JPH0776502A - Noxious animal-repelling composition - Google Patents

Abstract

PURPOSE:To obtain a noxious animal-repelling composition having higher effect than that of a conventional noxious animal-repelling composition and having long acting property and lower toxicity to human beings and beasts. CONSTITUTION:This strong repelling composition for noxious animals is obtained by using a microcupsulated component of Guinea pepper and capsaicines in Guinea pepper component, powder horseradish, pepper oil or isothiocyanates in the pepper oil component as an olfactory repellent or a gustatory repellent in spices and condiments for human being and a specific ingredient of a terpenoid as a strong repellent component derived from natural and having low toxicity to human beings and beasts and further, a specific organic amine compound having imparting proper odor, a polyoxyalkylenealkylamine having a noxious animal-repelling function and a surface active function by itself, a quaternary ammonium salt amphoteric activating agent and a fixative for limiting volatilizing rate thereof.

Description

Detailed Description of the Invention

[0001]

The present invention relates to dogs, cats, mice, rabbits, boars, moles, deer, weasels, crows, crows, sparrows, pigeons, starlings, flies, mosquitoes, cockroaches,
The present invention relates to a repellent composition for harmful or unpleasant animals such as ants.

[0002]

2. Description of the Related Art Today, global warming, ozone depletion, acid rain,
The environment is deteriorated due to global pollution caused by human factors such as radiation pollution. As measures against this, worldwide approaches are being discussed and their cooperation is requested. This idea, which is also called a kind of global environmentalism, is becoming a United Nations movement that should be prioritized over each country and nationalism. In other words, measures such as reduction of carbon dioxide to prevent global warming, ban on the production of CFC compounds to protect the ozone layer, and prevention of forest felling have come to be considered.

In order to ensure peace and prosperity and endurance of human beings in the age of prioritizing the protection of the global environment, in relation to organisms other than human beings in the production of food and the improvement of the living environment, it is necessary for humans to interact with each other, especially with animals. It is most desirable to seek shared mutual prosperity.

A mixture of fish oil and naphthalene has been used in Hokkaido since the Meiji era as a repellent for harmful animals such as rodents, hares, boars, sparrows and ducks of agricultural crops. It was the first repellent in Japan. It is said that.

After that, creosote, cycloheximide, β-naphthol, chulam, thiophenes, lemongrass oil, diallyl sulfide and iron oxide powder are used. For blood-sucking insects such as mosquitoes, mites and fleas, dimethyl phthalate, ethylhexanediol, indarone and diethyltoluamide are used.

In general, the repellents include olfactory repellant (olfactory repellant) and taste repellant (gustatory repelle).
nt) and the former is essential oil (essential o
il) and vegetable gum resins, and the latter include organic acids, alcohols, alkaloids, tannins, glycosides and the like.

In addition, a tactile repellant such as adhesion (toucho)
It is also effective to have a function such as "ry repeat".

[0008] In the living world, animals that have an unpleasant odor and taste are generally common to animals attacking from the outside due to self-preservation. This is especially seen in plants, and essential oils, alkaloids, and glycosides have this significance, and formic acid, butyric acid, salicylaldehyde, mercaptans, allyl compounds, etc. play a role in preservation of species between animals. .

Conventionally, pest repellents have been disclosed in many patent publications. Unsaturated alcohols and aldehydes (Japanese Patent Application Laid-Open No. 53-101531) are used in birds, and higher ketones are used in dogs, cats and birds and beasts. Aoba alcohol, cinnamic aldehyde and ketone (Japanese Patent Publication No. 57-25521), rat and rabbit guasazine (Japanese Patent Publication No. 57-67507), harmful birds and beasts guasazine and churum (Japanese Patent Publication No. 59-25306). Gazette), prothiophos and chulam for birds (JP-A-59-10504), and menthol and ethyltoluamide for dogs and cats (JP-A-60-142).
903), creosote and pyridine for bird damage (JP-A-61-56110), chum and animal and vegetable oils for forest harmful animals (JP-A-61-12005), and lemongrass oil for dogs, cats, etc. Etc. impregnated with ethylene-vinyl acetate copolymer beads (JP-A-61-272801), glycol ethers for dogs, cats and the like (JP-A-61-1827).
194001, JP 61-267501 A), dogs, cats and the like higher ketones, alcohols, aldehydes (JP 61-289003 A), and murine shikimic acid and mustard glycosides (JP Sho 61). 61-291507), bis (2-chloroisopropyl) ether for dogs and cats (JP 62-12702 A), shikimic acid and mustard glycosides for moles (JP 62-45508 A),
Limonene (Japanese Patent Application Laid-Open No. 62-164602) is effective for pigeons, flies and the like.

Further, as a pest repellent, a combination of a specific terpenoid compound monomer and a low polymer or low copolymer having an average molecular weight of 1000 or less (JP-A-1-29460).
No. 1) or a specific terpene monomer and a low copolymer compound having an average molecular weight of 3000 or less selected from phenolic, styrene, vinylic, and maleic monomers, and a pest repellent composition (JP-A-4-288003). ), Brassic acid (JP-A-1-96101), cashew nut oil (JP-A-1-96102),
Alkylbenzene, diphenyl, alkylphenol,
Combined use of at least one diethylene glycol alkyl ether acetate type and a terpenoid compound (Japanese Patent Laid-Open No. 4-2 / 1992).
No. 88003) is disclosed.

Further, as a repellent for dogs, cats, and birds,
There are combined use of capsicum, mustard, horseradish, spice repellent and specific limonene, but microencapsulation of spice components and terpenoid compounds are also disclosed (Japanese Patent Laid-Open No. HEI-1)
No. 139515).

Further, there is a specific monoterpene as a murine repellent (Japanese Patent Laid-Open No. 3-181402), and a rodent-proof foam containing 0.1% or more of a microcapsule of a rat repellent in a polyolefin resin. Naramycin and mercaptan have only been found as mouse repellents (JP-A-4-270738).

Further, a specific amine-based repellent composition is disclosed in Japanese Patent Application No. 3-233478, and the synthesis of capsaicins and the microcapsuling method in the wet system are disclosed in JP-A-4-36201. It is also disclosed that a resin molding composition such as an electric wire hose, tape or plate using the above is prepared from an animal bite-preventing composition to obtain a resin molding (Japanese Patent Laid-Open No. 5-907).

[0014]

The object of the present invention is to provide a pest repellent composition which is more effective than the above-mentioned conventional pest repellents, has a long-lasting effect, and is less toxic to humans and animals. To do.

[0015]

The pest repellent composition of the present invention is a capsicum in a spice of natural plant origin.
cum annuum L. ) Pericarp powder or its component capsaicins, or hawaii, western hawaii (Horse
rhizome of cruciform plants such as radish, mustard (Peppp)
er) seed oil or its allyl isothiocyanate or isobutyl isothiocyanate as an olfactory and taste repellent component, and a pest repellent composition derived from a specific terpenoid or a certain high boiling point (760 mmH
(g boiling point 150 ° C. or more) and an organic amine-based harmful animal repellent composition having a corrosive surface-active function.

At this time, the repellent component derived from the spices is a method in which plant micropowder is dispersed in gelatin or an aqueous solution of gum arabic and coated by spray-drying microencapsulation, extraction from plant ground matter or chemical synthesis. The water-insoluble components of capsaicins and isothiocyanates obtained by the above are dispersed to about 1 to 150 μm, and the core substance and water-insoluble polymer film are subjected to an interfacial polymerization method or polymerization (in
In situ, the microencapsulation method or the like is used, but the method is not limited to these two methods.

The allyl isothiocyanate (C ₄ H ₅ NS = 99.2) used in the present invention is obtained by reacting allylbenzyl sulfide with bromine cyanide or allyl p-toluenesulfonate with potassium thiocyanate. To be Freezing point -80 ° Boiling point 151 ° (56 ° / 22m
mHg) shows a specific gravity of about 1.0155. Isobutyl isothiocyanate (C ₅ H ₇ NS = 115) is obtained by reacting isobutylamine with thiophosgene and has a boiling point of 16
It shows 2 ° (31 ° / 10 mmHg) and a specific gravity of 0.9638.

As capsaicins, for example, N
-(4-Hydroxy-3-methoxyvezyl) -8-methylnon-trans-6-enamide (capsaicin), N
-(4-Hydroxy-3-methoxybenzyl) -8-methylnonanamide (dihydrocapsaicin), N- (4-
Hydroxy-3-methoxybenzyl) -7-methyloctanamide (nordihydrocapsaicin), N- (4-hydroxy-3-methoxybenzyl) -9-methyldecanamide (homodihydrocapsaicin), N- (4-hydroxy-3) -Methoxybenzyl) -9-methyldecoutrans-7-enamide (homocapsaicin), N- (4-
Hydroxy-3-methoxybenzyl) -nonanamide and the like can be mentioned.

Of these, a typical one is N- (4
-Hydroxy-3-methoxybenzyl) -8-methylnon-trans-6-enamide (C ₁₈ H ₂₇ NO ₃ ) with a melting point of 64 to 65 ° and a boiling point of 0.01 mmHg of 210 to 220.
℃ can be raised.

As an example of this microcapsule, 29.2 g of allyl isothiocyanate dissolved in 20 g of soybean oil.
Polymethylene polyphenyl isocyanate (3.7 g) was dissolved in the mixture, heated to 50 ° C., and added to a solution prepared by dissolving 0.9 g of sodium lignin sulfonate in 41.3 g of water while stirring and emulsifying, and high-speed shearing and stirring with a homogenizer. Raise the liquid temperature to ℃. To this 3.5% 1,6
Hexamethylenediamine (4.9 g) was added, stirring was loosened, and after 30 minutes, microcapsules with a diameter of 1 to 10 μm were obtained. About 100% of this solution contains about 55% of microcapsules of about 52% allyl isothiocyanate. Similarly, isobutyl isothiocyanate is also microencapsulated. It can be used as a wet powder, powder, granule, wettable powder, aqueous emulsion and the like.

Further, synthetic capsaicin [N- (4-hydroxy-3-) of the repellent taste olfactory component used in the present invention is used.
Methoxybenzyl) -8-methylnon-trans-6-
Enamide

[Chemical 6] _{C 18 H 27 O 3 N =} 305, mp 64-65 °, boiling point 21
0-220 ° / 0.01 mmHg] and the microcapsule manufacturing method thereof, the following method can be adopted.

A solution of 4.7 parts of 4-hydroxy-3-methoxybenzylamine in 25 parts of diethyl ether was added with 8-methylnon-trans-6-enoic acid chloride.
Add 7 parts and pyridine 0.2 parts and stir at room temperature for 4 hours.

Next, 10 parts of water is added, and after stirring for 5 minutes, the mixture is allowed to stand for 5 minutes, and the lower aqueous layer is discharged. Removal of the ether almost completely under reduced pressure gave (E) -N- (4-hydroxy-3-methoxybenzyl) -8-methylnon-6.
A crude enamide can be obtained. Collect an extremely small amount and use N- (4-hydroxy-3-methoxybenzyl)
The purity of -8-methylnon-6-enamide was determined by HPLC to be 90.5%.
In particular, the irritation to the mucous membrane was intense. 21.5 parts of dimethyl phthalate, 3.0 parts of sebacic acid dichloride, 3.0 parts of polymethylene polyphenyl isocyanate and 0.1 part of polyoxyethylene (n = 10) nonyl phenyl ether were added to this reactor and stirred uniformly. A mixed solution is obtained. Further, 50 parts of a 1.5% polyvinyl alcohol aqueous solution is added thereto, and the mixture is stirred at a rotation speed of 650 rpm for 10 minutes to obtain a dispersion system. Next, the stirring speed was reduced to 250 rpm, 1.0 part of sodium hydroxide and 1.
An aqueous solution prepared by adding water to 0 part and 1.0 part of diethylenetriamine to 13.9 parts was gradually added dropwise to this system, and after the addition, the liquid temperature was set to 60 ° C. and reacted for 2 hours, and N- (4-
About 98.9 parts of microcapsules in suspension containing 7.5% of hydroxy-3-methoxybenzyl) -8-methylnon-6-enamide are obtained. The free component ratio of this product is as low as 0.6%, and the stimulativeness is remarkably reduced, and the preparation can be easily handled.

As the terpenoid repellent component, terpenoid monomers include myrcene, alloocimene, citral, linalool, limonene, dipentene, terpinene, terpineol, anethole, pinene, nopol,
Camphene, nopyr acetate, geraniol, isobornyl acetate, etc. can be used. In addition, the combined use of these homo- or hetero-co-oligomers and terpenoid monomers with phenol-based, styrene-based, vinyl-based or maleic acid-based monomers and low copolymers having a molecular weight of 3,000 or less (hetero-co-oligomers) is also repellent. Significantly improve.

The primary amines of organic amines having the boiling point and the atmospheric pressure of 150 ° C. or higher are shown in the order of the molecular formula, the molecular weight and the boiling point.

Heptylamine (C ₇ H ₁₅ NH
₂ 115.2 155 ° C.) Octylamine (C ₈ H ₁₇ NH ₂ 12
9.2 177 ° C.) Nonylamine (C ₉ H ₁₉ NH ₂ 14
3.2 202 ° C.) Decylamine (C ₁₀ H ₂₁ NH ₂ 15
7.3 217 ° C.) Undecylamine (C ₁₁ H ₂₃ NH ₂ 17
1.3 240 ° C.) Dodecylamine (C ₁₂ H ₂₅ NH ₂ 18
5.3 248 ° C.) Tridecylamine (C ₁₃ H ₂₇ NH ₂ 19
9.4 265 ° C.) tetradecylamine (C ₁₄ H ₂₉ NH ₂ 21
3.4 291 ° C.) Hexadecylamine (C ₁₆ H ₃₃ NH ₂ 21
4.5 330 ° C.) Octadecylamine (C ₁₈ H ₃₇ NH ₂ 26
9.5 349 ° C.) Oleylamine (C ₁₈ H ₃₅ NH ₂ 26
7.5 330 ° C.) Monoethanolamine (NH ₂ C ₂ H ₄ OH 6
1.1 170 ° C.) Isopropanolamine (NH ₂ C ₃ H ₆ OH 7
5.1 160 ° C.) Parachloroaniline (C ₆ H ₄ ClNH ₂ 1
27.6 232 ° C.) 3,4-dichloroaniline (C ₆ H ₃ Cl ₂ NH ₂
162 272 ° C.) 2,5-dichloroaniline (C ₆ H ₃ Cl ₂ NH ₂
162 251 ° C.) Benzylamines (C ₆ H ₅ CH ₂ NH ₂
107.2 185 ° C.) α-naphthylamine (C ₁₀ H ₇ NH ₂ 14
3.2 299 ° C.) β-naphthylamine (C ₁₀ H ₇ NH ₂ 14
3.2 299 ° C) Piperazino ethyleneamine (NHC ₄ H ₈ NC ₂ H ₄ N
H ₂ 129.2222 ° C.) Tris (hydroxymethyl) aminomethane ((CH ₂ O
H) ₃ CNH ₂ 121.1 219 219 ° C.) Or, as the symmetric type among secondary amines, the following ones can be mentioned.

Dihexylamine ((C ₆ H ₁₃ )
₂ NH 185.4 193 ° C.) Dioctylamine ((C ₈ H ₁₇ ) ₂ NH 2
41.5 297 ° C.) Dilaurylamine ((C ₁₂ H ₂₅ ) ₂ NH 3
54 melting point 47 ° C.) dihexadecylamine ((C ₁₆ H ₃₃ ) ₂ NH 4
66 melting point 67 ° C.) dioctadecylamine ((C ₁₈ H ₃₇ ) ₂ NH 5
22 melting point 72.3 ° C.) diethanolamine ((C ₂ H ₄ OH) ₂ NH
105.1 269 ° C) Diisopropanolamine ((C ₃ H ₇ OH) ₂ NH
133.2 249 ° C.) A large number of mixed secondary amines may be mentioned, and one example thereof is ethylhexadecylamine ((C ₂ H ₅ ) (C ₁₆ H
₃₃ ) NH 269195 ° C./15 mmHg) Propylisoamylamine ((C ₃ H ₇ ) (C ₅ H ₁₁ ).
NH 129 150 ° C.) Butylisobutylamine ((C ₄ H ₉ ) (isoC ₄
H ₉ ) NH 12982 ° C./80 mmHg) Butylhexadecylamine ((C ₄ H ₉ ) (C ₁₆ H ₃₃ ).
NH 297 195 ° C./6 mmHg) As a tertiary amine, a symmetrical type is tri-n-propylamine ((C ₃ H ₇ ) ₃ N 14
3 156 ° C.) tri-n-butylamine ((C ₄ H ₉ ) ₃ N 18
5 216 ° C) Triisobutylamine ((isoC ₄ H ₉ ) ₃ N
185 192 ° C.) tri -n- amylamine _{((nC 5 H 11) 3} N 2
30 130 ° C./14 mmHg) Triisoamylamine ((isoC ₅ H ₁₁ ) ₃ N
230 235 ° C.) trihexylamine _{((C 6 H 13) 3} N 26
9 264 ° C.) triheptylamine ((C ₇ H ₁₅ ) ₃ N 31
0 330 ° C.) Trioctylamine ((C ₈ H ₁₇ ) ₃ N 36
5 365 ° C.) Trihexadecylamine ((C ₁₆ H ₃₃ ) ₃ N 68
9 melting point 39 ° C.) triethanolamine ((C ₂ H ₄ OH) ₃ N
149.2 360 ° C.) Triisopropanolamine ((isoC ₃ H ₆ OH)
₃ N 191.2306 ° C.) methyldiethanolamine _{((C 2 H 4 OH)} 2 NCH
₃ 119 242 ° C.) Diethylethanolamine ((C ₂ H ₅ ) ₂ NC ₂ H ₄
OH 117.2162 ° C) dipropyl ethanolamine _{((C 3 H 7) 2} NC 2 H
₄ OH 145.3191 ° C.) dibutyl ethanolamine _{((C 4 H 9) 2} NC 2 H 4
OH 173.3229 ° C.) Dimethyloctylamine (C ₈ H ₁₇ N (CH ₃ ) ₂
213.4 191 ° C.) Dimethyldodecylamine (C ₁₂ H ₂₅ N (CH ₃ ) ₂
213 122 ° C./5 mmHg) Dimethylhexadecylamine (C ₁₆ H ₃₃ N (CH ₃ ) ₂
269 174 ° C./5 mmHg) Dimethyl octadecylamine (C ₁₈ H ₃₇ N (CH ₃ ) ₂
297 193 ° C./5 mmHg) Diethylhexadecylamine ((C ₂ H ₅ ) ₂ (C ₆ H
₁₃ ) N 157 355 ° C).

As another amine, methylpropyldecylamine ((CH ₃ ) (C ₃ H ₇ )
(C ₁₀ H ₂₁ ) N 203 90 ° C./5 mmHg) Methylbutylisobutylamine ((CH ₃ ) (C
₄ H ₉ ) (iC ₄ H ₉ ) N143 82 ° C / 75m
mHg). Further, a compound obtained by adding 2 to 20 mol of ethylene oxide to dodecylamine.

[Chemical 7] (However, m and n are 1 to 30.), and this product also acts as an emulsifier and is useful.

Further, a compound similarly added to stearylamine

[Chemical 8] (However, m and n are 1 to 30.), and this product can also be widely used as an emulsifier.

The fatty acid polyamine has two or more amino groups and is synthesized from an aliphatic polyhalide and ammonia. A diamine having two amino groups is a liquid or a solid having a low melting point and is soluble in water. Ethylenediamine becomes piperazine when dried and easily forms a coordination compound with many metals.

The raw material names (molecular formula, boiling point) are shown in this order: diethylethylethylenediamine ((C ₂ H ₅ ) ₂ NC
₂ H ₄ NH (C ₂ H ₅ ) 55 ° C./13 mmHg) Tetraethylethylenediamine ((C ₂ H ₅ ) ₂ NC ₂
H ₄ N (C ₂ H ₅ ) ₂ 65 ° C./8 mmHg) Dipropylethylenediamine ((C ₃ H ₇ ) ₂ NC ₂ H
₄ NH ₂ 88 ° C./30 mmHg) Dibutylethylenediamine ((C ₄ H ₉ ) ₂ NC ₂ H ₄
NH ₂ 99 ° C./13 mmHg) Tetramethylethylenediamine ((CH ₃ ) ₂ NC ₂ H
₄ N (CH ₃ ) ₂ 166 ° C.) Next, a solid material having a boiling point of 150 ° C. or higher is used as a raw material name (molecular formula,
Melting point), N-octylethylenediamine (C ₈ H ₁₇ NHC ₂ H ₄
NH ₂ 30 ° C.) N-decylethylenediamine (C ₁₀ H ₂₁ NHC ₂ H ₄ N
H ₂ 36 ° C.) N-dodecylethylenediamine (C ₁₂ H ₂₅ NHC ₂ H ₄
NH ₂ 37 ° C.) N-hexadecyl ethylenediamine (C ₁₆ H ₃₃ NHC ₂
H ₄ NH ₂ 56 ° C.) N-octadecylethylenediamine (C ₁₈ H ₃₇ NHC ₂
(H ₄ NH ₂ 64.5 ° C.) is also repellent to pests,
As a raw material having the surface-active function, it is widely used for formulation of repellent compositions.

The primary, secondary and tertiary amines are
Many of them easily form an adduct with an acidic substance and solidify. For example, dodecylamine acetate and hydrochloride, stearylamine acetate, oleate, phenolate, pentachlorphenolate and the like are also effective.

As the quaternary ammonium salt, there are many tetraalkylammonium salt-type combinations of various alkyl residues, and dimethyldidecylammonium chloride has the strongest bactericidal activity. Examples of the benzalkonium type include lauryldimethylbenzylammonium chloride, and examples of the benzethonium salt include dimethylbenzyloctaphenoxyethoxyethylammonium chloride. Alkylimidazoline or aminoethyleneimidazoline having ethylenediamine or ethanolaminoethyleneamine and a fatty acid also has the pest repellent function of the present invention.

The molecular formula of the quaternary ammonium salt is shown below. Dimethyldidecyl ammonium chloride (CH ₃ ) ₂ (C ₁₀
H _{21) 2} N ⁺ Cl ^- downy chloride Nzarukoniumu _{(CH 3) 2 (C 13} H 27) (C 6
^{_{H 5 CH 2) N + Cl}} - downy chloride Nzetoniumu _{(CH 3) 2 (C 6} H 5 CH 2)
_{[C 8 H 17 C 6 H 5} (OC 2 H 4) 2 ] N ⁺ Cl ^- lauryl pyridinium chloride salt ^{_{[(C 5 H 5 N +)}} C 12 H
_25] Cl ^- stearyl chlorides 3 Pikoriumu salt [(CH ₃ C ₅ H
₄ N ⁺⁾ C ₁₆ H _33] Cl ^- lauryl methylimidazolium chloride salt

[Chemical 9] Etc.

As the amphoteric surfactant, there are carboxybetaine type, aminocarboxylate type and imidazoline type, and those having an anionic hydrophilic group and a cationic hydrophilic group in the molecular formula can be used in the present invention.

These are obtained by heating dimethylalkylamine and sodium chloroacetate at 60 to 80 ° C., for example, dimethyllauryl carboxybetaine.

[Chemical 10] Further, as the RNH- (CH ₂ ) nCOOH type, for example, N-laurylaminoacetate C ₁₂ H ₂₅ NHCH
There is ₂ COOH.

Further, 2-lauryl-N-carboxymethylhydroxyethylimidazolium betaine obtained by the reaction of higher fatty acid and aminoethylethanolamine

[Chemical 11] There is. Although it is less irritating to the eyes and is used as a detergent for cosmetics, it has a wide range of applications as an emulsifier functional component of the composition of the present invention.

Further, a retention agent (Fixative) having a function of adjusting the evaporation rate of these spice-based microencapsulated repellent components, terpene-based repellent components or amine-based repellent components.
In general cosmetics, waxes and resins having a slight odor are used in the field of general cosmetics, but in the present invention, those which do not impair the olfactory repellent function with a large molecular weight and a small vapor pressure can be used. The materials listed below by name of raw material (molecular formula, boiling point under 760 mmHg) can be used.

Benzoic acid ester (methyl C ₈ H ₈ O ₂ 200 °, ethyl C ₉ H ₁₀ O ₂ as an acid ester system)
213 °, phenyl C ₁₃ H ₁₀ O ₂ 315 °, benzil C ₁₄ H ₁₂ O ₂ 323 °) phthalic acid ester (dimethyl C ₁₀ H ₁₀ O ₄ 282 °, diethyl C ₁₂ H ₁₄ O ₄
296 °, dibutyl C ₁₆ H ₂₂ O ₄ 341 °), benzyl acetate (C ₉ H ₁₀ O ₂ 215 °), diphenyl ether (C ₁₂ H ₁₀ O 259 °) as an ether, dibenzyl ether (C ₁₄ H ₁₄ O) 297 °), phenoxyethanol (C ₈ H ₁₀ O ₂ 245 °), diethylene glycol monobutyl ether (C ₈ H ₁₈ O ₃ 230
°), diethylene glycol dibutyl ether (C ₁₂ H
₂₆ O ₂ 255 °), triethylene glycol monoethyl ether (C ₈ H ₁₈ O ₄ 255 °), benzyl alcohol (C ₇ H ₈ O 205 °) as an alcohol system,
Methylbenzyl alcohol [C ₈ H ₁₀ O 233 °
(O), 216 ° (m) 217 ° (p)] 1-decanol (C ₁₀ H ₂₂ O 229 °) oleyl alcohol (C
₁₈ H ₃₆ O 335 °), stearyl alcohol [(C ₁₀
H ₃₈ O 210 ° (15 mmHg)] Diphenyl (C ₁₂ H ₁₀ 255 °) methylnaphthalene [C
₁₁ H ₁₀ 245 ° (α), 241 ° (β)], ethylnaphthalene [(C ₁₂ H ₁₂ 259 ° (α), 258 °
(Β)].

The present invention also provides another animal repellent compound,
Higher ketone, cinnamic aldehyde, alkyl (6 to 1 carbon atoms
8) Aldehydes, allyl halides, isobornyl thiocyanate, octachlorodipropyl ether, dodecylbenzene, ethyldiphenyl, diethyldiphenyl,
Terphenyl, alkyl (C4-12) phenol, phenylphenol, diphenylthioether, dibenzylthiophenol, methylnaphthyl ether, ethylnaphthyl ether, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, polyoxypropylene glycerol, Vitrex, 8 -One or more selected from acetyl sucrose can be used in combination.

As described above, peppers (synthetic ingredients capsaicins), which are spices derived from individual raw materials having an olfactory or taste repellent function for harmful animals, or mustard oil, horseradish, horseradish (synthetic ingredients) (Isothiocyanates) finely coated particles, a terpene compound having repellent property and / or a repellent organic amine, and a retaining agent thereof can be combined to produce a product.

As described above, various forms of powders, emulsions, granules, liquids, pastes, wettable powders, and smoke agents can be used as the formulation form of the pest repellent of the present invention. . Furthermore, raw rubber, recycled rubber, acrylic resin,
From rosin, corpar, dammar, polyterpene resin, polybutene chloride, polyalkylene chloride resin, polyurethane resin, petroleum resin, coumarone resin, indene resin, polyolefin resin, polyamide resin, polycarbonate resin, epoxy resin, fluorine resin, carbon resin, silicon resin One or more selected may be compatible with each other to form a pattern.
That is, electric wires, optical fibers, OA equipment plastics,
It can be molded into sheets, mats, files, plates, blocks, nets, etc.

In this way, the molded products have no harmful animals,
For example, it can give a repellent function to flies, mosquitoes, rats, cockroaches, termites, house flies, dogs, cats, weasels, moles and the like.

The abbreviations for the raw materials of the composition of the present invention are shown below.

Microcapsule component 55% suspension of microcapsules containing 1.52% allyl isothiocyanate (AITC 28.6% product (52 × 0.55 = 2
Abbreviated as 8.6) 2. Isobutyl isothiocyanate 28.6% containing capsule suspension (abbreviated as IBITC 28.6%) 3.7.5% capsaicin suspension (CS, abbreviated as 7.5%) Terpene component 1. β-myrcene (C ₁₀ H ₁₆ ) (Component T-No.
1) 2. Alloocimene (C ₁₀ H ₁₆ ) (Component T-No.
2) 3. Limonene (C ₁₀ H ₁₆₎ (component T-No.3) 4. Dipentene (C ₁₀ H ₁₆₎ (component T-No.4) 5. Terpineol (C ₁₀ H ₁₈ O) (Component TN
o. 5) 6. Pinene (α-40%, β-60% mixture) (C
₁₀ H ₁₆ ) (Component T-No. 6) 7. Isobornyl acetate (C ₁₂ H ₂₀ O ₂ ) (Component T-No. 7) 8. Geraniol (C ₁₀ H ₁₈ O) (component T-No.
8) 9. Cineole (C ₁₀ H ₁₈ O) (component T-No.
9) 10. α-Pinene oligomer (molecular weight 460) (Component T-No. 10) 11. Pinenedipentene co-oligomer (molecular weight approx. 85
0) (Component T-No.ll) 12. α-Pinenephenol cooligomer (molecular weight about 330) (Component T-No. 12) 13. d-limonene styrene cooligomer (molecular weight about 1200) (component T-No. 13) amine compound 1. Dodecylamine _{(C 12 H 25 NH 2)} ( component A-
No. 1) 2. Oleylamine _{(C 18 H 35 NH 2)} ( component A-
No. 2) 3. Stearylamine _{(C 18 H 37 NH 2)} ( component A-
No. 3) 4. Diethanolamine _{(C 2 H 4 OH) 2} NH ( component A-No.4) 5. Polyoxyethylene dodecylamine HLB14.0
(Component A-No. 5) 6. Polyoxyethylene stearylamine HLB4.0
(Component A-No. 6) 7. Benzalkonium chloride [(CH ₃ ) ₂ C ₁₂ H ₂₅ C ₆
H ₅ CH ₂ N] C ₁ (Component A-No.7) fixative ingredient compound 1. Benzoate _{(C 8 H 8 O 2)} ( component F-N
o. 1) 2. Benzylic Benzoate (C ₁₄ H ₁₂ O ₂ ) (Component F-
No. 2) 3. Dibutyl phthalate (C ₁₆ H ₂₂ O ₄ ) (Component F-
No. 3) 4. Diphenyl ether (C ₁₂ H ₁₀ O) (Component F-
No. 4) 5. Dibenzyl ether (C ₁₄ H ₁₄ O) (Component F-
No. 5) 6. Diethylene glycol monobutyl ether (C ₈
H ₁₈ O ₃ ) (Component F-No. 6) 7. Stearyl alcohol (C ₁₈ H ₃₈ O) (Component F
-No7) 8. Diphenyl (C ₁₂ H ₁₀ ) (Component F-No. 8) 9. α-Methylnaphthalene (C ₁₁ H ₁₀ ) (Component F-
No. 9) 10. Benzylic alcohol (C ₇ H ₈ O) (component F
-No _. 10)

[0046]

[Function] As an olfactory repellent component or a taste repellent component in human food spices, capsicum and its components, capsaicin, powdered horseradish, mustard oil, and microcapsulated components of isothiocyanates in the components, A specific component of terpenoids as a low-toxic, naturally-derived strong repellent component, a specific organic amine compound having a flavoring and aroma-imparting function, and a polyoxyalkylene which itself has a pest repellent function and a surface-active function. By using an alkylamine, a quaternary ammonium salt amphoteric activator and a retention agent that controls the volatilization rate of these, a strong pest repellent composition can be obtained.

[0047]

【Example】

 Example 1. The example which prepared this invention as a powder is shown.

Fine pearlite powder (average particle size 46 μm) 40
10 parts of the component blended liquid of Table 1 was allowed to absorb oil, and 50 parts of kaolin fine powder (average particle size 40 μm) was mixed to obtain a repellent powder.

[0049]

[Table 1] This agent can be effective as a repellent for dogs, cats, mice, cockroaches, ants, etc. by dusting it in the passage.

Example 2. An example in which the present invention is prepared as an emulsion will be shown.

5.6 parts of polyoxyethylene (n = 20) nonylphenyl ether and 2.4 parts of calcium dodecylbenzene sulfonate were mixed and dissolved in 92 parts of the component liquid mixture shown in Table 2 to obtain a repellent emulsion.

[0052]

[Table 2] This agent can be used by spraying and coating it with water at a constant dilution ratio (2 to 10 times).

Example 3. The example which prepared this invention as an aerosol agent is shown.

A pressure resistant aerosol container was filled with 360 ml of a 50% aqueous emulsion containing 50% of the component-containing emulsion stock solution shown in Table 3 to obtain a repellent aerosol.

[0055]

[Table 3] This product can be used for domestic use as a repellent for dogs, cats, cockroaches, mice, etc.

Example 4. An example in which the present invention is applied to a repellent tape will be shown.

4 parts of 50% polymethacryl emulsion polymerization solution was added to 90 parts of the component mixture solution of Table 4 and mixed, and 6 parts of tolylene diisocyanate (TDI) was added to the solution to give a thickness of 1
mm, width 5 cm non-woven tape (30% cotton, 20% polyester, 50% nylon fiber) so that the repellent compatible resin content is 70%, after dip coating, cure,
I got a repellent tape. Can be used as a repellent by installing it at the entrance of dogs, cats, wild boars, weasels, snakes, etc.

[0058]

[Table 4] Example 5. The example which applied this invention to the harmful animal repellent paint is shown.

75 parts of the component blending liquid of Table 5, 15 parts of vinyl propionate resin, and 10 parts of methyl isobutyl ketone were mixed and dissolved to obtain a harmful animal repellent paint.

[0060]

[Table 5] This agent can be applied to electric wires, propane gas pipes, and underground cables to prevent invasion of rats, ants, cockroaches, etc. It can also be used as an antifouling paint for fishing nets.

Example 6. An example in which the present invention is applied to a repellent wire will be shown.

An impregnated product of 15 parts of the component mixture liquid of Table 6 and 85 parts of chlorinated polyethylene was extrusion-coated with a thickness of 0.2 mm on a 1 mmφ5 Kv crosslinked polyethylene insulated cable to obtain a pest repellent electric wire.

[0063]

[Table 6] This treated electric wire can be used for electric wires, computer wiring, etc. that can prevent bites from rats, ants, and bees.

Example 7. An example in which the present invention is applied to a rabbit repellent will be shown.

40 parts of the component liquid of Table 7 is heated to about 50 ° C. and mixed with 60 parts of warm water with stirring to emulsify to obtain a rabbit repellent.
This product could be applied to the resin of young cypress trees to prevent the damage of rabbits.

[0066]

[Table 7] Example 8. An example of applying the present invention to an adhesive repellent, a pigeon, a rat, a repellent such as a boar to obtain an adhesive repellent aqueous emulsion is shown.

30 parts of the component liquid of Table 8 was added to 70 parts of water with stirring to obtain a water repellent adhesive emulsion.

[0068]

[Table 8] The compositions shown in the above examples were applied to the following tests, but they had a repellent action against harmful animals such as dogs, cats, rats, pigeons and the like.

Test Example 1 An example applied to a cat will be shown.

100 g of commercially available cat food (crude tuna meat boiled product) was placed in each of 5 circular plastic containers having a diameter of 25 cm and a height of 7 cm, and four of them were used in Example 1.
Samples (Sample Nos. 1 to 4) were uniformly removed for each 8 g.
The remaining one was used as a control, and 8 g of perlite and kaolin fine powder were removed instead of the sample.

These 5 pieces were placed in a cage made of wire mesh of about 2 m ³ , and 2 pieces of Bermuse cats (hybrid) (2 years old and 4 years old) fasted for 1 day were put in this cage.

The weight of the cat food was weighed daily, and the repellent effect was judged by the residual rate. In addition, the control untreated section is 3
100 g of cat food was added every day for comparison. The results are shown in Table 9.

[0073]

[Table 9] Test Example 2 An example applied to a rat (rat) will be shown.

Two rats after 5 weeks of age were placed in a plastic cage for breeding (the lid was made of stainless steel), and the samples of Examples 2, 3 and 5 (Sample Nos. 5 to 10 and No. 1) were placed.
4 to 16) applied to an electric wire (diameter 7 mm × length 10 cm, fixed portion 1 cm) was inserted into the cage through the lid and fixed, and the repellent activity was examined by gnawing the electric wire by a rat. The coating amount is about 25 for each repellent component.
It was applied so as to have a ratio of g / m ² . The results are shown in Table 10.

[0075]

[Table 10] Experimental Example 3 The present invention was applied to a mouse (mouse).

Two mice after 5 weeks of age were placed in a cage for breeding in the same manner as in Test Example 2, and the samples of Examples 2, 3 and 5 (Sample Nos. 5 to 10 and No. 14 to 16) were corrugated cardboard pieces. (2.5 cm x 3.5 cm) each with repellent components applied at a rate of about 25 g / m ² , insert it into the cage through the lid, and fix it in place. The repellent activity was examined by the degree. The results are shown in Table 11.

[0077]

[Table 11] Test Example 4 Similarly, an example in which the present invention is applied to a mouse (rat) is shown. The repellent wire of Example 6 (Sample Nos. 17 and 1)
8) was used and tested in the same manner as in Test Example 2, and the repellent activity was examined by the degree of galling of the wire by the rat. The results are shown in Table 12.

[0078]

[Table 12] Test Example 5 An example in which the present invention is applied to a cockroach will be shown. A rice straw cut into a length of 2 cm was laid on a circular plastic container having a diameter of 1 m and a height of 30 cm to prepare a test container. 30 male and female adult and larvae of the German cockroach were released.

On the other hand, four rectangular filter papers of 10 cm × 12 cm were prepared, and each of the samples of Example 3 (aerosols of sample Nos. 8 to 10) was sprayed for 1 second on the center of each of the three filter papers. After air-drying, it was folded so that there were 3 mountains to make a shelter. Fold the remaining one in the same way,
The untreated plot was used as a shelter.

These four shelters were appropriately placed in the test container and the number of individuals gathered in the shelter was counted over time. The results are shown in Table 13.

From the above test examples, it can be seen that the repellent effect of the repellent composition of the present invention is extremely remarkable.

[0082]

[Table 13]

[0083]

The following effects can be obtained by the repellent composition of the present invention.

(1) When used, it is not harmful to humans and animals and effectively acts on a considerable range of harmful animals.

(2) It can be used in various forms as an olfactory repellent for harmful unpleasant animals such as dogs, cats, mice, cockroaches, and ants.

(3) It can be used as an antifouling paint for fishing nets.

(4) It can be used as a repellent for a wide range of harmful and unpleasant animals in combination with natural synthetic components such as capsicum and horseradish, and natural terpide agents such as phytoncide in forest baths.

(5) A so-called perfume-holding agent is used in combination with a harmless component having a low vapor pressure and a high boiling point to provide a technique which can be used in a wide range of types having a long-term residual effect repellent function for preventing volatilization and disappearance. It is a thing.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 16, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

Heptylamine (C ₇ H ₁₅ NH
₂ 115.2 155 ° C.) Octylamine (C ₈ H ₁₇ NH ₂ 12
9.2 177 ° C.) Nonylamine (C ₉ H ₁₉ NH ₂ 14
3.2 202 ° C.) Decylamine (C ₁₀ H ₂₁ NH ₂ 15
7.3 217 ° C.) Undecylamine (C ₁₁ H ₂₃ NH ₂ 17
1.3 240 ° C.) Dodecylamine (C ₁₂ H ₂₅ NH ₂ 18
5.3 248 ° C.) Tridecylamine (C ₁₃ H ₂₇ NH ₂ 19
9.4 265 ° C.) tetradecylamine (C ₁₄ H ₂₉ NH ₂ 21
3.4 291 ° C.) Hexadecylamine (C ₁₆ H ₃₃ NH ₂ 21
4.5 330 ° C.) Octadecylamine (C ₁₈ H ₃₇ NH ₂ 26
9.5 349 ° C.) Oleylamine (C ₁₈ H ₃₅ NH ₂ 26
7.5 330 ° C.) Monoethanolamine (NH ₂ C ₂ H ₄ OH 6
1.1 170 ° C.) Isopropanolamine (NH ₂ C ₃ H ₆ OH 7
5.1 160 ° C.) Parachloroaniline (C ₆ H ₄ ClNH ₂ 1
27.6 232 ° C.) 3,4-dichloroaniline (C ₆ H ₃ Cl ₂ NH ₂
162 272 ° C.) 2,5-dichloroaniline (C ₆ H ₃ Cl ₂ NH ₂
162 251 ° C.) Benzylamines (C ₆ H ₅ CH ₂ NH ₂
107.2 185 ° C.) α-naphthylamine (C ₁₀ H ₇ NH ₂ 14
3.2 299 ° C.) β-naphthylamine (C ₁₀ H ₇ NH ₂ 14
3.2 299 ° C) Piperazino ethyleneamine (NHC ₄ H ₈ NC ₂ H ₄ N
H ₂ 129.2222 ° C.) Tris (hydroxymethyl) aminomethane ((CH ₂ O
H) ₃ CNH ₂ 121. 1 2 19 ° C.) or, as a symmetrical type of secondary amines, the following may be mentioned.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location A01N 37/18 A 43/40 101 Z 43/50 Z 47/46 65/00 A (72) Invention Person Yuuki Taro 1090 Kamiochiai, Yono City, Saitama Prefecture

Claims (5)

[Claims] 1. A microencapsulated repellent taste,
A pest repellent composition comprising a mixture of an olfactory component, a specific terpenoid repellent component and / or a specific amine repellent component, and a retention agent that controls the volatilization rate of these repellent functional components. 2. The microencapsulated repellent taste and olfactory component according to claim 1, or a capsicum extract component, or a compound represented by the following general formula: (Wherein R represents an alkyl group, an alkenyl group or an alkynyl group having 4 to 12 carbon atoms), or a pest animal which is natural horseradish, mustard oil or synthetic allyl isothiocyanate or isobutyl isothiocyanate Repellent composition. 3. The specific terpenoid repellent component according to claim 1, wherein the specific terpenoid repellent component is myrcene, alloocimene, citral, linalool, terpinene, limonene, dipentene, pinene,
Terpineol, anethole, nopol, camphene,
Terpene monomers selected from nopyruacetate, geraniol, and isobornyl acetate and their low-polymerization products or low-copolymerization products, or these terpene monomers and phenol-based, styrene-based, vinyl-based, and maleic acid-based monomers. And a pest repellent composition which is used in combination with a low copolymer having an average molecular weight of 3000 or less. 4. The specific amine-based repellent component according to claim 1, has the general formula: (In the formula, R ₁ and R ₂ are hydrogen, or have 1 to 3 carbon atoms, or
8-18 alkyl group, C1-C3 alkanol group, haloaryl group, benzyl group, naphthyl group, poly (n = 4-24) oxyethylene group, alkylaminopoly (n = 4-24) oxyethylene Group, R ₃ has 1 carbon atom
To 3 or 8 to 18 alkyl groups, alkylcarboxyl groups, hydroxyalkylene groups and pyrazinoethylene groups. 760 mmHg. Lower boiling point 1
Alkylamines at 50 ° C. or higher, or organic / inorganic acid adducts thereof, or the general formula: (In the formula, R ₁ and R ₂ are alkyl groups having 4 to 18 carbon atoms,
A benzyl group, an alkylphenyldiethoxy group, and X represents halogen. ) A quaternary alkylarylamine represented by the formula: or a compound represented by the general formula: (In the formula, R ₁ is hydrogen or an alkyl group having 1 to 3 carbon atoms, R _1
2 represents an alkyl group having 8 to 18 carbon atoms, and X represents halogen. ) Or a general formula: (In the formula, R ₁ represents an alkyl group having 12 to 18 carbon atoms, and R ₂ represents an alkyl group having 1 to 4 carbon atoms or 8 to 24 carbon atoms.)
A pest repellent composition comprising an imidazole salt represented by or a carboxybetaine-type or aminocarboxylate-type amphoteric surfactant. 5. The method according to claim 1, wherein the retaining agent is acetic acid, benzoic acid, phthalic acid alkyl ester or aryl ester, ether type diphenyl ether, dibenzyl ether, phenoxyethanol, diethylene glycol dibutyl ether and triethylene glycol monoethyl ether. A pest repellent composition comprising any of benzyl alcohol, methylbenzyl alcohol, decanol, oleyl alcohol and stearyl alcohol as an alcohol, and diphenyl and alkylnaphthalene as a hydrocarbon.