CA1142771A - Herbicidal compositions - Google Patents
Herbicidal compositionsInfo
- Publication number
- CA1142771A CA1142771A CA000345307A CA345307A CA1142771A CA 1142771 A CA1142771 A CA 1142771A CA 000345307 A CA000345307 A CA 000345307A CA 345307 A CA345307 A CA 345307A CA 1142771 A CA1142771 A CA 1142771A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- linuron
- phthalic acid
- crystallization
- herbicidal composition
- 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
Links
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
-
- 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
- A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
- A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
Abstract
HERBICIDAL COMPOSITIONS
Abstract of the disclosure:
Liquid emulsifiable herbicidal compositions containing linuron as the active ingredient, organic solvents and emulsifiers, which are characterized by a content of com-pounds inhibiting a crystallization of active ingredient in the aqueous emulsions of the concentrates, of from 0.2 to 5 weight %, these compounds being phthalic acid dialkyl ester or phthalic acid alkyd resins or oil-modified phtha-lic acid alkyd resins or terpene-phenol resins or mixtures thereof.
Abstract of the disclosure:
Liquid emulsifiable herbicidal compositions containing linuron as the active ingredient, organic solvents and emulsifiers, which are characterized by a content of com-pounds inhibiting a crystallization of active ingredient in the aqueous emulsions of the concentrates, of from 0.2 to 5 weight %, these compounds being phthalic acid dialkyl ester or phthalic acid alkyd resins or oil-modified phtha-lic acid alkyd resins or terpene-phenol resins or mixtures thereof.
Description
`"` ~ 7~1
- 2 - HOE 79/F 023 The present invention relates to herbicidal composi~
tions in the fcrm of emulsifiable conc~trates containing
tions in the fcrm of emulsifiable conc~trates containing
3-(3,4-dichlorophenyl) 1-methyl-~-~c-:tho~y-urea (common name: linuron) as active substance, organic solvents, emul-sifiers and compounds inhibiting the crystallization ofactive matter in the aqueous emulsions of the concentrates.
It is known from German patent 1,028,986 to use linuron as herbicidal agent. In most cases this active substance is applied in the form of suspensions in water which are obtainable by stirring a wettable powder of linuron with water. However, prior to preparing the spray lia.uors in the form of aqueous suspensions, the wettable powders have to be weighed out very exactly by the applicant. When per-formed in the open field, weighing is expensive and often inexactly, especially in the case of wind, as the powder is dusty and may hence may readily blown away. The appli-cant, too, is exposed directly to this dust. The prepa-ration of wettable powders of linuron, too, is expensive, since the low melting point of the active matter of from 93 to 9l~C and its soft, non-brittle consistancy require the use of expensive, fine absorptive carriers such as synthetic silicic acid in order to prevent a sintering of the product to be ground during milling in high-speed, high-efficiency mills such as blowing mills or pinned disk mills or jet mills as may be caused by the heat engaged during the milling process. As regards the suspendibility of linuron wettable powders in water, the international WHO and CIPAC standards are hardly complied with, notwith-standing the above-described great expenditure, although the particles of the wettable powder have mean sizes rang-ing of from 5 to 20 microns.
Hence it ~1as long been a need to apply linuron in emulsified form via an emulsifiable concentrate. The liquid emulsifiable concentrates are easier to handle and far easier to measure than wettable powder formulations.
Their preparation, too, is easy. It is generally done by dissolving the active substance in appropriate solvents , ~
27~1 with the addition of adequate émulsifiers. This only requires vessels provided with a stirrer.
Linuron is distinguished by a good solubility in aro-matic solvents as used generally for the preparation of emulsifiable concentrates. Moreover there may be used conventional emulsifier mixtures that are capable of form-ing emulsifiable concentrates with linuron solutions of the above type.
For example, British patent 982,344 describes in addi-tion to powder formulations an emulsifiable concentratecontaining 10 weight % of linuron.
However, the known emulsifiable concentrates of linuron have not been used hitherto in practice, since considerable difficulties arise during the application of aqueous emul-sions thereof. For example, emulsifiable concentrates oflinuron containing the conventional solvents or mixtures of solvents, certainly, form emulsions on dilution with water, however, after a short period of time, for example after 5 to 15 minutes, and especially in cold water of from 1Q to 15C, solid linuron precipitates from these emulsions in the form of crystal needles of from 100 to 250 microns length.
Crystallization is accelerated when stirring the spray emulsion. When applying aqueous spray emulsions based on linuron of the above type, the nozzles of the spraying equipments used for plant protection may obtstruct by the precipitated crystal particles. A further disadvantage is that emulsion spray liquors of the above type are less efficient than aqueous wettable powder suspensions of comparable concentration, as the active matter in linuron emulsions is present in a far coarser and a far more inho-mogeneous state of distribution owing to crystallization phenomena than in wettable powder suspensions.
Japanese patent Sho 4510359 (patent application No Sho 42-13123) points to these disadvantages of the emulsifiable concentrates of linuron and describes an emulsifiable for-mulation containing great portions of cyclohexylidene-cyc-ll~Z771 lohexanone as the solvent. Thus crystallization of linuron from the aqueousemulsion drops forming the deposit on the plant may be prevented when the emulsifiable concentrate contains of from 15 to 30 weight % of cyclohexylidene-cyclohexanone in addition to 20 weight % of linuron. However~ owing to the high costs of the solvent described hereinbefore, a formulation of the above type has not been used in practice. However, as is shown in Comparative Example 4 below, cyclohexylidene-cyclohexanone, neither is capable of preventing a crystallization of linuron from the aqueous emulsion in the spray container.
It has now been found that liquid emulsifiable herbicidal concen-trates that do not have the above disadvantages and that contain linuron as the active matter, organic solvents and emulsifiers can be obtained when adding to the concentrates as crystallization-inhibiting component, preventing a crystal-lization of active matter in the aqueous emulsions of the concentrates, of from 0.2 to 5 weight %, preferably from 1 to 2 weight %, of phthalic acid dialkyl ester and/or phthalic acid alkyd resins and/or oil-modified phthalic acid alkyd resins and/or terpene-phenol resins.
Thus, the present invention provides liquid, emulsifiable herbicidal composition containing 3-(3,4-dichlorophenyl)-1-methyl-1-methoxy-urea (linuron) as the active ingredient, an organic solvent and an emulsifier, which include as crystallization-inhibiting component preventing the crystallization of active ingredients in the aqueous emulsion of the concentrate, from 0.2 to 5 weight % of a phthalic acid dialkyl ester in which the alkyl groups contain from 1 to 18 carbon atoms, or a phthalic acid alkyd resin, oil-modified phthalic acid alkyd resin or terpene-phenol resin, soluble in organic solvent, or a mixture of these compounds. The crystallization-inhibiting component preferably comprises from 1 to 2 weight % of the composition.
Subject of the present invention are especially emulsifiable , ~Z~
herbicidal concentrates containing linuron as the active ingredient organic solvents and emulsifiers characterized in that they contain of from 10 to 25 weight % of linuron, of from 84.8 to 60 weight % of organic solvents, preferably -4a-~, ~2'.~
of from 24.8 to 40 weight % of ketones, especially isophorone, and of from 50 to 20 weight % of aromatic solvents, especially xylene, of from 5 to 10 weight % of emulsifiers and of from 0.2 to 5 weight % of phthalic acid dialkyl ester or phthalic acid alkyd resins or oil-modified phthalic acid alkyd resins or terpene-phenol resins or mixtures of these compounds.
Preferred crystallization-inhibiting compounds are oil-modified phthalic acid alkyd resins and terpene-phenol - resins.
Particularly preferred solvents are combinations of isophorone and xylene.
Preferred aromatic solvents are, for example, alkyl-benzenes, preferably xylene, or higher-boiling industrial distillation products of aromatic compounds, for example those based on mineral oil of a boiling point of from 156 to 312C (under normal pressure).
Preferred ketones are especially aliphatic or cyclo-aliphatic ketones, especially liquid ketones of a flash point above 400C (measured in a closed recipient). The ketones are used to improve the solubility of linuron in aromatic solvents and to improve the stability of low tem-peratures of the emulsifiable linuron concentrates, for example at a temperature of from about 0C to -10C. Espe-cially appropriate ketones are, for example, isophorone and cyclohexanone, isophorone being the most preferred ; compound.
Emulsifiable concetrates are obtained, for example, on dissolution of the active ingredient in an organic sol-vent or in mixtures of solvents, such as those containing xylene and isophorone, and on addition of an emulsifier.
Appropriate emulsifiers are all the known surfactants used as auxiliary in the formulation of emulsifiable con-centrates and which are soluble in xylene, Por example cal-cium salts of dodecylbenzene-sulfonic acids or calcium -~ HOE 79/~ 0?3 salts of chlorinated (C13 15) alkane-sulfonic acids or po-lyglycol ethers, for example of nonylphenols or polyglycol ethers, for example of fatty alcohols or for example, reac-tion products of castor oil and ethylene oxide.
Appropriate phthalic acid esters are ~e~e~Rb~ phtha-lic acid dialkyl esters whose alkyl groups each have up to 18 carbon atoms, especially up tc 12 carbon a~oms and which may ie substituted, for example phthalic acid dime-thyl or especially phthalic acid diisooctyl ester, as used as plasticizers in plastic processing. In plant protec-tion compositions, phthalic acid esters of the above type ha~e somtimes been used as evaporation-inhibiting additives in the formulation of phosphor~s ester as the active ingre-dient (cf. German Offenlegungsschrift 2,738,87~; French patent 2,092,898). However, they have not been used hlther-to as crystallization-inhibiting agent for active su~stances in aqueous emulsions of emulsifiable concentrates, espe-cially of linuron.
Further appropriate crystallization-inhibiting corn-pounds with regard to linuron in aqueous emulsions i.n addi-tion to the simple phthalic acid dialkyl esters are espe-cially phthalic acid ester groups-containing polyconden-sates that arP soluDle in organic so'~ents, for example those as known as phthalic acid alkyd resins or espccially as oil-modifi.ed phthalic acid alkyd resins.
By oil-modified phthalic acid alkyd resins there are to be understood polyesters soluble in organic sol~ents and containing phthalic acid ester groups. These polyesters are obtained by directly esterifying, for example either phthalic acid or phthalic acid anhydride with aliphatic fatty acids and polyalcohols, such as glycerol, sorbitol, pentaerythritol, in a single-stage process or by trans-esterifying fatty acid triglycerides with polyalcohols-(alcoholysis) and subsequently esterifying the resulting reactior. product with phthalic acid or phthalic acid anhy-dride in a ~second process step.
The fatty acids used as such or the fatty acids ob-~Z'7~1 tained from the fatty oils, which are used subsequently for esterification, may be saturated or unsat.urated.
Phthalic acid alkyd resins as well as their prepara-tion are described, for example in "Winnacker-Kuchler, Chemische Technologie", Volume 5, pages 410 - 422, Carl Hanser Verlag, Munich, 1972.
Especially appropriate oil-modified phthalic acid alkyd resins are, for example those obtained by synthesis of, for example inter alia 40 weight % of castor oil and 37 weight g of phthalic acid anhydride (alkyd resin A) or those obtained by synthesis of especially selected, unsa-turated drying oils (for example cotton seed oil) in an amount of 45 weight % and of 27 weight % of phthalic acid anhydride (alkyd resin B), or those obtained by synthesis ~5 of inter alia 37 weight % of isononanic acid, calculated as triglyceride and of 40 weight % of phthalic acid anhy-dride (alkyd resin C).
The terpene-phenol resins further used in accordance with the present invention for the crystallization-inhibit-ing stabilization of emulsifiable concentrates of linuronsand which are soluble in organic solvents, are described, ~or example in "Winnacker-Kuchler, Chemische Technologie", volume 3, page 506, Karl Hanser Verlag, Munich 1971. They are obtainable by condensation of terpene-type hydrocarbons such as~ pinene or oil of turpentine with phenols or alkyl-phenols in the presence of catalysts, such as boron fluoride (cf. Ullmann, Enzyklopadie der Technischen Chemie, 4th edi-tion, (1976), vol. 12, page 543; Rompp, Chemielexikon, 7th edition (1977), vol. 6, pa~e 3506).
Preferred resins are not-hardening, oil-soluble ter-pene-phenol resins (terpene-phenol resin A).
The emulsifiable concentrates of linuron stabilized by cr-ystallization-inhibiting compounds in accordance with the present invention are distinguished by an outstanding resistance to storage as regards their chemical and physi-cal properties and their utilitariar. properties, which has been demonstra'ed by storage tests under severe conditions, Z~
- 8 - HOE 79tF 023 for example storage for 3 months at 50C or the cold test at -10C.
The emulsifiable concentrates of linuron are prepared in simple manner by adding to the solvents and dissolving therein while stirring linuron, emulsifiers and the phtha-lic esters, phthalic ester resins, oil-modified phthalic ester resins, terpene-phenol resins or mixtues of said compounds.
Surprisingly the emulsifiable concentrates of linuron in accordance with the present invention with the same quantities applied, are distinguished by a better herbici-dal action as compared with linuron wettable powders, upon emulsification of comparable formu]ations in water or upon application in suspended form, which means an economy of active matter in practice. For combating weeds, the herbi-cidal concentrates in accordance with the present invention are applied from an aqueous emulsion in efficient amounts, for example an amount of from 0.03 to 0.13 kg of active matter per hectar.
The following examples demonstrate the action of the crystallization-inhibiting components in accordance with the present invention and the biological activity of the emulsifiable linuron concentrates in accordance with the invention.
The emulsifiable concentrates used for the comparative tests contained 10 or 20 weight ~, respectively, of linuron.
Corresponding results are obtained as well when adjusting the concentration of linuron in the concentrates, for ex-ample to 15 or 25 weight %, respectively, it being possible to vary the solvent portions simultaneously accordingly.
The action of the crystallization-inhibiting compo-nents on the crystallization behavior of linuron in aque-ous emulsions of emulsifiable concentrates is examined by testir.g the emulsions under the microscope for crystals formed and optionally by determining the crystal size. To this end, there are prepared emulsions each of which con-tain 2.5 weight ~ of emulsifiable concentrate in 97.5 Z~
weight parts of water of 342 ppm hardness (WHO svandard1 cf. CIPAC-~andbook (1970), page 878) and of a temperature of 10C or 30C, respectively. The emulsions are stirred at 10C or 30C, with microscopic examinations for linuron crystals formed and optionally with determinations of the crystal sizes being carried out after 15, 30 and 120 minutes and after a 3 hours' standing.
_ormulation Examples COMPARATIVE EXAMPLE 1: (corresponding to British patent 982,344, Example 4) 10 weight % of linuron 70 weight % of xylene 20 weight % of emulsifier mixture from polyoxethylated B ethers and~oil-soluble petroleum sulfona-tes (Emcol H 140).
After a 15 minutes' stirring of the 2.5 % aqueous emul-sion linuron crystal needles of 70 to 80 microns and after 30 minutes those of 220 to 240 microns size have formed.
COMPARATIVE EXAMPLE 2: (analogously to Japanese patent Sho 45 10 359) 20 weight % of linuron 20 weight % of 2~cyclohexylidene-cyclohexanone 50 weight ~ of xylene 5 weight % of chlorinated calcium salt of (C13 15) alkane-sulfonic acid 1 weight % of oleylalcohol polyglycol ether (8 AeO)
It is known from German patent 1,028,986 to use linuron as herbicidal agent. In most cases this active substance is applied in the form of suspensions in water which are obtainable by stirring a wettable powder of linuron with water. However, prior to preparing the spray lia.uors in the form of aqueous suspensions, the wettable powders have to be weighed out very exactly by the applicant. When per-formed in the open field, weighing is expensive and often inexactly, especially in the case of wind, as the powder is dusty and may hence may readily blown away. The appli-cant, too, is exposed directly to this dust. The prepa-ration of wettable powders of linuron, too, is expensive, since the low melting point of the active matter of from 93 to 9l~C and its soft, non-brittle consistancy require the use of expensive, fine absorptive carriers such as synthetic silicic acid in order to prevent a sintering of the product to be ground during milling in high-speed, high-efficiency mills such as blowing mills or pinned disk mills or jet mills as may be caused by the heat engaged during the milling process. As regards the suspendibility of linuron wettable powders in water, the international WHO and CIPAC standards are hardly complied with, notwith-standing the above-described great expenditure, although the particles of the wettable powder have mean sizes rang-ing of from 5 to 20 microns.
Hence it ~1as long been a need to apply linuron in emulsified form via an emulsifiable concentrate. The liquid emulsifiable concentrates are easier to handle and far easier to measure than wettable powder formulations.
Their preparation, too, is easy. It is generally done by dissolving the active substance in appropriate solvents , ~
27~1 with the addition of adequate émulsifiers. This only requires vessels provided with a stirrer.
Linuron is distinguished by a good solubility in aro-matic solvents as used generally for the preparation of emulsifiable concentrates. Moreover there may be used conventional emulsifier mixtures that are capable of form-ing emulsifiable concentrates with linuron solutions of the above type.
For example, British patent 982,344 describes in addi-tion to powder formulations an emulsifiable concentratecontaining 10 weight % of linuron.
However, the known emulsifiable concentrates of linuron have not been used hitherto in practice, since considerable difficulties arise during the application of aqueous emul-sions thereof. For example, emulsifiable concentrates oflinuron containing the conventional solvents or mixtures of solvents, certainly, form emulsions on dilution with water, however, after a short period of time, for example after 5 to 15 minutes, and especially in cold water of from 1Q to 15C, solid linuron precipitates from these emulsions in the form of crystal needles of from 100 to 250 microns length.
Crystallization is accelerated when stirring the spray emulsion. When applying aqueous spray emulsions based on linuron of the above type, the nozzles of the spraying equipments used for plant protection may obtstruct by the precipitated crystal particles. A further disadvantage is that emulsion spray liquors of the above type are less efficient than aqueous wettable powder suspensions of comparable concentration, as the active matter in linuron emulsions is present in a far coarser and a far more inho-mogeneous state of distribution owing to crystallization phenomena than in wettable powder suspensions.
Japanese patent Sho 4510359 (patent application No Sho 42-13123) points to these disadvantages of the emulsifiable concentrates of linuron and describes an emulsifiable for-mulation containing great portions of cyclohexylidene-cyc-ll~Z771 lohexanone as the solvent. Thus crystallization of linuron from the aqueousemulsion drops forming the deposit on the plant may be prevented when the emulsifiable concentrate contains of from 15 to 30 weight % of cyclohexylidene-cyclohexanone in addition to 20 weight % of linuron. However~ owing to the high costs of the solvent described hereinbefore, a formulation of the above type has not been used in practice. However, as is shown in Comparative Example 4 below, cyclohexylidene-cyclohexanone, neither is capable of preventing a crystallization of linuron from the aqueous emulsion in the spray container.
It has now been found that liquid emulsifiable herbicidal concen-trates that do not have the above disadvantages and that contain linuron as the active matter, organic solvents and emulsifiers can be obtained when adding to the concentrates as crystallization-inhibiting component, preventing a crystal-lization of active matter in the aqueous emulsions of the concentrates, of from 0.2 to 5 weight %, preferably from 1 to 2 weight %, of phthalic acid dialkyl ester and/or phthalic acid alkyd resins and/or oil-modified phthalic acid alkyd resins and/or terpene-phenol resins.
Thus, the present invention provides liquid, emulsifiable herbicidal composition containing 3-(3,4-dichlorophenyl)-1-methyl-1-methoxy-urea (linuron) as the active ingredient, an organic solvent and an emulsifier, which include as crystallization-inhibiting component preventing the crystallization of active ingredients in the aqueous emulsion of the concentrate, from 0.2 to 5 weight % of a phthalic acid dialkyl ester in which the alkyl groups contain from 1 to 18 carbon atoms, or a phthalic acid alkyd resin, oil-modified phthalic acid alkyd resin or terpene-phenol resin, soluble in organic solvent, or a mixture of these compounds. The crystallization-inhibiting component preferably comprises from 1 to 2 weight % of the composition.
Subject of the present invention are especially emulsifiable , ~Z~
herbicidal concentrates containing linuron as the active ingredient organic solvents and emulsifiers characterized in that they contain of from 10 to 25 weight % of linuron, of from 84.8 to 60 weight % of organic solvents, preferably -4a-~, ~2'.~
of from 24.8 to 40 weight % of ketones, especially isophorone, and of from 50 to 20 weight % of aromatic solvents, especially xylene, of from 5 to 10 weight % of emulsifiers and of from 0.2 to 5 weight % of phthalic acid dialkyl ester or phthalic acid alkyd resins or oil-modified phthalic acid alkyd resins or terpene-phenol resins or mixtures of these compounds.
Preferred crystallization-inhibiting compounds are oil-modified phthalic acid alkyd resins and terpene-phenol - resins.
Particularly preferred solvents are combinations of isophorone and xylene.
Preferred aromatic solvents are, for example, alkyl-benzenes, preferably xylene, or higher-boiling industrial distillation products of aromatic compounds, for example those based on mineral oil of a boiling point of from 156 to 312C (under normal pressure).
Preferred ketones are especially aliphatic or cyclo-aliphatic ketones, especially liquid ketones of a flash point above 400C (measured in a closed recipient). The ketones are used to improve the solubility of linuron in aromatic solvents and to improve the stability of low tem-peratures of the emulsifiable linuron concentrates, for example at a temperature of from about 0C to -10C. Espe-cially appropriate ketones are, for example, isophorone and cyclohexanone, isophorone being the most preferred ; compound.
Emulsifiable concetrates are obtained, for example, on dissolution of the active ingredient in an organic sol-vent or in mixtures of solvents, such as those containing xylene and isophorone, and on addition of an emulsifier.
Appropriate emulsifiers are all the known surfactants used as auxiliary in the formulation of emulsifiable con-centrates and which are soluble in xylene, Por example cal-cium salts of dodecylbenzene-sulfonic acids or calcium -~ HOE 79/~ 0?3 salts of chlorinated (C13 15) alkane-sulfonic acids or po-lyglycol ethers, for example of nonylphenols or polyglycol ethers, for example of fatty alcohols or for example, reac-tion products of castor oil and ethylene oxide.
Appropriate phthalic acid esters are ~e~e~Rb~ phtha-lic acid dialkyl esters whose alkyl groups each have up to 18 carbon atoms, especially up tc 12 carbon a~oms and which may ie substituted, for example phthalic acid dime-thyl or especially phthalic acid diisooctyl ester, as used as plasticizers in plastic processing. In plant protec-tion compositions, phthalic acid esters of the above type ha~e somtimes been used as evaporation-inhibiting additives in the formulation of phosphor~s ester as the active ingre-dient (cf. German Offenlegungsschrift 2,738,87~; French patent 2,092,898). However, they have not been used hlther-to as crystallization-inhibiting agent for active su~stances in aqueous emulsions of emulsifiable concentrates, espe-cially of linuron.
Further appropriate crystallization-inhibiting corn-pounds with regard to linuron in aqueous emulsions i.n addi-tion to the simple phthalic acid dialkyl esters are espe-cially phthalic acid ester groups-containing polyconden-sates that arP soluDle in organic so'~ents, for example those as known as phthalic acid alkyd resins or espccially as oil-modifi.ed phthalic acid alkyd resins.
By oil-modified phthalic acid alkyd resins there are to be understood polyesters soluble in organic sol~ents and containing phthalic acid ester groups. These polyesters are obtained by directly esterifying, for example either phthalic acid or phthalic acid anhydride with aliphatic fatty acids and polyalcohols, such as glycerol, sorbitol, pentaerythritol, in a single-stage process or by trans-esterifying fatty acid triglycerides with polyalcohols-(alcoholysis) and subsequently esterifying the resulting reactior. product with phthalic acid or phthalic acid anhy-dride in a ~second process step.
The fatty acids used as such or the fatty acids ob-~Z'7~1 tained from the fatty oils, which are used subsequently for esterification, may be saturated or unsat.urated.
Phthalic acid alkyd resins as well as their prepara-tion are described, for example in "Winnacker-Kuchler, Chemische Technologie", Volume 5, pages 410 - 422, Carl Hanser Verlag, Munich, 1972.
Especially appropriate oil-modified phthalic acid alkyd resins are, for example those obtained by synthesis of, for example inter alia 40 weight % of castor oil and 37 weight g of phthalic acid anhydride (alkyd resin A) or those obtained by synthesis of especially selected, unsa-turated drying oils (for example cotton seed oil) in an amount of 45 weight % and of 27 weight % of phthalic acid anhydride (alkyd resin B), or those obtained by synthesis ~5 of inter alia 37 weight % of isononanic acid, calculated as triglyceride and of 40 weight % of phthalic acid anhy-dride (alkyd resin C).
The terpene-phenol resins further used in accordance with the present invention for the crystallization-inhibit-ing stabilization of emulsifiable concentrates of linuronsand which are soluble in organic solvents, are described, ~or example in "Winnacker-Kuchler, Chemische Technologie", volume 3, page 506, Karl Hanser Verlag, Munich 1971. They are obtainable by condensation of terpene-type hydrocarbons such as~ pinene or oil of turpentine with phenols or alkyl-phenols in the presence of catalysts, such as boron fluoride (cf. Ullmann, Enzyklopadie der Technischen Chemie, 4th edi-tion, (1976), vol. 12, page 543; Rompp, Chemielexikon, 7th edition (1977), vol. 6, pa~e 3506).
Preferred resins are not-hardening, oil-soluble ter-pene-phenol resins (terpene-phenol resin A).
The emulsifiable concentrates of linuron stabilized by cr-ystallization-inhibiting compounds in accordance with the present invention are distinguished by an outstanding resistance to storage as regards their chemical and physi-cal properties and their utilitariar. properties, which has been demonstra'ed by storage tests under severe conditions, Z~
- 8 - HOE 79tF 023 for example storage for 3 months at 50C or the cold test at -10C.
The emulsifiable concentrates of linuron are prepared in simple manner by adding to the solvents and dissolving therein while stirring linuron, emulsifiers and the phtha-lic esters, phthalic ester resins, oil-modified phthalic ester resins, terpene-phenol resins or mixtues of said compounds.
Surprisingly the emulsifiable concentrates of linuron in accordance with the present invention with the same quantities applied, are distinguished by a better herbici-dal action as compared with linuron wettable powders, upon emulsification of comparable formu]ations in water or upon application in suspended form, which means an economy of active matter in practice. For combating weeds, the herbi-cidal concentrates in accordance with the present invention are applied from an aqueous emulsion in efficient amounts, for example an amount of from 0.03 to 0.13 kg of active matter per hectar.
The following examples demonstrate the action of the crystallization-inhibiting components in accordance with the present invention and the biological activity of the emulsifiable linuron concentrates in accordance with the invention.
The emulsifiable concentrates used for the comparative tests contained 10 or 20 weight ~, respectively, of linuron.
Corresponding results are obtained as well when adjusting the concentration of linuron in the concentrates, for ex-ample to 15 or 25 weight %, respectively, it being possible to vary the solvent portions simultaneously accordingly.
The action of the crystallization-inhibiting compo-nents on the crystallization behavior of linuron in aque-ous emulsions of emulsifiable concentrates is examined by testir.g the emulsions under the microscope for crystals formed and optionally by determining the crystal size. To this end, there are prepared emulsions each of which con-tain 2.5 weight ~ of emulsifiable concentrate in 97.5 Z~
weight parts of water of 342 ppm hardness (WHO svandard1 cf. CIPAC-~andbook (1970), page 878) and of a temperature of 10C or 30C, respectively. The emulsions are stirred at 10C or 30C, with microscopic examinations for linuron crystals formed and optionally with determinations of the crystal sizes being carried out after 15, 30 and 120 minutes and after a 3 hours' standing.
_ormulation Examples COMPARATIVE EXAMPLE 1: (corresponding to British patent 982,344, Example 4) 10 weight % of linuron 70 weight % of xylene 20 weight % of emulsifier mixture from polyoxethylated B ethers and~oil-soluble petroleum sulfona-tes (Emcol H 140).
After a 15 minutes' stirring of the 2.5 % aqueous emul-sion linuron crystal needles of 70 to 80 microns and after 30 minutes those of 220 to 240 microns size have formed.
COMPARATIVE EXAMPLE 2: (analogously to Japanese patent Sho 45 10 359) 20 weight % of linuron 20 weight % of 2~cyclohexylidene-cyclohexanone 50 weight ~ of xylene 5 weight % of chlorinated calcium salt of (C13 15) alkane-sulfonic acid 1 weight % of oleylalcohol polyglycol ether (8 AeO)
4 weight % of castor oil polyglycol ether (40 AeO) After a 15 minutes' stirring of the 2.5 % aqueuos emulsion linuron crystals of 90 to 140 microns and after 30 30 minutes crystals of 190 to 240 microns have formed.
COMPARATI~E _XAMPLE 3:
20 weight p of linuron 35 weight % of xylene 35 weight % of isophorene 4.5 weight % of castor oil polyglycol ether (40 AeO) 2.0 weight % of oleyl alcohol polyglycol ether (8 AeO) 3.5 weight ~ of calcium salt of dodecylbenzer,e-sulfo ~7~ J~
l~ ~Z7~
nic acid After ~ 10 minutes' stirring of the 2.5 % aqueous emul-sion linuron crystals of 90 to 150 microns and after 30 mi-nutes crystals of 200 to 260 microns have formed.
COMPARATIVE EXAMPLE 4:
weight g of linuron weight % of xylene weight % of cyclohexanone 4.5 weight % of castor oil polyglycol ether (40 AeO) 2.0 weight % of oleyl alcohol polyglycol ether (8 AeO) 3.5 weight d of chlorinated calcium salt of (C13 15) alkane-sulfonic acid.
- After a 10 minutes' stirring of the 2.5 % aqueous emul-sion linuron crystals of 90 to 110 microns and after 30 mi-r.utes crystals of 200 to 250 microns have formed.
COMPARATIVE EXAMPLE 5:
A linuron-50-wettable powder (having a conter.t of ac-tive substance of 50 weight %) was prepared for this bio]ogical test by grinding the following mixture twice in a pinned disk mill at a rotational speed of the mill disk of 150 m/sec. to a fineness below 10 microns:
50.0 weight % of linuron 30.0 weight % of finely divided synthetic silicic acid 10.0 weight % of sodium salt of dinaphthylmethane-di-sulfonic acid 0.5 weight % of sodium salt of oleyolmethyltauride 2.0 weight % of sodium salt of dibutylnaphthalene-sulfonic acid 7.5 weight % of diatomaceous earth.
The formulations according to the invention have the fol]owing compositions:
E X A M P L E 1:
10 weight % of linuron - 15 weight ~ of isophorone 63 weight % of industrial distillate of aromatic pro-ducts b.p. 183-270C
4.5 weight % of calcium salt of dodecylben~ene-sul-fonic acid 4.5 weight % of castor oil polyglycol ether (40 AeO) 1.0 weight % of oley]. alcohol polyglycol ether t8 AeO) 2.0 weight ~ of alkyd resin A.
S After a 2 hours' stirri.ng of the 2.5 % aqueous emul-sion a crystal formation was not observed, neither after a further 3 hours' standing.
E X A M P L E 2:
_ 20.0 weight % of linuron 35.0 weight % of isophorone 33.0 weight % of xylene 4.5 weight % of castor oil polyglycol ether (40 AeO) 2.0 weight % of oleyl alcohol polyglycol ether (8 AeO) 3.5 weight % of calcium salt of dodecylbenzene-sul-fonic acid 2.0 weight % of alkyd resin A.
After a 4 hours' stirring and after a 4 hours' standing of the 2.5 % aqueous emulsion a crystal formation could not be observed.
E X A M P L E S 3, 4, 5, ~:
These examples are carried out as Example 2, except that 2 weight ~ of alkyd resin C or of alkyd resin B or of terpene-phenol resin A or 1 weight ~ of alkyd resin A + 1 weight % of terpene-phenol resin A are used instead of 2 weight % of alkyd resin A.
After a 3 hours' stirring and after a 4 hours' stand-ing a crystal formation was not observed in the 2.5 % aque-ous emulsions of the concentrates in all of the examples.
E X A M P L E ?
20.0 weight % of linuron 35.0 weight % of isophorone 33.0 weight % of industrial distillate of aromatic compounds, b.p. 183 to 312C
4.5 weight ~ of castor oil polyglycol ether (40 AeO) 3.2 weight % of calcium salt of dodecylbenzene-sulfo-nic acid ~l~Z~l - 12 - _OE_79JF 023 2.3 weight ~ of oleyl alcohol polyglycol ether (8 AeO) 2.0 weight % of alkyd resin A.
After a 2 hours' stirring and after a further 3 hours' standing a crystal formation of the 2.5 ~ aqueous emulsions was not observed.
E X A M P L E S 8, 9:
20.0 weight % of linuron 35.0 weight % of isophorone 30.0 weight % of xylene
COMPARATI~E _XAMPLE 3:
20 weight p of linuron 35 weight % of xylene 35 weight % of isophorene 4.5 weight % of castor oil polyglycol ether (40 AeO) 2.0 weight % of oleyl alcohol polyglycol ether (8 AeO) 3.5 weight ~ of calcium salt of dodecylbenzer,e-sulfo ~7~ J~
l~ ~Z7~
nic acid After ~ 10 minutes' stirring of the 2.5 % aqueous emul-sion linuron crystals of 90 to 150 microns and after 30 mi-nutes crystals of 200 to 260 microns have formed.
COMPARATIVE EXAMPLE 4:
weight g of linuron weight % of xylene weight % of cyclohexanone 4.5 weight % of castor oil polyglycol ether (40 AeO) 2.0 weight % of oleyl alcohol polyglycol ether (8 AeO) 3.5 weight d of chlorinated calcium salt of (C13 15) alkane-sulfonic acid.
- After a 10 minutes' stirring of the 2.5 % aqueous emul-sion linuron crystals of 90 to 110 microns and after 30 mi-r.utes crystals of 200 to 250 microns have formed.
COMPARATIVE EXAMPLE 5:
A linuron-50-wettable powder (having a conter.t of ac-tive substance of 50 weight %) was prepared for this bio]ogical test by grinding the following mixture twice in a pinned disk mill at a rotational speed of the mill disk of 150 m/sec. to a fineness below 10 microns:
50.0 weight % of linuron 30.0 weight % of finely divided synthetic silicic acid 10.0 weight % of sodium salt of dinaphthylmethane-di-sulfonic acid 0.5 weight % of sodium salt of oleyolmethyltauride 2.0 weight % of sodium salt of dibutylnaphthalene-sulfonic acid 7.5 weight % of diatomaceous earth.
The formulations according to the invention have the fol]owing compositions:
E X A M P L E 1:
10 weight % of linuron - 15 weight ~ of isophorone 63 weight % of industrial distillate of aromatic pro-ducts b.p. 183-270C
4.5 weight % of calcium salt of dodecylben~ene-sul-fonic acid 4.5 weight % of castor oil polyglycol ether (40 AeO) 1.0 weight % of oley]. alcohol polyglycol ether t8 AeO) 2.0 weight ~ of alkyd resin A.
S After a 2 hours' stirri.ng of the 2.5 % aqueous emul-sion a crystal formation was not observed, neither after a further 3 hours' standing.
E X A M P L E 2:
_ 20.0 weight % of linuron 35.0 weight % of isophorone 33.0 weight % of xylene 4.5 weight % of castor oil polyglycol ether (40 AeO) 2.0 weight % of oleyl alcohol polyglycol ether (8 AeO) 3.5 weight % of calcium salt of dodecylbenzene-sul-fonic acid 2.0 weight % of alkyd resin A.
After a 4 hours' stirring and after a 4 hours' standing of the 2.5 % aqueous emulsion a crystal formation could not be observed.
E X A M P L E S 3, 4, 5, ~:
These examples are carried out as Example 2, except that 2 weight ~ of alkyd resin C or of alkyd resin B or of terpene-phenol resin A or 1 weight ~ of alkyd resin A + 1 weight % of terpene-phenol resin A are used instead of 2 weight % of alkyd resin A.
After a 3 hours' stirring and after a 4 hours' stand-ing a crystal formation was not observed in the 2.5 % aque-ous emulsions of the concentrates in all of the examples.
E X A M P L E ?
20.0 weight % of linuron 35.0 weight % of isophorone 33.0 weight % of industrial distillate of aromatic compounds, b.p. 183 to 312C
4.5 weight ~ of castor oil polyglycol ether (40 AeO) 3.2 weight % of calcium salt of dodecylbenzene-sulfo-nic acid ~l~Z~l - 12 - _OE_79JF 023 2.3 weight ~ of oleyl alcohol polyglycol ether (8 AeO) 2.0 weight % of alkyd resin A.
After a 2 hours' stirring and after a further 3 hours' standing a crystal formation of the 2.5 ~ aqueous emulsions was not observed.
E X A M P L E S 8, 9:
20.0 weight % of linuron 35.0 weight % of isophorone 30.0 weight % of xylene
5.0 weight % of phthalic acid diisooctyl ester or di methyl ester 4.0 weight % of castor oil polyglycol ether (40 AeO) 2.0 weight % of oleyl alcohol polyglycol ether (8 AeO) 4.0 weight ~ of calcium salt of chlorinated (C13 15) alkane-sulfonic acid.
The 2.5 % aqueous eMulsions showed no crystal formation after stirring for 1 and a half hours.
Biological Examples E X_A M P L E 1:
Comparative Test of Linuron 20 EC with Linuron 50 Wettable Powder (WP) The crop plants oats (Avena), mustard (Sinapsis) and horse beans (Vicia faba) were grown in test pots in loamy soil and after emergence of the plants the products were sprayed in an amount of 300 l/ha under 3 bars. The degree of damage, expressed in percentages, was determined after 4 weeks, compared to the untreated control O
ProductDose kg/ha Damage in Percentage with A.l. Oats Mustard ) Horse beans Linuron 20 EC 0.03 0 87 7 ~according to 0.06 0 96 10 Example 2)0.13 16 100 13 ~l~Z771 Product Dose l~g/ha Damage in Percentage with A.I. Oats Mustard ) Horse beans Linuron 50 % WP 0.03 0 70 7 (according to 0.06 0 90 10 Comp. Ex. 5) 0.13 16 99 16 -) Mustard is used as test plant for dicotyledonous weeds.
A comparison of both formulations shows that the EC
formulation, which can be seen with mustard, has a higher efficiency (87 %3 than the WP formu:lation ('70 %), with comparable quantities applied of active matter. With the orop plants oats (for cereals) and horse beans (for leguminosae) the EC formulation exhibited as tolerant as the WP formulation.
The 2.5 % aqueous eMulsions showed no crystal formation after stirring for 1 and a half hours.
Biological Examples E X_A M P L E 1:
Comparative Test of Linuron 20 EC with Linuron 50 Wettable Powder (WP) The crop plants oats (Avena), mustard (Sinapsis) and horse beans (Vicia faba) were grown in test pots in loamy soil and after emergence of the plants the products were sprayed in an amount of 300 l/ha under 3 bars. The degree of damage, expressed in percentages, was determined after 4 weeks, compared to the untreated control O
ProductDose kg/ha Damage in Percentage with A.l. Oats Mustard ) Horse beans Linuron 20 EC 0.03 0 87 7 ~according to 0.06 0 96 10 Example 2)0.13 16 100 13 ~l~Z771 Product Dose l~g/ha Damage in Percentage with A.I. Oats Mustard ) Horse beans Linuron 50 % WP 0.03 0 70 7 (according to 0.06 0 90 10 Comp. Ex. 5) 0.13 16 99 16 -) Mustard is used as test plant for dicotyledonous weeds.
A comparison of both formulations shows that the EC
formulation, which can be seen with mustard, has a higher efficiency (87 %3 than the WP formu:lation ('70 %), with comparable quantities applied of active matter. With the orop plants oats (for cereals) and horse beans (for leguminosae) the EC formulation exhibited as tolerant as the WP formulation.
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Liquid, emulsifiable herbicidal composition containing 3-(3,4-dichlorophenyl)-1-methyl-1-methoxy-urea (linuron) as the active ingredient, an organic solvent and an emulsifier, which include as crystallization-inhibiting component preventing the crystallization of active ingredients in the aqueous emulsion of the concentrate, from 0.2 to 5 weight % of a phthalic acid dialkyl ester in which the alkyl groups contain from 1 to 18 carbon atoms, or a phthalic acid alkyd resin, oil-modified phthalic acid alkyd resin or terpene-phenol resin, soluble in organic solvent, or a mixture of these compounds.
2. Herbicidal composition as claimed in claim 1, wherein the portion of crystallization-inhibiting component is from 1 to 2 weight %.
3. Herbicidal composition as claimed in claim 1, which contains from 10 to 25 weight % of linuron, 84.8 to 60 weight % of organic solvent, 5 to 10 weight % of emulsifier and 0.2 to 5 weight % of crystallization-inhibiting component.
4. Herbicidal composition as claimed in claim 3, which contains as organic solvent from 24.8 to 40 weight % of ketone and 60 to 20 weight % of aromatic solvent.
5. Herbicidal composition as claimed in claim 4, which contains isophorone as the ketone and xylene as the aromatic solvent.
6. Herbicidal composition as claimed in claim 3, 4 or 5, wherein there are contained as crystallization-inhibiting component an oil-modified phthalic acid alkyd resin or terpene-phenol resin or a mixture of these compounds.
7. Process for combating weeds, which comprises applying onto the areas attacked thereby a herbicidally effective amount of a composition as claimed in claim 1, 2 or 3 from an aqueous emulsion.
8. Process for combating weeds, which comprises applying onto the areas attacked thereby a herbicidally effective amount of a composition as claimed in claim 4 or 5, from an aqueous emulsion.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2905122.7 | 1979-02-10 | ||
| DE19792905122 DE2905122A1 (en) | 1979-02-10 | 1979-02-10 | HERBICIDAL AGENTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1142771A true CA1142771A (en) | 1983-03-15 |
Family
ID=6062647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000345307A Expired CA1142771A (en) | 1979-02-10 | 1980-02-08 | Herbicidal compositions |
Country Status (8)
| Country | Link |
|---|---|
| AU (1) | AU529280B2 (en) |
| CA (1) | CA1142771A (en) |
| DE (1) | DE2905122A1 (en) |
| FR (1) | FR2448293A1 (en) |
| HU (1) | HU185782B (en) |
| IT (1) | IT1147303B (en) |
| NZ (1) | NZ192834A (en) |
| SU (1) | SU1079159A3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170118979A1 (en) * | 2012-07-12 | 2017-05-04 | Adjuvants Unlimited, LLC | Methods And Compositions For Reducing Or Inhibiting Spray Drift And Driftable Fines |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3203779A1 (en) * | 1982-02-04 | 1983-08-11 | Hoechst Ag, 6230 Frankfurt | HERBICIDAL AGENTS |
| GB8308749D0 (en) * | 1983-03-30 | 1983-05-11 | Dow Chemical Co | Emulsifiable concentrate formulations of pesticides |
| RU2067831C1 (en) * | 1987-06-24 | 1996-10-20 | Мицуи Тоацу Кемикалз Инк. | Liquid pesticide composition |
| AU749607B2 (en) * | 1997-04-14 | 2002-06-27 | Dow Agrosciences Llc | Pesticide compositions |
-
1979
- 1979-02-10 DE DE19792905122 patent/DE2905122A1/en not_active Withdrawn
-
1980
- 1980-02-08 IT IT19820/80A patent/IT1147303B/en active
- 1980-02-08 AU AU55345/80A patent/AU529280B2/en not_active Ceased
- 1980-02-08 SU SU802878002A patent/SU1079159A3/en active
- 1980-02-08 NZ NZ192834A patent/NZ192834A/en unknown
- 1980-02-08 HU HU80288A patent/HU185782B/en unknown
- 1980-02-08 CA CA000345307A patent/CA1142771A/en not_active Expired
- 1980-02-11 FR FR8002933A patent/FR2448293A1/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170118979A1 (en) * | 2012-07-12 | 2017-05-04 | Adjuvants Unlimited, LLC | Methods And Compositions For Reducing Or Inhibiting Spray Drift And Driftable Fines |
Also Published As
| Publication number | Publication date |
|---|---|
| IT8019820A0 (en) | 1980-02-08 |
| AU5534580A (en) | 1980-08-14 |
| HU185782B (en) | 1985-03-28 |
| DE2905122A1 (en) | 1980-08-14 |
| NZ192834A (en) | 1982-03-09 |
| AU529280B2 (en) | 1983-06-02 |
| FR2448293B1 (en) | 1983-04-01 |
| SU1079159A3 (en) | 1984-03-07 |
| IT1147303B (en) | 1986-11-19 |
| FR2448293A1 (en) | 1980-09-05 |
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