JP2009120549A - Improved pesticide composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pestside composition capable of keeping a uniform dispersion of an active component in a diluted aqueous solution over a long period of time in the case of using in the form of an emulsion. <P>SOLUTION: Provided is a pesticide composition containing an emulsion stabilizer selected from lactic acid, glycolic acid, citric acid, succinic acid, benzoic acid and their mixture, 2-(thiazol-4-ine)benzimidazole optionally in combination with a triazole-based fungicide component, a pyrethroidal insecticide component or a (thia)nicotinyl insecticide component or other insecticide components, a mixed solvent containing a glycol-based solvent and benzyl alcohol, and a surfactant. The pesticide composition has a pesticidal effect, especially antimicrobial effect for protecting industrial materials (e.g. wood, pulp, paper, fiber, adhesive and film) from degradation (decay), and contamination with insects and especially microorganisms. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an improved emulsifying stable pesticidal composition having mainly ant control effect, termite control effect, rot control effect and mildew control effect, and more particularly, the pesticidal property of the present invention. When the biological composition is used as an emulsion, it relates to a composition that can maintain a uniform dispersion of the active ingredient in a dilute aqueous solution over an extended period of time. Furthermore, the present invention provides a pesticide effect, in particular an anti-microbial effect, for protecting industrial materials (eg wood, pulp, paper, fibers, adhesives, films) from deterioration (rot) and contamination by insects and in particular microorganisms. The present invention relates to a composition having a microbial effect. Furthermore, the present invention relates to compositions that prevent insect damage (including termite damage and in particular ant damage) caused, for example, by pests that eat wood.

  The present invention also relates to a method for protecting an industrial material by controlling the pest responsible for damage to the industrial material, the method applying the pesticide composition of the present invention to the industrial material. Process.

  The invention also relates to the use of the pesticidal composition of the invention as an ant control agent, termite control agent, decay control agent or mildew control agent.

  There is a growing trend in the importance of solving and adapting to common global problems represented by issues such as deforestation, greenhouse effects, ozone layer destruction and environmental pollution. In developed countries, including Japan, there is increasing interest in the impact on human and pet health of indoor air pollution from chemicals in newly constructed or renovated homes and buildings. This is primarily the result of chemicals that are dispersed (or evaporated) from building materials, furniture and contained items (eg household items), and are associated with dizziness, headaches, and painful irritation of the eyes, nose and throat. Cause such a condition. There were 13 types of volatile substances originally defined as substances responsible for these conditions. However, it was later determined from the results of later studies that most of these conditions were caused by specific solvents.

  Many compounds have been previously invented and marketed for use as insecticides, particularly as antimicrobial agents. However, universally effective compounds that can provide practical use against any type of microorganism, taking into account factors such as economy, safety during and after use, and contamination, are very Very few. Of course, when considering only antimicrobial properties, antimicrobial agents are effective against many microorganisms classified as bacteria, yeast, mold, etc. by increasing the concentration. However, high concentrations of antimicrobial agents are disadvantageous in terms of economy and environmental pollution.

  For example, benzethonium chloride, which is characterized as a quaternary ammonium salt, is effective against pathogens (bacteria) such as Escherichia coli and Salmonella typhi even when actually used as an aqueous solution having a concentration of 0.01% by weight. Aspergillus spp. Is effective, but not practically used at a concentration of 3-5% by weight. And Penicillium spp. It is not effective against such mold.

  It is therefore necessary to use a mixture of compounds having different effects in order to obtain a broad spectrum of pesticidal efficacy against a wide variety of pests and microorganisms.

  Thus, compounds used as both insecticides and antimicrobial agents preferably do not cause environmental destruction or pollution and have a detrimental effect on humans, livestock, fish, beneficial insects, plants, etc. It is a compound that does not have. Furthermore, they can preferably show a strong effect even when used in small amounts.

  One example of a chemical that meets these requirements is 2- (thiazol-4-yne) benzimidazole (or 2- (4-thiazolyl) -1H-benzimidazole; generic name: thiabendazole). This thiabendazole is used, for example, as a mildew control agent by adding or mixing it into paints, resins, adhesives, paper products and the like. Furthermore, it is used as an agrochemical, food additive (citrus fruits, bananas, etc.) and animal pesticides due to its high level of safety.

  Furthermore, it is used as a mildew control agent that can be mixed into the resin because it has a suitable and stable heat resistance.

  Furthermore, in view of environmental and government regulatory pressures, there is an increasing desire to reduce or eliminate certain compounds that are no longer acceptable for use in processing materials.

  Accordingly, the present invention seeks to provide an improved composition that does not include any of the disadvantages of prior art compositions.

  The object of the present invention is therefore to develop an emulsion stabilizer for use in emulsions containing the above thiabendazole. The emulsion stabilizer has the effect of maintaining a uniform emulsion and preventing precipitation, sedimentation, and liquid phase separation even when the emulsion is diluted with water. The resulting emulsion exhibits excellent permeability to the material to which the emulsion is added, while also providing superior adhesion and processing non-uniformity compared to wettable powders and aqueous suspensions. Show.

  Furthermore, the object of the present invention is to add to industrial materials such as wood, pulp, paper, fibers, adhesives and films, these intermediate materials and their final products, which can prevent deterioration and contamination by microorganisms, It is to provide a stabilized emulsion composition that exhibits good workability and can be expected to produce a uniformly treated finish and a reliable rot control and mildew control effect.

  Furthermore, the object of the present invention is to provide a satisfactory combination of emulsifying stabilizer, solvent and surfactant that achieves the emulsion stability of thiabendazole, despite the poor solubility of thiabendazole and the difficulty in formulating into preparations. Is to provide.

  Furthermore, the object of the present invention is even more difficult to prepare solutions by including multiple active ingredients containing thiabendazole, a triazole-based fungicide and other insecticide ingredients with different solubilities. In some cases, it is to provide a pesticidal composition that is capable of achieving satisfactory emulsion stability.

  We have mixed certain emulsion stabilizers such as lactic acid into compositions containing active ingredients such as thiabendazole, solvents such as glycol-based solvents and benzyl alcohol, and surfactants. It has been identified that the emulsion stability of the above composition can be obtained, thereby leading to the completion of the present invention.

Accordingly, the present invention provides the following:
(A) an emulsion stabilizer selected from the group consisting of lactic acid, glycolic acid, citric acid, succinic acid, benzoic acid and mixtures thereof;
(B) 2- (thiazol-4-yne) benzimidazole,
(C) A pesticide composition comprising a glycol-based solvent and a mixed solvent of benzyl alcohol, and (d) a surfactant.

  Furthermore, the present invention also further comprises an additional triazole fungicide component in a mass ratio of 1: 1 to 4: 1 between 2- (thiazol-4-yne) benzimidazole and this further triazole fungicide. It relates to the pesticidal composition. The most preferred mass ratio between 2- (thiazol-4-yne) benzimidazole and this further triazole component is 2: 1 to 3: 1.

  Furthermore, the present invention also provides the above pesticidal composition further comprising an insecticide. In certain embodiments, the insecticide is a neonicotinoid insecticide.

  Furthermore, the present invention relates to a pyrethroid insecticide component selected from cyphenothrin, cypermethrin, permethrin, bifenthrin, or mixtures thereof; imidaclopridmipriprid , Thiamethoxam, clothianidin and mixtures thereof (thia) nicotinyl insecticide ingredients; etofenprox, silafluofen, fipronil, chlorfiryl Mixing Concerning the pesticidal composition further comprises another insecticide component selected from.

  The present invention still further provides that the further triazole fungicide component is selected from azaconazole, tebuconazole, propiconazole, cyproconazole, difenoconol and a mixture of difenoconazole. The above composition is provided.

  The present invention still further provides a pesticidal composition comprising lactic acid, methyl diglycol, benzyl alcohol, thiamethoxam, cyproconazole and thiabendazole.

  The present invention still further provides an amount sufficient to prevent the formation of sediment in the composition when the composition is stored at about −5 ° C. to about 50 ° C. for at least one month. There is provided a pesticidal composition as described above comprising In certain embodiments, the composition is stored for at least one month. In a further embodiment, the composition is stored for at least 2 months. In a further embodiment, the composition is stored for at least 3 months. In a further embodiment, the composition is stored for at least 4 months. In a further embodiment, the composition is stored for at least 5 months. In a further embodiment, the composition is stored for at least 6 months. In a further embodiment, the composition is stored for more than 6 months.

  The present invention still further provides an amount sufficient to prevent the formation of sediment in the composition when the composition is stored at about −5 ° C. to about 50 ° C. for at least 3 months. There is provided a pesticidal composition as described above comprising

  The present invention still further provides an amount sufficient to prevent the formation of sediment in the composition when the composition is stored at about −5 ° C. to about 50 ° C. for at least 6 months. There is provided a pesticidal composition as described above comprising

  The present invention still further provides the pesticidal composition as described above, wherein the composition comprises about 2.5% w / w to about 10% w / w water. In certain embodiments, the composition comprises about 2.5% w / w water. In a further embodiment, the composition comprises about 5.6% w / w water. In still further embodiments, the composition comprises about 7.5% w / w water. In still further embodiments, the composition comprises about 10% w / w water. In certain embodiments, the water is deionized water (also known as ion exchange water).

  The present invention still further provides an amount sufficient to prevent the formation of sediment in the composition when the composition is stored under conditions such as those described in the examples presented herein. A composition comprising water is provided. In particular, the present invention provides the compositions disclosed in the examples. Furthermore, the present invention provides a composition further comprising an amount of water such that when the composition is stored at the temperature and time provided in the Examples, the composition does not contain any sediment.

  The present invention further provides a method for protecting an industrial material by controlling the pest responsible for damage to the industrial material, the method comprising applying the inventive pesticide composition to the industrial material. The process applied to is included.

  The present invention still further provides the use of the pesticidal composition of the present invention as an ant control agent, termite control agent, spoilage control agent or mildew control agent.

  The present invention still further provides an industrial material comprising the composition of the present invention. In certain embodiments, the industrial material includes wood.

According to the present invention, the following is provided to achieve the above object.
(Item 1)
A pesticidal composition comprising: (a) an emulsion stabilizer selected from the group consisting of lactic acid, glycolic acid, citric acid, succinic acid, benzoic acid and mixtures thereof; A pesticide composition comprising b) 2- (thiazol-4-yne) benzimidazole and (c) a mixed solvent comprising a glycol-based solvent and benzyl alcohol, and (d) a surfactant.
(Item 2)
The pesticidal composition according to item 1, wherein the further triazole fungicide component is added between 1: 1 and 4 between the 2- (thiazol-4-yne) benzimidazole and the further triazole fungicide. A pesticidal composition further comprising a mass ratio of 1: 1.
(Item 3)
Item 3. The pesticide composition according to Item 1 or Item 2, wherein the glycol-based solvent is methyl diglycol, ethyl diglycol, propyl diglycol, butyl diglycol, methyl glycol, ethyl glycol, ethylene glycol, diethylene glycol. A pesticidal composition selected from polyethylene glycol, propylene glycol, polypropylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether and mixtures thereof.
(Item 4)
The pesticidal composition according to item 2 or item 3, wherein the further triazole fungicide component is selected from azaconazole, tebuconazole, propiconazole, cyproconazole, difenoconazole, and mixtures thereof. Pest composition.
(Item 5)
Item 5. The pesticidal composition according to any one of items 1 to 4, further comprising an insecticide.
(Item 6)
6. The pesticidal composition according to item 5, wherein the insecticide is a neonicotinoid insecticide.
(Item 7)
Item 6. The pesticide composition according to Item 5, wherein the insecticide is (a) a pyrethroid insecticide selected from ciphenothrin, cypermethrin, permethrin, bifenthrin, (b) imidacloprid, acetamiprid, thiamethoxam, A pesticide composition selected from (thia) nicotinyl insecticides selected from clothianidin, (c) insecticides selected from etofenprox, silafluophene, fipronil, chlorfenapyr, and mixtures thereof.
(Item 8)
Item 8. The pesticidal composition according to any one of Items 1-7, wherein when the composition is stored at about -5C to about 50C for at least 1 month, A pesticidal composition comprising an amount of water sufficient to prevent the formation of sediment in the composition.
(Item 9)
Item 9. The pesticidal composition of item 8, wherein when the composition is stored at about -5C to about 50C for at least 3 months, A pesticidal composition comprising an amount of water sufficient to prevent formation.
(Item 10)
Item 10. The pesticidal composition of item 9, wherein when the composition is stored at about -5C to about 50C for at least 6 months, A pesticidal composition comprising an amount of water sufficient to prevent formation.
(Item 11)
Item 13. The pesticidal composition according to any one of items 8-10, wherein the composition comprises about 2.5% w / w to about 10% w / w water. .
(Item 12)
12. A pesticidal composition according to item 11, wherein the composition comprises about 2.5% w / w water.
(Item 13)
12. A pesticidal composition according to item 11, wherein the composition comprises about 5.6% w / w water.
(Item 14)
12. A pesticidal composition according to item 11, wherein the composition comprises about 7.5% w / w water.
(Item 15)
12. A pesticidal composition according to item 11, wherein the composition comprises about 10% w / w water.
(Item 16)
A method for protecting an industrial material by controlling a pest that causes damage to the industrial material, wherein the pesticide composition according to any one of items 1 to 15 is applied to the industrial material. A method comprising the step of applying.
(Item 17)
Use of the pesticidal composition according to any one of Items 1 to 15 as an ant control agent, termite control agent, rot control agent or mildew control agent.
(Item 18)
Item 16. The pesticidal composition according to any one of items 1 to 15, wherein the pesticidal composition comprises lactic acid, methyl diglycol, benzyl alcohol, thiamethoxam, cyproconazole and thiabendazole. Biological composition.
(Item 19)
An industrial material comprising the composition according to any one of items 1 to 15 or 18.
(Item 20)
20. Industrial material according to item 19, wherein the material comprises wood.

  An improved composition is provided that does not include any disadvantages of the compositions in the prior art.

  An emulsion stabilizer for use in emulsions containing the thiabendazole is developed.

  Added to industrial materials such as wood, pulp, paper, fibers, adhesives and films, these intermediate materials and their final products, which can prevent deterioration and microbial contamination, show excellent workability and evenly A stabilized emulsion composition is provided that can be expected to produce a treated finish and a reliable anti-rot and mildew control effect.

  Despite the poor solubility of thiabendazole and the difficulty in formulating it into a preparation, a satisfactory combination of emulsifying stabilizer, solvent and surfactant is provided that achieves the emulsion stability of thiabendazole.

  Satisfactory emulsification stability in cases where it is even more difficult to prepare solutions by including multiple active ingredients containing thiabendazole, triazole-based fungicides and other insecticide ingredients with different solubilities A pesticidal composition is provided that is capable of achieving

  “Industrial materials” includes materials used in construction and the like. For example, industrial materials include structural materials, doors, cupboards, storage devices, carpets, especially natural fiber carpets (eg, wool and hessian (coarse linen)), plastics, wood (including processed wood), and wood It can be a plastic composite.

  In certain embodiments, the industrial material is a coating. A “coating” is a composition applied to a substrate (eg, paint, dye, varnish, lacquer, primer, semi-gloss coating, gloss coating, flat coating, top coat, dye blocking coating, for porous substrates Permeable sealers, concrete and marble, elastomeric coatings, mastics, caulking materials and sealants, substrate and panel coatings, transport coatings, furniture coatings and coil coatings, bridge and tank coatings, and surface marking paints, leather coatings and treatments, Floor care coating, paper coating, personal care coating (eg for hair, skin, nails), woven or non-woven fabric coating and pigment paste, and adhesion Coatings (e.g., pressure-sensitive adhesives, as well as wet and dry layer of adhesive and plaster) a).

  In a particular embodiment, coating means paint; varnish; dye, lacquer or plaster. In a further embodiment, the coating is lacquer. In certain embodiments, coating refers to paint. The paint may include, for example, a film former and a carrier (which may be water and / or an organic solvent) and optionally a pigment.

  In addition, industrial materials include adhesives, sealants, bonding materials and joints, and insulating materials. In certain embodiments, “industrial material” means a structural material. In a further embodiment, “industrial material” means processed wood. In a further embodiment, “industrial material” means plastic.

  Plastics include plastic polymers and plastic copolymers, including: acrylonitrile-butadiene-styrene, butyl rubber, epoxy, fluoropolymer, isoprene, nylon, polyethylene, polyurethane, polypropylene, polyvinyl chloride, polystyrene, polycarbonate, poly Vinylidene fluoride, polyacrylate, polymethyl methacrylate, polyurethane, polybutylene, polybutylene terephthalate, polyethersulfone, polyphenylene oxide, polyphenylene ether, polyphenylene sulfide, polyphthalamide, polysulfene, polyester, silicone, styrene butadiene rubber, and polymer combinations . In a further embodiment, “industrial material” means polyvinyl chloride (PVC). In a further embodiment, “industrial material” means polyurethane (PU). In a further embodiment, “industrial material” means wood plastic composite (WPC). Wood plastic composite materials are well known in the art. A review of WPC can be found in the publication Craig Cremons-Forrest Products Journal. June 2002, Vol. 52, No. 6, pp. 10-18.

  “Wood” should be understood to mean wood and wood products. For example, it means: extracted timber product, timber, lumber, plywood, waste wood plywood, flakeboard, laminated beams, oriented strandboard, Hardboards and particle boards, tropical wood, structural materials, wooden beams, sleepers, bridge components, breakwaters, wooden vehicles, boxes, pallets, containers, utility poles, wooden fences, wooden insulation, As well as windows and doors made from wood, plywood, wood plywood, joinery or wood products very commonly used to build houses or decks, and building fixtures commonly used in house construction Or wood products (processed wood, buildings and woodwork Can be mentioned).

  “Industrial materials” also includes lubricants for cooling and cooling and heating systems, ventilation and air conditioning systems, and parts of manufacturing machinery (eg, cooling water circuits).

  “Industrial materials” also includes wall coverings such as plaster-based wall coverings.

The present invention further provides a composition comprising:
(A) a neonicotinoid-based insecticidal component selected from the group consisting of thiamethoxam, imidacloprid, and dinotefuran; and (b) cyproconazole, propiconazole (propiconazole) at least one triazole-based antiseptic component selected from the group consisting of propiconazole and diphenoconazole; and (c) from the group consisting of thiabendazole and 2-thiocyanomethylthiobendazole (TCMTB) A selected triazole-based fungicidal component; and (d) a nonionic surfactant and (e ) A mixed solvent of benzyl alcohol and glycol solvent; and (f) Lactic acid added as a component for adjusting HLB (hydrophilic lyophilic balance) and maintaining dispersion (storage).
The term “dispersion maintenance (storage)” means maintenance (storage) of the dispersibility of the component particles in a dilute solution diluted with water during use.

  The present invention also provides a composition as described above, wherein the triazole family preservative component and the triazole family fungicidal component are mixed in a mixing ratio (mass ratio) of 1: 1 to 4: 1. A composition is provided.

  The present invention is also a composition as described above, which has a relatively high compatibility with amphoteric solvents such as water and ethanol as insecticidal components (with solubility in water at 20 ° C. Provided is a composition in which neonicotinoid compounds (> 500 ppm or greater) are used.

  The present invention also provides an amount of water sufficient to prevent the formation of sediment in the composition when the composition is stored at about −5 ° C. to about 50 ° C. for at least one month. The above composition is provided.

  The composition of the present invention has almost no odor of any solvent and has excellent practicality. Furthermore, the composition of the present invention can be stored for a long time without compromising the quality of the composition.

  The composition of the present invention allows for uniform processing without the occurrence of processing heterogeneity. This is because this composition has excellent formulation stability without causing separation.

  The present invention provides compositions having improved emulsion stability and permeability.

  When the composition of the invention is used by diluting in water, the operation can be carried out efficiently and economically. This is because separation, sedimentation and crystal precipitation hardly occur.

  The present invention can provide a processing method, a processing chemical, or a processing product that is easy to the environment.

  The composition of the present invention can be expected to show a high level of ant control effect, termite control effect, rot control effect, and mildew control effect depending on the type of active ingredient contained in the composition. .

  Furthermore, the composition of the present invention can contain a plurality of hardly soluble active ingredients due to the high level of emulsion stability of the composition. Thus, a number of different insecticidal and antimicrobial effects can be demonstrated using one composition. Accordingly, the compositions of the present invention are useful as ant control agents, termite control agents, decay control agents, or mildew control agents, depending on the type of active ingredient contained in the composition. Furthermore, these pesticidal effects can be maintained over a long period of time.

  The composition of the present invention contains an emulsion stabilizer, an active ingredient, a solvent and a surfactant. The following provides a description of each component. As used herein, the term “pesticidal composition” refers to insecticidal activity, ant venomicidal activity that can eliminate not only insects such as ants and termites, but also microorganisms such as bacteria and fungi (antibacterial). It should be noted that it encompasses the meaning of a composition having antimicrobial activity, ant control activity, spoilage control activity, and mildew control activity.

  The emulsion stabilizer used in the present invention is used to stabilize the emulsification over a long period of time by adjusting the pH of the pesticidal composition of the present invention. The emulsion stabilizer used in the present invention is preferably a weakly acidic organic carboxylic acid having a pKa value (20 ° C.) of, for example, about 2.2 to 4.2, and preferably about 2.5 to 4.0. Should be an acid based emulsion stabilizer. Examples of this emulsion stabilizer include carboxylic acid based emulsion stabilizers selected from the group consisting of lactic acid, glycolic acid, citric acid, succinic acid, benzoic acid and mixtures thereof, with lactic acid being particularly preferred. . The emulsion stabilizer of the present invention is suitably, for example, from 1% to 10% by weight, and preferably from 2% to 8% by weight, based on the total weight of the pesticidal composition of the present invention, Contained. When the contained amount is 1% by mass or more, the pH value of the composition of the present invention can be easily changed, and when the contained amount is 10% by mass or less, the pH of the composition The values can be easily varied and the stability over time can be fully guaranteed for the compositions of the present invention. Therefore, preferably such a mass value is used.

  In the broad sense, the active ingredient used in the present invention refers to an ingredient having an insecticidal effect, an antimicrobial effect, an insect repellent effect, an ant control effect, a rot control effect, a mildew control effect, and a microbial repellent effect. . Here, the insect repellent effect has a broader meaning than the insecticidal effect and includes not only an insecticidal effect but also an insect repellent effect that prevents insects from approaching. This applies to ant control effects, spoilage control effects, mildew control effects, and microbial protection effects as well. The preferred active ingredient used in the present invention is 2- (thiazol-4-yne) benzimidazole (ie 2- (4-thiazolyl) -1H-benzimidazole; generic name: thiabendazole). This thiabendazole has excellent efficacy against microorganisms such as bacteria, molds and yeasts, and in particular, has excellent effect against molds and bacteria.

  When thiabendazole is used as a spoilage control composition or a mildew control composition, considering the solubility of thiabendazole in a solvent (particularly, a mixed solvent of a glycol-based solvent and benzyl alcohol), for example, It is appropriate to contain 0.1% to 20% by weight, and preferably 1.0% to 15% by weight, based on the total weight of the pesticide composition. When the amount contained is 20% by mass or less, there is no risk of precipitation of crystals when diluted with low temperature or water, and when the amount contained is 0.1% by mass or more, water When diluted, it can be expected that a sufficient mildew control effect will be obtained.

  Examples of other pesticidal components used in the present invention include triazole-based fungicidal components (eg, azaconazole, tebuconazole, propiconazole, cyproconazole, difenoconazole, and the like, which have excellent spoilage control effects. A pyrethroid-based insecticidal component having an excellent insect repellent effect (e.g., cyphenothrin, cypermethrin, permethrin and bifenthrin or mixtures thereof), ) Nicotinyl-based insecticidal components (eg, imidacloprid, acetamiprid, thiamethoxa) ) And clothianidin or mixtures thereof), and other insecticidal ingredients such as etofenprox, silafluofen, fipronil and chlorfenapyr or mixtures thereof. . Cyproconazole has a particularly excellent spoilage control effect, while thiamethoxam is preferably used due to its excellent insect repellent and ant control effects.

  Compounds thiabendazole (790), azaconazole (40), tebuconazole (761), propiconazole (675), cyproconazole (207), difenoconazole (247), ciphenothrin (206), cypermethrin (201), permethrin (626) ), Bifenthrin (76), imidacloprid (458), acetamiprid (4), thiamethoxam (792), clothianidin (165), etofenprox (319), silafluophene (728), fipronil (354) and chlorfenapyr (130) For example, The e-Pesticide Manual, version 3.0, 13th edition, editor CDC Tomlin, British Crop Protection Council, 20 It is described in the 3-2004.

  When using these other pesticidal components, these other pesticidal compositions are preferably based on 1 part by weight of thiabendazole, taking into account the effects of pesticides, safety and environmental pollution. 0.01 parts by weight to 1.25 parts by weight, preferably 0.05 parts by weight to 1.0 parts by weight, and more preferably 0.05 parts by weight to 0.5 parts by weight. . In particular when using a combination of thiabendazole and a triazole-based fungicidal component, these are preferably contained in a mass ratio of thiabendazole to triazole-based fungicidal component of 1: 1 to 4: 1. The ratio used can also be a ratio as described in the examples.

  The solvent used in the present invention is preferably a mixed solvent of a glycol-based solvent and benzyl alcohol. Examples of glycol-based solvents include methyl diglycol, ethyl diglycol, propyl diglycol, butyl diglycol, methyl glycol, ethyl glycol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ethylene glycol monomethyl ether, And propylene glycol monomethyl ether.

  The solvent of the present invention is suitably, for example, 40% to 85%, preferably 45% to 80%, and more preferably, based on the total weight of the pesticidal composition of the present invention. 45 mass% to 70 mass%. When the contained amount is 40% by mass or more, the active ingredient of the present invention can be sufficiently dissolved, and when the contained amount is 85% by mass or less, the active ingredient is sufficiently harmful. It can be contained to the extent that it has a biological effect, thereby making the composition preferred. Benzyl alcohol is suitably contained, for example, from 1% to 10% by weight and preferably from 3% to 8% by weight, based on the total weight of the pesticidal composition of the invention. Further, benzyl alcohol is suitably used such that the mass ratio of glycol-based solvent to benzyl alcohol is, for example, 1: 0.5 to 1: 4 (including 1: 1 to 1: 2). Is done.

  Examples of surfactants used in the present invention include nonionic surfactants and anionic surfactants. This surfactant may be used alone, or a plurality of surfactants may be mixed.

  Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene castor oil, hydrogenated castor oil, fatty acid monoglycid, fatty acid monoglyceride, polyoxyethylene alkylphenyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene Examples include sorbitan fatty acid esters and propylene glycol fatty acid esters. Further examples of anionic surfactants include alkyl benzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl phenyl ether sulfates, and polyoxyethylene alkyl ether sulfates. The surfactant of the present invention is suitably contained in an amount of 3-30% by weight, and preferably 3-20% by weight, based on the total weight of the pesticidal component of the present invention. When the contained amount is in the range of 3% by mass to 30% by mass, a sufficient emulsification effect is preferably obtained.

  Active ingredient stabilizers (eg, antioxidants), colorants, rust inhibitors and the like can be added to the compositions of the present invention.

  The pesticidal composition of the present invention can be prepared, for example, as shown below.

(1)
((1-1) Solvent)
The solvent used in the present invention is a mixed solvent of a glycol solvent and benzyl alcohol. Examples of the glycol solvent include methyl diglycol, ethyl diglycol, propyl diglycol, butyl diglycol, methyl glycol, ethyl glycol, ethylene glycol, diethylene glycol, polyethylene glycol, and propylene glycol monomethyl ether.

  In this invention, it is preferable to mix the said solvent in the ratio of 40 mass% or more with respect to the total mass of the said biocide composition. This is because when the solvent is mixed in a proportion of 40% by weight or more, the solvent can completely dissolve the active ingredient of the present invention, whereby the solvent completely exhibits insecticidal and microbicidal effects. It is because the active ingredient which can be included.

  However, in this example, the concentration of benzyl alcohol should be such that the amount of benzyl alcohol is 20% by weight or more based on the total weight of the biocide.

((1-2) Surfactant)
The surfactant used in the present invention is only a nonionic surfactant. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene castor oil, hydrogenated castor oil, fatty acid monoglyceride, polyoxyethylene polycyclic phenyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene Examples include sorbitan fatty acid esters and propylene glycol fatty acid esters. Of the above surfactants, polyoxyethylene polycyclic phenyl ether is most suitable as the surfactant in the composition of the present invention. This polyoxyethylene polycyclic phenyl ether is preferably mixed in an amount of 20% to 35% by weight relative to the total weight of the biocide of the present invention.

((1-3) Dispersion maintenance (holding) agent)
In the present invention, a dispersion maintaining (retaining) agent helps to dissolve the active ingredient in the composition of the present invention, adjusts the pH value of this composition, delays the increase in sedimentation, and further the above ingredients. In order to maintain (hold) a uniform dispersion of the particles. The agent used in this example for maintaining (holding) the dispersibility of the particles of the above components is lactic acid.

  Lactic acid as a drug for maintaining (holding) the dispersion (dispersibility) of the particles of the above components is 12% by mass to 20% by mass (preferably 13% by mass to the total weight of the composition of this example). 17% by weight). When the pH value of the lactic acid can be maintained within the range of 2.5 to 3.5, ensuring sufficient maintenance stability of the component particles regardless of whether the composition is diluted or not Is possible.

((1-4) Other ingredients)
It is possible to add active ingredient stabilizers (eg antioxidants), colorants, rust inhibitors and the like.
((2) Preparation of biocide of the present invention)
The biocides of the present invention can be prepared, for example, as follows: 2- (thiazolyl) benzimidazole (thiabendazole) as the active ingredient, cyproconazole and thiamethoxam as the other active ingredients, and lactic acid An appropriate amount of a mixed solvent of glycol solvent and benzyl alcohol is placed in a container. The mixture is stirred and heated at about 40 ° C. for dissolution.

  Thereafter, a nonionic surfactant is added, and the remaining amount of the mixed solvent of the glycol solvent and benzyl alcohol is added. The mixture is further stirred. When diluting the above composition with water, and thus preparing the composition of the present invention as follows, lactic acid is mixed to maintain (retain) the uniform dispersibility of the component particles, for example lactic acid Sometimes mixed slightly (for example, 20 w / w% → 20.05 w / w%).

Thiamethoxam 2w / w%
Cyproconazole 2w / w%
Thiabendazole 4w / w%
Lactic acid 20w / w%
Benzyl alcohol 30w / w%
Methyl diglycol 17w / w%
Newcol 2614 ^* 25 w / w%
Total 100w / w%
(Note) ^* Newcol 2614 is a non-ionic surfactant.

  More specifically, the pH value of the biocide composition is preferably in the range of 2.5 to 4.0. The pH value is adjusted at room temperature except when the first heating and dissolving operation is performed.

(3)
((3-1) Emulsification stability test, solubility test, and uniform dispersibility maintenance (retention) test)

（（３−２）時間経過に伴う溶解度、乳化安定性／均一分散性、および安定性の研究）

((3-2) Study of solubility, emulsification stability / uniform dispersion, and stability over time)

（（３−３）効力試験（実施例１））
木材用殺真菌剤の効力を、日本木材保存協会規格第２号（ｔｈｅ Ｊａｐａｎ Ｗｏｏｄ Ｐｒｅｓｅｒｖｉｎｇ Ａｓｓｏｃｉａｔｉｏｎ Ｓｔａｎｄａｒｄ Ｎｏ．２）（１９９２）によって定義される木材用殺真菌剤の効力を試験する方法によって試験した。より具体的には、所定のサイズを有するブナノキの断片物質（試験片）を、組成物の希釈液体（標本液体）中に３分間浸漬した。処理済み断片を浸漬直後にこの希釈液体から取り出し、この処理済み断片の表面上の過剰な薬剤液を、軽く拭き取り、その後、それらの試験片の重量を測定した。

((3-3) Efficacy test (Example 1))
The efficacy of wood fungicides was tested by a method of testing the efficacy of wood fungicides as defined by the Japan Wood Preserving Association Standard No. 2 (1992). More specifically, a beech tree fragment material (test piece) having a predetermined size was immersed in a diluted liquid (specimen liquid) of the composition for 3 minutes. The treated pieces were removed from the diluted liquid immediately after immersion, the excess drug solution on the treated piece surface was gently wiped, and then the weights of the specimens were measured.

  These specimens were placed on a net in a manner that they did not touch each other and air dried for 2 days to produce treated specimens.

  Groups of these specimens (each group consisting of 3 pieces) were placed on a Petri dish. Approximately 2 ml of suspension (each containing one spore) was dropped onto a Petri dish using a pipette. These spores were cultured for 4 weeks at a temperature of 26 ± 2 ° C. and a relative humidity of 70-80%. The assessment value was then determined from the bacterial growth state, thereby calculating the damage value.

損傷値（Ｄ）を算出するための式：損傷値（Ｄ）＝Ｓ_１／Ｓ_０×１００。

Formula for calculating the damage value (D): Damage value (D) = S ₁ / S ₀ × 100.

((3-3) Efficacy test (Example 2))
As in Test Example 1, the efficacy of the wood fungicide was tested according to the Japan Wood Preservation Association Standard No. 2 (Japan Wood Preserving Association Standard No. 2).

^＊１：Ｚｅｅｋｌｉｔｅ［Ｚｅｅｋｌｉｔｅ Ｃｏ．，Ｌｔｄ．から入手可能］
^＊２：ＰＣ−１０００［Ｎｏｓａｎ Ｃｏｒｐｏｒａｔｉｏｎから入手可能］。

^* 1: Zeeklite [Zeeklite Co. , Ltd., Ltd. Available from]
^* 2: PC-1000 [available from Nosan Corporation].

（注意：この試験のための真菌は、試験実施例１における真菌と同じであった）。

(Note: The fungus for this test was the same as the fungus in Test Example 1).

  This study was conducted to confirm the difference between the efficacy of fungicides caused by differences between dosage forms. The solubilizer was more active than other dosage forms.

((3-3) Efficacy test (Example 3))
This potency test is an indoor potency test method for surface treatment wood preservatives as defined by the Japan Wood Preserving Association Standard No. 1 (JWPS-FW-S.1) and Based on performance criteria.

In this efficacy test, the same specimen as the above efficacy test (Example 2) was used. As fungi for this test, Tyromyces palustris and Coriolus
Versicolor was used as described above, and its mass reduction ratio was calculated, thereby evaluating its antiseptic performance. It should be noted that the specimen is judged to have preservative performance when the weight loss ratio of the preservative is less than 3%. As a result of this test, it was determined that the composition (dissolving agent) of the present invention had excellent antiseptic performance.

上記効力試験を実施するための方法は、以下の通りである：試験片を７日間以上風乾し、それらの試験片をさらに静水中に５時間（２０±３℃）浸漬する作業、およびそれらの試験片を温度４０±２℃にて循環乾燥機中に１９時間放置する作業を、１０回反復して実施した。その後、それらの試験片を温度６０±２℃にて４８時間風乾した後、それらの試験片をデシケーター中に約８０分間放置し、その質量を測定した（Ｗ_３）。抗菌作業において、それらの試験片を培養細菌の細菌床に配置し、温度２６±２℃、相対湿度７０％以上にて１２週間放置した。その後、それらの試験片を２４時間風乾し、温度６０±２℃にて４８時間さらに風乾した。その後、それらの試験片をデシケーター中に８０分間放置し、その質量を測定した。

The method for performing the efficacy test is as follows: air-drying the test pieces for 7 days or more, further immersing the test pieces in still water for 5 hours (20 ± 3 ° C.), and The operation of leaving the test piece in a circulating dryer for 19 hours at a temperature of 40 ± 2 ° C. was repeated 10 times. Then, after air-drying those test pieces at a temperature of 60 ± 2 ° C. for 48 hours, the test pieces were left in a desiccator for about 80 minutes, and the mass was measured (W ₃ ). In antibacterial work, these test pieces were placed on a bacterial bed of cultured bacteria and left for 12 weeks at a temperature of 26 ± 2 ° C. and a relative humidity of 70% or more. Thereafter, the test pieces were air-dried for 24 hours, and further air-dried at a temperature of 60 ± 2 ° C. for 48 hours. Thereafter, these test pieces were left in a desiccator for 80 minutes and their masses were measured.

Mass reduction ratio (%) = (W ₃ −W ₄ ) / W ₃ × 100

  The present invention relates to an emulsion stabilizer selected from the group consisting of lactic acid, glycolic acid, citric acid, succinic acid, benzoic acid and mixtures thereof, 2- (thiazol-4-yne) benzimidazole, and further triazole-based killing agents. A pesticidal composition comprising a fungicide component, a pyrethroid insecticide component, or a (thia) nicotinyl insecticide or another insecticide component, a mixed solvent comprising a glycol-based solvent and benzyl alcohol, and a surfactant I will provide a. In a further embodiment, the composition comprises an amount of water sufficient to prevent the formation of sediment in the composition. This composition has a pesticidal effect, in particular an antimicrobial, to protect industrial materials (eg wood, pulp, paper, fibers, adhesives, films) from deterioration (rot) and contamination by insects and in particular microorganisms. Has an effect.

Claims (20)

A pesticidal composition comprising: (a) an emulsion stabilizer selected from the group consisting of lactic acid, glycolic acid, citric acid, succinic acid, benzoic acid and mixtures thereof; A pesticide composition comprising b) 2- (thiazol-4-yne) benzimidazole and (c) a mixed solvent comprising a glycol-based solvent and benzyl alcohol, and (d) a surfactant. 2. The pesticidal composition according to claim 1, wherein the further triazole fungicide component is added between the 2- (thiazol-4-yne) benzimidazole and the further triazole fungicide 1: 1. A pesticide composition further comprising a 4: 1 mass ratio. 3. The pesticidal composition according to claim 1 or 2, wherein the glycol-based solvent is methyl diglycol, ethyl diglycol, propyl diglycol, butyl diglycol, methyl glycol, ethyl glycol, ethylene glycol. A pesticidal composition selected from diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether and mixtures thereof. 4. The pesticidal composition according to claim 2 or claim 3, wherein the further triazole fungicide component is selected from azaconazole, tebuconazole, propiconazole, cyproconazole, difenoconazole, and mixtures thereof. , Pesticide composition. The pesticidal composition according to any one of claims 1 to 4, further comprising an insecticide. 6. A pesticidal composition according to claim 5, wherein the insecticide is a neonicotinoid insecticide. 6. A pesticidal composition according to claim 5, wherein the insecticide is (a) a pyrethroid insecticide selected from ciphenothrin, cypermethrin, permethrin, bifenthrin, (b) imidacloprid, acetamiprid, thiamethoxam A pesticide composition selected from: (thia) nicotinyl insecticides selected from clothianidin, (c) insecticides selected from etofenprox, silafluophene, fipronil, chlorfenapyr, and mixtures thereof. A pesticidal composition according to any one of claims 1 to 7, wherein the composition is stored at about -5C to about 50C for at least one month, A pesticidal composition comprising an amount of water sufficient to prevent the formation of sediment in the composition. 9. A pesticidal composition according to claim 8, wherein the composition settles in the composition when stored at about -5C to about 50C for at least 3 months. A pesticidal composition comprising an amount of water sufficient to prevent the formation of. 10. The pesticidal composition of claim 9, wherein the composition settles in the composition when stored at about -5C to about 50C for at least 6 months. A pesticidal composition comprising an amount of water sufficient to prevent the formation of. 11. A pesticidal composition according to any one of claims 8 to 10, wherein the composition comprises about 2.5% w / w to about 10% w / w water. object. 12. The pesticidal composition according to claim 11, wherein the composition comprises about 2.5% w / w water. 12. The pesticidal composition according to claim 11, wherein the composition comprises about 5.6% w / w water. 12. A pesticidal composition according to claim 11, wherein the composition comprises about 7.5% w / w water. 12. A pesticidal composition according to claim 11, wherein the composition comprises about 10% w / w water. A method for protecting industrial materials by controlling the pests that cause damage to the industrial materials, wherein the pesticide composition according to any one of claims 1 to 15 is applied to the industrial materials. A method comprising the steps of: Use of the pesticidal composition according to any one of claims 1 to 15 as an ant control agent, termite control agent, rot control agent or mildew control agent. 16. A pesticidal composition according to any one of claims 1 to 15, wherein the pesticidal composition comprises lactic acid, methyl diglycol, benzyl alcohol, thiamethoxam, cyproconazole and thiabendazole. Pest composition. The industrial material containing the composition as described in any one of Claims 1-15 or 18. 20. Industrial material according to claim 19, wherein the material comprises wood.