Spreading agents, fertilizer compositions and agricultural chemical compositions

Abstract

Provided is a spreading agent that has high solubility in water and can effectively improve the adhesion of a fertilizer component or an agricultural agent to a plant. The spreading agent contains at least one oligosaccharide selected from the group consisting of chitinous oligosaccharides, fibrous oligosaccharides, and xyloglucan oligosaccharides.

Description

Technical Field

[0001] This invention relates to spreading agents, fertilizer compositions, and agricultural pesticide compositions containing oligosaccharides. Background Technology

[0002] In agriculture, spreading agents are agents added to the field when distributing pesticides such as insecticides, fungicides, and herbicides, which are the main active ingredients. Spreading agents are used to improve the physicochemical properties of the main active ingredient, thereby stabilizing or enhancing its biological activity.

[0003] Surfactants are a representative active ingredient in spreading agents. Examples of surfactants include, for instance, single nonionic surfactants, substances containing anionic surfactants mixed with nonionic surfactants, and substances containing cationic surfactants mixed with nonionic surfactants (Non-Patent Document 1). Examples of surfactants actually used include nonionic surfactants such as polyoxyethylene alkyl ethers, sorbitol fatty acid esters, and polyether-modified silicone (Patent Document 1), as well as anionic surfactants such as polyvinyl alcohol (Patent Document 2), alkyl sulfosuccinate base salts, and dinaphthyl methanesulfonate base salts.

[0004] As a pesticide formulation that uses sugars of natural origin, an example has been reported of a compound containing anionic polysaccharides (glucose, glucuronic acid, glucose, and rhamnose) in the main chain as repeating basic units (Patent Document 3).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2000-1404

[0008] Patent Document 2: Japanese Patent Application Publication No. 2015-134704

[0009] Patent Document 3: Japanese Patent Publication No. 2011-528674

[0010] Non-patent literature

[0011] Non-patent literature 1: Plant Disease Prevention, Vol. 68, No. 11, 2014, pp. 60-63 Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] However, the spreading agent composition in Patent Document 1 has low solubility in water and requires the use of an alcohol solvent. The agricultural liquid dispersant in Patent Document 2 also has low solubility in water, leading to polyvinyl alcohol precipitation if left for extended periods. For the pesticide formulation in Patent Document 3, polysaccharides are used as thickeners, requiring the addition of polyalkoxytriglycerides as penetration enhancers.

[0014] The present invention was made in view of the above circumstances, and its subject is to provide an adhesion promoter that is highly soluble in water and can effectively improve the adhesion of fertilizer components or agricultural agents to plants.

[0015] Methods for solving problems

[0016] In order to solve the above-mentioned problems, the inventors have repeatedly conducted in-depth research and have considered using oligosaccharides, which are compounds with high solubility in water and are environmentally and human-friendly, as spreading agents.

[0017] The results showed that spreading agents containing at least one oligosaccharide selected from chitin oligosaccharides, cellulose oligosaccharides, and xylooligosaccharides exhibited excellent adhesion to plants.

[0018] That is, the present invention includes the following [1] to

[15] . [1]

[0020] An adhesive comprising at least one oligosaccharide selected from chitin oligosaccharides, cellulose oligosaccharides, and xylooligosaccharides. [2]

[0022] The spreading agent according to [1] contains chitin oligosaccharides as the oligosaccharides, wherein the chitin oligosaccharides are chitin oligosaccharides in which at least a portion of the glycosidic bonds contain α-1,6-glycosidic bonds. [3]

[0024] According to the spreading agent described in [2], the ratio of the above-mentioned α-1,6-glycosidic bond to all polymeric bonds contained in the above-mentioned chitin oligosaccharide is 1 to 50%. [4]

[0026] According to the spreading agent described in [2] or [3], the number-average molecular weight of the above-mentioned chitin oligosaccharides is 420 to 2050. [5]

[0028] The spreading agent according to [1] contains a cellulose oligosaccharide as the oligosaccharide, wherein the cellulose oligosaccharide is a cellulose oligosaccharide in which at least a portion of the glycosidic bond contains an α-1,6-glycosidic bond. [6]

[0030] According to the spreading agent described in [5], the ratio of the above-mentioned α-1,6-glycosidic bond to all polymeric bonds contained in the above-mentioned cellulosic sugar is 1 to 50%. [7]

[0032] According to the spreading agent described in [5] or [6], the number average molecular weight of the above-mentioned cellulose oligosaccharides is 340 to 1640. [8]

[0034] The spreading agent according to any one of [1] to [7] comprises two or more oligosaccharides selected from chitin oligosaccharides, cellulose oligosaccharides and xylooligosaccharides. [9]

[0036] The spreading agent according to [8] contains chitin oligosaccharides and cellulose oligosaccharides as the above-mentioned oligosaccharides.

[10]

[0038] The spreading agent according to [9] contains chitin oligosaccharide, cellulose oligosaccharide and xylooligosaccharide as the above oligosaccharides.

[11]

[0040] According to the spreading agent described in

[10] , the proportions of each oligosaccharide relative to the total content of chitin oligosaccharide, cellulose oligosaccharide and xylooligosaccharide of 100% by mass are 10-50% by mass for chitin oligosaccharide, 10-50% by mass for cellulose oligosaccharide and 10-60% by mass for xylooligosaccharide.

[12]

[0042] A fertilizer composition comprising at least one fertilizer component selected from nitrogen, phosphoric acid and potassium, and an spreading agent as described in any one of [1] to

[11] .

[13]

[0044] According to the fertilizer composition described in

[12] , the total content of at least one oligosaccharide selected from chitin oligosaccharides, cellulose oligosaccharides and xylooligosaccharides is 1 to 15% by mass relative to 100% by mass of the fertilizer composition.

[14]

[0046] An agricultural pesticide composition comprising at least one agricultural pesticide selected from insecticides, acaricides, fungicides, herbicides, plant growth regulators, lodging prevention agents and plant nutrients, and a spreading agent as described in any one of [1] to

[11] .

[15]

[0048] According to the agricultural pesticide composition described in

[14] , the total content of at least one oligosaccharide selected from chitin oligosaccharides, cellulose oligosaccharides and xylooligosaccharides is 1 to 15% by mass relative to 100% by mass of the agricultural pesticide composition.

[0049] The effects of the invention

[0050] The spreading agent of this invention has high solubility in water and can effectively improve the adhesion of fertilizer components or agricultural agents to plants. Attached Figure Description

[0051] Figure 1 Chitin oligosaccharides 1 H-NMR spectrum.

[0052] Figure 2 For fiber oligosaccharides (1) 1 H-NMR spectrum.

[0053] Figure 3 For fiber oligosaccharides (2) 1 H-NMR spectrum.

[0054] Figure 4 Photographs of the adhesion test for comparative Example 1 and Example 5. Detailed Implementation

[0055] Hereinafter, embodiments of the present invention will be described. Furthermore, the embodiments described below show representative examples of the present invention and are not limited to them.

[0056] One embodiment of the spreading agent comprises at least one oligosaccharide selected from chitin oligosaccharides, cellulose oligosaccharides, and xylooligosaccharides.

[0057] [Chitin oligosaccharides]

[0058] Chitin oligosaccharides are oligosaccharides composed of several N-acetylglucosamines linked together, including some deacetylated deacetylated chitin oligosaccharides. Generally, they are obtained by hydrolyzing chitin derived from crustaceans, etc., and are also known as oligo-N-acetylglucosamines.

[0059] As chitinous oligosaccharides, it is preferable to use one or more mixtures selected from N-acetylchitobiose, N-acetylchitotriose, N-acetylchitotetraose, N-acetylchitopentose, N-acetylchitohexaose, N-acetylchitoheptaose, and N-acetylchitooctaose. Among these, N-acetylchitotriose, N-acetylchitotetraose, and N-acetylchitopentose are preferred.

[0060] The number-average molecular weight of chitin oligosaccharides is preferably 420–2050, more preferably 520–1650, and even more preferably 620–1240. A number-average molecular weight of 420 or higher can improve the adhesion of fertilizer or pesticide components to plants. A number-average molecular weight of 2050 or lower results in higher solubility of chitin oligosaccharides in water, thus reducing the likelihood of precipitation. The number-average molecular weight of chitin oligosaccharides can be determined by the method described in the examples below.

[0061] Chitin oligosaccharides may also contain chitin oligosaccharides in which a portion of the acetyl group (-COCH3) of N-acetylglucosamine is deacetylated to NH2. The proportion of such deacetylated glucosamine units is preferably 30 mol% or less of the total glucosamine units of the chitin oligosaccharide, more preferably 20 mol% or less, and even more preferably 15 mol% or less.

[0062] Chitin oligosaccharides can be linear chitin oligosaccharides formed by N-acetylglucosamine linked by β-1,4-glycosidic bonds (hereinafter, sometimes referred to as "linear chitin oligosaccharides"), or branched chitin oligosaccharides in which at least a portion of the glycosidic bonds contains α-1,6-glycosidic bonds (hereinafter, sometimes referred to as "branched chitin oligosaccharides").

[0063] Specifically, as a linear chitinous oligosaccharide, the substance shown in the following formula (1) can be used.

[0064]

[0065] In branched chitin oligosaccharides, the position of the α-1,6-glycosidic bond is not particularly limited and can branch from the 6-hydroxyl group of any N-acetylglucosamine unit constituting the chitin oligosaccharide. The number of α-1,6-glycosidic bonds in branched chitin oligosaccharides is also not particularly limited; it can be only one or more.

[0066] In one embodiment, the spreading agent contains chitin oligosaccharides, and more preferably, it contains branched chitin oligosaccharides. By including branched chitin oligosaccharides in the spreading agent, the adhesion to plants is further improved. When branched chitin oligosaccharides are included as chitin oligosaccharides, the ratio of α-1,6-glycosidic bonds to all polymeric 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%, further preferably 5-30%, and particularly preferably 5-20%. In this disclosure, "polymeric bond" refers to the bond that links monosaccharides together to form an oligosaccharide, typically a glycosidic bond. If the degree of branching is 1% or more, the adhesion of fertilizer or pesticide components to plants can be improved. If the degree of branching is 50% or less, decomposability decreases, and the duration of the spreading effect can be prolonged. The degree of branching is determined by the area ratio of the NMR spectrum using the method described in the examples below.

[0067] Chitin oligosaccharides can be commercially available or manufactured. One method for manufacturing chitin oligosaccharides is by chemically or enzymatically hydrolyzing chitin. Methods described, for example, in Japanese Patent Application Publication No. 2012-217396, can be used. Specifically, chitin oligosaccharides can be manufactured by neutralizing a reaction solution obtained from hydrolyzing chitin at 5°C to 30°C using concentrated hydrochloric acid of 30% or more, filtering the solution, desalting the filtrate through electrodialysis and ion exchange resin, and then freeze-drying the solution. In the case of manufacturing branched-chain chitin oligosaccharides, the "acid catalyst method" described later is preferred.

[0068] [Fiber oligosaccharides]

[0069] Cellulose oligosaccharides are oligosaccharides formed by the polymerization of multiple glucose molecules through β-glycosidic bonds.

[0070] As a fiber oligosaccharide, it is preferable to use one or more mixtures selected from cellobiose, cellotriose, cellotetraose, cellopentaose, cellohexaose, celloheptaose, and cellooctaose. Among them, cellotetraose, cellopentaose, and cellohexaose are preferred.

[0071] The number-average molecular weight of the cellulose oligosaccharide is preferably 340–1640, more preferably 420–1320, and even more preferably 500–990. If the number-average molecular weight is 340 or higher, the adhesion of fertilizer or pesticide components to plants can be improved. If the number-average molecular weight is 1640 or lower, the cellulose oligosaccharide has higher solubility in water, and therefore is less prone to precipitation. The number-average molecular weight of the cellulose oligosaccharide can be determined by the method described in the examples below.

[0072] Cellulose oligosaccharides can be linear cellulose oligosaccharides composed of glucose linked by β-1,4-glycosidic bonds (hereinafter, sometimes referred to as "linear cellulose oligosaccharides"), or branched cellulose oligosaccharides in which at least a portion of the glycosidic bonds contains α-1,6-glycosidic bonds (hereinafter, sometimes referred to as "branched cellulose oligosaccharides").

[0073] Specifically, as a linear cellulose oligosaccharide, the substance shown in the following formula (2) can be used.

[0074]

[0075] In branched-chain cellulose oligosaccharides, the position of the α-1,6-glycosidic bond is not particularly limited and can branch from the 6-position hydroxyl group of any glucose unit constituting the cellulose oligosaccharide. The number of α-1,6-glycosidic bonds in branched-chain cellulose oligosaccharides is also not particularly limited; it can be only one or more.

[0076] In one embodiment, the spreading agent contains a cellulose oligosaccharide, more preferably a branched-chain cellulose oligosaccharide. By including a branched-chain cellulose oligosaccharide in the spreading agent, the adhesion to plants is further improved. When a branched-chain cellulose oligosaccharide is included as the cellulose oligosaccharide, the ratio of α-1,6-glycosidic bonds to all polymeric bonds of the cellulose oligosaccharide (hereinafter, sometimes referred to as the "degree of branching" of the cellulose oligosaccharide) is preferably 1-50%, more preferably 3-40%, further preferably 5-30%, and particularly preferably 5-20%. If the degree of branching is 1% or more, the adhesion of fertilizer or pesticide components to plants can be improved. If the degree of branching is 50% or less, decomposability decreases, and the duration of the spreading effect can be prolonged. The degree of branching is determined by the area ratio of the NMR spectrum using the method described in the examples below.

[0077] Cellulose oligosaccharides can be commercially available or manufactured. One method for manufacturing cellulose oligosaccharides is by chemically or enzymatically hydrolyzing cellulose. For example, they can be manufactured using a hydrolysis reaction of plant biomass using a carbon catalyst, as described in International Publication No. 2017 / 104687, etc. In the case of manufacturing branched-chain cellulose oligosaccharides, the "acid catalyst method" described later is preferred.

[0078] [Xylooligosaccharides]

[0079] Xylooligosaccharides are oligosaccharides formed by the polymerization of multiple xyloses through β-glycosidic bonds. Generally, they are obtained by the hydrolysis of xylan, the main component of hemicellulose.

[0080] As xylo-oligosaccharides, it is preferable to use one or more mixtures selected from xylobiose, xylotriose, xylotetraose, xylopentose, xylohexaose, xyheptaose, and xyoctaose. Among these, xylopentose, xylohexaose, and xyheptaose are preferred.

[0081] Specifically, the substance shown in formula (3) below can be used as a xylo-oligosaccharide.

[0082]

[0083] Xylo-oligosaccharides can be commercially available or manufactured. One method for manufacturing xylo-oligosaccharides is to chemically or enzymatically partially hydrolyze xylan. For example, they can be manufactured by hydrolyzing corn cobs with the culture supernatant of cellulose-degrading apical spores that have produced xylan hydrolytic enzymes.

[0084] [Methods for manufacturing branched-chain oligosaccharides]

[0085] As a method for manufacturing the aforementioned branched chitin oligosaccharides or branched cellulosic oligosaccharides, an acid catalyst method is preferred, which hydrolyzes polysaccharides in the presence of an acid catalyst.

[0086] In the manufacture of chitin oligosaccharides, chitin is used as the polysaccharide raw material. In the manufacture of cellulose oligosaccharides, cellulose or a mixture of cellulose and xylan can be used as the polysaccharide raw material. When using a mixture of cellulose and xylan as the raw material, the xylan content relative to the total content of cellulose and xylan (100% by mass) is preferably 5-50% by mass, more preferably 7-40% by mass, further preferably 10-30% by mass, and particularly preferably 15-25% by mass.

[0087] As an acid catalyst, conventionally known acids can be used. Specifically, at least one acid selected from sulfuric acid, sulfurous acid, hydrochloric acid, perchloric acid, nitric acid, nitrous acid, and phosphoric acid, or a partially neutralized salt thereof, can be used. Examples of partially neutralized salts of the aforementioned acids include potassium dihydrogen phosphate, ammonium dihydrogen phosphate, and potassium hydrogen sulfate. The acid catalyst is preferably phosphoric acid or a partially neutralized salt thereof, and more preferably phosphoric acid.

[0088] The preferred amount of acid catalyst used is an amount in which the mass ratio of polysaccharide to acid catalyst is (polysaccharide) / (acid catalyst) = 2 to 100, more preferably an amount in which the mass ratio is (polysaccharide) / (acid catalyst) = 4 to 20, and even more preferably an amount in which the mass ratio is (polysaccharide) / (acid catalyst) = 3 to 10. If the mass ratio of polysaccharide to acid catalyst is 100 or less, hydrolysis proceeds at a practically harmless rate. If the mass ratio of polysaccharide to acid catalyst is 2 or more, side reactions such as dehydration and carbon-carbon bond breaking can be suppressed during hydrolysis.

[0089] Furthermore, the mass of polysaccharides referred to here is the actual mass (dry mass) after removing the moisture contained in the raw material. Typically, since polysaccharides contain physically adsorbed moisture, this adsorbed moisture is analyzed, and the mass ratio of polysaccharides to the acid catalyst is determined by the mass of the polysaccharides after moisture removal. One method for analyzing the adsorbed moisture content is to add the polysaccharides used as raw materials to a constant-temperature dryer at 100°C–150°C and dry them until their mass no longer decreases, thus quantifying the quantity. To prevent the influence of side reactions such as dehydration during drying, it is desirable to use a vacuum dryer to dry them at a lower temperature for quantification. In addition, the mass of the acid catalyst is also the actual mass of the acid catalyst (dry mass).

[0090] As mentioned above, polysaccharides before hydrolysis already contain approximately 1-12% by mass of physically adsorbed water. Furthermore, commercially available acid catalysts such as hydrochloric acid and phosphoric acid often contain water. Therefore, hydrolysis can proceed using the water physically adsorbed on the polysaccharides and the water contained in the acid catalyst, even without adding water. Usually, the water content is sufficient even without adding water, but for polysaccharides with high dryness, water can be added for hydrolysis.

[0091] Both with and without added water, the polysaccharides contain approximately 1-12% by mass of physically adsorbed water. Therefore, the water content in the hydrolysis reaction includes the water physically adsorbed on the polysaccharides and the water contained in the acid catalyst, and further includes this water content even when water is added. This water content is preferably 0.1 to 15 parts by mass relative to 100 parts by mass of the actual polysaccharide (dry weight), more preferably 0.5 to 8 parts by mass. If it is 15 parts by mass or less, a sufficient hydrolysis rate can be obtained, and inoperability caused by adhesion to the device can be prevented. Furthermore, if it is 0.1 parts by mass or more, side reactions such as dehydration reactions can be suppressed.

[0092] Ideally, during hydrolysis, mechanical force is applied to the polysaccharides through a pulverizing process. Examples of pulverizing devices used in this process include, for instance, rotary ball mills such as can mills, tube mills, and conical mills; jet mills such as vortex jet mills, impact jet mills, fluidized bed jet mills, and wet jet mills; shear mills such as grinding mixers (pounders) and angle mills; colloid mills such as mortars and pestles; impact mills such as hammer mills, cage mills, pin mills, demilling mills, sieve mills, turbine mills, and centrifugal classifying mills; vibratory mills that pulverize by vibrating a drum to move the internal media; stirred mills that pulverize by adding media and raw materials to a tank with stirring blades and causing them to rotate; and planetary ball mills, which are types of pulverizers employing rotation and revolution.

[0093] The pulverizing device is preferably a ball mill, vibratory mill, or stirred mill that applies strong compressive force to the polysaccharides and applies stress by stretching them in both directions of the main chain. The pulverizing device is more preferably a planetary ball mill, rotary ball mill, vibratory mill, or stirred mill, and even more preferably a planetary ball mill or vibratory mill.

[0094] The grinding process can be carried out continuously or intermittently. To suppress the temperature rise of the workpiece during grinding, intermittent grinding is preferred. In the case of intermittent grinding, the optimal temperature varies greatly depending on the grinding apparatus; however, for example, in the case of a planetary ball mill, it can be carried out by repeatedly performing grinding operations for 5 to 15 minutes, interspersed with 5 to 15-minute intervals. In the case of continuous grinding, it is preferable to maintain a suitable temperature while performing grinding by cooling the grinding apparatus with a jacket or similar device.

[0095] In the case of hydrolysis without pulverization, methods that do not involve pulverization include using a pressure kneader for mixing and using an extruder to react the mixture after kneading.

[0096] The hydrolysis temperature is preferably between room temperature and 110°C, more preferably between 50°C and 100°C. At temperatures above room temperature, the decomposition process does not slow down, and the time required for decomposition is not excessive. To further accelerate the decomposition rate, hydrolysis can also be carried out at higher temperatures. If the hydrolysis temperature is below 110°C, side reactions such as dehydration can be suppressed. Since shear heating can be significant depending on the reaction apparatus, it is preferable to repeatedly perform cycles with intervals as described above, or to control the hydrolysis temperature by flowing cooling water through the jacket of the reaction apparatus.

[0097] The hydrolysis time depends on the reaction apparatus 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 hydrolysate can be obtained more efficiently. Furthermore, in the case of hydrolysis by pulverization, when the pulverization process is performed intermittently, the hydrolysis time refers to the net pulverization time excluding the intervals.

[0098] Following the above hydrolysis reaction, a step of adding water to the reactants to extract water-soluble components can be performed, if needed. When the amount of water used during hydrolysis is small and the reactants are in a solid state, the extraction step is preferable.

[0099] Following the above hydrolysis reaction, a neutralization step can be performed by adding an alkaline compound, if necessary. Since the reactants obtained through the above hydrolysis reaction contain residual acid catalyst used in the hydrolysis, this acid catalyst can be neutralized by adding an alkaline compound. The alkaline compound used for neutralization is preferably selected from at least one of potassium salts, phosphates, ammonium salts, and ammonia. When performing the neutralization step, since precipitation sometimes occurs by shifting the pH to the neutral side, it is preferable to separate the solid components by filtration after the neutralization reaction.

[0100] The oligosaccharides produced by the acid-catalyst method have a higher degree of branching compared to those produced by the carbon-catalyst method described in International Publication No. 2017 / 104687, etc. Therefore, the acid-catalyst method is preferred as a method for producing branched chitinous oligosaccharides or branched cellulosic oligosaccharides.

[0101] [Composition of spreading agent]

[0102] One embodiment of the agent contains at least one oligosaccharide selected from chitinous oligosaccharides, cellulose oligosaccharides, and xylooligosaccharides, preferably two or more of the aforementioned oligosaccharides. When the spreading agent contains two or more oligosaccharides, a synergistic effect of further improved adhesion to plants is obtained compared to the case containing the same amount of a single type of oligosaccharide. It is presumed that this synergistic effect arises because the inclusion of two or more oligosaccharides compensates for the varying dispersion power of pesticides or fertilizers and the spreading power on leaf surfaces, depending on the type of oligosaccharide.

[0103] When the spreading agent contains two oligosaccharides, the combination is not limited and can be any combination of chitin oligosaccharides and cellulose oligosaccharides, chitin oligosaccharides and xylooligosaccharides, or cellulose oligosaccharides and xylooligosaccharides. Among these, the combination of chitin oligosaccharides and cellulose oligosaccharides is more preferred.

[0104] When the spreading agent contains both chitin oligosaccharides and cellulose oligosaccharides, the chitin oligosaccharides preferably contain branched-chain chitin oligosaccharides, and the cellulose oligosaccharides preferably contain branched-chain cellulose oligosaccharides.

[0105] When the spreading agent contains both chitin oligosaccharides and cellulose oligosaccharides, the mass ratio of chitin oligosaccharides to cellulose oligosaccharides (chitin oligosaccharide content / cellulose oligosaccharide content) is preferably 0.2 to 5, more preferably 0.3 to 3, and even more preferably 0.5 to 1.5.

[0106] The spreading agent preferably contains three oligosaccharides: chitin oligosaccharides, cellulose oligosaccharides, and xylooligosaccharides. When the spreading agent contains these three oligosaccharides, the aforementioned synergistic effect is significant, and the adhesion to plants is particularly excellent.

[0107] When the spreading agent contains chitin oligosaccharides, cellulose oligosaccharides and xylooligosaccharides, the chitin oligosaccharides preferably contain branched-chain chitin oligosaccharides, and the cellulose oligosaccharides preferably contain branched-chain cellulose oligosaccharides.

[0108] When the spreading agent contains chitin oligosaccharides, cellulose oligosaccharides, and xylooligosaccharides, the preferred proportions of each oligosaccharide relative to a total content of 100% by mass are 10-50% by mass for chitin oligosaccharides, 10-50% by mass for cellulose oligosaccharides, and 10-60% by mass for xylooligosaccharides. More preferably, the proportions are 20-40% by mass for chitin oligosaccharides, 20-40% by mass for cellulose oligosaccharides, and 20-55% by mass for xylooligosaccharides.

[0109] [Applications to plants]

[0110] In one embodiment, the spreading agent is preferably added to fertilizer compositions, agricultural pesticide compositions, etc. (hereinafter, sometimes referred to as "spreading agent compositions") and applied to plants. The spreading agent composition is preferably dispersed on the leaves, trunk, fruit surface, seeds, or soil of plants where a spreading effect is particularly needed, and more preferably dispersed on the leaves of plants.

[0111] There are no particular restrictions on the plants to be used, but they are typically crops, including plants from the Brassicaceae, Solanaceae, Asteraceae, Cucurbitaceae, Chenopodiaceae, Apiaceae, Fabaceae, Convolvulaceae, Liliaceae, Rosaceae, Malvaceae, Zingiberaceae, Nelumbo nucifera, and Poaceae families.

[0112] Specifically, examples include cruciferous plants such as Chinese cabbage, kale, broccoli, cauliflower, komatsuna, mizuna, radish, and turnip; solanaceous plants such as potatoes, tomatoes, eggplants, bell peppers, chili peppers, and tobacco; Asteraceae plants such as garland chrysanthemum, lettuce, head lettuce, burdock, and buttercup; Cucurbitaceae plants such as watermelon, cantaloupe, pumpkin, cucumber, bitter melon, loofah, and bottle gourd; Chenopodiaceae plants such as spinach, sorghum, chard, wingless hogweed, and beets; and carrots. Plants of the Apiaceae family such as celery, parsley, and watercress; plants of the Fabaceae family such as soybean, red bean, common bean, broad bean, pea, winged bean, and peanut; plants of the Convolvulaceae family such as sweet potato and water spinach; plants of the Liliaceae family such as leek, allium, onion, garlic, and asparagus; plants of the Rosaceae family such as strawberry, apple, pear, and loquat; plants of the Malvaceae family such as amaryllis and cotton; plants of the Zingiberaceae family such as ginger; plants of the Nelumbo nucifera family such as lotus; and plants of the Gramineae family such as corn, rice, barley, wheat, and sugarcane.

[0113] Of the above, more preferred are leafy vegetables with water-repellent properties, such as Chinese cabbage, kale, komatsuna, and spinach.

[0114] The spreading agent composition is preferably applied to plants at a concentration of 20 to 500 ppm by mass, more preferably at a concentration of 50 to 150 ppm by mass, where the total content of at least one oligosaccharide selected from chitinous oligosaccharides, cellulose oligosaccharides, and xylooligosaccharides is 20 to 500 ppm by mass. If the concentration is 20 ppm by mass or higher, sufficient adhesion to the plant can be achieved. If the concentration is 500 ppm by mass or lower, costs caused by excessive use of the spreading agent can be reduced.

[0115] [Fertilizer Composition]

[0116] One embodiment of the fertilizer composition comprises at least one fertilizer component selected from nitrogen, phosphoric acid, and potassium, and the aforementioned spreading agent. More preferably, it comprises all three fertilizer components: nitrogen, phosphoric acid, and potassium.

[0117] In the fertilizer composition, the total content of at least one oligosaccharide selected from chitin oligosaccharides, cellulose oligosaccharides, 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.

[0118] Fertilizer compositions may contain other effective ingredients as fertilizers. Examples of these other ingredients 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 aid plant growth, such as sodium (Na), silicon (Si), selenium (Se), cobalt (Co), aluminum (Al), and vanadium (V).

[0119] For example, magnesium nitrate, magnesium phosphate, magnesium chloride, and magnesium sulfate can be used as raw materials for magnesium. For example, ferric sulfate, ferric chloride, and ferric nitrate can be used as raw materials for iron. For example, manganese nitrate, manganese phosphate, manganese chloride, and manganese sulfate can be used as raw materials for manganese. For example, borax, boric acid, or their metal salts can be used as raw materials for boron. For example, zinc sulfate, zinc chloride, and zinc nitrate can be used as raw materials for zinc. For example, sodium molybdate and ammonium molybdate can be used as raw materials for molybdenum. For example, copper sulfate, copper chloride, and copper nitrate can be used as raw materials for copper.

[0120] [Agricultural pesticide compositions]

[0121] One embodiment of the agricultural pesticide composition comprises at least one agricultural pesticide selected from insecticides, acaricides, fungicides, herbicides, plant growth regulators, lodging prevention agents, and plant nutrients, as well as the aforementioned spreading agent.

[0122] In the agricultural pesticide composition, the total content of at least one oligosaccharide selected from chitin oligosaccharides, cellulose oligosaccharides, 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.

[0123] Example

[0124] The present invention will now be described in more detail with reference to embodiments, but the present invention is not limited to these embodiments.

[0125] <Preparation of Oligosaccharides>

[0126] The oligosaccharides used in the examples and comparative examples were prepared as follows.

[0127] [Chitin oligosaccharides]

[0128] 3.83 kg of chitin (manufactured by Fuji Film and Wako Pure Pharmaceutical Co., Ltd., refined chitin) was mixed with 0.54 kg of 85% phosphoric acid aqueous solution (manufactured by Fuji Film and Wako Pure Pharmaceutical Co., Ltd., premium reagent) using a Henschel mixer (equipment name: FM20C / I, manufactured by Japan Corners Industries Co., Ltd.). The mixing conditions were set at a speed of 1400 rpm and a ventilation rate of 0.4 m³ / h. 3 / Hr.

[0129] The mixture was transferred to a vibratory mill (model MB-1, manufactured by Chuo Kagaki Co., Ltd.) and hydrolyzed while being pulverized at 75°C for 72 hours. The pulverization conditions were set at a total amplitude of 8 mm and a frequency of 16.2 Hz, using φ3 / 4 inch carbon steel balls.

[0130] The pulverized material was removed from the vibratory mill and separated from the grinding balls. 641g of the pulverized material was transferred to a dissolving apparatus (10L container). 5771g of ion-exchanged water was added, and the mixture was stirred at 25°C for 1 hour using a slurry (registered trademark). This dissolved the water-soluble components, yielding a hydrolysate extract.

[0131] 114 g of a 48% potassium hydroxide aqueous solution was added to the extract, and the mixture was stirred at 25°C for 1 hour using a slurry. 262 g of perlite #31 (manufactured by Showa Chemical Industry Co., Ltd.) was added as a filter aid, and the mixture was filtered using a pressure filter (KST-293-20, manufactured by Adbank Toyo Co., Ltd.), yielding 5289 g of filtrate.

[0132] The filtrate was analyzed and found to have a pH of 6.8 and contain 404 g of chitin hydrolysate.

[0133] The filtrate was then freeze-dried to obtain chitin oligosaccharide powder.

[0134] [Fiber oligosaccharide(1)]

[0135] Cellrose Arbocel B600 (manufactured by Redenmile Co., Ltd.) was used as the raw material. Analysis of Cellrose Arbocel B600 revealed a cellulose content of 80% by mass and a xylan content of 20% by mass.

[0136] 3.79 kg of the above raw material (moisture content 3.4% by mass, dry weight 3.66 kg) was mixed with 0.53 kg of 85% phosphoric acid aqueous solution (premium grade reagent manufactured by Fuji Film & Television Co., Ltd.) using a Henschel mixer (equipment name: FM20C / I, manufactured by Corns Industries, Ltd., Japan). The mixing conditions were set at a speed of 1400 rpm and an aeration rate of 0.4 m³ / h. 3 / Hr.

[0137] 350g of the mixture was transferred to a vibratory mill (model MB-1, manufactured by Chuo Kagaki Co., Ltd.) and hydrolyzed while being pulverized at 75°C for 72 hours. The pulverization conditions were set at a total amplitude of 8mm and a frequency of 16.2Hz, using φ3 / 4-inch carbon steel balls.

[0138] The pulverized material was removed from the vibratory mill and separated from the grinding balls. 300g of the pulverized material was transferred to a dissolving apparatus (5L container). 2817g of deionized water was added, and the mixture was stirred at 25°C for 1 hour using a slurry (registered trademark). This dissolved the water-soluble components, yielding a hydrolysate extract.

[0139] 61g of a 48% potassium hydroxide aqueous solution was added to the extract, and the mixture was stirred at 25°C for 1 hour using a slurry. 122g of perlite #31 (manufactured by Showa Chemical Industry Co., Ltd.) was added as a filter aid, and the mixture was filtered using a pressure filter (KST-293-20, manufactured by Adbank Toyo Co., Ltd.), yielding 2533g of filtrate.

[0140] The filtrate was analyzed and found to have a pH of 6.8, containing 167g of cellulose hydrolysate and 42g of xylan hydrolysate.

[0141] The filtrate was then freeze-dried to obtain a cellulose oligosaccharide powder. Additionally, the xylan hydrolysate contained in the filtrate was freeze-dried without separation.

[0142] [Fiber oligosaccharides(2)]

[0143] 10g of abisel (Merck-manufactured crystalline micronized cellulose), 1.5g of activated carbon BA50 (manufactured by Ajinomoto Co., Ltd.), and 2000g of alumina balls with a diameter of 1.5cm were added to a 3600mL ceramic jar mill and placed on a benchtop jar mill rotary table (Nippon Tok Science Co., Ltd., benchtop jar mill model ANZ-51S). The reaction mixture was processed at 60rpm for 48 hours to obtain the reaction raw materials. Regarding temperature, the reaction started at room temperature, and the temperature rise due to shear heating was allowed to proceed naturally.

[0144] Next, 0.374 g of the reaction raw material and 40 mL of water were added to a high-pressure reactor (100 mL internal volume, high-pressure vessel manufactured by Oemurabot Co., Ltd., manufactured by Hastelloy C22). While stirring at 600 rpm, the reaction temperature was heated to 230°C at 10–30°C / min (average heating rate 11.3°C / min). Heating was then immediately stopped, and the reactor was cooled by air cooling at 10–30°C / min (average cooling rate 16.7°C / min) to produce the reaction solution.

[0145] Next, the supernatant recovered from the reaction solution by centrifugation was freeze-dried to obtain cellulose oligosaccharide powder.

[0146] [Xylooligosaccharides]

[0147] Acremonium Cellulolyticus TN strain (FERM P-18508) was cultured for 6 days at 30°C with shaking in a 500mL flask containing 100mL of liquid culture medium (50g / L abisel, 24g / L KH2O4, 5g / L ammonium sulfate, 4.7g / L potassium tartrate 1 / 2H2O, 4g / L urea, 1g / L Tween 80, 1.2g / L MgSO4·7H2O, 10mg / L ZnSO4·7H2O, 10mg / L MnSO4·5H2O, 10mg / L CuSO4·5H2O). 50mL of the supernatant from centrifugation was used to suspend 5g of corn cob powder, and the mixture was stirred at 50°C for 72 hours to allow the reaction to proceed. The supernatant from centrifugation of the resulting reaction solution was freeze-dried to obtain xylooligosaccharide powder.

[0148] Regarding the chitin oligosaccharides, cellulose oligosaccharides (1) and cellulose oligosaccharides (2) prepared by the above method, the number-average molecular weight and degree of branching were determined by the following method.

[0149] [Analytical methods for number-average molecular weight]

[0150] The number-average molecular weight was determined by GPC (gel permeation chromatography) analysis using an HPLC (high performance liquid chromatography) apparatus.

[0151] For each formulation sample prepared under the conditions shown in Table 1, ultrasonic irradiation for 5 minutes was used to disperse and dissolve it. After the resulting substance was left to stand overnight, it was filtered through a 0.45 μm PTFE membrane filter (model: 25HP045AN, manufactured by Advantech Toyo Co., Ltd.) to prepare standard samples. "Standard 1" and "Standard 2" were used in the analysis of chitin oligosaccharides, and "Standard 1" and "Standard 3" were used in the analysis of cellulosic oligosaccharides (1) and cellulosic oligosaccharides (2). In Table 1, "Mp" represents the peak molecular weight.

[0152] The analytical sample was prepared by dissolving each oligosaccharide powder in 1g of water at a ratio of 0.050g, and then preparing the sample using the same method as the standard sample.

[0153] Table 1

[0154]

[0155] Using a GPC-LS (Agilent Technologies, 1260 Infinity) as the analytical apparatus, the number-average molecular weights of all peaks in each analytical sample were determined under the following analytical conditions.

[0156] (Analysis conditions)

[0157] Columns: Shodex (registered trademark) SB-G 6B (protect column) + SB802.5HQ (analytical column) × 3 columns; Column temperature: 40℃

[0158] Eluent: 30 v / v acetonitrile + 70 v / v water + 0.2 M acetic acid aqueous solution

[0159] Flow rate: 0.5 mL / min

[0160] Injection volume: 20 μL

[0161] Detector: Differential refractometer (RI)

[0162] [Analysis methods for branching degree]

[0163] Branching degree was determined using an NMR (nuclear magnetic resonance) apparatus under the conditions shown below.

[0164] (NMR conditions)

[0165] Device: Bruker AVANCE 500 (500MHz)

[0166] Determination method: 1 H-NMR, 13 C-NMR, 13 C-DEPT135, HSQC

[0167] Locked solvent: D2O

[0168] Internal standard: TSP-d4 (sodium trimethylsilyl propionate) = 0 ppm

[0169] Temperature: Room temperature

[0170] Sample preparation: Powdered sample (50 mg) / D2O (1 mL) + TSP-d4 (5 mg)

[0171] The sample was prepared as follows: 50 mg of powdered sample was accurately weighed and dissolved in 1 mL of D2O in a 50 mL sample vial. After ultrasonic washing for 5 minutes, the sample was dried and solidified using a vacuum dryer (30°C). The dehydrated amount was calculated by accurately weighing the sample again. 5 mg of TSP-d4 and 1 mL of D2O were added again, and the sample was ultrasonically washed for 5 minutes. The sample was then filtered through a 0.45 μm disposable filter (model: 25HP045AN, manufactured by Adbank Toyo Co., Ltd.). The resulting substance was sealed in a 5 mm φ NMR sample tube and NMR analysis was performed immediately after sampling.

[0172] The degree of branching was calculated using the following mathematical formula based on the area ratio of the spectra of “α-1,6-H1” and “β-1,4-H1” shown in Table 2.

[0173] Degree of branching=(α-1,6-H1)÷[(α-1,6-H1)+(β-1,4-H1)]×100(%)

[0174] Table 2

[0175]

[0176] Figure 1 The text appears to contain fragments related to chitin oligosaccharides. 1 H-NMR spectrum, Figure 2 The text shows the presence of fiber oligosaccharides (1). 1 H-NMR spectrum, Figure 3 The text appears to contain information about fiber oligosaccharides (2). 1 H-NMR spectrum.

[0177] The results of the analysis are shown in Table 3. The results show that chitin oligosaccharides and cellulosic oligosaccharides (1) contain branched oligosaccharides, while cellulosic oligosaccharides (2) are linear oligosaccharides that do not contain branched groups.

[0178] Table 3

[0179] Number average molecular weight branching degree Chitin oligosaccharides 810 10％ Fiber oligosaccharides (1) 800 14％ Fiber oligosaccharides (2) 780 0％

[0180] <Preparation of Fertilizer Compositions>

[0181] [Example 1]

[0182] 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.

[0183] [Examples 2-8]

[0184] The fertilizer composition was prepared by changing the type and content of oligosaccharides as described in Table 4, otherwise operating in the same manner as in Example 1.

[0185] [Comparative Example 1]

[0186] Fertilizer components were dissolved in water to prepare a fertilizer composition containing 8.1% by mass of fertilizer components (a total of P2O5 and K2O).

[0187] <Spreadability Test>

[0188] Leaf samples of spinach and cabbage were prepared, cut 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.

[0189] The fertilizer compositions of Examples 1-8 and Comparative Example 1 were diluted with water to a ratio of 1000:1, and 50 mL (hereinafter referred to as "treatment solution") was added to a 100 mL glass bottle. The leaf sample was held with tweezers and vertically immersed in the treatment solution for 3 seconds, and then slowly lifted out.

[0190] The soaked leaf samples were placed on a flat table with the leaf surface facing up, and the wetting condition of the surface was observed by visual inspection and photographic photography.

[0191] The results of evaluating the spreading effect of each treatment solution based on the following criteria are shown in Table 4. Furthermore, photographs of Comparative Example 1 and Example 5, which showed the best results, are shown in Table 4. Figure 4 middle.

[0192] (Evaluation Criteria)

[0193] A: A large number of water droplets adhere to one side.

[0194] B: Water droplets adhere to one side.

[0195] C: The water droplets are almost attached to one side.

[0196] D: Water droplets adhered.

[0197] E: A few water droplets adhered.

[0198] F: Basically does not adhere.

[0199] Table 4

[0200]

[0201] According to the results in Table 4, compared with Comparative Example 1 without oligosaccharides, the effect on leaf spreading was confirmed in Examples 1 to 8 with oligosaccharides.

[0202] Comparing the results of Examples 1-4, which each contained 8.0% by mass of a single type of oligosaccharide, Examples 1 and 2, which contained oligosaccharides with high branching degree, showed higher spreading effects. Furthermore, comparing the results of Example 2 and Example 3, Example 2, which contained cellulose oligosaccharide (1), showed a higher spreading effect compared to Example 3, which contained cellulose oligosaccharide (2). Therefore, it is evident that using oligosaccharides with high branching degree results in a higher spreading effect.

[0203] The results of Examples 1-4 and Example 5 show that even with the same amount of oligosaccharides added, the effect is significantly improved and a synergistic effect is obtained by mixing multiple types of oligosaccharides compared to using a single type.

[0204] The results from Examples 6-8 confirm that even with a reduction in the amount of oligosaccharides added compared to 8.0% by mass, a significant improvement was achieved.

[0205] Comparing the results of Example 7 and Example 8, which contain both chitin oligosaccharides and cellulose oligosaccharides, Example 7, which contains cellulose oligosaccharides (1), shows a higher developmental effect compared to Example 8, which contains cellulose oligosaccharides (2). Therefore, it can be confirmed that using oligosaccharides with high branching degree results in a higher developmental effect.

[0206] <Storage Stability Test>

[0207] Regarding the chitin oligosaccharides and cellulosic oligosaccharides (1) produced by the above method, the freeze-dried powders were dissolved in water at a sugar concentration (the concentration of cellulosic oligosaccharides (1) also includes xylan hydrolysate) of 5% by mass to prepare sample solutions. The presence or absence of turbidity and the turbidity of the sample solutions were observed immediately after preparation and after storage for 7 days. The results are shown in Table 5.

[0208] The sample solution is preserved by filling a 50 mL container with 40 mL of the sample solution and placing it in a constant temperature bath set at 30 °C.

[0209] The turbidity was determined using the following method. A well-dispersed sample solution (sample 1) and a sample solution of sample 1 filtered through a 0.45 μm membrane (sample 2) were prepared. Each sample was added to a 1 cm square cuvette, and the absorbance at a wavelength of 660 nm was measured. The turbidity was calculated from the measured absorbance using the following formula.

[0210] Turbidity = (Absorbance of Sample 1) - (Absorbance of Sample 2)

[0211] Table 5

[0212]

[0213] As shown in Table 5, chitin oligosaccharides and cellulose oligosaccharides (1) did not become cloudy after 7 days of storage, and were particularly useful as spreading agents.

[0214] Industry availability

[0215] By using the spreading agent of the present invention, the adhesion of fertilizer components and agricultural agents to plants can be effectively improved.

Claims

1. Use of oligosaccharides in the manufacture of spreading agents, said oligosaccharides comprising chitin oligosaccharides, cellulose oligosaccharides, and xylooligosaccharides. The chitin oligosaccharide is a chitin oligosaccharide in which at least a portion of the glycosidic bonds include α-1,6-glycosidic bonds, and the proportion of the α-1,6-glycosidic bonds to all polymeric bonds contained in the chitin oligosaccharide is 5 to 30%.

2. According to claim 1, the number-average molecular weight of the chitin oligosaccharide is 420 to 2050.

3. The use according to claim 1, wherein the cellulose oligosaccharide is a cellulose oligosaccharide in which at least a portion of the glycosidic bonds comprises α-1,6-glycosidic bonds.

4. In the use according to claim 3, the ratio of the α-1,6-glycosidic bond to all polymeric bonds contained in the cellulose oligosaccharide is 1 to 50%.

5. In the use according to claim 1, the number-average molecular weight of the cellulose oligosaccharide is 340 to 1640.

6. According to the use of claim 1, relative to the total content of chitin oligosaccharides, cellulose oligosaccharides and xylooligosaccharides of 100% by mass, the proportion of each oligosaccharide is 10-50% by mass of chitin oligosaccharides, 10-50% by mass of cellulose oligosaccharides and 10-60% by mass of xylooligosaccharides.

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