AU613136B2 - Herbicidal o-carbomethoxysulfonylurea - Google Patents

Description

I :f OPI DATE 14/06/89 w AOJP DATE 20/07/89 APPLN. ID 28203 89 PCT NUMBER PCT/US88/04099 PCT INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 4 A01N 47/36, 57/20// (A01N 57/20 A01N 47:36).

(11) Interna, Publication Number: Al (43) International Publication Date: WO 89/ 04606 1 June 1989 (01.06.89) (21) International Application Number: PCT/USWI 409# (22) International Filing Date: 23 November 1988 (23.11.88) (31) Priority Application Number: 125,302 (32) Priority Date: (33) Priority Country: 25 November 1987 (25.11.87) (Desigste StesA, AT (European patent), AU, BB, SBE Eur an nt), BG, BJ (OAPI patent), BR, CF (OAPI patent), CG (OAPI patent), CH, CH (European patent), CM (OAPI patent), DE, DE (European patent), DK, FT, FR (European patent), GA (OAPI patent), GB, GB (European patent). HU, IT (European patent), JP, KP, KR, LK, LU, LU (European patent), MC, MG, ML (OAPI patent), MR (OA- 'PI patent), MW, NL, NL (European patent), NO, RO, SD, SE, SE (European patent), SN (OAPI patent), SU, TD (OAPI patent), TG (OAPI patent).

Published With international search report.

Before the expiration of the time limit for amending the claims and to be republished in the event of the receipt of amendments.

(71) Applicant: E.I. DU PONT DE NEMOURS AND COMPANY [US/US]; 1007 Market Street, Wilmington, DE 19898 (US).

(72) Inventor: CHANG, Siew, Hoong Du Pont Far East, Wisma Budiman 6th Floor, 50776 Kuala Lumpur

(MY).

(74) Agent: COSTELLO, James, E.I. du Pont de Nemours and Company, Legal Department, 1007 Market Street, Wilmington, DE 19898 (US).

(54) Title: HERBICIDAL o-CARBOMETHOXYSULFONYLUREA (57) Abstract The compound methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl] benzoate has high herbicidal activity and is particularly useful for weed control in plantation crops.

JL

1A Title HERBICIDAL O-CARBOMETHOXYSULFONYLUREA Background of the Invention The compound methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin- 2 yl)amino]carbonyl]amino]sulfonyl]-benzoate has high herbicidal activity and a desirable spectrum of weed control for use in plantation crops.

The compound of interest is disclosed in U.S. Patent 4,383,113, for uses other than weed control in plantation crops.

SUMMARY OF THE INVENTION 10 This invention pertains to the use of the compound of Formula I and its I agriculturally suitable salts for broad spectrum weed control in plantation crops.

CO

2

CH

3 2 3 O CH 3 0 N

SO

2 NHCNH O N z0: OCH 3

I

The compound is methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2- Syl)amino]carbonyl]amino]-sulfonyl]benzoate.

According to a broad form of the invention there is provided a method for controlling undesired weeds in plantation crops which comprises applying to the locus of the weeds a herbicidally effective amount of methyl 2-[[[[(4-methoxy-6methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate, the plantation crops selected from the group coffee, cocoa, oil palm, rubber, banana and citrus.

Synthesis The title compound of Formula I (metsulfuron methyl) can be prepared according to the procedure disclosed in U.S. 4,383,113 as follows: WO 89/04606 PCT/US88/04099 2 To an anhydrous suspension of 1.4 g of 2-amino- 4-methoxy-6-rnethyl-1,3,5-trjazine in 25 ml of methylene chloride is added with stirring at ambient temperature and pressure 2.4 9 of 2-,,nethoxycarbonylbenzenesulfony1isocyanate. The mixture is thereafter stirred for 16 hours and filtered. TIhe filtrate is evaporated to dryness, the residue is triturated with butyl chloride and the product removed by filtration.

WO 89/04606 PCT/US88/04099' 3 Formulations Useful formulations of the compound of Formula I can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly.

Sprayable formulations can be extended in suitable media and used at spray volumes of from a few liters to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations, broadly, contain about 0.1% to 99% by weight of active ingredient(s) and at least one of about 0.1% to surfactant(s) and about 1% to 99.9% solid or liquid diluent(s). More specifically, they will contain these ingredients in the following approximate proportions: Weight Percent* Active Ingredient Diluent(s) Surfactant(s) Wettable Powders 20-90 0-74 1-10 Oil Suspensions, 3-50 40-95 0-15 Emulsions, Solutions, (ineluding Emulsifiable Concentrates) Aqueous Suspension 10-50 40-84 1-20 Dusts 1-25 70-99 Granules and Pellets 0.1-95 5-99.9 0-15 High Strength 90-99 0-10 0-2 i Compositions Active ingredient plus at least one of a Surfactant or a Diluent equals 100 weight percent.

4 WO 89/04606 PCT/US88/04099 Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable, and are achieved by incorporation into the formulation or by tank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey, but other solids, either mined or manufactured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are described in Marsden, "Solvents Guide," 2nd Edo, Interscience, New York, 1950. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0*C. "McCutcheon's Detergents and Emulsifiers Annual," MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents," Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foaming, caking, corrosion, microbiological growth, and the like.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or Sfluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, WO 89/04606 PCT/US88/04099 December 4, 1967, pp. 147ff. and "Perry's Chemical Engineer's Handbook", 5th Ed., McGraw-Hill, New York, 1973, pages 8 to 57 and following.

For further information regarding the art of formulation, see for example: U.S. Patent 3,235,361, column 6, line 16 through column 7, line 19 and Exampies 10 through 41; U.S. Patent 3,309,192, column line 43 through column 7, line 62 and Examples 8, 12, 39, 41, 52, 53, 58, 132, 138 to 140, 162 to 164, 166, 167 and 169 to 182; U.S. Patent 2,891,855, column 3, line 66 through column 5, line 17 and Examples 1 to 4; Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961, pages 81 to 96; and 1 Fryer et al., "Weed Control Handbook", 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101 to 103.

In the following Exam;4es, all parts are by weight unless otherwise indicated.

Example 2 Wettable Powder Methyl 2-[[[[(4-methoxy-6-methyl-l,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate sodium alkylnaphthalenesulfonate 2% low viscosity methyl cellulose 2% Sdiatomaceous earth 46% The ingredients are blended, coarsely hammer- V milled and then air-milled to produce particles essentially all below 10 microns in diameter. The product is reblended before packaging.

Example 3 Granule Wettable Powder of Example 2 attapulgite granules 20 to 40 mesh; 0.84 to 0.42 mm) WO 89/04606 PCT/US88/04099 6 A slurry of wettable powder containing 25% solids is sprayed on the surface of attapulgite granules in a double-cone blender. The granules are dried and packaged.

Example 4 Extruded Pellet Methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate anhydrous sodium sulfate crude calcium ligninsulfonate sodium alkylnaphthalenesulfonate 1% calcium/magnesium bentonite 59% The ingredients are blended, hammer-milled and then moistened with about 12% water. The mixture is extruded as cylinders about 3 mm diameter which are cut to produce pellets about 3 mm long. These may be used directly after drying, or the dried pellets may be crushed to pass a U.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S. No. 40 sieve (0.42 mm openings)-may be packaged for use and the fines recycled.

Example Low Strength Granule Methyl 2-[[[[(4-methoxy-6-methyl-l,3,5-triazin-2-yl)aminolcarbonyl]amino]sulfonyl]benzoate 1% N,N-dimethylformamide 9% attapulgite granules 20 to 40 sieve) The active ingredient is dissolved in the solvent and the solution is sprayed upon dedusted granules in a double cone blender. After spraying of the solution has been completed, the blender is allowed to run for a short period and then the granules are packaged.

WO 89/04606 PCT/US88/04099 7 Example 6 Aqueous Suspension Methyl 2-[[[[(4-methoxy-6-methyl-l,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate polyacrylic acid thickener 0.3% dodecylphenol polyethylene glycol ether disodium phosphate 1% monosodium phosphate polyvinyl alcohol water 56.7% The ingredients are blended and ground together in a sand mill to produce particles essentially all under microns in size.

Example 7 Oil Suspension Methyl 2 -[[[[(4-methoxy-6-methyl-l,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate blend of polyalcohol carboxylic 6% esters and oil soluble petroleum sulfonates' xylene 59% The ingredients are combined and ground together in a sand mill to produce particles essentially all below 5 microns. The product can be used'directly, extended with oils, or emulsified in water.

Example B Granule Methyl 2 -[[[[(4-methoxy-6-methyl-l,3,5-triazin-2-yl)aminolcarbonyl]amino]sulfonyl]benzoate wetting agent 1% crude ligninsulfonate salt (containing to 20% of the natural sugars) attapulgite clay 9% WO 89/04606 PCT/US88/04099 8 The ingredients are blended and pilled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is adjusted to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized material. The fluidization and spraying are continued until granules of the desired size range are made. The spraying is stopped, but fluidization is continued, optionally with heat, until the water content is reduced to the desired level, generally less than The material is then discharged, screened to the desired size range, generally 14 to 100 mesh (1410 to 149 microns), and packaged for use.

Example 9 Hiah Strength Concentrate Methyl 2-[[[[(4-methoxy-6-methyl-l,3,5-triazin-2-yl)amino]carbonyllamino]sulfonyllbenzoate 99% silica aerogel synthetic amorphous silica The ingredients are blended and ground in a 2 0 hammer-mill to produce a material essentially all passing a U.S.S. No, 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.

Example Wettable Powder Methyl 2-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyllamino]sulfonyl]benzoate dioctyl sodium sulfosuccinate 0.1% synthetic fine silica 9.9% The ingredients are blended and ground in a hammer-mill to produce particles essentially all below 100 microns. The material is sifted through a U.S.S.

No. 50 screen and then packaged.

WO 89/04606 PCT/US88/04099 9 SExample 11 Wettable Powder Methyl [(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate sodium ligninsulfonate montmorillonite clay The ingredients are thoroughly blended, coarsely hammer-milled and then air-milled to produce particles essentially all below 10 microns in size. The material 0 is reblended and then packaged.

Example 12 Dust Methyl 2-[[[[(4-methoxy-6-methyl-l,3,5-triazin-2-yl)amino]carbonyllamino]sulfonyl]benzoate attapulgite Pyrophyllite The active ingredient is blended with attapulgite and then passed through a hammer-mill to produce particles substantially all below 200 microns. The ground concentrate is then blended with powdered pyrophyllite until homogeneous.

The compound of this invention can be specially formulated with diluents and/or carriers and/or other pesticides for application to plantation crops. The following list exemplifies some of the herbicides suitable for use in mixtures.

Common Name Chemical Name dalapon 2,2-dichloropropionic acid diuron 3-(3,4-dichlorophenyl)-l,l-dimethylurea DSMA disodium methanearsonate glufosinate 4-[hydroxy(methyl)phosphinoyl]-DL-homoalanine and its agriculturally suitable salts especially the ammonium salt WO 89/04606 Common Name glyphosate hexazinone

MSMA

paraquat triclopyr 2,4-D 2, 4 B imazapyri sop ropylammnonium picioram PCT/US88/04099 Chemical Name N-(phosphonomethyl)glycine arnd herbicidally acceptable salts especially the rono(isopropylammonium) and trixnethylsulfonium salts 3-cyclohexyl-6-(dimethyl amino) -l-methyl- ±1,3,5-triazirie-2,4 (1H,3H)dione monosodium methanearsonate 1&,Vi-dimethyl-4,4'-bipy-ridinium ion 3,5, 6-trichl.oro-2-pyridyloxyacetic acid (7,4-dichlorophenoxy)acetic acid and its agriculturally suitable salts especially the dimethyl ammnonium salt 4-(2,4-dichilorophenioxy)butyric acid 2-=(4-isopropyl-4-miethyl-5-oxo-2-imidazolin-2-yl)nicotinic acid with isopropyl amine (1:1) 4-amino-3, 5, 6-trichioropicolinic acid T- I WO 89/04606 PCT/US88/04099 11 Utility The compound employed in the method of the present invention is an active herbicide for selective broadleaf and grass weed control with safety to plantation crops such as coffee, cocoa, oil palm, rubber, banana, citrus and certain conifers.

Compound I can be applied as a preemergence or postemergence treatment using techniques of banding, directed sprays or broadcast applications. In general, the compound of this invention is used at 0.5 to 500 g/ha with a preferred rate range of 1 to 250 g/ha rate. One skilled in the art can select the proper rates for ,a given situation.

The compound of this invention may be tised in combination with other pesticides. It is particularly useful in combination with broadleaf herbicides used in plantation crops including: triazine, triazole, uracil, urea, amide, carbamate, bipyridylium, phenoxys, sulfonylurea and imidazolinone types.

2 The preferred mixture for use in plantation crops includes glyphosate and its agriculturally suitable salts.

The herbicidal properties of the subject compound were discovered in field tests conducted as described below.

Test A This test was conducted in the field with the postemergence spraying of circles around oil palm.

The weed species, Calopooonium caerulium IA) Mikania Smicrantha BII and Paspalum coniugatum IL ranged in height from 10-20 cm up to mature plants and were sprayed with Compound I or its mixtures with Compounds II and III, dissolved in a nonphytotoxic solvent containing a surfactant. The degree of weed control WO 89/04606 12 PCT/US88/04099 was visually rated 0 to 125 days after treatment. The control ratings are averages of the readings and are expressed on a scale of 0 to 100 where 0 no effect, minimal control and 100 complete control. The results are summarized in Table A.

Compound II 1,1'-dimethyl-4,4'-bipyridinium ion Compound III mono(isopropylammonium)N-(phosphonomethyl)glycine Weed Control in Oil P1_m Treatment Average Control Rincf Compound A I 1(10) II (990) 99 48 41 75 1.4 0 I(II) III (615) 91 40 61 1(20) II (990) 100 60 36 1(20) 90 1.2 0 1(20) III (615) 97 41 This test was conducted in the field with the postemergence spraying of strips in rubber. The weed species Boreri.a latifolia, Cjlidemi hir±A, Dicranopteri inaAri E; atpr tium a~ aitvn, Euhorbip heterophylla, mhJ t EAcvlin dri Lantanh ZmAMA r, Melastona Lalabathr~uo e, Nehrlal is bisexrat.a and Pennisetum .edicellatum ranged in height from 10-20 cm up to mature plants and were sprayed with Compound I or its mixtures with Compounds II and III, dissolved in a nonphytotoxic solvent containing a surfactant.

The degree of weed control was visually rated 0 to 125 days after treatment. The control ratings are

-"T

I i WO 89/04606 PCT/US88/04099 averages of the readings and are expressed on a scale of 0 to 100 where 0 no effect, 20 minimal control and 100 cLmplete control. The results are summarized in Tables B to K.

Compound II 1,1'-dimethyl-4,4'-bipyridinium ion Compound III mono(isopropylammonium)N-(phosphonomethyl)glycine Treatment Compound (a/hal I (15) I (15) II (55( I (15) III (1: I (15) III (6; I (15) III (8z I (20) I (20) II (55 I (20) III (1i I (30) I (30) II (55 I (30) III (1.

I (40) I (40) II (55C I (40) III (12 I (90) 0) 25 25 0) 25 25 Weed Control in Rubber Averace Control Rating hauxiea latifolia 97 96 94 I) 84 98 0) 97 83 98 0) 99 83 99 99 83

L

h WO 89/04606 PCT/US88/04099 14 Table C Weedontol n Rbbe Treatmen Compound (W/ha) 1 (10) 1 (10) II (990) 1 (20) 1 (20) 11 (990) I (40) i (40) 11 (990) I (5) 1 II "(090) Average Control Rating ClidemiA hirti 71 69 78 96 87 Wel n be Weed Conttsrol in Rupbl=f Treamine-mmk Combound (g/ha 1 (10) 11 (445) 1 (10) I (20) II (445) I (20) Avgrae Contro. Ratine icrannters UP&UJAa~f~ 96 97 58 otol E Weed Cgnt~ol in :RubbeX Tre tment 1 (1p) 1 (10) 1I (990) 1 (15) I (15) III (615) 1 (20) 1 (20) 11 (990) I (20) II (615) 1 (25) I (30) 1 (30) III (615) 3 (35) 1 Avex-e Control Rating gdorgtum 29 67 34 56 69 48 47 WO 89/04606 PCT/US88/04099 Table F Weed Control in Rubber Average Control Ratin Treatment Compound (o/hal I (15) I (15) II (55( I (15) III (1; I (15) III (6; I (15) III (8: I (20) I (20) II I (20) III (1; I I (30) II I (30) III (12 I I (40) II I (40) III (12 I 0) 250) 25) 35) 250) Euphorbia heterophylla 61 88 77 48 Table G Weed Control in Rubber Treatment Compound (g/ha) I I (15) II (550) I (15) III (1250) I I (20) II (550) I (20) III (1250) I I (30) II (550) I (30) III (1250) I I (40) II (550) 2 (40) III (1250) Average Control Rating Imperata cvlindrica WO 89/04606 WO 8904606PCT/US88/04099 16 Weed-Control in Rubber Compound (g/ha) 1 (10) 1 (20) Treatment Compound (g/ha) 1 (10) 1 (10) 11 (990) 1 (20) 1 (20) 11 (990) I. 1 (40) Average Contrgl.B.atia Lantana, camizr 93 98 lable I Weed Control in Rubber Averae CgntxYQlRinqj ieastom., malabathriu 94 73 97 8l 98 Weed Control in.Laubb~x Cgmpound (a/ha) 1 (10) 11 (445) 1 (10) 1 (20) 11 (445) I (20) Averace ontrol Ratin NevhLe~ia bisrrat 92 48 92 62 WO 89/04606 WO 8904606PCT/US88/04099 Treatmnt Compgund (a/ha) 1 1(15) 1 (15) 11 (55( I C (15) III G1; 1 (20) 1 (20) II (55C 1 (20) 111 (1: 1 (30) 1 (30) 11 (55( 1 (30) 111 (1; 1 (40) is (40) 11 (55c 1 (40) 111 (1: Table K Weed Control in Rubber Average Control Rating pennistu pgdicellatuzn 68 ~50) ~50) ~50) Z50) 97 100 66 96 100 62 82 100 56 99 100

Claims (6)

1. A method for controlling undesired weeds in plantation crops which comprises applying to the locus of the weeds a herbicidally effective amount oi methyl 2 -[[[[(4-methoxy-6-methyl-1,3,5-triazin-2- yl)amino]carbonyllamino]sulfonyl]benzoate, the plantation crops selected from the group coffee, cocoa, oil palm, rubber, banana and citrus.

2. A method according to claim 1, wherein the plantation crop is coffee.

3. A methGd according to claim 1, wherein the plantation croup is rubber or oil palm.

4. A method according to claim 1, wherein the plantation crop is banana.

5. A method according to claim 1, wherein mono-(isopropylammonium)N- (phosphonomethyl)glycine is included in admixture with methyl 2-[[[[(4-methoxy-6- methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]-sulfonyllbenzoate.

6. A method for controlling undesired weeds in plantation crops which method is substantially as herein described with reference to any one of the Examples but excluding the Comparative Examples. S 5* 0 0 5 S@ S S. S S 5 1. DATED this 9th day of April 1991. E.I. DU PONT DE NEMOURS By their Patent Attorneys: CALLINAN LAWRIE 3 a-L- 2 II -1 INTERNATIONAL SEARCH REPORT International Application No PC/US 88/04099 I. CLASSIFICATION OF SUBJECT MATTER (it several classification symbols apply, Indicate all) P-T/U 88- /04099 According to International Patent Classification (IPC) or to both National Classification and IPC IPC :A 01 N 47/36; A 01 N 57/20; 01 N 57/20, 47:36) II. FIELDS SEARCHED Minimum Documentation Searched I Classification System Classification Symbols IPC IC4 A 01 N t i Docurtlentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched 0 III. DOCUMENTS CONSIDERED TO BE RELEVANT* Category Citation of Documen', ii with indication, where appropriate, of the relevant passages 2 Relevant to Claim No. X US, A, 4379717 LEVITT et al.) 1,5,7,8 12 April 1983 see column 1, lines 34-54; column 2, lines 1,4,5,36-45 X US, A, 4383113 LEVITT) 1-9 May 1983 see claims 27,51,59; column 94, lines 38-41; column 95, line 61; column 97, lines 20-33 cited in the application I Special categories of cited documents: to later document published after the International filing date document defining the general state of the art which is not or priority date and not in conflict with the application but considered to be of particular relevance cited to understand the principle or theory underlying the invention earlier document but published on or after the International document of particular relevance: the claimed invention cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or Involve an Inventive step which Is cited to establish the publication date of another document of particular relevance; the claimed invention citation or Other special reason (as speified) cannot be considered to involve an inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvlous to a person skilled document published prior to the international filing date but in the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Search Report 3rd March 1989 "1 0. f 89 International Searching Authority EUROPEAN PATENT OFFICE -Jr-TcGYNr R PUTLFI Form PCTIISA/210 (second sheet) (January 1915) ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. US 8804099 SA 2594.5 This annex lists the patent family members relating to the patent documents cited in the ao o'metied international search report. The members are as contained in the European Patent Office EDP ile on 30/03/89 The European Patent Office is in no way liable for these particulars which are merely giv.en for the,purpose of information. Patent document Publication [Iatent family Publihcation cited in sear-ch report date member(s) date US-A- 4379717 12-04-83 None US-A- 4383113 10-05-83 EP-A, B JP-A- AU-A- CA-A- US-A- AU-B- AT-B- US-A- US-A- US-A- US-A- EP-A, B US-A- EP-A, B CA-A- AT-B- JP-A- AU-B- CA-C- US -A- AU-A- US-A- U S-A- US-A- US-A- US-A- 0030138 56090068 6479280 1150255 4394506 534499 E7840 4545808 4592978 4627873 4689072 0007687 4238621 0046626 1129857 371668 55013266 530575 1199033 4687507 4754579 4536576 4564384

4591.378 4647303 4721520 10-06-81 21-07-81 0 1-10-81 19-07-83 19-07-83 02-02-84 15-06-84 08-10-85 03-06-86 09-12-86 25-08-87 06-02-80 09-12-80 03-03-82 17-08-82 25-07-83 30-01-80 2 1-07-83 07-01-86 18-08-87 03-01-80 20-08-85 14-01-86 27-05-86 03--03-87 26-01-88 06 M For more details about this annex :see Official Journal of the European Patent Office, No. 12/82