US 3046188 A
Description (OCR text may contain errors)
Unt ed SW Pets? Offi 3,645,188 Patented July FUNGICIDAL COMPOSITION.
s tart fia tl ana f otsam li t hw t ntari Canada, and Gunter Goezc, Koin-Bayenthal, Gcr napy Fahlherg-Lint G.:t1.b.!-l. ,Chemischc Fahrilt, Gflllldt llat1. 1],Posfiaehl tfl, Wolfenbu'tttgl, Germany) "Noprayving'. Filed July 27,1959, seam). 829,505
' If-Claims. "(Gl.167--14) i --'"I h'isinvention-relates to improvements'in the"composition'of- -'fungicidal' preparations effective in protecting plants-"agat't'tst diseus'essuch as Phytophlhora, Fu'sicladium Oercospora, Perono'spor'a and the like. More particularly it relates-to-improvements in fttgicidai composi' tions in which the constituents imparting, fungicidal properties are copper compounds supplemented by specific zinc compounds whichp roduce a synergistic effect so that the resulting composition possesses fungicidal properties greatly in excess of those attributable to the use of simi-' lar amounts of copper compounds and zinc compound sep arately.
It is well known that protection against diseases of the groups listed above may be obtained by using copper compounds; When, howeven this method is used the quantity'of coppercompounds' necessary for an effective protection of fields of some acreage is prodigious. For in-- stance, in actual'pra'cticcithas been found that the amount of afo'pper compound necessary to keep a potato field free of"Phytophthora,"spraycd only once is between 2.5 and 5.0 kg.of cupric oxychloride or l.2 and 2.4 kg. of'cup'rous oxide for'an acreage of one hectare (2.417 acres).
' It is well known that ziin'c cor'n'pounds do not possess any noticeable fungicide properties in thetnirelvesfl However, prior efforts to dimnish the amount of copper compounds necessary to effectively protect the plants from diseases mentioned above have included proposals to use acombination of zinc or zinc compounds with copper compounds in" order to produce effective parasiticidcs.
One such proposal has been to dissolve copper and zinc salts in water and to produce by means of alkaline matetials precipitateswhich are soluble to a small extent only. According to this proposition, a protective sub stance is formed which consists of a combination of basic copper and zinc sulphate. This composition, according to its 'author is said to have a synergistic effect and to pro duce a saving of copper up to 50%.
However various patents relating to this subject matter indicate that any suchsynergistic effect is not the general -rule,,but rather the exception, notod only with specific combinationsof zinc and copper compounds, and not with most combinations. For instance, in US. Patent 1,905,532 it is stated that soluble zin'c compounds damage the foliage of solanaceous plants andthe use .of basiccopper and zinc sulphate is proposed as a fungi'eide, hydratcd lime being added toreduc'e' the damage to the foliage. There is no mentiot't'of a synergistic effect and the mixture is proposed to prevent ihe'damaging effect of zinc sulphate. per so. on the plants. 1
Another proposal is set forth in US. Patent 2.051910 wherein 'the physicahproperties of copper silicate fungicides are said to be improvcd by replacing a portion of thezcopperwith zine; Lower damage to the foliage was noted without a noticeable impairment in toxicity. 2-.ln UIS. Patent'2;225,867 a specific synergistic effect is noted when zine oxide'is used in combination with copper oxide; which is not evident in the case of'othcr compounds, according to the patcntee. indeed in other combinations, the patentee reported that the use of zinc compottnds-actuallydocrcased the effectiveness of the product.
The atents; further n'ogtes j that' when other com; pounds such ajs zinc carbonate, zines-names; "gincottala tc were used plac eof iinc iotiide, tho result-s ,w'pr nerciy additiveandno synergistic effe'c tfcoiu ldbefound. 11 In stillanqther. US. Patent 2,540,209itfisstafeditl'iai zirtc s uifitejis .the only 'zinc salt 'whiehlig ive s' the desired protection against copper injury in coppcrfuogicides i s ,b f flt m -hi5. z
In summary then,. prior patents in'thisfie ld would ite nd to indicate that it is by no means recognized that cop; per and zinccompounds .ir general, when used ;in.-com bination, produce synergistic effects, and lhatone prevail ing view is that .a huge number OfliItC compounds can only be used if they canbe converted to basiccornpounds.
According to the present invcntiotra marked improve; ment in the effectiveness offungicidcscopper compounds over the improvements previously reported is obtained by the use of zinc chromate and/or zincsulphide in adnti t tut'e \vithtungicide copper compounds.
Specifically it has been found that the amount of-cop: per compounds, .such as cuprous. oxide,' copper-oxychloride, basic copper carbonate, and ,the, lik e may be re; duced by as much as 75% whcn uscd with the proper proportions of the zinc compounds specified.
Thus in the prior art above noted, the besureported results amounted to a saving of 50% of copper w,hc n,a -c om; bination of a basic copper-zinc .sulphate is. uscd,,when compared with the action of a qoppcr-sul-phate-limemlution. Howevcr,,wo have found that with a sttitttble ww per compound used in combination with zinc sulphide or zinc chromate, an unexpectedly high saving with respect to the copper compound is obtained and that only about one-fourth of the amount of copper compound heretofore deemed necessary need actually be used to effectively control the diseases mentioned.
For instance, if a copper sulphate solution with 0.75% of copper sulphate is used in order to keep p tato fields free of Phytophthora, it is necessary. according to'the accepted practice, to use about-600 liters for treutingnne hectare (2.417 acres) in order to treat .the plants. uniformly. it is therefore. necessary to expendfor each hcc tare, 4.5 kg. of copper sulphate, a figure which corresponds to 1.8 kg. of metallic copper.
However, if according to the invention-n-cotnbination of for instance, copper oxychloride and zinc sulphide is used, actual field tests have proved that/for each hectare only 600 goof copper oxychloride must be used which con tains 350 g. of metallic copper, Thisis clettrlyan effect which could not have been foreseen. The savings thus obtained are about fottr times the savings obtainable by the best method of saving so far mentioned in the literature above quoted. The savings are still greater if compared with those plant protection compoundsand. mixturcs wbich are now used and which hnv bcon endorsed officially by Governmentuuthoritics. One of these-rec ognizcd spraying means containing copperguses 2.5 kg. of copper oxychloride witlna content of 1445 kg. ofcoppor metal-for each hectare sprayed.v This is-the bcst'com pound now known whichhasfound general rocogx'ttn'om Therefore, when compared with the most modernzooppot spraying fungicide the combination according to thc in'v'ention has the advarnage that -it uses..only-oheifourth -of the copper or, otherwise stated, that a quantity equal to three times the quantity actually used can be considered as having been saved. I
A further advantage. of -thb tnvention'consists in lhe fact that the-rather cumbersome convcrsioh of the and zinc compounds into their basic stilts by m'eans of substances of alkaline reaction can be dispensed with. j A further advantage of the combination consists in the fact that no damage to the foliage results, even if the aces, 188
dosage should for some reason or other be excessive. While applicants do not want to advance any theory for this increased elfectiveness, they assume that zinc chromate as well as Zinc sulphide activate the copper compounds to a high degree. This has been deduced from experiments with other zinc compounds (e.g. with zinc carbonate) which do not produce any increase in the effectiveness of the copper salts as a fungicide.
Before illustrating this invention in the specific examples which follow, certain limiting and critical featuresdust or spray is to be applied. The relative proportions of zinc compound: copper compound in the mixture should preferably be between 1:4 and 1:8; that is, for every five parts by weight of zinc compound, between 20 and 40 parts by weight of a suitable copper fungicide should be present.
(4) Other ingredients which may be present in the composition include diluents commonly used in the preparation of sprays, pastes or dusts.
The examples which follow are intended to be taken as illustrative of the invention and not as limitative.
Example 1.Spraying Powder [Proportions in grams] g. copper oxychloride, and 5 g. zinc chromate are intimately mixed with 55 g. kaolin. In this mixture 5 g. of a higher molecular weight aliphatic sulfonic acid acting as a wetting agent and as an emulsifier such as sodium sulforicinate and 10 g. of an adhesive known as cell powder are worked.
A suspension of 3 kg. of a mixture, prepared with the above proportions indicated in grams, in 600 liters of water is prepared. This quantity is sprayed uniformly on each hectare of a potato field.
In an experimental test the potato plants on a ground parcel Were treated and those on an adjacent ground parcel were not treated by spraying. On the non-treated section the plants on account of infestation with Phytophthora died, on the sprayed section the plants remained healthy and completely free of Phytophthora.
Example 2.S praying Paste [Proportions in grams] g. copper oxychloride and 5 g. zinc sulphide are stirred and intimately and thoroughly mixed by agitation with 25 g. of a watery dispersion of polyvinylacetate, 0.5 g. animal glue powder, the latter acting as a stabilizer, and 39.5 g. of water.
The mix has the consistency of a paste and 3 kg. of this paste are suspended in 600 liters of water. This quantity is sprayed on one hectare (2.417 acres) of potato plants.
The experiment mentioned in Example 1, was also made with this mixture of Example 2.
Example 3.Spraying Paste [Proportions in grams] The same effect as that described in Examples 1 and 2 is obtained with a mix of 22 g. cuprous oxide, 5 g. zinc sulphide, 25 g. of a watery dispersion of polyvinyl propionate, 0.5 g. of animal glue serving as a stabilizer, and 47.5 g. of water which are intimately mixed to form a paste. 3 kg. of the paste suspended in 600 liters of water 4 are again the quantity sprayed for each hectare of a potato field.
Example 4.-Spraying Paste [Proportions in grams] 30 g. copper oxychloride, 5 g. zinc sulphide, are mixed intimately and thoroughly with 25 g. of a water dispersion of polyvinylacetate, 0.5 g. of animal glue and 39.5
g. of water.
In order to prevent Peronospora on hops, the hops are sprayed with a 0.5% suspension of the paste in water.
Experimental tests similar to those described in Example 1 were made on two adjacent ground parcels planted with hops. The hops on one ground parcel-was sprayed and the other left unsprayed. The hops in the untreated ground parcel were severely attacked by Peronospora while the hops which were sprayed did not show any Peronospora attack and remained healthy.
Example 5 .-Spraying Paste The spray prepared according to Example 4 was tested on beets attacked by Cercospora. A test was made exactly as described in Example 4 with the same results.
Example 6.-Spraying Powder [Proportions in grams] 20 g. of copper oxychloride, 5 g. zinc sulphide are mixed with 60 g. kaolin. Into this mix 5 g. of a higher molecular weight aromatic sulfonic acid, acting as a wetting and dispersion agent and 10 g. of powder acting as an adhesive agent were worked, until complete homw geneity was obtained. A 0.30% suspension of this spraying powder in water was sprayed on apple trees during the pre-blossoming period to prevent infestation with Fusicladium. The effect when compared with trees which had not been sprayed was very marked.
To this spray insecticides were added, especially gamma hexachlorocyclophexane and dichlordiphenyltrichlorethane.
Example 7.-Spraying Powder [Proportions in grams] 30 g. cuprous oxide, 5 g. zinc sulphide are mixed with 45 g. of kaolin. Into this mix 5 g. of high molecular weight aliphatic sulfonic acid such as sodium sulforicinate and 10 g. of an adhesive known as cell powder and 5 g. hexachlorocyclohexane are worked.
2 kg. of this spraying powder are suspended in 600 liters of water and are sprayed over 1 hectare of ground with potato plants. Infection with Phytophthora was completely prevented. The Colorado potato beetle and its larvae were completely killed by the spraying.
Example '8.-Spray Powder 35 g. basic copper carbonate and 4 g. zinc sulphide are mixed with 46 g. kaolin, 5 g. of a high molecular weight aliphatic sulfonic acid, as wetting and emulsifying agent, and 10 g. cellulose powder, as binding agent, are worked into the mixture.
3 kg. of the powder was dispersed in 600 liters of water and uniformly sprayed over one hectare of potato plants. Lots not sprayed developed a Phytophthora infection. 'Illhe sprayed lots remained healthy and free of Phytopht ora.
Example 9.Spray Paste 30 g. basic copper carbonate and 5 g. zinc chromate are stirred with 25 g. of an aqueous dispersion of polyvinyl acetate, 0.5 g. lime powder as stabilizer and 39.5 g. water.
3 kg. of this pasty mass was disposed in 600 liters of water and sprayed over one hectare of potato plants. The effectiveness against Phytophthora was the same as in Example 8.
Example 10.Spray Powder v 25 g. copper hydroxide and 5 g. zinc sulphide are mixed PF piwith 55 g. kaolin, g. of a high molecular weight aliphatic sulfonic acid, as wetting and emulsifying agent, and g. cellulose powder, as binding agent, are worked into the mixture.
Field experimentation, employing 3-6 kg. of this spray powder dispersed in 600 liters of water as a spray over one hectare of beets, produced inhibition of infection by Cercospora.
Example JL-Spray Paste 30 g. copper hydroxide and 5 g. zinc chromate are stirred with 25 g. of an aqueous dispersion of polyvinyl acetate, 0.5 g. lime powder as stabilizer and 39.5 g. water.
3 kg. of this pasty mass is dispersed in 600 liters of water and sprayed over one hectare of beets. The effectiveness against Cercospora was the same as in Example 10.
This application is a continuation-in-part of Serial No. 547,303, filed November 16, 1955, now abandoned in favor of the present application.
What is claimed as new is as follows:
1. A mixture for protecting plants against fungicidal diseases such as Phytophthora, Fusicladium, Cercospora, and Peronospora comprising for each 5 parts in weight of a zinc compound of the group consisting of zinc sulphide and zinc chromate, between and 45 parts by Weight of an insoluble fungicidal copper compound of the group consisting of cuprous oxide, copper hydroxide, copper oxychloride and basic copper carbonate; and from 3 to 12 parts by weight of kaolin.
2. A fungicidal mixture consisting essentially of 5 parts by weight of Zinc chromate and parts by Weight of copper oxychloride.
3. A fungicidal mixture consisting essentially of between 20 and parts by weight of copper oxychloride and about 5 parts by weight of Zinc sulphide.
4. A fungicidal mixture consisting essentially of zinc sulphide and basic copper carbonate in the relative proportions of about 1 part of zinc sulfide to between 4 and 9 parts of basic copper carbonate, by weight.
5. A fungicidal mixture consisting essentially of zinc sulphide and copper hydroxide in the relative proportions of about 1 part of zinc sulfide to between about 4 and 9 parts of copper hydroxide, by weight.
6. The process of controlling fungus growth of a fungus selected from the group consisting of Phytophthora, Fusicladium, Cercospora, and Peronospora on living plants which comprises applying to the plant a fungicidal composition having as an active ingredient a mixture consisting of a zinc compound selected from the group consisting of zinc sulphide and Zinc chromate and a copper compound selected from the group consisting of cuprous oxide, copper hydroxide, copper oxychloride and basic copper carbonate the relative proportions of said Zinc compound and said copper compound being between about 4 and 9 parts by weight of copper compound for each part of weight of zinc compound.
7. The method of claim 6, wherein the mixture contains between 20 and parts by weight of copper compound for each 5 parts by weight of zinc compound.
8. The method of claim 6 wherein the zinc compound is zinc chromate and the copper compound is copper oxychloride.
9. The method of claim 6 wherein the zinc compound is zinc sulphide and the copper compound is copper oxychloride.
10. The method of claim 6 wherein the zinc compound is Zinc sulphide and the copper compound is basic copper carbonate.
11. The method of claim 6 wherein the zinc compound is zinc sulphide and the copper compound is copper hydroxide.
Frear: A Catalogue of Insecticides and Fungicides (1948), vol. 1, page 173; vol. 2, pages 51, 52, 56.