WO2021235515A1 - Sustained-release mammal repelling composition - Google Patents

Abstract

Provided is a sustained-release mammal repelling composition capable of releasing a thiazoline compound for a long period of time while sustaining the activity of the thiazoline compound.　Provided is a sustained-release mammal repelling composition containing a mammal repelling agent and an oily gel or an oil/fat.

Description

Modified-release mammalian repellent composition

The present invention relates to a sustained release mammalian repellent composition, a method for repelling mammals, and a method for producing a sustained release mammalian repellent composition.

Wild animals cause great damage in various industries. Among wild animals, mice cause serious damage to agriculture, forestry, and livestock industry due to feeding damage to vegetables, soybeans, rice, etc., feeding damage in grain warehouses, feeding damage to young trees and bark, and transmission of infectious diseases. I keep giving. For example, according to an epidemiological study by the Ministry of Agriculture, Forestry and Fisheries, it is mentioned that mice are involved in the transmission of the virus between farms or from wild animals as a factor in the outbreak of classical swine fever, and preventive measures against the transmission of classical swine fever. Is an urgent issue. In addition, mice are a major problem in that they mediate food poisoning in commercial facilities such as restaurants and cause power outages and mechanical failures by biting electric wires, causing serious damage not only in the primary industry.

On the other hand, effective repellent techniques for wild animals including mice have not been sufficiently developed to date. The murine repellents currently on the market use the odor of wasabi and the odor of herbs as effective substances. All of these rat repellents have a weak repellent effect, and have a problem that they become acclimatized after repeatedly smelling.

In recent years, in order to overcome the problems of conventional repellents, the development of strong and incompatible new repellents based on thiazolin compounds has been promoted (Patent Document 1, Non-Patent Document 1). Animal odors are equipped with a special olfactory system that accepts odors from objects that have been identified as dangerous to the species during evolution (eg, predators for small animals and herbivores). Thiazoline compounds are odor molecules accepted by this special sensory system, which have extremely strong repellent effects on small animals such as mice, mogras, rabbits, and deer and herbivores, and can be repeatedly sniffed. Has the excellent property that habituation does not occur at all. Therefore, if a thiazolin compound is used as an active ingredient of a repellent, it will be possible to overcome the acclimation problem, which has been a serious drawback of conventional repellents, and to provide a new repellent that is strong and does not acclimatize. It is conceivable (Patent Document 1).

Repellents for wild animals need to be used indoors or outdoors for a long period of time. However, thiazolin compounds are highly volatile and easily denatured under conditions of contact with air, which is a weak point in long-term use. In addition, its high volatility and denaturable properties are obstacles to the application of thermal processing and sustained release techniques for formulation. Therefore, there is a need for a new technique for sustaining the repellent effect over a long period of time without impairing the activity of thiazolin compounds.

Patent No. 5350494

An object of the present invention is to provide a sustained release mammalian repellent composition capable of releasing a thiazolin compound for a long period of time without impairing the activity of the thiazolin compound.

In order to solve the above problems, the present inventors tried to prepare a sustained-release composition of a thiazolin compound by mixing a thiazolin compound and an oil. However, as shown in FIG. 4, the composition in which the thiazolin compound and the oil are mixed has a problem that a solid substance precipitates with the passage of time and the thiazolin compound is denatured. Therefore, it was found that by adding a gelling agent to oil to form an oil gel and embedding the thiazolin compound in the oil gel, the thiazolin compound can be stably and long-term dissipated without destabilizing the thiazolin compound. rice field. The present invention is based on the above findings and provides the following.

(1) A sustained-release mammalian repellent composition containing a mammalian repellent and an oily gel or fat, and the mammalian repellent has the following formulas (I) to (VI) :.

(In the formula, R ₁ , R ₂ and R ₃ independently indicate hydrogen, halogen atom, C _1-6 alkyl group or C _1-6 alkyl thio group, respectively.)
The sustained release mammalian repellent composition comprising one or more compounds or salts thereof selected from the compounds indicated by.
(2) The compound represented by the formula (I) is any compound selected from 2-methylthiazole, 2-ethylthiazole, 2-bromothiazole, 4-methylthiazole, and 2,4-dimethylthiazole. The sustained-release mammalian repellent composition according to (1).
(3) The compound represented by the formula (II) or (III) is 2-methyl-2-thiazolin, 2-methylthio-2-thiazolin, 4-methyl-2-thiazolin, 2,4-dimethyl-2-. The sustained-release mammalian repellent composition according to (1), which is any compound selected from thiazolin and 2,2-dimethylthiazolidine.
(4) The sustained-release mammalian repellent composition according to (1), wherein the compound represented by the formula (IV) is thiomorpholine.
(5) The sustained release according to (1), wherein the compound represented by the formula (V) is any compound selected from 2,5-dimethyl-2-thiazolin and 5-methyl-2-thiazolin. Sex mammal repellent composition.
(6) The sustained-release mammalian repellent composition according to any one of (1) to (5), wherein the oily gel is composed of an oil and a gelling agent.
(7) The sustained release mammalian repellent composition according to (6), wherein the oil is a mineral oil, a vegetable oil, and / or an animal oil.
(8) The sustained release mammalian repellent composition according to (6) or (7), wherein the gelling agent is a small molecule gelling agent, an inorganic gelling agent, and / or a polymer gelling agent. thing.
(9) The sustained-release mammalian repellent composition according to any one of (1) to (5), wherein the fat is vegetable oil, lard, beef tallow, fish oil, whale oil, wax, and / or mineral oil.
(10) A mammal repellent device comprising the sustained-release mammalian repellent composition according to any one of (1) to (9) and a container containing the sustained-release mammalian repellent composition inside.
(11) The mammal repellent device according to (10), wherein the container has one or more open portions in contact with the outside world.
(12) The mammal repellent device according to (10) or (11), wherein all or part of the container is made of a polymer compound.
(13) The polymer compound consists of a group consisting of a polyolefin polymer, an acrylic polymer, a urethane polymer, a polyvinyl chloride polymer, a polyester polymer, a polyvinyl polymer, a vinylidene polymer, an epoxy resin, and a polystyrene polymer. The mammalian repellent device according to (12), which is one or more polymers of choice.
(14) A method for repelling mammals, which is the sustained-release mammal repellent composition according to any one of (1) to (9), or the mammal according to any one of (10) to (13). The repellent method comprising arranging the repellent device in a space that repels mammals.

(15) A method for producing a sustained release mammalian repellent composition, wherein the following formulas (I) to (VI):

(In the formula, R ₁ , R ₂ and R ₃ independently indicate hydrogen, halogen atom, C _1-6 alkyl group or C _1-6 alkyl thio group, respectively.)
The production method comprising a step of mixing a mammalian repellent, an oil, and a gelling agent consisting of one or more compounds selected from the compounds shown in the above or salts thereof.

(16) A method for producing a sustained release mammalian repellent composition, which comprises a step of liquefying fats and oils, and the following formulas (I) to (VI):

(In the formula, R ₁ , R ₂ and R ₃ independently indicate hydrogen, halogen atom, C _1-6 alkyl group or C _1-6 alkyl thio group, respectively.)
The production method comprising a step of mixing a mammalian repellent composed of one or more compounds selected from the compounds shown in (1) or a salt thereof and the liquefied fat and oil.
This specification includes the disclosure content of Japanese Patent Application No. 2020-089149, which is the basis of the priority of the present application.

According to the sustained release mammalian repellent composition of the present invention, the thiazolin compound can be released for a long period of time without impairing the activity of the thiazolin compound.

It is a figure which shows the polyethylene container (A) which contains the empty polyethylene container (A), and the polyethylene container (B) which contains the oil gel which embeds the repellent. The remaining amount of 2MT under the condition that the stock solution of 2-methyl-2-thiazolin (2MT) was placed on a petri dish and the condition that 2-methyl-2-thiazolin (2MT) was embedded in an oil gel in a polyethylene container. It is a figure which shows the change with time. When air is left in the head space of the container (1), when the space above the oil gel is filled with oil gel (2), and when the side surface of the container is covered with vinyl tape (3), the appearance of the container (A) , (1)-(3) is a figure which shows the time-dependent change (B) of the remaining amount of 2-methyl-2-thiazolin (2MT). It is a figure which shows the precipitate (arrow) which formed after mixing 2-methyl-2-thiazolin (2MT) with salad oil and letting it stand indoors at room temperature for 1 week.

1. 1. Sustained Release Mammalian Repellent Composition 1-1. Overview The first aspect of the present invention is a sustained release mammalian repellent composition. The sustained release mammalian repellent composition of the present invention contains a mammalian repellent (hereinafter often also referred to as "repellent") and an oily gel or fat, and releases the repellent for a long period of time without inactivating it. be able to.

1-2. Definitions The terms frequently used herein are defined below.
As used herein, "sustained release" means that a substance is gradually released into space. As used herein, it means that odorous substances are gradually released into the air. Specifically, it means that the odorant is naturally released into the air at a speed slower than the speed at which the odorant is released under normal conditions. For example, it is released into the air at a slower rate than the undiluted undiluted odorant or the odorant diluted with a commonly used solvent. When a repellent odorant is released slowly, the animal can repel the space due to the presence of odor molecules in the surrounding space for a long period of time.

As used herein, the term "long term" or "long term" means a period longer than the period during which the odorant continues to be released under normal conditions. Specifically, it means that the undiluted stock solution odorant or the odorant diluted in a commonly used solvent continues to be released under the same conditions. The specific period varies depending on the type of odorant, but for example, 1 hour or more, 2 hours or more, 3 hours or more, 6 hours or more, half a day or more, 1 day or more, 2 days or more, 3 days or more, 1 week or more, 2 weeks or more, 1 month or more, 2 months or more, 3 months or more, 4 months or more, 5 months or more, 6 months or more, 1 year or more, 2 years or more, 3 years or more, 5 years or more, Or a period of 10 years or more is applicable.

In this specification, the type of "mammal" is not limited. For example, harmful mammals that cause damage to crops, forests, livestock or homes. More specific examples include mammals such as mice, mogras, rabbits, weasels, deer, wild boars, monkeys, cats and bears, preferably mice or deer.

In the present specification, "rat" is not limited as long as it is an animal belonging to the order Rat. Myomorpha includes Hystricomorpha, Myomorpha, and Sciuromorpha. Examples include, but are not limited to, black rats, brown rats, mice, voles, voles, bamboo rats, squirrels, porcupines, degu and nutria.

In this specification, "deer" is an animal belonging to the deer family. Examples thereof include, but are not limited to, sika deer such as sika deer, sika deer, sika deer, and sika deer.

In this specification, "mole" is an animal belonging to the mole family. Examples include, but are not limited to, the Japanese mole, the small Japanese mole, the Sado mole, and the Echigo mole.

In the present specification, "rabbit" is an animal belonging to the order Rabbit. Examples include, but are not limited to, European rabbits and hares.

As used herein, the term "thiazolin compound" means a compound having a thiazolin ring or a thiazolidine ring, or a compound having a thiomorpholine ring. Not limited, but for example, compounds that are volatile and can be perceived by the animal's sense of smell, and as a result, compounds that can induce repellent behavior in the animal are preferred. Thiazoline compounds have the effect of mimicking substances contained in predator urine for small animals and herbivores, and are therefore potent against small animals and herbivores such as mice, mogras, rabbits, and deer. Shows a repellent effect.

As used herein, the term "gel" refers to colloidal particles that self-assemble in a dispersion medium and lose their fluidity to become solid or semi-solid. Not limited to this, the sol is solidified or semi-solidified due to a temperature change or the addition of a gelling agent. Gels are divided into oil-based gels and aqueous gels (hydrogels) based on the properties of the dispersion medium, but in the present specification, gels are referred to as oil-based gels unless otherwise specified.

In the present specification, "oil-based gel" (often referred to as "oil gel" in the present specification) means a liquid oil that has lost its fluidity and changed to a gel state (gelled). For example, organogels using an organic solvent as a dispersion medium and organogels using alcohol as a dispersion medium are exemplified.

As used herein, the term "sol" refers to a liquid state in which colloidal particles are dispersed in a dispersion medium and have fluidity.

As used herein, the term "gelling agent" means a substance that can gel a substance in a sol state.

In the present specification, "fat and oil" means a substance containing an ester of a fatty acid and glycerin. In the present specification, the fat and oil shall contain any one or more of triacylglycerol, diacylglycerol, or monoacylglycerol.

1-3. Composition The sustained release mammalian repellent composition of the present invention contains a mammalian repellent as an essential component and an oily gel or fat, and includes other components as a selective component.

1-3-1. Components The components will be specifically described below.

(1) Mammalian repellent The mammalian repellent contained in the sustained-release mammalian repellent composition of the present invention is a heterocyclic compound represented by the following general formula (1) or a salt thereof, a chain sulfide compound and a chain sulfide compound. It contains at least one selected from alkyl isothiocyanates as an active ingredient.

(In the equation, ring A represents a 3-7-membered heteroatom containing at least one heteroatom selected from a nitrogen atom, a sulfur atom and an oxygen atom, and R ₁ and R ₂ are independently hydrogen. Halogen atom, optionally substituted alkyl group, optionally substituted alkoxy group, acyl group, optionally esterified carboxyl group, optionally substituted thiol group, optionally substituted amino Indicates a group or an oxo group.)

Ring A of the general formula (1) is a 3-7 member containing at least one (preferably 1-3, more preferably 1 or 2) heteroatoms selected from nitrogen, sulfur and oxygen atoms. Shows the heterocycle of. Ring A is preferably a 3-7 membered heterocycle containing a nitrogen atom and / or a sulfur atom. Ring A is more preferably a 3-7 membered heterocycle containing a nitrogen atom and a sulfur atom. The number of members of the ring A is preferably 3 to 6, and more preferably 5 or 6.

Examples of the heterocycle include, but are not limited to, pyrrol, pyridine, pyridazine, pyrimidine, pyrazine, piperazine, pyrrolidine, hexahydropyridazine, imidazole, imidazolidine, piperidine, ethylene sulfide, trimethylene sulfide, thiophene, thiorane, and the like. Tetrahydro-2H-thiopyran, thiazolin (eg 2-thiazolin, 3-thiazolin, 4-thiazolin), thiazole, thiazolidine, isothiazole, isothiazoline, thiomorpholine, thiaziazoline, thiaziazol, thiaziazolidine, 1,3-thiazan, 5 , 6-Dihydro-4H-1,3-thiazine, furan, 2H-pyran, 4H-pyran, oxazole, isothiazole, morpholine, oxazoline and the like. Preferably, thiazolin (eg, 2-thiazolin), thiazole, thiazolidine, isothiazole, isothiazole, thiomorpholin, thiadiazole, thiadiazole, thiadiazolidine, 1,3-thiazan, 5,6-dihydro-4H-1,3- Thiazine, more preferably thiazolin (eg, 2-thiazolin), thiazole, thiazolidine, 1,3-thiazan, 5,6-dihydro-4H-1,3-thiazine, thiomorpholin.

The "halogen atom" used here is preferably selected from fluorine, chlorine, bromine and iodine.

As used herein, the term "alkyl group" (when used as a group or part of a group) refers to a linear or branched alkyl group having a specified number of carbon atoms. Examples of the alkyl group include a C _1-6 alkyl group, preferably a C _1-4 alkyl group. The C _1-6 alkyl group means a straight chain or branched chain alkyl group having 1 to 6 carbon atoms. C _1-6 alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, tert-butyl group, pentyl group, 1-methylbutyl group, 2 -Methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, 1-methylpentyl group, 2- Methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1,2-dimethylbutyl group, 1, Includes, but is not limited to, 3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group or 1-ethyl-2-methylpropyl group. Preferred alkyl groups include, for example, linear or branched alkyl groups having 1 to 4 carbon atoms, more preferably methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group. Groups are particularly preferred.

The alkyl group may be substituted, and examples of the substituent include a halogeno group and the like. Examples of the halogeno group include a fluoro group, a chloro group, a bromo group and the like. The C _{1-6 haloalkyl group means a C 1-6} alkyl group substituted with 1 to 5 halogeno groups, and the type of each halogeno group when there are two or more halogeno groups is the same or different. May be. Examples of the C _1-6 haloalkyl group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chlorodifluoromethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, a 2-chloroethyl group and a 2-bromoethyl group. , 1,1-difluoroethyl group, 1,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 1,1,2,2,2 -Pentafluoroethyl group, 1-fluoropropyl group, 1,1-difluoropropyl group, 2,2-difluoropropyl group, 3-fluoropropyl group, 3,3,3-trifluoropropyl group, 4-fluorobutyl group , 4,4,4-trifluorobutyl group, 5-fluoropentyl group, 5,5,5-trifluoropentyl group, 6-fluorohexyl group, 6,6,6-trifluorohexyl group and the like. can.

As used herein, the term "alkoxy group" (when used as a group or part of a group) refers to an —O (alkyl) group having a specified number of carbon atoms. Examples of the alkoxy group include a C _1-6 alkoxy group. C _1-6 alkoxy groups include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, 1-methylpropoxy group, 2-methylpropoxy group, tert-butoxy group, pentyloxy group and 1-methylbutoxy. Group, 2-methylbutoxy group, 3-methylbutoxy group, 1,1-dimethylpropoxy group, 2,2-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, hexyloxy group, 1- Methylpentyloxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, 4-methylpentyloxy group, 1,1-dimethylbutoxy group, 2,2-dimethylbutoxy group, 3,3-dimethylbutoxy group, Although 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2,3-dimethylbutoxy group, 1-ethylbutoxy group, 2-ethylbutoxy group, 1-ethyl-2-methylpropoxy group and the like are included. , Not limited to these.

The alkoxy group may be substituted, and examples of the substituent include a halogeno group and the like. Examples of the halogeno group include the same group as the above-mentioned substituent of the alkyl group. The C _{1-6 haloalkoxy group means a C 1-6} alkoxy group substituted with 1 to 5 halogeno groups, and the type of each halogeno group when there are two or more halogeno groups is the same or different. May be. Examples of the C _1-6 haloalkoxy group include a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a 1-fluoroethoxy group, a 2-fluoroethoxy group, a 2-chloroethoxy group, a 2-bromoethoxy group, and 1 , 1-difluoroethoxy group, 1,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, 1,1,2,2,2-penta Fluoroethoxy group, 1-fluoropropoxy group, 1,1-difluoropropoxy group, 2,2-difluoropropoxy group, 3-fluoropropoxy group, 3,3,3-trifluoropropoxy group, 2,2,3,3 , 3-Pentafluoropropoxy group, 4-fluorobutoxy group, 4,4,4-trifluorobutoxy group, 5-fluoropentyloxy group, 5,5,5-trifluoropentyloxy group, 6-fluorohexyloxy group , 6,6,6-trifluorohexyloxy group and the like.

Examples of the "acyl group" used here include a formyl group and a C _1-6 alkyl-carbonyl group. Examples of the C _1-6 alkyl-carbonyl group include, but are not limited to, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, a hexanoyl group and the like.

The term "carboxyl group" used herein (when used as a group or part of a group) refers to a -COOH group. The carboxyl group may be esterified. Specific examples of the carboxyl group that may be esterified include a carboxyl group and a C _1-6 alkoxycarbonyl group. _{C 1-6} alkoxy moiety of the C _1-6 alkoxycarbonyl groups are as defined _{C 1-6} alkoxy group in the alkoxy group which may be substituted.

The term "thiol group" used herein (when used as a group or part of a group) refers to a -SH group. The thiol group may be substituted, the substituent, for example, a C _1-6 alkyl group and the like, C _1-6 alkyl groups, C _1-6 in the optionally substituted alkyl group It has the same meaning as an alkyl group. Specific examples of the thiol group which may be substituted include a thiol group and a C _1-6 alkylthio group. Examples of the C _1-6 alkylthio group include, but are not limited to, a methylthio group, an ethylthio group, a propylthio group, a butylthio group and the like.

The term "amino group" used herein (when used as a group or part of a group) refers to _two -NH groups. The amino group may be substituted with one or two substituents, and examples of the substituent include, for example, a C _1-6 alkyl group and -COR ₅ (in the formula, R ₅ is hydrogen or C _1-6 alkyl. (Indicating a group) and the like, the C _1-6 alkyl group has the same meaning as the _{C 1-6} alkyl group in the alkyl group which may be substituted. Specific examples of the optionally substituted amino group include an amino group, a C _1-6 alkyl amino group, a di (C _1-6 alkyl) amino group, and -NR ₄ COR ₅ (in the formula, R ₄ and R _5). Independently indicate hydrogen or C _1-6 alkyl group). The C _1-6 alkylamino group includes, for example, a methylamino group, an ethylamino group, a 1-methylethylamino group and the like, and the di (C _1-6 alkyl) amino group includes, for example, a dimethylamino group, N-ethyl-N-methylamino group, bis (1-methylethyl) amino group and the like are included, but the present invention is not limited thereto.

The term "oxo" used here (when used as a group or part of a group) indicates = O group.

Suitable heterocyclic compounds used as the active ingredient of the mammalian repellent contained in the sustained-release mammalian repellent composition of the present invention include, for example, thiazol, 2-methylthiazole, 2-ethylthiazole, 2-bromo. Thiazol, 4-methylthiazole, 2-formylthiazole, 2-aminothiazole, 5-methylthiazole, 2,4-dimethylthiazole, 4,5-dimethylthiazol, 2-thiazolin, 2-methyl-2-thiazolidine, 2- Ethyl-2-thiazolin, 2-bromo-2-thiazolin, 2,4-dimethyl-2-thiazolin, 4-methyl-2-thiazolin, 2-methylthio-2-thiazolin, 2-methyl-4-ethyl-2- Thiazolidine, 2-amino-2-thiazolidine, 5-methyl-2-thiazolidine, 4,5-dimethyl-2-thiazolidine, 2,5-dimethyl-2-thiazolidine, 2-mercapto-2-thiazolidine, 2-propyl- 2-thiazolin, 2- (1-methylethyl) -2-thiazolin, 2- (1-methylpropyl) -2-thiazolidine, thiazolidine, 2-methylthiazolidine, 4-methylthiazolidine, 5-methylthiazolidine, 2,4 -Dimethylthiazolidine, 2,2-dimethylthiazolidine, 2,5-dimethylthiazolidine, 4,5-dimethylthiazolidine, 2,4,5-trimethylthiazolidine, 1,3-thiazan, 5,6-dihydro-4H-1, 3-Thiazin, 2-Methyl-2-oxazolidine, 2-ethyl-2-oxazoline, 2-isopropyl-2-oxazolidine, 2-propyl-2-oxazoline, 2,4,4-trimethyl-2-oxazolidine, 4, Examples include, but are not limited to, 4-dimethyl-2-oxazolidine, oxazole, thiophene, thiolan (tetrahydrothiophene), imidazole, thiomorpholin, morpholin, isobutylene sulfide and the like.

Another preferred embodiment of the heterocyclic compound used as an active ingredient of the mammalian repellent contained in the sustained-release mammalian repellent composition of the present invention is a compound represented by the following formulas (I) to (VIII). Examples thereof include a compound selected from the above or a salt thereof.

Here, in the formula, R ₁ , R ₂ and R ₃ are independently hydrogen, halogen atom, C _1-6 alkyl group, C _1-6 haloalkyl group, C _1-6 alkoxy group and C _1-6 halo, respectively. Alkoxy group, formyl group, C _1-6 alkyl-carbonyl group, carboxyl group, C _1-6 alkoxycarbonyl group, thiol group, C _1-6 alkylthio group, amino group, C _1-6 alkylamino group, di (C) _1-6 alkyl) Amino group, -NR ₄ COR ₅ or oxo group, R ₄ and R ₅ independently indicate hydrogen or C _1-6 alkyl group, respectively. However, in formula (I), R ₁ and R ₂ are not oxo groups, in formula (II), formula (VII) and formula (V), R ₁ is not an oxo group, and in formula (III), R ₁ and R are R. ₃ may be combined to form an oxo group.

As a more preferable example of the compounds represented by the above formulas (I) to (VIII), in the formula, R ₁ , R ₂ and R ₃ are independently hydrogen, halogen atom, C _1-6 alkyl group or C _{1 respectively. Examples} thereof include a compound showing a -6 alkylthio group or a salt thereof.

As another preferred embodiment of the heterocyclic compound, among the heterocyclic compounds represented by the formulas (I) to (VIII), the 2-position and / or 4-position, or the 2-position and / or 5-position are used. Substituted thiazole, thiazolin, thiazolidine, as well as thiophene, thiomorpholin and the like can be mentioned. Such a heterocyclic compound contains a substance generally known as a reagent, a commercially available product can be used, and a substance can be obtained by a known method.

As a preferable example of the compound represented by the above formula (I), (II), (III), (VII), or (VIII), in the formula, R ₁ , R ₂ and R ₃ are independently hydrogen. Halogen atom, C _1-6 alkyl group, C _1-6 haloalkyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, formyl group, C _1-6 alkyl-carbonyl group, carboxyl group, C _{1- 6} Alkoxycarbonyl group, thiol group, C _1-6 alkylthio group, amino group, C _1-6 alkylamino group, di (C _1-6 alkyl) amino group, -NR ₄ COR ₅ or oxo group, R ₄ And R ₅ are compounds showing hydrogen or C _1-6 alkyl group or salts thereof, respectively. However, in formula (I), R ₁ and R ₂ are not oxo groups, in formula (II) and formula (VII), R ₁ is not an oxo group, and in formula (III), R ₁ and R ₃ are combined. May form an oxo group.

As a more preferable example of the compound represented by the formula (I), (II), (III), (VII), or (VIII), in the formula, R ₁ , R ₂ and R ₃ are independently hydrogen. halogen _atoms, and _{C 1-6} compound or a salt thereof an alkyl group or a _{C 1-6} alkylthio group.

As a particularly preferable example of the compounds represented by the formulas (I) to (III), in the formula, R ₁ , R ₂ and R ₃ are independently hydrogen, halogen atom, C _1-6 alkyl group or C _{1-. 6} Examples thereof include a compound showing an alkylthio group or a salt thereof.

In formulas (I)-(III), R ₁ is a hydrogen, halogen atom (eg, bromine atom), C _1-6 alkyl group (eg, methyl, ethyl) or C _1-6 alkylthio group (eg, methylthio). A compound or a salt thereof is more preferred, wherein R ₂ represents hydrogen or a C _1-6 alkyl group (eg, methyl) and R ₃ represents hydrogen or a C _{1-6 alkyl group (eg, methyl).}

In formulas (I) to (III), compounds in which R ₁ , R ₂ and R ₃ independently represent hydrogen or a C _1-6 alkyl group (eg, methyl, ethyl) or salts thereof are more preferable.

Another preferred embodiment of the heterocyclic compound used as an active ingredient of the mammalian repellent contained in the sustained-release mammalian repellent composition of the present invention is the above formula (I) or (II) in the formula. R ₁ and R ₂ are independently hydrogen, halogen atom, C _1-6 alkyl group, C _1-6 alkoxy group, formyl group, C _1-6 alkyl-carbonyl group, carboxyl group, amino group, thiol group, respectively. C _1-6 haloalkyl group, C _1-6 alkyl amino group, di (C _1-6 alkyl) amino group, C _1-6 alkyl thio group or -NR ₄ COR ₅ are shown, and in the compound of formula (II), R ₂ may represent an oxo group, _{where if either R 1} or R ₂ is hydrogen, the other is not hydrogen, and R ₄ and R ₅ each independently have a hydrogen or C _1-6 alkyl group. Examples thereof include the compounds shown or salts thereof.

Another preferred embodiment of the heterocyclic compound used as an active ingredient of the mammalian repellent contained in the sustained-release mammalian repellent composition of the present invention is described in the above formulas (I) to (VI). R ₁ represents hydrogen, halogen atom (eg, bromine atom), C _1-6 alkyl group (eg, methyl, ethyl) or C _1-6 alkylthio group (eg, methylthio), R ₂ is hydrogen or C _{1-. Examples thereof include a compound showing a 6-} alkyl group (eg, methyl) and R ₃ showing hydrogen or a C _1-6 alkyl group (eg, methyl) or a salt thereof.

In the above formulas (I) to (VI), compounds in which R ₁ , R ₂ and R ₃ are independently hydrogen or C _1-6 alkyl groups (eg, methyl, ethyl) or salts thereof are more preferable.

Another preferred embodiment of the heterocyclic compound used as an active ingredient of the mammalian repellent contained in the sustained-release mammalian repellent composition of the present invention is in the above formula (I) or (II), in the formula. R ₁ and R ₂ independently represent hydrogen or a C _1-6 alkyl group (eg, methyl, ethyl) _{, respectively, and if either R 1} or R ₂ is hydrogen, the other is a non-hydrogen compound or a compound thereof. Salt is mentioned.

Another preferred embodiment of the heterocyclic compound used as an active ingredient of the mammalian repellent contained in the sustained-release mammalian repellent composition of the present invention is the above formula (III) in the formulas R ₁ and R _2. And R ₃ are compounds or salts thereof that independently exhibit hydrogen or a C _1-6 alkyl group (eg, methyl), respectively.

Sustained-release Another preferred embodiment of the heterocyclic compound used as an active ingredient of a mammal repellents contained in mammalian repellent composition, wherein in the formula (V) of the present invention, R ₁ and R _{2 Can be} a compound or a salt thereof independently showing hydrogen or a C 1-6 alkyl group (eg, methyl).

In formula (V), when _{either R 1} or R ₂ is hydrogen, the other is more preferably a non-hydrogen compound or a salt thereof.

As another preferred embodiment of the heterocyclic compound used as an active ingredient of the mammalian repellent contained in the sustained-release mammalian repellent composition of the present invention, R ₁ and R ₂ are described in the formula (VI). Examples thereof include compounds or salts thereof that independently exhibit hydrogen or a C _{1-6 alkyl group (eg, methyl).}

Preferred examples of the compound of the formula (I) include 2-methylthiazole, 2-ethylthiazole, 2-bromothiazole, 4-methylthiazole, 2,4-dimethylthiazole and the like.

Preferred examples of the compound of the formula (II) include 2-methyl-2-thiazolin, 2-methylthio-2-thiazolin, 4-methyl-2-thiazolin, 2,4-dimethyl-2-thiazolin and the like.

Preferred examples of the compound of the formula (III) include thiazolidine, 2-methylthiazolidine, 2,2-dimethylthiazolidine, 4-methylthiazolidine, 2,4-dimethylthiazolidine and the like.

Preferred examples of the compound of the formula (IV) include thiomorpholine and the like.

Preferred examples of the compound of the formula (V) include 2,5-dimethyl-2-thiazolin or 5-methyl-2-thiazolin.

Preferred examples of the compound of the formula (VI) include 5-methylthiazolidine and the like.

Preferred examples of the compound of formula (VII) are 5,6-dihydro-4H-1,3-thiazine, 2-methyl-5,6-dihydro-4H-1,3-thiazine or 2,4-dimethyl-. 5,6-dihydro-4H-1,3-thiazine and the like can be mentioned.

Preferred compounds of formula (VIII) include 1,3-thiazan, 2-methyl-tetrahydro-1,3-thiazine or 2,4-dimethyl-tetrahydro-1,3-thiazine.

The compound having a repellent activity contained in the mammalian repellent is not limited to the above heterocyclic compound, and may be a compound having a chain structure without forming a ring (hereinafter, also referred to as a chain compound). .. The chain compound contains at least one heteroatom selected from nitrogen, sulfur and oxygen atoms. As the chain compound, for example, a chain sulfide compound or an alkyl isothiocyanate is preferably mentioned. Examples of the chain sulfide compound include, but are not limited to, allyl methyl sulfide. Examples of the alkyl isothiocyanate include, but are not limited to, _{C 1-6 alkyl isothiocyanate such as ethyl isothiocyanate.}

Salts of the compounds constituting the mammalian repellent include any pharmaceutically, agriculturally or industrially acceptable salts, such as alkali metal salts such as sodium salt and potassium salt. Alkaline earth metal salts such as magnesium salts, calcium salts; ammonium salts such as dimethylammonium salts, triethylammonium salts; inorganic acid salts such as hydrochlorides, perchlorates, sulfates, nitrates; acetates, Examples include organic acid salts such as methanesulfonate.

The mammalian repellent contained in the sustained release mammalian repellent composition of the present invention may additionally contain a further compound having repellent activity in addition to the above. Examples of such compounds that may be additionally contained include, but are not limited to, mint and camphor conventionally used as a murine repellent.

The concentration of the mammalian repellent contained in the sustained-release mammalian repellent composition of the present invention is 1 × 10 ^-6 % by weight or more, 1 × 10 ^-5 % by weight or more, 1 × 10 ^-4 % by weight or more, 1 × 10 ^-3 % by weight or more, 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 50% by weight or more, and / Or 50% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 1% by weight or less, 0.1% by weight or less, 0.01% by weight or less, 1 × 10 ^-3 % by weight or less, 1 It may be × 10 ^-4 % by weight or less, 1 × 10 ^-5 % by weight or less, or 1 × 10 ^-6 % by weight or less.

(2) Oil-based gel or oil-based gel or fat The sustained-release mammalian repellent composition of the present invention contains oil-based gel or oil-based fat. In the sustained release mammalian repellent composition of the present invention, the mammal repellent of (1) above is embedded in an oily gel or fat.

The oily gel or fat contained in the sustained-release mammalian repellent composition of the present invention does not inactivate or denature the repellent, or is difficult to inactivate or denature, and enables long-term sustained release of the repellent. Applicable to what you want to do. Hereinafter, the case of using an oily gel and an oily fat will be described separately.

(2-1) Oil-based gel As the oil-based gel, any organic solvent or a gelled oil can be used.

The oily gel may be composed of, for example, an organic solvent and a gelling agent, or may be composed of an oil and a gelling agent. The oil may be mineral oil, vegetable oil, animal oil, or any combination thereof.

Mineral oil shall also include hydrocarbons derived from underground resources such as petroleum, natural gas and coal, or hydrocarbons obtained by refining or modifying these. The hydrocarbons referred to here include aromatic compounds, naphthenic ring compounds, paraffinic compounds and the like.

Vegetable oil is an oil made from plants. For example, soybean oil, rice oil, rapeseed oil, cottonseed oil, sesame oil, safflower oil, almond oil, sunflower oil, olive oil, cacao oil, camellia oil, sunflower oil, palm oil, flax oil, perilla oil, shea oil, palm oil, jojoba. Examples include, but are not limited to, oils, grapeseed oils, corn oils, salad oils, and avocado oils.

Animal oil is an animal-derived oil. For example, fish oil obtained from fish (squid oil, mackerel oil, herring oil, saury oil, tuna oil, cod liver oil, etc.), as well as lard fat, chicken fat, butter fat, beef fat, beef bone fat, deer fat, dolphin fat. , Horse fat, pork fat, bone oil, sheep fat, neatsfoot oil, rat dolphin oil, shark oil, mackerel whale oil, whale oil, etc., but are not limited thereto.

The organic solvent may be, for example, alcohol.

Examples of the alcohol include, but are not limited to, ethanol, methanol, n-butanol, 2-butanol, isopropyl alcohol, n-propanol, 2-methylpropyl alcohol, benzyl alcohol, cholesterol, phenol and the like.

The gelling agent corresponds to one that can gel the above oil. Examples of the gelling agent include a small molecule gelling agent, an inorganic gelling agent, a high molecular weight gelling agent, or any combination thereof. Examples of the small molecule gelling agent include 12-hydroxystearic acid. Examples of the inorganic gelling agent include clay and silica particles. Examples of the polymer gelling agent include polyethylene glycol and crosslinked acrylic polymers.

The mixing ratio of oil and gelling agent is not limited as long as it can gel. For example, 50% or less, 40% or less, 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, or 1% or less, and / or 1% or more, 5 with respect to the weight of the oil. % Or more, 10% or more, 15% or more, 20% or more, 30% or more, 40% or more, or 50% or more of the gelling agent may be mixed.

The oily gel is preferably in the form of a gel, solid or semi-solid at room temperature.

(2-2) Oils and fats The oils and fats may be mineral oils, vegetable oils, animal oils, processed oils and fats, or any combination thereof. Mineral oil, vegetable oil and animal oil are as described above. The fat may be, for example, vegetable oil, lard, beef tallow, fish oil, whale oil, wax, and / or mineral oil. The fats and oils are preferably solid, semi-solid, or gel-like at room temperature, and those that liquefy at a temperature higher than room temperature can be used. Specifically, oils and fats that liquefy at 100 ° C. or lower, 80 ° C. or lower, 60 ° C. or lower, or 50 ° C. or lower, and / or 50 ° C. or higher, 60 ° C. or higher, or 80 ° C. or higher may be used. As an example, a wax having a melting point of 100 ° C. or lower, 80 ° C. or lower, 60 ° C. or lower, or 50 ° C. or lower can be used.

The mixing ratio of the repellent and the oil-based gel or fat is a ratio at which the oil-based gel or fat can be solidified, semi-solidified, or gelled without inactivating the repellent. For example, 1x or more, 2x or more, 3x or more, 4x or more, 5x or more, 10x or more, 100x or more, or 1000x or more, and / or 1000x or less, 100x or less with respect to the repellent. An oily gel or fat of 10 times or less, 5 times or less, 4 times or less, 3 times or less, 2 times or less, or 1 times or less may be mixed.

(3) Other Ingredients The sustained release mammalian repellent composition of the present invention may contain ingredients other than the mammalian repellent and the oily gel or fat.

The sustained-release mammalian repellent composition of the present invention is formulated as other components in the fields of insect repellents, insecticides, fungicides, fungicides, fragrances, colorants, and / or pharmaceuticals, pesticides, foods, and the like. Additives, solvents, carriers and the like usually used for the conversion may be contained. Additives are not limited, but for example, surfactants, organic solvents, polymer materials and the like can be used.

Examples of the surfactant include anionic surfactants, nonionic surfactants, and amphoteric surfactants. For example, examples of the anionic surfactant include alkylbenzene sulfonates, alkane sulfonates, olefin sulfonates, monoalkyl sulfates, polyoxyethylene alkyl ether sulfates, and polyoxyethylene alkylphenyl ether sulfates. And so on. Examples of these salts include alkali metal salts such as sodium salt and potassium salt, and alkanolamine salts such as monoethanolamine, diethanolamine and triethanolamine. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene block copolymer and the like represented by nonylphenyl ether and ethylene oxide adduct of higher alcohol. Be done. Examples of the amphoteric tenside include betaine-type amphoteric tenside agents such as alkylbetaine, alkylamide betaine, carbobetaine and hydroxysulfobetaine, and imidazoline-type amphoteric tenside agents. These surfactants can be used by selecting one kind or two or more kinds.

Examples of the organic solvent include methanol, ethanol, propanol, isopropanol, ethylene glycol or propylene glycol, and polymers thereof such as polyethylene glycol or polypropylene glycol, methyl cellosolve, cellosolve, butyl cellosolve, propyl cellosolve, diethylene glycol and methylcarbitol. , Carbitol, Butyl Carbitol, Propylene Carbitol, Propylene Glycol Monomethyl Ether, Propylene Glycol Monoethyl Ether, Propylene Glycol Monobutyl Ether, Propylene Glycol Monopropyl Ether, Dipropylene Glycol, Dipropylene Glycol Monomethyl Ether, Dipropylene Glycol Monoethyl Ether , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, glycerin and its derivatives and the like. As the organic solvent, one kind or two or more kinds can be selected and used.

1-3-2. Dosage Form The dosage form of the sustained release mammalian repellent composition of the present invention is such that the mammalian repellent does not inactivate or denature, or is difficult to inactivate or denature, and the sustained release of the present invention. The sex mammal repellent composition is not limited as long as it does not impair or substantially impair the sustained release properties. For example, a lump, a plate, a linear, a combination thereof, and the like can be mentioned.

The sustained release mammalian repellent composition of the present invention may be used by being encapsulated in a container described later, or may be placed or applied to a target space without being encapsulated in the container.

1-3-3. Method of Use The method of using the sustained release mammalian repellent composition of the present invention conforms to the description of the third aspect.

1-4. Effect According to the sustained release mammalian repellent composition of the present invention, the thiazolin compound can be released for a long period of time without impairing the activity of the thiazolin compound.

2. 2. Mammal repellent device 2-1. Overview A second aspect of the present invention is a mammalian repellent device. The mammalian repellent device of the present invention contains the sustained release mammalian repellent composition of the first aspect inside the container. According to the mammalian repellent device of the present invention, the repellent can be released slowly to repel the animal for a long period of time.

2-2. Configuration The mammalian repellent device of the present invention includes a sustained release mammalian repellent composition and a container containing the composition. The composition of the sustained release mammalian repellent composition conforms to the description of the first aspect. Therefore, other configurations will be described below.

2-2-1. Container The term "container" as used herein means a container having an internal storage space. In the mammalian repellent device of this embodiment, the container is characterized by containing the sustained release mammalian repellent composition according to the first aspect. The shape of the container is not particularly limited. Examples thereof include a polyhedral shape, a cylindrical shape, a pyramid shape, a conical shape, a spherical shape, an elliptical spherical shape, a spindle shape, an indefinite shape, or a combination thereof.

The container containing the sustained release mammalian repellent composition may have an open portion. For example, the container may have one or more open portions in contact with the outside world. If the container has an open portion, the repellent can be released primarily from the open portion to the outside world. The shape and size of the open portion can be appropriately selected in consideration of the release rate of the repellent.

The container may have no open portion or substantially no open portion. If the container has no open or substantially no open, the repellent can be dissipated to the outside world through the sides of the container. In this case, the material and thickness of the container can be appropriately selected in consideration of the release rate of the repellent. It is also possible to dissipate the repellent from the tiny gap between the container and the lid of the container, even if the container has substantially no open portion.

The container can be, for example, a stationary type or a hanging type container depending on the usage conditions such as the installation location.

The volume of the container is, for example, 0.1 mL or more, 0.5 mL or more, 1 mL or more, 5 mL or more, 10 mL or more, 15 mL or more, 20 mL or more, 30 mL or more, 50 mL or more, 100 mL or more, 200 mL or more, 300 mL or more, 400 mL or more, 500mL or more, 1L or more, 2L or more, 3L or more, 4L or more, 5L or more, or 10L or more, and / or 10L or less, 5L or less, 4L or less, 3L or less, 2L or less, 1L or less, 500mL or less, 400mL or less, 300mL Below, it may be 200 mL or less, 100 mL or less, 50 mL or less, 30 mL or less, 20 mL or less, 15 mL or less, 10 mL or less, 5 mL or less, 1 mL or less, 0.5 mL or less, or 0.1 mL or less.

The material of the container may be entirely or partially composed of a polymer compound. The polymer compound is selected from the group consisting of, for example, a polyolefin polymer, an acrylic polymer, a urethane polymer, a polyvinyl chloride polymer, a polyester polymer, a polyvinyl polymer, a vinylidene polymer, an epoxy resin, and a polystyrene polymer. It may be, but is not limited to, one or two or more polymers.

The polyolefin-based polymer is a polymer compound synthesized using an alkene as a monomer. Examples thereof include, but are not limited to, polyethylene, polypropylene (PP), ethylene-ethyl acrylate copolymer (EEA), ethylene-vinyl acetate copolymer (EVA), ethylene-styrene copolymer and the like.

The acrylic polymer is a polymer of acrylic acid-based monomer or methacrylic acid-based monomer. Examples of the acrylic acid-based monomer include acrylic acid, acrylic acid ester, and acrylamide. Examples of the methacrylic acid-based monomer include methacrylic acid, methacrylic acid ester, and methacrylamide.

Urethane-based polymers include, but are not limited to, for example, polyurethane obtained by reacting a polyol and polyisocyanate, and polyurethane obtained by reacting a polyol, polyisocyanate and a chain extender.

The polyvinyl chloride polymer is, for example, polyvinyl chloride.

Polyester-based polymers include polycarboxylic acids, polyols, and polyesters synthesized by polycondensation reactions of these ester compounds. Examples of the polycarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Examples of the polyol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol. Examples of the polyester-based polymer include, but are not limited to, polyethylene terephthalate (PET).

The polyvinyl-based polymer is, for example, polyvinyl alcohol.

The vinylidene polymer is, for example, polyvinylidene chloride.

Epoxy resin is not limited. For example, bisphenol A type epoxy resin and the like can be mentioned.

The polystyrene-based polymer is, for example, polystyrene.

2-2-2. Other Configurations The mammalian repellent device of the present invention may contain components other than the sustained release mammalian repellent composition inside the device.

For example, the space inside the apparatus that is not filled with the sustained release mammalian repellent composition, for example, the container head space may contain additional components other than the sustained release mammalian repellent composition. The additional component may be an oily gel or fat containing or without a repellent. The oily gel or fat or oil containing no repellent shall be the same as the oily gel or fat or oil according to the first aspect.

2-3. Effect According to the mammalian repellent device of the present invention, the repellent can be released slowly for a long period of time to repel the animal for a long period of time.

If the container headspace is filled with ingredients other than the sustained release mammalian repellent composition and the contact between the repellent and air is blocked, the stability of the repellent can be further enhanced.

3. 3. Mammal repellent method 3-1. Overview A third aspect of the present invention is a method of repelling mammals. According to the repellent method of this aspect, the sustained-release mammalian repellent composition according to the first aspect is placed in a closed space or an open space, and the sustained-release mammalian repellent composition is placed within a predetermined range in the space. By slowly releasing the repellent contained in the composition, it is possible to repel the animal for a long period of time and prevent the animal from invading the space.

3-2. Method The method of repelling mammals of the present invention includes a placement step as an essential step.
The "arrangement step" is a step of arranging the sustained release mammalian repellent composition according to the first aspect or the mammal repellent device according to the second aspect in a space for repelling mammals.

As used herein, the term "animal repellent space" means a habitat or potentially invading space for repelling animals, such as fields, orchards, forests, livestock farms, roads, and highways. , Railroad, airport, golf course, dust collection area, park, garden, garden, flower bed, parking lot, building, house, factory, warehouse, store, commercial facility, restaurant, kitchen, washroom, veranda, storeroom, underfloor, Examples include, but are not limited to, attics, electric poles, electric wires, communication cables, wire mesh, fences, etc.

The repellent composition or device may be installed indoors or outdoors.
The repellent composition or repellent device is not limited, but for example, 1 hour or more, 2 hours or more, 3 hours or more, 6 hours or more, half a day or more, 1 day or more, 2 days or more, 3 days or more, 1 week or more, 2 Week or more, 1 month or more, 2 months or more, 3 months or more, 4 months or more, 5 months or more, 6 months or more, 1 year or more, 2 years or more, 3 years or more, 5 years or more, or 10 years or more and / or 10 years or less, 5 years or less, 3 years or less, 2 years or less, 1 year or less, 6 months or less, 5 months or less, 4 months or less, 3 months or less, 2 months Use for a period of 1 month or less, 2 weeks or less, 1 week or less, 3 days or less, 2 days or less, 1 day or less, half a day or less, 6 hours or less, 3 hours or less, 2 hours or less, or 1 hour or less can do.

The animals to be repelled by the repellent composition or the repellent device are not particularly limited. For example, crops, forests, livestock or pests that cause damage to homes. Examples of harmful animals include mammals such as rats, mogras, rabbits, weasels, deer, wild boars, monkeys, cats and bears, birds such as pigeons and crows, reptiles such as snakes, ants, mukade, butterflies and cockroaches. Examples include insects.

The sustained release mammalian repellent composition of the present invention can be used so that the repellent is released at an effective concentration. As used herein, the "effective concentration" is the concentration of odor molecules in the air that allows the repellent to repel the animal of interest. This effective concentration varies depending on the type of repellent used and the combination of animals to be repelled, for example, 0.01 ppm or more, 0.1 ppm or more, 0.2 ppm or more, 0.3 ppm or more, 0.4 ppm. 0.5 ppm or more, 1 ppm or more, 5 ppm or more, or 10 ppm or more, and / or 10 ppm or less, 5 ppm or less, 1 ppm or less, 0.5 ppm or less, 0.4 ppm or less, 0.3 ppm or less, 0.2 ppm or less, 0 . It can be 1 ppm or less, or 0.01 ppm or less. For example, it is 5 ppm or more and 10 ppm or less. The concentration of odor molecules in the air can be directly measured under the conditions of use, but in the case of outdoors where measurement is difficult, the value measured in a closed space can be used as a reference value.

In addition to the above, the content of the repellent, the capacity of the repellent composition or the repellent device, the installation position, the installation density, etc. are the target animal type, dosage form, outdoor or indoor usage conditions, and / or air temperature. It can be appropriately determined according to the weather conditions such as humidity and humidity.

The installation density of the repellent composition or repellent device is, for example, 500 m 1 or more per ² lines, 100 m 1 or more per ² lines, 50 m 1 or more per ² lines, 40 m 1 or more per ² lines, 30 m 1 or more per ^{2 lines, 20 m 2} around one or more, or 10 m ² around one or more, and / or 10 m ² per or less, 20 m ² per or less, 30 m ² per or less, 40 m ² per or less, 50 m ² per or less , 100m ² per area 1 or less, or 500m ² per area 1 or less.

The installation position is not limited. If it is outdoors, it may be installed on the windward side of a space that repels animals in consideration of the wind direction.

According to the repellent method of this embodiment, for example, 1 hour or more, 2 hours or more, 3 hours or more, 6 hours or more, half a day or more, 1 day or more, 2 days or more, 3 days or more, 1 week or more, 2 weeks or more, 1 month or more, 2 months or more, 3 months or more, 4 months or more, 5 months or more, 6 months or more, 1 year or more, 2 years or more, 3 years or more, 5 years or more, or 10 years or more It is possible to repel mammals.

4. Method for Producing Sustained Release Mammalian Repellent Composition 4-1. Overview A fourth aspect of the present invention is a method for producing a sustained release mammalian repellent composition. In the production method of the present invention, the steps differ depending on whether the repellent is embedded in an oil-based gel or in an oil or fat. According to the method for producing a sustained release mammalian repellent composition of this embodiment, a sustained release mammalian repellent composition capable of releasing the repellent for a long period of time without impairing the activity of the repellent is produced. can do.

4-2. Method 4-2-1. Method using oil-based gel When the repellent is embedded in the oil-based gel in the production method of this embodiment, the production method of this embodiment includes a mixing step as an essential step.

(1) Mixing step The "mixing step" is a step of mixing a mammalian repellent, an oil, and a gelling agent.
The mammal repellent referred to here may be any of the mammal repellents described in the first aspect. For example, the following equations (I) to (VI):

(In the formula, R ₁ , R ₂ and R ₃ independently indicate hydrogen, halogen atom, C _1-6 alkyl group or C _1-6 alkyl thio group, respectively.)
It may be one or more compounds selected from the compounds indicated by or salts thereof.

In the mixing step, the order in which the mammalian repellent, the oil, and the gelling agent are mixed may be any order as long as the repellent is mixed before the gelation of the oily gel is completed. For example, the repellent and the oil may be mixed and then the gelling agent may be mixed, the repellent and the gelling agent may be mixed and then the oil may be mixed, or the repellent, the oil and the gelling agent may be mixed at the same time. May be mixed.

4-2-2. Method using fats and oils When the repellent is embedded in fats and oils in the manufacturing method of this embodiment, the manufacturing method of this embodiment includes a liquefaction step and a mixing step as essential steps, and a solidification step as a selection step.

(1) Liquefaction step The "liquefaction step" is a step of liquefying fats and oils.
The method of liquefying fats and oils in the liquefaction step is not limited. For example, fats and oils can be liquefied by heating.

(2) Mixing step The "mixing step" is a step of mixing the mammalian repellent and the liquefied fat and oil. The mammalian repellent is according to the above-mentioned "4-2-1. Method using oil-based gel".
The mixing step is a step of mixing the fats and oils liquefied in the liquefaction step with the repellent. This step is preferably carried out in a temperature range in which the repellent does not volatilize, inactivate or denature, or is less likely to volatilize, inactivate or denature. For example, mixing under temperature conditions of 200 ° C. or lower, 150 ° C. or lower, 100 ° C. or lower, 90 ° C. or lower, 80 ° C. or lower, 70 ° C. or lower, 60 ° C. or lower, 50 ° C. or lower, 40 ° C. or lower, or 35 ° C. or lower. Is preferable.

(3) Solidification step The "solidification step" is a step of solidifying, semi-solidifying, or gelling a mixture of fats and oils and a repellent after the mixing step.
The solidification step can be performed, for example, by cooling.

<Example 1: Long-term sustained release effect based on oil gel>
(Purpose)
Embed the repellent in an oil gel and verify whether a long-term sustained release effect can be obtained.
(Method)
2-Methyl-2-thiazolin (2MT) was encapsulated as a repellent in an oil gel obtained by gelling salad oil with 12 hydroxystearic acid, which is a gelling agent derived from a natural product. Specifically, 3 g of 2 MT (Tokyo Chemical Industry Co., Ltd., M0285), 5. Add 5 g of salad oil (Nisshin Oillio) and 1.5 g of 12 hydroxystearic acid (12HSA, Tokyo Chemical Industry Co., Ltd., H0308), heat in a microwave to dissolve, and then allow to cool to gel (12HSA, Tokyo Chemical Industry Co., Ltd., H0308). (Oil gelation) (Fig. 1B).

The container was left in the open air with the lid closed and shielded from light, and the release behavior of the repellent was measured by gas chromatography. Specifically, the repellent in the gel left in the field is periodically sampled, and the residual amount of the repellent in the gel is measured by Shimadzu equipped with InertCap WAX (Cat. No. 1010-67244) manufactured by GL Science. It was measured using a gas chromatograph GC-2014.

In addition, the vaporization rate of the undiluted solution of 2MT was measured as a comparative control when not sealed in the oil gel. Specifically, 3 g of a stock solution of 2 MT was placed on a petri dish, and the petri dish was left uncovered, and then the residual amount of 2 MT was recorded over time.

(result)
When the 2MT was installed on a petri dish, almost all of the 2MT evaporated in one day (Fig. 2).
On the other hand, when 2MT was embedded in oil gel, 9% or more of 2MT was released in the first 7 days, and 25% or more remained after 90 days (FIG. 2).

From this result, it was shown that the repellent embedded in the oil gel was gradually released over a long period of 100 days or more.

<Example 2: Effect of air in the container head space>
(Purpose)
Thiazoline repellents are not stable in contact with air. For example, 2MT is a liquid at room temperature, but if it is left in contact with air for several days or more, a dimer of 2MT is generated as a solid substance, and the repellent activity is lost. Therefore, it was examined whether the repellent could be stabilized and the sustained-release effect could be enhanced by expelling the air in the head space of the polyethylene container.

(Method)
In the oil gel used in Example 1, air was left in the head space above the oil gel in the polyethylene container (FIG. 3A, (1)). In order to block the contact between the oil gel and the air, a salad oil containing 12HSA (5% by weight) was layered on the oil gel to gel it, and the air was expelled from the head space (FIG. 3A, (2)).
This repellent sample was left in the field in a light-shielded state, and the release behavior of the repellent was measured by gas chromatography.

(result)
In samples with air left in the headspace, more than 60% of the repellent was released within 60 days, followed by gradual release by 120 days (Fig. 3B, square). On the other hand, in the sample in which the air was expelled from the head space, the release rate was further reduced, and about 40% of the repellent remained even after 180 days (FIG. 3B, triangle).

Therefore, it was shown that the sustained release effect can be further enhanced by expelling air from the headspace.

<Example 3: Dissipation of repellent through the side surface of the container>
To verify whether the repellent could be dissipated through the sides of the polyethylene container, the sides of the container containing the oil gel were covered with vinyl tape (Nitoms S19MM). In other respects, the same experimental conditions as in Example 2 were used, and the sustained release rate of the repellent was examined.

When the side surface of the polyethylene container was covered with vinyl tape (Fig. 3B, black circle), the sustained release rate was further reduced compared to the condition without vinyl tape (Fig. 3B, triangle). On the other hand, the residual amount after 180 days was almost the same under the two conditions.

From this result, it was shown that at least a part of the release of the repellent to the outside of the container is through the side surface of the container.

<Example 4: Modification of repellent in liquid oil>
(Purpose)
Examine the stability of repellents in liquid oils.

(Method and result)
In order to examine the stability of the repellent in the liquid oil, the repellent (2MT) was mixed with the salad oil and allowed to stand indoors at room temperature for 1 week. As a control, a gelling agent was added to prepare a sample in which a repellent was embedded in an oil gel, and the mixture was also allowed to stand for 1 week.

As a result, yellow solids were deposited in the liquid oil (Fig. 4, lower right of the photo). Such precipitates were not seen when the repellent was embedded in the oil gel using a gelling agent.

From this result, it was shown that the repellent can be denatured in liquid oil, whereas 2MT is chemically stabilized in oil gel.

<Example 5: Field test of repellent effect on mice>
(Purpose)
The repellent composition will be installed in stores and food factories in downtown areas to verify the repellent effect on mice.

(Method and result)
A sample of repellent composition was installed at a clothing store in Nankinmachi, Chuo-ku, Kobe City, Hyogo Prefecture, and a food factory in Nishinomiya City, Hyogo Prefecture, and field tests were conducted on the repellent effect on mice. The repellent composition sample was an oil gel containing a repellent contained in a polyethylene container, and the one prepared in the same manner as in Example 1 was used. The repellent composition sample was ^{placed at a ratio of about 1 per 10 m 2} and replaced with a new sample 3 months after the setting.

At the clothing store, before installing the repellent composition sample, rat footsteps in the attic were frequent. However, during the period when the repellent composition sample was installed (July 2019-December 2019), the rat's footsteps were not heard at all.

Even in food factories, mice were witnessed at least once a month before the repellent composition sample was installed, but during the period when the repellent composition sample was installed (July 2019-January 2020), the mice were witnessed even once. There wasn't.

From this result, it was demonstrated by the field test that the repellent composition sample of the present invention has a long-term repellent effect on mice.
All publications, patents and patent applications cited herein are incorporated herein by reference in their entirety.

Claims (16)

1. A sustained release mammalian repellent composition,
   Contains mammalian repellents and oily gels or fats and oils
   The mammalian repellent has the following formulas (I) to (VI):
   

   

   (In the formula, R ₁ , R ₂ and R ₃ independently indicate hydrogen, halogen atom, C _1-6 alkyl group or C _1-6 alkyl thio group, respectively.)
   The sustained release mammalian repellent composition comprising one or more compounds or salts thereof selected from the compounds indicated by.
2. Claimed that the compound represented by the formula (I) is any compound selected from 2-methylthiazole, 2-ethylthiazole, 2-bromothiazole, 4-methylthiazole, and 2,4-dimethylthiazole. Item 2. The sustained-release mammalian repellent composition according to Item 1.
3. The compounds represented by the formula (II) or (III) are 2-methyl-2-thiazolin, 2-methylthio-2-thiazolin, 4-methyl-2-thiazolin, 2,4-dimethyl-2-thiazolin, and The sustained-release mammalian repellent composition according to claim 1, which is any compound selected from 2,2-dimethylthiazolidine.
4. The sustained-release mammalian repellent composition according to claim 1, wherein the compound represented by the formula (IV) is thiomorpholine.
5. The sustained release mammal according to claim 1, wherein the compound represented by the formula (V) is any compound selected from 2,5-dimethyl-2-thiazolin and 5-methyl-2-thiazolin. Repellent composition.
6. The sustained release mammalian repellent composition according to any one of claims 1 to 5, wherein the oily gel is composed of an oil and a gelling agent.
7. The sustained release mammalian repellent composition according to claim 6, wherein the oil is a mineral oil, a vegetable oil, and / or an animal oil.
8. The sustained release mammalian repellent composition according to claim 6 or 7, wherein the gelling agent is a small molecule gelling agent, an inorganic gelling agent, and / or a polymer gelling agent.
9. The sustained-release mammalian repellent composition according to any one of claims 1 to 5, wherein the fat is vegetable oil, lard, beef tallow, fish oil, whale oil, wax, and / or mineral oil.
10. A mammal repellent device comprising the sustained release mammalian repellent composition according to any one of claims 1 to 9 and a container containing the sustained release mammalian repellent composition inside.
11. The mammal repellent device according to claim 10, wherein the container has one or more open portions in contact with the outside world.
12. The mammal repellent device according to claim 10 or 11, wherein all or part of the container is made of a polymer compound.
13. The polymer compound is selected from the group consisting of polyolefin-based polymers, acrylic-based polymers, urethane-based polymers, polyvinyl chloride-based polymers, polyester-based polymers, polyvinyl-based polymers, vinylidene-based polymers, epoxy resins, and polystyrene-based polymers. The mammal repellent device according to claim 12, which is one or more polymers.
14. A method of repelling mammals
    The sustained-release mammalian repellent composition according to any one of claims 1 to 9 or the mammalian repellent device according to any one of claims 10 to 13 is arranged in a space for repelling mammals. The repellent method comprising the steps of
15. A method for producing a sustained release mammalian repellent composition.
    The following formulas (I) to (VI):
    

    

    (In the formula, R ₁ , R ₂ and R ₃ independently indicate hydrogen, halogen atom, C _1-6 alkyl group or C _1-6 alkyl thio group, respectively.)
    The production method comprising a step of mixing a mammalian repellent, an oil, and a gelling agent consisting of one or more compounds selected from the compounds shown in the above or salts thereof.
16. A method for producing a sustained release mammalian repellent composition.
    The process of liquefying fats and oils, and the following formulas (I) to (VI):
    

    

    (In the formula, R ₁ , R ₂ and R ₃ independently indicate hydrogen, halogen atom, C _1-6 alkyl group or C _1-6 alkyl thio group, respectively.)
    The production method comprising a step of mixing a mammalian repellent composed of one or more compounds selected from the compounds shown in (1) or a salt thereof and the liquefied fat and oil.

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