Efficacy-enhancing agent composition for amino acid-based agrochemicals

Abstract

The present invention is an efficacy-enhancing agent composition for amino acid-based agrochemicals, containing, in a specific ratio, specific three quaternary ammonium salts having an ester group, and a specific fatty acid.

Claims

1. An agrochemical composition, comprising 2 to 10% by mass of a compound (A1) represented by the following formula (1-1), 0.01 to 0.7% by mass or less of a compound (B) represented by the following formula (2), 10 to 70% by mass of amino acid-based agrochemical active ingredient (C), water, and 0.5 to 5.0% by mass of a compound (A2) represented by the following formula (1-2), and 0.05 to 1.0% by mass of a compound (A3) represented by the following formula (1-3), wherein a mass ratio of a content of the compound (A3) to a sum of a content of the compound (A1) and a content of the compound (A2), [content of compound (A3)]/[sum of content of compound (A1) and content of compound (A2)], is in the range from 1/99 through 9/91; a mass ratio of the content of the compound (A2) to the content of the compound (A1), [content of compound (A2)]/[content of compound (A1)], is in the range from 5/95 through 60/40; and a mass ratio of a content of the compound (B) to the content of the compound (A1), [content of compound (B)]/[content of compound (A1)], is in the range from 1/500 through 1/5.2: ##STR00016## wherein R.sup.1 denotes a linear alkyl group having from 1 to 4 carbon atoms, a linear alkenyl group having from 2 to 4 carbon atoms, a branched alkyl group having 3 or 4 carbon atoms, or a branched alkenyl group having 3 or 4 carbon atoms; R.sup.2 denotes a linear or branched alkyl group or alkenyl group having from 5 to 17 carbon atoms; each of 1, m, and n denotes an average number of moles of added CH.sub.2CH.sub.2O group, a total of l, m, and n [l+m+n] being in the range from 1 through 15; and X.sup. denotes a counter ion; and
R.sup.3COOH(2) wherein R.sup.3 denotes a linear or branched alkyl group or alkenyl group having from 5 to 17 carbon atoms.

2. The agrochemical composition according to claim 1, comprising an efficacy-enhancing agent composition for amino acid-based agrochemicals; wherein the efficacy-enhancing agent composition for amino acid-based agrochemicals comprises a compound (A1) represented by the following formula (1-1), a compound (B) represented by the following formula (2), a compound (A2) represented by the following formula (1-2), and a compound (A3) represented by the following formula (1-3), wherein a mass ratio of a content of the compound (A3) to a sum of a content of the compound (A1) and a content of the compound (A2), [content of compound (A3)]/[sum of content of compound (A1) and content of compound (A2)], is in the range from 1/99 through 9/91; a mass ratio of the content of the compound (A2) to the content of the compound (A1), [content of compound (A2)]/[content of compound (A1)], is in the range from 5/95 through 60/40; and a mass ratio of a content of the compound (B) to the content of the compound (A1), [content of compound (B)]/[content of compound (A1)], is in the range from 1/500 through 1/5.2: ##STR00017## wherein R.sup.1 denotes methyl or ethyl; R.sup.2 denotes a linear or branched alkyl group or alkenyl group having from 5 to 17 carbon atoms; each of l, m, and n denotes an average number of moles of added CH.sub.2CH.sub.2O group, a total of l, m, and n [l+m+n] being in the range from 1 through 15; and X.sup. denotes a halide ion or an alkyl sulfate anion; and
R.sup.3COOH(2) wherein R.sup.3 denotes a linear or branched alkyl group or alkenyl group having 5 to 17 carbon atoms.

3. The agrochemical composition according to claim 2, wherein amino acid-based agrochemical active ingredient (C) is N-(phosphonomethyl)glycine or a salt thereof.

4. A weeding method, comprising spraying, on a plant, an agrochemical spray solution prepared from an agrochemical composition according to claim 1.

Description

EXAMPLES

Synthesis Examples

Synthesis Example A1: Synthesis of Triethanolamine EO Adduct A1

(1) An autoclave was charged with 298 g of triethanolamine and 1.1 g of potassium hydroxide. Conditions inside the autoclave were set to 100 C. and a pressure of 3.9 kPa, and a dehydration reaction was performed for 1 hour under these conditions. Then, the temperature was increased to 150 to 160 C., 264 g of ethylene oxide was introduced into the autoclave at this temperature to perform an addition reaction, and thus, triethanolamine EO adduct A1 (having an average number of moles of added EO of 3 moles) was obtained.

Synthesis Example A2: Synthesis of Triethanolamine EO Adduct A2

(2) In the same manner as in Synthesis Example A1, 529 g of ethylene oxide was introduced into the autoclave to obtain triethanolamine EO adduct A2 (having an average number of moles of added EO of 6 moles).

Synthesis Example A3: Synthesis of Triethanolamine EO Adduct A3

(3) In the same manner as in Synthesis Example A1, 793 g of ethylene oxide was introduced into the autoclave to obtain triethanolamine EO adduct A3 (having an average number of moles of added EO of 9 moles).

Synthesis Example A4: Synthesis of Triethanolamine (EO) Adduct A4

(4) In the same manner as in Synthesis Example A1, 1057 g of ethylene oxide was introduced into the autoclave to obtain triethanolamine EO adduct A4 (having an average number of moles of added EO of 12 moles).

Synthesis Example 1: Synthesis of Reaction Product a-1

(5) A four-necked flask having a volume of 500 mL was charged with 94.1 g of lauric acid and 211.8 g of triethanolamine EO adduct A1 (with a molar ratio of lauric acid/triethanolamine EO adduct A1 set to 0.6/1), and a reaction was performed under conditions of normal pressure and at 140 C. for 1 hour, further followed by a dehydration condensation reaction under reduced pressure of 220 hPa and at 180 C. to obtain an ester amine. A quaternization reaction was performed by using 267.3 g of the thus obtained ester amine and 84.1 g of dimethyl sulfate at 60 C. for 2 hours to obtain reaction product a-1.

Synthesis Example 2: Synthesis of Reaction Product a-2

(6) In the same manner as in Synthesis Example 1, 100.3 g of a coconut oil fatty acid and 205.4 g of triethanolamine EO adduct A1 were used to obtain an ester amine. In the same manner as in Synthesis Example 1, 262.5 g of the thus obtained ester amine and 80.2 g of dimethyl sulfate were used to obtain reaction product a-2.

Synthesis Example 3: Synthesis of Reaction Product a-3

(7) In the same manner as in Synthesis Example 1, 75.8 g of a coconut oil fatty acid and 227.7 g of triethanolamine EO adduct A2 were used to obtain an ester amine. In the same manner as in Synthesis Example 1, 187.7 g of the thus obtained ester amine and 43.8 g of dimethyl sulfate were used to obtain reaction product a-3.

Synthesis Example 4: Synthesis of Reaction Product a-4

(8) In the same manner as in Synthesis Example 1, 81.4 g of a coconut oil fatty acid and 321.1 g of triethanolamine EO adduct A3 were used to obtain an ester amine. In the same manner as in Synthesis Example 1, 336.5 g of the thus obtained ester amine and 62.8 g of dimethyl sulfate were used to obtain reaction product a-4.

Synthesis Example 5: Synthesis of Reaction Product a-5

(9) In the same manner as in Synthesis Example 1, 66.2 g of a coconut oil fatty acid and 334.9 g of triethanolamine EO adduct A4 were used to obtain an ester amine. In the same manner as in Synthesis Example 1, 345.0 g of the thus obtained ester amine and 55.0 g of dimethyl sulfate were used to obtain reaction product a-5.

Synthesis Example 6: Synthesis of Reaction Product a-6

(10) In the same manner as in Synthesis Example 1, 120.5 g of a coconut oil fatty acid and 285.5 g of triethanolamine EO adduct A3 were used to obtain an ester amine. In the same manner as in Synthesis Example 1, 342.6 g of the thus obtained ester amine and 56.8 g of dimethyl sulfate were used to obtain reaction product a-6.

Synthesis Example 7: Synthesis of Reaction Product a-7

(11) A four-necked flask having a volume of 500 mL was charged with 81.4 g of a coconut oil fatty acid and 321.1 g of triethanolamine EO adduct A3, and a reaction was performed under conditions of normal pressure and at 140 C. for 3 hours, further followed by a dehydration condensation reaction under reduced pressure of 220 hPa and at 180 to 185 C. to obtain an ester amine. In the same manner as in Synthesis Example 1, 336.5 g of the thus obtained ester amine and 56.8 g of dimethyl sulfate were used to obtain reaction product a-7.

Comparative Synthesis Example 1: Synthesis of Comparative Reaction Product a-1

(12) An autoclave was charged with 100 g of triethanolamine, 99 g of lauric acid and 0.7 kg of a 48% potassium hydroxide aqueous solution. Conditions inside the autoclave were set to 100 C. and 4.0 kPa (30 torr), and a dehydration reaction was performed for 1 hour under these conditions. Then, the temperature was increased to 150 C., and 259 g of ethylene oxide was introduced into the autoclave at this temperature to perform an addition reaction. After completing the reaction, the thus obtained reaction mixture was transferred to a treatment tank. 7 g of an adsorbent (Kyowaad 600S, Kyowa Chemical Industry Co., Ltd.) was added to the reaction mixture, and the thus obtained mixture was stirred at 80 C. and 4.0 kPa (30 torr) for 1 hour. The resultant reaction mixture was filtered to obtain a filtrate as a product. In an autoclave, 183.7 g of the thus obtained product and 40.1 g of methyl chloride were reacted by stirring at 60 C. for 3 hours, the resultant was then stirred at 60 C. and 25 kPa for 1 hour with nitrogen introduced thereinto at 6 L/hr.Math.kg, and an unreacted portion of the methyl chloride was distilled off for quaternization to obtain comparative reaction product a-1.

(13) The structures, compositions and composition ratios of reaction products a-1 to a-7 and comparative reaction product a-1 obtained as described above are shown in Table 1. It is noted that each of reaction products a-1 to a-7 and comparative reaction product a-1 contains an unreacted fatty acid, namely, compound (B).

(14) TABLE-US-00001 TABLE 1 Composition (% by mass) Structure in general formulas (1-1) to (1-4) Compound Symbol R.sup.1 R.sup.2 l + m + n X (A1) (A2) (A3) (A4) Fatty acid Reaction Methyl C.sub.11 linear 3 Methyl sulfate 50.8 21.0 3.0 24.0 1.2 product a-1 group alkyl group anion Reaction Methyl C.sub.11-13 linear 3 Methyl sulfate 50.8 19.9 3.0 25.0 1.3 product a-2 group alkyl group *.sup.1 anion Reaction Methyl C.sub.11-13 linear 6 Methyl sulfate 51.2 21.1 3.0 23.0 1.7 product a-3 group alkyl group *.sup.1 anion Reaction Methyl C.sub.11-13 linear 9 Methyl sulfate 51.3 21.1 3.0 23.1 1.5 product a-4 group alkyl group *.sup.1 anion Reaction Methyl C.sub.11-13 linear 12 Methyl sulfate 50.9 20.9 3.0 23.9 1.3 product a-5 group alkyl group *.sup.1 anion Reaction Methyl C.sub.11-13 linear 9 Methyl sulfate 45.4 33.8 6.5 13.0 1.3 product a-6 group alkyl group *.sup.1 anion Reaction Methyl C.sub.11-13 linear 9 Methyl sulfate 51.6 21.2 2.9 23.8 0.5 product a-7 group alkyl group *.sup.1 anion Comparative Methyl C.sub.11 linear 12 Chloride ion 56.0 16.0 8.0 19.0 1.0 reaction group alkyl group product a-1 Composition ratio (mass ratio) Mass ratio to (A4)/ (A1) + (A2) + (A3) (A3)/ (A4)/ [(A1) + Symbol (A1) (A2) (A3) [(A1) + (A2)] (A2)/(A1) [(A1) + (A2)] (A2) + (A3)] Reaction 68 28 4 4/96 29/71 25/75 24/76 product a-1 Reaction 69 27 4 4/96 28/72 26/74 25/765 product a-2 Reaction 68 28 4 4/96 29/71 24/76 23/77 product a-3 Reaction 68 28 4 4/96 29/71 24/76 23/77 product a-4 Reaction 68 28 4 4/96 29/71 25/75 24/76 product a-5 Reaction 53 39 8 8/92 43/57 14/86 13/87 product a-6 Reaction 68 28 4 4/96 29/71 25/76 24/76 product a-7 Comparative 70 20 10 10/90 22/78 21/79 19/81 reaction product a-1 *.sup.1 corresponding to residue of coconut oil fatty acid
<Efficacy-Enhancing Agent Composition for Agrochemicals>

Example 1-1, Examples 1-4 to 1-9 and Comparative Example 1-3

(15) The reaction products shown in Table 1 were directly used as efficacy-enhancing agent compositions for agrochemicals. The products were each referred to by signs shown in Table 2.

Example 1-2, Example 1-3, Comparative Example 1-1 and Comparative Example 1-2

(16) Reaction product a-4 and a coconut oil fatty acid were weighed to obtain each composition shown in Table 2 so that a total weight of the resultant efficacy-enhancing agent composition for agrochemicals could be 50 g, and the resultant was stirred and mixed for 10 minutes by a stirrer to obtain the efficacy-enhancing agent composition for agrochemicals.

(17) Compositions of the efficacy-enhancing agent compositions for agrochemicals of Examples 1-1 to 1-9 and Comparative Examples 1-1 to 1-3, and mass ratios of [content of compound (A3)]/[sum of content of compound (A1) and content of compound (A2)], [content of compound (A2)]/[content of compound (A1)], [content of compound (B)]/[content of compound (A1)], and [content of compound (B)]/[content of compound (A)] therein are shown in Table 2.

(18) TABLE-US-00002 TABLE 2 Eficacy-enhancing agent Example composition for agrochemicals 1-1 1-2 1-3 1-4 1-5 1-6 Formulation Reaction Reaction Reaction Reaction Reaction Reaction Reaction composition product product a-4 product a-4 product a-4 product a-1 product a-2 product a-3 100% by mass 97% by mass 94% by mass 100% by mass 100% by mass 100% by mass Fatty acid None Coconut oil Coconut oil None None None fatty acid fatty acid 3% by mass 6% by mass Content Compound (A) 98.5 95.5 92.6 98.8 98.7 98.3 (% by mass) Compound (A1) 51.3 49.7 48.2 50.8 50.8 51.2 Compound (A2) 21.1 20.5 19.8 21.0 19.9 21.1 Compound (A3) 3.0 2.9 2.8 3.0 3.0 3.0 Compound (A4) 23.1 22.4 21.8 24.0 25.0 23.0 Compound (B) 1.5 4.5 7.4 1.2 1.3 1.7 Mass (A3)/[(A1) + (A2)] 4/96 4/96 4/96 4/96 4/96 4/96 ratio (A2)/(A1) 29/71 29/71 29/71 29/71 28/72 29/71 (B)/(A1) 1/34.2 1/11.0 1/6.5 1/42.3 1/39.1 1/30.1 (B)/(A) 1/65.7 1/21.2 1/12.5 1/82.3 1/75.9 1/57.8 (B)/[(A) + (B)] 100 1.5 4.5 7.4 1.2 1.3 1.7 (B)/(A1) 0.029 0.091 0.154 0.024 0.026 0.033 (A2)/[(A) + (B)] 100 21.1 20.5 19.8 21.0 19.9 21.1 (A3)/[(A) + (B)] 100 30 2.9 2.8 3.0 3.0 3.0 (A4)/[(A) + (B)] 100 23.1 22.4 21.8 24.0 25.0 23.0 (A4)/[(A1) + (A2)] 0.319 0.319 0.321 0.334 0.354 0.318 (A4)/[(A1) + (A2) + (A3)] 0.306 0.309 0.308 0.321 0.339 0.305 (A1)/(A) 0.521 0.520 0.521 0.514 0.515 0.521 Efficacy-enhancing agent Example Comparative Example composition for agrochemicals 1-7 1-8 1-9 1-1 1-2 1-3 Formulation Reaction Reaction Reaction Reaction Reaction Reaction Comparative composition product product a-5 product a-6 product a-7 product a-4 product a-4 reaction 100% by mass 100% by mass 100% by mass 92% by mass 90% by mass product a-1 100% by mass Fatty acid None None None Coconut oil Coconut oil None fatty acid fatty acid 8% by mass 10% by mass Content Compound (A) 98.7 98.7 99.5 90.6 88.7 99.0 (% by mass) Compound (A1) 50.9 45.4 51.6 47.2 46.2 56.0 Compound (A2) 20.9 33.8 21.2 19.4 19.0 16.0 Compound (A3) 3.0 6.5 2.9 2.8 2.7 8.0 Compound (A4) 23.9 13.0 23.8 21.2 20.8 19.0 Compound (B) 1.3 1.3 0.5 9.4 11.3 1.0 Mass (A3)/[(A1) + (A2)] 4/96 8/92 4/96 4/96 4/96 10/90 ratio (A2)/(A1) 29/71 43/57 29/71 29/71 29/71 22/78 (B)/(A1) 1/39.2 1/34.9 1/103 1/5.0 1/4.1 1/56.0 (B)/(A) 1/75.9 1/75.9 1/199 1/9.6 1/7.8 1/99.0 (B)/[(A) + (B)] 100 1.3 1.3 0.5 9.4 11.3 1.0 (B)/(A1) 0.026 0.029 0.010 0.199 0.245 0.018 (A2)/[(A) + (B)] 100 20.9 33.8 21.2 19.4 19.0 16.0 (A3)/[(A) + (B)] 100 3.0 6.5 2.9 2.8 2.7 8.0 (A4)/[(A) + (B)] 100 23.9 13.0 23.8 21.2 20.8 19.0 (A4)/[(A1) + (A2)] 0.333 0.164 0.327 0.318 0.319 0.264 (A4)/[(A1) + (A2) + (A3)] 0.320 0.152 0.314 0.305 0.306 0.238 (A1)/(A) 0.516 0.460 0.519 0.521 0.521 0.566
<Agrochemical Composition>

Examples 2-1 to 2-10 and Comparative Examples 2-1 to 2-3

(19) One of the efficacy-enhancing agent compositions for agrochemicals, amino acid-based agrochemical active ingredient (C) and water were weighed to obtain each composition shown in Table 3 so that a total weight of the resultant agrochemical composition could be 100 g, and the resultant was stirred and mixed for 10 minutes by a stirrer to obtain the agrochemical composition.

(20) It is noted that agrochemical active ingredients c-1 and c-2 used are as follows:

(21) c-1: glyphosate isopropylamine salt

(22) c-2: glufosinate ammonium salt

(23) Compositions of the agrochemical compositions of Examples 2-1 to 2-10 and Comparative Examples 2-1 to 2-3 are shown in Table 3.

(24) Besides, the agrochemical compositions were tested for the formulation stability and herbicidal property as follows. These test results are also shown in Table 3.

(25) [Formulation Stability of Agrochemical Composition]

(26) 40 g of each agrochemical composition immediately after the preparation was placed in a transparent glass container (volume: 50 ml), and the resultant was stored at 60 C. to evaluate the number of days during which a transparent and homogeneous appearance could be retained.

(27) 5: Transparence and homogeneity were retained for 10 days or more.

(28) 4: Transparence and homogeneity were retained for 8 to 9 days.

(29) 3: Transparence and homogeneity were retained for 3 to 7 days.

(30) 2: Transparence and homogeneity were retained for 1 to 2 days.

(31) 1: Separation or precipitation occurred within 1 day.

(32) [Herbicidal Property Test]

(33) A barnyard grass was grown in a 12 cm-pot, and a plant body thereof having a height of about 30 cm was used for the test. An agrochemical composition having a composition shown in the table was prepared and diluted with water by 185 times to be used as an agrochemical spray solution. This agrochemical spray solution was used for foliar spray so as to be applied on the entire plant body at an application amount of 500 L/ha, and an herbicidal efficacy was evaluated. For the evaluation of the herbicidal efficacy, a mass of the above-ground part was measured on day 14 after the spraying, and an herbicidal rate was calculated, with a mass of an above-ground part of a plant grown in a non-treated area used as a reference, in accordance with the following equation. As the value of the herbicidal rate is larger, the agrochemical efficacy (herbicidal effect) is higher. The term non-treated area used herein refers to an area where the diluted mixture (the agrochemical spray solution) of the agrochemical and the efficacy-enhancing agent composition for agrochemicals was not sprayed (the same is applied to other tests).
Herbicidal Rate (%)=(Mass of above-ground part in non-treated areaMass of above-ground part in treated area)/Mass of above-ground part in non-treated area100

(34) One having an herbicidal rate of less than 80% is at such a level that an herbicidal effect cannot be expected.

(35) Besides, no herbicidal property test was conducted on one having an evaluation score of 1 in the formulation stability test.

(36) TABLE-US-00003 TABLE 3 Agrochemical composition Eficacy-enhancing Agrochemical agent composition active Evaluation for agrochemicals ingredient (C) Content (% by mass) Herbi- Content Content Com- Com- Com- Com- Com- Formu- cidal (% by (% by Water pound pound pound pound pound lation property Type mass) Type mass) Content (A1) (A2) (A3) (A4) (B) stability (%) Example 2-1 Example 1-1 7.5 c-1 41 Balance *.sup.1 3.85 1.58 0.23 1.73 0.11 5 85 2-2 Example 1-2 7.5 c-1 41 Balance *.sup.1 3.73 1.54 0.22 1.68 0.34 5 88 2-3 Example 1-3 7.5 c-1 41 Balance *.sup.1 3.62 1.48 0.21 1.64 0.56 5 90 2-4 Example 1-4 7.5 c-1 41 Balance *.sup.1 3.81 1.58 0.23 1.80 0.09 5 85 2-5 Example 1-5 7.5 c-1 41 Balance *.sup.1 3.81 1.49 0.23 1.88 0.10 5 88 2-6 Example 1-6 7.5 c-1 41 Balance *.sup.1 3.84 1.58 0.23 1.73 0.13 5 90 2-7 Example 1-7 7.5 c-1 41 Balance *.sup.1 3.82 1.57 0.23 1.79 0.10 5 85 2-8 Example 1-1 7.5 c-2 20 Balance *.sup.1 3.85 1.58 0.23 1.73 0.11 5 85 2-9 Example 1-8 7.5 c-1 41 Balance *.sup.1 3.41 2.54 0.49 0.98 0.10 5 82 2-10 Example 1-9 7.5 c-1 41 Balance *.sup.1 3.87 1.59 0.22 1.79 0.04 5 83 Com- 2-1 Comparative 7.5 c-1 41 Balance *.sup.1 3.54 1.46 0.21 1.59 0.71 1 parative Example1-1 Example 2-2 Comparative 7.5 c-1 41 Balance *.sup.1 3.47 1.43 0.20 1.56 0.85 1 Example1-2 2-3 Comparative 7.5 c-1 41 Balance *.sup.1 4.20 1.20 0.60 1.43 0.06 4 71 Example1-3 *.sup.1 Amount necessary for making total content of agrochemical composition 100% by mass