CN117425818A - Heterocyclic red azo colorants for seed treatment applications - Google Patents

Heterocyclic red azo colorants for seed treatment applications Download PDF

Info

Publication number
CN117425818A
CN117425818A CN202280040270.8A CN202280040270A CN117425818A CN 117425818 A CN117425818 A CN 117425818A CN 202280040270 A CN202280040270 A CN 202280040270A CN 117425818 A CN117425818 A CN 117425818A
Authority
CN
China
Prior art keywords
alkyl
red
colorant
seed
oxyalkylene
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.)
Pending
Application number
CN202280040270.8A
Other languages
Chinese (zh)
Inventor
W·A·弗罗因德
I·穆罕默德
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Milliken and Co
Original Assignee
Milliken and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US17/714,298 external-priority patent/US20220411387A1/en
Application filed by Milliken and Co filed Critical Milliken and Co
Publication of CN117425818A publication Critical patent/CN117425818A/en
Pending legal-status Critical Current

Links

Landscapes

  • Pretreatment Of Seeds And Plants (AREA)

Abstract

The present invention relates to heterocyclic red azo colorants for seed treatment applications. Seeds for horticultural/agricultural applications coated with the heterocyclic azo colorants provide the coated seeds with anti-counterfeit properties. When the coated seed is exposed to an acidic material (e.g., vinegar)A color change phenomenon was observed and provided evidence of authenticity of the coated seeds. The invention also relates to agricultural formulations containing heterocyclic red azo colorants that can be used as anti-counterfeit agents. The heterocyclic red azo colorant has the following formula (II),wherein R is 2 And R is 3 Independently selected from H, alkyl, and poly (oxyalkylene) moieties, and wherein R 2 And R is 3 Is a poly (oxyalkylene) moiety.

Description

Heterocyclic red azo colorants for seed treatment applications
Technical Field
The present invention relates to heterocyclic red azo colorants for seed treatment applications. The red azo colorant contains a heterocyclic ring including one nitrogen atom and one sulfur atom, and does not contain an electron withdrawing group on the heterocyclic ring. Seeds coated with the heterocyclic azo colorants for horticultural/agricultural applications provide anti-counterfeiting properties to the coated seeds. When the coated seed is exposed to an acidic material (e.g., vinegar), a color change phenomenon is observed and provides evidence of the authenticity of the coated seed. The invention also relates to the use of these heterocyclic red azo colorants as anti-counterfeit agents in agricultural formulations.
Background
Seed safety is critical to agriculture. In markets around the world, counterfeit or fake seeds may flood the market. These counterfeit seeds may be of poor quality. Seed companies need the ability to distinguish their own seeds from other seeds that might attempt to mimic their brands in order to protect their own image. In addition, farmers should have tools available to determine if the seeds they purchase are authentic seeds and if they will obtain the quality crop they desire from their investment.
In addition to counterfeit seeds, agricultural formulations containing one or more non-authentic agricultural active ingredients may also be introduced into the market place. To verify agricultural formulations, a clear index test is required. The use of counterfeit agricultural formulations may cause crop damage or crop losses to the farmer. This in turn may also cause damage to the reputation of the agricultural product provider.
There are only a few techniques presented in the literature for handling counterfeit seeds and agricultural formulations. However, most of them depend on the use of fluorescent dyes. For example, CN101403694a discloses a fluorescent anti-counterfeiting and detection method for granular seeds. For these inventions to function, the seeds must be exposed to a UV light source to observe the fluorescent effect. In the field of obvious seed use, this is not always easy to do. Thus, there is a need for a technique that allows for easy identification of agricultural formulations of active ingredients and seeds treated therewith.
It has been found that certain heterocyclic red azo colorants are capable of acting as anti-counterfeit formulations for canned agricultural active ingredient formulations as well as for seeds coated with such formulations. The use of these specific colorants allows for simple testing to quickly identify authentic seeds using readily available household chemicals such as vinegar and toilet cleaners. Red dyes (such as FD & C Red 40 and FD & C Red 33) and Red pigments (such as pigment Red 48:2 and pigment Red 112) currently available in the united states and approved for use as seed treatments/coatings do not provide the same visual change in the presence of acidic materials as exhibited by the heterocyclic azo colorants of the present invention. In addition, non-polymeric dyes, such as those presented herein, often do not cover well and stain poorly when applied to seeds. The present invention addresses these shortcomings and provides additional benefits over other types of colorants, such as water solubility, non-staining performance, improved processor accumulation, and improved processor cleaning. Thus, the heterocyclic red azo colorants of the present invention represent an advance over the prior art and further satisfy the need to prevent counterfeit agricultural products from being used in a market environment.
Disclosure of Invention
In one aspect, the present invention relates to a method for determining the authenticity of a seed or agricultural formulation comprising the steps of:
(a) Providing a seed or agricultural formulation comprising a red azo colorant represented by the formula:
wherein R is 1 Comprising at least one 5-membered ring, said 5-membered ring having one N and one S atom incorporated in the ring system, and wherein the ring system is free of electron withdrawing groups; r is R 2 And R is 3 Independently selected from H, alkyl, and poly (oxyalkylene) moieties, wherein R 2 And R is 3 Is a poly (oxyalkylene) moiety; and R is 4 Independently selected from the group consisting of H, alkyl, substituted alkyl, nitrogen, substituted nitrogen, oxygen, halogen, and ether;
(b) Adding an acidic material to the seed or agricultural formulation of step "a"; and
(c) Visual observation changes in color from red to violet as the acidic material is added.
In another aspect, the invention relates to a composition comprising: (a) An agricultural formulation comprising at least one agriculturally active ingredient, and (b) at least one red azo colorant represented by the formula:
wherein R is 1 Comprising at least one 5-membered ring, said 5-membered ring having one N and one S atom incorporated in the ring system, and wherein the ring system is free of electron withdrawing groups; r is R 2 And R is 3 Independently selected from H, alkyl, and poly (oxyalkylene) moieties, wherein R 2 And R is 3 Is a poly (oxyalkylene) moiety; and R is 4 Independently selected from the group consisting of H, alkyl, substituted alkyl, nitrogen, substituted nitrogen, oxygen, halogen, and ether.
In a further aspect, the present invention relates to a composition comprising: (a) An agricultural formulation comprising at least one agriculturally active ingredient, and (b) at least one red azo colorant selected from formulas I and II:
wherein R is 2 And R is 3 Independently selectFrom H, alkyl and poly (oxyalkylene) moieties, wherein R 2 And R is 3 Is a poly (oxyalkylene) moiety; r is R 4 Independently selected from the group consisting of H, alkyl, substituted alkyl, nitrogen, substituted nitrogen, oxygen, halogen, and ether; and R is 5 Independently selected from the group consisting of H, alkyl, substituted alkyl, hydroxy, substituted hydroxy, aryl, and substituted aryl.
In yet another aspect, the present invention relates to a composition comprising: (a) An agricultural formulation comprising at least one agriculturally active ingredient, and (b) at least one red azo colorant represented by formula III:
wherein R is 2 And R is 3 Independently selected from H, alkyl, and poly (oxyalkylene) moieties, and wherein R 2 And R is 3 Is a poly (oxyalkylene) moiety.
In another aspect, the invention relates to a composition comprising: (a) An agricultural formulation comprising at least one agriculturally active ingredient, and (b) a red azo colorant represented by formula IV:
Detailed Description
The present invention relates to a red azo colorant containing a heterocyclic ring containing at least one nitrogen atom and one sulfur atom and containing no electron withdrawing group on the heterocyclic ring. The colorant is selected to provide anti-counterfeiting properties to the seed coated therewith. The invention further includes seeds coated with the heterocyclic azo colorants described herein.
In addition, the colorants selected are capable of providing anti-counterfeit properties to an agriculturally active ingredient or polymer formulation containing a heterocyclic azo colorant as described herein.
The anti-forgery properties of seeds coated with the heterocyclic colorants of the present invention were evaluated using ordinary household articles that are acidic in nature and have a pH of 3 or less. When exposed to an acidic substance having a pH of 3 or less (e.g., vinegar or a toilet bowl cleaner containing hydrochloric acid), the coated seed will exhibit a transition in the hue of the colorant from red to violet. Such a test may be used to identify that the colorant on the seed is authentic and may be used as a marker for the seed or agricultural formulation, thereby preventing counterfeit formulations or seeds from being sold and/or put on the market.
As used herein, the terms "heterocycle" and "heterocyclic" are intended to describe/include cyclic compounds containing at least one heteroatom in the ring system. Examples of heterocycles include, but are not limited to, thiazole, benzothiazole, imidazole, thiophene, furan, benzofuran, thiadiazole, oxazole, isoxazole, oxadiazole, benzoxazole, triazole, and pyridinyl.
As used herein, the term "electron withdrawing group" is intended to include an atom or group that attracts electron density toward itself from an adjacent atom, typically by resonance or induction effects. Some examples of electron withdrawing groups may include halogen, sulfonate, carboxylic acid, ester, ketone, aldehyde, nitrile, amide, phosphate, and nitro groups.
As used herein, the term "alkoxy" is intended to include C 1 -C 8 Alkoxy groups and alkoxy derivatives of polyols having repeating units such as butylene oxide, glycidol oxide, ethylene oxide or propylene oxide.
As used herein, unless otherwise indicated, the terms "alkyl" and "alkyl-terminated" are intended to include C 1 To C 100 Alkyl group, C 1 To C 50 Alkyl group, C 5 To C 25 Alkyl groups or even C 10 To C 20 An alkyl group.
As used herein, unless otherwise indicated, the term "aryl" is intended to include C 6 To C 12 An aryl group.
As used herein, the term "arylalkyl" is intended to include C unless otherwise indicated 1 To C 18 An alkyl group, and in one aspect, comprisesC is drawn together 1 To C 6 An alkyl group.
In one aspect, the present invention relates to the use of a poly (oxyalkylene) -substituted red azo colorant in seed coating applications, wherein the colorant is mixed with an agricultural formulation containing at least one agriculturally active ingredient, such as a pesticide (pesticide), including but not limited to fungicides, insecticides, nematicides, and the like, and applied directly to the seed surface. Seeds include, but are not limited to, row crops (corn, soybean, etc.), grass seeds, or any other type of seed that will be directly treated with an agricultural formulation.
In another aspect, the present invention relates to the use of a poly (oxyalkylene) -substituted red azo colorant in an agricultural formulation containing at least one agriculturally active ingredient, wherein the agricultural formulation is colored with the poly (oxyalkylene) -substituted red azo colorant.
The colorant of the present invention is represented by the following formula:
wherein R is 1 Comprising at least one 5-membered ring, said 5-membered ring having one N and one S atom incorporated in the ring system, and wherein the ring system is free of electron withdrawing groups;
R 2 and R is 3 Independently selected from H, alkyl, and poly (oxyalkylene) moieties, wherein R 2 And R is 3 Is a poly (oxyalkylene) moiety; and is also provided with
R 4 Independently selected from the group consisting of H, alkyl, substituted alkyl, nitrogen, substituted nitrogen, oxygen, halogen, and ether.
In one aspect of the invention, R 1 May be further selected from the group consisting of thiazole, isothiazole, benzisothiazole and benzothiazole. R is R 1 May preferably be selected from the group consisting of thiazoles and benzothiazoles. One or more heterocycles R 1 May additionally include on one or more rings a member selected from the group consisting of H, alkyl, substituted alkyl, hydroxy, substituted hydroxy, aryl, substituted aryl, and the likeThe substituents in the group are each provided that the substituent is not considered an electron withdrawing group.
The poly (oxyalkylene) moieties include, for example, ethylene oxide (EO; also known as ethyleneoxy), propylene oxide (PO; also known as propyleneoxy), butylene oxide (BO; also known as butyleneoxy), and combinations thereof. The total number of alkylene oxide residues per colorant molecule is in the range of 4 to 250, preferably 5 to 100, where 5 to 20 represents the optimum level of fugitive (evasion), viscosity and color intensity.
Examples of azo chromophore groups suitable for use in the present invention include monoazo, disazo, trisazo, tetrazo, polyazo, formazan (formazans), azomethine and metal complexes thereof.
The heterocyclic azo red colorant may be present in the seed coating in an amount ranging from about 0.001% to about 50% by weight of the coating, or may even be present in the seed coating in an amount ranging from about 0.5% to about 10% by weight of the coating.
The heterocyclic azo red colorant may be present in the formulation in an amount ranging from about 0.001% to about 50% by weight of the agricultural formulation, or may even be present in the formulation in an amount ranging from about 0.5% to about 10% by weight of the agricultural formulation.
The synthesis of heterocyclic azo colorants involves the reaction of an aromatic amine with nitrous acid to form a diazonium salt. This diazonium salt is then coupled with a suitable coupling agent to form an azo bond. Preferred aromatic amines are aromatic amines containing thiazole or benzothiazole ring systems. Preferred coupling agents are alkoxylated aniline derivatives.
In another aspect of the invention, the seed coating composition includes at least one heterocyclic azo colorant and at least one agriculturally active ingredient. An "agriculturally active ingredient" will exert a biologically relevant effect on the seed or plant. For example, agricultural active ingredients may exert insecticidal effects. Alternatively, the agriculturally active ingredient may function to provide nutrition or control one or more plant diseases.
Some examples of agriculturally active ingredients include, but are not limited to, fungicidal agents, insecticidal agents, nematicidal agents, biological agents, pesticides, and biocides. The additional agriculturally active ingredient may also be comprised of a rodent killing agent, herbicide, plant growth regulator, plant growth stimulant, nutrient, hormone, and the like. Any combination of the foregoing agriculturally active ingredients may also be used as the agriculturally active ingredient.
The recommended dosing rate of the agricultural active ingredient varies depending on the application, the seed type, the particular active ingredient used and the desired result. The agriculturally active ingredients may be blended together into the same seed treatment formulation. Typically, the amount of one or more agriculturally active ingredients is in the range of from about 0.001 to about 200g/kg seed. One skilled in the art can determine the appropriate amount of agriculturally active ingredient depending on the active ingredient and seed type used. Technical data sheets or active ingredient labels available from suppliers of these ingredients will also provide additional guidance.
The following is a list of agriculturally active ingredients that may be used in seed coating compositions as described herein, and is intended to further illustrate possible active ingredients, without imposing any limitation.
Non-limiting commercial examples of fungicidal ingredients include metalaxyl (available under the trade name from BayerObtained), fludioxonil (available under the trade name +.>4FS commercially available), tebuconazole, thiabendazole, azoxystrobin, and the like.
Non-limiting examples of commercially available insecticides include thiamethoxam (thiomethoxam) (available from Syngenta under the trade name) Chlorantraniliprole (available under the trade name Lumivia from Dupont TM Obtained), fipronil (from BASF, trade name +.>) Imidacloprid and clothianidin (from Bayer, trade name->) Etc.
Non-limiting examples of commercially available nematicidal ingredients include abamectin (available under the trade name Syngenta from SyngentaObtained from Valent under the trade name Aveo), bacillus amyloliquefaciens strain PTA-4838 TM EZ Nematide), thiodicarb (available under the trade name +.>Obtained), and the like.
One or more additional components may optionally be included in the seed coating composition of the present invention. These additional components may be selected from binders, waxes, coloring agents, thickeners, dispersants, surfactants, anti-foaming agents, antifreeze agents, bactericidal agents, solvents, or combinations thereof. One or more of these additional components may be present in the seed coating composition in an amount ranging from about 0.001% to about 50% by weight of the coating.
The seed coating composition may include a binder or a film-forming polymer. The binder may be any suitable binder approved for agricultural use. A list of suitable adhesives can be found in U.S. code of Federal Regulations Title, part 180.960, which is incorporated in its entirety by reference.
The binder may be a polymer selected from the group consisting of: vinyl acetate-ethylene copolymers, vinyl acetate homopolymers, vinyl acetate-acrylic copolymers, vinyl acrylic, ethylene-vinyl chloride, vinyl ether maleic anhydride, butadiene styrene, and the like, and combinations thereof.
Suitable binders included in the list are acrylic polymers comprising one or more of the following monomers: acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylateEsters, hydroxyethyl acrylate, hydroxybutyl acrylate, carboxyethyl acrylate, methacrylic acid, methyl methacrylate, hydroxybutyl methacrylate, lauryl methacrylate and stearyl methacrylate; without the following monomers and/or with one or more of the following monomers: acrylamide, N-methylacrylamide, N-dimethylacrylamide, N-octylacrylamide, maleic anhydride, maleic acid, monoethyl maleate, diethyl maleate, monooctyl maleate, dioctyl maleate; and their corresponding sodium, potassium, ammonium, isopropylamine, triethylamine, monoethanolamine and/or triethanolamine salts. Other suitable binders in this list include: copolymers of methyl vinyl ether with maleic anhydride or monoalkyl esters of maleic anhydride (e.g. from ISP VEMA series products); polyvinylpyrrolidone; copolymers of vinyl pyrrolidone with vinyl acetate (e.g., agrimer VA series products from ISP); copolymers of vinylpyrrolidone with vinylalkyl groups (e.g.from ISP +.>AL series 45 products); polyvinyl acetate; ethylene/vinyl acetate copolymers (e.g.. From Uniqema +.>SemKote E product series); vinyl acetate acrylic copolymers (e.g.. From Uniqema +.>Semkote V product series); an a-B block copolymer of ethylene oxide and propylene oxide; A-B-A triblock 50 copolymer of EO-PO-EO (e.g., +.>A series); polyvinyl alcohol.
Examples of suitable waxes include polyethylene waxes, polypropylene waxes, carnauba waxes (carnauba wax), fischer-Tropsch waxes, paraffin waxes, triglycerides, metal soaps, and combinations thereof.
Suitable surfactants, including dispersants or emulsifiers, are aromatic sulphonic acids (e.g. lignosulphonic acid @Types, borregard, norway), phenolsulfonic acid, naphthalenesulfonic acid (++>Type Akzo Nobel, u.s.a.)) and alkali metal, alkaline earth metal and ammonium salts of fatty acids, alkyl sulfonates, alkylaryl sulfonates, alkyl sulfates, lauryl ether sulfates, fatty alcohol sulfates, and sulfated hexadec-, hepta-and octadecanoates, sulfated fatty alcohol glycol ethers, in addition, condensates of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, tristearylphenyl polyethylene glycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, laureth acetals, sorbitol esters, maleic anhydride-diisobutylene copolymers, polyvinyl alcohol ( >Type, clariant, switzerland), polycarboxylic esters (++>Type, BASF, germany) and polyalkoxylate.
Examples of thickeners are polysaccharides and organic and inorganic clays, such as attapulgite clay, bentonite clay, montmorillonite clay, hectorite clay, cellulosic materials, xanthan gum or guar gum. The preferred thickener is xanthan gumC P Kelco，U.S.A.)。
Bactericides may be added to preserve and stabilize the combinationAnd (3) an object. Some examples of suitable bactericides are bactericides based on isothiazolinone derivatives such as Benzisothiazolinone (BIT), methylisothiazolinone (MIT), chloromethyl isothiazolone (CMIT) and combinations thereof. Suitable bactericides are available from ThorTrade names are commercially available.
Examples of suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerol. A preferred example of an anti-freeze agent is propylene glycol.
Examples of anti-foaming agents are silicone emulsions, long chain alcohols, fatty acids, fatty acid salts and mixtures thereof.
Additional coloring agents may be blended with the colorants of the present invention. Preferred additional coloring agents are pigments of low water solubility and water-soluble dyes. Non-limiting examples of coloring agents include Milliken Blue 5200, acid Blue 9, pigment Blue 15, c.i. pigment Blue 29, pigment violet 23, pigment yellow 1, acid yellow 23, pigment red 112, pigment red 48:2, pigment red 48:1, acid red 33, food red 17, pigment green 7, solvent green 3, pigment white 6, carbon black, pearlescent pigments composed of mica flakes coated with titanium dioxide and/or iron oxide, and combinations thereof.
Preferably, the seed coating composition is applied as an aqueous composition and thereafter cured (including cured and/or dried) to form the seed coating. The total coating composition may be in the form of a suspension, solution, emulsion or dispersion. The pH of the coating composition may be in the range of ph=3-12, preferably ph=5-10 and most preferably ph=6-9. In order for the present invention to function properly as an anti-counterfeit agent, the pH of the seed coating composition should be greater than 3.
In one aspect of the invention, all components of the seed coating composition are blended and mixed together at room temperature until homogenized into a slurry, which is then applied to the seed. Alternatively, the various components of the formulation may be applied to the seed separately in stages during the seed treatment/seed coating process. The seeds may be coated using conventional coating means. Various applicators are available to those skilled in the art. Some common techniques include the use of drum applicators, spin applicators, and fluid bed techniques. The coating may be air-dried or heat-dried on the seeds prior to packaging.
Generally, the amount of seed coating composition applied to the seed may be in the range of 0.5-50g/kg seed, or even 1-40g/kg seed, or 2-35g/kg seed, or 3-30g/kg seed.
In a further aspect, the invention includes a composition comprising:
(a) Agricultural formulation comprising at least one agriculturally active ingredient, and
(b) At least one red azo colorant represented by the formula:
wherein R is 1 Comprising at least one 5-membered ring, said 5-membered ring having one N and one S atom incorporated in the ring system, and wherein the ring system is free of electron withdrawing groups;
R 2 and R is 3 Independently selected from H, alkyl, and poly (oxyalkylene) moieties, wherein R 2 And R is 3 Is a poly (oxyalkylene) moiety; and is also provided with
R 4 Independently selected from the group consisting of H, alkyl, substituted alkyl, nitrogen, substituted nitrogen, oxygen, halogen, and ether.
The agricultural formulation is present in the composition in an amount ranging from 95% to 99.999%. The at least one red azo colorant is present in the composition in an amount ranging from 0.001% to 95%.
The invention further includes seeds coated with such a composition comprising an agricultural formulation and at least one red azo colorant.
The composition may further comprise at least one of a polymeric binder and a film-forming polymer as described herein.
The invention also encompasses a composition comprising:
(a) Agricultural formulation containing at least one agriculturally active ingredient, and
(b) At least one red azo colorant selected from formulas I and II:
wherein R is 2 And R is 3 Independently selected from H, alkyl, and poly (oxyalkylene) moieties, wherein R 2 And R is 3 Is a poly (oxyalkylene) moiety;
R 4 independently selected from the group consisting of H, alkyl, substituted alkyl, nitrogen, substituted nitrogen, oxygen, halogen, and ether; and is also provided with
R 5 Independently selected from the group consisting of H, alkyl, substituted alkyl, hydroxy, substituted hydroxy, aryl, and substituted aryl.
In the composition, the total number of alkylene oxide residues per colorant molecule is in the range of 5 to 20. The invention further includes seeds coated with such a composition comprising an agricultural formulation and at least one red azo colorant of formula I and formula II.
The invention also encompasses a composition comprising:
(a) Agricultural formulation comprising at least one agriculturally active ingredient, and
(b) At least one red azo colorant represented by formula III:
wherein R is 2 And R is 3 Independently selected from H, alkyl, and poly (oxyalkylene) moieties, and wherein R 2 And R is 3 Is a poly (oxyalkylene) moiety.
The invention further includes seeds coated with such a composition comprising an agricultural formulation and at least one red azo colorant represented by formula III.
In addition, the present invention includes a composition comprising:
(a) Agricultural formulation comprising at least one agriculturally active ingredient, and
(b) A red azo colorant represented by formula IV:
the invention further includes seeds coated with such a composition comprising an agricultural formulation and at least one red azo colorant represented by formula IV.
As previously discussed, the red azo colorants of the present invention can be used to determine the authenticity of seeds coated with the colorant or agricultural formulations containing the red azo colorant. A method for determining the authenticity of a seed or agricultural formulation comprising the steps of:
(a) Providing a seed or agricultural formulation comprising a red azo colorant represented by the formula:
wherein R is 1 Comprising at least one 5-membered ring, said 5-membered ring having one N and one S atom incorporated in the ring system, and wherein the ring system is free of electron withdrawing groups;
R 2 and R is 3 Independently selected from H, alkyl, and poly (oxyalkylene) moieties, wherein R 2 And R is 3 Is a poly (oxyalkylene) moiety; and is also provided with
R 4 Independently selected from the group consisting of H, alkyl, substituted alkyl, nitrogen, substituted nitrogen, oxygen, halogen, and ether;
(b) Adding an acidic material to the seed or agricultural formulation of step "a";
(c) Visual observation changes in color from red to violet as the acidic material is added.
The pH of the acidic material is generally < 3. A further feature of the method includes placing the seeds of step "a" in an aqueous solution prior to adding the acidic material. When placed in solution, the red azo colorant may be present in the coating on the seed. The red azo colorant of step "a" may be present in an amount in the range of about 0.001% to about 50% by weight of the coating, or may even be present in an amount in the range of about 0.5% to about 10% by weight of the coating.
In a further method of the present invention, the red azo colorant of step "a" may be represented by formula I or formula II:
wherein:
R 2 and R is 3 Independently selected from H, alkyl, and poly (oxyalkylene) moieties, and wherein R 2 And R is 3 Is a poly (oxyalkylene) moiety;
R 4 independently selected from the group consisting of H, alkyl, substituted alkyl, nitrogen, substituted nitrogen, oxygen, halogen, and ether; and is also provided with
R 5 Independently selected from the group consisting of H, alkyl, substituted alkyl, hydroxy, substituted hydroxy, aryl, and substituted aryl.
In another method of the present invention, the red azo colorant of step "a" is represented by formula III:
wherein R is 2 And R is 3 Independently selected from H, alkyl, and poly (oxyalkylene) moieties, and wherein R 2 And R is 3 Is a poly (oxyalkylene) moiety.
In another alternative method of the present invention, the red azo colorant of step "a" is represented by formula IV:
the invention also encompasses kits and/or systems for determining the authenticity of seeds or agricultural formulations. The kit and/or system comprises the following components: (1) Seeds coated with various forms of red azo colorants as described herein or agricultural formulations containing the red azo colorants, and (2) an acidic material having a pH of less than or equal to 3.
Examples
The following examples are provided for illustrative purposes and should not be construed as limiting the scope of the invention. These examples are intended to demonstrate the preparation and anti-counterfeiting properties of the heterocyclic red azo colorants of the present invention.
Inventive example 1
A diazonium solution was prepared by charging 50 grams (g) of 2-amino-4-methylbenzothiazole and 500g of 85% phosphoric acid into a 1000mL round bottom flask. Once the diazonium solution mixture was cooled to-5 ℃ to 0 ℃, 24.29g of sodium nitrite was slowly added over 30 minutes. The diazonium solution is then vigorously stirred for 2.5 hours, maintaining at-5℃to 0 ℃. Sulfamic acid is added to the diazonium solution to destroy excess nitrous acid. An additional 2000mL round bottom flask was charged with 178.73g of aniline 10EO (10 moles of ethylene oxide polymerized from aniline nitrogen) and 650g of water. The solution was cooled to 0 ℃. The diazonium solution is then slowly added to the aniline 10EO mixture, maintaining the temperature at 0-10 ℃. The resulting mixture was then stirred at 0-10 ℃ for one hour, then the ice bath was removed. The solution was then neutralized to pH 7 with 50% sodium hydroxide and heated to 70 ℃. The neutralized mixture was then added to a separatory funnel and placed in an oven at 70 ℃ overnight. The aqueous layer was separated and the red product recovered.
Inventive example 2
A diazonium solution was prepared by charging 80g of 2-amino-5-methylthiazole, 400g of water and 204g of sulfuric acid into a 1L round bottom flask. The contents were cooled to 0 ℃ to 5 ℃. 52.8g of sodium nitrite was dissolved in 160g of water and slowly added to the round bottom flask, maintaining a temperature of 0℃to 5 ℃. The solution was then stirred at 0 ℃ to 5 ℃ for 1 hour, after which the excess nitrous acid was destroyed by adding sulfamic acid. An additional 2L beaker was charged with 252g of m-toluidine 5EO and 400g of water and cooled to 0℃to 5 ℃. The diazonium solution is then slowly added to a 2L beaker containing m-toluidine 5EO, maintaining the temperature at 0℃to 5 ℃. The resulting solution temperature was maintained for 30 minutes, after which the solution was allowed to slowly warm to room temperature over 1 hour. The solution was then neutralized to pH 7 using 50% sodium hydroxide. Once neutralized, the solution was added to a separatory funnel and placed in an oven at 70 ℃ for 3 hours. The aqueous layer was separated and the red product recovered.
Comparative example 1
A diazonium solution was prepared by charging 5g of 2-amino-5-chlorothiazole hydrochloride and 100g of 85% phosphoric acid into a 250mL round bottom flask and cooling it to-5 deg.c to 0 deg.c. 9.70g of sulfuric acid containing 40% by weight of nitrososulfuric acid was added dropwise to the diazonium solution and stirred at-5℃to 0℃for 1 hour. Sulfamic acid and urea are added to destroy excess nitrous acid. An additional 250mL round bottom flask was charged with 17.78g of aniline 10EO and 25g of water. The solution was cooled to 0 ℃ to 5 ℃. The diazonium solution is then slowly added to the aniline 10EO solution, maintaining the temperature between 0 ℃ and 5 ℃. The resulting solution temperature was maintained for 60 minutes after which the solution was slowly warmed to room temperature. The solution was then neutralized to pH 7 using 50% sodium hydroxide. Once neutralized, the solution was added to a separatory funnel and placed in an oven at 70 ℃ for 3 hours. The aqueous layer was separated and the red product recovered.
Comparative example 2
2-amino-5-bromothiazole hydrobromide was converted to the free base by combining 5g of 2-amino-5-bromothiazole hydrobromide, 4.23g of sodium bicarbonate and 50mL of water in a 100mL round bottom flask. The contents were stirred for several hours. The solid was then filtered using vacuum filtration and dried in a vacuum oven at room temperature overnight. A diazonium solution was prepared by charging 2g of 2-amino-5-bromothiazole (prepared as above) and 58g of 85% phosphoric acid into a 250mL round bottom flask and cooling to-5 ℃ to 0 ℃. 3.90g of sulfuric acid containing 40% NSA was added dropwise to the diazonium solution and stirred at <0℃for 1 hour. Sulfamic acid and urea are added to destroy excess nitrous acid. An additional 250mL round bottom flask was charged with 7.15g of aniline 10EO and 15g of water. The solution was cooled to 0 ℃ to 5 ℃. The diazonium solution is then slowly added to the aniline 10EO solution, maintaining the temperature between 0 ℃ and 5 ℃. The resulting solution temperature was maintained for 60 minutes after which the solution was slowly warmed to room temperature. The solution was then neutralized to pH 7 using 50% sodium hydroxide. Once neutralized, the solution was added to a separatory funnel and placed in an oven at 70 ℃ for 3 hours. The aqueous layer was separated and the red product recovered.
Comparative example 3
A diazonium solution was prepared by combining 3.8g of 2-amino-1, 3, 4-thiadiazole with 120mL of 85% phosphoric acid in a 250mL 4-necked round bottom flask equipped with a temperature probe, stirring shaft, paddle and guide assembly attached on top to a mechanical stirrer. The mixture was stirred until a homogeneous solution formed. The reaction mixture was stirred and cooled to-5 ℃ to 0 ℃. 2.59g of sodium nitrite was added to the round bottom flask in portions and the reaction mixture was stirred at 0℃to 5℃for 1.5 hours. 0.36g of sulfamic acid was added to the reaction to quench excess nitrous acid, and the reaction was maintained at 0 ℃ for 30 minutes. The coupling agent solution was formulated by attaching a 1000ml 4-neck round bottom flask with a temperature probe, stirring shaft, paddle and guide assembly attached on top to a mechanical stirrer. The round-bottomed flask was charged with 22.28g of 2, 5-dimethoxyaniline 10EO and 250g of water. The mixture was stirred and cooled to below 5 ℃. The diazonium solution is added dropwise to the coupling agent solution over about 30 minutes, maintaining the temperature below 5 ℃. The resulting mixture was stirred for 1 hour and allowed to warm to room temperature, at which time 250mL of water was added. 50% sodium hydroxide was added to neutralize the excess acid to a pH of about 7, maintaining the temperature at 35℃to 40 ℃. The reaction mixture was allowed to phase separate in an oven at 70 ℃ for 2 hours, then the bottom layer was removed and the product layer was collected to give a red liquid.
Comparative example 4
A diazonium solution was prepared by combining 7g of 2-amino-1, 3, 4-thiadiazole with 202g of 85% phosphoric acid in a 250ml 4-necked round bottom flask equipped with a temperature probe, stirring shaft, paddle and guide assembly attached on top to a mechanical stirrer. The mixture was stirred until a homogeneous solution formed. The reaction mixture was stirred and cooled to-5 ℃ to 0 ℃. 4.78g of sodium nitrite are added in portions to the round-bottomed flask and the reaction mixture is stirred at 0℃to 5℃for 1.5 hours. 0.36g of sulfamic acid was added to the reaction to quench excess nitrous acid, and the reaction was maintained at 0 ℃ for 30 minutes. The coupling agent solution was formulated by attaching a 1000ml 4-neck round bottom flask with a temperature probe, stirring shaft, paddle and guide assembly attached on top to a mechanical stirrer. The round bottom flask was charged with 25.85g of 2, 5-dimethoxyaniline 5EO and 250g of water. The mixture was stirred and cooled to 0 ℃ to 5 ℃. The diazonium solution is added dropwise to the coupling agent solution over about 30 minutes, maintaining the temperature at 0 ℃ to 5 ℃. The resulting mixture was stirred for 1 hour and allowed to warm to room temperature, at which time 250mL of water was added. 50% sodium hydroxide was added to neutralize the excess acid to a pH of about 7, maintaining the temperature below 40 ℃. The reaction mixture was allowed to phase separate in an oven at 70 ℃ for 2 hours, then the bottom layer was removed and the product layer was collected to give a red liquid.
Method for testing anti-counterfeiting colorant in solution
A colorant sample to be tested (10 mg) was dissolved in water (10 mL) to obtain a solution. In the case of pigments, a suspension of the pigment is obtained. The color of the water is recorded in table 1. Then about 1mL of this aqueous solution was added to about 20mL of household vinegar (publicx distilled white vinegar, water with 5% acetic acid, ph=2.81) and any change in color was visually recorded. The test results are shown in table 1.
Table 1: anti-counterfeit color change
Coloring agent Water containing colorant Vinegar diluted colorant
Inventive example 1 Red color Purple color
Inventive example 2 Red color Purple color
Comparative example 1 Red color Red color
Comparative example 2 Red color Red color
Comparative example 3 Red color Red color
Comparative example 4: pigment Red 112 Red color Red color
Comparative example 5: pigment Red 48:2 Pink color Pink color
Comparative example 6: FD (FD)&C Red 40 Red color Red color
Comparative example 7: d (D)&C Red 33 Red color Red color
The test results show that examples 1 and 2 of the present invention containing thiazole heterocycles having no electron withdrawing group on the heterocycle show a visual change in color from red to purple when dissolved in acid vinegar at pH 2.81, relative to when dissolved in neutral water, indicating the anti-forgery property of the present invention. The authenticity of agricultural formulations (e.g., pesticide formulations) containing these colorants can be readily confirmed using this test method. The comparative example showed no color change in the presence of vinegar and therefore would not provide a visual cue to verify the formulation. Comparative examples 1 and 2 do not work in this application because they contain an electron withdrawing group attached to the thiazole moiety. Comparative examples 4-7 do not work in this application because they do not contain thiazole heterocycles.
Method for testing anti-counterfeiting colorant on seeds
According to table 2, the film coating was applied to 1kg of corn seed, wherein the agricultural formulation, water, binder and colorant were combined to form a colored seed coating composition. A slurry of these components was made and applied to corn seeds using a Aginnovation Rotary seed applicator. The treatment was applied to corn seeds in a rotating bowl within 5 seconds. The seeds were allowed to dwell in the disposer for an additional 20-30 seconds, then discharged from the bowl and collected.
Table 2: colored coating composition
1. Seed treatment insecticides available from Syngenta, greensboro, NC
2. Seed treatment fungicides obtainable from Syngenta, greensboro, NC
3. Available from Milliken&Seed treatment Polymer formulations obtained by Company, spartanburg, SC
4. Available from Milliken&Pigment Red 48:2 pigment Dispersion obtained by Company, spartanburg, SC
After 24 hours of curing, the samples in table 2 were tested for color change using the test methods described herein. Three seeds were removed from each treatment sample from table 2 and placed into separate plastic beakers. About 10mL of household vinegar (publicx distilled white vinegar, 5% acetic acid in water, ph=2.81) or water was added to each beaker, the seeds were gently swirled for about 10 seconds, and any color difference between the water and the vinegar solution was visually recorded. The test results are provided in table 3.
Table 3: anti-counterfeit color change on seeds
Colorant formulations Placing seeds into water Placing seeds in
Color coating A No color transfer into water No color transfer into vinegar
Color coating B Red solution Purple solution
Color coating C Red solution Red solution
The test results in table 3 show that visual cues are evident when the seeds coated with inventive example 1 were placed in water, as opposed to in vinegar. When the comparative examples (color coating a containing a pigment and color coating C containing a heterocyclic thiadiazole azo dye containing one sulfur and 2 nitrogen atoms in the heterocycle) were placed in water, no color change was shown relative to when placed in vinegar. Thus, this approach provides a visual cue to the seed purchaser/consumer that the seed is authentic.
Measurement of the authenticity of agricultural formulations for coloringTest on test
Colored agricultural formulations were prepared by blending the components in weight percent in table 4. Specifically, the components were combined into 20mL scintillation vials and mixed using vortex mixer until uniformity of the formulation was achieved.
Table 4: colored agricultural formulations
5. Seed treatment insecticides and biological seed treatments available from BASF, florham Park, NJ
6. Seed treatment insecticides and fungicides available from syngeneta, greensboro, NC
7. Available from Milliken&Pigment Red 48:2 pigment Dispersion obtained by Company, spartanburg, SC
A 10mg sample of the composition from table 4 was added to a separate 20mL scintillation vial. 10mL of each diluent from Table 5 was added separately to the scintillation vial, which was briefly swirled (5 seconds), and the observed color was recorded in Table 5. The pH of the diluent was measured using an Oakton pH 150 meter (available from Oakton Instruments, vernon Hills, IL) and also recorded in table 5.
Table 5: anti-counterfeit testing of colored agricultural formulations
8. Publicx distilled white vinegar, water containing 5% acetic acid
9. Lysol Power toilet bowl cleaners-diluted 1:9 with distilled water
10. Lemon-lime soda water manufactured by Keurig dr. Pepper
11. Publicx old lemon water
The test results in table 5 show that colored agricultural compositions 2 and 4 containing the colorant of example 1 of the present invention exhibit a color change from red to purple when exposed to common household ingredients (such as vinegar, lemonade and toilet bowl cleaners) having a pH measurement of less than 3. In contrast, pigmented agricultural compositions 1 and 3 containing pigment red 48:2 exhibited no color change. Thus, the colorants of the present invention can be used to verify agricultural formulations by an easy-to-use test method using common household ingredients.
Without wishing to be bound by theory, it is believed that the amine present in the red azo colorant containing thiazole and/or benzothiazole ring systems that do not contain electron withdrawing groups on the heterocyclic ring system will be protonated at a pH of 3 or less, thereby converting the observed hue of the dye to a higher maximum absorption wavelength (lambda max). With this shift in chromophore maximum absorbance to higher wavelengths, the observed color change will shift from red to purple. For those colorants containing electron withdrawing groups, the basicity of the heterocyclic nitrogen is reduced and the nitrogen group is not protonated, so the color of the chromophore does not change.
Additional experiments were performed with the colorant of example 1 of the present invention to show the performance after application to white wheat seeds. Coating formulations were prepared according to table 6. A slurry of these components was made and applied to white wheat seeds using a Aginnovation Rotary seed applicator. The treatment was applied to white wheat seeds in a rotating bowl within 5 seconds. The seeds were allowed to dwell in the disposer for an additional 20-30 seconds, then discharged from the bowl and collected.
Table 6: seed coating formulation for white wheat
12. Seed treatment fungicides obtainable from Syngenta, greensboro, NC
The treated seeds from Table 6 were stored at 50-55% relative humidity and 68-72℃for 48 hours and then subjected to dust emission tests. The dust exhaust was run using a Heubach dust meter. The dust removal protocol required 200g of seeds. The Heubach dust meter was set to 40rpms and the air flow was 20L/min for 5 minutes. The results are reported in grams of dust per 100,000 seeds. The test was repeated twice and the average of the two tests was reported. The results are shown in table 7.
TABLE 7 dust removal results from white wheat
Treatment formulation Dust exhaust (g dust/100,000 seeds)
W-1 0.02
W-2 0.02
W-3 0.02
W-4 0.05
As can be seen from the results in table 7, the use of the red azo colorants of the present invention shows an improvement in the level >50% reduction in the dust emission level of all treatments relative to the pigment formulation.
Additional experiments were performed with the colorant of example 1 of the present invention to show the performance after application to corn seeds. Coating formulations were prepared according to table 8. A slurry of these components was made and applied to corn seeds using a Aginnovation Rotary seed applicator. The treatment was applied to corn seeds in a rotating bowl within 5 seconds. The seeds were allowed to dwell in the disposer for an additional 20-30 seconds, then discharged from the bowl and collected.
Table 8: seed coating formulation for corn
The treated seeds from Table 8 were stored at 50-55% relative humidity and 68-72℃for 48 hours and then subjected to dust emission testing. The dust exhaust was run using a Heubach dust meter. The dust removal protocol required 200g of seeds. The Heubach dust meter was set to 40rpms and the air flow was 20L/min for 5 minutes. The results are reported in grams of dust per 100,000 seeds. The test was repeated twice and the average of the two tests was reported. The results are shown in table 9.
TABLE 9 dust removal results for corn
Treatment formulation Dust exhaust (g dust/100,000 seeds)
C-1 0.12
C-2 0.12
C-3 0.13
C-4 0.28
As can be seen from the results in table 9, the use of the red azo colorants of the present invention shows an improvement in the level >50% reduction in the dust emission level of all treatments relative to the pigment formulation. Thus, an improvement in seed coating quality can be obtained by using a colorant (as in example 1 of the present invention).
All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
The use of the terms "a" and "an" and "the" and similar referents in the context of describing the subject matter of the present application (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Unless otherwise noted, the terms "comprising," "having," "including," and "containing" are to be construed as open-ended terms (i.e., meaning "including, but not limited to"). Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the subject matter of the application and does not pose a limitation on the scope of the subject matter unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the subject matter described herein.
Preferred embodiments of the subject matter of this application are described herein, including the best mode known to the inventors for carrying out the claimed subject matter. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the subject matter described herein to be practiced otherwise than as specifically described herein. Accordingly, this disclosure includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Furthermore, unless indicated otherwise or the context clearly contradicts otherwise, this disclosure covers any combination of the above-described elements in all possible variations thereof.

Claims (16)

1. A method for determining the authenticity of a seed or agricultural formulation comprising the steps of:
(a) Providing a seed or agricultural formulation comprising a red azo colorant represented by the formula:
wherein R is 1 Comprising at least one 5-membered ring, said 5-membered ring having one N and one S atom incorporated in the ring system, and wherein said ring system is free of electron withdrawing groups;
R 2 And R is 3 Independently selected from H, alkyl, and poly (oxyalkylene) moieties, wherein R 2 And R is 3 Is a poly (oxyalkylene) moiety; and is also provided with
R 4 Independently selected from the group consisting of H, alkyl, substituted alkyl, nitrogen, substituted nitrogen, oxygen, halogen, and ether;
(b) Adding an acidic material to the seed or agricultural formulation of step "a"; and
(c) Visual observation changes in color from red to violet as the acidic material is added.
2. The method of claim 1, wherein the acidic material has a pH of 3 or less.
3. The method according to claim 1, wherein the seeds of step "a" are in aqueous solution prior to adding the acidic material.
4. The method of claim 1, wherein R 1 Selected from the group consisting of thiazole, isothiazole, benzisothiazole and benzothiazole.
5. The method of claim 4, wherein R 1 Selected from the group consisting of thiazoles and benzothiazoles.
6. The method of claim 1, wherein R 1 One or more substituents included on the ring selected from the group consisting of H, alkyl, substituted alkyl, hydroxy, substituted hydroxy, aryl, and substituted aryl.
7. The method of claim 1, wherein the poly (oxyalkylene) moiety is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and combinations thereof.
8. The method of claim 1, wherein the total number of alkylene oxide residues per colorant molecule is in the range of 4 to 250.
9. The method of claim 1, wherein the total number of alkylene oxide residues per colorant molecule is in the range of 5 to 100.
10. The method of claim 1, wherein the total number of alkylene oxide residues per colorant molecule is in the range of 5 to 20.
11. The method of claim 1, wherein the red azo colorant of step "a" is present in an amount ranging from about 0.001 wt% to about 50 wt%.
12. The method of claim 1, wherein the red azo colorant of step "a" is present in an amount ranging from about 0.5% to about 10% by weight.
13. The method of claim 1, wherein the red azo colorant of step "a" is represented by formula I or formula II:
wherein the method comprises the steps of
R 2 And R is 3 Independently selected from H, alkyl, and poly (oxyalkylene) moieties, and wherein R 2 And R is 3 Is a poly (oxyalkylene) moiety;
R 4 independently selected from the group consisting of H, alkyl, substituted alkyl, nitrogen, substituted nitrogen, oxygen, halogen, and ether; and is also provided with
R 5 Independently selected from the group consisting of H, alkyl, substituted alkyl, hydroxy, substituted hydroxy, aryl, and substituted aryl.
14. The method of claim 1, wherein the red azo colorant of step "a" is represented by formula III:
wherein R is 2 And R is 3 Independently selected from H, alkyl, and poly (oxyalkylene) moieties, and wherein R 2 And R is 3 Is a poly (oxyalkylene) moiety.
15. The method of claim 1, wherein the red azo colorant of step "a" is represented by formula IV:
16. a kit or system for determining the authenticity of a seed or agricultural formulation, the kit or system comprising: (1) A seed coated with the colorant of claim 1 or an agricultural formulation comprising the colorant of claim 1, and (2) an acidic material having a pH of less than or equal to 3.
CN202280040270.8A 2021-06-10 2022-05-02 Heterocyclic red azo colorants for seed treatment applications Pending CN117425818A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US63/208,996 2021-06-10
US17/714,298 2022-04-06
US17/714,298 US20220411387A1 (en) 2021-06-10 2022-04-06 Heterocyclic red azo colorants for seed treatment applications
PCT/US2022/027292 WO2022260777A1 (en) 2021-06-10 2022-05-02 Heterocyclic red azo colorants for seed treatment applications

Publications (1)

Publication Number Publication Date
CN117425818A true CN117425818A (en) 2024-01-19

Family

ID=89528886

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202280040270.8A Pending CN117425818A (en) 2021-06-10 2022-05-02 Heterocyclic red azo colorants for seed treatment applications

Country Status (1)

Country Link
CN (1) CN117425818A (en)

Similar Documents

Publication Publication Date Title
US8273684B2 (en) Seed coating composition
JP4026829B2 (en) Microbicidal composition
US7368466B2 (en) Low-temperature-stable preservatives
JPH11116412A (en) Solid biocide composition
CA2420126C (en) Anti-microbial latex compositions comprising a polymeric biguanide and an isothiazolinone
EP0789987B1 (en) Coated seed improved colorant
KR101385507B1 (en) Synergistic combination of a glyphosate compound and zpt
CN101011055A (en) Microbicidal composition
MX2010014576A (en) Biocidal compositions.
CA2703049A1 (en) Enhancement of plant growth
US20080113868A1 (en) Colorant compositions and their use as pH sensitive color indicators
CN117425818A (en) Heterocyclic red azo colorants for seed treatment applications
CN117460412A (en) Heterocyclic red azo colorants for seed treatment applications
US20100189811A1 (en) Biocide compositions comprising 3-methylisothiazolin-3-one and a haloalkyl sulphone
US5387745A (en) Process for identifying a location to which an agrochemical has been applied
US20220411387A1 (en) Heterocyclic red azo colorants for seed treatment applications
EP4351333A1 (en) Heterocyclic red azo colorants for seed treatment applications
AU7200300A (en) 5-carboxanilido-haloalkylthiazoles as antimicrobial and marine antifouling agents
KR101362849B1 (en) Synergistic combination of a glyphosate compound and tbz
WO2024066591A1 (en) Environment-friendly antimicrobial mildew-proof water-based pigment paste as well as preparation method therefor and use thereof
EP0997068A1 (en) Synergistic microbicidal combinations
KR101385503B1 (en) Synergistic combination of a glyphosate compound and dmits
BRPI1107137A2 (en) synergistic antimicrobial composition, method for inhibiting the growth of, or for controlling the growth of microorganisms in a building material, coating composition, and dry film
JP3916216B2 (en) Novel dibromonitroalcohol derivatives and their uses
CN114007418B (en) Stable aqueous suspension formulations

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination