CN1361662A - Aqueous concentrate pesticidal compositions having improved dermal and ocular safety - Google Patents

Abstract

An aqueous concentrate pesticidal composition is provided, comprising (a) a water-soluble pesticide in an amount of about 50 to about 500 g/l; (b) an etheramine surfactant; and (c) an anionic surfactant having the chemical formula (III) R<7>-(O-R<8>)n-O-X where R<7> is a C4-22 linear or branched, saturated or unsaturated, aliphatic hydrocarbyl or a (C8-12 alkyl)phenyl group, R<8> groups are independently C2-4 alkylidene groups, n is 0 to about 60 and X is an anionic radical selected from carboxylate, ether carboxylate, sulfate and phosphate; the weight ratio of the anionic surfactant to the etheramine surfactant being about 1:10 to about 1:1. Compositions of the invention have reduced injuriousness to skin and/or eyes than otherwise similar compositions lacking only the anionic surfactant.

Description

Aqueous concentrated insecticide compositions with improved skin and eye safety

field of invention

This invention relates to aqueous concentrate formulations containing water-soluble insecticides or plant growth regulators useful in agricultural and other situations. Hereinafter for the sake of brevity, the term "pesticide" will include plant growth regulators. More particularly, the present invention relates to formulations which also contain an etheramine surfactant which enhances the efficacy of the insecticide, but makes handling of such aqueous concentrates in the event of accidental contact with human skin and/or the eyes, causing an undesired degree of damage. While reducing or overcoming such damage, the present invention at least retains the high efficacy imparted by etheramine surfactants to insecticides.

Background of the invention

Water-soluble insecticides including, without limitation, herbicides, fungicides, insecticides, acaricides, nematicides and plant growth agents can be conveniently formulated as aqueous concentrates wherein the insecticide active ingredient is present in concentrated aqueous solution. Here, "concentrate" is a composition in which the concentration of the active ingredient is greater than about 50 g/l, up to the solubility limit of the active ingredient in water; where the active ingredient is a salt of an acid with insecticidal activity, the lower limit of about 50 g/l can be understood For refers to the active ingredient concentration expressed as acid equivalent (a.e.). Here, "aqueous concentrate" is a liquid concentrate having a single phase, which is an aqueous solution of the pesticide, or a continuous phase which is an aqueous solution of the pesticide, and a discontinuous phase or one or more non-aqueous phases, such as oil-in-water Emulsions, aqueous suspension concentrates or suspoemulsions. The end user can dilute the aqueous concentrate with a suitable volume of water, and the resulting diluted composition is usually applied by spraying.

Especially when the insecticide is to be used on the foliage of plants such as crops or weeds, it is common for aqueous concentrates to contain one or more surfactants. Surfactants help the sprayed droplets to stay on the leaves, adhere to the surface of the leaves, and allow water-soluble surfactants to penetrate through the hydrophobic cuticles covering the leaves, by this or possibly other means Increased bioefficacy of insecticides. A particularly useful class of surfactants which enhance bioefficacy are described herein by the generic term "etheramines". Combinations of certain etheramine surfactants with the herbicide glyphosate or a salt thereof are disclosed in US Patent 5,750,468 to Wright.

其中R¹为C_6-22直链或支链的，饱和或不饱和的脂肪族烷基，R²和R³基团相互独立地为C_2-4亚烷基，m为1-约5的平均数，x和y为使x+y是0-约60的平均数的平均数，R⁴基团独立地为氢、C_1-4烷基或苯甲基，R⁵为氢、C_1-4烷基或苯甲基或选自氧化物(-O^-)和-R⁶-COO^-基团的阴离子片段，其中R⁶为C_1-4亚烷基，t为1或2，A^t-为合适的阴离子，v为1除非R⁵为阴离子片断，在那种情况下，v为0。When ether amine surfactant exists in the aqueous medium that pH value is about 4, be as the compound of general chemical formula (I)

Wherein R ¹ is a C _6-22 linear or branched, saturated or unsaturated aliphatic alkyl group, R ² and R ³ groups are independently C _2-4 alkylene groups, and m is 1 to about 5 The average number of , x and y is the average number of the average number such that x+y is 0 to about 60, the R ⁴ group is independently hydrogen, C _1-4 alkyl or benzyl, R ⁵ is hydrogen, C _1-4 alkyl or benzyl or an anionic moiety selected from oxide (-O ^- ) and -R ⁶ -COO ^- groups, wherein R ⁶ is C _1-4 alkylene, t is 1 or 2, ^At- is a suitable anion, v is 1 unless ^R is an anionic moiety, in which case v is 0.

Among the etheramine surfactants shown in general formula (I) above, where R is hydrogen, it is generally referred to herein as "tertiary etheramines" (but ^when x and y are all 0, and each R Except when all ⁴ groups are hydrogen, it is a primary ether amine at this time). At certain pH values above 4, such as at a pH of about 8, the nitrogen atom of such a tertiary ether amine is generally not protonated, and the tertiary ether amine does not carry an At ^- anion with it Coordination, at this time can be described by the general chemical formula (II) wherein R ¹ , R ² , R ³ , R ⁴ , m, x and y are as defined in general formula (I) above.

In the ether amine surfactants shown in the general formula (I) above, wherein ^R When being C _1-4 alkyl or benzyl, it is generally referred to as "quaternary ether amines" (but when x and y are all 0, except when each ^R group is hydrogen, which is a secondary ether amine). Among the ether amine surfactants shown in the above general formula (I), wherein ^R is an anionic moiety and v is 0, it is generally referred to as "amphoteric ether amines" and includes "ether amine oxides" (R ⁵ is -O ^- at this time) and "ether betaines" (R ⁵ is -CH ₂ -COO ^- at this time).

Many etheramine surfactants have amine functionality which, when added to an aqueous concentrated insecticide composition at a concentration effective to increase insecticide efficacy, unfortunately renders the composition vulnerable to accidental contact during handling. Undesirable degree of damage to human skin and/or eyes. Regulations in the United States and many other countries prescribe skin and/or eye damage due to the presence of surfactants in pesticide formulations, resulting in restrictions on such labeled formulations.

U.S. Patent 5,703,015 to Berger et al. (the '015 patent) discloses that eye irritation due to the presence of polyoxyalkylene alkylamine surfactants in aqueous concentrated insecticide compositions can be prevented by including in the composition C _8-20 alkyl or alkyl phenyl acidic surfactant components to ease. Specific types of acid surfactants disclosed as effective are polyoxyalkylene alkylphenol sulfates, alcohol sulfates, polyoxyalkylene alcohol sulfates, mono- and diol phosphates, mono- and di(polyoxyalkylene alcohol) Phosphate esters, mono- and di(polyoxyalkylene alkylphenol) phosphate esters, polyoxyalkylene alkylphenol carboxylates and polyoxyalkylene alcohol carboxylates. The amount of acidic surfactant relative to the amount of polyoxyalkylene alkylamine surfactant appears to be somewhat related to reducing eye irritation. For example, when the weight ratio of polyoxyethylene (4) nonylphenol phosphate and polyoxyethylene (16-17) tallow amine is about 1:5.5 (Example 20 in the '015 patent), eye irritation The post-irritation effect persisted at a relatively high level up to 21 days; while with the same total surfactant concentration, but the weight of polyoxyethylene (4) nonylphenol phosphate and polyoxyethylene (16-17) tallow amine At a ratio of about 1:1.5 (Example 26 in the '015 patent), the irritative effects were reduced to relatively low levels after 7 days of eye irritation.

US Patent 5,389,598 to Berk et al. discloses that alkyl mono- and dicarboxylic acids are also effective in reducing eye irritation of insecticide compositions containing polyoxyalkylene alkylamine surfactants.

Summary of the invention

It has now been found that certain etheramine surfactants enable aqueous concentrate compositions containing water-soluble insecticides to cause undesirable levels of skin and/or eye damage. This damage manifests itself as one or more of several side effects, including eye irritation, skin irritation, and skin irritation.

A method is now provided to address the problem of damage to the skin and/or eyes. According to the present invention, there is provided an aqueous concentrated insecticide composition, which contains: (a) a water-soluble insecticide whose content is about 50-500 g/l; (b) an ether amine represented by general formula (I) A surfactant, if it is the only surfactant present, in an amount that increases the degree of skin and/or eye damage of the composition; and (c) an anionic surfactant having the general chemical formula (III)

R ⁷ -(OR ⁸ ) _n -OX wherein R ⁷ is C _4-22 linear or branched, saturated or unsaturated aliphatic alkyl or (C _8-12 alkyl) phenyl, R ⁸ is independently Be the alkylene group of C _2-4 , n is 0-about 60, and X is the anion group selected from carboxylate, ether carboxylate, sulfate and phosphate; the weight ratio of anion surfactant and ether amine surfactant It is about 1:10-1:1.

Also provided is a method of reducing skin and/or eye damage from an aqueous concentrated insecticide composition comprising (a) a water-soluble insecticide in an amount of about 50-600 g/l, and ( B) ether amine surfactant shown in general formula (I); Described method comprises adding the anionic surfactant shown in general formula (III), the weight ratio of anionic surfactant and ether amine surfactant is about 1 :10-1:1.

In a preferred embodiment of the present invention, the etheramine surfactant is a tertiary etheramine represented by general formula (II).

In a particularly preferred embodiment of the present invention, the anionic surfactant is mono(polyoxyethylene alkyl or alkyl phenyl ether) phosphate, which can also be described as mono(polyoxyethylene alkyl or alkyl phosphate) phosphate phenyl) esters, optionally with the corresponding phosphodiesters.

The compositions of the present invention exhibit less eye irritation and skin irritation and/or skin sensitization than corresponding compositions having the same total surfactant concentration but containing no anionic surfactant. Preferred compositions of the present invention exhibit eye irritation and skin irritation and/or skin sensitization compared to corresponding compositions having the same concentration of etheramine surfactant but wherein the anionic surfactant is completely replaced with water. to a lesser degree. The invention has proven to be particularly effective when the water-soluble insecticide is a salt of the herbicide glyphosate. Detailed description of the invention

The present invention relates to aqueous concentrate compositions, including formulations well known in the art, such as soluble concentrates (SL), oil-in-water emulsions (EW), water-based suspension concentrates (SC) and suspoemulsions. In all cases, the water-soluble insecticide is present in solution in the aqueous phase of the composition. Here, the concentration of the water-soluble insecticide is expressed on the basis of the active ingredient (a, i.), except when the active ingredient is a salt of a biologically active acid, in which case the concentration is expressed in acid equivalent (a.e.). The concentration of insecticide in the composition (either a.i. or a.e. as appropriate) generally ranges from about 50-600 g/l; preferably the composition has an insecticide concentration of about 360-540 g/l.

Here, "water-soluble" insecticides include salts or other water-soluble derivatives of insecticides having a solubility in deionized water at 20°C of not less than about 50 g/l, more preferably not less than about 200 g/l.

Examples of water-soluble fungicides and bactericides that may be used in the compositions of the present invention include sodium pyroborate, sec-butylamine, polycalcium sulfide, copper sulfate, galenphos, biguanide salts, hydroxyquinoline salts, biguanide caprylate , kasugamycin, mercuric acid, metabam, sodium dyson, polyoxin B, propycin and validamycin and/or its water-soluble salts. Examples of water-soluble insecticides, acaricides and nematocides that can be used in the composition of the present invention include fenfofos, butoxycarbazol, albutan, dicrotofos, fencloprid, hydrogen cyanide, formazan, Aminophos, methedone, memephos, monocrotophos, nicotine, nitrapyridine, omethoate, methotrexate, methyl demeton sulfoxide, phosphamide, thicycline, trichlorfon , Aphidol and/or its water-soluble salts. Examples of water-soluble plant regulators that can be used in the compositions of the present invention include chlormequat cation, phosphonium chloride, phenpyridonic acid, citric acid, calcium cyanamide, butyrhydrazide, dizacil, ethephon, bik and/or its water-soluble salts.

In one embodiment of the present invention, the water-soluble insecticide is a herbicide or an agriculturally acceptable salt thereof, including without limitation the salts of the following compounds: acifluorfen, orazopyr, azafoxate, diazepam, bis Alanyl phosphine, diquat, bromoxynil, chlorpyramid, diclopicolinic acid, 2,4-D, 2,4-DB, thatraquat, dicamba, 2,4-dipropionic acid, chlorine Agrass, wild swallow, diquat, grass algae, voxaprop, fluoxaprop, fluroxypyr, fluroxypyr, ethyl carboxyfluorfen, fendanthamfen, phosphonium , glufosinate-ammonium, glyphosate, haloxyfop, imazethapyr, imazethapyr, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, ioxynil, MCPA, MCPB, 2-methyl-4-chloropropionic acid, methyl arsinic acid, oxazan, nonanoic acid, paraquat, picloram, sulfamic acid, 2,3,6-TBA, TCA and imazethapyr.

Preferred water-soluble herbicides are salts of acid compounds having at least one of amine, carboxylate, or phosphonate or phosphonite functional groups in their molecular structure. Such compounds include salts of the herbicides N-phosphoromethylglycine (glyphosate) and DL-homoalanin-4-yl(methyl)phosphonite (glufosinate). Another preferred class of herbicides are the salts of imidazolinones, including imazethapyr, imazazone, imazamox, imazapic, imazapyr, imazaquin and imazethapyr.

Examples of suitable counterions for the formation of agriculturally acceptable salts when the herbicide is cationic or forms a cation in the presence of an acid, as for example in the case of glyphate, diquat or paraquat, include chlorine, bromine , iodine, sulfate, phosphate, acetate, and succinate anions.

Agriculturally acceptable salts are formed when the herbicide is anionic or forms an anion in the presence of a base, as in, for example, most of the herbicides listed above, except in the case of triquat, diquat, paraquat Examples of suitable counterions include sodium, potassium, ammonium, organoammonium and organosulfonium cations, wherein the organoammonium or organosulfonium cations have from 1 to about 16 carbon atoms. Preferred organoammonium cations are dimethylammonium, monoethanolammonium, n-propylammonium and isopropylammonium cations. A preferred organic sulfonium cation may be trimethylsulfonium cation. When the herbicide is glyphosate, particularly preferred counterions are potassium and monoethanolammonium cations.

It is understood that more than one water-soluble herbicide may be present, in which case the concentration ranges listed above represent the total amount of water-soluble herbicide in the composition. Optionally, in addition to one or more water-soluble herbicides, the composition of the present invention may also contain one or more herbicides with low water solubility. If a herbicide of low water solubility is present, it will generally be present primarily in the discontinuous, non-aqueous phase of the composition, eg, the oil phase of an oil-in-water emulsion or the solid particulate phase of a suspension concentrate.

其中R¹为C_6-22直链或支链的，饱和或不饱和的脂肪族烷基，R²和R³基团相互独立地为C_2-4亚烷基，m为1-约5的平均数，x和y为使x+y是0-约60的平均数的平均数，R⁴基团独立地为氢、C_1-4烷基或苯甲基，R⁵为氢、C_1-4烷基或苯甲基或选自氧化物(-O^-)和-R⁶-COO^-基团的阴离子片段，其中R⁶为C_1-4亚烷基，t为1或2，A^t-为合适的阴离子，v为1除非R⁵为阴离子片段，在那种情况下，v为0。As shown above, the composition of the present invention contains ether amine surfactant, and its general chemical formula (I) in the aqueous medium that pH value is 4 is

Wherein R ¹ is a C _6-22 linear or branched, saturated or unsaturated aliphatic alkyl group, R ² and R ³ groups are independently C _2-4 alkylene groups, and m is 1 to about 5 The average number of , x and y is the average number of the average number such that x+y is 0 to about 60, the R ⁴ group is independently hydrogen, C _1-4 alkyl or benzyl, R ⁵ is hydrogen, C _1-4 alkyl or benzyl or an anionic moiety selected from oxide (-O ^- ) and -R ⁶ -COO ^- groups, wherein R ⁶ is C _1-4 alkylene, t is 1 or 2, ^At- is a suitable anion, v is 1 unless ^R is an anionic moiety, in which case v is 0.

In preferred etheramines, ^R1 has at least about 8 carbon atoms, more preferably about 12-18 carbon atoms. Preferably all m( ^OR2 ) units are identical and are preferably ethylene oxide, isopropylene oxide or n-propylene oxide units. When the (OR ² ) unit is ethylene oxide or propylene oxide unit, m is preferably 1-5, and in the case of ethylene oxide unit, m is most preferably 3, and in the case of isopropylene oxide unit In this case, m is most preferably 2. When (OR ² ) is propylene oxide, m is preferably 1. All x+y( ^R3 -O) units are preferably ethylene oxide, each of x and y is preferably at least 1, and x+y is preferably from 2 to about 15, more preferably from 2 to about 7. The R ⁴ group is preferably hydrogen, except for the case where x and y are 0, in which case the R ⁴ group is preferably a C _1-4 alkyl group, more preferably methyl.

When R ⁵ is C _1-4 alkyl or benzyl, the surfactant is a quaternary ether amine, more specifically a quaternary ether ammonium salt. In quaternary ammonium ethers, ^R5 is preferably methyl. The anion At- in complex with one or two etheramine cations is ^preferably selected from the group consisting of chlorine, bromine, iodine, sulfate, ethylsulfate, phosphate, acetate, propionate, succinate, lactate, citrate and tartrate Anion, most preferably chlorine. Illustrative examples of suitable quaternary ether amines are disclosed in US Patent 5,750,468, cited above.

其中R¹，R²，R³，R⁴，m，x和y如上面的通式(I)的定义。合适的叔醚胺类的说明性例子公开在上面引用的美国专利5,750,468中。In the currently preferred embodiment of the present invention, the surfactant is a tertiary ether amine according to the general formula (I), wherein R ⁵ is hydrogen. It should be noted that the tertiary ether amines described by general formula (I) are in their protonated form, as normally present in acidic aqueous media. When protonated, the tertiary ether amine complexes with the anion ^At- ion, again illustrative examples of which are chlorine, bromine, iodine, sulfate, phosphate, acetate, succinate, or tartrate, but acidic insecticides are present When , it may be the anion of the pesticide, such as the glyphosate anion. In neutral to basic aqueous media, tertiary ether amines are generally not protonated and can be more precisely described by the general chemical formula (II):

wherein R ¹ , R ² , R ³ , R ⁴ , m, x and y are as defined in the above general formula (I). Illustrative examples of suitable tertiary ether amines are disclosed in US Patent 5,750,468, cited above.

The concentration of the etheramine surfactant in the composition of the present invention is not very critical, but in the absence of the anionic surfactant represented by general formula (III), other similar surfactants in which the etheramine surfactant is replaced by water This concentration is sufficient to increase the degree of skin and/or eye damage compared to the composition. In particular, the concentration of ether amine is sufficient to increase the degree of at least one of eye irritation, skin irritation and skin sensitization, especially eye irritation and skin sensitization. Skin sensitization is considered a relatively uncommon property of etheramine surfactants. However, skin and eye safety is an important consideration for insecticide products. Thus, the present invention is useful for compositions in which the concentration of etheramine is high enough to have adverse effects on any of the aforementioned safety aspects, even if such adverse effects are mild.

The concentration of the etheramine surfactant is preferably sufficient to substantially increase the biological efficacy of the insecticide when the composition is diluted with a suitable volume of water and applied to the foliage of a plant. Typically the weight ratio of etheramine surfactant to water soluble insecticide is about 1:10 to 2:1. For example, when the water-soluble insecticide is a salt of glyphosate, the weight ratio of etheramine surfactant to glyphosate a.e. is about 1:9-1:3.

Optionally more than one etheramine surfactant may be present; in such cases, the amounts or concentrations given herein in relation to the etheramine surfactant are based on the total amount of etheramine surfactant present or total concentration.

Emphasis of the present invention is to have the anionic surfactant shown in general chemical formula (III)

R ⁷ -(OR ⁸ ) _n -X wherein R ⁷ is a C _4-22 linear or branched, saturated or unsaturated aliphatic alkyl or (C _8-12 alkyl) phenyl group, R ⁸ group Independently C _2-4 alkylene, n is 0 to about 60, X is an anionic group selected from carboxylate (-COO ^- ), ether carboxylate (-OCH ₂ COO ^- ), sulfate (-OSO ₃ ^- ) and phosphates (-OPO ₃ H ^- and -OPO ₃ ^2- ). Surprisingly, anionic surfactants reduce the degree of skin and/or eye damage of compositions caused by etheramine surfactants. In particular, where etheramine surfactants cause or contribute to damage in the form of eye irritation or skin sensitization, such damage can be mitigated or eliminated by the presence of anionic surfactants. According to one embodiment of the present invention, replacing a small portion (not more than about half) of the etheramine surfactant with the same weight of anionic surfactant can improve the eye and/or skin safety of the composition. According to another embodiment of the present invention, the addition of anionic surfactant without reducing the amount of etheramine surfactant present improves the skin and/or eye safety of the composition.

The weight ratio of anionic surfactant to etheramine surfactant is not less than about 1:10 and not greater than about 1:1. Surprisingly, an improved eye and skin safety effect can be obtained at a low weight ratio of anionic surfactant to etheramine surfactant, for example about 1:10-1:4. Preferably the weight ratio of anionic surfactant to etheramine surfactant is from about 1:8 to 1:5.

Optionally more than one anionic surfactant may be present; in such cases, the amounts or concentrations given herein in relation to anionic surfactants are based on the total amount or total concentration of anionic surfactants present Let's count.

Illustrative types of anionic surfactants useful in the compositions of the present invention include alkyl carboxylates, such as fatty acids, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl phenyl ether carboxylates , alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates (including those with cyclic sulfonates), mono- and dialkyl phosphates, mono- and bis(polyoxyethylene alkyl ether) phosphates, mono- and bis(polyoxyethylene alkyl phenyl ether) phosphates and their salts. In the case of such salts, examples of suitable cationic counterions include sodium, potassium, ammonium, dimethylammonium, isopropylammonium, monoethanolammonium and trimethylsulfonium cations. Etheramine surfactants in the form of etherammonium cations can also form salts with anionic surfactants.

Among the preferred anionic surfactants, ^R in general formula (III) is (C _8-12 alkyl) phenyl, such as octylphenyl, nonylphenyl or dodecylphenyl or is C _{8 -22} , more preferably a C _12-18 straight or branched, saturated or unsaturated aliphatic alkyl group. Suitable alkyl groups include, without limitation, lauryl, myristyl, cetyl, palmitoleyl, stearyl, oleyl, linoleyl, linolenoyl, isotridecyl. Such fatty alkyl groups are conveniently derived from natural oils or fats and include mixtures of fatty alkyl chains such as cocoa and tallow. (The term "alkyl" as used in surfactant nomenclature is not necessarily fully saturated).

The (OR ⁸ ) units in the general formula (III) are preferably ethylene oxide units. The number (n) of such units is preferably from 0 to about 10.

In a preferred embodiment of the present invention, X in the general formula (III) is phosphate, so the anionic surfactant is monoalkyl ether phosphate or mono(alkylphenyl) ether phosphate. Such phosphate monoesters are often accompanied by corresponding diesters; the amount or concentration of phosphate ester surfactant is understood here to be based on the total amount of monoester and diester. Preferably the weight ratio of monoester to diester is greater than about 1:1, more preferably greater than about 2:1. Phosphate ester surfactants are in principle all present as monoesters, but in practice it is difficult and not necessary to ensure that no diesters are present.

Inert or excipient ingredients other than water, etheramine surfactants and anionic surfactants may optionally be included in the compositions of the present invention. Such ingredients include those other than surfactants represented by general formula (I) and general formula (III), such as polyoxyethylene alkylamines, alkylammonium salts and nonionic surfactants such as polyoxyethylene Vinyl alkyl ethers, polyoxyethylene alkylphenyl ethers, sorbitan esters and alkyl polyglycosides. Other optional excipient ingredients include oils, solvents, stabilizers, antifreeze and pour point depressants such as glycols, dyes, inorganic salts such as ammonium sulfate, fertilizers, foam regulators, thickeners, Drift control agent, etc.

The present invention is not limited by the method of evaluation for any aspect of skin or eye damage, including eye irritation and skin sensitization. However, eye irritation can be evaluated by the Draize test or a suitable modification thereof, and skin sensitization can be evaluated by the Buehler test or a suitable modification thereof. Details of specific methods can be found in the U.S. Environmental Protection Agency Pesticide Assessment Guideline, Guideline 81-4 (Draize Test) and Guideline 81-6 (Modified Buehler Test) of Subdivision F.

Example

Compositions in the following examples 1 and 2 all contain the ether amine surfactant shown in general formula (II) Wherein R ¹ is a C _12-14 alkyl group, (OR ² ) units are isopropylene oxide units, m is 2, (OR ³ ) units are ethylene oxide units, x+y is the average number 5, and R ⁴ is hydrogen. This surfactant is

It is called etheramine I in the examples.

The compositions of the invention exemplified in Examples 1 and 2 also contain an anionic surfactant which is a mixture of polyoxyethylene (4) isotridecyl ether phosphate monoesters and diesters, monoesters and diesters The weight ratio is about 7:3. This surfactant is referred to as Phosphate I in the examples.

Composition A, included as a comparative reference in Examples 1 and 2, is a water-soluble concentrated formulation of glyphosate isopropylammonium salt. It was prepared from MON0139, a concentrated aqueous solution of the isopropylammonium salt of glyphosate, which was assayed to contain 46% acid equivalent (a.e.) of glyphosate. Composition A consists of (all percentages by weight):

MON0139 (46.0%a.e.) 86.96%

Etheramine I 10.00%

Deionized water 3.04%

The a.e. concentration of glyphosate in composition A was 40% by weight or 482 g/l. Composition A has a specific gravity (20/15.6°C) of 1.2053 and a cloud point higher than 90°C, indicating excellent high temperature stability.

Composition B of the present invention has the following ingredients (all percentages are by weight):

MON0139 (46.0%a.e.) 86.96%

Etheramine I 10.00%

Phosphate I 1.00%

Deionized water 2.04%

The a.e. concentration of glyphosate in composition B was 40% by weight or 483 g/l. Composition B has a specific gravity (20/15.6°C) of 1.2086 and a cloud point of 77°C, indicating excellent high temperature stability.

Composition C of the present invention has the following ingredients (all percentages are by weight):

MON0139 (45.8% a.e.) 87.34%

Etheramine I 8.80%

Phosphate I 1.26%

Deionized water 2.60%

The a.e. concentration of glyphosate in composition C was 40% by weight or 483 g/l. Composition B has a specific gravity (20/15.6°C) of 1.2076 and a cloud point of 80°C, indicating excellent high temperature stability.

Composition D of the present invention has the following ingredients (all percentages are by weight):

MON0139 (45.8% a.e.) 81.00%

Etheramine I 8.16%

Phosphate I 1.17%

Deionized water 9.67%

The a.e. concentration of glyphosate in composition D was 37% by weight or 442 g/l. Composition D has a specific gravity (20/15.6°C) of 1.1945 and a cloud point of 74°C, indicating excellent high temperature stability.

When reading the following examples, it should be understood that for composition A, the eye irritation and skin sensitization effects are obviously completely due to the surfactant component of the composition. MON0139 itself has no eye irritation and will not sensitize the skin.

Example 1

According to U.S.Environmental Protection Agency Pesticide Assessment Guideline, Guideline 81-4 of Subdivision F, compositions A-D were tested for eye irritation by Draize test method. A single dose of 0.1 ml of the composition was applied without dilution to the conjunctival sac of the right eyes of 6 New Zealand white rabbits. Each composition was evaluated for corneal opacity, iris damage and conjunctival redness, bulbar conjunctival edema and discharge at 8 times after administration, using a scale of 0-3 where 0 means no effect and 3 means most severe Impact. The average values are listed in Tables 1-3.

Table 1 Average corneal opacity values Time after medication: 1 hour 1 day 2 days 3 days 7 days 10 days 14 days 21 days Composition A 1.5 1.8 1.7 1.7 1.0 0.8 0.5 0.5 Composition B 1.0 1.2 1.7 1.7 1.2 0.7 0.7 0.3 Composition C 0.8 1.3 1.7 1.2 0.0 0.0 0.0 0.0 Composition D 0.7 1.7 1.3 1.0 0.2 0.0 0.0 0.0 Table 2 Average iris damage values Time after medication: 1 hour 1 day 2 days 3 days 7 days 10 days 14 days 21 days Composition A 1.0 1.0 0.8 0.5 0.2 0.2 0.2 0.0 Composition B 1.0 1.0 0.8 0.7 0.3 0.0 0.0 0.0 Composition C 1.0 0.8 0.3 0.2 0.2 0.0 0.0 0.0 Composition D 1.0 1.0 1.0 0.7 0.0 0.0 0.0 0.0

Table 3 Mean values of conjunctival damage (redness, conjunctival edema and discharge) Time after medication: 1 hour 1 day 2 days 3 days 7 days 10 days 14 days 21 days Composition A 2.2 2.0 1.8 1.6 0.7 0.6 0.4 0.2 Composition B 1.8 1.9 1.9 1.7 1.1 0.6 0.5 0.3 Composition C 1.9 1.8 1.4 1.1 0.5 0.1 0.0 0.0 Composition D 1.5 1.8 1.4 1.1 0.4 0.0 0.0 0.0

It should be noted that in the tests of the examples, the treated eyes were not rinsed to remove the added composition. The prolonged exposure effects shown in the table above do not necessarily represent the situation, as most likely, where the eye is accidentally exposed to an irritant composition and the irritant is quickly removed by thorough rinsing. Eye damage measured 1 hour after application in this test is probably the most relevant index of the potential damage of the composition when the eye is rinsed.

It should be noted that compositions B, C, D according to the invention were less damaging to the cornea and conjunctiva than composition A used as a reference 1 hour after application. Compositions B and A had similar damage values at a later time, but compositions C and D of the present invention caused significantly less damage, and the recovery of eye effects after administration was improved after 21 days. improve.

Example 2

According to U.S.Environmental Protection Agency Pesticide Assessment Guideline, Guideline 81-6 of Subdivision F, the sensitization of compositions A and D to the skin was tested with the improved Buehler test method. A dose of 0.4 ml of each composition was applied undiluted on the trimmed intact skin of 10 albino guinea pigs once a week for 3 weeks for 6 hours each, using a Hilltop Chamber and an sorbent. A single 0.4 ml competitive dose was applied undiluted on natural skin for 6 hours two weeks after the last dose. Three weeks after the last dose, a recompeting dose of 0.4 ml of the composition diluted 50% with deionized water was used for 6 hours.

The results showed that Composition A caused skin sensitization while Composition B did not cause skin sensitization in guinea pigs.

The above descriptions of specific embodiments of the present invention are not intended to be exhaustive of every possible embodiment of the present invention. Those skilled in the art will recognize that variations from the specific embodiments described herein are still within the scope of the invention.

Claims (11)

1. aqueous concentrate pesticidal compositions, it contains:

(a) water soluble insecticide of about 50-500g/l;

(b) etheramine surfactants, its chemical general formula that has in pH value is about 4 water-bearing media is

R wherein ¹Be C _6-22Straight or branched, saturated or undersaturated aliphatic alkyl, R ²And R ³Group is C independently of each other _2-4Alkylidene, m are the mean of 1-about 5, and x and y are that to make x+y be the mean of the mean of 0-about 60, R ⁴Group is hydrogen, C independently _1-4Alkyl or benzyl, R ⁵Be hydrogen, C _1-4Alkyl or benzyl or be selected from oxide (O ^-) and-R ⁶-COO ^-The anionic moiety of group, wherein R ⁶Be C _1-4Alkylidene, t are 1 or 2, A ^T-Be suitable anion, unless v is 1 R ⁵Be anionic moiety, under the sort of situation, v is 0; Described etheramine surfactants has enough amounts, if it is existing only table surface-active agent, will increase the degree of injury of composition to skin and/or eyes; With

(c) has the anion surfactant of following chemical general formula

R ⁷-(O-R ⁸) _n-O-X is R wherein ⁷Be C _4-22Straight or branched, saturated or undersaturated aliphatic alkyl or be (C _8-12Alkyl) phenyl, R ⁸Be C independently _2-4Alkylidene, n is that 0-is about 60, and X is the anion base that is selected from carboxylate radical, ether carboxylate radical, sulfate radical and phosphate radical;

The weight ratio of anion surfactant and etheramine surfactants is about 1: 10-1: 1.

2. the composition of claim 1, wherein etheramine surfactants is uncle's ether amine, its chemical general formula below not having to have when protonated

R wherein ¹Be C _6-22Straight or branched, saturated or undersaturated aliphatic alkyl, R ²And R ³Group is C independently of each other _2-4Alkylidene, m are the mean of 1-about 5, and x and y are that to make x+y be the mean of the mean of 0-about 60, R ⁴Group is hydrogen, C independently _1-4Alkyl or benzyl.

3. the composition of claim 2, wherein in the general formula of uncle's ether amine, R ¹Has about 12-18 carbon atom, (O-R ²) unit is the different propane of oxirane or epoxy unit, m is 1-5, (R ³-O) unit is an ethylene oxide group, and each x and y are at least 1, and x+y is that 2-is about 15, and R ⁴Group is a hydrogen.

4. the composition of claim 1, wherein the ratio of etheramine surfactants and water soluble insecticide is about 1: 10-2: 1.

5. the composition of claim 1, wherein anion surfactant is selected from alkyl carboxylic acid ester, polyoxyethylene alkyl ether carboxylate, polyoxyethylene alkyl phenyl ether carboxylate, alkyl sulfate, polyoxyethylene alkyl ether sulfuric ester, polyoxyethylene alkyl phenyl ether sulfuric ester, list-and dialkyl phosphate, list-and two (polyoxyethylene alkyl ether) phosphate, list-and two (polyoxyethylene alkyl phenyl ether) phosphate, and salt.

6. the composition of claim 5, wherein anion surfactant is the mixture of single (polyxyethylated or alkyl phenyl ether) phosphate or itself and corresponding two (polyxyethylated or alkyl phenyl ether) phosphate, or the salt of such phosphate or such phosphate mixture.

7. the composition of claim 1, wherein water soluble insecticide is selected from sodium pyroborate, sec-butylamine, poly-calcium sulfide, copper sulphate, fosetyl, guazatine, cxine sulphate, biguanide spicy acid salt, kasugarnycin, mercuric chloride, metham-sodium, Dithane A40, Polyoxin AL, hundred dimension spirits, valida, orthen, the butoxy carboxin, Padan, Carbicron, Carzol, hydrogen cyanide, acephatemet, methomyl, Menite, nuvacron, nicotine, nitenpyram, flolimat, methomyl, metilomerkaptofosoksid, phosphamidon, thiocyclarn, chlorophos, Kilval, chlormequat phosphonium chloride, the acid of benzene pyridazone, cloxyfonac, Aero cyanamid, daminozide, dikegulac, ethrel, Bick, acifluorfen, asulam, benazolin, bentazon, bilanafos, bromacil, Brominal, Amiben, morpholine acid dichloride picoline, 2,4-D, 2,4-DB, dalapon, dicamba, 2,4-drips propionic acid, chloroformate grass, difenzoquat, diquat, endothall, Fenac oxazole diclofop-methyl, FLAMPROP, fluazifop, fluoroglycofen-ethyl, Fomesafen, phosphine ammonium element, grass ammonium phosphine, glyphosate, the spirit of pyrrole fluorine chlorine standing grain, cigarette imidazoles grass, miaow grass ester, imazamox, imazapic, the weed eradication cigarette, the weed eradication quinoline, Imazethapyr, ioxynil, MCPA, MCPB, Vi par, methanearsonic acid, alanap, n-nonanoic acid, paraquat, picloram, sulfamic acid, 2,3,6-TBA, TCA and triclopyr, and salt.

8. the composition of claim 1, wherein water soluble insecticide is the salt of herbicide glyphosate.

9. the composition of claim 8, wherein water soluble insecticide is the sylvite of glyphosate.

10. the composition of claim 8, wherein water soluble insecticide is the single ethanol ammonium salt of glyphosate.

11. an aqueous concentrate pesticidal compositions that contains water soluble insecticide and etheramine surfactants, the chemical general formula of this etheramine surfactants in the water-bearing media of pH value about 4 is R wherein ¹Be C _6-22Straight or branched, saturated or undersaturated aliphatic alkyl, R ²And R ³Group is C independently of each other _2-4Alkylidene, m are the mean of 1-about 5, and x and y are that to make x+y be the mean of the mean of 0-about 60, R ⁴Group is hydrogen, C independently _1-4Alkyl or benzyl, R ⁵Be hydrogen, C _1-4Alkyl or benzyl or be selected from oxide (O ^-) and-R ⁶-COO ^-The anionic moiety of group, wherein R ⁶Be C _1-4Alkylidene, t are 1 or 2, A ^T-Be suitable anion, v is 1, unless R ⁵Be anionic moiety, under the sort of situation, v is 0; Improvement comprises the adding anion surfactant, and its ratio with etheramine surfactants is about 1: 10-1: 1, and the chemical general formula of this anion surfactant is

R ⁷-(O-R ⁸) _n-O-X is R wherein ⁷Be C _4-22Straight or branched, saturated or undersaturated aliphatic alkyl or be (C _8-12Alkyl) phenyl, R ⁸Be C independently _2-4Alkylidene, n are that 0-is about 60, and X is the anion base that is selected from carboxylate radical, ether carboxylate radical, sulfate radical and phosphate radical.