JP5459763B2 - Insecticide composition and spray insecticide - Google Patents

Description

The present invention relates to an insecticide composition and a spray insecticide.

  Conventionally, insecticides are used for prevention of epidemics, control of harmful and unpleasant insects, agricultural use, horticultural use, and the like. Due to the ease of application, spray insecticides are preferred and used especially at home.

  As a conventional spray-type insecticide, an insecticide composition containing a solvent such as kerosene or kerosene has been disclosed for the purpose of dissolving an insecticide component as a component (Patent Document 1, Patent Document 2). Insecticide compositions formulated with solvents have problems such as the risk of flammability and odor of the solvents. A method for preparing a suspension composition has been proposed (Patent Document 3).

JP 2005-60295 A JP 2008-94769 A JP 2000-119103 A

However, as described above, those described in Patent Documents 1 and 2 have problems such as the danger of ignition due to the solvent to be blended and the odor of the solvent.

In the thing of patent document 3, although the problem resulting from solvent mixing is solved,
There is no mention of whether the composition can be sprayed.
Furthermore, in order to stably emulsify and suspend an insecticide active ingredient in water instead of blending a solvent, a large amount of surfactant is added as an emulsifier, which is not economical. When used outdoors, since there is no water resistance, there is a problem that the insecticide composition applied by rain or moisture flows out and the sustainability of the insecticidal effect is lowered.
Furthermore, since the viscosity of the insecticide composition is low in the conventional ones described in Patent Documents 1 to 3, liquid dripping after application occurs, and when the insecticide composition is applied by spraying the insecticide composition directly on the pest. , Poor adherence to pest control insects, worsening insecticidal effect. When applied to the habitat of the pests, especially when applied to a vertical surface or pest nest, there is a problem that the insecticidal composition is not effectively used due to liquid dripping and the insecticidal effect is reduced. It was.
If a thickener is added to increase the viscosity of the insecticide composition for the purpose of solving the problem of such dripping, there is a problem that spraying becomes difficult this time.

  The present invention has been made in view of such circumstances, and there is no problem such as danger of ignition or solvent odor, excellent water resistance, no dripping, and good sprayability. And it aims at provision of the spray type insecticide using the same.

In order to achieve the above object, the first gist of the present invention is an insecticide composition containing the following components (A), (B) and (C).
(A) Cellulose fibers having a number average fiber diameter of 2 to 150 nm, the cellulose having a cellulose I-type crystal structure, and the hydroxyl group at the C6 position of the glucose unit in the cellulose molecule is selectively oxidized to form an aldehyde Cellulose fiber (B) pesticide component which has been modified into a group and a carboxyl group and the amount of carboxyl group is 0.6 to 2.0 mmol / g (however, it is used for the purpose of protecting insect repellent components and essential oils, and crops) Except in cases.)
(C) Water That is, the present inventors have disclosed an insecticide composition which has no problems such as danger of ignition and solvent odor, is excellent in water resistance, does not drip, and has good sprayability. In order to obtain the spray type insecticide used, earnest research was repeated. In the course of the research, the cellulose fiber has a number average fiber diameter of 2 to 150 nm, the cellulose has a cellulose I-type crystal structure, and the hydroxyl group at the C6 position of the glucose unit in the cellulose molecule is selectively oxidized. If the cellulose fiber is modified to aldehyde group and carboxyl group, and the amount of carboxyl group is 0.6 to 2.0 mmol / g, it is excellent in water resistance, does not cause dripping, and has sprayability. The present invention was found out to be satisfactory.

The insecticide composition of the present invention is a cellulose fiber having a number average fiber diameter of 2 to 150 nm, and the cellulose has a cellulose I-type crystal structure, and the hydroxyl group at the C6 position of the glucose unit in the cellulose molecule is selected. The above-mentioned specific cellulose fiber is conventionally known by blending cellulose fiber that is oxidized and modified to aldehyde group and carboxyl group, and the amount of carboxyl group is 0.6-2.0 mmol / g It is possible to provide sprayable sprayable pesticides due to its large thixotropy index compared to the thickeners that are present, and when sprayed directly on the pests to be controlled, the pesticide composition to the pests Adhesion efficiency is good, and when sprayed on the application object, dripping does not occur even on a vertical surface, and the use efficiency of the insecticide composition is high. The insecticidal performance is high and the insecticidal effect lasts for a long time.
Furthermore, the insecticide composition of the present invention is for dissolving the insecticide component due to the high thixotropy index of the above-mentioned specific cellulose fiber and good emulsification dispersibility with respect to the insecticide component which is generally an oily substance. Water-based insecticide composition can be made without reducing or blending solvents such as kerosene and kerosene, so the emulsion dispersion stability of the preparation is excellent, the solvent odor of the preparation is reduced, and safety to the human body , Exerts an excellent effect of excellent safety during use. In addition, the above-mentioned specific cellulose fibers are excellent in the ability to emulsify and disperse oily substances in water, so even if the solvent such as kerosene or kerosene for dissolving the insecticide component is not reduced or blended, Since it is possible to reduce or not add the amount of emulsifier (surfactant) for emulsifying and dispersing the insecticide component in the aqueous system, it is economical, and when the insecticide composition is used outdoors, The water resistance is improved, and the outflow of the insecticide composition applied by rain or moisture is reduced, and as a result, the excellent effect of sustaining the insecticidal effect is exhibited.

  Next, the form for implementing this invention is demonstrated.

  The insecticide composition of the present invention can be obtained using a specific cellulose fiber (component A), an insecticide component (component B), and water (component C).

  The specific cellulose fiber (component A) is a cellulose fiber having a number average fiber diameter of 2 to 150 nm, and the cellulose has a cellulose I-type crystal structure and a hydroxyl group at the C6 position of the glucose unit in the cellulose molecule. Is a cellulose fiber which is selectively oxidized and modified to aldehyde groups and carboxyl groups, and the amount of carboxyl groups is 0.6 to 2.0 mmol / g. Hereinafter, the cellulose fibers used in the composition of the present invention will be described in more detail.

  The specific cellulose fiber (component A) is a fiber obtained by surface oxidizing a cellulose solid raw material derived from a natural product having an I-type crystal structure and miniaturizing it to nano size. Cellulose derived from natural products, which is the raw material, has almost no exception, because nanofibers called microfibrils are bundled into a high-order structure, so it cannot be easily refined and dispersed to nano size as it is. . The above-mentioned specific cellulose fiber (component A) is partially dispersed by oxidizing part of its hydroxyl groups and introducing aldehyde groups and carboxyl groups, weakening the hydrogen bonds between the surfaces that are the driving force of strong cohesion between microfibrils. Processed and refined to nano size.

The number average fiber diameter of the specific cellulose fiber (component A) is 2 to 150 nm. From the viewpoint of dispersion stability, the number average fiber diameter is more preferably 3 to 80 nm. If the number average fiber diameter is less than 2 nm, it is essentially dissolved in the dispersion medium. Conversely, if the number average fiber diameter exceeds 150 nm, the dispersion stability of the cellulose fiber itself is poor, and cellulose fibers are blended. Functionality due to cannot be expressed.
The number average fiber diameter can be measured, for example, as follows. That is, after a sample diluted with water added to the specific cellulose fiber (component A) is dispersed, it is cast on a carbon film-coated grid that has been hydrophilized and observed with a transmission electron microscope (TEM). The number average fiber diameter and the maximum fiber diameter can be measured and calculated from the obtained image.
The cellulose constituting the specific cellulose fiber (component A) has an I-type crystal structure, for example, in the diffraction profile obtained by wide-angle X-ray diffraction image measurement, Theta can be identified by having typical peaks at two positions near 22 to 23 °.
The amount of the carboxyl group of the specific cellulose fiber (component A) is preferably in the range of 0.6 to 2.0 mmol / g. When the amount of the carboxyl group is less than 0.6 mmol / g, the dispersion stability of the cellulose fibers is poor, the cellulose fibers may be precipitated, and the dispersion stability of the hydrophobic solid is lowered. When the amount of the carboxyl group is 2.0 mmol / g or more, the water-solubility of the cellulose fiber becomes strong and the feeling of use tends to be lowered.
The measurement of the carboxyl group amount of the specific cellulose fiber (component A) can be performed, for example, by potentiometric titration. That is, the dried cellulose fiber is dispersed in water, a 0.01N aqueous sodium chloride solution is added, and the cellulose fiber is dispersed by sufficiently stirring. Next, 0.1N hydrochloric acid solution is added until the pH reaches 2.5 to 3.0, and 0.04N aqueous sodium hydroxide solution is added dropwise at a rate of 0.1 ml / min. The amount of carboxyl groups can be calculated from the difference between the neutralization point of excess hydrochloric acid and the neutralization point of carboxyl groups derived from cellulose fibers.

In addition, adjustment of the said carboxyl group amount can be performed by controlling the addition amount and reaction time of the co-oxidant used at the oxidation process of a cellulose fiber so that it may mention later.
Whether or not only the hydroxyl group at the C6 position of the glucose unit constituting the specific cellulose fiber (component A) is selectively oxidized to an aldehyde group and a carboxyl group can be confirmed by, for example, ¹³ C-NMR analysis. . That is, the 62 ppm peak corresponding to the C6 position of the primary hydroxyl group of the glucose unit, which can be confirmed on the ¹³ C-NMR chart of cellulose before oxidation, disappears after the oxidation reaction, and instead a peak derived from the carboxyl group at 178 ppm. It can be confirmed by appearing.
Next, an insecticide component (component B) is used with the said specific cellulose fiber (component A) for the insecticide composition of this invention.
The above-mentioned insecticide component (component B) is not particularly limited. For example, the insecticide active ingredient described in the Agricultural Handbook published by the Japan Plant Protection Association (2008 edition), organophosphorus insecticide, carbamate Insecticides, pyrethroid insecticides, nereistoxin insecticides, neonicotinoid insecticides, insect growth regulators, other synthetic insecticides, natural insecticides, acaricides, nematicides, fumigants, Examples include biologically derived insecticides.
More specifically, examples of the compound names include dinotefuran, d, d-T-cyphenothrin, trichlorfone, cartap, acetamiprid, nitenpyram, imidacloprid, nitenpyram, thiacloprid, clothianidin, thiamethoxam, propoxurine, pymetrozine, fenitrothion, fenthione, methofurtoline, Insect chrysanthemum extract, pyrethrin, d-arethrin, phthalthrin, framethrin, praretrin, terrareslin, resmethrin, permethrin, phenothrin, cypermethrin, cyphenothrin, transfluthrin, fenfluthrin, empentrin, pyrimiphosmethyl, fenitrothion, methofurthrone, methofultrion , Methoxadiazone, S-1295, a Examples include, but are not limited to, miprothrin, fipronil, methoprene, S-hydroprene, pyriproxyfen, 2- [1-methyl-2- (phenoxyphenoxy) ethoxy] pyridine, diflubenzuron, teflubenzuron, and the like.

In the insecticide composition of the present invention, water (component C) is used in addition to the specific cellulose fiber (component A) and the insecticide component (component B). In the insecticide composition of the present invention, the remaining amount excluding the contents of cellulose fiber (component A), insecticide component (component B) and the following optional components is the content of water (component C).
Arbitrary components may be added to the insecticide composition of the present invention as long as the effect thereof is not hindered.
The optional components are as follows. That is, clay minerals, fillers; fillers, pigments, dyes; surfactants, alcohols, esters, ketones, ethers, hydrocarbons, aromatics, and other water-miscible solvents and Solvents immiscible with water; diol compounds, glycerin and derivatives thereof, glycols and saccharides such as pentaerythritol, sorbitol, xylitol, sucrose, glucose, fructose; natural water-soluble polymers, synthetic water-soluble polymers, cellulose derivatives Water-soluble polymers such as acrylic polymers, silicone oils, vegetable oils, animal oils, synthetic oils, etc .; preservatives / storage stabilizers, inorganic salts, UV screening agents, latexes, emulsions, Examples include foaming agents, pH adjusting agents, fragrances and deodorants, herbal medicines, repellents such as DEET, bactericides, and fertilizers.
Among these optional components, surfactants are preferably added in the minimum necessary amount because they reduce the water resistance of the insecticide.
Among these optional components, the solvent is preferably added in the minimum necessary amount from the viewpoint of the safety and odor of the insecticide.
Among these optional components, the water-soluble polymer may reduce the sprayability of the insecticide, so that it is preferably added in the minimum necessary amount.

  Clay minerals that are optional components include alumina, zirconia, glazed clay, kaolinite, kaolin, calcium bentonite, chromite sand, silica sand, silica silica, zirconium silicate, silica powder, diatomaceous earth, aluminum nitride, barium carbonate , Saponite, diamond, colemanite, gadolinium oxide, lanthanum oxide, chamotte, calcined diatomaceous earth, shirasu, shirasu balloon, silicon carbide, zircon sand, zircon, zircon flower, aluminum hydroxide, zeolite, quartz glass powder, cerium abrasive, sericite , Sodium bentonite, sodium montmorillonite, boron carbide, silicon nitride, feldspar powder, porcelain stone, halosite, borax, magnesia, kibushi clay, wax stone, perlite, cement, and the like.

As optional fillers, pigments and dyes, zinc white, cuprous oxide, lead monoxide, whisker-like calcium carbonate, watching red, mica, chlorine-based titanium oxide pigment, oil furnace black, yellow lead, yellow oxidation Iron, oxysulfide phosphor, kaolin clay, talc, stone, soapstone, cadmium yellow, cadmium red, calcium phosphate, glass beads, spherical alumina, ultramarine, wollastonite, wollastonite, fluorescent pigment, light calcium carbonate, Synthetic hydrotalcite, synthetic mica, graphite, black iron oxide, ultra-fine calcium carbonate, cobalt blue, cobalt green, cobalt purple, pepper powder, bitumen, thermal black, chromium oxide, titanium oxide (Atanus), titanium oxide (rutile), Terbium oxide, copper oxide, disazo yellow, heavy calcium carbonate, baked Clay, silk powder, slaked lime, red iron oxide, selenite, granulated carbon black, silicon carbide whisker, calcium carbonate, carbon fiber (powder), silicon nitride whisker, boron nitride, brown iron oxide, channel black, ultrafine alumina, Ultrafine zinc oxide, ultrafine titanium oxide, precipitated barium sulfate, iron black, natural graphite powder, natural earth graphite, copper phthalocyanine blue, copper phthalocyanine green, dolomite powder, nylon powder, permanent red, vanadate phosphor, Surface treatment barium sulfate, fine particle titanium oxide, fine particle barium sulfate, fine particle aluminum hydroxide, fast yellow 10G, carbon fluoride, bengara, polyethylene wax, white carbon, rounded alumina, molybdenum red, organic bentonite, fused silica, C stone, hexagonal boron nitride, and the like.
Examples of the surfactant that is an optional component include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.
Examples of the anionic surfactant include alkyl (carbon number 10 to 15) benzene sulfonate, alkyl (carbon number 6 to 18) sulfate ester, polyoxyalkylene (addition mole number 1 to 30 mole) alkyl (carbon number). 6-18) ether sulfate ester salt, fatty acid (carbon number 6-18) salt, alkane (carbon number 6-18) sulfonate, olefin (carbon number 8-18) sulfonate, naphthalene sulfonate condensate, Alkyl (carbon number 6-18) sulfosuccinic acid ester salt, polyoxyalkylene (addition mole number 1 mol-30 mol) alkyl (carbon number 6-18) ether sulfosuccinate, alkyl (carbon number 18-18) phosphate ester Salt, polyoxyalkylene (addition mole number 1 mol-30 mol) alkyl (carbon number 6-18) ether phosphate ester salt, poly Examples include reoxyalkylene (addition mole number 1 to 30 moles) alkyl (carbon number 6 to 18) ether acetate, and the like. Examples of the salt include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, amines such as ammonia and alkanolamine, and the like.
Examples of the nonionic surfactant include polyoxyalkylene (addition mole number 1 to 50 mol) alkyl (carbon number 6 to 18) ether, polyoxyalkylene (addition mole number 1 to 50 mol) acyl (carbon number 6). -18) ester, alkyl (carbon number 6-18) diethanolamide, polyoxyalkylene (addition mole number 1 mol-100 mol) triglyceride (fatty acid carbon number 6-18) ether, sorbitan fatty acid (carbon number 6-18) ester Sucrose fatty acid (carbon number 6-18) ester, polyoxyalkylene (addition mole number 1-50 mol) sorbitan fatty acid (carbon number 6-18) ester, alkyl (carbon number 6-18) polyglycoside, polyoxy And ethylene polyoxypropylene block polymer.

Examples of the cationic surfactant include monoalkyl (carbon number 6-18) amine salt, dialkyl (carbon number 6-18) amine salt, trialkyl (carbon number 6-18) amine salt, alkyl (carbon number 6-18). ) Trimethylammonium salt, dialkyl (C6-18) dimethylammonium salt, alkyldimethylbenzylammonium salt, alkyl (C6-18) dimethylaminopropylamide, and the like. Examples of the salt include halogens such as chlorine and bromine.
Examples of the amphoteric surfactant include alkyl (carbon number 6-18) betaine, fatty acid (carbon number 6-18) amidopropyl betaine, 2-alkyl (carbon number 6-18) -N-carboxylmethyl-N-hydroxyethyl. -Imidazolinium betaine, alkyl (C6-C18) diethylenetriaminoacetic acid, dialkyl (C6-C18) diethylenetriaminoacetic acid, alkyl (C6-C18) amine oxide, etc. are mentioned.

  The said specific cellulose fiber (component A) can be produced as follows, for example. That is, sodium bromide and an N-oxy radical catalyst are added to a slurry of natural cellulose, such as wood pulp, dispersed in water and dispersed and dissolved with sufficient stirring. Next, a co-oxidant such as a sodium hypochlorite aqueous solution is added, and the reaction is carried out while dropping a 0.5 N aqueous sodium hydroxide solution so as to maintain a pH of 10 to 11 until there is no pH change. In order to remove unreacted raw materials, catalysts and the like from the slurry obtained by the above reaction, purification is performed by washing with water and filtering. The target cellulose fiber is obtained as an aqueous dispersion of a specific cellulose fiber having an oxidized fiber surface.

  Examples of the N-oxy radical catalyst include 2,2,6,6-tetramethylpiperidine nooxy radical (TEMPO) and 4-acetamido-TEMPO. Particularly preferred is 2,2,6,6-tetramethylpiperidine nooxy radical (TEMPO). The addition amount of the N-oxy radical catalyst is sufficient as a catalytic amount, preferably 0.1 to 4 mmol / l, more preferably 0.2 to 2 mmol / l.

  Examples of the co-oxidant include hypohalous acid or a salt thereof, halous acid or a salt thereof, perhalogen acid or a salt thereof, hydrogen peroxide, a perorganic acid, and the like. These may be used alone or in combination of two or more. Of these, alkali hypohalites such as sodium hypochlorite and sodium hypobromite are preferable. And when using the said sodium hypochlorite, it is preferable in terms of reaction rate to advance reaction in presence of alkali bromide metals, such as sodium bromide. The addition amount of the alkali metal bromide is about 1 to 40 times mol, preferably about 10 to 20 times mol for the N-oxy radical catalyst.

  The insecticide composition of the present invention is obtained by mixing an aqueous dispersion of cellulose fibers obtained as described above, an insecticide component, and, if necessary, concentration-adjusting water and other optional additives. It is obtained by preparing an insecticide composition by dispersing and filling the resulting insecticide composition into a container.

There are no restrictions on the mixing method, but for example, selected from vacuum emulsifiers, dispersers, propeller mixers, kneaders, wet pulverizers, blenders, homogenizers, ultrasonic homogenizers, colloid mills, bead mills, sand mills, high-pressure homogenizers, ultra-high pressure homogenizers, etc. Can be used. The type and operating conditions of the mixing / dispersing apparatus are selected in accordance with the physicochemical properties of any additive and so as to obtain the desired physical properties of the composition.
For example, a highly transparent composition can be obtained by using a device having a strong dispersion force such as an ultrahigh pressure homogenizer during mixing.
The compounding quantity of an insecticide component (component B) changes with application objects. For extermination of harmful pests and unpleasant pests other than horticulture and agriculture, the range is usually 0.01% to 5%, preferably 0.05% to 3%. In horticultural / agricultural applications, it is usually in the range of 0.00001% to 3%, preferably 0.0001% to 1%. Below this range, a sufficient insecticidal effect cannot be obtained, and even if added above this range, an insecticidal effect sufficient for the amount added cannot be obtained.
The amount of the specific cellulose fiber (component A) is usually 0.1% to 5%, preferably 0.2% to 3%. If it is 0.1% or less, the viscosity of the insecticide composition is low, and dripping occurs. If it is 5% or more, the viscosity of the insecticide composition is too high, and handling during production deteriorates.
The viscosity of the insecticide composition of the present invention is in the range of 1,000 mPa · s to 100,000 mPa · s, preferably in the range of 2,000 mPa · s to 80,000 mPa · s.

  Viscosity here refers to a rotor number 4 (viscosity less than 80,000 mPa · s) or rotor number 5 (viscosity 80,000 mPa · s or more), 2.5 rpm at 25 ° C. using a BH viscometer. The viscosity measured after 180 seconds.

When the viscosity of the insecticide composition of the present invention is increased to finish it in a gel or cream form, it can be dealt with by increasing the amount of the specific cellulose fiber (component A) added. On the contrary, when it is desired to have fluidity, the amount of the specific cellulose fiber (component A) added may be reduced within a range in which liquid dripping does not occur.

The spray container filled with the insecticide composition of the present invention is not limited in any way, and can be easily filled with the insecticide composition of the present invention as a container having a spray / spray function and functions as a spray. However, in view of versatility and high spray accuracy, the following three spray containers (1) to (3) are particularly preferable.
(1) Dispenser-type spray container equipped with a sprayable pump-type nozzle: This spray container can be sprayed at atmospheric pressure, does not require pressurized gas, etc., and has a relatively simple container structure, so it is safe. It is a high and portable spray container. The structure is composed of an extrusion pump type nozzle equipped with a suction type tube and a screw type container which is fixed and filled with contents. The dispenser-type spray container here depends on the hole diameter of the pump-type nozzle and the pumping volume per pump to enhance the spray function, but these conditions depend on the application object and the target pest. Select and adjust.
(2) Trigger-type spray container: A trigger-type spray container is equipped with a pistol-type trigger-type spray device at the mouth of the container body that fills the contents. It is highly versatile. The trigger-type spray container referred to here includes all modified trigger-type spray containers in order to enhance the spray function.
(3) Aerosol-type spray container: The aerosol-type spray container enables continuous spraying that cannot be realized by the above two spray devices by filling the container with a propellant. The aerosol-type spray container here includes all the improvements made to the spray device portion of the aerosol-type container. In general, the spray using this spray container enables finer mist compared to the above two sprays carried out under atmospheric pressure. Examples of the propellant used in the aerosol spray container include dimethyl ether, liquefied petroleum gas, carbon dioxide gas, nitrogen gas, argon gas, air, oxygen gas, and chlorofluorocarbon gas. These may be used alone or in combination of two or more. Used in combination.

  The insect pests of the insecticidal composition of the present invention are not limited, and include mosquitoes, gnats, moths, horn flies, mites, fleas, bedbugs, bees, abs, ants, white ants, tsutsugamushi, cockroaches, centipedes, scarabs, moths Sanitary pests and unpleasant pests such as squirrel, spider, slug, brackish beetle, snail, stink bug, gejigeji, etc. , Scarlet beetle, Caterpillar, Shibatatsuga, Rice-spotted leaffly, Rice-spotted leaffly, Bean-spotted leaffly, Citrus-winged leafhopper, Golden-winged moth, Green-spotted moth, Awanomiga, Shiba-Osoue-shi, Gomadara-kamikiri, Kibo-shi-kamikiri, Baga, Bean beetle, White-faced spider moth, Uridae, Nashihime-shikui, Peach-spotted moth, Prunus serrata, Prunus, Leafhopper, Aphid, Onsit Whitefly, Tsuya-okamemushi, Minami-kisami-mushima-mushima-mushima-mui-mushima-mami Examples include crop pests such as stag beetle, rice weevil, seed fly, nephide, scarab beetle, nematode, kissing flea beetle, onion flies, cricket, and the like.

  The application target of the insecticide composition of the present invention is not limited at all, and it is a pest for indoor control such as clothing, kitchen, floor, wall, furniture, and pest nests, exterior wall, screen door, roof, eaves, etc. Products, trees and ground in outdoor non-agricultural land, structures, agricultural land, agricultural crops, horticultural crops, and the like.

  Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples.

First, prior to Examples, cellulose fibers were prepared as follows [Creation of Cellulose Fibers T1 (for Examples)]
After adding 150 g of water, 0.025 g of sodium bromide and 0.025 g of 2,2,6,6-tetramethylpiperidinenooxy radical (TEMPO) to 2 g (dry weight) of softwood pulp, the mixture was sufficiently stirred and dispersed. A 13% by weight aqueous sodium hypochlorite solution was added so that the amount of sodium hypochlorite was 5.4 mmol / g-cellulose with respect to 1 g of pulp, and 0.5 to maintain the pH at 10-11. The reaction was continued until no pH change was observed while dropping a normal sodium hydroxide solution. (Reaction time is 120 minutes) After completion of the reaction, 0.1N hydrochloric acid was added for neutralization, followed by purification by repeated filtration and washing to obtain cellulose fibers having oxidized fiber surfaces.
[Creation of cellulose fibers T2, T3 (for examples), cellulose fibers H1, H2 (for comparative examples)]
Each cellulose fiber was produced according to production of cellulose fiber T1, except that the amount of sodium hypochlorite aqueous solution to be added and the reaction time were changed as shown in Table 1 below.

このようにして得られたセルロース繊維T１〜T3（実施例用）、セルロース繊維H1、H2（比較例用）を用い、下記の基準に従って各項目の測定を行った。これらの結果を、上記の表１に併せて示した。
<数平均繊維径>
セルロース繊維に水を加え希釈した試料を真空乳化装置を用いて１２０００rpmで１５分間分散させた後、親水化処理済みのカーボン膜被覆グリッド上にキャストして、これを透過型電子顕微鏡（TEM）(日本電子社製、JEM-1400)で観察し、得られた画像（倍率１００００倍または５００００倍）から、数平均繊維径を測定算出した。
<カルボキシル基量の測定>
セルロース繊維表面のカルボキシル基の定量は、電位差滴定により行った。すなわち、乾燥させたセルロース繊維０．３ｇを水５５ｍｌに分散させ、０．０１規定の塩化ナトリウム水溶液５ｍｌを加えて、十分に攪拌してセルロース繊維を分散させた。つぎに、０．１規定の塩酸溶液をｐH２．５〜３．０になるまで加え、０．０４規定の水酸化ナトリウム水溶液を毎分０．１ｍｌの速度で滴下し、得られたｐH曲線から過剰の塩酸の中和点と、セルロース繊維由来のカルボキシル基の中和点との差から、カルボキシル基量を算出した。
<アルデヒド基量の測定>
セルロース繊維（試料）表面のアルデヒド基量は、以下のようにして測定した。
すなわち、資料を水に分散させ、酢酸酸性下で亜塩酸ナトリウムを用いてアルデヒド基を全てカルボキシル基まで酸化させた試料のカルボキシル基量を測定し、酸化前のカルボキシル基量との差をもってアルデヒド基量とした。
<セルロースＩ型結晶構造の確認>
上記各セルロース繊維がＩ型結晶構造を有することの確認を次のようにして確認した。すなわち、広角X線回折像測定により得られた回折プロファイルにおいて、２シータ＝１４〜１７°付近と、２シータ＝２２〜２３°付近の２つの位置に典型的なピークを持つことからＩ型結晶構造を有することを確認した。その結果、上記セルロース繊維T１〜T3（実施例用）、セルロース繊維H1、H2（比較例用）はＩ型結晶構造を有することを確認した。
<アルデヒド基およびカルボキシル基の確認>
各セルロース繊維を構成するグルコースユニットのC6位の水酸基のみが選択的にアルデヒド基およびカルボキシル基に酸化されているかどうか、次のようにして確認した。すなわち、酸化前のセルロースの¹³C-NMRチャートで確認されたグルコース単位の１級水酸基のC6位に相当する６２ｐｐｍのピークが、酸化反応後は消失し、代わりに１７８ppmにカルボキシル基に由来するピークが現れたことを確認した。その結果、上記セルロース繊維T１〜T3（実施例用）、セルロース繊維H1、H2（比較例用）は、セルロース分子中のグルコースユニットのC6位の水酸基が酸化されてなるカルボキシル基およびアルデヒド基も有することが確認された。

Using the cellulose fibers T1 to T3 (for examples) and the cellulose fibers H1 and H2 (for comparative examples) obtained in this way, each item was measured according to the following criteria. These results are also shown in Table 1 above.
<Number average fiber diameter>
A sample diluted by adding water to cellulose fiber was dispersed at 12000 rpm for 15 minutes using a vacuum emulsifier, and then cast on a carbon film-coated grid that had been subjected to a hydrophilic treatment, and this was subjected to a transmission electron microscope (TEM) ( JEM-1400 (manufactured by JEOL Ltd.) was observed and the number average fiber diameter was measured and calculated from the obtained image (magnification 10,000 times or 50000 times).
<Measurement of carboxyl group content>
The quantification of the carboxyl group on the cellulose fiber surface was performed by potentiometric titration. That is, 0.3 g of the dried cellulose fiber was dispersed in 55 ml of water, 5 ml of 0.01N sodium chloride aqueous solution was added, and the mixture was sufficiently stirred to disperse the cellulose fiber. Next, 0.1N hydrochloric acid solution is added until the pH reaches 2.5 to 3.0, and 0.04N aqueous sodium hydroxide solution is added dropwise at a rate of 0.1 ml / min. The amount of carboxyl groups was calculated from the difference between the neutralization point of excess hydrochloric acid and the neutralization point of carboxyl groups derived from cellulose fibers.
<Measurement of aldehyde group amount>
The amount of aldehyde groups on the surface of the cellulose fiber (sample) was measured as follows.
In other words, the amount of carboxyl groups in a sample in which the sample was dispersed in water and all aldehyde groups were oxidized to carboxyl groups using sodium nitrite under acetic acid acidity was measured, and the difference from the amount of carboxyl groups before oxidation was determined. The amount.
<Confirmation of cellulose I type crystal structure>
Confirmation that each of the above cellulose fibers has an I-type crystal structure was confirmed as follows. That is, in the diffraction profile obtained by the wide-angle X-ray diffraction image measurement, there are typical peaks at two positions of 2 theta = 14 to 17 ° and 2 theta = 22 to 23 °. It was confirmed to have a structure. As a result, it was confirmed that the cellulose fibers T1 to T3 (for Examples) and the cellulose fibers H1 and H2 (for Comparative Examples) have an I-type crystal structure.
<Confirmation of aldehyde group and carboxyl group>
Whether or not only the hydroxyl group at the C6 position of the glucose unit constituting each cellulose fiber was selectively oxidized to an aldehyde group and a carboxyl group was confirmed as follows. That is, the 62 ppm peak corresponding to the C6 position of the primary hydroxyl group of the glucose unit confirmed by the ¹³ C-NMR chart of cellulose before oxidation disappeared after the oxidation reaction, and instead a peak derived from the carboxyl group at 178 ppm. Confirmed that appeared. As a result, the cellulose fibers T1 to T3 (for Examples) and the cellulose fibers H1 and H2 (for Comparative Examples) also have a carboxyl group and an aldehyde group formed by oxidizing the hydroxyl group at the C6 position of the glucose unit in the cellulose molecule. It was confirmed.

Next, using the cellulose fibers (T1 to T3, H1, H2) obtained above, a spray insecticide was prepared as follows.
[Example 1]
The cellulose fiber T1 was measured to be 1.2 parts by weight (hereinafter abbreviated as “parts”) in terms of solid content, 1.2 parts of imiprotrine and 0.1 part of resmethrin as insecticide components, and 100 parts by adding water. Next, it processed at 12000 rpm for 15 minutes using the vacuum emulsifier, and obtained the insecticide composition. The obtained insecticide composition was filled in a trigger spray container having a capacity of 500 ml to produce a spray insecticide.
[Examples 2-7, Comparative Examples 1-4]
As shown in Table 2 below, a spray insecticide was produced in the same manner as in Example 1 except that the type and amount of each component were changed.

Each spray type insecticide thus obtained was used to evaluate each property according to the following criteria. These results are also shown in Table 2 above.
(Evaluation of viscosity)
The viscosity of the insecticidal composition measured after 180 seconds at 25 ° C. with rotor number 5 and 2.5 rpm was measured using a BH viscometer.
(Evaluation of dispersion stability)
The obtained insecticide composition was allowed to stand at 40 ° C. for 1 month, and then the separation state of the composition was visually determined according to the following criteria.
(Double-circle): Separation is not recognized at all.
○: Almost no separation is observed.
Δ: Slight separation is observed.
X: Completely separated.
(Evaluation of sprayability)
The obtained spray insecticide was sprayed, and the state of fog dispersion was visually determined according to the following criteria.

◎: Sprayed as a fine mist ○: Sprayed as a droplet △: Spouted into a rod shape ×: Dripping from the nozzle or not coming out of the nozzle (evaluation of liquid sag)
The obtained spray insecticide was sprayed on a vertical surface, and the degree of dripping of the insecticide composition adhering to the vertical surface was visually determined according to the following criteria.
A: No dripping at all O: Almost no dripping Δ: There is a slight dripping X: Clearly dripping (evaluation of water resistance)
The obtained insecticide was sprayed on a glass plate and dried to form a film, and then immersed in water at 40 ° C., and the collapsed state of the film was visually determined according to the following criteria.
A: The film does not collapse at all.
○: The film is hardly disintegrated.
Δ: The film disintegrates after a while.
X: The film disintegrates immediately.

As is clear from the results in Table 2 above, all of Examples 1 to 7 were excellent in dispersion stability, sprayability, liquid dripping property, and water resistance. In addition, the number average fiber diameter of the cellulose fibers (T1 to T3) contained in the products of Examples 1 to 3 was measured and calculated by the method described above, and as a result, there was no substantial change from before the blending of the insecticide components. It was. In addition, the present inventors replaced the cellulose fibers T1 to T3 with a cellulose fiber having a carboxyl group amount of 0.6 mmol / g (lower limit) and a cellulose fiber having a carboxyl group amount of 2.0 mmol / g (upper limit). It has been confirmed by experiments that the same excellent effects as in the case of using the cellulose fibers T1 to T3 can be obtained even when using.
On the other hand, instead of the cellulose fibers T1 to T3 of the example products, the comparative example 1 product using the cellulose fibers H1 has a low carboxyl group content of 0.5 mmol / g in the cellulose fibers. The viscosity was as low as 600 mPa · s, and the dispersion stability and dripping property were inferior to those of the examples. When cellulose fiber H2 was used, the amount of carboxyl groups in the cellulose fiber was as high as 2.2.mmol / g, so that the dispersion stability and spray water resistance were inferior to those of the examples.

  Instead of the cellulose fibers T1 to T3 of the example product, the comparative example product 3 using xanthan gum was inferior to the example product in terms of dispersion stability, sprayability, liquid dripping property and water resistance.

  The comparative product 4 using polyoxyethylene lauryl ether as an emulsifying dispersant instead of the cellulose fibers T1 to T3 of the product in Example has insufficient spraying of the viscosity of the insecticide composition, so that the sprayability is good. However, the dripping property and water resistance were inferior to those of Examples.

As an application example of the present invention, it can be used as a spray-type insecticide for home use, business use, industrial use, for prevention of epidemics, harmful and unpleasant pests, agriculture, horticulture and the like.

Claims (3)

An insecticide composition comprising the following components (A), (B) and (C):
(A) Cellulose fibers having a number average fiber diameter of 2 to 150 nm, the cellulose having a cellulose I-type crystal structure, and the hydroxyl group at the C6 position of the glucose unit in the cellulose molecule is selectively oxidized to form an aldehyde Cellulose fiber (B) pesticide component that has been modified into a group and a carboxyl group, and the amount of carboxyl group is 0.6 to 2.0 mmol / g (however, it is used for insect repellent components and essential oils, and for crop protection purposes) Except in cases.)
(C) Water   The insecticide composition according to claim 1, wherein the cellulose fiber as the component (A) is oxidized using a co-oxidant in the presence of an N-oxyl compound.   A spray-type insecticide filled with the insecticide composition of claim 1 or 2.