JP4780977B2 - Gastropod control agent - Google Patents

Description

  The present invention relates to a gastropod pesticide, and more particularly, to a pest control agent for harmful gastropods, such as slugs, snails such as Uskawamaimai, which damage useful crops.

  Land-use or freshwater gastropods such as snails such as Uskawamaimai, slugs, and scallop apple mussels appear everywhere in fields, greenhouses, gardens, etc. It is known to eat and cause great damage.

  Conventionally, a metaaldehyde formulation as described in Patent Document 1 has been used as an attracting poison bait as a pesticide against these. However, since this preparation is an attractive poison bait, it does not have a direct killing ability even when contacted, and has no repellency, it cannot be said that it exerts a sufficient effect. Furthermore, the immediate action was insufficient. On the other hand, Patent Document 2 describes a method of using menthol having a function of preventing the mucus from being thrown off as a pesticide.

Japanese Patent Laid-Open No. 9-110603 JP 2001-163715 A

  However, since menthol itself has weak activity, it has been insufficient in effect to be used as a disinfectant that repels and kills gastropods even though it can prevent the effect from being removed by throwing it off.

  Accordingly, the present invention provides a disinfectant that exhibits a repellent and killing effect that is sufficiently effective and immediately effective against gastropods such as snails such as mussel, slugs, and apple mussels With the goal.

  The present invention solves the above problems by a gastropod pesticide containing a vinyl polymer having an amino group or an ammonium group in the side chain.

  When using a pesticide containing a vinyl polymer having a repeating unit having an amino group or an ammonium group in the side chain, it can be killed sufficiently and immediately if it directly contacts gastropods such as slugs and snails. Is obtained. In addition, if it is placed in advance, made into a paste, or carried on a carrier such as a sheet, a sufficient repellent effect can be obtained for gastropods.

The present invention will be described in detail below.
The present invention is a gastropod pesticide containing a vinyl polymer having an amino group or an ammonium group in part or all of the side chain.

  The amino group or ammonium group in a part or all of the side chain may be directly connected to the main chain of the vinyl polymer as a side chain, or may be a carbon atom connected to the main chain. It may be a part of the side chain connected to. The amino group or ammonium group may have a hydrocarbon group having 1 to 4 carbon atoms as a substituent. Among these, vinylamine polymers having a primary amino group or a primary ammonium group not substituted with a substituent are particularly preferable. Furthermore, the primary amino group of the side chain may have the amino group or ammonium group as a part of the cyclic amidine group formed by reacting with the nitrile group in the adjacent side chain in the same molecule. Good.

  Among the vinyl polymers, the side chain having the amino group or ammonium group is preferably at least 5% or more of all side chains, and more preferably 10% or more. Of course, all, that is, 100% of the side chains may have an amino group or an ammonium group.

  The above-mentioned vinyl polymer is a polymer in which a carbon atom chain forms a main chain, and indicates a polymer obtained by polymerization of a vinyl monomer having a vinyl group or a derivative thereof. It is necessary that at least a part of the vinyl monomer has a substituent which becomes the amino group or ammonium group or a precursor thereof.

  The vinyl polymer obtained by polymerization of the vinyl monomer has a structure in which a vinyl monomer unit or a repeating unit composed of two units thereof is combined, and a side chain of the repeating unit. A part or all of these contain an amino group or an ammonium group.

Examples of the repeating unit having a side chain containing an amino group or an ammonium group include a repeating unit represented by the following structural formula (1). Moreover, the repeating unit which is a salt of the repeating unit represented by following Structural formula (1) is also included. This salt is an ammonium salt of the amino group of the following structural formula (1), and in addition to adding an acid to the repeating unit of the following structural formula (1), the above vinyl polymer is produced. When it is obtained by hydrolyzing the amide group with an acid, it is obtained as an ammonium salt. Examples of the acid include hydrochloric acid, sulfuric acid, and aliphatic carboxylic acids having 1 to 5 carbon atoms, and the anions of ammonium salts obtained from each of them are Cl ⁻ , 1 / 2SO ₄ ²⁻ , R ^8. COO ^- to become. In the following structural formula (1), R ¹ , R ² and R ³ each represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. However, when there is a hydrocarbon group, it is general in production that only one of R ^{1 to} R ³ is a hydrocarbon group. Of these, vinylamine polymers, all of which are hydrogen atoms, are most easily produced and are preferred. Moreover, R < ⁸ > in said anion shows a hydrogen atom or a C1-C4 hydrocarbon group.

Examples of the method for producing a polymer having a hydrocarbon group as R ^{1 to} R ³ include, for example, replacing a vinylamine polymer in which all of R ¹ , R ² and R ³ are hydrogen atoms with a methyl group, Examples thereof include a method in which a -methyl-N-vinylformamide polymer is obtained by polymerization and then hydrolyzed. Note that the vinylamine polymer in which R ^{1 to} R ³ are all hydrogen atoms is obtained by hydrolysis of an N-vinylformamide polymer.

  The vinyl polymer having the repeating unit of the structural formula (1) is a homopolymer of N-vinylcarboxylic amide monomers such as N-vinylformamide and N-vinylacetamide, and these N-vinylcarboxylic amides. It can be obtained by hydrolyzing an amide group possessed by a copolymer of monomers or a copolymer of an N-vinylcarboxylic acid amide monomer and another vinyl monomer. At this time, when hydrolyzed with a base, it has a repeating unit of the structure of the above structural formula (1), and when it is treated with an acid, it has a repeating unit of its ammonium salt. Of the amide group contained in the homopolymer or copolymer that is a precursor of the vinyl polymer, the ratio of hydrolysis to amino group or ammonium group is usually the entire original amide group Is 5% or more, preferably 10% or more. On the other hand, since the effect as a disinfectant increases as the ratio changed is higher, 100% may be the repeating unit of the structural formula (1) or an ammonium salt thereof.

  As the other repeating unit of the vinyl polymer having the repeating unit of the above structural formula (1) or a repeating unit which is a salt thereof, the following structural formula (3) which remains without being hydrolyzed and has an amide group. In addition to the repeating units of N-vinylcarboxylic acid amides such as), repeating units obtained by polymerizing the above-mentioned other vinyl monomers can be mentioned. As such a repeating unit derived from another vinyl monomer, in addition to the acrylonitrile repeating unit described in the following structural formula (4), it is described in the following structural formula (5) obtained by hydrolysis of this acrylonitrile unit. Acrylic acid units, acrylamide units described in the following structural formula (6), and repeating units formed by reaction of side chains of these repeating units. Moreover, the group by which the alpha-position hydrogen atom of the side chain which these repeating units have was substituted by the C1-C4 hydrocarbon group is mentioned. Among these repeating units, the repeating unit of the structural formula (1) is particularly preferable. Furthermore, examples of the repeating unit other than these contained in the vinyl polymer include a repeating unit such as a vinyl acetate unit, a vinyl alcohol unit derived therefrom, an acrylate unit, and an acrylamide unit.

  The molecular weight of the vinyl polymer having a repeating unit of the structural formula (1) or a repeating unit thereof is not particularly limited, but is generally 1000 or more, and is 10,000 or more. More preferred. If it is less than 1000, the viscosity is too low, so that the effect cannot be exhibited sufficiently. On the other hand, it is generally 10 million or less, and more preferably 1 million or less. This is because if it exceeds 10 million, the viscosity of the aqueous solution is too high and handling becomes difficult.

  Of the repeating units constituting the vinyl polymer, the repeating unit of the structural formula (1) and the repeating unit comprising a salt thereof preferably occupy 5% or more, more preferably 10% or more. On the other hand, all of the repeating units may be repeating units of the above structural formula (1) or repeating units thereof, but such vinyl polymers are difficult to produce, so the above structural formula You may have other repeating units, such as (3).

Other examples of the repeating unit of the above-mentioned vinyl polymer include a repeating unit having a 5-membered amidine structure represented by the following structural formula (2), which is the above-mentioned two units. Similarly, in the structural formula (2), R ⁴ and R ⁵ each represent a hydrocarbon group having 1 to 4 carbon atoms or a hydrogen atom, and among them, a vinyl polymer in which all are hydrogen atoms. Is preferable because it is the easiest to manufacture. Furthermore, X in the structural formula (2) represents an anion, and examples thereof include Cl, 1 / 2SO ₄ , and R ⁸ COO.

In addition, the repeating unit of the above structural formula (2) is a structure of a repeating unit of two units as shown in the following structural formula (7) formed by a copolymer of an acrylonitrile monomer and an N-vinylformamide monomer. It is obtained by acid-hydrolyzing a polymer having the above and reacting an ammonium group and a nitrile group in adjacent side chains to form a cyclic amidine. R ⁶ and R ⁷ each represent a hydrocarbon group having 1 to 4 carbon atoms or a hydrogen atom, and among these, a vinyl polymer having a repeating unit in which both R ⁶ and R ⁷ are hydrogen atoms. Most easy to manufacture and preferred.

  In the polymer having the repeating unit of the structural formula (2), the proportion of the repeating unit of the structural formula (2) is usually 5% or more, and more preferably 10% or more. If it is less than 5%, the effect of the pesticide according to the present invention may be lowered. However, these values are values obtained by calculating the structural formula (2) as two repeating units. On the other hand, only the repeating unit of the structural formula (2), or the repeating unit of the structural formula (1) or a repeating unit composed of a salt thereof and the repeating unit of the structural formula (2) are among the vinyl polymers. However, since it is difficult to manufacture, other repeating units may remain.

  In this case, the repeating unit other than the repeating unit of the structural formula (2) constitutes the vinylamine repeating unit described in the structural formula (1) or a repeating unit composed of a salt thereof, or the structural formula ( In addition to the N-vinylformamide repeating unit described in 3) and the acrylonitrile repeating unit described in Structural Formula (4), the acrylic acid unit described in Structural Formula (5) obtained by hydrolysis of an acrylonitrile unit, Examples include the acrylamide unit described in Structural Formula (6), and further, a repeating unit produced by a reaction of the side chains of these repeating units. Moreover, the group by which the alpha-position hydrogen atom of the side chain which these repeating units have was substituted by the C1-C4 hydrocarbon group is mentioned.

  The molecular weight of the vinyl polymer having the repeating unit of the structural formula (2) is generally 1000 or more, and on the other hand, it is generally 10 million or less.

  When the vinyl polymer contains both the repeating unit described in the structural formula (1) or a repeating unit thereof and the repeating unit described in the structural formula (2), It is preferable to occupy 5% or more of all the repeating units constituting the vinyl polymer together with the repeating units, and more preferably occupy 10% or more.

  As the pesticide according to the present invention, the above-mentioned vinyl polymer may be used as it is, or may be used by dissolving it in a solvent such as water or making it into a paste. Examples of the dosage form of this pesticide include liquids, powders, granules, aqueous solutions, pastes, sheets, and the like, which are formulated into these types for use.

  Depending on the usage and purpose of each preparation, other fungicides, insecticides, herbicides, repellents, fertilizers, etc. may be added to, mixed with the above vinyl polymer, and applied simultaneously. Also good. For example, by mixing fertilizer with a pesticide used for cultivated land, the work of spraying the medicine can be summarized.

  Moreover, when combined with natural or synthetic attractants such as cereals, bark, protein products, casein, dry yeast, essential oils, etc., it can be an attractant control agent. Furthermore, the convenience of the preparation may be enhanced in combination with a fragrance component, an antioxidant, a light stabilizer and the like.

  Examples of the other fungicides include kitadine P, thiabendazole, and the repellents include p-menthane-3,8-diol, 2-hydroxymethyl-trimethylcyclohexanol, N, N-diethyl-m. -Toluamide, dimethyl phthalate, 2-ethyl-1,3-hexanediol, sinepirin (registered trademark) 222, 2,3,4,5-bis (Δ2-butylene) tetrahydrofurfural, di-n-propylisocincomero Nate, di-n-butyl succinate, 2-hydroxyethyl octyl sulfide, empentrin, curan-3,4-diol, copper compounds such as thymol, copper sulfate, copper gluconate, aluminum compounds such as aluminum sulfate, etc. Can be mentioned.

  Examples of the fragrance component include eugenol, cineole, eucalyptus oil, moon peach oil, tea tree oil, clove, menthol, anethole, hinokitiol, camphor and the like.

  Examples of the antioxidant and the light stabilizer include butylhydroxyanisole, dibutylhydroxytoluene, propyl gallate, tocopherol, γ-oryzanol, ascorbic acid, capsaicin, triphenylphosphite, diphenylisodecylphosphite, pt- And butylphenyl salicylate.

  The gastropods that exhibit the useful effects of the pesticide according to the present invention are gastropods that particularly damage useful crops. For example, the amphipods belonging to the family Lamicadae (Limacidae), the amphipods, Slugs belonging to Pyromycidae), slugs such as Japanese slugs, etc., slugs such as Nymphalidae belonging to the family Nymphalidae (Milacidae), etc .; , Snails such as Usukawamaimai belonging to the Bradybaenidae family, and apple oysters such as Sukurimingaigai (Jumbotanishi)In particular, it is highly effective against slugs such as the amphipod family, the slug family, and the elder family.

  Examples of the method for controlling gastropods using the pesticide according to the present invention include a direct method and an indirect method. The direct method is a method in which a pesticide is directly brought into contact with the gastropod to exert a killing effect. For example, a method of spraying or sprinkling a solution prepared by dissolving a pesticide according to the present invention in water or a powder into the gastropod is mentioned. In the gastropod, when the above-mentioned pesticide exceeding the lethal dose comes into direct contact with the body, the body fluid coagulates and die.

  On the other hand, the above-mentioned indirect method is a method in which a repellent effect is exerted on the gastropods by installing a formulation of the above-mentioned pesticide, so that the gastropods can be prevented from entering the place where the gastropods are to be excluded, such as plants that are damaged by food. . For example, a method of spraying the powder of the above-mentioned pesticide in a place that becomes a path of the gastropod, a method of attaching the powder paste to the periphery of a plant that protects the paste, a path of the gastropod with the above-mentioned pesticide supported on a sheet or the like The method etc. which are put in the place which becomes are mentioned.

  Examples of the method of supporting the above-mentioned pesticide on a sheet include a method of kneading the vinyl polymer directly into a resin or applying it on a sheet. The material of the sheet used here is not particularly limited. For example, polyolefins such as polyethylene and polypropylene, synthetic resins or synthetic fibers such as polyester, polyamide and polylactic acid, and natural fibers such as cotton, paper and cellulose. Etc.

  The concentration when using the pesticide according to the present invention may be adjusted to an optimum concentration according to the application. For example, when spraying as the aqueous solution, the component concentration is preferably 0.01% by weight or more, and more preferably 0.1% by weight or more. If the amount is less than 0.01% by weight, the killing effect may be insufficient, and there is a possibility of resuscitation even if it becomes temporarily asphyxia. On the other hand, it is preferably 20% by weight or less, and more preferably 5% by weight or less. This is because if it exceeds 20% by weight, there is a risk of causing phytotoxicity to the flowers to be protected.

Further, the concentration when the vinyl polymer is carried on the above sheet as a pesticide is preferably 0.1 g / m ² or more, more preferably 1 g / m ² or more. . This is because if it is less than 0.1 g / m ² , the repellent effect on the gastropod is not sufficient and the gastropod may be invaded. On the other hand, it is preferably 50 g / m ² or less, and more preferably 5 g / m ² or less. This is because if it is 50 g / m ^{2, a} sufficient effect can be exhibited, and even if the concentration is increased further, there is a high possibility that it will be wasted.

  When the pesticide according to the present invention is used, the amino group or ammonium group of the vinyl polymer contained therein can effectively exhibit the repellent effect and killing effect on gastropods.

  Hereinafter, the present invention will be described more specifically with reference to examples. First, the used vinyl polymer will be described.

(Physical properties of the vinyl polymer used)
Examples 1, 2, 5, 7... Vinylamine polymer (described as “PVAM” in the table). An N-vinylformamide-vinylamine copolymer obtained by hydrolyzing an N-vinylformamide polymer (manufactured by Daianitrix Co., Ltd .: PNVF0500) in the presence of sodium hydroxide. Vinylamine (the structural formula (1) wherein R ^{1 to} R ³ are hydrogen atoms) repeating unit content: 95%, N-vinylformamide repeating unit content: 5%. Weight average molecular weight: 60000.
Examples 3, 4, 6, 8... Vinylamidine polymer (described as “PAMD” in the table). It has a 5-membered ring amidine structure obtained by hydrolyzing a copolymer (manufactured by Daianitrix Co., Ltd .: PVADL) having a monomer molar ratio of N-vinylformamide / acrylonitrile of 50/50 in the presence of hydrochloric acid. polymer. Repeating unit of the above structural formula (2): 25%, vinylamine hydrochloride (hydrochloride of the above structural formula (1)) repeating unit: 16%, acrylonitrile repeating unit: 38%, N-vinylformamide repeating unit: 21%, The remaining amount was water. Weight average molecular weight: 100,000.
Comparative Examples 1, 2, 3... N-vinylformamide polymer (referred to as “PNVF” in the table) N-vinylformamide polymer (manufactured by Daianitrix Co., Ltd., PNVF0500) was used as it was. It has no amino group and no ammonium group, the content of the N-vinylformamide repeating unit described in Structural Formula (3) is 100%, and the weight average molecular weight is 100,000.

[Destruction effect by aqueous solution]
(Examples 1-4)
The above vinylamine polymer and vinylamidine polymer were diluted with water to prepare 5% and 0.5% aqueous solutions, respectively, as shown in Table 1. These were dripped 0.4 ml at a time in Chakoura slugs, and the number of drops until lethal was measured. The results are shown in Table 1. At the time of death, all the black-tailed slugs died while struggling.

(Comparative Example 1)
An N-vinylformamide polymer composed of repeating units of N-vinylformamide described in the structural formula (3) was diluted with water to prepare a 5% aqueous solution. As in Example 1, 0.4 ml of this was dripped onto the chakoura slug, but even when 5 drops were added, no effect was observed on the slug.

[Destruction effect by powder]
(Examples 5 and 6)
1 g of vinylamine polymer (Example 5) and vinylamidine polymer (Example 6) were adsorbed per 100 g of zeolite (Ishikawa Light Industry Co., Ltd .: Ishikawa Light No. 5), respectively, to prepare powders. As a specific adsorption method, a vinylamine polymer or vinylamidine polymer according to the present invention diluted with water to give a 50% solution is dropped in an amount of 2 g per 100 g of zeolite (of which vinylamine polymer or vinylamidine heavy polymer is added). The amount of the combined component was 1 g), which was stirred well to obtain a powder. About 1 g of this powder was taken per slug, sprinkled over the whole slug body, and the state of the slug was observed. The results are shown in Table 2. In both cases, slugs died because fluids had solidified and could not move.

(Comparative Example 2)
The N-vinylformamide polymer used in Comparative Example 1 was adsorbed on zeolite in the same manner as in Example 5 and Example 6 to obtain a powder, and when sprinkled on slugs as in Example 5, the effect on slugs was It was not seen and survived without change.

[Repellent effect by powder]
(Examples 7 and 8)
As shown in FIG. 1, 5 g of the powder 2 used in each of Examples 5 and 6 is arranged in an annular shape having an outer diameter of 12.5 cm, an inner diameter of 9.5 cm, and a width of 1.5 cm. Slug 1 was placed and the subsequent behavior was observed. The examples are Example 7 (vinylamine polymer) and 8 (vinylamidine polymer), and the results are shown in Table 3. All of them disliked contact with the powder, and remained in the center circle even after 1 hour.

(Comparative Example 3)
The powder (N-vinylformamide polymer) used in Comparative Example 2 was placed in the same manner as in Example 7. A slug was placed on the center circle, and the subsequent behavior was observed. After 30 seconds, the powder exceeded the powder. Escaped out of the circle.

Schematic of repellent test in Examples 7 and 8 and Comparative Example 3

Explanation of symbols

1 slug 2 powder

Claims (3)

A part or all of side chains having a repeating unit represented by the following structural formula (1), a repeating unit represented by a salt thereof, and / or a repeating unit represented by the following structural formula (2) A gastropod pesticide containing a vinyl polymer having a group or an ammonium group.

(Wherein R ^{1 to} R ⁵ each represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. X represents Cl, 1 / 2SO ₄ or R ⁸ COO, and R ⁸ represents a carbon atom. The number represents an alkyl group having 1 to 4 or a hydrogen atom.) The gastropod pesticide according to claim 1 , wherein the gastropod is a slug. The gastropod pesticide according to claim 1 or 2 , wherein the dosage form is a liquid, a powder, a granule, an aqueous solution, a paste, or a sheet.

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