US2848297A - Manganese ethylenebisdithiocarbamate stabilized by desiccant; method and package - Google Patents
Manganese ethylenebisdithiocarbamate stabilized by desiccant; method and package Download PDFInfo
- Publication number
- US2848297A US2848297A US385687A US38568753A US2848297A US 2848297 A US2848297 A US 2848297A US 385687 A US385687 A US 385687A US 38568753 A US38568753 A US 38568753A US 2848297 A US2848297 A US 2848297A
- Authority
- US
- United States
- Prior art keywords
- desiccant
- ethylenebisdithiocarbamate
- container
- package
- stabilized
- 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.)
- Expired - Lifetime
Links
- 239000002274 desiccant Substances 0.000 title claims description 27
- 238000000034 method Methods 0.000 title claims description 9
- YKSNLCVSTHTHJA-UHFFFAOYSA-L maneb Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S YKSNLCVSTHTHJA-UHFFFAOYSA-L 0.000 title claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 3
- 239000012990 dithiocarbamate Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 23
- 230000000855 fungicidal effect Effects 0.000 description 15
- QRNATDQRFAUDKF-UHFFFAOYSA-N 2-carbamothioylsulfanylethyl carbamodithioate Chemical compound NC(=S)SCCSC(N)=S QRNATDQRFAUDKF-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 6
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 5
- AWYFNIZYMPNGAI-UHFFFAOYSA-N ethylenebis(dithiocarbamic acid) Chemical compound SC(=S)NCCNC(S)=S AWYFNIZYMPNGAI-UHFFFAOYSA-N 0.000 description 5
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- AMHNZOICSMBGDH-UHFFFAOYSA-L zineb Chemical compound [Zn+2].[S-]C(=S)NCCNC([S-])=S AMHNZOICSMBGDH-UHFFFAOYSA-L 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
- A01N47/14—Di-thio analogues thereof
Definitions
- This invention relates to fungicidal compositions comprising a metal salt of ethylenebisdithiocarbamic acid. More particularly, it relates to methods for protecting such compositions from oxidation in closed containers and to the resulting packaged compositions so protected.
- Metal ethylenebisdithiocarbamates have in general fungicidal properties. Two members of the class, namely manganous ethylenebisdithiocarbamateand zinc ethylenebisdithiocarbamate, are currently marketed commercially and used effectively for the control of a wide variety of plant attacking fungi. Manganous ethylenebisdithiocarbamate and fungicidal compositions containing it are described and claimed in U. S. Patent 2,504,404.
- metal ethylenebisdithiocarbamates are relatively unstable on storage.
- a serious problem has existed heretofore in marketing manganous ethylenebisdithiocarbamate fungicidal compositions, and to a significant though lesser extent in marketing zinc ethylenebisdithiocarbamate fungicidal compositions, because these compounds tend to decompose relatively rapidly on storage in conventional shipping containers such as multi-wall bags, fiber drums, glass bottles, and the like.
- metal ethylenebisdithiocarbamate fungicidal compositions can be protected against decomposition in closed containers by including within the container a minor amount of a desiccant.
- the mechanism of the protective action provided by the desiccant is not understood.
- the result is unexpected since available evidence shows that the decomposition in packaged material not containing a desiccant is relatively independent of the breathing properties of the package and thus the humidity in the air surrounding the package, and since it has also been found that there is relatively little change in the free-moisture content of stored packaged material whether or not it is protected by a desiccant according to this invention.
- desiccant as used herein with reference to the protective agent is employed in the conventional sense to describe a material that will pick up water if exposed to humid conditions. Such materials are also sometimes called hygroscopic materials or agents. Illustrative of such materials are calcium bromide, zinc bromide, calcium chloride, anhydrous copper sulfate, anhydrous sodium sulfate, low temperature fired alumina, and silica gel. These and other desiccants which will be apparent to those skilled in the art can be used in preparing the packaged compositions of the invention.
- the metalethylenebisdithiocarbamate-containing fun-- gicidal composition employed in practicing the methods of the invention canbe unformulated metal ethylenebisdithiocarbamate or formulated material.
- manganousethylenebisdithiocarbamate or other metal ethylenebisdithiocarbamate can be admixed with adjuvants, carriers or other biologically active materials as desired as is disclosed in S. Patent 2,504,404.
- the desiccant is included within the container for the metal ethylenebisdithiocarbama-te fungicidal composition in any convenient manner; placing one or more small porous paper or fabric bags containing the desiccant within the container for the fungicidal composition.
- the desiccant can be placed in any other convenient receptacle adapted for avoiding direct contact of the metal ethylenebisdithiocarbamate composition without preventing vapor passage; if multi-wall bags are used forpackaging the fungicidal composition, the desiccant can, for example, be placed between the walls of the multi-wall bag.
- the desiccant can be directly admixed with the fungicidal composition prior to packaging or it can be introduced loosely in the packaging container before, during, or after introduction of the fungicidal composition.
- the amount of desiccant employed in the methods and packaged materials of the invention can be varied rather widely depending upon the relative action of the desiccant used and the period and temperature of storage for which protection is to be required. In general, the desiccant will amount to from about 2 to 15% by weight based on the weight of the composition which is packaged.
- a method for protecting manganese ethylenebisdithiocarbamate from decomposition on storage in a closed container which comprises including Within the container a minor amount of a desiccant, suflicient to stabilize the dithiocarbamate.
- a package comprising a closed container, manganese ethylenebisdithiocarbamate disposed within said container and a minor amount of a desiccant, sutficient to stabilize the dithiocarbamate.
- a package comprising a closed container, manganese ethylenebisdithiocarbamate disposed within said container and from 2 to 15% by weight base on the manganese ethylenebisdithiocarbamate of anhydrous cupric sulphate.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Storage Of Fruits Or Vegetables (AREA)
- Packages (AREA)
Description
United States Patent 2,848,297 MANGANESE E'IHYLENEBISDITHIOCARBAMATE STABHJIZED BY DESICCANT; METHOD AND PACKAGE Sanford J. Hill, Wilmington, DeL, assignor to E. I. du,
This invention relates to fungicidal compositions comprising a metal salt of ethylenebisdithiocarbamic acid. More particularly, it relates to methods for protecting such compositions from oxidation in closed containers and to the resulting packaged compositions so protected.
Metal ethylenebisdithiocarbamates have in general fungicidal properties. Two members of the class, namely manganous ethylenebisdithiocarbamateand zinc ethylenebisdithiocarbamate, are currently marketed commercially and used effectively for the control of a wide variety of plant attacking fungi. Manganous ethylenebisdithiocarbamate and fungicidal compositions containing it are described and claimed in U. S. Patent 2,504,404.
Unfortunately, metal ethylenebisdithiocarbamates are relatively unstable on storage. Thus a serious problem has existed heretofore in marketing manganous ethylenebisdithiocarbamate fungicidal compositions, and to a significant though lesser extent in marketing zinc ethylenebisdithiocarbamate fungicidal compositions, because these compounds tend to decompose relatively rapidly on storage in conventional shipping containers such as multi-wall bags, fiber drums, glass bottles, and the like.
It has been found, for example, that commercial formulations containing initially about 70% by weight of manganous ethylenebisdithiocarbamate packaged and closed for shipment in containers such as mentioned above lose from to 50% by weight of the manganous ethylenebisdithiocarbamate content over a six-month period (February-July) under normal storage conditions, with losses in the higher part of the range occurring in relatively Warm areas such as the Gulf Coast of the United States, and lesser losses for example in the New York City area.
It has now been found according to this invention that metal ethylenebisdithiocarbamate fungicidal compositions can be protected against decomposition in closed containers by including within the container a minor amount of a desiccant. The mechanism of the protective action provided by the desiccant is not understood. The result is unexpected since available evidence shows that the decomposition in packaged material not containing a desiccant is relatively independent of the breathing properties of the package and thus the humidity in the air surrounding the package, and since it has also been found that there is relatively little change in the free-moisture content of stored packaged material whether or not it is protected by a desiccant according to this invention.
The term desiccant as used herein with reference to the protective agent is employed in the conventional sense to describe a material that will pick up water if exposed to humid conditions. Such materials are also sometimes called hygroscopic materials or agents. Illustrative of such materials are calcium bromide, zinc bromide, calcium chloride, anhydrous copper sulfate, anhydrous sodium sulfate, low temperature fired alumina, and silica gel. These and other desiccants which will be apparent to those skilled in the art can be used in preparing the packaged compositions of the invention.
The metalethylenebisdithiocarbamate-containing fun-- gicidal composition employed in practicing the methods of the inventioncanbe unformulated metal ethylenebisdithiocarbamate or formulated material. For example, manganousethylenebisdithiocarbamate or other metal ethylenebisdithiocarbamate can be admixed with adjuvants, carriers or other biologically active materials as desired as is disclosed in S. Patent 2,504,404.
In practicing the processes of' the invention, the desiccant is included within the container for the metal ethylenebisdithiocarbama-te fungicidal composition in any convenient manner; placing one or more small porous paper or fabric bags containing the desiccant within the container for the fungicidal composition. Instead of-plaeihg the desiccant in a small bag, it can be placed in any other convenient receptacle adapted for avoiding direct contact of the metal ethylenebisdithiocarbamate composition without preventing vapor passage; if multi-wall bags are used forpackaging the fungicidal composition, the desiccant can, for example, be placed between the walls of the multi-wall bag.
Alternatively if care is taken to avoid the use of a desiccant which is reactive with the metal ethylenebisdithiocarbamate or other components of the fungicidal composition, the desiccant can be directly admixed with the fungicidal composition prior to packaging or it can be introduced loosely in the packaging container before, during, or after introduction of the fungicidal composition.
The amount of desiccant employed in the methods and packaged materials of the invention can be varied rather widely depending upon the relative action of the desiccant used and the period and temperature of storage for which protection is to be required. In general, the desiccant will amount to from about 2 to 15% by weight based on the weight of the composition which is packaged.
In order that the invention may be better understood, the following examples are given in addition to the examples already given above.
Commercial manganous ethylenebisdithiocarbamic fungicidal compositions were placed in various kinds of contained as shown in the tabulation below and stored in a warehouse for six months. Finely divided anhydrous cupric sulfate was included as the desiccant in each container in which compositions were packaged according to this invention. The cupric sulfate was contained within a cloth pack which was enclosed in the container, the amount of cupric sulfate used being shown in the table as percent desiccant and said percentage being based on the amount of packaged manganous ethylenebisdithiocarbamate fungicidal composition in the container. In each case there was a control, that is,
a like packaged composition in which the cupric sulfate was omitted.
Percent Manganous Ethylenebisdithio- Percent earbamate Example Container Desiccant As After Packed Six Months 50 1b., 5 ply multiwall paper 5.5 74.7 68.7 bag with asphalt vapor bar- None 74. 7 58.2 rier. 251b. fibre drum with asphalt 2.1 75.1 68. 7 vapor barrier. None 74. 7 60. 2 3 1b., 2 ply paper bag with 13.2 74.7 68.2 vapor barrier. None 74.7 56. 5 3 1b., 2 ply paper bag with 5 13.2 74.7 68.7 mil. polyethylene liner. None 74. 7 60.6
One relatively simplemanner involves It will be seen from the above examples that the decomposition rate in packages not containing the desiccant was from two to three times as great as the decomposition rate in compositions packaged according to this invention. The analyses for manganous ethylenebisdithiocarbamate given in the above table were determined according to the carbon disulfide evolution method as described by W. K. Lowen, Journal of the Association of Ofiicial Agricultural Chemists, May 1953, page 484 et seq.
The invention has been illustrated in the detailed examples with specific reference to manganous ethylenebisdithiocarbamate because the decomposition problem is acute with that material, and with reference to cupric sulfate as the desiccant in all such examples so that the results would be on a comparable basis. It will be understood, however, that other metal ethylenebisdithiocarbamates and desiccants can be used in place of those shown in the examples. Thus any departure from the foregoing detailed description which conforms to the principle of the invention, namely, to the utilization of a desiccant to prevent decomposition of metal ethylenebisdithiocarbamates on storage in closed containers, is intended to be included within the scope of the claims below.
I claim:
1. A method for protecting manganese ethylenebisdithiocarbamate from decomposition on storage in a closed container which comprises including Within the container a minor amount of a desiccant, suflicient to stabilize the dithiocarbamate.
2. A package comprising a closed container, manganese ethylenebisdithiocarbamate disposed within said container and a minor amount of a desiccant, sutficient to stabilize the dithiocarbamate.
3. A package comprising a closed container, manganese ethylenebisdithiocarbamate disposed within said container and from 2 to 15% by weight base on the manganese ethylenebisdithiocarbamate of anhydrous cupric sulphate.
References Cited in the file of this patent UNITED STATES PATENTS 789,176 Smith May 9, 1905 1,631,903 Van Der Lande June 7, 1927 2,283,867 Flosdorf May 19, 1942 2,428,861 Waring et al. Oct. 14, 1947 2,531,114 Deitz Nov. 21, 1950 2,665,285 Johnson Jan. 5, 1954 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2, 848,297 August 19, 1958 Sanford J. Hill It is hereby certified that error appears in the printed specification of the above numb ered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 2, line 28, for "in" read as into hine 44, for "contained" read container column 4, line 13,. for "base-""read based Signed and sealed this 28th day of October 1958.
(SEAL) Attest:
KARL Ho AXLINE ROBERT C. WATSON Attesting Oflicer Commissioner of Patents
Claims (1)
1. A METHOD FOR PROTECTING MANGANESE ETHYLENEBISDITHIOCARBAMATE FROM DECOMPOSITION ON STORAGE IN A CLOSED CONTAINER WHICH COMPRISES INCLUDING WITHIN THE CONTAINER A MINOR AMOUNT OF A DESICCANT, SUFFICIENT TO STABILIZE THE DITHIOCARBAMATE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US385687A US2848297A (en) | 1953-10-12 | 1953-10-12 | Manganese ethylenebisdithiocarbamate stabilized by desiccant; method and package |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US385687A US2848297A (en) | 1953-10-12 | 1953-10-12 | Manganese ethylenebisdithiocarbamate stabilized by desiccant; method and package |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2848297A true US2848297A (en) | 1958-08-19 |
Family
ID=23522445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US385687A Expired - Lifetime US2848297A (en) | 1953-10-12 | 1953-10-12 | Manganese ethylenebisdithiocarbamate stabilized by desiccant; method and package |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2848297A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1175937B (en) * | 1959-12-11 | 1964-08-13 | Schering Ag | Nematicide based on N, N'-dimethylthiuram disulfide |
| US3278373A (en) * | 1963-05-07 | 1966-10-11 | Du Pont | Stabilized 3, 3'-ethylenebis(tetrahydro-4, 6-dimethyl-2h-1, 3, 5-thiadiazene-2-thione) fungicidal composition |
| JPS5314614B1 (en) * | 1968-04-10 | 1978-05-18 | ||
| US4217293A (en) * | 1978-08-21 | 1980-08-12 | E. I. Du Pont De Nemours And Company | Stabilized maneb and preparation thereof |
| US4394316A (en) * | 1980-09-11 | 1983-07-19 | Rohm And Haas Company | Copper modified mancozeb |
| EP0568378A1 (en) * | 1992-05-01 | 1993-11-03 | Rohm And Haas Company | Fungicidal compositions |
| US5389674A (en) * | 1992-05-01 | 1995-02-14 | Rohm And Haas Company | Fungicidal compositions and methods for production thereof |
| TR27968A (en) * | 1993-04-28 | 1995-11-14 | Rohm & Haas Comp | Fungicide compounds containing dithiocarbamate or bisditiocarbamoyl disulfides. |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US789176A (en) * | 1903-02-26 | 1905-05-09 | American Agricultural Chemical Company | Insecticide and method of dehydrating moist materials. |
| US1631903A (en) * | 1924-10-18 | 1927-06-07 | Novadel Process Corp | Stable peroxidized composition and process of making same |
| US2283867A (en) * | 1939-12-19 | 1942-05-19 | Stokes Machine Co | Packaging and preserving dried biologicals, pharmaceuticals, and the like |
| US2428861A (en) * | 1943-03-22 | 1947-10-14 | Gen Motors Corp | Machine gun package |
| US2531114A (en) * | 1949-08-03 | 1950-11-21 | Beam Products Inc | Antitarnish composition |
| US2665285A (en) * | 1951-07-06 | 1954-01-05 | Du Pont | Stabilization of derivatives of dithiocarbamic acids |
-
1953
- 1953-10-12 US US385687A patent/US2848297A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US789176A (en) * | 1903-02-26 | 1905-05-09 | American Agricultural Chemical Company | Insecticide and method of dehydrating moist materials. |
| US1631903A (en) * | 1924-10-18 | 1927-06-07 | Novadel Process Corp | Stable peroxidized composition and process of making same |
| US2283867A (en) * | 1939-12-19 | 1942-05-19 | Stokes Machine Co | Packaging and preserving dried biologicals, pharmaceuticals, and the like |
| US2428861A (en) * | 1943-03-22 | 1947-10-14 | Gen Motors Corp | Machine gun package |
| US2531114A (en) * | 1949-08-03 | 1950-11-21 | Beam Products Inc | Antitarnish composition |
| US2665285A (en) * | 1951-07-06 | 1954-01-05 | Du Pont | Stabilization of derivatives of dithiocarbamic acids |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1175937B (en) * | 1959-12-11 | 1964-08-13 | Schering Ag | Nematicide based on N, N'-dimethylthiuram disulfide |
| US3278373A (en) * | 1963-05-07 | 1966-10-11 | Du Pont | Stabilized 3, 3'-ethylenebis(tetrahydro-4, 6-dimethyl-2h-1, 3, 5-thiadiazene-2-thione) fungicidal composition |
| JPS5314614B1 (en) * | 1968-04-10 | 1978-05-18 | ||
| US4217293A (en) * | 1978-08-21 | 1980-08-12 | E. I. Du Pont De Nemours And Company | Stabilized maneb and preparation thereof |
| US4394316A (en) * | 1980-09-11 | 1983-07-19 | Rohm And Haas Company | Copper modified mancozeb |
| EP0568378A1 (en) * | 1992-05-01 | 1993-11-03 | Rohm And Haas Company | Fungicidal compositions |
| US5389674A (en) * | 1992-05-01 | 1995-02-14 | Rohm And Haas Company | Fungicidal compositions and methods for production thereof |
| TR27968A (en) * | 1993-04-28 | 1995-11-14 | Rohm & Haas Comp | Fungicide compounds containing dithiocarbamate or bisditiocarbamoyl disulfides. |
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