Spreading agents, fertilizer compositions, and agricultural chemical compositions

Abstract

Provided is a spreading agent that has a high water solubility and can effectively enhance the adhesion force of a fertilizer component or an agricultural chemical to a plant. This spreading agent contains at least one oligosaccharide selected from the group consisting of a chitin oligosaccharide, a cello-oligosaccharide and a xylo-oligosaccharide.

Description

Technical Field

[0001] The present invention relates to a spreading agent containing oligosaccharide, a fertilizer composition, and an agricultural chemical composition.

Background Art

[0002] In agriculture, a spreading agent is a chemical added on-site when spraying pesticides such as insecticides, fungicides, and herbicides, which are the main agents. The spreading agent is used to improve the physicochemical properties of the main agent and stabilize or enhance its biological activity.

[0003] Typical active ingredients of spreading agents include surfactants. Examples of surfactants include, for example, nonionic surfactants alone, those obtained by blending anionic surfactants with nonionic surfactants, those obtained by blending cationic surfactants with nonionic surfactants, etc. (Non-Patent Document 1). Surfactants actually used include nonionic surfactants such as polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyether-modified silicone, etc. (Patent Document 1), polyvinyl alcohol (Patent Document 2), and anionic surfactants such as alkali salts of alkyl sulfosuccinic acid and alkali salts of dinaphthylmethane sulfonic acid.

[0004] As a pesticide preparation using naturally derived carbohydrates, an example has been reported in which an anionic polysaccharide containing four sugar molecules (glucose, glucuronic acid, glucose, rhamnose) in the main chain as repeating basic units is blended (Patent Document 3).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

[0006] [Non-Patent Document 1] Plant Protection, Vol. 68, No. 11, 2014, pp. 60-63 [Overview of the project] [Problems that the invention aims to solve]

[0007] However, the spreading agent composition in Patent Document 1 had low solubility in water and required the use of an alcohol solvent. The liquid agricultural spray in Patent Document 2 had low solubility in water and a problem in which polyvinyl alcohol precipitated when left standing for a long time. In the pesticide preparation in Patent Document 3, polysaccharides were used as thickeners and it was necessary to incorporate polyalkoxytriglycerides as penetration enhancers.

[0008] This invention has been made in view of the above circumstances, and aims to provide a spreading agent that has high solubility in water and can effectively enhance the adhesion of fertilizer components or agricultural chemicals to plants. [Means for solving the problem]

[0009] To solve the above problems, the inventors conducted extensive research and came up with the idea of ​​using oligosaccharides as a spreading agent, as they are compounds that are highly soluble in water and are environmentally friendly and safe for the human body.

[0010] As a result, we found that a spreading agent containing at least one oligosaccharide selected from the group consisting of chitin oligosaccharides, cellooligosaccharides, and xylooligosaccharides exhibits excellent adhesion to plants.

[0011] In other words, the present invention encompasses the following [1] to

[15] .

[0012] [1] A spreading agent comprising at least one oligosaccharide selected from the group consisting of chitin oligosaccharides, cellooligosaccharides, and xylooligosaccharides. [2] The spreading agent according to [1], wherein the oligosaccharide includes chitin oligosaccharide, and the chitin oligosaccharide is a chitin oligosaccharide containing an α-1,6-glycosidic bond in at least a part of the glycosidic bond. [3] The spreading agent according to [2], wherein the ratio of the α-1,6-glycosidic bond to all the polymerization bonds contained in the chitin oligosaccharide is 1 to 50%. [4] The spreading agent according to any one of [2] or [3], wherein the number average molecular weight of the chitin oligosaccharide is 420 to 2050. [5] The spreading agent according to [1], wherein the oligosaccharide includes cello-oligosaccharide, and the cello-oligosaccharide is a cello-oligosaccharide containing an α-1,6-glycosidic bond in at least a part of the glycosidic bond. [6] The spreading agent according to [5], wherein the ratio of the α-1,6-glycosidic bond to all the polymerization bonds contained in the cello-oligosaccharide is 1 to 50%. [7] The spreading agent according to any one of [5] or [6], wherein the number average molecular weight of the cello-oligosaccharide is 340 to 1640. [8] The spreading agent according to any one of [1] to [7], wherein the oligosaccharide includes two or more selected from the group consisting of chitin oligosaccharide, cello-oligosaccharide, and xylo-oligosaccharide. [9] The spreading agent according to [8], wherein the oligosaccharide includes chitin oligosaccharide and cello-oligosaccharide.

[10] The spreading agent according to [9], wherein the oligosaccharide includes chitin oligosaccharide, cello-oligosaccharide, and xylo-oligosaccharide.

[11] The spreading agent according to

[10] , wherein the ratio of each oligosaccharide to the total content of 100% by mass of chitin oligosaccharide, cello-oligosaccharide, and xylo-oligosaccharide is 10 to 50% by mass of chitin oligosaccharide, 10 to 50% by mass of cello-oligosaccharide, and 10 to 60% by mass of xylo-oligosaccharide.

[12] A fertilizer composition comprising at least one fertilizer component selected from the group consisting of nitrogen, phosphoric acid, and potassium, and a spreading agent described in any one of [1] to

[11] .

[13] The fertilizer composition according to

[12] , wherein the total content of at least one oligosaccharide selected from the group consisting of chitosan oligosaccharide, cellooligosaccharide, and xylooligosaccharide is 1 to 15% by mass based on 100% by mass of the fertilizer composition.

[14] An agricultural chemical composition comprising at least one agricultural chemical selected from the group consisting of insecticides, acaricides, fungicides, herbicides, plant growth regulators, lodging preventives, and plant nutrients, and a spreading agent described in any one of [1] to

[11] .

[15] The agricultural chemical composition according to

[14] , wherein the total content of at least one oligosaccharide selected from the group consisting of chitosan oligosaccharide, cellooligosaccharide, and xylooligosaccharide is 1 to 15% by mass based on 100% by mass of the agricultural chemical composition. [Effect of the Invention]

[0013] The spreading agent of the present invention has high solubility in water and can effectively enhance the adhesion of fertilizer components or agricultural chemicals to plants. [Brief Description of the Drawings]

[0014] [Figure 1] 1H-NMR chart of chitosan oligosaccharide. [Figure 2] 1H-NMR chart of cellooligosaccharide (1). [Figure 3] 1H-NMR chart of cellooligosaccharide (2). [Figure 4] Photographs of the spreading property test of Comparative Example 1 and Example 5. [Modes for Carrying Out the Invention]

[0015] The embodiments of the present invention will be described below. The embodiments described below are representative examples of the present invention and are not limited to them.

[0016] The spreading agent in one embodiment contains at least one oligosaccharide selected from the group consisting of chitin oligosaccharides, cellooligosaccharides, and xylooligosaccharides.

[0017] [Chitin oligosaccharide] Chitin oligosaccharides are oligosaccharides consisting of several N-acetylglucosamine units linked together, and some of them contain deacetylated chitosan oligosaccharides. They are generally obtained by hydrolyzing chitin derived from crustaceans and are also called oligo-N-acetylglucosamine.

[0018] Preferably, one or a mixture of several chitin oligosaccharides selected from N-acetylchitobiose, N-acetylchitotriose, N-acetylchitotetraose, N-acetylchitopentaose, N-acetylchitohexaose, N-acetylchitoheptaose, N-acetylchitooctaose, etc., is used as the chitin oligosaccharide. Among these, N-acetylchitotriose, N-acetylchitotetraose, and N-acetylchitopentaose are preferred.

[0019] The number-average molecular weight of chitin oligosaccharides is preferably 420 to 2050, more preferably 520 to 1650, and even more preferably 620 to 1240. A number-average molecular weight of 420 or higher enhances the adhesion of fertilizer or pesticide components to plants. A number-average molecular weight of 2050 or lower increases the solubility of chitin oligosaccharides in water, making them less likely to precipitate. The number-average molecular weight of chitin oligosaccharides can be determined by the method described in the examples below.

[0020] The chitin oligosaccharide may also contain chitin oligosaccharides in which the acetyl group (-COCH3) of N-acetylglucosamine has been partially removed, resulting in NH2. The proportion of such deacetylated glucosamine units is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 15 mol% or less of the total glucosamine units of the chitin oligosaccharide.

[0021] Chitin oligosaccharides may be linear chitin oligosaccharides in which N-acetylglucosamine is linked by β-1,4-glycosidic bonds (hereinafter sometimes referred to as "linear chitin oligosaccharides"), or they may be branched chitin oligosaccharides in which at least a portion of the glycosidic bonds contain α-1,6-glycosidic bonds (hereinafter sometimes referred to as "branched chitin oligosaccharides").

[0022] Specifically, the linear chitin oligosaccharide represented by the following formula (1) can be used. [ka]

[0023] In branched chitin oligosaccharides, the position of the α-1,6-glycosidic bond is not particularly limited, and it may branch from the hydroxyl group at position 6 of any N-acetylglucosamine unit constituting the chitin oligosaccharide. In branched chitin oligosaccharides, the number of α-1,6-glycosidic bonds is not particularly limited, and there may be only one or two or more.

[0024] In one embodiment, if the spreading agent contains chitin oligosaccharide, it is more preferable that it contains branched chitin oligosaccharide. The presence of branched chitin oligosaccharide in the spreading agent further improves its adhesion to plants. When branched chitin oligosaccharide is included as the chitin oligosaccharide, the ratio of α-1,6-glycosidic bonds to the total polymerization bonds of the chitin oligosaccharide (hereinafter sometimes referred to as the "degree of branching" of the chitin oligosaccharide) is preferably 1-50%, more preferably 3-40%, even more preferably 5-30%, and particularly preferably 5-20%. In this disclosure, "polymerization bond" refers to a bond that links monosaccharides together to form an oligosaccharide, typically a glycosidic bond. A degree of branching of 1% or more can increase the adhesion of fertilizer components or pesticide components to plants. A degree of branching of 50% or less reduces degradability and extends the duration of the spreading effect. The degree of branching is determined from the area ratio of the NMR spectrum by the method described in the examples below.

[0025] Chitin oligosaccharides may be commercially available or manufactured. Methods for producing chitin oligosaccharides include chemical or enzymatic partial hydrolysis of chitin. For example, the method described in Japanese Patent Publication No. 2012-217396 can be used. Specifically, chitin can be produced by neutralizing a reaction solution obtained by hydrolyzing chitin with 30% or more concentrated hydrochloric acid at 5°C to 30°C, filtering the solution, and then desalting the filtrate using electrodialysis and ion exchange resin, followed by freeze-drying. When producing branched chitin oligosaccharides, it is preferable to use the "acid catalyst method" described later.

[0026] [Cellooligosaccharides] Cellooligosaccharides are oligosaccharides in which multiple glucose molecules are polymerized by β-glycosidic bonds.

[0027] Preferably, one or a mixture of several cellooligosaccharides selected from cellobiose, cellotriose, cellotetraose, cellopentaose, cellohexaose, celloheptaose, cellooctaose, etc., is used as the cellooligosaccharide. Among these, cellotetraose, cellopentaose, and cellohexaose are preferred.

[0028] The number-average molecular weight of cellooligosaccharides is preferably 340 to 1640, more preferably 420 to 1320, and even more preferably 500 to 990. A number-average molecular weight of 340 or higher enhances the adhesion of fertilizer or pesticide components to plants. A number-average molecular weight of 1640 or lower increases the solubility of cellooligosaccharides in water, making them less likely to precipitate. The number-average molecular weight of cellooligosaccharides can be determined by the method described in the examples below.

[0029] Cellooligosaccharides may be linear cellooligosaccharides in which glucose is linked by β-1,4-glycosidic bonds (hereinafter sometimes referred to as "linear cellooligosaccharides"), or they may be branched cellooligosaccharides in which at least a portion of the glycosidic bonds contain α-1,6-glycosidic bonds (hereinafter sometimes referred to as "branched cellooligosaccharides").

[0030] Specifically, linear cellooligosaccharides can be those represented by the following formula (2). [ka]

[0031] In branched cellooligosaccharides, the position of the α-1,6-glycosidic bond is not particularly limited and may branch from the hydroxyl group at position 6 of any glucose unit constituting the cellooligosaccharide. In branched cellooligosaccharides, the number of α-1,6-glycosidic bonds is not particularly limited and may be one or two or more.

[0032] In one embodiment, if the spreading agent contains cellooligosaccharide, it is more preferable that it contains branched cellooligosaccharide. The presence of branched cellooligosaccharide in the spreading agent further improves its adhesion to plants. When branched cellooligosaccharide is included as the cellooligosaccharide, the ratio of α-1,6-glycosidic bonds to the total polymerization bonds of the cellooligosaccharide (hereinafter sometimes referred to as the "degree of branching" of the cellooligosaccharide) is preferably 1-50%, more preferably 3-40%, even more preferably 5-30%, and particularly preferably 5-20%. A degree of branching of 1% or more can increase the adhesion of fertilizer components or pesticide components to plants. A degree of branching of 50% or less can reduce degradability and extend the duration of the spreading effect. The degree of branching is determined from the area ratio of the NMR spectrum by the method described in the examples below.

[0033] Cello-oligosaccharides may be commercially available or manufactured. Methods for producing cello-oligosaccharides include chemical or enzymatic partial hydrolysis of cellulose. For example, they can be produced by a hydrolysis reaction of plant biomass using a carbon catalyst, as described in International Publication No. 2017 / 104687, etc. When producing branched cello-oligosaccharides, it is preferable to use the "acid-catalyzed method" described later.

[0034] [Xylooligosaccharides] Xylooligosaccharides are oligosaccharides in which multiple xylose molecules are polymerized by β-glycosidic bonds. They are generally obtained by hydrolysis of xylan, the main component of hemicellulose.

[0035] Preferably, one or a mixture of several xylooligosaccharides selected from xylobiose, xylotriose, xylotetraose, xylopentaose, xylohexaose, xyloheptaose, xylooctaose, etc., is used as the xylooligosaccharide. Among these, xylopentaose, xylohexaose, and xyloheptaose are preferred.

[0036] Specifically, xylooligosaccharides represented by the following formula (3) can be used. [ka]

[0037] Xylooligosaccharides may be commercially available or manufactured. Methods for producing xylooligosaccharides include chemical or enzymatic partial hydrolysis of xylan. For example, corn cob can be produced by hydrolyzing it with the culture supernatant of Acremonium cellulose that has produced xylan hydrolase.

[0038] [Method for producing branched oligosaccharides] As a method for producing the branched chitin oligosaccharide or branched cellooligosaccharide described above, it is preferable to use an acid-catalyzed method, in which polysaccharides are hydrolyzed in the presence of an acid catalyst.

[0039] When producing chitin oligosaccharides, chitin is used as the raw material polysaccharide. When producing cello-oligosaccharides, cellulose may be used as the raw material polysaccharide, or a mixture of cellulose and xylan may be used. When a mixture of cellulose and xylan is used as the raw material, the xylan content is preferably 5 to 50% by mass, more preferably 7 to 40% by mass, even more preferably 10 to 30% by mass, and particularly preferably 15 to 25% by mass, relative to 100% by mass of the total content of cellulose and xylan.

[0040] As the acid catalyst, conventionally known acids can be used. Specifically, at least one acid selected from the group consisting of sulfuric acid, sulfurous acid, hydrochloric acid, perchloric acid, nitric acid, nitrite, and phosphoric acid, or a partially neutralized salt thereof, can be used. Examples of the partially neutralized salts of the acid include monopotassium dihydrogen phosphate, monoammonium dihydrogen phosphate, and potassium bisulfate. The acid catalyst is preferably phosphoric acid or a partially neutralized salt thereof, and more preferably phosphoric acid.

[0041] The amount of acid catalyst used is preferably such that the mass ratio of polysaccharide to acid catalyst is (polysaccharide) / (acid catalyst) = 2 to 100, more preferably (polysaccharide) / (acid catalyst) = 4 to 20, and even more preferably (polysaccharide) / (acid catalyst) = 3 to 10. If the mass ratio of polysaccharide to acid catalyst is 100 or less, hydrolysis proceeds at a rate that does not pose practical problems. If the mass ratio of polysaccharide to acid catalyst is 2 or more, side reactions such as dehydration and carbon-carbon bond cleavage can be suppressed during hydrolysis.

[0042] Note that the mass of polysaccharides referred to here is the true mass (dry mass) after removing the water contained in the raw material. Since polysaccharides usually contain physically adsorbed water, the amount of this adsorbed water is analyzed, and the mass ratio of polysaccharides to acid catalyst is determined by the mass of the polysaccharides after removing the water. One method for analyzing the amount of adsorbed water is to dry the polysaccharides used as raw materials in a constant temperature dryer at 100°C to 150°C until there is no further mass loss and then quantify them. To prevent the influence of side reactions such as dehydration during drying, it is more desirable to dry and quantify at a lower temperature using a vacuum dryer. The mass of the acid catalyst is also the true mass (dry mass) of the acid catalyst.

[0043] As mentioned above, polysaccharides before hydrolysis already contain approximately 1-12% by mass of physically adsorbed water. Furthermore, acid catalysts such as hydrochloric acid and phosphoric acid often contain water in their commercially available forms. Therefore, hydrolysis can proceed using the water physically adsorbed by the polysaccharides and the water contained in the acid catalyst, even without adding water. While the water content is usually sufficient without adding water, water can be added to highly desiccated polysaccharides to facilitate hydrolysis.

[0044] Whether water is added or not, polysaccharides contain approximately 1 to 12% by mass of physically adsorbed water. Therefore, the amount of water in the hydrolysis reaction, including the water physically adsorbed to the polysaccharides, the water contained in the acid catalyst, and the amount of water added if water is added, is preferably 0.1 to 15 parts by mass, and more preferably 0.5 to 8 parts by mass, per 100 parts by mass of true polysaccharide (dry mass). If the amount is 15 parts by mass or less, a sufficient hydrolysis rate can be obtained, and operation failure due to adhesion to the apparatus can be prevented. Furthermore, if the amount is 0.1 parts by mass or more, side reactions such as dehydration can be suppressed.

[0045] When performing hydrolysis, it is preferable to apply mechanical external force to the polysaccharides through pulverization. Examples of pulverization equipment used for pulverization include rolling ball mills such as pot mills, tube mills, and conical mills; jet pulverizers such as swirling flow jet mills, impact type jet mills, fluidized bed jet mills, and wet type jet mills; shear mills such as grinders and ong mills; colloidal mills such as mortars and stone mortars; impact type pulverizers such as hammer mills, cage mills, pin mills, disintegrators, screen mills, turbo mills, and centrifugal classification mills; vibrating mills that pulverize by moving the medium inside by vibrating a drum; stirring mills that pulverize by placing the medium and raw material in a tank with stirring blades and rotating them; and planetary ball mills, which are types of pulverizers that employ rotational and revolutionary motion.

[0046] The grinding device is preferably a ball mill, vibratory mill, or agitator mill, which applies strong compressive force to the polysaccharide and tensile stress in both directions of the main chain. More preferably, the grinding device is a planetary ball mill, rolling ball mill, vibratory mill, or agitator mill, and even more preferably a planetary ball mill or a vibratory mill.

[0047] The grinding process can be carried out continuously or intermittently. To suppress the temperature rise of the material being processed during the grinding process, it is preferable to perform the grinding process intermittently. When performing the grinding process intermittently, the optimal values ​​vary greatly depending on the grinding equipment, but for example, in the case of a planetary ball mill, it can be carried out by repeating a cycle of 5 to 15 minutes of grinding followed by an interval of 5 to 15 minutes. When performing the grinding process continuously, it is preferable to maintain an appropriate temperature while performing the grinding process by installing a jacket or the like on the grinding equipment to cool it.

[0048] When hydrolysis is performed without grinding, methods that do not involve grinding include a method of kneading using a pressure kneader, and a method of reacting the mixture using an extrusion molding machine after kneading with a kneader.

[0049] The hydrolysis temperature is preferably between room temperature and 110°C, and more preferably between 50°C and 100°C. If the temperature is above room temperature, the decomposition process will not slow down, and the time required for decomposition will not become too long. Hydrolysis can also be performed at higher temperatures to further accelerate the decomposition rate. If the hydrolysis temperature is below 110°C, side reactions such as dehydration can be suppressed. In some reactors, shear heat may be large, so it is preferable to control the hydrolysis temperature by repeating cycles with intervals in between, as described above, or by circulating cooling water through the reactor jacket.

[0050] The hydrolysis time depends on the reactor used, but is generally preferred to be 2 to 150 hours, more preferably 5 to 80 hours, even more preferably 10 to 60 hours, and particularly preferably 15 to 40 hours. If the hydrolysis time is 2 hours or more, the decomposition of polysaccharides is promoted. If the hydrolysis time is 150 hours or less, the hydrolyzed product can be obtained more efficiently. In the case of hydrolysis performed by grinding, when the grinding process is performed intermittently, the hydrolysis time refers to the net grinding time excluding the intervals.

[0051] After the hydrolysis reaction described above, if necessary, a step may be taken to add water to the reactants and extract the water-soluble components. If the amount of water used during hydrolysis is small, the reactants will be in a solid state, and it is preferable to perform the extraction step.

[0052] After the hydrolysis reaction described above, a step to neutralize the reactants by adding a basic compound may be performed as needed. Since the reactants obtained from the hydrolysis reaction still contain the acid catalyst used for hydrolysis, the acid catalyst can be neutralized by adding a basic compound. The basic compound used for neutralization is preferably at least one selected from the group consisting of potassium salts, phosphates, ammonium salts, and ammonia. When performing the neutralization step, precipitates may form as the pH is brought to the neutral side, so it is preferable to separate the solids by filtration after the neutralization reaction.

[0053] As described above, oligosaccharides produced by the acid catalyst method have a higher degree of branching compared to the production method using a carbon catalyst described in International Publication No. 2017 / 104687, etc. For this reason, the acid catalyst method is preferred as a method for producing branched chitin oligosaccharides or branched cellooligosaccharides.

[0054] [Composition of the spreading agent] One embodiment of the spreading agent contains at least one oligosaccharide selected from the group consisting of chitin oligosaccharide, cellooligosaccharide, and xylooligosaccharide, and preferably contains two or more of the above oligosaccharides. When the spreading agent contains two or more oligosaccharides, a synergistic effect is obtained in which the adhesion to plants is further improved compared to when it contains the same amount of a single type of oligosaccharide. This synergistic effect is presumed to be due to the fact that by containing two or more oligosaccharides, the dispersive power to pesticides or fertilizers and the adhesion power to the leaf surface, which differ depending on the type of oligosaccharide, are complemented.

[0055] When the spreading agent contains two types of oligosaccharides, the combination is not limited and may be any combination of chitin oligosaccharide and cellooligosaccharide, chitin oligosaccharide and xylooligosaccharide, or cellooligosaccharide and xylooligosaccharide. Among these, the combination of chitin oligosaccharide and cellooligosaccharide is more preferred.

[0056] When the spreading agent contains two types, chitin oligosaccharide and cello-oligosaccharide, it is preferable that the chitin oligosaccharide contains branched-type chitin oligosaccharide, and it is preferable that the cello-oligosaccharide contains branched-type cello-oligosaccharide.

[0057] When the spreading agent contains two types, chitin oligosaccharide and cellooligosaccharide, the mass ratio of chitin oligosaccharide to cellooligosaccharide (chitin oligosaccharide content / cellooligosaccharide content) is preferably 0.2 to 5, more preferably 0.3 to 3, and even more preferably 0.5 to 1.5.

[0058] The spreading agent is particularly preferably composed of three types of oligosaccharides: chitin oligosaccharide, cellooligosaccharide, and xylooligosaccharide. When the spreading agent contains these three types of oligosaccharides, the synergistic effect described above is remarkable, resulting in particularly excellent adhesion to plants.

[0059] When the spreading agent contains chitin oligosaccharide, cellooligosaccharide, and xylooligosaccharide, it is preferable that the chitin oligosaccharide contains branched-type chitin oligosaccharide, and it is preferable that the cellooligosaccharide contains branched-type cellooligosaccharide.

[0060] When the spreading agent contains chitin oligosaccharide, cellooligosaccharide, and xylooligosaccharide, the proportion of each oligosaccharide relative to the total content of chitin oligosaccharide, cellooligosaccharide, and xylooligosaccharide (100% by mass) is preferably 10-50% by mass for chitin oligosaccharide, 10-50% by mass for cellooligosaccharide, and 10-60% by mass for xylooligosaccharide. More preferably, the proportions of each oligosaccharide are 20-40% by mass for chitin oligosaccharide, 20-40% by mass for cellooligosaccharide, and 20-55% by mass for xylooligosaccharide.

[0061] [Application to plants] The spreading agent of one embodiment is preferably added to a fertilizer composition, agricultural chemical composition, etc. (hereinafter sometimes referred to as "spreading agent composition") described later and applied to plants. The spreading agent composition is preferably sprayed on the leaves, trees, fruit surfaces, seeds, or soil of plants where a spreading effect is particularly needed, and is more preferably sprayed on the leaves of plants.

[0062] The plants to which this applies are not particularly limited, but are typically agricultural crops, including plants from families such as Brassicaceae, Solanaceae, Asteraceae, Cucurbitaceae, Chenopodiaceae, Apiaceae, Fabaceae, Convolvulaceae, Liliaceae, Rosaceae, Malvaceae, Zingiberaceae, Nelumbonaceae, and Poaceae.

[0063] Specifically, this includes Brassicaceae plants such as Chinese cabbage, cabbage, broccoli, flowering vegetables, komatsuna, mizuna, radish, and turnip; Solanaceae plants such as potatoes, tomatoes, eggplants, bell peppers, chili peppers, shishito peppers, and tobacco; Asteraceae plants such as garland chrysanthemum, lettuce, leaf lettuce, burdock, and butterbur; Cucurbitaceae plants such as watermelon, melon, pumpkin, cucumber, bitter melon, loofah, and gourd; Chenopodiaceae plants such as spinach, Swiss chard, sea beans, and beets; carrots, and celery. Examples include plants of the Apiaceae family such as parsley and Japanese parsley; plants of the Fabaceae family such as soybeans (edamame), adzuki beans, kidney beans, broad beans, peas, winged beans, and peanuts; plants of the Convolvulaceae family such as sweet potatoes and water spinach; plants of the Liliaceae family such as chives, leeks, onions, garlic, and asparagus; plants of the Rosaceae family such as strawberries, apples, pears, and loquats; plants of the Malvaceae family such as okra and cotton; plants of the Zingiberaceae family such as ginger; plants of the Nelumbonaceae family such as lotus; and plants of the Poaceae family such as corn, rice, barley, wheat, and sugarcane.

[0064] Among the above, leafy vegetables with water-repellent properties, such as Chinese cabbage, cabbage, komatsuna, and spinach, are more preferred.

[0065] The spreading agent composition is preferably applied to plants at a concentration such that the total content of at least one oligosaccharide selected from the group consisting of chitin oligosaccharides, cellooligosaccharides, and xylooligosaccharides is 20 to 500 ppm by mass, and more preferably at a concentration of 50 to 150 ppm by mass. When the concentration is 20 ppm by mass or higher, sufficient adhesion to plants can be achieved. When the concentration is 500 ppm by mass or lower, costs due to excessive use of the spreading agent can be reduced.

[0066] [Fertilizer composition] The fertilizer composition of one embodiment comprises at least one fertilizer component selected from the group consisting of nitrogen, phosphorus, and potassium, and the spreading agent. It is more preferable that the fertilizer component contains all three of nitrogen, phosphorus, and potassium.

[0067] In the fertilizer composition, the total content of at least one oligosaccharide selected from the group consisting of chitin oligosaccharides, cellooligosaccharides, and xylooligosaccharides is preferably 1 to 15% by mass, more preferably 3 to 12% by mass, and even more preferably 5 to 10% by mass.

[0068] The fertilizer composition may also contain other components that are effective as fertilizers. These other components include essential elements such as calcium (Ca), magnesium (Mg), sulfur (S), iron (Fe), manganese (Mn), boron (B), zinc (Zn), nickel (Ni), molybdenum (Mo), copper (Cu), and chlorine (Cl), as well as useful elements that help plant growth, such as sodium (Na), silicon (Si), selenium (Se), cobalt (Co), aluminum (Al), and vanadium (V).

[0069] For example, magnesium nitrate, magnesium phosphate, magnesium chloride, and magnesium sulfate can be used as magnesium raw materials. For example, iron sulfate, iron chloride, and iron nitrate can be used as iron raw materials. For example, manganese nitrate, manganese phosphate, manganese chloride, and manganese sulfate can be used as manganese raw materials. For example, borax, boric acid, or their metal salts can be used as boron raw materials. For example, zinc sulfate, zinc chloride, and zinc nitrate can be used as zinc raw materials. For example, sodium molybdate and ammonium molybdate can be used as molybdenum raw materials. For example, copper sulfate, copper chloride, and copper nitrate can be used as copper raw materials.

[0070] [Agricultural chemical composition] An agricultural chemical composition of one embodiment comprises at least one agricultural chemical selected from the group consisting of insecticides, acaricides, fungicides, herbicides, plant growth regulators, lodging inhibitors, and plant nutrients, and the spreading agent.

[0071] In the agricultural chemical composition, the total content of at least one oligosaccharide selected from the group consisting of chitin oligosaccharide, cellooligosaccharide, and xylooligosaccharide is preferably 1 to 15% by mass, more preferably 3 to 12% by mass, and even more preferably 5 to 10% by mass. [Examples]

[0072] The present invention will be described more specifically below based on examples, but the present invention is not limited to these examples.

[0073] <Preparing Oligosaccharides> Each oligosaccharide used in the examples and comparative examples was prepared as follows.

[0074] [Chitin oligosaccharide] 3.83 kg of chitin (purified chitin, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was mixed with 0.54 kg of 85% phosphoric acid aqueous solution (special grade reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) using a Henschel mixer (device name: FM20C / I, manufactured by Nippon Coke Industries, Ltd.). The mixing conditions were a rotation speed of 1400 rpm and aeration of 0.4 m. 3 / Hr

[0075] This mixture was transferred to a vibratory mill (device name: MB-1, manufactured by Chuo Kakoki Co., Ltd.) and hydrolyzed while being ground at 75°C for 72 hours. The grinding conditions were a total amplitude of 8 mm and a vibration frequency of 16.2 Hz, using φ3 / 4 inch carbon steel balls.

[0076] The pulverized material was removed from the vibrating mill and separated from the balls. 641g of the pulverized material was transferred to a dissolution apparatus (10L container). 5771g of deionized water was added, and the mixture was stirred at 25°C for 1 hour using a Three One Motor (registered trademark). This dissolved the water-soluble components and yielded an extract of the hydrolyzed product.

[0077] To this extract, 114 g of 48% potassium hydroxide aqueous solution was added, and the mixture was stirred at 25°C for 1 hour using a three-one motor. 262 g of perlite #31 (manufactured by Showa Chemical Industry Co., Ltd.) was added as a filtration aid, and the mixture was filtered using a pressure filter (KST-293-20, manufactured by Advantec Toyo Co., Ltd.) to obtain 5289 g of filtrate.

[0078] Analysis of the filtrate revealed a pH of 6.8 and a content of 404g of chitin hydrolysate.

[0079] Next, the above filtrate was freeze-dried to obtain chitin oligosaccharide powder.

[0080] [Cellooligosaccharide (1)] Cellulose Arbocell B600 (manufactured by Rettenmeyer) was used as the raw material. Analysis of Cellulose Arbocell B600 revealed a cellulose content of 80% by mass and a xylan content of 20% by mass.

[0081] 3.79 kg of the above raw material (moisture content 3.4% by mass, dry mass 3.66 kg) was mixed with 0.53 kg of 85% phosphoric acid aqueous solution (special grade reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) using a Henschel mixer (device name: FM20C / I, manufactured by Nippon Coke Industries, Ltd.). The mixing conditions were a rotation speed of 1400 rpm and aeration of 0.4 m. 3 / Hr

[0082] 350g of this mixture was transferred to a vibratory mill (device name: MB-1, manufactured by Chuo Kakoki Co., Ltd.) and hydrolyzed while being ground at 75°C for 72 hours. The grinding conditions were a total amplitude of 8mm, a vibration frequency of 16.2Hz, and a φ3 / 4 inch carbon steel ball was used.

[0083] The pulverized material was removed from the vibrating mill and separated from the balls. 300g of the pulverized material was transferred to a dissolution apparatus (5L container). 2817g of deionized water was added, and the mixture was stirred at 25°C for 1 hour using a Three One Motor (registered trademark). This dissolved the water-soluble components and yielded an extract of the hydrolyzed product.

[0084] To this extract, 61 g of a 48% potassium hydroxide aqueous solution was added, and the mixture was stirred at 25°C for 1 hour using a three-one motor. 122 g of perlite #31 (manufactured by Showa Chemical Industry Co., Ltd.) was added as a filtration aid, and the mixture was filtered using a pressure filter (KST-293-20, manufactured by Advantec Toyo Co., Ltd.) to obtain 2533 g of filtrate.

[0085] Analysis of the filtrate revealed a pH of 6.8, and it contained 167g of cellulose hydrolysate and 42g of xylan hydrolysate.

[0086] Next, the filtrate was freeze-dried to obtain cellooligosaccharide powder. The xylan hydrolysate contained in the filtrate was freeze-dried without separation.

[0087] [Cellooligosaccharide (2)] 10g of Avicel (crystalline fine cellulose manufactured by Merck) and 1.5g of activated carbon BA50 (manufactured by Ajinomoto Fine Techno Co., Ltd.) were placed together with 2000g of 1.5cm diameter alumina balls in a 3600mL ceramic pot mill. This was then set on a benchtop pot mill turntable (manufactured by Nittokagaku Co., Ltd., benchtop pot mill model ANZ-51S) and processed at 60rpm for 48 hours to obtain the reaction raw materials. The process was started at room temperature, and the temperature rise due to shear heating was left to occur naturally.

[0088] Next, 0.374 g of reaction raw materials and 40 mL of water were placed in a high-pressure reactor (internal volume 100 mL, autoclave manufactured by OM Labtec Co., Ltd., made of Hastelloy C22). The mixture was then heated to 230 °C at a rate of 10-30 °C / min (average heating rate 11.3 °C / min) while stirring at 600 rpm. Immediately after heating, the reactor was cooled by air cooling at a rate of 10-30 °C / min (average cooling rate 16.7 °C / min) to prepare the reaction solution.

[0089] Next, the supernatant liquid recovered from the reaction mixture using a centrifuge was freeze-dried to obtain cellooligosaccharide powder.

[0090] [Xylooligosaccharides] Acremonium Cellulolyticus strain TN (FERM P-18508) was cultured in a 500 mL flask containing 100 mL of liquid medium (Avicel 50 g / L, KH2O4 24 g / L, ammonium sulfate 5 g / L, potassium tartrate 1 / 2H2O 4.7 g / L, urea 4 g / L, Tween80 1 g / L, MgSO4·7H2O 1.2 g / L, ZnSO4·7H2O 10 mg / L, MnSO4·5H2O 10 mg / L, CuSO4·5H2O 10 mg / L) at 30 °C for 6 days with shaking. 5 g of corn cob powder was suspended in 50 mL of the supernatant from the resulting culture medium after centrifugation and the mixture was stirred at 50 °C for 72 hours. The supernatant from the resulting reaction mixture was freeze-dried to obtain xylooligosaccharide powder.

[0091] The number-average molecular weight and degree of branching of chitin oligosaccharide, cellooligosaccharide (1), and cellooligosaccharide (2) prepared by the method described above were determined by the following method.

[0092] [Method for analyzing number-average molecular weight] The number-average molecular weight was determined by GPC (gel permeation chromatography) analysis using an HPLC (high-performance liquid chromatography) instrument.

[0093] Standard samples were prepared by irradiating each standard sample, as shown in Table 1, with ultrasound for 5 minutes to disperse and dissolve the material. After standing overnight, the mixture was filtered through a 0.45 μm PTFE membrane filter (model number: 25HP045AN, manufactured by Advantec Toyo Co., Ltd.) to prepare standard samples. Standards 1 and 2 were used for the analysis of chitin oligosaccharides, and Standards 1 and 3 were used for the analysis of cellooligosaccharides (1) and cellooligosaccharides (2), respectively. In Table 1, "Mp" represents the peak top molecular weight.

[0094] The analytical samples were prepared in the same manner as the standard samples by dissolving each oligosaccharide powder in a ratio of 0.050 g per 1 g of water.

[0095] [Table 1]

[0096] A GPC-LS (Agilent 1260 Infinity) was used as the analytical instrument, and the number-average molecular weight of all peaks in each analytical sample was determined under the following analytical conditions. (Analysis conditions) Columns: Shodex® SB-G 6B (guard column) + SB802.5HQ (analytical column) x 3 Column temperature: 40℃ Eluent: 30v / v% acetonitrile + 70v / v% water 0.2M acetic acid aqueous solution Flow rate: 0.5mL / min Injection volume: 20μL Detector: Differential refractometer (RI)

[0097] [Method for analyzing branching points] The degree of branching was determined using an NMR (nuclear magnetic resonance) spectrometer under the following conditions. (NMR conditions) Equipment: Bruker AVANCE 500 (500MHz) Measurement method: 1 H-NMR, 13 C-NMR, 13 C-DEPT135, HSQC Lock solvent: D2O Internal standard: TSP-d4 (sodium trimethylsilylpropionate) = 0 ppm Temperature: room temperature Sample preparation: Powdered sample (50 mg) / D2O (1 mL) + TSP-d4 (5 mg)

[0098] The measurement samples were prepared using the following method: 50 mg of the powder sample was accurately weighed, dissolved in 1 mL of D2O in a 50 mL sample bottle, shaken in an ultrasonic cleaner for 5 minutes, dried in a vacuum dryer (30°C), and weighed again to calculate the amount of water removed. TSP-d4 (5 mg) and D2O (1 mL) were added again, shaken in an ultrasonic cleaner for 5 minutes, filtered through a 0.45 μm disposable filter (model number: 25HP045AN, manufactured by Advantec Toyo Co., Ltd.), sealed in a 5 mmφ NMR sample tube, and NMR measurement was performed immediately after sampling.

[0099] The degree of branching was calculated using the following formula, based on the area ratio of the spectra of "α-1,6-H1" and "β-1,4-H1" shown in Table 2. Branching degree = (α-1,6-H1)÷[(α-1,6-H1)+(β-1,4-H1)]×100(%)

[0100] [Table 2]

[0101] Figure 1 shows chitin oligosaccharides 1 H-NMR chart, Figure 2 shows cellooligosaccharide (1) 1 H-NMR chart, Figure 3 shows cellooligosaccharide (2)1 The H-NMR charts are shown below.

[0102] The analysis results are shown in Table 3. From these results, it was found that chitin oligosaccharide and cellooligosaccharide (1) contain branched oligosaccharides, while cellooligosaccharide (2) does not contain branched oligosaccharides and is a linear oligosaccharide.

[0103] [Table 3]

[0104] <Preparation of fertilizer compositions> [Example 1] Fertilizer components and chitin oligosaccharides obtained by the above method were dissolved in water to prepare a fertilizer composition containing 8.1% by mass of fertilizer components (total of P2O5 and K2O) and 8.0% by mass of chitin oligosaccharides.

[0105] [Examples 2-8] The fertilizer composition was prepared in the same manner as in Example 1, except that the type and content of oligosaccharides were changed as shown in Table 4.

[0106] [Comparative Example 1] A fertilizer composition containing 8.1% by mass of fertilizer components (total of P2O5 and K2O) was prepared by dissolving only the fertilizer components in water.

[0107] <Spreadability Test> Leaf samples were prepared by cutting spinach and cabbage leaves into 2cm x 3cm pieces. Spinach is a leafy vegetable with general water-repellent properties, while cabbage is a leafy vegetable with high water-repellent properties.

[0108] The fertilizer compositions prepared in Examples 1-8 and Comparative Example 1 were each diluted 1000 times with water, and 50 mL of each was placed in a 100 mL glass bottle (hereinafter referred to as "treatment solution"). Leaf samples were picked up with tweezers and immersed vertically in the treatment solution, held vertically for 3 seconds, and then slowly removed.

[0109] After immersion, the leaf samples were placed on a flat table with the leaf surface facing upwards, and the degree of wetness on the surface was observed visually and by photography.

[0110] Table 4 shows the results of evaluating the spreading effect of each treatment solution based on the following criteria. Figure 4 shows photographs taken for Comparative Example 1 and Example 5, which showed the best results. (Evaluation Criteria) A: Many water droplets adhered to the surface. B: Water droplets covered the entire surface. C: Water droplets covered almost the entire surface. D: Water droplets have adhered to it. E: A few water droplets were present. F: Almost nothing adhered.

[0111] [Table 4]

[0112] As shown in Table 4, compared to Comparative Example 1, which did not contain oligosaccharides, Examples 1-8, which contained oligosaccharides, all demonstrated an adhesion effect to the leaf surface.

[0113] Comparing the results of Examples 1-4, in which 8.0% by mass of a single type of oligosaccharide was added, Examples 1 and 2, which contained highly branched oligosaccharides, showed higher spreading effects. Furthermore, comparing the results of Examples 2 and 3, Example 2, which contained cellooligosaccharide (1), showed a higher spreading effect than Example 3, which contained cellooligosaccharide (2). From the above, it was found that using highly branched oligosaccharides resulted in a higher spreading effect.

[0114] The results from Examples 1-4 and 5 show that even with the same amount of oligosaccharide added, mixing multiple types of oligosaccharides significantly improves the spreading effect and produces a synergistic effect compared to using a single type.

[0115] The results from Examples 6-8 confirmed that a spreading effect can be obtained even when the amount of oligosaccharide added is reduced to less than 8.0% by mass.

[0116] Comparing the results of Example 7 and Example 8, which contained two types of oligosaccharides, chitin oligosaccharide and cello-oligosaccharide, Example 7, which contained cello-oligosaccharide (1), showed a higher spreading effect than Example 8, which contained cello-oligosaccharide (2). This confirms that using oligosaccharides with a high degree of branching results in a higher spreading effect.

[0117] <Storage Stability Test> For chitin oligosaccharide and cellooligosaccharide (1) produced by the above method, the freeze-dried powders were dissolved in water to a sugar concentration (for cellooligosaccharide (1), this concentration also includes xylan hydrolysate) of 5% by mass to prepare sample solutions. The presence or absence of turbidity in the sample solutions was observed and the turbidity was measured immediately after preparation and after storage for 7 days. The results are shown in Table 5.

[0118] The sample solution was stored by filling a 50 mL container with 40 mL of the sample solution and leaving it standing in a constant temperature bath set to 30°C.

[0119] Turbidity was measured using the following method: A well-dispersed sample solution (Sample 1) and a sample solution obtained by filtering Sample 1 through a 0.45 μm membrane (Sample 2) were prepared. Each sample was placed in a 1 cm square cell and its absorbance at a wavelength of 660 nm was measured. From the measured absorbance, turbidity was calculated using the following formula. Turbidity = (Absorbance of Sample 1) - (Absorbance of Sample 2)

[0120] [Table 5]

[0121] The results in Table 5 show that chitin oligosaccharide and cellooligosaccharide (1) did not develop turbidity even after 7 days of storage, indicating particularly high usefulness as spreading agents. [Industrial applicability]

[0122] By using the spreading agent of the present invention, the adhesion of fertilizer components and agricultural chemicals to plants can be effectively enhanced.

Claims

1. A spreading agent comprising at least one oligosaccharide selected from the group consisting of chitin oligosaccharide, cellooligosaccharide, and xylooligosaccharide, wherein the oligosaccharide comprises cellooligosaccharide, and the cellooligosaccharide is a cellooligosaccharide having an α-1,6-glycosidic bond in at least a portion of its glycosidic bond.

2. The spreading agent according to claim 1, wherein the oligosaccharide comprises chitin oligosaccharide, and the chitin oligosaccharide is a chitin oligosaccharide in which at least a portion of the glycosidic bond contains an α-1,6-glycosidic bond.

3. The spreading agent according to claim 2, wherein the ratio of the α-1,6-glycosidic bond to the total polymerization bond contained in the chitin oligosaccharide is 1 to 50%.

4. The spreading agent according to claim 2 or 3, wherein the number-average molecular weight of the chitin oligosaccharide is 420 to 2050.

5. The spreading agent according to claim 1, wherein the ratio of the α-1,6-glycosidic bond to the total polymerization bond contained in the cellooligosaccharide is 1 to 50%.

6. The spreading agent according to claim 1 or 5, wherein the number-average molecular weight of the cellooligosaccharide is 340 to 1640.

7. The spreading agent according to any one of claims 1 to 6, further comprising one or more selected from the group consisting of chitin oligosaccharides and xylooligosaccharides as the oligosaccharide.

8. The spreading agent according to claim 7, comprising chitin oligosaccharide and cellooligosaccharide as the oligosaccharide.

9. The spreading agent according to claim 8, wherein the oligosaccharide comprises chitin oligosaccharide, cellooligosaccharide, and xylooligosaccharide.

10. The spreading agent according to claim 9, wherein the proportion of each oligosaccharide relative to the total content of chitin oligosaccharide, cello oligosaccharide, and xylooligosaccharide is 10 to 50% by mass for chitin oligosaccharide, 10 to 50% by mass for cello oligosaccharide, and 10 to 60% by mass for xylooligosaccharide.

11. A fertilizer composition comprising at least one fertilizer component selected from the group consisting of nitrogen, phosphorus, and potassium, and a spreading agent according to any one of claims 1 to 10.

12. The fertilizer composition according to claim 11, wherein the total content of at least one oligosaccharide selected from the group consisting of chitin oligosaccharides, cellooligosaccharides, and xylooligosaccharides is 1 to 15% by mass, based on 100% by mass of the fertilizer composition.

13. An agricultural chemical composition comprising at least one agricultural chemical selected from the group consisting of insecticides, acaricides, fungicides, herbicides, plant growth regulators, lodging inhibitors, and plant nutrients, and a spreading agent according to any one of claims 1 to 10.

14. The agricultural chemical composition according to claim 13, wherein the total content of at least one oligosaccharide selected from the group consisting of chitin oligosaccharide, cellooligosaccharide, and xylooligosaccharide is 1 to 15% by mass, based on 100% by mass of the agricultural chemical composition.

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