Herbicide composition and herbicidal method

Abstract

To provide a novel herbicide composition having superior herbicidal effect and reduced environmental load.SOLUTION: A herbicide composition contains a neutralized salt of rosin. The neutralized salt of rosin is at least one selected from the group consisting of alkali metal salts of rosin and ammonium salts of rosin.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a herbicide composition and a weeding method.

Background Art

[0002] In crop cultivation areas such as paddy fields and fields, lawns, or non-agricultural lands, herbicides are used for the purpose of weed control. However, many of the commercially available herbicides have a problem in that they may contaminate soil, plants, etc. by remaining in them after use, and have a large environmental load. On the other hand, for example, in Patent Document 1, a herbicidal composition containing a fatty acid, which is a natural component, and a surfactant has been proposed, but their herbicidal effects were low.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide a novel herbicide composition having an excellent herbicidal effect and a reduced environmental load.

Means for Solving the Problems

[0005] As a result of intensive studies, the present inventors have found that the above problems can be solved by a herbicide composition containing a neutralized salt of rosins as an active ingredient.

[0006] Conventionally, rosins and rosin derivatives have been used as various additives such as coating agents, spreading agents, binders, and solvents in various agricultural chemicals such as fertilizers. However, the present inventors have found that neutralized salts of rosins have a herbicidal effect, and have completed the present invention by using them as active ingredients of herbicides. That is, the present invention relates to the following herbicide composition and weeding method.

[0007] 1. A herbicide composition comprising a neutral salt of rosins.

[0008] 2. The herbicide composition according to item 1 above, wherein the neutral salt of rosins is at least one selected from the group consisting of an alkali metal salt of rosins and an ammonium salt of rosins.

[0009] 3. The herbicide composition according to item 1 or 2 above, wherein the rosins is at least one selected from the group consisting of disproportionated rosin, α,β-unsaturated carboxylic acid-modified rosin, and α,β-unsaturated carboxylic acid-modified rosin ester.

[0010] 4. The herbicide composition according to item 3 above, wherein the disproportionated rosin contains 40 to 100% by mass of dehydroabietic acid.

[0011] 5. The herbicide composition according to item 3 or 4 above, wherein the α,β-unsaturated carboxylic acid-modified rosin is at least one selected from the group consisting of maleic anhydride-modified rosin, maleic acid-modified rosin, and fumaric acid-modified rosin.

[0012] 6. The herbicide composition according to item 3 or 4 above, wherein the α,β-unsaturated carboxylic acid-modified rosin ester is at least one selected from the group consisting of maleic anhydride-modified rosin ester, maleic acid-modified rosin ester, and fumaric acid-modified rosin ester.

[0013] 7. The herbicide composition according to any one of items 2 to 6 above, wherein the alkali metal in the alkali metal salt of rosins is at least one selected from the group consisting of sodium and potassium.

[0014] 8. The herbicide composition according to any one of items 1 to 7 above, further comprising water.

[0015] 9. The herbicide composition according to item 8 above, wherein the solid content concentration of the herbicide composition is 10 to 90% by mass.

[0016] A weeding method comprising the step of treating the herbicide composition according to any one of Items 1 to 9 above with a plant or soil.

Advantages of the Invention

[0017] Since the herbicide composition of the present invention contains a salt derived from rosin, which is a natural product, as an active ingredient, the environmental load is reduced and the herbicidal effect is excellent. Further, the weeding method of the present invention uses the above herbicide composition, so it is an environmentally friendly method with excellent herbicidal effect.

Best Mode for Carrying Out the Invention

[0018] [Herbicide Composition] The herbicide composition of the present invention contains a neutralized salt of rosins (hereinafter also simply referred to as a neutralized salt) as an active ingredient.

[0019] <Neutralized Salt of Rosins> The above neutralized salt is not particularly limited as long as it is a salt obtained by neutralizing rosins. The above neutralized salt may be used alone or in combination of two or more. When unneutralized rosins are used in the herbicide composition of the present invention, the herbicidal effect tends to be inferior.

[0020] <Rosins> Rosins are not particularly limited, and various known ones can be used. Rosins may be used alone or in combination of two or more.

[0021] Rosins include, for example, natural rosins (gum rosin, tall oil rosin, wood rosin) derived from Pinus massoniana, Pinus elliottii, Pinus merkusii, Pinus caribaea, Pinus kesiya, Pinus taeda, Pinus palustris, etc., purified rosins (hereinafter, natural rosins and purified rosins are collectively referred to as unmodified rosins), hydrogenated rosins, disproportionated rosins, polymerized rosins, α,β-unsaturated carboxylic acid-modified rosins, and α,β-unsaturated carboxylic acid-modified rosin esters, etc.

[0022] (Purified rosin) The above purified rosin can be obtained by using various known means. Specifically, for example, it can be obtained by using various known purification means such as distillation method, extraction method, recrystallization method, adsorption method, etc. The distillation method includes, for example, a method of distilling the above natural rosin at a temperature of about 200 to 300 °C and a reduced pressure of about 0.01 to 3 kPa. The extraction method includes, for example, a method of making the above natural rosin into an alkaline aqueous solution, extracting insoluble unsaponifiable matter with various organic solvents, and then neutralizing the aqueous layer. The recrystallization method includes, for example, a method of dissolving the above natural rosin in an organic solvent as a good solvent, then distilling off the solvent to obtain a concentrated solution, and further adding an organic solvent as a poor solvent. Good solvents include, for example, aromatic hydrocarbon solvents such as benzene, toluene, xylene, chlorinated hydrocarbon solvents such as chloroform, lower alcohols, ketones such as acetone, and acetate esters such as ethyl acetate. Poor solvents include, for example, n-hexane, n-heptane, cyclohexane, isooctane, etc. The adsorption method includes, for example, a method of bringing molten natural rosin or natural rosin in solution dissolved in an organic solvent into contact with a porous adsorbent. Porous adsorbents include, for example, activated carbon, metal oxides such as alumina, zirconia, silica, molecular sieves, zeolites, and porous clays with micropores.

[0023] In addition, as the purified rosin, each of the disproportionation and hydrogenation operations described below may be performed on the obtained purified rosin alone or in combination of two or more kinds.

[0024] (Disproportionated rosin) The above disproportionated rosin can be obtained by using various known means. Specifically, for example, it can be obtained by a method of heating the above unmodified rosin in the presence of a disproportionation catalyst (disproportionation). As the disproportionation catalyst, various known supported catalysts such as palladium-carbon, rhodium-carbon, platinum-carbon; and metal powders such as nickel and platinum can be used. The amount of the catalyst used is usually about 0.01 to 5 parts by mass, preferably about 0.01 to 1 part by mass, based on 100 parts by mass of the unmodified rosin. The reaction temperature is about 100 to 300 °C, preferably about 150 to 290 °C.

[0025] In addition, as the above disproportionated rosin, each of the above purification, disproportionation, and hydrogenation operations described below may be performed on the obtained disproportionated rosin alone or in combination of two or more kinds.

[0026] (Hydrogenated rosin) The above hydrogenated rosin can be obtained by using various known means. Specifically, for example, it can be obtained by hydrogenating the above unmodified rosin under known hydrogenation conditions. The hydrogenation conditions include, for example, a method of heating the above unmodified rosin to about 100 - 300°C under a hydrogen pressure of about 2 - 20 MPa in the presence of a hydrogenation catalyst. Also, the hydrogen pressure is preferably about 5 - 20 MPa, and the reaction temperature is preferably about 150 - 300°C. As the hydrogenation catalyst, various known ones such as supported catalysts and metal powders can be used. Examples of supported catalysts include palladium-carbon, rhodium-carbon, ruthenium-carbon, platinum-carbon, etc. Examples of metal powders include nickel, platinum, etc. Among these, palladium, rhodium, ruthenium, and platinum-based catalysts are preferred because they can increase the hydrogenation rate of the above unmodified rosin and shorten the hydrogenation time. The amount of the hydrogenation catalyst used is usually about 0.01 - 5 parts by mass, preferably about 0.01 - 2 parts by mass, based on 100 parts by mass of the above unmodified rosin.

[0027] The above hydrogenation may be carried out in a state where the above unmodified rosin is dissolved in a solvent if necessary. The solvent to be used is not particularly limited as long as it is inert to the reaction and the raw materials and products are easily soluble. Specifically, for example, cyclohexane, n-hexane, n-heptane, decalin, tetrahydrofuran, dioxane, etc. can be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, but it is usually used so that the solid content is 10% by mass or more, preferably about 10 - 70% by mass, based on the above unmodified rosin.

[0028] Also, as the above hydrogenated rosin, the obtained hydrogenated rosin may be further subjected to the above purification, hydrogenation, disproportionation operations alone or in combination of two or more.

[0029] (Polymerized rosin) The above-mentioned polymerized rosin can be obtained by using various known means. Specifically, for example, the above-mentioned unmodified rosin is reacted in a solvent such as toluene or xylene containing a catalyst such as sulfuric acid, hydrogen fluoride, aluminum chloride, or titanium tetrachloride at a reaction temperature of about 40 to 160°C for about 1 to 5 hours. Examples of such methods include this one.

[0030] Specific examples of the above-mentioned polymerized rosin include gum-based polymerized rosin using gum rosin as a raw material (for example, trade name "Polymerized Rosin B-140", manufactured by Xinzhou (Wuping) Forest Chemical Co., Ltd.), tall oil-based polymerized rosin using tall oil rosin (for example, trade name "Silvatac 140", manufactured by Arizona Chemical), wood-based polymerized rosin using wood rosin (for example, trade name "Dymarex", manufactured by ASHLAND), and the like.

[0031] Also, as the above-mentioned polymerized rosin, those obtained by subjecting the obtained polymerized rosin to various treatments such as the above-mentioned purification, hydrogenation, disproportionation, and α,β-unsaturated carboxylic acid modification such as acrylation, maleinization, and fumarization described later may be used. Also, the various treatments may be used alone or in combination of two or more.

[0032] (α,β-unsaturated carboxylic acid-modified rosin) The above-mentioned α,β-unsaturated carboxylic acid-modified rosin is obtained by subjecting the above-mentioned unmodified rosin to an addition reaction with an α,β-unsaturated carboxylic acid.

[0033] The above-mentioned α,β-unsaturated carboxylic acid is not particularly limited, and various known ones can be used. Specifically, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, muconic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, muconic anhydride, maleic acid half ester, fumaric acid half ester, itaconic acid half ester, and the like can be mentioned. Among these, maleic acid, maleic anhydride, and fumaric acid are preferred. The amount of the α,β-unsaturated carboxylic acid used is usually about 1 to 20 parts by mass, preferably about 1 to 6 parts by mass, based on 100 parts by mass of the above-mentioned unmodified rosin.

[0034] The above α,β-unsaturated carboxylic acid-modified rosin can be obtained by using various known means. Specifically, for example, the above unmodified rosin melted under heating is added with the above α,β-unsaturated carboxylic acid and reacted at a temperature of about 180 to 240°C for about 1 to 9 hours to obtain it. Further, the above reaction may be carried out while blowing an inert gas such as nitrogen into a sealed reaction system. Furthermore, in the above reaction, known catalysts such as Lewis acids such as zinc chloride, iron chloride, and tin chloride, and Bronsted acids such as p-toluenesulfonic acid and methanesulfonic acid may be used. The usage amount of these catalysts is usually about 0.01 to 10% by mass based on the above unmodified rosin.

[0035] The above α,β-unsaturated carboxylic acid-modified rosin may contain resin acids derived from the above unmodified rosin.

[0036] In addition, as the above α,β-unsaturated carboxylic acid-modified rosin, various treatments such as the above purification, hydrogenation, disproportionation, etc. may be further applied to the obtained α,β-unsaturated carboxylic acid-modified rosin. Also, the various treatments may be used alone or in combination of two or more.

[0037] (α,β-unsaturated carboxylic acid-modified rosin ester) The above α,β-unsaturated carboxylic acid-modified rosin ester is a reaction product of the above α,β-unsaturated carboxylic acid-modified rosin and an alcohol.

[0038] The above-mentioned alcohol is not particularly limited, and various known ones can be used. The above-mentioned alcohol includes, for example, monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, decyl alcohol, lauryl alcohol, cyclohexanol, benzyl alcohol, borneol, etc.; dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, neopentyl glycol, trimethylene glycol, cyclohexanedimethanol, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, 4,4'-isopropylidenedicyclohexanol, 4,8-bis(hydroxymethyl)tricyclo[5.2.1.02,6]decane, etc.; trihydric alcohols such as glycerin, trimethylolethane, trimethylolpropane, etc.; tetrahydric alcohols such as pentaerythritol, diglycerin, di(trimethylolpropane), etc.; pentahydric alcohols such as triglycerin, etc.; hexahydric alcohols such as dipentaerythritol, etc. In addition, glycidyl ethers, glycidol, etc. that react with carboxylic acids to form esters may be used for the alcohol. The above-mentioned alcohol may be used alone or in combination of two or more kinds.

[0039] The above-mentioned alcohol is preferably a tri- to hexahydric alcohol, more preferably glycerin, pentaerythritol, diglycerin, or dipentaerythritol.

[0040] The above α,β-unsaturated carboxylic acid-modified rosin ester can be obtained by using various known means. Specifically, for example, the above α,β-unsaturated carboxylic acid-modified rosin and the above alcohol can be reacted at a temperature of about 150 to 300°C for about 1 to 24 hours. The amounts of the above α,β-unsaturated carboxylic acid-modified rosin and alcohol used are not particularly limited, but in order to perform the neutralization reaction described later, it is adjusted so that unreacted COOH groups of rosins remain. Usually, the equivalent of the COOH group of rosins is determined to be in excess with respect to the equivalent of the OH group of the alcohol.

[0041] In the method for producing the above α,β-unsaturated carboxylic acid-modified rosin ester, for the purpose of shortening the reaction time, the esterification reaction can proceed in the presence of a catalyst. Examples of the catalyst include acid catalysts such as p-toluenesulfonic acid, acetic acid, methanesulfonic acid, hypophosphorous acid, and sulfuric acid; metal hydroxides such as calcium hydroxide and magnesium hydroxide; metal oxides such as calcium oxide and magnesium oxide; metal salts such as iron chloride and calcium formate, etc. The catalyst may be used alone or in combination of two or more. Also, since water is generated as a result of the esterification reaction, the reaction can proceed while removing the generated water out of the system. Considering the color tone of the obtained α,β-unsaturated carboxylic acid-modified rosin ester, it is desirable to carry out the reaction under an inert gas stream. Further, the reaction can be carried out under pressure if necessary.

[0042] In the method for producing the above α,β-unsaturated carboxylic acid-modified rosin ester, the reaction may be carried out in an organic solvent that is non-reactive with the above α,β-unsaturated carboxylic acid-modified rosin and alcohol. Examples of the organic solvent include hexane, cyclohexane, toluene, xylene, etc. When an organic solvent is used, the organic solvent or unreacted raw materials can be distilled off under reduced pressure if necessary.

[0043] In addition, the method for producing the α,β-unsaturated carboxylic acid-modified rosin ester may be a method in which a modification reaction with an α,β-unsaturated carboxylic acid is carried out on the reaction product of the above unmodified rosin and the above alcohol.

[0044] Further, as the α,β-unsaturated carboxylic acid-modified rosin ester, various treatments such as the above purification, hydrogenation, disproportionation, etc. may be further performed on the obtained α,β-unsaturated carboxylic acid-modified rosin ester. Also, the various treatments may be performed alone or in combination of two or more.

[0045] From the viewpoint of excellent herbicidal effect, at least one selected from the group consisting of disproportionated rosin, α,β-unsaturated carboxylic acid-modified rosin, and α,β-unsaturated carboxylic acid-modified rosin ester is more preferable as the above rosins.

[0046] The above rosins may contain various additives as long as the effects of the present invention are not impaired. Examples of the additive include dehydrating agents, crystal nucleating agents, plasticizers, fluidity improvers, weathering agents, antioxidants, ultraviolet absorbers, heat stabilizers, light stabilizers, etc. The additive may be used alone or in combination of two or more.

[0047] (Physical properties of rosins) The acid value of the above rosins is not particularly limited, but is preferably about 90 to 350 mgKOH / g. In this specification, the acid value is the value measured according to JIS K0070.

[0048] The above rosins are usually solid substances at normal temperature (25°C), and their softening point is not particularly limited, but is preferably about 60 to 200°C from the viewpoint of excellent herbicidal effect. In this specification, the softening point is the value measured by the ring and ball method of JIS K 2531.

[0049] When the above-mentioned rosins are substances that are liquid at normal temperature (25°C), the content of resin acids in the above-mentioned rosins is low and the content of low-molecular-weight components is high in the rosins, so the herbicidal effect in the herbicide composition tends to be low. In the present specification, resin acids are a concept including resin acids which are diterpene carboxylic acids having 20 carbon atoms, α,β-unsaturated carboxylic acid modified products of the resin acids, esterified products of the α,β-unsaturated carboxylic acid modified products, and dimers of the resin acids.

[0050] Examples of the above-mentioned resin acids include abietic acid, levopimaric acid, neoabietic acid, palustric acid, pimaric acid, isopimaric acid, sandaracopimaric acid, dehydroabietic acid, dihydroabietic acid, tetrahydroabietic acid, seco-dehydroabietic acid, communic acid, dihydroagat acid, anticopalic acid, lambertianic acid, acetylisocupressic acid, acetylibricataloic, ibricataloic acid, etc. Examples of the α,β-unsaturated carboxylic acid modified products of the above-mentioned resin acids include maleopimaric acid, fumaropimaric acid, acrylopimaric acid, citraconopimaric acid, etc.

[0051] Examples of the above-mentioned low-molecular-weight components include monoterpenes, sesquiterpenes, saponification products, decarboxylation products of the above-mentioned resin acids, fatty acids, etc.

[0052] The content of resin acids in the above-mentioned rosins is usually 80 to 100% by mass, and preferably 85 to 100% by mass from the viewpoint of excellent herbicidal effect. When the content of resin acids in the above-mentioned rosins is less than 80% by mass, the herbicidal effect tends to be low. The content of the resin acids can be quantified by various known means. For example, it can be obtained by dividing the peak area attributed to the resin acids, which is measured by gel permeation chromatography (GPC) of the above-mentioned rosins, by the total peak area of the above-mentioned rosins.

[0053] In addition, if the above-mentioned rosins are solid substances at normal temperature (25°C), the content of their resin acids is usually about 80 to 100% by mass.

[0054] The content of dehydroabietic acid in the disproportionated rosin is not particularly limited, but it is preferably large from the viewpoint of excellent herbicidal effect, and about 40 to 100% by mass is preferred. The content of the dehydroabietic acid can be quantified by various known means. For example, it can be obtained by dividing the peak area derived from dehydroabietic acid, which is measured by gas chromatography (GC) of the disproportionated rosin, by the peak area of all resin acids contained in the disproportionated rosin.

[0055] From the viewpoint of excellent herbicidal effect, the neutralized salt is preferably at least one selected from the group consisting of alkali metal salts of rosins (hereinafter also simply referred to as metal salts) and ammonium salts of rosins (hereinafter also simply referred to as ammonium salts).

[0056] (Alkali metal salts of rosins) The metal salt is a neutralized salt obtained by a metal compound containing an alkali metal of the rosins.

[0057] (Alkali metal) The alkali metal contained in the metal salt is not particularly limited. Examples of the alkali metal include lithium, sodium, potassium, rubidium, cesium, etc. The alkali metal may be used alone or in combination of two or more.

[0058] From the viewpoint of excellent herbicidal effect, at least one selected from the group consisting of sodium and potassium is preferred as the alkali metal.

[0059] (Method for producing alkali metal salts of rosins) The metal salt is obtained by reacting (neutralizing) the rosins with a metal compound containing an alkali metal.

[0060] The above metal compound is not particularly limited as long as it forms a salt with the above rosins. Examples of the above metal compound include hydroxides, oxides, chlorides, nitrates, acetates, sulfates, carbonates, etc. of the above alkali metals. The above metal compound may be used alone or in combination of two or more.

[0061] From the viewpoint of high reactivity and excellent herbicidal effect, sodium hydroxide and potassium hydroxide are preferable for the above metal compound. Further, the form of the above metal compound is not particularly limited, but an aqueous solution is preferable.

[0062] Examples of the method for reacting the above rosins with the above metal compound include a method of directly reacting rosins and a metal compound in the presence or absence of a solvent (direct method), a method of reacting a metal salt other than an alkali metal salt of rosins with a metal compound in the presence of a solvent to effect salt exchange (double decomposition method), etc. The reaction temperature is not particularly limited, but is usually in the range from room temperature to the boiling point of the solvent. The reaction time varies depending on the reaction temperature, but is usually about 10 minutes to 24 hours. Further, after completion of the reaction, the solvent may be distilled off.

[0063] Examples of the above solvent include water; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, ethylene glycol, propylene glycol; ether alcohol solvents such as diethylene glycol, triethylene glycol, 2-methoxyethanol; aromatic hydrocarbon solvents such as toluene, xylene; ester solvents such as ethyl acetate, butyl acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone. Water is preferable as the above solvent.

[0064] The reaction between the above rosins and the above metal compound is usually carried out such that the introduction amount of the alkali metal with respect to the COOH group of the rosins is 5 to 100 equivalent %, preferably 10 to 100 equivalent %.

[0065] (ammonium salt of rosins) The ammonium salt is a neutralization salt of the above rosins with ammonia.

[0066] Examples of the above ammonia include ammonia, ammonium carbonate, etc. The above ammonia may be used alone or in combination of two or more.

[0067] (Method for producing ammonium salt of rosins) The ammonium salt is obtained by reacting (neutralizing) the above rosins with the above ammonia.

[0068] The method for reacting the above rosins with the above ammonia is not particularly limited and can be obtained using various known means. Specifically, for example, a method of directly reacting rosins with ammonia in the presence or absence of a solvent can be mentioned. The reaction temperature is not particularly limited, but is usually in the range from normal temperature to the boiling point of the solvent. The reaction time varies depending on the reaction temperature, but is usually about 10 minutes to 24 hours. Also, after the reaction is completed, the solvent may be distilled off.

[0069] Examples of the above solvent include alcohol solvents such as water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, ethylene glycol, and propylene glycol. Water is preferred as the above solvent.

[0070] The reaction between the above rosins and the above ammonia is carried out so that at least 50% or more, preferably 80 to 100% of the COOH groups of the rosins are neutralized.

[0071] (Solvent) By further containing a solvent, the above herbicide composition may be in the form of a dispersible composition such as a solution or an emulsion. Examples of the solvent include those described above. Water is preferable as the solvent from the viewpoints of excellent herbicidal effect and reduced environmental load. When the solvent is water, since the above metal salt can be easily dissolved or emulsified in water, the herbicide composition has excellent dispersion stability without using a surfactant (emulsifier).

[0072] (Additive) The above herbicide composition may further contain various additives such as an antifoaming agent, a viscosity modifier, a filler, an antioxidant, a water resistance agent, a film-forming aid, a preservative, a pH adjuster such as aqueous ammonia and sodium bicarbonate, a surfactant, an anti-aging agent, an ultraviolet absorber, an antioxidant, and a light stabilizer, as long as the effects of the present invention are not impaired, in addition to the above solvent. These additives may be used alone or in combination of two or more kinds.

[0073] (Physical properties of herbicide composition) The content of the above metal salt in the above herbicide composition is not particularly limited, but is usually about 10 to 100 parts by mass with respect to 100 parts by mass of the above herbicide composition.

[0074] When the above herbicide composition contains a solvent, the content of the above metal salt in the above herbicide composition is preferably about 10 to 90 parts by mass with respect to 100 parts by mass of the above herbicide composition. Further, the content of the solvent in the above herbicide composition is preferably contained in a range such that the solid content concentration of the above herbicide composition is about 10 to 90% by mass from the viewpoint of excellent herbicidal effect.

[0075] When the above herbicide composition contains water, the pH of the above herbicide composition is usually about 9 to 12.

[0076] (Method for producing herbicide composition) The method for producing the herbicide composition is not particularly limited. The herbicide composition may use the metal salt as it is, or may be obtained by mixing the metal salt with the solvent and the additive as necessary. In addition, the solvent used in the method for producing the metal salt may be used as it is as the solvent in the herbicide composition.

[0077] (Formulation form of the herbicide composition) The herbicide composition may use the metal salt itself, but may be formulated so as to be more conveniently used as long as the effects of the present invention are not impaired.

[0078] The formulation form of the herbicide composition is not particularly limited. For example, the above-described dispersible composition and the formulation forms usually used as agricultural chemicals, specifically, granules, fine granules, wettable powders, granule wettable powders, flowables, dry flowables, water-soluble agents, granule water-soluble agents, emulsions, EW agents, liquids, ME liquids, surfactants, pastes, aerosol agents, microcapsule agents, pack agents, etc. can be mentioned.

[0079] The herbicide composition may contain necessary auxiliary agents according to its formulation form. Examples of the auxiliary agents include carriers such as solid carriers and liquid carriers, surfactants, dispersants, wetting agents, binders, thickeners, colorants, spreading agents, sticking agents, antifreezing agents, anti-caking agents, disintegrants, anti-decomposition agents, etc. Other additives such as preservatives and plant pieces may be used as additive components as necessary. These auxiliary agents may be used alone or in combination of two or more.

[0080] Examples of the solid carrier include natural minerals such as quartz, clay, kaolinite, pyrophyllite, sericite, talc, bentonite, acid clay, attapulgite, zeolite, and diatomaceous earth, inorganic salts such as calcium carbonate, ammonium sulfate, sodium sulfate, and potassium chloride, organic solid carriers such as synthetic silicic acid, synthetic silicate, starch, cellulose, and plant powders (e.g., sawdust, coconut husk, corn cob, tobacco stem, etc.), plastic carriers such as polyethylene, polypropylene, and polyvinylidene chloride, urea, inorganic hollow bodies, plastic hollow bodies, fumed Examples include silica (fumed silica, white carbon), etc.

[0081] Examples of the liquid carrier include, for example, the solvents described above, lactones such as γ-butyrolactone, amides such as dimethylformamide, diethylformamide, dimethylacetamide, and N-alkylpyrrolidinone, nitriles such as acetonitrile, sulfur compounds such as dimethyl sulfoxide, and vegetable oils such as soybean oil, rapeseed oil, cottonseed oil, and castor oil.

[0082] Surfactants used as the above-mentioned dispersants and wetting agents include, for example, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene resin acid esters, polyoxyethylene fatty acid diesters, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene dialkyl phenyl ethers, polyoxyethylene alkyl phenyl ether formalin condensates, polyoxyethylene polyoxypropylene block copolymers, polystyrene polyoxyethylene block polymers, alkyl polyoxyethylene polypropylene block copolymer ethers, polyoxyethylene alkyl amines, polyoxyethylene fatty acid amides, polyoxyethylene fatty acid bisphenyl ethers, polyalkylene benzyl phenyl ethers, polyoxyalkylene styryl phenyl ethers, acetylene diols, polyoxyalkylene-added acetylene diols, polyoxyethylene ether type silicones, ester type silicones, fluorine-based surfactants, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil and other nonionic surfactants, alkyl sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, polyoxyethylene styryl phenyl ether sulfates, alkyl benzene sulfonates, alkyl aryl sulfonates, lignin sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, alkyl naphthalene sulfonates, salts of formalin condensates of naphthalene sulfonic acids, salts of formalin condensates of alkyl naphthalene sulfonic acids, fatty acid salts, polycarboxylic acid salts, polyacrylate salts, N-methyl-fatty acid sarcosinates, resin acid salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates and other anionic surfactants, lauryl amine hydrochloride, stearyl amine hydrochloride, oleyl amine hydrochloride, stearyl amine acetate, stearyl aminopropyl amine acetate, alkyl trimethyl ammonium chloride, alkyl dimethyl benzalkonium chloride and other cationic surfactants such as alkyl amine salts.Examples include amphoteric surfactants such as amino acid type or betaine type, etc.

[0083] Examples of the above binder include carboxymethyl cellulose and its salts, dextrin, water-soluble starch, xanthan gum, guar gum, sucrose, polyvinyl pyrrolidone, gum arabic, polyvinyl alcohol, polyvinyl acetate, sodium polyacrylate, polyethylene glycol with an average molecular weight of 6,000 to 20,000, polyethylene oxide with an average molecular weight of 100,000 to 5,000,000, phospholipids (such as cephalin, lecithin, etc.), cellulose powder, dextrin, modified starch, polyaminocarboxylic acid chelate compound, cross-linked polyvinyl pyrrolidone, copolymer of maleic acid and styrenes, (meth)acrylic acid copolymer, half ester of polymer composed of polyhydric alcohol and dicarboxylic anhydride, water-soluble salt of polystyrene sulfonic acid, paraffin, terpene, polyamide resin, polyacrylate, polyoxyethylene, wax, polyvinyl alkyl ether, alkylphenol formalin condensate, synthetic resin emulsion, etc.

[0084] Examples of the above thickener include xanthan gum, guar gum, daiyuutan gum, carboxymethyl cellulose, polyvinyl pyrrolidone, carboxyvinyl polymer, acrylic polymer, starch derivative, water-soluble polymer such as polysaccharide, high-purity bentonite, inorganic fine powder such as fumed silica (white carbon), etc.

[0085] Examples of the above colorant include inorganic pigments such as iron oxide, titanium oxide, Prussian blue, and organic dyes such as alizarin dye, azo dye, metal phthalocyanine dye, etc.

[0086] Examples of the above antifreezing agent include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, etc.

[0087] Examples of the auxiliary agents for preventing consolidation and promoting disintegration include polysaccharides such as starch, alginic acid, mannose, and galactose, polyvinylpyrrolidone, fumed silica (white carbon), ester gum, petroleum resin, sodium tripolyphosphate, sodium hexametaphosphate, metal stearates, cellulose powder, dextrin, copolymers of methacrylic acid esters, polyvinylpyrrolidone, polyaminocarboxylic acid chelate compounds, sulfonated styrene·isobutylene·maleic anhydride copolymers, starch·polyacrylonitrile graft copolymers, and the like.

[0088] Examples of the decomposition inhibitors include desiccants such as zeolite, quicklime, and magnesium oxide, antioxidants such as phenolic compounds, amine compounds, sulfur compounds, and phosphate compounds, and ultraviolet absorbers such as salicylic acid compounds and benzophenone compounds.

[0089] Examples of the preservatives include potassium sorbate, 1,2-benzothiazolin-3-one, and the like. Furthermore, if necessary, functional spreading agents, activity enhancers such as metabolic decomposition inhibitors like piperonyl butoxide, antifreeze agents such as propylene glycol, antioxidants such as BHT, ultraviolet absorbers, and other auxiliary agents can also be used.

[0090] The above herbicide composition may be further used by mixing or combining it with other known active compounds, other agricultural chemicals, such as fungicides, insecticides, herbicides, acaricides, phytotoxicity reducing agents (safeners), plant growth regulators, fertilizers, soil conditioners, and the like.

[0091] [Weed Control Method] The weed control method of the present invention includes the step of treating the above herbicide composition on plants or soil. Examples of the plants include weeds to be controlled. Examples of the soil include the soil at the location where the weeds to be controlled are growing or will grow.

[0092] The step of treating the above herbicide composition on plants includes, for example, the step of spraying the herbicide composition on the foliage of weeds. The step of treating the above herbicide composition on soil includes, for example, the step of spraying the herbicide composition on the soil surface at a place where weeds are growing or will grow, the step of mixing and treating the herbicide composition with the soil where weeds grow, and the like. Further, when the above herbicide composition is in the form of a dispersible composition such as a solution or an emulsion, the above herbicide composition may be sprayed on soil or plants using a spraying device such as a sprayer, an aerosol container, an agricultural sprayer, a nebulizer, etc. In that case, the above herbicide composition may be further diluted with a solvent such as water.

[0093] The weeds to be controlled above are not particularly limited. Such weeds include, for example, as genera of dicotyledonous weeds, Ipomoea, Lindernia, Sesbania, Abutilon, Matricaria, Rorippa, Urtica, Lamium, Xanthium, Sinapis, Rotala, Veronica, Papaver, Chenopodium, Trifolium, Portulaca, Viola, Pharbitis, Galeopsis, Datura, Solanum, Capsella, Cirsium, Sonchus, Galinsoga, Stellaria, Senecio, Amaranthus, Ambrosia, Kochia, Lamium, Leipidium, Polygonum, Galium, Centaurea, Artemisia, etc.

[0094] Examples of monocotyledonous weed genera include Leptochloa, Phleum, Poa, Festuca, Setaria, Eleusine, Sagittaria, Agropyron, Ischaemum, Cyperus, Avena, Bromus, Panicum, Cynodon, Monochoria, Alopecurus, Paspalum, Commelina, Fimbristylis, Lolium, Brachiaria, Agrostis, Eleocharis, Echinochlona, Scirpus, Digitaria, Sorghum, etc.

[0095] Specific examples of other weeds include Amaranthus retroflexus, Amaranthus viridis, Setaria faberi, Leptochloa chinensis, Lindernia angustifolia, Lindernia procumbens, Ipomoea hederacea, Lindernia dubia, Sida spinosa, Polygonum pensylvanicum, Sesbania exaltata, Geranium carolinense, Conyza bonariensis, Amaranthus powellii, Polygonum cuspidatum, Abutilon theophrasti, Matricaria perforata, Polygonum longisetum, Echinochloa crus-galli, Amaranthus lividus, Solanum nigrum, Bromus tectorum, Sagittaria pygmaea Miq, Rumex obtusifolius, Setaria viridis, Cassia obtusifolia, Conyza sumatrensis, Veronica persica, Xanthium canadens, Panicum dichotomiflorum, Asclepias syriaca, Euphorbia maculata, Plantago asiatica, Amaranthus palmeri, Xanthium strumarium, Avenasterilis), Goosegrass (Eleusine indica), Arrowhead (Sagittaria trifolia), Redstem filaree (Erodium cicutarium), Mouse-ear chickweed (Cerastium glomeratum), Scentless mayweed (Matricaria matricarioides), Chamomile (Matricaria chamomilla), Narrow-leaved vetch (Vicia angustifolia), Rye brome (Bromus secalinus), Wild oat (Avena fatua), Indian toothcup (Rotala indica Koehne), Japanese dock (Rumex japonicus), Yellow nutsedge (Cyperus esculentus), Yellow foxtail (Setaria glauca), Kudzu (Pueraria lobata), Black bulrush (Eleocharis kuroguwai Ohwi), Giant ragweed (Ambrosia trifida), Corn marigold (Chrysanthemum segetum), Small-flowered umbrellaplant (Cyperus iria), Monochoria (Monochoria vaginalis), Jungle rice (Echinochloa colona), Water plantain (Alisma plantago-aquatica), Weedy rice (Oryza sativa), Pale smartweed (Polygonum lapathifolium), Quackgrass (Agropyron repens), Johnson grass (Sorghum vulgare), Soft brome (Apera spica-venti), Lambsquarters (Chenopodium album), White clover (Trifolium repens), Jimsonweed (Datura stramonium), Field horsetail (Equisetum arvense), Annual bluegrass (Poa annua), Japanese brome (Bromus japonicus), Equal awn foxtail (Alopecurus aequalis), Purslane (Portulaca oleracea), Tall goldenrod (Solidago altissima), Johnsongrass (Sorghum halepense), Wild mustard (Brassicajuncea), Taraxacum officinale, Convolvulus arvensis, Oenanthe javanica, Polygonum convolvulus, Echinochloa oryzicola Vasing, Ischaemum rugosum, Veronica arvensis, Cyperus difformis L., Amaranthus rudis, Ludwigia prostrata Roxburgh, Commelina communis, Panicum texanum, Euphorbia helioscopia, Rumex crispus, Capsella bursa-pastoris, Euphorbia pseudochamaesyce, Brachiaria plantaginea, Lolium multiflorum, Alopecurus myosuroides, Sinapis arvensis, Galinsoga ciliata, Stellaria media, Cyperus rotundus, Amaranthus spinosus, Polygonum persicaria, Papaver rhoeas, Helianthus annuus, Lamium purpureum, Kyllinga gracillima, Ammannia multiflora, Conyza canadensis, Potamogeton distinctus A. Benn, Amaranthus tuberculatus, Viola arvensis, AmbrosiaArtemisiifolia, Veronica hederaefolia, Alopecurus myosuroides, Desmodium tortuosum, Plantago lanceolata, Alisma canaliculatum A. Br. et Bouche, Kochia scoparia, Lolium rigidum, Ammannia coccinea, Lolium perenne, Scirpus juncoides Roxburgh, Lamium amplexicaule, Amaranthus hybridus, Eleocharis acicularis L., Ipomoea lacunosa, Ipomoea purpurea, Ipomoea hederacea var integriuscula, Commelina bengharensis, Monochoria korsakowii, Cyperus serotinus Rottboel, Elatine triandra Schk, Digitaria ciliaris, Digitaria sanguinalis, Sorghum bicolor, Galium aparine, Artemisia princeps, Viola tricolor, Raphanus raphanistrum, Myosotis arvensis, Alisma canaliculatum, Cyperus flaccidus, etc.

[0096] The useful plants to which the above herbicide composition can be applied are not particularly limited. Examples of such useful plants include cereals (e.g., rice, barley, wheat, rye, oats, corn, etc.), legumes (soybeans, adzuki beans, broad beans, peas, green beans, peanuts, etc.), fruit trees and fruits (apples, citrus fruits, pears, grapes, peaches, plums, cherries, walnuts, chestnuts, almonds, bananas, etc.), leafy and fruit vegetables (cabbage, tomatoes, spinach, broccoli, lettuce, onions, leeks (Welsh onions, Japanese bunching onions), bell peppers, eggplants, strawberries, peppers, okra, chives, etc.), root vegetables (carrots, potatoes, sweet potatoes, taro, daikon radishes, turnips, lotus roots, burdocks, garlic, Chinese chives, etc.), industrial crops (cotton, hemp, sugar beets, hops, sugarcane, sugar beets, olives, rubber, coffee, tobacco, tea, etc.), cucurbits (pumpkins, cucumbers, watermelons, muskmelons, melons, etc.), forage grasses (orchardgrass, sorghum, timothy, clover, alfalfa, etc.), ornamental crops such as spices (lavender, rosemary, thyme, parsley, pepper, ginger, etc.), flowers (chrysanthemums, roses, carnations, orchids, tulips, lilies, etc.), garden trees (ginkgoes, cherry trees, oaks, etc.), forest trees (fir trees, Siberian firs, pine trees, hiba arborvitae, cedar trees, Japanese cypress trees, eucalyptus trees, etc.), and the like.

Examples

[0097] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In the Examples, "parts" and "%" are based on mass unless otherwise specified.

[0098] [Production of Herbicide Composition] Example 1 To a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube, 0.3 part of 5% palladium carbon (water content 50%) as a disproportionation catalyst was added to 1000 parts of Chinese gum rosin (acid value 172 mg KOH / g, softening point 75°C), and the mixture was stirred at 280°C for 4 hours under a nitrogen seal to carry out a disproportionation reaction, obtaining disproportionated rosin with an acid value of 160 mg KOH / g and a softening point of 80°C. The dehydroabietic acid content of the disproportionated rosin was 45%.

[0099] Into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 100 parts of the disproportionated rosin in powder form, 33.3 parts of a 48% potassium hydroxide aqueous solution, and 330 parts of water were added, and the mixture was stirred at 90 °C for 1 hour under a nitrogen seal. By cooling to room temperature, an aqueous solution of the disproportionated rosin potassium salt with a solid content concentration of 25% and a pH of 10.2 to 10.8 was obtained.

[0100] Example 2 Into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 0.3 part of 5% palladium carbon (water content 50%) as a disproportionation catalyst was added to 1000 parts of Chinese gum rosin (acid value 172 mgKOH / g, softening point 75 °C), and the mixture was stirred at 280 °C for 4 hours under a nitrogen seal to carry out a disproportionation reaction, and a disproportionated rosin with an acid value of 160 mgKOH / g and a softening point of 80 °C was obtained. The dehydroabietic acid content of the disproportionated rosin was 45%.

[0101] Into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 100 parts of the disproportionated rosin in powder form, 23.8 parts of a 48% sodium hydroxide aqueous solution, and 495 parts of water were added, and the mixture was stirred at 90 °C for 1 hour under a nitrogen seal. By cooling to room temperature, an aqueous solution of the disproportionated rosin sodium salt with a solid content concentration of 18% and a pH of 9.7 to 10.1 was obtained.

[0102] Example 3 Into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 600 parts of a melt of Chinese gum rosin at about 160 °C and 36 parts of maleic anhydride were added, and the mixture was reacted at 200 °C for 2 hours while stirring under a nitrogen stream to obtain maleic anhydride-modified rosin. The maleic anhydride-modified rosin was solid at room temperature (25 °C).

[0103] Into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 100 parts of the powdered maleic anhydride-modified rosin, 42.4 parts of a 48% aqueous potassium hydroxide solution, and 27.9 parts of water were added, and the mixture was stirred at 90 °C for 2 hours under a nitrogen seal. Next, a 48% aqueous potassium hydroxide solution was added to adjust the pH, and the mixture was cooled to room temperature to obtain an aqueous solution of potassium maleate-modified rosin with a solid content concentration of 30% and a pH of 10.4 to 11.0.

[0104] Example 4 Into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 100 parts of Chinese gum rosin and 24.6 parts of maleic anhydride were charged, and the reaction was carried out at 220 °C for 2 hours under a nitrogen gas stream. Thereafter, 36.1 parts of pentaerythritol were charged and the reaction was carried out at 230 °C for 2 hours to obtain a maleic anhydride-modified rosin pentaerythritol ester with an acid value of 110 mgKOH / g and a softening point of 185 °C.

[0105] Into a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 100 parts of soft water, 20 parts of the above maleic anhydride-modified rosin pentaerythritol ester, and 2.4 parts of 28% aqueous ammonia (100 mol% based on the acid value) were added to obtain an aqueous solution of maleic anhydride-modified rosin ester ammonium salt (solid content concentration 20%, pH 9.0).

[0106] <Weeding test on lawn> Evaluation Example 1 The aqueous solution of the disproportionated rosin potassium salt of Example 1 was diluted with water to prepare a diluted solution with a solid content concentration of 10%. Next, 500 parts of the diluted solution were placed in a spraying device equipped with a shower cap (trade name "Joro for PET bottle" manufactured by Fujiwara Sangyo Co., Ltd.) attached to the pouring mouth of a 2,000 ml PET bottle, and the diluted solution was sprayed over the entire commercially available lawn (Himekorea lawn, area 260 mm × 350 mm). Seven days later, the appearance of the lawn was visually observed to evaluate the weeding effect.

[0107] Evaluation Example 2 In Evaluation Example 1, the procedure was the same as in Evaluation Example 1, except that the aqueous solution of disproportionated rosin potassium salt in Example 1 was changed to the aqueous solution of disproportionated rosin sodium salt in Example 2.

[0108] Evaluation Example 3 In Evaluation Example 1, the procedure was the same as in Evaluation Example 1, except that the aqueous solution of disproportionated rosin potassium salt in Example 1 was changed to the aqueous solution of maleic anhydride-modified rosin potassium salt in Example 3.

[0109] Evaluation Example 4 In Evaluation Example 1, the procedure was the same as in Evaluation Example 1, except that the aqueous solution of disproportionated rosin potassium salt in Example 1 was changed to the aqueous solution of maleic anhydride-modified rosin ester ammonium salt in Example 4.

[0110] Comparative Evaluation Example 1 In Evaluation Example 1, the procedure was the same as in Evaluation Example 1, except that 500 parts of water was used instead of the diluted solution of the aqueous solution of disproportionated rosin potassium salt.

[0111] Comparative Evaluation Example 2 50 parts of powder of Chinese gum rosin was diluted with 500 parts of water to prepare an aqueous dispersion. Next, the whole of a commercially available lawn (Himekorei lawn, area 260 mm × 350 mm) was sprayed with the aqueous dispersion, and after 7 days, the appearance of the lawn was visually observed to evaluate the herbicidal effect.

[0112] (Evaluation of herbicidal effect) The appearance of the lawn after 7 days was visually observed, and the herbicidal effect was evaluated according to the criteria shown below. ○: The lawn had turned brown and was withered. ×: The lawn remained green and was not withered.

[0113]

Table 1

Claims

1. containing a neutral salt of rosins, wherein the rosins are substances in solid form at normal temperature (25 °C), wherein the rosins are at least one selected from the group consisting of disproportionated rosin, α,β-unsaturated carboxylic acid-modified rosin, and α,β-unsaturated carboxylic acid-modified rosin ester, wherein the disproportionated rosin contains 40 to 100% by mass of dehydroabietic acid, a herbicide composition.

2. The herbicide composition according to claim 1, wherein the neutral salt of rosins is at least one selected from the group consisting of an alkali metal salt of rosins and an ammonium salt of rosins.

3. The herbicide composition according to claim 1 or 2, wherein the α,β-unsaturated carboxylic acid-modified rosin is at least one selected from the group consisting of maleic anhydride-modified rosin, maleic acid-modified rosin, and fumaric acid-modified rosin.

4. The herbicide composition according to claim 1 or 2, wherein the α,β-unsaturated carboxylic acid-modified rosin ester is at least one selected from the group consisting of maleic anhydride-modified rosin ester, maleic acid-modified rosin ester, and fumaric acid-modified rosin ester.

5. The herbicide composition according to any one of claims 2 to 4, wherein the alkali metal in the alkali metal salt of rosins is at least one selected from the group consisting of sodium and potassium.

6. The herbicide composition according to any one of claims 1 to 5, further containing water.

7. The herbicide composition according to claim 6, wherein the solid content concentration of the herbicide composition is 10 to 90% by mass.

8. A herbicide method comprising the step of treating the herbicide composition according to any one of claims 1 to 7 with respect to a plant or soil.

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