

typically 1h

Application

Irrigation

Drying over night

Collection of leaves

not irrigated

irrigated

Drying over night

Collection of leaves

Active in&on leaf

Active in&on leaf


90

0

0

0 50 100

Untreated

OD

Tank Mix

85

7

7

0 50 100

80

0

6

0 50 100

without irrigation 15 min after application (20mm)

60 min after application (20mm)

• Glasshouse test brown rust

3 days curative: Application 3 days after inoculation


Rain Fastness

Improved as rain fastness with = right formulation type for this mixture!

% brown rust attack


Future: more sustainable pesticides formulations

More convenient for farmer

No compromise on performance

Less chemical /ha

Chemicals with better profile

More profitable


Description of Technical Target

Perf

orm

ance

Sustainability

Typically EC

Typically SC

Free from critical

solvents & inerts

High performance Target


More Sustainable Formulation Example

Epox. Metc. Mixture with Tailored Polymer

Polymer CP 633, custom made for conazoles, partially replace solvents

30% more azole loading: 2 lt/ha instead of 3 lt/ha

– co-solvent, dispersing agent, adjuvant, retention improver,

beter rain fastness

with

CP633 without

CP633

Pe

rfo

rman

ce

Sustainability

Target

Enhanced bio-availability Performance

Less solvents Sustainability

Boost formul. properties Efficiency

Reduced volume Convenience


35

A.I. element

Hydrophilic element

Lipophilic element

Active ingredients

A.I. element

Hydrophilic element

Lipophilic element

Active ingredients

Diluted in water

How does polymer CP 633 works!

Polymer at least with three different functional groups 35 06/09/ 2012 Dr. Murat Mertoglu (BASF SE)

Conazole Mixture in Polymer EC

Quick uptake allows strong curative action and excellent rain fastness


Authorities:

tox & ecotox

profile

Customer:

Effective Product

Marketing:

Profitable product

Formulation

•Stability,

•Drift,

•Retention,

•Spreading,

•Uptake,

•Rain Fastness

•Tox & Ecology

•Efficacy

•Cost

• Manufacturing

•IP

•Stability,

•Drift,

•Retention,

•Spreading,

•Uptake,

•Rain Fastness

Different properties are improvable, but no perfect

formulation superior in all properties exists!

Good formulations are the ones that finds the best compromise among needs of customers, authorities, environment, and producers!


Backup Slides!


Bead milling: basis for SC, SE, OD, etc…

Active ingredients

Formulants

Water

Bead mill

1. Rotor 2. Inlet 3. Grinding beads 4. Cooling jacket 5. Separation system

~ 200 µ ~ 80 % <2 µ

bead mill

SC

EC

SE

Beads


Active ingredient

+ formulants

+ water

Wet milling

Drying air Exhaust air

Suspension

Dry (solid) Formulations

Wetable Granulate (WG) Fluidized bed granulation


Documents

Betydningen af svampemidlernes formulering samt ... · PDF fileplays a key role in the field the performance and the market success 06/09/ 2012 Dr. Murat Mertoglu ... boscalid 250