AU684942B2 - Dispersing agent for solid plant-protection formulations - Google Patents
Dispersing agent for solid plant-protection formulations Download PDFInfo
- Publication number
- AU684942B2 AU684942B2 AU23345/95A AU2334595A AU684942B2 AU 684942 B2 AU684942 B2 AU 684942B2 AU 23345/95 A AU23345/95 A AU 23345/95A AU 2334595 A AU2334595 A AU 2334595A AU 684942 B2 AU684942 B2 AU 684942B2
- Authority
- AU
- Australia
- Prior art keywords
- constituent
- weight
- ethoxylated
- phenylethyl
- oxyethylene units
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
- A01N25/14—Powders or granules wettable
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of compounds
Abstract
Dispersant for solid plant health prepn. comprises: a) at least one alkali or alkaline-earth metal or ammonium lignosulphonate; b) at least one ethoxylated di- or tri-(1-phenyl ethyl)phenol, opt. sulphated, and contg. 7-20 ethylene oxide units. The (a)/(b) ratio is 95/5-70/30, pref. 90/10-75/25.
Description
1
AUSTRALIA
PATENTS ACT 1990 COMPLETE S P EC I F I C A T I O N FOR A STANDARD PATENT
ORIGINAL
S.
Name of Applicant: Actual Inventors: Address for Service: Invention Title: RHONE-POULENC CHIMIE Valerio BRAMATI, Isabelle GUBELMAN and Antonio MARCHETTO SHELSTON WATERS 60 Margaret Street SYDNEY NSW 2000 "DISPERSING AGENT FOR SOLID PLANT-PROTECTION
FORMULATIONS"
The following statement is a full description of this invention, including the best method of performing it known to us:- I I la The present invention relates to a new dispersing agent for solid plant-protection formulations, to the use of the said agent for the preparation of dispersible plant-protection granulates and to the said granulates themselves.
Solid plant-protection formulations, namely "wettable powders" and "dispersible granulates" are currently undergoing wide development because they make it possible to avoid the use of potentially toxic solvents and may be packaged in packages which are easily recyclable or in water-soluble sachets. The applicator or the user forming part of the general public is thus better protected.
Besides the plant-protection active substance, these solid formulations are made of dispersing agents, binders and wetting and disintegrating agents. They are generally obtained by pregrinding the solid active matter with the various solid additives, before preparing, by adding water, a 20 concentrated dispersion which will be subsequently C C agglomerated in a coater or in a turbosphere, or which will be extruded before being dried with the aid of a fluid bed.
At present, the dispersing agents used must *S 25 be solid; they are polymers such as lignosulphonates (sodium, calcium or ammonium salts), maleic anhydride/ isobutylene copolymers (sodium or ammonium salts), condensed phenylsulphonic acids (sodium salts) or 2 condensed naphthalenesulphonate/formaldehyde polymers (sodium or ammonium salts).
This restriction is due to the requirements of the process, which does not permit the addition of a liquid additive unless a premix in water is produced, which will be subsequently employed for the granulation.
Consequently, surface-active agents which are liquid or viscous at ambient temperature, such as ethoxylated alkylphenols or ethoxylated di- or tristyrylphenols, commonly employed as dispersing agents in liquid formulation (in particular in microemulsions, concentrated emulsions, emulsifiable concentrates or concentrated suspensions) cannot be employed. Furthermore, when these products are evaluated in solid formulations, in particular in "dispersible granulates", it is found that, besides the fact that they are difficult to process, they are not good dispersants, that is to say that they produce 20 granulates which have a mediocre dispersibility and suspensivity.
The Applicant Company has found that the association of a lignosulphonate and of some optionally sulphated, ethoxylated di- or tristyrylphenols results 25 in a dispersing agent for solid plant-protection formulations and does so with a "performance/price ratio" which is particularly advantageous.
In fact, a synergism has been found between these two types of dispersants, and this provides their mixture with dispersing properties, in the case of a good number of active substances, which are much superior to those of an (inexpensive) lignosulphonate taken in isolation, and at least close to those of the most ef 'ctive (but costly) dispersing polymers in this type of application.
The subject of the present invention is a dispersing agent for solid plant-protection formulations, characterized in that it consists: of at least one alkali or alkalineearth metal or ammonium lignosulphonate [constituent used in combination with at least one optionally sulphated, ethoxylated di- or tri(l-phenylethyl)phenol containing from 7 to fewer than 20 oxyethylene units [constituent the weight ratio constituent (a)/constituent being of the order of 95/5 to 70/30, preferably of the order 20 of 90/10 to 75/25.
The dispersing agent forming the subject of the invention may be prepared by mixing its constituents.
It is very particularly advantageous to 25 obtain this mixture in a handlable solid form, especially of a pourable powder. One means for obtaining such a powder is to spray an aqueous solution containing the two constituents and The subject of the present invention is therefore more particularly a dispersing agent in powder form, capable of being obtained by spraying an aqueous solution containing at least one alkali or alkaline-earth metal or ammonium lignosulphonate [constituent and at least one optionally sulphated, ethoxylated di- or tri(1-phenylethyl)phenol containing from 8 to fewer than 20 oxyethylene units [constituent the weight ratio constituent (a)/constituent being of the order of 95/5 to 70/30, preferably of the order of 90/10 to 75/25, in a quantity corresponding to approximately 40 to parts by weight of water per 100 parts by weight of the mixture of the two constituents. Constituents in a totally sulfated form are also particularly interesting constituents of the composition according to the invention.
Among the constituents there may be 20 mentioned Na, K, Ca, Mg and NH 4 lignosulphonates and very particularly that of Na and, for economic reasons, that of Ca.
Among the constituents there may be mentioned ethoxylated di(1-phenylethyl)phenol containing oxyethylene units ethoxylated di(1-phenylethyl)phenol containing 7 oxyethylene units sulphated ethoxylated di(1-phenylethyl)phenol containing 7 oxyethylene units ethoxylated tri(1-phenylethyl)phenol containing 8 oxyethylene units ethoxylated tri(1-phenylethyl)phenol containing 16 oxyethylene units sulphated ethoxylated tri(l-phenylethyl)phenol containing 16 oxyethylene units.
The spraying operation may be carried out in a sprayer according to techniques which are well known to a person skilled in the art; the air temperature at the entry is generally near 150-300 0 C, and that at the exit near 80-100 0
C.
The dispersing agent forming the subject of the invention is very particularly suited for the preparation of pesticide (herbicide, insecticide, fungicide) granulates, since it is preferably in the form of a flowable powder.
Another subject of the invention consists of solid plant-protection formulations, especially in granulate form, based on a solid plant-protection 20 active substance and the dispersing agent described above.
The said solid plant-protection formulations are favourably made up: of 0.01 to 90 by weight of plant-protection active S25 substance of 0.1 to 20 by weight of the dispersing agent forming the subject of the invention of 0 to 10 by weight of a disintegrating binding and/or binding agent of 0 to 10 by weight of an anticlotting agent of 0 to 10 by weight of a chemical stabilizing agent and of 0 to 50 by weight of inert fillers relative to the weight of solid formulation.
The following may be mentioned among the active substances which may be present in the said formulations: diuron linuron neburon carbaryl atrazine ametryn carboxim fentin acetate ziram manab zineb carbondazim chlorothalonil copper oxychloride By way of example there may be mentioned as: wetting agent: anionic agents such as alkylnaphthalene sulphonates, alkylbenzenesulphonates, alkylsulphosuccinates, taurates, alkyl sulphates, etc or nonionic ones such as acetylenic diols, ethoxylated alkylphenols, etc disintegrating and/or binding agent: starch, crosslinked polyvinylpyrrolidones, microcrystalline cellulose, crosslinked sodium carboxymethyl cellulose, soya polysaccharides, ion exchange resins, ethylene oxide/propylene oxide copolymers, polyethoxylated alkylphenols, etc anticlotting agent: ammonium or sodium phosphates, sodium carbonate or bicarbonate, sodium acetate, sodium metasilicate, magnesium, zinc or calcium sulphates, magnesium hydroxide, calcium chloride, molecular r r 7 sieves, sodium alkylsulphosuccinates, barium or calcium oxides, etc chemical stabilizing agent: alkaline-earth or transition metal sulphates, sodium hexametaphosphate, calcium chloride, boric anhydride, etc, inert fillers: cays, synthetic and diatomaceous silicas, calcium or magnesium silicates, titanium dioxide, aluminium, zinc or calcium oxides, calcium or magnesium carbonates, sodium, ammonium, calcium sulphates, carbon black, etc.
The said formulations may be obtained by mixing these constituents, grinding the said mixture dry, agglomeration by addition of water to the ground particles, extrusion or granulation and then drying with the aid of a fluid bed until granulates are Sobtained which have a residual moisture of the order of 0.1 to 2 by weight.
SFor a good implementation of the invention .9 the agglomeration of the ground particles is carried 20 out by adding from approximately 10 to 20 by weight o* of water relative to the weight of particles; the extrusion or granulation operation is carried out using techniques which are well known to a person skilled in the art, for example extrusion through a die, a grid, 25 etc, granulation with the aid of a coater, a turbosphere, etc.
The following examples are given by way of illustration.
Example 1 Preparation of the dispersing agent A mixture consisting of 90 parts by weight of calcium lignosulphonate and 10 parts by weight of ethoxylated tri(1-phenylethyl)phenol containing 16 oxyethylene units is introduced into 100 parts of water.
The solution obtained is introduced into a sprayer at a rate of 5 1/h, the air temperature at the entry is 300 0 C, that at the exit of the order of 90-100 0
C.
A flowable powder is obtained.
15 Preparation of the plant-protection formulation o* 6* A mixture is prepared, containing: ziram 80 by weight S- Supragil WP® 2 by weight 4 (wetting agent, sodium diisopropylnaphthalenesulphonate 20 marketed by Rh8ne-Poulenc) o*e the dispersing agent prepared above 10 by weight lignosulphonate/tri(1-phenylethyl)phenol 16 EO (90/10) starch (disintegrating agent) 8 by weight 25 This mixture is ground dry in an air jet mill; particles of size of the order of 10 to 20 pm are obtained.
The particles are next agglomerated with the aid of 18 parts of water per 100 parts of particles in a Lodige® apparatus (marketed by Lodige).
The agglomerate is then extruded through a 0.8 mm diameter die.
The granules are then dried in an Aeromatic® fluid bed (marketed by Niro) until a residual moisture of 2 of the said granules is obtained.
Dispersibility g of granules are poured into a 250-ml test tube filled with water of hardness D (342 ppm according to CIPAC standard MT-18 described in Collaborative International Pesticides Analytical Council Handbook, Vol. 1, Ed. G.R.AW 1970 The test tube is closed with a ground-glass 15 stopper and then inverted until all of the granules have disintegrated and dispersed. The number of inversions needed is noted.
The number of inversions is 5; the dispersibility is therefore good.
20 Suspensivity The suspensivity ratio of the granules in water D is determined according to CIPAC standard It is 100 25 Example 2 (comparative) Granules are prepared according to the procedure of Example 1, by using 10 of calcium lignosulphonate by itself instead of 10 of calcium I I lignosulphonate/tri(l-phenylethyl)phenol 16 EO (90/10) mixture.
The characteristics of the formulation are as follows: dispersibility: good (5 inversions) suspensivity ratio: 50 Example 3 (comparative) Granules are prepared according to the procedure of Example 1, by using 10 of sodium lignosulphonate by itself instead of 10 of calcium lignosulphonate/tri(1-phenylethyl)phenol 16 EO (90/10) mixture.
The characteristics of the formulation are as follows: 15 dispersibility: good (5 inversions) suspensivity ratio: 67 Example 4 (comparative) Preparation of the plant-protection formulation A mixture is prepared, containing: 20 ziram 80 parts by weight sodium diisopropylnaphthalenesulphonate (wetting agent) 2 parts by weight starch (disintegrating agent) 8 parts by weight This mixture is ground dry in an air jet 25 mill; particles of size of the order of 10 to 20 gm are obtained.
After introduction of 10 parts by weight of tri(1-phenylethyl)phenol 16 EO as the only dispersing 11 agent, the particles are agglomerated with the aid of 18 parts of water per 100 parts of particles in a LSdige® apparatus (marketed by LSdige).
The agglomerate is then extruded through a 0.8 mm diameter die.
The granules are then dried in an Aeromatic® fluid bed (marketed by Niro) until a residual moisture of 2 of the said granules is obtained.
The characteristics of the formulation are as follows: dispersibility: good (10 inversions) suspensivity ratio: 32 Example Preparation of the dispersing agent 15 A mixture consisting of 90 parts by weight of calcium S* lignosulphonate and 10 parts by weight of ethoxylated tri(1-phenylethyl)phenol containing 16 oxyethylene 20 units is introduced into 100 parts of water.
The solution obtained is introduced into a sprayer at a rate of 5 1/h, the air temperature at the entry is 300*C, that at the exit of the order of 25 90-100 0
C.
A flowable powder is obtained.
IV^MHHUHWHMSHHUWMHWI^-"*^^
'U6 L 12 Preparation of the plant-protection formulation A mixture is prepared, containing: diuron 85 by weight Soprophor AS/860® 5 by weight (wetting agent, ethoxylated C 0 i fatty alcohol absorbed on silica, marketed by Rh8ne-Poulenc) the dispersing agent prepared above 10 by weight lignosulphonate/tri(1-phenyiethyl)phenol 16 EO (90/10) n1 This mixture is ground dry in an air jet mill; particles of size of the order of 10 to 20 pm are obtained.
The particles are then agglomerated with the aid of 18 parts of water per 100 parts of particles, in 15 a Lodige® apparatus (marketed by Lbdige).
The agglomerate is then extruded through a S0.8 mm diameter die.
The granules are then dried in an Aeromatic® fluid bed (marketed by Niro) until a residual moisture 20 of 2 of the said granules is obtained.
The characteristics of the formulation are as follows: dispersibility: good (5 inversions) suspensivity ratio: 95 25 Example 6 (comparative) Grar'iles are prepared according to the procedure of Example 5 by using 10 of calcium lignosulphonate by itself instead of 10 of calcium 1 13 lignosuiphonate/tri (l-phenylethyl) phenol 16 EO (90/10) mixture.
The characteristics of the formulation are as follows: dispersibility: good (5 inversions) suspensivity ratio: 21 Example 7 and Comparative Example 7 The object of these examples is to compare the properties of the formulatioii according to the invention and those comprising ethoxylated alkylphenols.
The following compositions have been prepared: Composition Example 7 according Comparative to the invention example 7 DIURON (herbicide) 84 t 84 !k 15 calcium lignosulfonate/ 10 1% SOPROPHOR DSS-7N ratio 90/10 calcium lignosulfona7te! 10 !k ethoxylated sulfated raport 90/10, nonylphenol ANTAROX BO/3271%1 fillers: kaolin 2 %k 2% starch 3% Le SOPROPHOR DSS-7N is an ethoxylated sulfated distyrylphenol, neutralised by triethanolamin, under t ,he form, of an ammonium salt.
The ethoxylated nonylphenol (30 OE) is sulfated and under the form of an ammonium salt.
ANTAROX BO/327 is a C 9 -C 11 etho-propoxylated tensioactive product.
30 The lignosulf onate is a calcium salt (BRETAX®) of the ligni.n type.
S
S. S S. S S S 5555 5 5 14 The suspensivity tests are determined according to the CIPAC norm with water of hardness D.
The accelerated aging tests are deterr.ined according to the following procedure: 5 g of granules are poured into a test tube. Said tube is further immersed and maintained in a water at 70 0 C during 2 hours.
The results are indicated in the following table: Test Example 7 according Comparative to the invention example 7 Initial suspensivity 76 20 Suspensivity after the accelerated aging 71 19 test 9 9 9 o 9 99 9 9999 i I I--1
Claims (8)
1. Dispersing agent for solid plant- protection formulations, characterized in that it consists: of at least one alkali or alkaline- earth metal or ammonium lignosulphonate [constituent used in combination with at least one optionally sulphated, ethoxylated di- or tri(l-phenylethyl)phenol containing from 7 to fewer than 20 oxyethylene units (constituent the weight ratio constituent (a)/constituent being of the order of 95/5 to 70/30, preferably of the order of 90/10 to 75/25.
2. Dispersing agent in powder form, :i characterized in that it is capable of being obtained by spraying an aqueous solution containing at least one alkali or alkaline-earth metal or ammonium lignosulphonate [constituent and at least one optionally sulphated, ethoxylated di- or tri(1-phenylethyl)phenol containing from 8 to fewer than 20 oxyethylene units (constituent the weight ratio constituent (a)/constituent being 25 of the order of 95/5 to 70/30, preferably of the order of 90/10 to 75/25, in a quantity corresponding to approximately 40 to parts by weight of water per 100 parts by weight of 16 the mixture of the two constituents.
3. Dispersing agent according to Claim 1 or 2, characterized in that the constituent is Na or Ca lignosulphonate.
4. Dispersing agent according to any one of the preceding claims, characterized in that the constituent is chosen from ethoxylated di(1-phenylethyl)phenol containing oxyethylene units ethoxylated di(l-phenylethyl)phenol containing 7 oxyethylene units sulphated ethoxylated di(1-phenylethyl)phenol containing 7 oxyethylene units ethoxylated tri(l-phenylethyl)phenol containing 8 15 oxyethylene units ethoxylated tri(l-phenylethyl)phenol containing 16 oxyethylene units sulphated ethoxylated tri(l-phenylethyl)phenol containing 16 oxyethylene units. 20
5. Use of the dispersing agent forming the subject of any one of the preceding claims for the preparation of solid plant-protection formulations.
6. Plant-protection formulations based on a solid plant-protection active substance and dispersing 25 agent forming the subject of any one of Claims 1 to 4.
7. Plant-protection formulations according to Claim 6, characterized in that they consist of 0.01 to 90 by weight of plant-protection active I substance 0.1 to 20 by weight of the dispersing agent forming the subject of the invention 0 to 10 by weight of a disintegrating binding and/or binding agent 0 to 10 by weight of an anticlotting agent 0 to 10 by weight of a chemical stabilizing agent and 0 to 50 by weight of inert fillers relative to the weight of solid formulation.
8. A dispersing agent for solid plant- protection formulations, substantially as herein described with reference to Example 1, 5 or 7. DATED this 29th Day of June, 1995 RHONE-POULENC CHIMIE Attorney: RUTH M. CLARKSON Fellow Institute of Patent Attomeys of Australia of SHELSTON WAFERS S* S II ABSTRACT Dispersing agents for solid plant-protection formulations, consisting of at least one alkali or alkaline- earth metal or ammonium lignosulphonate [constituent used in combination with at least one optionally sulphated, ethoxylated di- or tri(l-phenylethyl)phenol containing from 7 to fewer than 20 oxyethylene units [constituent the weight ratio constituent (a)/constituent being of the order of 95/5 to 70/30, preferably of the order of 90/10 to 75/25. a It is capable of being prepared by spraying an aqueous solution containing the two constituents. 0 a e 15 It may be employed for the preparation of f solid plant-protection formulations (granulates). o 0e o o 00 C ~rr PaP ~s~
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9407996 | 1994-06-29 | ||
| FR9407996A FR2721835B1 (en) | 1994-06-29 | 1994-06-29 | DISPERSING AGENT FOR SOLID PHYTOSANITARY FORMULATIONS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| AU2334595A AU2334595A (en) | 1996-01-11 |
| AU684942B2 true AU684942B2 (en) | 1998-01-08 |
| AU684942C AU684942C (en) | 1998-06-25 |
Family
ID=
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3986979A (en) * | 1969-05-15 | 1976-10-19 | Westvaco Corporation | Process for making combination wetting-dispersing agent |
| US4310520A (en) * | 1977-07-30 | 1982-01-12 | Mikasa Chemical Industry Company, Limited | Solidified emulsifiable concentrate and method for application thereof |
| FR2524261A1 (en) * | 1982-04-01 | 1983-10-07 | Rhone Poulenc Agrochimie | FENARIMOL FUNGICIDE POWDER COMPOSITION |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3986979A (en) * | 1969-05-15 | 1976-10-19 | Westvaco Corporation | Process for making combination wetting-dispersing agent |
| US4310520A (en) * | 1977-07-30 | 1982-01-12 | Mikasa Chemical Industry Company, Limited | Solidified emulsifiable concentrate and method for application thereof |
| FR2524261A1 (en) * | 1982-04-01 | 1983-10-07 | Rhone Poulenc Agrochimie | FENARIMOL FUNGICIDE POWDER COMPOSITION |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0689866B1 (en) | 2003-04-02 |
| NZ272468A (en) | 1997-01-29 |
| ATE235955T1 (en) | 2003-04-15 |
| FR2721835B1 (en) | 1996-09-20 |
| DE69530146D1 (en) | 2003-05-08 |
| DE69530146T2 (en) | 2003-12-04 |
| AU2334595A (en) | 1996-01-11 |
| CA2152872A1 (en) | 1995-12-30 |
| ZA955395B (en) | 1996-02-09 |
| IL114275A0 (en) | 1995-10-31 |
| IL114275A (en) | 2000-02-29 |
| BR9502978A (en) | 1996-03-12 |
| JPH0826905A (en) | 1996-01-30 |
| EP0689866A1 (en) | 1996-01-03 |
| JP2843819B2 (en) | 1999-01-06 |
| FR2721835A1 (en) | 1996-01-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |