Pesticide additives

Abstract

The present invention aims to provide an additive for agricultural chemicals that exhibits excellent spreading properties. [Solution] The present invention provides an additive for pesticides and an additive for pesticides for paddy fields or hydroponics, which contains a lignin derivative having a weight-average molecular weight of 5,000 to 43,000, preferably 5,000 to 36,000, an organic sulfur content of 1.5 to 7.0% by mass, preferably 1.5 to 5.5% by mass, a water solubility of 10 to 100% by mass, an extractant content and a methoxy group content of 0.01 to 2.5% by mass and 3 to 17% by mass, respectively, with a mass ratio of extractant content to methoxy group content of 0.001 to 0.25, and having a functional group represented by formula (1):-SO3M. The lignin derivative preferably satisfies the following conditions: a total decomposition product yield by alkaline nitrobenzene oxidation of 14% or less, and a polydispersity of at least one selected from 1.5 to 4.7.

Description

Technical Field

[0001] The present invention relates to an additive for agricultural chemicals.

Background Art

[0002] Lignin, which is one of the main components of the plant cell wall, has been separated on a large scale by digestion treatment for the purpose of pulping in the pulp and paper industry. The obtained lignin may be denatured during digestion and is classified into kraft lignin, lignin sulfonate, etc. by the digestion method. Some lignin sulfonates, etc. are further chemically modified as required and are used for various purposes on a large scale and commercially.

[0003] Patent Document 1 describes an agricultural chemical composition containing a lignin sulfonate having a purity of 85% by mass or more with a reducing sugar content of less than 5% by mass and a sugar sulfonate content of less than 6% by mass as a surfactant.

[0004] Patent Document 2 describes an aqueous suspension agricultural chemical composition containing a low melting point agricultural chemical active ingredient A, a metal salt of lignin sulfonate B, a sucrose fatty acid ester C, and a thickener as essential components, which exhibits resistance to particle growth of the low melting point agricultural chemical active ingredient.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] One important physical property of pesticide formulations is spreadability. Spreadability generally refers to the property of a substance containing pesticide components to disperse uniformly and rapidly in water. However, the pesticide composition in Patent Document 1, or the aqueous suspension pesticide composition in Patent Document 2, has insufficient spreadability, which may limit the areas in which it can be used.

[0007] The present invention aims to provide an additive for agricultural chemicals that exhibits excellent spreading properties. [Means for solving the problem]

[0008] The present invention provides the following [1] to [8]. [1] A pesticide additive containing a lignin derivative that satisfies the following conditions (A) to (G). (A) The weight-average molecular weight is between 5,000 and 43,000. (B) The organic sulfur content is 1.5 to 7.0% by mass. (C) The solubility in water is 10 to 100% by mass. (D) The amount of extracted components per solid content is 0.01 to 2.5% by mass. (E) The amount of methoxy groups per solid content is 3 to 17% by mass. (F) The mass ratio of the amount of extracted components per solid to the amount of methoxy groups is 0.001 to 0.25. (G) Having a functional group represented by formula (1):-SO3M (wherein M represents a hydrogen atom, a monovalent metal, or a divalent metal) [2](A) The pesticide additive described in [1], wherein the weight-average molecular weight is 5,000 to 36,000. In [3](B), the pesticide additive described in [1] or [2], wherein the organic sulfur content is 1.5 to 5.5% by mass. [4] The lignin derivative is an agrochemical additive according to any one of items [1] to [3], further satisfying that the total decomposition product yield by (H) alkaline nitrobenzene oxidation is 14% or less. [5] A pesticide additive according to any one of items [1] to [4], wherein the lignin derivative further satisfies (I) having a polydispersity of 1.5 to 4.7. [6] A pesticide additive for solid pesticides, as described in any one of items [1] to [5]. [7] A pesticide additive for liquid pesticides, as described in any one of items [1] to [5]. [8] A pesticide additive described in any one of items [1] to [7], for use in rice paddies or hydroponics. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide an additive for pesticides that has excellent spreading properties, and when incorporated into pesticides, it can improve the dispersibility of components in the pesticide. [Modes for carrying out the invention]

[0010] [1. Lignin derivatives] The agricultural additive of the present invention contains a lignin derivative. In this specification, lignin derivatives are typically compounds having structural units derived from lignin and structural units derived from non-lignin sources. Examples include ligninsulfonic acid, kraft lignin, soda lignin, soda-anthraquinone lignin, organosorb lignin, explosion lignin, lignin sulfate, and modified versions thereof. Of these, ligninsulfonic acid, kraft lignin, and modified versions thereof are preferred.

[0011] [1.1 Lignosulfonic acid and its modified products] Ligninsulfonic acid is a compound having a skeleton in which a sulfo group is introduced by cleaving the carbon at the α-position of the side chain of the hydroxyphenylpropane structure of lignin. The structure of the above skeleton is shown in formula (2). [ka]

[0012] Lignin sulfonate may be in the form of an acid or a salt, but is usually in the form of a salt. Examples of salts include monovalent metal salts, divalent metal salts, ammonium salts, and organic ammonium salts. Among these, calcium salts, magnesium salts, sodium salts, potassium salts, and calcium-sodium mixed salts are preferred.

[0013] [Modified lignin sulfonic acid] Modified lignin sulfonic acid is usually a modified product of a compound having the skeleton represented by the above formula (2). For example, it can be obtained through chemical modification methods such as alkylation, alkoxylation, sulfonation, sulfonic acid esterification, sulfomethylation, aminomethylation, desulfonation, alkali treatment, alkali oxygen treatment, oxidation treatment using active oxygen species such as ozone and hydrogen peroxide, and polyalkylene glycolation. Among these, modified lignin sulfonic acid produced through desulfonation by alkali treatment, alkali oxidation treatment, or both is preferred.

[0014] The production method and origin of lignin sulfonic acid and modified lignin sulfonic acid are not particularly limited and may be either natural products or synthetic products. Lignin sulfonic acid is one of the main components of the waste liquid of sulfite pulp obtained by digesting wood under acidic conditions. Therefore, lignin sulfonic acid-based compounds derived from sulfite pulp waste liquid may also be used.

[0015] [Production method of lignin sulfonic acid and modified lignin sulfonic acid] Examples of the production method of lignin sulfonic acid include, for example, a method of producing by subjecting a lignocellulosic raw material or lignin itself to sulfite treatment, preferably a method of producing by subjecting a lignocellulosic raw material or lignin itself to sulfite digestion treatment.

[0016] - Lignocellulosic raw material - The lignocellulosic raw material is not particularly limited as long as it contains lignocellulose in its composition. For example, pulp raw materials such as wood and non-wood can be mentioned. Examples of wood include coniferous woods such as radiata pine, spruce, red pine, cedar, and cypress, and broad-leaved woods such as birch and beech. The tree age and harvesting site of the wood are not limited. Therefore, woods harvested from trees with different tree ages or woods harvested from different parts of the tree may be combined and used. Examples of non-wood include bamboo, kenaf, reed, and rice. The lignocellulosic raw material may be used alone or in combination of two or more kinds.

[0017] Lignin sulfonate may be prepared from raw materials other than lignocellulosic raw materials, for example, lignin. Examples of lignin include those of natural origin and those artificially manufactured (for example, dehydrogenation polymers of hydroxycinnamic alcohol analogs), and any of them can be used. The preparation of lignin sulfonate from lignin can be carried out, for example, by a method of decomposing lignin and sulfonating it.

[0018] - Sulfite treatment - The sulfite treatment can be carried out by bringing at least one of sulfurous acid and sulfite into contact with the lignocellulosic raw material. The conditions of the sulfite treatment are not particularly limited, as long as they are conditions under which a sulfonic group can be introduced into the α-carbon atom of the side chain of lignin contained in the lignocellulosic raw material.

[0019] The sulfite treatment is preferably carried out by the sulfite digestion method. Thereby, the lignin in the lignocellulosic raw material can be more quantitatively sulfonated. The sulfite digestion method is a method of reacting the lignocellulosic raw material at a high temperature in a solution of at least one of sulfurous acid and sulfite (for example, an aqueous solution: a digestion solution). Since this method is industrially established and implemented as a method for producing sulfite pulp, it is advantageous in terms of economy and ease of implementation.

[0020] Examples of sulfite salts used in sulfite pulping include magnesium salts, calcium salts, sodium salts, and ammonium salts.

[0021] The sulfurous acid (SO2) concentration in at least one of the sulfurous acid and sulfite solutions is not particularly limited, but the ratio of the mass (g) of SO2 to 100 mL of the reaction solution is preferably 1 g / 100 mL or more, and more preferably 2 g / 100 mL or more when sulfurous acid pulping is performed. The upper limit is preferably 20 g / 100 mL or less, and more preferably 15 g / 100 mL or less when sulfurous acid pulping is performed. The SO2 concentration is preferably between 1 g / 100 mL and 20 g / 100 mL, and more preferably between 2 g / 100 mL and 15 g / 100 mL when sulfurous acid pulping is performed.

[0022] The pH value for sulfurous acid treatment is not particularly limited, but is usually 10 or less. When performing sulfurous acid pulping, it is preferable to do so under acidic conditions, more preferably with a pH of 5 or less, and even more preferably with a pH of 3 or less, or 2.5 or less. This allows for efficient extraction of lignin derivatives (e.g., lignin sulfonates), resulting in higher quality pulp. The lower limit of the pH value is preferably 0.1 or higher, and more preferably 0.5 or higher when performing sulfurous acid pulping. The pH value during sulfurous acid treatment is preferably 0.1 to 10, more preferably 0.5 to 5 when performing sulfurous acid pulping, and even more preferably 0.5 to 3.

[0023] The temperature for sulfur dioxide treatment is not particularly limited, but is preferably 170°C or lower, and more preferably 150°C or lower when sulfur dioxide pulping is performed. The lower limit is preferably 70°C or higher, and more preferably 100°C or higher when sulfur dioxide pulping is performed. The temperature conditions for sulfur dioxide treatment are preferably 70 to 170°C, and more preferably 100 to 150°C when sulfur dioxide pulping is performed. The treatment time for sulfur dioxide treatment is not particularly limited and depends on the conditions of the sulfur dioxide treatment, but 0.5 to 24 hours is preferred, and 1.0 to 12 hours is more preferred.

[0024] In sulfur dioxide treatment, it is preferable to add a compound that supplies countercations (salts). By adding a compound that supplies countercations, the pH value during sulfur dioxide treatment can be kept constant. The countercations are usually monovalent or divalent metals, and magnesium ions, sodium ions, and calcium ions are preferred. Examples of compounds that supply countercations include MgO, Mg(OH)2, CaO, Ca(OH)2, CaCO3, NH3, NH4OH, NaOH, NaHCO3, and Na2CO3.

[0025] In sulfurous acid treatment, when using a solution of at least one of sulfurous acid and sulfites, the solution may, if necessary, contain, in addition to SO2, the above-mentioned countercation (salt) and pulping agents (e.g., cyclic ketone compounds such as anthraquinone sulfonates, anthraquinones, and tetrahydroanthraquinones).

[0026] There are no restrictions on the equipment used for sulfur dioxide treatment; for example, generally known equipment for manufacturing dissolved pulp can be used.

[0027] To separate at least one of the solutions of sulfurous acid and sulfites (intermediate products), conventional methods can be used. One example of a separation method is the separation of the sulfurous acid effluent after sulfurous acid pulping (e.g., filtration).

[0028] The lignin sulfonate obtained by sulfite treatment (for example, as the filtrate or filtration residue after filtering the insoluble matter of the sulfite solution, preferably as the filtrate) may be used as is, or concentrated as necessary, as a lignin derivative. Alternatively, lignin sulfonic acid that has undergone further treatment as necessary may be used. This makes it possible to obtain a lignin derivative with high purity and / or an appropriate degree of sulfonation (S content). Preferred other treatments include purification, denaturation, or a combination thereof. Examples of purification treatments include dialysis and UF treatment, while examples of denaturation treatments include alkali treatment, oxidation treatment, and combinations thereof. For example, when oxidation treatment is performed, the physical properties of the lignin derivative can be controlled by adjusting the conditions. For instance, by adjusting pH, temperature, and time, desulfonation can be controlled, and the sulfur content of the lignin derivative can be adjusted.

[0029] -Alkaline treatment- Alkaline treatment involves placing the sample under alkaline conditions. Alkaline conditions typically mean placing the sample in an aqueous solution with a pH of 8 or higher, preferably 9 or higher. The upper limit of the pH value is usually 14.

[0030] In alkaline treatment, an alkaline substance is typically brought into contact with the sample. The alkaline substance is not particularly limited, but examples include calcium hydroxide, magnesium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and ammonia. Among these, sodium hydroxide and calcium hydroxide are preferred. The alkaline substance may be used alone or in combination of two or more.

[0031] Examples of methods for contacting a sulfurous acid-treated material with an alkaline substance include preparing a dispersion or solution (e.g., an aqueous dispersion, an aqueous solution) of the target sample and adding the alkaline substance to the dispersion or solution, or adding a solution or dispersion (e.g., an aqueous dispersion, an aqueous solution) of the alkaline substance to the target sample.

[0032] The temperature of the alkali treatment is not particularly limited, but is preferably 40°C or higher, and more preferably 60°C or higher. The upper limit is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 170°C or lower.

[0033] The amount of alkaline substance in the alkaline treatment is preferably 0.5 to 40% by mass, and more preferably 1.0 to 30% by mass, relative to the mass of the aqueous solution or dispersion when preparing an aqueous solution or dispersion by dispersing the alkaline treatment extract in an aqueous solvent (e.g., water).

[0034] The duration of the alkaline treatment is not particularly limited, but is preferably 0.1 hours or longer, and more preferably 0.5 hours or longer. The upper limit is preferably 10 hours or less, and more preferably 6 hours or less.

[0035] Prior to the alkaline treatment, if necessary, the sulfurous acid-treated material may be dissolved, dispersed, or its concentration adjusted (preparation of a solution or dispersion in an aqueous solvent such as water). Dispersion can be performed, for example, by passing through a disc refiner, using a mixer, adding to a disperser, or kneading. Concentration can be adjusted, for example, using an aqueous solvent such as water. Furthermore, filtration may be performed after the alkaline treatment, and it is preferable to subject the filtrate and / or precipitate after filtration to the oxidation treatment. The sample to be subjected to the oxidation treatment is preferably both the filtrate and the precipitate (alkali-treated pulp), and a mixture of the filtrate and precipitate in an appropriate ratio (for example, filtrate:precipitate = 9.5 / 0.5~5 / 5) is more preferable, and a treated product (e.g., powder) obtained by further concentrating and dehydrating this mixture (e.g., by a drying treatment such as spray drying) is even more preferable.

[0036] -Oxidation treatment- The oxidation treatment can be carried out using an appropriate oxidizing agent. If the oxidizing agent is a gas, it can be carried out by passing the gas through the filtrate. If the oxidizing agent is a liquid, it can be carried out by adding the liquid to the sample to be treated. The oxidizing agent is preferably air, oxygen, hydrogen peroxide, ozone, or a combination thereof. Reactive oxygen species such as ozone and hydrogen peroxide, or air, are preferred, and the inclusion of air (air oxidation) is more preferred. The oxidation treatment is preferably carried out under alkaline conditions (alkali oxidation treatment, alkaline air oxidation treatment). The treatment pH for alkali oxidation treatment is usually 8 or higher, preferably 10 or higher, and more preferably 12 or higher. The temperature for oxidation treatment is usually 20 to 200°C, preferably 50 to 180°C. The oxidation treatment time is usually preferably 0.1 hours or more, more preferably 0.5 hours or more. The upper limit is preferably 5 hours or less, and more preferably 3 hours or less. After the reaction, the pH can be lowered by adding acid (for example, to pH 5 or less) and the precipitate can be separated and recovered. The precipitate may be used as is as modified ligninsulfonic acid, but if necessary, it may be further dehydrated by redissolving it in an alkaline solution (e.g., an aqueous sodium hydroxide solution) or by spray drying.

[0037] -Dialysis treatment or UF treatment- Dialysis can be performed on the treated material obtained after sulfurous acid treatment (e.g., the filtrate after filtration). Examples of dialysis membranes include regenerated cellulose such as cellulose acetate, cellulose-based membranes such as cellulose esters, and synthetic polymer membranes such as ethylene vinyl alcohol, polyacrylonitrile, polymethyl methacrylate, polysulfone, and polyethersulfone. The molecular weight fraction is usually 5,000 to 100,000, preferably 7,000 to 80,000, and more preferably 10,000 to 50,000.

[0038] Ultrafiltration (UF) treatment can be used instead of dialysis. Known UF membranes can be used, such as hollow fiber membranes, spiral membranes, tubular membranes, and flat membranes. The material of the UF membrane can be a known material, such as cellulose acetate, aromatic polyamide, polyvinyl alcohol, polysulfone, polyvinylidene fluoride, polyethylene, polyacrylonitrile, or ceramic. Commercially available UF membranes may also be used.

[0039] The molecular weight cutoff of the UF membrane is preferably 5,000 to 30,000, more preferably 10,000 to 25,000, and even more preferably 15,000 to 23,000. Using a UF membrane with a molecular weight cutoff of 5,000 or more can prevent the separation rate of the processing solution from becoming excessively slow. Using a UF membrane with a molecular weight cutoff of 30,000 or less can prevent lignin from not being separated from the processing solution.

[0040] The concentration ratio achieved by UF treatment using a UF membrane can be set arbitrarily. In other words, the UF treatment should be stopped when the amount of concentrated liquid flowing out reaches the desired amount. Preferably, the concentration is 2 to 6 times. Concentrating by 2 to 6 times means that the amount of the original solution (black liquor) is reduced to 1 / 2 to 1 / 6 of its original volume.

[0041] The temperature of the treatment solution during UF treatment is not particularly limited. For example, 20 to 80°C is preferred, and 20 to 70°C is more preferred considering the heat resistance of the UF film material. The pH value of the treatment solution during UF treatment is preferably 2 to 11. The solid content concentration (w / w) of the black liquor during UF treatment is preferably 2 to 30%, and more preferably 5 to 20%. After dialysis and UF treatment, further treatments such as concentration (e.g., heating, spray drying, etc.) may be performed as needed. The treated product after dialysis and UF treatment (including any concentrated product as needed) may be used as modified ligninsulfonic acid, or subjected to other treatments such as oxidation.

[0042] Another example of a method for producing lignin sulfonates is the sulfonation of Kraft lignin. As for the Kraft Lignin, the same type as exemplified in the section "Method for Producing Sulfomethylated Kraft Lignin" can be used. In addition, various types of Kraft Lignin can be produced by the same method as exemplified in "Method for Producing Sulfomethylated Kraft Lignin".

[0043] [1.2 Kraft lignin] Kraft lignin is also called thiolignin or sulfate lignin. Kraft lignin may be isolated from the manufacturing process of kraft pulp (e.g., the kraft pulp digestion process) or commercially available products may be used. The raw material for kraft lignin may be either coniferous trees (N wood) or hardwoods (L wood), but N wood is preferred. N wood lignin consists only of guaiacyl lignin (G nucleus) with the 5th position of the aromatic kernel being unsubstituted, and tends to undergo sulfomethylation easily. Examples of lignin components containing kraft lignin isolated from raw materials include UF-treated kraft black liquor, alkaline solution of kraft lignin, powdered kraft lignin obtained by spray-drying the alkaline solution of kraft lignin, and acid-precipitated kraft lignin obtained by precipitating the alkaline solution of kraft lignin with acid.

[0044] [Modified Kraft Lignin] Examples of modified products of Kraft lignin include chemically modified products of Kraft lignin (e.g., alkylation, alkoxylation, sulfonation, sulfonic acid esterification, sulfomethylation, aminomethylation, desulfonation, alkalization, polyalkylene glycolation), with sulfomethylation being preferred. In this specification, sulfomethylated Kraft lignin is a reaction product obtained by sulfomethylating Kraft lignin as a starting material. In the sulfomethylation reaction of Kraft lignin, a sulfomethyl group (-CH2SO3M; M is a hydrogen atom, a monovalent metal, or a divalent metal) is generally introduced at the 5-position of the guaisial nucleus (G nucleus) of lignin.

[0045] [Method for producing Kraft Lignin and its modified products] -Craft Steaming Method- Kraft lignin can be produced by the Kraft pulping process. The Kraft pulping process is a method of pulping lignocellulose raw materials (similar to those described for ligninsulfonic acid) by adding chemicals mainly composed of caustic soda (NaOH) and sodium sulfide (Na2S). In the Kraft pulping process, the amount of caustic soda used is usually 1% by mass or more, preferably 10% by mass or more, per unit mass of the oven-dry raw material (e.g., wood chips). The upper limit is usually 50% by mass or less, preferably 30% by mass or less. Therefore, it is usually 1 to 50% by mass, preferably 10 to 30% by mass. It is preferable that the amount of caustic soda used is within the above numerical range because it is possible to sufficiently separate lignin while maintaining the yield and quality of the pulp. In the Kraft pulping process, the amount of sodium sulfide used is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more. The upper limit is usually 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less. Therefore, it is usually 1 to 30% by mass, preferably 2 to 20% by mass, and more preferably 3 to 10% by mass.

[0046] The pulverized liquid may further contain pulverizing aids. Examples of pulverizing aids include pulverizing agents (e.g., quinone compounds, hydroquinone compounds, and other quinones). Examples of quinones include anthraquinones, dihydroanthraquinones (e.g., 1,4-dihydroanthraquinone), tetrahydroanthraquinones (e.g., 1,4,4a,9a-tetrahydroanthraquinone, 1,2,3,4-tetrahydroanthraquinone), methylanthraquinones (e.g., 1-methylanthraquinone, 2-methylanthraquinone), methyldihydroanthraquinones (e.g., 2-methyl-1,4-dihydroanthraquinone), and methyltetrahydroanthraquinones (e.g., 1-methyl-1,4,4a,9a-tetrahydroanthraquinone). Examples include loanthraquinone (2-methyl-1,4,4a,9a-tetrahydroanthraquinone), anthrahydroquinone (e.g., 9,10-dihydroxyanthracene), methylanthrahydroquinone (e.g., 2-methylanthrahydroquinone), dihydroantradihydroxyquinone (e.g., 1,4-dihydro-9,10-dihydroxyanthracene), metal salts thereof (e.g., alkali metal salts such as sodium salts and disodium salts), and precursors of the above quinones (e.g., anthrone, anthranol, methylantrone, methylanthranol). Note that quinone precursors may be converted into quinone compounds and hydroquinone compounds under pulping conditions. The quinones may be one type or a combination of two or more types. When quinones are included, the amount added is preferably 0.01 to 5% by mass per oven-dried wood chips.

[0047] The pulverized liquor can have an active alkali addition rate (AA) of 8 to 55% by mass per unit mass of oven-dry wood chips, with 8 to 30% by mass or 8 to 20% by mass being preferable. An active alkali addition rate of 8% by mass or more avoids insufficient removal of lignin and hemilose, while an active alkali addition rate of 55% by mass or less prevents a decrease in yield and suppresses a decline in quality. Here, the active alkali addition rate is the rate of NaOH and Na2S addition converted to the rate of Na2O addition, which can be converted by multiplying the rate of NaOH addition by 0.775. A sulfidation degree of 15-40% is preferable. In the range of 15% or higher, a decrease in deligninability, a decrease in pulp viscosity, and an increase in the pulp content can be suppressed. By keeping it below 40%, an effect commensurate with the amount added can be obtained.

[0048] The H-factor (Hf) in pulping is preferably 250 to 2500, more preferably 400 to 2000, and even more preferably 600 to 1900. The H-factor is an indicator of the total amount of heat supplied to the reaction system during the pulping process and is expressed by the following formula (a). Hf=∫exp(43.20-16113 / T)dt (a) In equation (a), T represents the absolute temperature at a given point in time. The H-factor is calculated by integrating the time from the moment the wood chips and water are mixed until the end of digestion. The digestion temperature and digestion time can be appropriately set based on the H-factor.

[0049] The thawing may be carried out at high temperatures. The heating temperature is usually 120-180°C, preferably 140-180°C, and more preferably 150-170°C. The thawing time (the time from when the thawing temperature reaches its maximum temperature until it begins to decrease) is usually 60-600 minutes, preferably 120-360 minutes.

[0050] Digestion can be carried out using a container capable of containing lignocellulose raw materials such as wood chips and the digested liquid (for example, a pressure-resistant container such as an autoclave). The liquid ratio (ratio of digested liquid to the oven-dry weight of the lignocellulose raw materials) is usually 1.0 to 40 L / kg, preferably 1.5 to 30 L / kg, and more preferably 2.0 to 30 L / kg. Examples of digestion types include single-vessel liquid-phase, single-vessel gas-phase / liquid-phase, double-vessel liquid-phase / gas-phase, and double-vessel liquid-phase, and any of these may be used.

[0051] Lignin can be obtained after the pulping process, for example, by separating it from the pulping wastewater (black liquor). Such methods are not particularly limited and include filtration treatment such as UF treatment using an ultrafiltration membrane (UF membrane) and the Lignoboost® method (for example, the method described in Japanese Patent Publication No. 2008-513549), with the Lignoboost method being preferred. The Lignoboost method involves treating the black liquor with carbon dioxide, filtering out the precipitate, dispersing it again in water, and adding acid to precipitate and dehydrate it. This yields high-purity lignin.

[0052] An alkaline solution of Kraft lignin can be obtained, for example, by the method described in Japanese Patent Publication No. 2000-336589, namely, by electrolytic oxidation of an alkaline solution containing Na2S flowing through the Kraft pulp manufacturing process to produce an NaOH solution at the cathode, but is not limited to these methods.

[0053] As acid-precipitated Kraftlignin obtained by precipitating an alkaline solution of Kraftlignin with acid, powdered acid-precipitated Kraftlignin obtained by methods such as those described in International Publication Nos. 2006 / 038863, 2006 / 031175, and 2012 / 005677 can be used, but the method is not limited to these.

[0054] Kraft Lignin may be made using one type of lignin alone, or it may be made using a combination of two or more types with different raw materials, manufacturing conditions, separation methods, etc.

[0055] -Method for producing sulfomethylated Kraft lignin- Sulfomethylated Kraft lignin can be obtained by sulfomethylating Kraft lignin as a raw material.

[0056] (Sulfomethylation) Sulfomethylation can be produced, for example, by reacting Kraft lignin with sulfites and aldehydes.

[0057] An example of a method for sulfomethylating lignin components is disclosed in U.S. Patent No. 2,680,113. In this method, the sulfomethylation of lignin components is usually carried out in a temperature range of 50 to 200°C, preferably 80 to 170°C, and more preferably 90 to 170°C. The reaction time for the sulfomethylation treatment is preferably 1 to 30 hours, more preferably 1.5 to 25 hours.

[0058] Sodium sulfite is preferred as the sulfite. The amount of sulfite added is preferably 1 to 50% by mass, and more preferably 1 to 35% by mass, based on 100% by mass of the solid content of Kraft Lignin. By keeping the amount of sulfite added within the above range, the balance between hydrophilicity and hydrophobicity of the lignin can be adjusted, resulting in an agricultural additive with superior spreadability. Furthermore, by keeping the upper limit of the amount of sulfite added within the above range, the generation of unreacted substances such as sulfite can be suppressed, increasing the purity of the lignin and allowing for even better spreadability.

[0059] Formaldehyde is preferred as the aldehyde. The amount of aldehyde added is preferably 0.25 to 12.5% ​​by mass, and more preferably 0.3 to 10% by mass, based on 100% by mass of the solid content of the lignin component. When the aldehyde is within the above range, the sulfo group is suitably introduced into the lignin, resulting in an agricultural additive with superior spreadability.

[0060] Furthermore, a pH of 8 or higher is preferable, and 9 or higher is more preferable. By adjusting the above conditions in the sulfomethylation reaction, the physical properties of the lignin derivative can be controlled. For example, by adjusting the amount and molar ratio of sulfite and aldehyde added, the degree of crosslinking in the resulting lignin derivative (sulfomethylated lignin) can be adjusted, and the molecular weight can be controlled.

[0061] [1.3 Physical Properties of Lignin Derivatives] The lignin derivative is preferably such that its weight-average molecular weight, organic sulfur content, solubility in water, extractable component amount, methoxy group amount, and mass ratio of extractable component amount to methoxy group amount are within the following ranges, and that it has a functional group represented by formula (1):-SO3M, and more preferably that the total decomposition product yield and / or polydispersity by alkaline nitrobenzene oxidation are within the following ranges.

[0062] -Weight average molecular weight- The weight-average molecular weight of the lignin derivative is preferably 5,000 or more, more preferably 5,500 or more. Its upper limit is 43,000 or less, more preferably 40,000 or less, and even more preferably 36,000 or less. Therefore, the weight-average molecular weight is preferably 5,000 to 43,000, more preferably 5,000 to 40,000, and even more preferably 5,000 to 36,000. By satisfying the above numerical range for the weight-average molecular weight of the lignin derivative, an agricultural additive with excellent spreadability can be obtained.

[0063] The weight-average molecular weight and number-average molecular weight of the lignin derivative in this invention can be measured by conventional methods. For example, a known method of converting to pullulan equivalent using gel permeation chromatography (GPC) can be used. More specifically, the measurements can be performed under the conditions used in the examples described later.

[0064] -Sulfo group- The lignin derivative preferably has a group represented by formula (1):-SO3M. In formula (1), M is a hydrogen atom, a monovalent metal, or a divalent metal. Examples of monovalent and divalent metals include calcium salts, magnesium salts, sodium salts, and potassium salts.

[0065] -Organic S content- The organic sulfur (S) content of the lignin derivative is preferably 1.5% by mass or more, more preferably 1.6% by mass or more, and even more preferably 1.7% by mass or more. This makes it possible to obtain an agricultural additive with excellent spreadability. The upper limit is preferably 7.0% by mass or less, more preferably 6.0% by mass or less, and even more preferably 5.5% by mass or less. This allows the effects of the present invention to be suitably exhibited. Therefore, the organic S content is preferably 1.5 to 7.0% by mass, more preferably 1.6 to 6.0% by mass, and even more preferably 1.7 to 5.5% by mass.

[0066] The organic sulfur content can serve as an indicator of the proportion of constituent units derived from the lignin derivative containing the functional group represented by formula (1) in the lignin derivative. The organic sulfur content can be calculated by subtracting the inorganic sulfur content (both as a percentage of the solid content of the lignin derivative) from the total sulfur content of the lignin derivative. The total sulfur content and inorganic sulfur content can be measured by ICP emission spectroscopy and ion chromatography, respectively.

[0067] -Soluble in water- The solubility of the lignin derivative in water is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. The upper limit is preferably 100% by mass or less. Therefore, the solubility of the lignin derivative in water is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, and even more preferably 50 to 100% by mass. By satisfying the above numerical range for the solubility of the lignin derivative in water, an agricultural additive with excellent spreadability can be obtained.

[0068] The solubility of lignin derivatives in water can be calculated, for example, by the method used in the examples described later.

[0069] -Extracted component amount- In this specification, the extracted components (tree extracts) are trace components of plants (for example, plants used as pulp raw materials, preferably wood from plants of the genera Cryptomeria, Cypress, Pinus, Larch, Fir, and Eucalyptus), and can usually be obtained by extraction treatment of wood with organic solvents. Extracts are usually determinants of wood properties such as color, odor, durability, adhesion, and biological activity, and are said to be components that chemically characterize wood. After the skeleton of a tree is formed by the deposition of cellulose and hemicellulose, and the deposition of lignin, the tree is completed as a biological material only after the accumulation of extracts, which is linked to the formation of heartwood, occurs. Examples of organic solvents used to obtain extracts include hexane, benzene, ether, acetone, and alcohol. The amount of extracts per solid content of lignin derivatives is preferably 0.01% by mass or more, more preferably 0.02% by mass or more. The upper limit is preferably 2.5% by mass or less, more preferably 2.0% by mass or less, and even more preferably 1.5% by mass or less. Therefore, the amount of extracted components per solid content of the lignin derivative is preferably 0.01 to 2.5% by mass, more preferably 0.01 to 2.0% by mass, and even more preferably 0.02 to 1.5% by mass. By satisfying the above numerical range for the amount of extracted components per solid content of the lignin derivative, an agricultural additive with excellent spreadability can be obtained.

[0070] Furthermore, the amount of extracted components per unit of solid content of the lignin derivative can be measured, for example, by the method used in the examples described later.

[0071] -Methoxy base- Generally, methyl methoxy groups are present in the structure of lignin, attached to the aromatic nucleus; therefore, the amount of methyl methoxy groups is an indicator of the lignin and lignin derivative content.

[0072] The amount of methoxy groups per solid content of the lignin derivative is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more. The upper limit is preferably 17% by mass or less, more preferably 16.5% by mass or less, and even more preferably 16.2% by mass or less. Therefore, the amount of methoxy groups per solid content of the lignin derivative is preferably 3 to 17% by mass, more preferably 5 to 16.5% by mass, and even more preferably 8 to 16.2% by mass. By satisfying the above numerical range for the amount of methoxy groups per solid content of the lignin derivative, an agricultural additive with excellent spreadability can be obtained.

[0073] The amount of methoxy groups per unit of solid content of the lignin derivative can be measured, for example, by the method used in the examples described later.

[0074] -Mass ratio of extracted component amount to methoxy group amount- The mass ratio of the amount of extracted components per solid content of the lignin derivative to the amount of methoxy groups is preferably 0.001 or higher, more preferably 0.002 or higher. The upper limit is preferably 0.25 or lower, more preferably 0.2 or lower, and even more preferably 0.15 or lower. Therefore, the mass ratio of the amount of extracted components per solid content of the lignin derivative to the amount of methoxy groups is preferably 0.001 to 0.25, more preferably 0.001 to 0.2, and even more preferably 0.002 to 0.15. By satisfying the above numerical range for the mass ratio of the amount of extracted components per solid content of the lignin derivative to the amount of methoxy groups, an agricultural additive with excellent spreadability can be obtained.

[0075] -Polydispersity- The polydispersity (weight-average molecular weight / number-average molecular weight) of the lignin derivative is preferably 1.5 or higher, more preferably 1.6 or higher. Its upper limit is preferably 4.7 or lower, more preferably 4.4 or lower, and even more preferably 4.0 or lower. Therefore, the polydispersity is preferably 1.5 to 4.7, more preferably 1.5 to 4.4, and even more preferably 1.6 to 4.0.

[0076] -Total yield of decomposition products by alkaline nitrobenzene oxidation- The total yield of decomposition products by alkaline nitrobenzene oxidation of lignin derivatives is preferably 14.5% or less, more preferably 14% or less, even more preferably 13.5% or less, and even more preferably 13.4% or less. The lower limit is preferably 3.5% or more, and more preferably 4.0% or more. Therefore, the total yield of decomposition products by alkaline nitrobenzene oxidation is preferably 14.5% or less, more preferably 14% or less, even more preferably 3.5 to 13.5%, and even more preferably 4.0 to 13.4%.

[0077] The measurement of the total decomposition product yield by alkaline nitrobenzene oxidation is a method for measuring the yield of products (yield relative to the weight of the lignin derivative (solid content) before decomposition) when lignin components are oxidatively decomposed with nitrobenzene under strong alkali conditions, as in the example method, and can be carried out, for example, according to "Plant Cell Wall Experimental Methods" ("Plant Cell Wall Experimental Methods," pp. 128-131, 2016, Hirosaki University Press, see reference). Examples of decomposition products include p-hydroxybenzaldehyde, p-hydroxybenzoic acid, vanillin, vanillic acid, syringaldehyde, and syringic acid.

[0078] The weight-average molecular weight, organic sulfur content, solubility in water, amount of extractable components per solid, amount of methoxy groups per solid, polydispersity, and total decomposition product yield by alkaline nitrobenzene oxidation of lignin derivatives can be adjusted by the manufacturing conditions of the lignin derivatives described above. Specifically, these can be adjusted by the raw materials for kraft lignin (e.g., hardwoods or conifers, tree species), the method for preparing kraft lignin (method for preparing kraft lignin from pulp), the preparation conditions for sulfomethylated kraft lignin (amount of sulfites or aldehydes added, reaction temperature, reaction time, as described later), and the oxidation treatment.

[0079] [2. Ingredients other than lignin derivatives] Agricultural additives may contain components other than lignin derivatives. Examples include functional components and optional components.

[0080] [Functional ingredients] Examples of functional ingredients include the active ingredients in pesticides and fertilizers. Examples of pesticides include herbicides, insecticides, acaricides, nematicides, fungicides, and bactericides, as well as other chemicals containing ingredients that can control or eliminate harmful organisms.

[0081] [Optional ingredients] Optional components include, for example, excipients, colorants, preservatives, pH adjusters, stabilizers, disintegrants, carriers, binders, antifoamers, nonionic surfactants, cationic surfactants, and amphoteric surfactants (formulation aids). The amount of optional components used is usually 0 to 30% by mass relative to the lignin derivative.

[0082] [3. Targets of pesticide additives] The pesticide additive of the present invention exhibits spreading properties by containing the above-mentioned lignin derivative, and by including it in a pesticide, functional components and the like in the pesticide can be dispersed in the dispersion medium. In this specification, spreading properties mean the property of the substance to be spread to disperse in water or on a water surface, uniformly and quickly, and preferably over a wide area. The pesticide additive of the present invention exhibits spreading properties with respect to the substance to be spread (dispersed substance) when water is used as the dispersion medium, and is therefore useful as a pesticide additive for paddy fields, hydroponics, and irrigation, and is more preferably for hydroponics or paddy fields. The substance to be dispersed by the pesticide additive is not particularly limited, and for example, components in the pesticide to which the pesticide additive is added (usually functional components, but not particularly limited), such as the above-mentioned functional components and optional components, can be used as the dispersed substance.

[0083] [4. Formulations of pesticide additives] Examples of pesticide additives include granules, granular forms, and liquid forms, and are not particularly limited. Pesticide additives may be formulated together with functional components or other components that make up the pesticide, or they may be formulated separately. The manufacturing method for pesticide additives can be appropriately selected according to the formulation.

[0084] [5. Pesticides] The pesticide additive of the present invention can be used as a component of a pesticide.

[0085] [Functional and optional components in pesticides] The functional and optional components in pesticides are not particularly limited and are similar to those listed as examples of functional and optional components that can be added to pesticide additives.

[0086] [Pesticide formulations] Examples of pesticide formulations include solid forms (e.g., granules, tablets (e.g., flat plates, granules), powders) and liquid forms (e.g., liquids, aqueous suspensions, aqueous dispersions, flowables, emulsions), and are not particularly limited. Granular and granular forms can facilitate spraying. Liquid forms facilitate mixing with functional components and stabilize the slurry after mixing. The pesticide additive of the present invention may be formulated together with the functional component to form a pesticide, or it may be formulated separately. The method for producing the pesticide can be appropriately selected according to the formulation.

[0087] [Amount added / How to use] The amount of pesticide additive added to the pesticide should be an effective amount. For example, the amount of lignin derivative relative to the target substance in the pesticide for which the pesticide additive is intended is preferably 0.01 to 10% by mass, more preferably 0.1 to 8% by mass, and even more preferably 0.1 to 5% by mass.

[0088] If the pesticide additive is a separate formulation from the functional component, it may be added directly to the other components, or it may be added after being dissolved in water. For example, in a pesticide formulation, the above-mentioned functional component and optional component may be combined with the pesticide additive to form a pesticide formulation (e.g., a tablet-type pesticide formulation), or when using the pesticide formulation, the pesticide formulation and the pesticide additive may be dissolved together in water before use. [Examples]

[0089] The present invention will be described below with reference to examples. The following examples are not intended to limit the present invention.

[0090] (Measurement method and evaluation method) In the examples and comparative examples, measurements and evaluations were performed as follows.

[0091] (Measurement of weight-average molecular weight and polydispersity (weight-average molecular weight / number-average molecular weight)) The weight-average molecular weight and number-average molecular weight of the lignin produced in each manufacturing example were measured by gel permeation chromatography (GPC) (Table 1). GPC measurements were performed under the following conditions using a known method for converting to pullulan equivalent. The polydispersity (weight-average molecular weight / number-average molecular weight) was calculated using the measured weight-average molecular weight and number-average molecular weight (Table 1). Measuring device; manufactured by Tosoh Corporation. Columns used: Shodex Column OH-pak SB-806HQ, SB-804HQ, SB-802.5HQ Eluent: Aqueous solution of 1.0% sodium tetraborate and 0.3% isopropyl alcohol. Eluent flow rate; 1.00mL / min Column temperature: 50℃ Measured sample concentration: 0.2% by mass Standard material; pullulan (manufactured by Showa Denko) Detector; RI detector (manufactured by Tosoh Corporation) Calibration curve; pullulan standard

[0092] (Organic S content) The organic sulfur content of the lignin produced in each manufacturing example was determined by the following formula. Organic S content (mass%) = total S content (mass%) - inorganic S content (mass%) (The sulfur content in the formulas all represents the sulfur content relative to the solid content of the lignin sample.) In the formula, the total sulfur content was quantified by ICP emission spectrometry. Furthermore, the total amounts of SO3 ion content, SO4 ion content, and S2O3 ion content, quantified by ion chromatography, were used to calculate the inorganic sulfur content (Table 1).

[0093] (Total yield of decomposition products by alkaline nitrobenzene oxidation) The total yield of degradation products obtained by alkaline nitrobenzene oxidation of lignin produced in each manufacturing example was measured according to the method described in "Plant Cell Wall Experimental Methods" (see "Plant Cell Wall Experimental Methods," pp. 128-131, 2016, Hirosaki University Press). The total degradation product yield was determined as the percentage (w / w%) of the total weight of the six degradation products obtained in the measurement (p-hydroxybenzaldehyde, p-hydroxybenzoic acid, vanillin, vanillic acid, syringaldehyde, and syringic acid) relative to the sample solid content (Table 1).

[0094] (Solubility in water) The amount of lignin produced in each manufacturing example that dissolves in water was calculated as follows: A 10g (dry weight) sample was dispersed in 300g of water, stirred at 25°C and 300rpm for 60 minutes, and then filtered using a commercially available nylon mesh (passage particle size 13μm) and commercially available filter paper (particle retention capacity 5μm). The mass of the filtrate and the mass of the solids (dried filtrate) were measured. The amount of lignin that dissolves in water was calculated by dividing the mass of the solids in the filtrate by the mass of the sample (10g) and multiplying by 100 (Table 1).

[0095] (Methoxy group amount) The amount of methoxy groups in the lignin produced in each manufacturing example was determined by the Viebock and Schwappach method for the quantitative determination of methoxy groups (see "Lignin Chemistry Research Methods," pp. 336-340, 1994, published by Uni Publishing Co., Ltd.) (Table 1).

[0096] (Amount of extracted components) The amount of extracted lignin components produced in each manufacturing example was measured according to the method for measuring hexane-extractable substances described in JIS K 0102:2019 (Table 1).

[0097] (Manufacturing Example 1) (Production of sulfomethylated Kraft lignin 1) Coniferous (N-wood) Kraft lignin was isolated using a known method. Specifically, wood chips (radiata pine) were first treated with alkali based on the Kraft pulping method. The alkali treatment was carried out using a rotary reaction vessel under the following conditions: Activated alkali (compared to oven-dried chips): 20%, degree of sulfidation: 25%, liquid ratio: 3.2 L / kg, reaction temperature: 165°C, reaction time: 180 minutes. For the preparation of the reaction solution used in the alkali treatment, sodium hydroxide and sodium sulfide were dissolved in water to obtain an activated alkali concentration of 50 g / L. After the reaction, filtration was performed to obtain the black liquor of N-wood Kraft pulping as the filtrate. N-wood Kraft lignin was obtained from the black liquor of N-wood Kraft pulping according to the Lignoboost method. That is, first, carbon dioxide was passed through the black liquor of N-wood Kraft pulping to lower the pH of the black liquor to 10, and primary filtration was performed. Next, the material was dispersed again in water, the pH was lowered to 2 with sulfuric acid, secondary filtration was performed, and after washing with water, it was dried to obtain N-material Kraft Lignin. All filtration treatments were carried out by pressure filtration using a filter press. Next, 500 parts of a solution prepared by dissolving N-material Kraft Lignin in NaOH at pH 10 to a solid content of 17%, 26.0 parts of sodium sulfite, and 18.1 parts of 37% formaldehyde solution were charged into a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser. The reaction was carried out at 95°C for 24 hours under stirring. After cooling to room temperature, sulfomethylated Kraft Lignin 1 was obtained.

[0098] (Manufacturing example 2) (Production of sulfomethylated Kraft lignin 2) In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 500 parts of a solution prepared by dissolving the N-material Kraft Lignin obtained in Production Example 1 in NaOH at pH 10 to a solid content of 17%, 17.0 parts of sodium sulfite, and 12.0 parts of a 37% formaldehyde solution were charged, and the reaction was carried out at 95°C for 24 hours under stirring. After cooling to room temperature, sulfomethylated Kraft Lignin 2 was obtained.

[0099] (Manufacturing Example 3) (Production of sulfomethylated Kraft lignin 3) In an autoclave equipped with a thermometer, stirrer, and reflux condenser, 500 parts of a solution prepared by dissolving the N-material Kraft Lignin obtained in Production Example 1 in NaOH at pH 10 to a solid content of 17%, 17.0 parts of sodium sulfite, and 12.0 parts of a 37% formaldehyde solution were charged, and the mixture was reacted at 140°C for 2 hours under stirring. After cooling to room temperature, sulfomethylated Kraft Lignin 3 was obtained.

[0100] (Manufacturing example 4) (Production of sulfomethylated Kraft lignin 4) In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 500 parts of a solution prepared by dissolving the N-material Kraft Lignin obtained in Production Example 1 in NaOH at pH 10 to a solid content of 17%, 8.5 parts of sodium sulfite, and 6.0 parts of a 37% formaldehyde solution were charged, and the reaction was carried out at 92°C for 18 hours under stirring. After cooling to room temperature, sulfomethylated Kraft Lignin 4 was obtained.

[0101] (Manufacturing example 5) (Production of sulfomethylated Kraft lignin 5) In an autoclave equipped with a thermometer, stirrer, and reflux condenser, 500 parts of a solution prepared by dissolving the N-material Kraft Lignin obtained in Production Example 1 in NaOH at pH 10 to a solid content of 17%, 4.3 parts of sodium sulfite, and 3.0 parts of 37% formaldehyde solution were charged, and the mixture was reacted at 160°C for 2 hours under stirring. After cooling to room temperature, sulfomethylated Kraft Lignin 5 was obtained.

[0102] (Manufacturing example 6) (Production of sulfomethylated Kraft lignin 6) In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 500 parts of a solution prepared by dissolving the N-material Kraft Lignin obtained in Production Example 1 in NaOH at pH 10 to a solid content of 17%, 2.1 parts of sodium sulfite, and 1.5 parts of a 37% formaldehyde solution were charged, and the mixture was reacted at 95°C for 24 hours under stirring. After cooling to room temperature, sulfomethylated Kraft Lignin 6 was obtained.

[0103] (Manufacturing example 7) (Manufacturing of sulfomethylated Kraft lignin 7) In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 500 parts of a solution prepared by dissolving the N-material Kraft Lignin obtained in Production Example 1 in NaOH at pH 10 to a solid content of 17%, 2.1 parts of sodium sulfite, and 6.0 parts of a 37% formaldehyde solution were charged, and the reaction was carried out at 95°C for 24 hours under stirring. After cooling to room temperature, sulfomethylated Kraft Lignin 7 was obtained.

[0104] (Manufacturing example 8) (Manufacturing of sulfomethylated Kraft lignin 8) In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 500 parts of a solution prepared by dissolving the N-material Kraft Lignin obtained in Production Example 1 in NaOH at pH 10 to a solid content of 17%, 4.3 parts of sodium sulfite, and 6.0 parts of a 37% formaldehyde solution were charged, and the reaction was carried out at 95°C for 24 hours under stirring. After cooling to room temperature, sulfomethylated Kraft Lignin 8 was obtained.

[0105] (Manufacturing example 9) (Manufacturing of sulfomethylated Kraft lignin 9) Hardwood (L-grade) Kraft lignin was isolated using a known method. Specifically, wood chips (eucalyptus) were first treated with alkali based on the Kraft pulping method. The alkali treatment was carried out using a rotary reaction vessel under the following conditions: Activated alkali (compared to oven-dried chips): 20%, degree of sulfidation: 25%, liquid ratio: 3.2 L / kg, reaction temperature: 155°C, reaction time: 300 minutes. For the preparation of the reaction solution used in the alkali treatment, sodium hydroxide and sodium sulfide were dissolved in water to obtain an activated alkali concentration of 50 g / L. After the reaction, filtration was performed to obtain the black liquor of L-grade Kraft pulping as the filtrate. From the black liquor of L-grade Kraft pulping, L-grade Kraft lignin was obtained according to the Lignoboost method. That is, first, carbon dioxide was passed through the black liquor of L-grade Kraft pulping to lower the pH of the black liquor to 10, and primary filtration was performed. Next, the material was dispersed again in water, the pH was lowered to 2 with sulfuric acid, secondary filtration was performed, and after washing with water, it was dried to obtain L-grade Kraft Lignin. All filtration treatments were carried out by pressure filtration using a filter press. Next, 500 parts of a solution prepared by dissolving L-material Kraft Lignin in NaOH at pH 10 to a solid content of 17%, 17.0 parts of sodium sulfite, and 12.0 parts of a 37% formaldehyde solution were charged into a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser. The reaction was carried out at 95°C for 24 hours under stirring. After cooling to room temperature, sulfomethylated Kraft Lignin 9 was obtained.

[0106] (Manufacturing example 10) (Production of sulfomethylated Kraft lignin 10) In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 500 parts of a solution prepared by dissolving the L-material Kraft Lignin obtained in Production Example 9 in NaOH at pH 10 to a solid content of 17%, 2.1 parts of sodium sulfite, and 1.5 parts of a 37% formaldehyde solution were charged, and the mixture was reacted at 96°C for 24 hours under stirring. After cooling to room temperature, sulfomethylated Kraft Lignin 10 was obtained.

[0107] (Manufacturing Example 11) (Manufacturing of sulfomethylated Kraft lignin 11) In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 500 parts of a solution prepared by dissolving the L-material Kraft Lignin obtained in Production Example 9 in NaOH at pH 10 to a solid content of 17%, 1.3 parts of sodium sulfite, and 0.9 parts of a 37% formaldehyde solution were charged, and the reaction was carried out at 96°C for 24 hours under stirring. After cooling to room temperature, sulfomethylated Kraft Lignin 11 was obtained.

[0108] (Manufacturing Example 12) (Manufacturing of Lignin Sulfonate 1) Wood chips (radiata pine) were treated with sulfites based on the sulfite pulverization method. In the sulfite treatment, a sodium sulfite solution with an SO2 concentration of 4 g / 100 mL was used at a temperature of 140 °C, pH 2, and a treatment time of 4 hours. The resulting intermediate composition was filtered and dehydrated to obtain a filtrate. The obtained filtrate was concentrated in a rotary evaporator until the solid content was 50%. The pH of the solution was then adjusted to pH 4.5 with NaOH and powdered using a spray dryer. The obtained powder was dissolved in water to prepare an aqueous solution with a solid content of 25%, and dialyzed for 3 days using a dialysis membrane (molecular weight fraction: 20,000, Spectra / Pore cellulose ester dialysis tube). The solution in the dialysis tube was collected, concentrated until the original volume was 25%, and powdered using a spray dryer to obtain lignin sulfonate 1.

[0109] (Manufacturing Example 13) (Manufacturing of Modified Lignin Sulfonate 1) Wood chips (radiata pine) were treated with sulfites based on the sulfite pulping method. For the sulfite treatment, a sodium sulfite solution with an SO2 concentration of 2.5 g / 100 mL was used, at a temperature of 140°C, pH 3, and for a treatment time of 4 hours. Next, the intermediate composition was filtered and dehydrated to obtain filtrate (1) and pulp (sulfite-treated material). Subsequently, the pulp was suspended in 5% by mass of NaOH (relative to pulp solids) and then subjected to alkali treatment. After that, the alkali-treated pulp and alkali-treated extract were separated by filtration to obtain alkali-treated extract as filtrate (2). The alkali treatment was carried out by contacting 5% by mass of NaOH (relative to pulp solids) and treating at 100°C for 2 hours. The obtained filtrate (1) and alkali-treated extract (filtrate (2)) were mixed in a solids mass ratio of filtrate (1) / alkali-treated extract of 9 / 1 to obtain the raw material. The obtained raw materials were concentrated in a rotary evaporator until the solid content was 50%. The pH of the solution was then adjusted to pH 4.5 with NaOH and powdered using a spray dryer. The obtained powder was dissolved in water to prepare an aqueous solution with a solid content of 25%, and after adjusting the pH to 12 with 40% NaOH, it was oxidized with alkaline air at 150°C for 120 minutes. Then, 70% sulfuric acid was added to adjust the pH to 3, and the precipitate was separated and precipitated. 20 parts of the obtained precipitate was suspended in 80 parts of water, and after heating to 60°C, 40% NaOH was added while stirring until the pH became 9, completely dissolving the precipitate. The obtained solution was powdered using a spray dryer to obtain modified lignin sulfonate 1.

[0110] (Manufacturing Example 14) (Manufacturing of highly modified lignin sulfonate 2) Wood chips (radiata pine) were treated with sulfites based on the sulfite pulping method. For the sulfite treatment, a sodium sulfite solution with an SO2 concentration of 4 g / 100 mL was used, at a temperature of 140°C, pH 2, and for a treatment time of 4 hours. Next, the intermediate composition was filtered and dehydrated to obtain filtrate (1) and pulp (sulfite-treated material). Subsequently, the pulp was suspended in 5% by mass of NaOH (relative to pulp solids) and then subjected to alkali treatment. After that, the alkali-treated pulp and alkali-treated extract were separated by filtration to obtain alkali-treated extract as filtrate (2). The alkali treatment was carried out by contacting 5% by mass of NaOH (relative to pulp solids) and treating at 100°C for 2 hours. The obtained filtrate (1) and alkali-treated extract (filtrate (2)) were mixed in a solids mass ratio of filtrate (1) / alkali-treated extract of 9 / 1 to obtain the raw material. The obtained raw material was concentrated in a rotary evaporator until the solids content was 50%. The solution's pH was then adjusted to 4.5 with NaOH, and it was powdered using a spray dryer. The resulting powder was dissolved in water to obtain an aqueous solution with a solid content of 25%, and after adjusting the pH to 13 with 40% NaOH, it was oxidized with alkaline air at 160°C for 120 minutes. Then, 70% sulfuric acid was added to adjust the pH to 3, and the precipitate was separated and precipitated. The obtained precipitate was washed with water until the filtrate was neutral, 20 parts of the precipitate was suspended in 80 parts of water, and after heating to 60°C, 40% NaOH was added while stirring until the pH reached 9, completely dissolving the precipitate. The resulting solution was powdered using a spray dryer to obtain modified lignin sulfonate 2.

[0111] (Manufacturing example 15) (Manufacturing of Modified Lignin Sulfonate 3) In an autoclave equipped with a stirrer and temperature controller, 500 parts of the lignin sulfonate obtained in Production Example 12, 75 parts of sodium hydroxide, and 1,500 parts of water were charged. This mixture was heated to 140°C under stirring and maintained for 2 hours, then cooled to 70°C, and air was blown in at 500 mL / min for 3 hours. The resulting solution was powdered using a spray dryer to obtain modified lignin sulfonate 3.

[0112] (Manufacturing example 16) (Production of sulfomethylated Kraft lignin 12) In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 500 parts of a solution prepared by dissolving the N-material Kraft Lignin obtained in Production Example 1 in NaOH at pH 10 to a solid content of 15%, 3.8 parts of sodium sulfite, and 10.6 parts of a 37% formaldehyde solution were charged, and the mixture was reacted at 95°C for 24 hours under stirring. After cooling to room temperature, sulfomethylated Kraft Lignin 12 was obtained.

[0113] (Manufacturing example 17) (Manufacturing of Modified Lignin Sulfonate 4) In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 500 parts of a solution prepared by dissolving the modified lignin sulfonate 1 obtained in Production Example 13 in NaOH at pH 10 to a solid content of 15%, and 12.2 parts of a 37% formaldehyde solution were charged, and the reaction was carried out at 95°C for 24 hours under stirring. After cooling to room temperature, modified lignin sulfonate 4 was obtained.

[0114] (Manufacturing example 18) (Manufacturing of Modified Lignin Sulfonate 5) In a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 500 parts of a solution prepared by dissolving the modified lignin sulfonate 3 obtained in Production Example 15 in NaOH at pH 10 to a solid content of 15%, and 12.2 parts of a 37% formaldehyde solution were charged, and the reaction was carried out at 95°C for 24 hours under stirring. After cooling to room temperature, modified lignin sulfonate 5 was obtained.

[0115] (Manufacturing example 19) (Manufacturing of modified lignin sulfonic acid) Wood chips (radiata pine) were treated with sulfites based on the sulfite pulping method. For the sulfite treatment, a sodium sulfite solution with an SO2 concentration of 2.5 g / 100 mL was used, at a temperature of 140°C, pH 3, and for a treatment time of 4 hours. Next, the intermediate composition was filtered and dehydrated to obtain filtrate (1) and pulp (sulfite-treated material). Subsequently, the pulp was suspended in 5% by mass of NaOH (relative to pulp solids) and then subjected to alkali treatment. After filtration, the alkali-treated pulp and alkali-treated extract were separated to obtain alkali-treated extract as filtrate (2). The alkali treatment was carried out by contacting 5% by mass of NaOH (relative to pulp solids) and treating at 100°C for 2 hours. The obtained filtrate (1) and alkali-treated extract (filtrate (2)) were mixed in a solids mass ratio of filtrate (1) / alkali-treated extract of 9 / 1 to obtain the raw material. The obtained raw materials were concentrated in a rotary evaporator until the solid content was 50%. The pH of the solution was then adjusted to pH 4.5 with NaOH and powdered using a spray dryer. The obtained powder was dissolved in water to prepare an aqueous solution with a solid content of 25%, and after adjusting the pH to 12 with 40% NaOH, it was oxidized with alkaline air at 150°C for 120 minutes. Then, 70% sulfuric acid was added to adjust the pH to 3, and the precipitate was separated and precipitated. The obtained precipitate was dried to obtain modified ligninsulfonic acid 1.

[0116] (Manufacturing example 20) (Manufacturing of Modified Lignin Sulfonate 6) Wood chips (radiata pine) were treated with sulfites using the sulfite pulverization method. For the sulfite treatment, a sodium sulfite solution with an SO2 concentration of 4 g / 100 mL was used, at a temperature of 140°C, pH 2, and a treatment time of 4 hours. The resulting intermediate composition was filtered and dehydrated to obtain a filtrate. The obtained filtrate was concentrated using a rotary evaporator until the solid content was 50%. The pH of the solution was then adjusted to pH 4.5 with NaOH, and the mixture was powdered using a spray dryer. The resulting powder was dissolved in water to prepare an aqueous solution with a solid content of 25%, and dialysis was performed for 6 days using a dialysis membrane (molecular weight fraction: 20,000, Spectra / Pore cellulose ester dialysis tube). The solution in the dialysis tube was collected, concentrated to 25% of the original volume, and powdered using a spray dryer to obtain lignin sulfonate. The obtained lignin sulfonate was dissolved in NaOH at pH 10 to a solid content of 15% in 500 parts of a solution, and 12.2 parts of a 37% formaldehyde solution were charged into a glass reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser. The reaction was carried out at 95°C for 24 hours under stirring. After cooling to room temperature, modified lignin sulfonate 6 was obtained.

[0117] (Example 1) (Water surface spreading test) 0.1 g of calcium stearate was weighed using a precision balance and compacted in a tablet molding machine under conditions of 20 MPa x 1 minute to obtain a calcium stearate molded sheet (final weight 0.09 ± 0.002 g). A plastic container measuring 14 cm in length and 46 cm in width was filled with 200 mL of clean water (water temperature 16 °C), and the prepared calcium stearate molded sheet was floated on the edge of the plastic container. Then, 20 μL of an aqueous solution of sulfomethylated Kraft Lignin 1 obtained in Production Example 1 (concentration 1 mass%) was gently dropped 1 cm behind the calcium stearate molded sheet, and the spread distance of the calcium stearate molded sheet on the water surface after 1 minute (distance from the position of the molded sheet before sample drop to the position after drop (cm)) was measured (Table 2).

[0118] (Examples 2-15 and Comparative Examples 1-7) As shown in Table 1, the water surface spreadability test was performed in the same manner as in Example 1, except that sulfomethylated kraft lignin 2-12, lignin sulfonate 1, modified lignin sulfonate 1-6, modified lignin sulfonic acid 1, N-material kraft lignin obtained during the production of Example 1, or L-material kraft lignin obtained during the production of Example 9 were used instead of sulfomethylated kraft lignin 1 obtained in Production Example 1 (Table 2).

[0119] (Reference example) The water surface spreadability test was performed in the same manner as in Example 1, except that a lignin derivative was not added (Table 2).

[0120] [Table 1]

[0121] [Table 2]

[0122] The lignin derivatives of Examples 1 to 15, in which the weight-average molecular weight, organic sulfur content, solubility in water, amount of extracted components, amount of methoxy groups, amount of extracted components / methoxy groups, and the mass ratio of weight-average molecular weight, organic sulfur content, solubility in water, amount of extracted components, amount of methoxy groups, and amount of extracted components / methoxy groups to the functional group represented by formula (1) were within an appropriate range, showed a longer spreading distance and better spreading properties compared to Comparative Examples 1 to 7, which did not satisfy any of the above conditions.

[0123] The results above indicate that lignin derivatives that satisfy the specified parameters can exhibit good spreadability and are useful as agricultural additives.

Claims

1. A pesticide additive containing a lignin derivative that satisfies the following conditions (A) to (G). (A) The weight-average molecular weight is between 5,000 and 43,000. (B) The organic sulfur content is 1.5 to 7.0% by mass. (C) The solubility in water is 10 to 100% by mass. (D) The amount of extracted components per solid content is 0.01 to 2.5% by mass. (E) The amount of methoxy groups per solid content is 3 to 17% by mass. (F) The mass ratio of the amount of extracted components per solid to the amount of methoxy groups is 0.001 to 0.

25. (G) Formula (1): -SO ３ Having a functional group represented by M (wherein M represents a hydrogen atom, a monovalent metal, or a divalent metal).

2. The pesticide additive according to claim 1, wherein in (A), the weight-average molecular weight is 5,000 to 36,000.

3. (B) The pesticide additive according to claim 1 or 2, wherein the organic sulfur content is 1.5 to 5.5% by mass.

4. The pesticide additive according to claim 1 or 2, further satisfying that the lignin derivative has a total decomposition product yield of 14% or less by (H) alkaline nitrobenzene oxidation.

5. The lignin derivative further satisfies (I) having a polydispersity of 1.5 to 4.7, as an additive for pesticides according to claim 1 or 2.

6. An additive for pesticides according to claim 1 or 2, which is for use with solid pesticides.

7. An additive for pesticides according to claim 1 or 2, which is for use with liquid pesticides.

8. The pesticide additive according to claim 1 or 2, for use in pesticides for paddy fields or hydroponics.

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