JP2016069293A - Insecticide composition and spray type insecticide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an insecticide composition having no problem such s danger of inflammation or odor of a solvent, excellent in water resistance, hardly generating liquid sag and good in spray property, and a spray type insecticide using the same.SOLUTION: There is provided an insecticide composition containing following (A), (B) and (C) components and having the content of (A) of 0.1 mass% or more and 3 mass% or less, a maximum value of viscosity (ηmax) measured at 20°C in a shear rate range including 1×10Sto 1×10Sat a measurement of a corn plate type rotary viscometer of ηmax≥1×10mPa s and a minimum value (ηmin) of ηmin≤1×10mPa s. (A) is a cellulose fiber having a number average fiber diameter of 2 nm or more and 500 nm or less, a substituent introduced into a hydroxyl group in a cellulose molecule, a substitution degree of 0.01 or more and 0.5 or less, I type and/or II type crystal structures, and an aspect ratio of 50 or more. (B) is an insecticide component. (C) is water.SELECTED DRAWING: None

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 a solvent mixing | blending is solved, there is no description about whether this 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 pests and low insecticidal efficiency. 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.
For the purpose of solving such a problem of dripping, if a thickener is added to increase the viscosity of the insecticide composition, there is a problem that spraying becomes difficult.

  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 an insecticide composition with good sprayability. The object is to provide a product and a spray-type insecticide using the same.

That is, this invention relates to the invention hung up below.
[1] The following (A), (B) and (C) components are contained, and the content of (A) is 0.1% by mass or more and 3% by mass or less. In the shear rate region including 1 × 10 ⁻³ S ⁻¹ to 1 × 10 ³ S ⁻¹ by measurement, the maximum viscosity value (ηmax) measured at 20 ° C. is ηmax ≧ 1 × 10 ⁴ mPa · s. An insecticide composition having a minimum value (ηmin) of ηmin ≦ 1 × 10 ² mPa · s.
(A) Cellulose fibers having a number average fiber diameter of 2 nm or more and 500 nm or less, wherein a substituent is introduced into the hydroxyl group in the cellulose molecule, the degree of substitution is 0.01 or more and 0.5 or less, Cellulose fibers having a crystal structure of type II and / or an aspect ratio of 50 or more.
(B) Insecticide component (C) Water [2] A spray insecticide filled with the above insecticide composition.

  The insecticide composition of the present invention can provide an insecticide that has a viscosity and can be sprayed, and when sprayed directly on a pest to be controlled, the adhesion efficiency of the insecticide composition to the pest is good, and the application target When sprayed on an object, even if it is a vertical surface, no dripping occurs and the use efficiency of the insecticide composition is high, so the insecticidal performance is high and the insecticidal effect lasts for a long time. .

Furthermore, the insecticide composition of the present invention has good emulsification and dispersibility with respect to the insecticide component, which is generally an oily substance, and does not reduce or add a solvent such as kerosene or kerosene for dissolving the insecticide component. Since it can be used as an agent composition, the solvent odor of the preparation is reduced, and an excellent effect of being excellent in safety to the human body and safety in use is exhibited.
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, embodiments of the present invention will be described in detail.

  The insecticide composition of the present invention can be obtained using specific (A) cellulose fibers, (B) insecticide components, and (C) water.

The cellulose fiber (A) of the present invention has a number average fiber diameter of 2 nm or more and 500 nm or less, a substituent is introduced into the hydroxyl group in the cellulose molecule, and the degree of substitution is 0.01 or more and 0.5 or less. , I-type and / or II-type crystal structures and an aspect ratio of 50 or more.
The number average fiber diameter is 2 nm to 500 nm, more preferably 2 nm to 150 nm. When the number average fiber diameter exceeds 500 nm, the cellulose fibers are settled, so that the functionality due to the blending of the cellulose fibers cannot be expressed.

  Here, the analysis of the said number average fiber diameter can be performed as follows, for example. Specifically, an aqueous dispersion of cellulose fibers having a solid content of 0.05 to 0.1% by mass was prepared, and the dispersion was cast on a carbon film-coated grid that had been subjected to a hydrophilic treatment, and a transmission electron microscope. (TEM) observation sample. In addition, when the fiber of the big fiber diameter outside this invention is included, you may observe the scanning electron microscope (SEM) image of the surface cast on glass. Then, observation with an electron microscope image is performed at a magnification of 5000 times, 10000 times, or 50000 times depending on the size of the constituent fibers. At that time, an axis having an arbitrary vertical and horizontal image width is assumed in the obtained image, and the sample and observation conditions (magnification, etc.) are adjusted so that 20 or more fibers intersect the axis. Then, after obtaining an observation image that satisfies this condition, two random axes, vertical and horizontal, per image are drawn on this image, and the fiber diameter of the fiber that intersects the axis is visually read. In this way, images of at least three non-overlapping surface portions are taken with an electron microscope, and the fiber diameter values of the fibers intersecting with each of the two axes are read (thus, at least 20 × 2 × 3 = 120). Information on the fiber diameter of the book is obtained). The number average fiber diameter is calculated from the fiber diameter data thus obtained.

  The substituent is not particularly limited as long as it is a substituent that generates an ether bond with a hydroxyl group in the cellulose molecule. Specific examples include carboxymethyl group, methyl group, ethyl group, cyanoethyl group, hydroxyethyl group, hydroxypropyl group, ethylhydroxyethyl group, hydroxypropylmethyl group and the like. Of these, a carboxymethyl group is preferred.

  The degree of substitution represents the average value of the number of moles of substituents per mole of anhydroglucose unit.

  The degree of substitution of the (A) cellulose fiber of the present invention is 0.01 or more and 0.5 or less, preferably 0.01 or more and 0.25 or less. When the degree of substitution is less than 0.01, it is difficult to defibrate cellulose fibers, and when it exceeds 0.5, the viscosity and dispersion stability are lowered, and the effects of the present invention cannot be exhibited.

  The (A) cellulose fiber of the present invention has a crystal structure of type I and / or type II. Having a crystal structure means that, for example, in a diffraction profile obtained by wide-angle X-ray diffraction image measurement, an X-ray diffraction pattern typical for cellulose type I or type II (type I: diffraction angle 2θ = 12.1 °, 19 .8 °, 22.0 °, type II: diffraction angle 2θ = 12.1 °, 19.8 °, 22.0 °).

  The (A) cellulose fiber of the present invention has an aspect ratio of 50 or more. More preferably, it is 100 or more. When the aspect ratio is less than 50, there is a problem that it is difficult for the gel-like composition to maintain the gel-like properties.

The aspect ratio of the cellulose can be measured, for example, by the following method, that is, a TEM image (magnification: magnification: cellulose is cast on a carbon film-coated grid that has been hydrophilized and then negatively stained with 2% uranyl acetate. The number average width of the short width and the number average width of the long width were observed. That is, the number average width of the shorter width and the number average width of the longer width are calculated according to the methods described above, and the aspect ratio is calculated according to the following formula (1) using these values. .

本発明の（Ａ）セルロース繊維を得るためには、下記に例示するセルロースを公知の方法を用いてアニオン変性させることが必要である。その一例として次のような製造方法をあげることができる。セルロースを原料とし、溶媒に重量で３〜２０倍の低級アルコール、具体的にはメタノール、エタノール、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブチルアルコール、イソブチルアルコール、ｔ−ブチルアルコール等の単独、又は２種以上の混合物と水の混合媒体を使用する。なお、低級アルコールの混合割合は、６０〜９５質量％である。マーセル化剤としては、セルロースのグルコース残基当たり０．５〜２０倍モルの水酸化アルカリ金属、具体的には水酸化ナトリウム、水酸化カリウムを使用する。セルロースと溶媒、マーセル化剤を混合してマーセル化処理を行う。このときの反応温度は０〜７０℃、好ましくは１０〜６０℃であり、反応時間は１５分〜８時間、好ましくは３０分〜７時間である。その後、カルボキシメチル化剤をグルコース残基当たり０．０５〜１０．０倍モル添加してエーテル化反応を行う。このときの反応温度は３０〜９０℃、好ましくは４０〜８０℃であり、反応時間は３０分〜１０時間、好ましくは１時間〜４時間である。

In order to obtain the cellulose fiber (A) of the present invention, the cellulose exemplified below needs to be anion-modified using a known method. The following manufacturing method can be mention | raise | lifted as the example. Cellulose is used as a raw material, and the solvent is 3 to 20 times lower alcohol, specifically methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, etc. Use a mixture of two or more mixtures and water. In addition, the mixing ratio of a lower alcohol is 60-95 mass%. As the mercerizing agent, 0.5 to 20 times moles of alkali metal hydroxide, specifically sodium hydroxide or potassium hydroxide is used per glucose residue of cellulose. Cellulose is formed by mixing cellulose, a solvent, and a mercerizing agent. The reaction temperature at this time is 0 to 70 ° C., preferably 10 to 60 ° C., and the reaction time is 15 minutes to 8 hours, preferably 30 minutes to 7 hours. Thereafter, the etherification reaction is carried out by adding 0.05 to 10.0 times mole of carboxymethylating agent per glucose residue. The reaction temperature at this time is 30 to 90 ° C., preferably 40 to 80 ° C., and the reaction time is 30 minutes to 10 hours, preferably 1 to 4 hours.

  The cellulose raw material of the present invention is a natural cellulose such as cellulose produced by microorganisms such as bleached or unbleached wood pulp, refined linter, and acetic acid bacteria, and cellulose is dissolved in some solvent such as a copper ammonia solution and a morpholine derivative. Examples include spun regenerated cellulose and fine cellulose that has been depolymerized by hydrolysis, alkali hydrolysis, enzymatic decomposition, explosion treatment, vibration ball mill treatment, or the like, or mechanically processed fine cellulose.

  The cellulose fiber (A) of the present invention can be obtained by fibrillating anion-modified cellulose with a high-pressure homogenizer or the like. A high-pressure homogenizer is a device that pressurizes a fluid with a pump and ejects it from a very delicate gap provided in a flow path. It is possible to emulsify, disperse, defibrate, grind, and make ultrafine particles by using total energy such as collision between particles and shear force due to pressure difference.

The treatment conditions with the homogenizer of the present invention are not particularly limited, but the pressure conditions are 30 MPa or more, preferably 100 MPa or more, more preferably 140 MPa or more. In addition, prior to defibration / dispersion treatment with a high-pressure homogenizer, if necessary, pretreatment of anion-modified cellulose is performed using a known mixing, stirring, emulsifying, and dispersing device such as a high-speed shear mixer. Is also possible.
Next, (B) an insecticide component is used with the said (A) cellulose fiber for the insecticide composition of this invention.

  The (B) insecticide component is not particularly limited. For example, an insecticide active ingredient, an organophosphorus insecticide, or a carbamate-based compound described in the Agricultural Handbook (2013 edition) published by the Japan Plant Protection Association Insecticides, pyrethroid insecticides, nereistoxin insecticides, neonicotinoid insecticides, insect growth regulators, other synthetic insecticides, natural insecticides, acaricides, nematicides, fumigants, organisms Derived insecticides, and the like.

  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, (C) water is used in addition to the above (A) cellulose fiber and (B) insecticide component. In the insecticide composition of the present invention, the remaining amount excluding the contents of (A) cellulose fiber, (B) insecticide component, and the following optional components is the content of (C) water.

  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 / deodorants, herbal medicines, repellents such as N, N-diethyl-m-toluamide, 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 mol to 30 mol) alkyl (carbon number 6 to 18) ether acetate. Examples of the salt include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, and amines such as ammonia and alkanolamine.

  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 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 blending amount of the (B) insecticide component varies depending on the application target. For the purpose of controlling harmful pests and unpleasant pests other than horticulture and agriculture, it is usually in the range of 0.01% by mass to 5% by mass, preferably 0.05% by mass to 3% by mass. In horticultural / agricultural applications, it is usually in the range of 0.00001 mass% to 3 mass%, preferably 0.0001 mass% to 1 mass%. If it is less than this range, a sufficient insecticidal effect cannot be obtained, and even if this range is added, an insecticidal effect sufficient for the amount added cannot be obtained.

In the insecticide composition of the present invention, the viscosity and the content ratio of the (A) cellulose fiber are adjusted to a specific range from the viewpoint of the size of the mother droplet. That is, in the present invention, the content ratio of the (A) cellulose fiber is 0.1% by mass or more and 3.0% by mass or less, and 1 × 10 ⁻³ S measured by a cone / plate type rotational viscometer. ⁻¹ to 1 × 10 ³ S ⁻¹ in a shear rate region, the maximum value of viscosity measured at 20 ° C. (ηmax ) Is ηmax It is set as ≧ 1 × 10 ⁴ mPa · s, and thereby, good spray application is possible without dripping. In the present invention, the minimum value (ηmin) of the viscosity is ηmin. Since it is set to ≦ 1 × 10 ² mPa · s, it is sprayed as fine mother droplets, and unevenness does not occur. Conversely, ηmax In the case of a low-viscosity composition having a value of less than 1 × 10 ⁴ mPa · s, the prevention of dripping of spray droplets cannot be expected, and ηmin When the value exceeds 1 × 10 ² mPa · s, the mother droplets become large and spray unevenness occurs. If the application density in spraying is relatively low, ηmax If ≧ 1 × 10 ⁴ mPa · s is satisfied, sufficient anti-drip property can be expected. Even if ≧ 1 × 10 ⁴ mPa · s is satisfied, it may happen that the prevention of dripping cannot be prevented. Therefore, the effect of the spray composition of the present invention, such as dripping prevention, can be prevented under all conditions of application by spraying. In order to achieve sufficient expression, it is preferable that η _max ≧ 5 × 10 ⁴ mPa · s. Also, at normal coating density, ηmin If it satisfies ≦ 1 × 10 ² mPa · s, spray unevenness will not occur, but if you want to spray very thinly and uniformly, ηmin ≦ 5 × 10 ¹ mPa · s is preferable. Further, in the spray composition of the present invention, as a range in which spraying can be stably performed, ηmax It is desirable that the value of does not exceed 1 × 10 ⁹ mPa · s.

  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 handled by increasing the amount of the (A) cellulose fiber. Conversely, when it is desired to provide fluidity, the amount of the (A) cellulose fiber added may be reduced within a range in which 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, the pumping volume per pump, etc. in order 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 Freon 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 fly, and cricket.

  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.

<Measurement method of substitution degree per glucose unit>
Cellulose fiber is prepared in a slurry of 0.6% by mass, 0.1M hydrochloric acid aqueous solution is added to adjust the pH to 2.4, and 0.05N sodium hydroxide aqueous solution is added dropwise until the pH reaches 11. The amount of carboxyl groups was measured from the amount of sodium hydroxide consumed in the neutralization step of a weak acid with a gradual change in electrical conductivity, and calculated using the following formula. The degree of substitution referred to here represents the average value of the number of moles of substituents per mole of anhydroglucose unit.

＜数平均繊維径の測定方法＞
セルロース繊維に水を加えて２質量％のスラリーとして、ディスパー型ミキサーを用いて回転数８，０００ｒｐｍで１０分間微細化処理を行った。各セルロース繊維の最大繊維径および数平均繊維径を、透過型電子顕微鏡（ＴＥＭ）（日本電子社製、ＪＥＭ−１４００）を用いて観察した。すなわち、各セルロース繊維を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た後、２％ウラニルアセテートでネガティブ染色したＴＥＭ像（倍率：１００００倍）から、先に述べた方法に従い、数平均繊維径を算出した。

<Measurement method of number average fiber diameter>
Water was added to the cellulose fiber to make a slurry of 2 mass%, and a finer treatment was performed for 10 minutes at a rotation speed of 8,000 rpm using a disper type mixer. The maximum fiber diameter and the number average fiber diameter of each cellulose fiber were observed using a transmission electron microscope (TEM) (JEM-1400, manufactured by JEOL Ltd.). That is, after each cellulose fiber was cast on a hydrophilized carbon film-coated grid and negatively stained with 2% uranyl acetate, the number average fiber diameter was determined according to the method described above. Was calculated.

<Confirmation method of crystal structure>
A wide-angle X-ray diffraction image was measured using an X-ray diffractometer (RINT-Ultima 3 manufactured by Rigaku Corporation), and an X-ray diffraction pattern typical of cellulose type I or type II (type I: (Diffraction angle 2θ = 12.1 °, 19.8 °, 22.0 °, type II: diffraction angle 2θ = 12.1 °, 19.8 °, 22.0 °) I decided.

<Aspect ratio measurement method>
From the TEM image (magnification: 10000 times) that was negatively stained with 2% uranyl acetate after the cellulose was cast on a hydrophilic membrane-coated carbon film grid, the number average width and the long width of the short width of cellulose The number average width of was observed. That is, the number average width of the shorter width and the number average width of the longer width are calculated according to the methods described above, and the aspect ratio is calculated according to the above-described formula (1) using these values. .

[Production Example 1]
To the stirrer, 200 g of pulp (LBKP, Nippon Paper Industries Co., Ltd.) in dry mass and 18 g of sodium hydroxide in dry mass were added, and water was added so that the pulp solid content concentration was 15%. Then, after stirring for 30 minutes at 30 ° C., the temperature was raised to 70 ° C., and 23 g (in terms of active ingredient) of sodium monochloroacetate was added. After reacting for 1 hour, the reaction product was taken out, neutralized and washed to obtain anion-modified cellulose having a substitution degree of 0.01 per glucose unit. Thereafter, water was added to the anion-modified pulp to a solid content concentration of 5%, and it was treated 5 times with a high-pressure homogenizer at 20 ° C. and a pressure of 140 MPa, and the number-average fiber diameter was 74 nm, the aspect ratio was 67, and the cellulose having a crystal structure A dispersion of fiber 1 was obtained.

[Production Example 2]
A dispersion of cellulose fiber 2 was obtained in the same manner as in Production Example 1 except that 176 g of sodium hydroxide and 234 g of sodium monochloroacetate (active ingredient conversion) were changed. In addition, the substitution degree per glucose unit of the obtained cellulose fiber was 0.10, the number average fiber diameter was 10 nm, the aspect ratio was 140, and it had a crystal structure.

[Production Example 3]
A dispersion of cellulose fiber 3 was obtained in the same manner as in Production Example 1, except that sodium hydroxide was changed to 308 g and sodium monochloroacetate was changed to 410 g (in terms of active ingredient). In addition, the substitution degree per glucose unit of the obtained cellulose fiber was 0.25, the number average fiber diameter was 6 nm, the aspect ratio was 160, and it had a crystal structure.

[Production Example 4]
A dispersion of cellulose fiber 4 was obtained in the same manner as in Production Example 1, except that the sodium hydroxide was changed to 9 g and the sodium monochloroacetate was changed to 12 g (converted to the active ingredient). In addition, the substitution degree per glucose unit of the obtained cellulose fiber was 0.005, the number average fiber diameter was 620 nm, the aspect ratio was 18, and it had a crystal structure.

[Production Example 5]
A dispersion of cellulose fiber 5 was obtained in the same manner as in Production Example 1, except that sodium hydroxide was changed to 476 g and sodium monochloroacetate was changed to 632 g (in terms of active ingredient). In addition, the substitution degree per glucose unit of the obtained cellulose was 0.6, the number average fiber diameter could not be measured, and no crystal structure was observed.

[Production Example 6]
A dispersion of cellulose fiber 6 was obtained in the same manner as in Production Example 1, except that 308 g of sodium hydroxide, 410 g of sodium monochloroacetate (converted to active ingredients), and the treatment with the high-pressure homogenizer were changed to 20 times. In addition, the substitution degree per glucose unit of the obtained cellulose fiber was 0.25, the number average fiber diameter could not be measured, and no crystal structure was observed.

[Production Example 7]
To a stirrer, 200 g of pulp (LBKP, manufactured by Nippon Paper Industries Co., Ltd.) in dry mass and 308 g of sodium hydroxide in dry mass were added, and water was added so that the pulp solid content concentration was 15%. Then, after stirring for 9 hours at 70 ° C., 410 g of sodium monochloroacetate (in terms of active ingredient) was added. After reacting for 1 hour, the reaction product was taken out, neutralized and washed to obtain anion-modified cellulose having a substitution degree of 0.28 per glucose unit. Thereafter, water was added to the anion-modified pulp to a solid content concentration of 5%, and it was treated 5 times with a high-pressure homogenizer at 20 ° C. and a pressure of 140 MPa to obtain a dispersion of cellulose fibers 7. The number average fiber diameter could not be measured, and no crystal structure was observed.

<Evaluation of insecticide composition>
(Manufacture of insecticide composition)
[Example 1]
Cellulose fiber 1 was measured to be 1.5 parts by mass (hereinafter abbreviated as “parts”) in terms of solid content, 1.2 parts of imiprothrin 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.

[Examples 2 and 3, Comparative Examples 1 to 6]
Cellulose fiber 1 is made of cellulose fibers 2 to 7, listed in Table 1 below, xanthan gum (product name: K-OB, manufactured by Gokyo Sangyo Co., Ltd.), polyoxyethylene lauryl ether (product name: Neugen ET-120, Daiichi Kogyo) Manufacture was carried out in the same manner as in Example 1 except that the product was changed to (manufactured by Pharmaceutical Co., Ltd.) to obtain an insecticide composition.

<Evaluation of insecticide composition>
The insecticide compositions produced in Examples 1 to 3 and Comparative Examples 1 to 6 were evaluated according to the following evaluation criteria. The evaluation results are shown in Table 1 below.

[Flow characteristics]
In a shear rate region containing 1 × 10 ⁻³ S ⁻¹ to 1 × 10 ³ S ⁻¹ of an insecticidal composition measured by a cone-plate type rotational viscometer (Rhesol-G2000, manufactured by UBM), 20 The maximum value (ηmax) and minimum value (ηmin) of the viscosity measured at ° C were determined.
×: ηmax <1 × 10 ⁴ mPa · s or ηmin> 1 × 10 ² mPa · s.
O: ηmax ≧ 1 × 10 ⁴ mPa · s and ηmin ≦ 1 × 10 ² mPa · s.

[Dispersion stability]
After standing at 25 ° C. for 1 week, the appearance of the gel was confirmed and evaluated according to the following criteria.
Separation: Separation is observed.
X: There is fluidity.
○: There is no fluidity.

<Evaluation of spray characteristics of insecticide composition>
250 ml of each 500 ml capacity trigger spray container was filled with the insecticide composition produced in Examples 1 to 3 and Comparative Examples 1 to 7. A glass plate was set up vertically and sprayed from a position 20 cm at a horizontal distance, and the sprayed state and the presence or absence of dripping of the attached droplets were observed. The spray characteristics (spray characteristics) were evaluated according to the following criteria.

[Sprayed state]
X: Not sprayed in a mist state or clogging occurs and cannot be sprayed.
(Triangle | delta): The thing injected in mist form and the thing which does not become mist form coexist.
○: Sprayed in a mist form.

[Drip]
X: The liquid dripping within 1 minute after spraying.
○: No dripping from spray over 1 minute.

表１より、セルロース繊維１ないし３を使用した殺虫剤組成物は流動特性、分散安定性、スプレー特性おいて優れていることが明らかとなった。これに対し、置換度の低いセルロース繊維４を使用した殺虫剤組成物（比較例１）、セルロース繊維５ないし７を使用した殺虫剤組成物（比較例２〜４）は流動性、分散安定性に劣り、これに起因して、スプレー特性がセルロース繊維１ないし３に劣る結果となった。また、既存の増粘剤であるキサンタンガムを使用した殺虫剤組成物（比較例５）及び既存の分散剤であるポリオキシエチレンラウリルエーテルを使用した殺虫剤組成物（比較例６）の分散安定性はセルロース繊維１ないし３を使用した殺虫剤組成物（実施例１〜３）と同等であるが、流動特性が劣るため、これに起因してスプレー特性が劣る結果となった。

From Table 1, it became clear that the insecticide composition using the cellulose fibers 1 to 3 is excellent in flow characteristics, dispersion stability, and spray characteristics. On the other hand, the insecticide composition (Comparative Example 1) using the cellulose fiber 4 having a low degree of substitution and the insecticide composition (Comparative Examples 2 to 4) using the cellulose fibers 5 to 7 are fluid and dispersion stable. As a result, the spray characteristics were inferior to those of cellulose fibers 1 to 3. Moreover, the dispersion stability of the insecticide composition (Comparative Example 5) using the xanthan gum which is an existing thickener and the insecticide composition (Comparative Example 6) using the polyoxyethylene lauryl ether which is an existing dispersant Is equivalent to the insecticide composition using Examples 1 to 3 (Examples 1 to 3), but the flow characteristics are inferior, resulting in inferior spray characteristics.

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 (2)

The following (A), (B) and (C) components are contained, and the content of (A) is 0.1% by mass or more and 3% by mass or less, and measured by a cone plate type rotational viscometer, 1 In a shear rate region including × 10 ⁻³ S ⁻¹ to 1 × 10 ³ S ⁻¹ , the maximum viscosity value (ηmax) measured at 20 ° C. is ηmax ≧ 1 × 10 ⁴ mPa · s, and the minimum value ( ηmin) is ηmin ≦ 1 × 10 ² mPa · s.
(A) Cellulose fibers having a number average fiber diameter of 2 nm or more and 500 nm or less, wherein a substituent is introduced into the hydroxyl group in the cellulose molecule, the degree of substitution is 0.01 or more and 0.5 or less, Cellulose fiber having a crystal structure of // type II and an aspect ratio of 50 or more.
(B) Insecticide component (C) Water A spray insecticide filled with the insecticide composition of claim 1.