JPH07521B2 - Pest repellent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to dogs, cats, mice, rabbits, boars, moles,
Deer, weasels, crows, crows, sparrows, pigeons, starlings, cockroaches, termites, ants, mosquitoes, mites, mussels, runners, maimais, flying squirrels, snakes, mosquitoes, flies, planthoppers, leafhoppers, aphids, lice, sea fireflies, slugs The present invention relates to a repellent composition for harmful or unpleasant animals such as.

[Conventional technology]

A mixture of fish oil and naphthalene used in Hokkaido from the end of the Meiji era was used as a repellent for pests such as rodents, hares, wild boars, sparrows and ducks in agricultural products. It is said to be the first repellent in Japan. There is. 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.

Generally, repellents are olfact-ory repellants (olfact-ory rep
ellent) and taste repellent (gus-tatory repll)
ent), the former is essen-tial oil, vegetable rubber resin, and the latter is organic acids, alcohols, alkaloids, tannins, glycosides and the like.

In the living world, because of self-preservation, it is common for animals that have an unpleasant odor and taste to attack from the outside. This is particularly observed in plants, and essential oils, alkaloids and glycosides have this significance, and formic acid, butyric acid, salicylaldehyde, mercaptans, allyl compounds, etc. also play a role in the preservation of species between animals.

Conventionally used as a pest repellent, a cockroach monoterpenoid (JP-A-53-86021),
Unsaturated alcohols and aldehydes for birds (JP-A-53-10153)
No. 1), high-grade ketones and green leaf alcohols for dogs, cats, birds and beasts, cinnamon aredehyde, ketones (Japanese Patent Publication No. 57-25521), mice, rabbits, guasazine (Japanese Patent Publication No. 57-67507), harmful birds and beasts. Guassadine and Chulam (JP-A-59
No. -25306), cyclic terpene alcohol for blood-sucking pests (JP-A-57-179101), prothiophos and turum for birds (JP-A-59-10504), menthol and ethyltoluamide for dogs and cats (JP-A-59-10504). JP-A-60-142903), creosote and pyridine for bird damage (JP-A-61-56110),
Ethanol-vinyl acetate copolymer beads impregnated with chlam and animal / vegetable oil (Japanese Patent Laid-Open No. 61-12005) for dogs, cats, etc. in forest harmful animals (Japanese Patent Laid-Open No. 61-172801), Glycol ethers for dogs, cats, etc. (JP-A-61-194)
001, JP-A-61-267501), glycol ethers for mites and snakes (JP-A-61-289002), high-boiling-point ketones, alcohols, aldehydes for dogs and cats (JP-A-61-289002).
-289003), shikimic acid and mustard glycosides in mice (JP-A-61-291507), limonene in flies and mosquitoes (JP-A-61-409), and bis- (2) in dogs and cats. -Chloroisopropyl ether) (Japanese Patent Laid-Open No. 62-12702), Shikimi and mustard glycosides for Mole (Japanese Laid-Open Patent Publication No. 62-45508), and limonene for pigeons and flies (Japanese Laid-Open Patent Publication No. 62-164602). ), Barnacles and mussels with polycyclic terpenoid glycosides (JP-A-63
-41495 gazette) etc. Other Chemical Abstracts Decennial Index
Vol. 1 (1907) Collective Index (Co
llective Index) Vol. 11 (1986), various animal repellent compositions have been announced and described. However, the terpenoid compound of the present invention and a low polymer thereof and / or a harmful animal containing the low polymer thereof in combination are disclosed. There is no description of the repellent composition. However, in European Patent No. 0173410 (5, March, 1986), di-1-P-
There is a disclosure that menten (terpene dimer) and its highly polymerized product (terpene polymer) are used as efficacy enhancers for other defoliants such as 2,2-dichloropropionic acid, but each has almost no repellent action. Absent.

[Problems to be Solved by the Invention]

The object of the present invention is to provide a repellent composition which is more effective than the conventional pest repellents described above, and which is excellent in long-lasting effect, has a low toxic and mild odor to humans and animals, and which even perceives aroma. To do.

[Means for Solving the Problems]

The present inventors thoroughly studied terpenoid compounds in order to solve the above problems and found that the low polymerization compound and / or the low copolymerization compound (Olig) of the terpenoid compound monomer
We have found a very easy-to-use pest repellent that can be used in combination with other pesticides and has a wide range of target pests by using omer or Oligo-copolymer).

The present invention is a pest repellent composition comprising a terpenoid compound monomer and this low polymerization and / or low copolymerization compound.

The terpenoid compound monomers used in the present invention are a group of compounds contained in plant essential oils or resin gums obtained by steam distillation of various parts of plants. Its essence contains two or more isoprene, a substance having 10 carbon atoms (C ₅ × 2) is a monoterpenoid, a substance having 15 carbon atoms (C ₅ × 3) is a sesquiterpenoid, and a carbon number is 20. It is possible to use any terpenoid compound which is classified as a substance of a substance (C ₅ × 4) as a diterpenoid and a substance having a carbon number of 30 (C ₅ × 6) as a triterpenoid.
This terpenoid compound is a plant aroma and essential oil component and has no effect on the natural cycle. Further, among bioactive natural substances which are currently recognized as having a pesticidal function, for example, white sycamore (pyretrin component), deris (rotenone component), tobacco (nicotine component), sendan (azadilactin), acebi (acepotoxin). (Components) and the like can be so-called natural pesticides or natural pesticides that are less toxic to humans if the terpenoid of the present invention is given an animal repellent function. As its insecticidal mechanism, the so-called insect growth regulator, which aims at extinction of the pest fauna by inhibiting the peculiar growth process such as the transformation of pests as well as the direct insecticidal activity.
It can also be useful as an IGR).

Thus, since it can be used as a material for rationally producing a safe natural agricultural product in which organic-inorganic synthetic pesticides do not remain at all, its significance can be said to be enormous. The material of the present invention will be described below.

β-myrcene (C ₁₀ H ₁₆ ) (Component No. 1): contained in bay oil, hop oil, etc., having 3 double bonds at a boiling point of 166 to 167 ° C.,
Oligomer such as dimyrcene easily forms with the passage of time.

Alloocimene (C ₁₀ H ₁₆ ) (ingredient No. 2): α-type ocimene (C ₁₀ H ₁₆ ) 2,6-dimethyl-1,5, which is contained in Yamajido plants
It is an isomer of 7-octatriene or β-type ocimene (C ₁₀ H ₁₆ ) 2,6-dimethyl-2,5,7-octatriene. 2,6-
Dimethyl-2,4,6-octatriene structure, boiling point 81
It is easy to oxidize at ℃ (12mm), and it is easy to produce oligomers of 2-3 polymers.

Citral (C ₁₀ H ₁₆ O) (Ingredient No. 3): Contained in lemongrass oil, etc., it has two types, a and b, with a boiling point of 226 ° C. It is easily oxidized in air and polymerizes with strong acid. The chemical name is 3,7-dimethyloctadiene-1-al.

Linalool (C ₁₀ H ₁₆ O) (Component No. 4): Contained in orange oil and lavender oil, it has an optical isomer at a boiling point of 198-200 ℃ and is synthesized from β-pinene 3,7-dimethyl-1. , 6-Octadien-3-ol is used.

Limonene (C ₁₀ H ₁₆ ) (ingredient No. 5): It is contained in large amounts in citrus fruits and widely distributed in plants along with α-pinene. d
There are-, l- and dl types, and dl-limonene is called dipentene. Both of them have a boiling point of about 176 ° C and are relatively stable and can be distilled under atmospheric pressure, but they are oxidized when left in the air. When it is treated with an acid, it easily becomes dipentene, and when it is heated with sulfur, it changes into p-cymene.

Also, when treated with a mineral acid when cold, it is hydrated to produce terpineol and terepine hydrate.

Dipentene (C ₁₀ H ₁₆ ) (Component No. 6): An optically inactive form of limonene. Naturally, terpene oils from various pine trees,
It is contained in many plant essential oils such as citronella oil, lemongrass oil and camphor oil, and is easily polymerized by heat at a boiling point of 178 ° C.

Terpinene (C ₁₀ H ₁₆ ) (Ingredient No. 7): There are α, β and γ types, with boiling points of about 177 ° C, 173 ° C and 183 ° C, contained in Ceylon cardamom oil and coriander oil, like lemon Has a nice odor.

The α type polymerizes rapidly with air or light rays to become a resin.
The β form is obtained only by synthesis, but each isomer is difficult to separate.

Terpineol (C ₁₀ H ₁₈ O) (Component No. 8): Monocyclic monoterpene alcohol with α, β and γ types, boiling point approx. 220
Cardamom oil at ℃, 210 ℃ (752mmHg) and melting point of about 69 ℃,
It is found in neroli oil and pine essential oil and has a lilac-like aroma.

Anethole (C ₁₀ H ₁₂ O) (Component No. 9): p-propenylanisole, which is aromatic and has a boiling point of about 81 ° C (2.3 mmHg), 230 ° C (760 mmHg) and a melting point of about 21 ° C.

Pinene (C ₁₀ H ₁₆ ) (ingredient No. 10): There are α and β types, and they are most widely distributed in the plant kingdom. α-Pinene has a peculiar odor with a colorless color, and is contained in the resin of Pinaces plants and wood turpentine oil at a boiling point of about 155 ° C., and is mainly the main component of sulfate turpentine derived from pulp mills. Although it has optical isomers, it is easily isomerized by acid or hot alkali, and it becomes a high polymer while leaving a cyclic structure at -15 ° C with aluminum chloride as a catalyst. From α-pinene, in addition to dimer, softening point 65-97 ℃, molecular weight 600-70
A 0-trimer to tetramer, a so-called oligomer, is obtained. In addition, useful terpenoid compounds such as camphor, rhino and terpineol are derived, and they are important compounds as industrial raw materials.

Nopol (C ₁₁ H ₁₉ O) (Component No. 11): 6,6-Dimethylbicyclo [3,1,1] hept-2-ene-2-ethanol with β-pinene and formaldehyde at a boiling point of about 230-240 ℃ It is a bicyclic terpene alcohol obtained by condensation of.

Camphuen (C ₁₀ H ₁₆ ) (ingredient No. 12): Has a weak camphor-like odor with a melting point of about 50 ° C, such as pine needle oil. In addition, hydrogen chloride in excess of α-pinene yields bornyl chloride, which is further treated with alkali to induce camphorene. It becomes various oligomers and polymers and is used in various fields such as paints and adhesives.

Novyl Acetate (C ₁₃ H ₂₁ O ₂ ) (Component No. 13): Acetate ester of Nopol (Component No. 11), which is used as a synthetic fragrance at a boiling point of about 250-260 ° C. When it is used together with the following isobornyl acetate as a raw material for the pest repellent composition of the present invention, it is fragranced so as to give a human aroma, and is effectively used in cooperation with the animal repellent power.

Isobornyl acetate (C ₁₂ H ₂₀ O ₂ ) (Component No. 14):
It is an aromatic liquid with a boiling point of about 224 ℃ obtained by heating camphorene (component No. 12) with a 50% sulfuric acid / glacial acetic acid mixture.

Terpenoid compound monomers generally have aromatic boiling points
When this product is used alone at around 200 ° C, it may be effective as an olfactory or taste repellent component for harmful animals for a short period at the beginning of use, but it generally evaporates immediately due to temperature or air volume under outdoor ventilation. Becomes invalid. In the composition of the present invention, low polymerization or / and low copolymerization compounds (Oligomer & Cooligomer) having a polymerization average molecular weight of 1000 or less of these terpenoid monomers are added to the above terpenoid monomers as so-called retaining agents (Retaining Reagnts). ,
The evasion function can be maintained by volatilizing and diffusing at the same effective optimum concentration for a long period of time. This is similar to the way cosmetics are used by humans. That is, the fastest volatile component Top note,
The technique is exactly the same as the method of balancing a middle volatile component middle note and a high-boiling component Base note to maintain a constant basic fragrance for a long period of time. Generally, the oligomer has a weight average molecular weight of 10,000 or less, but the oligomer used in the present invention preferably has a weight average molecular weight of 1,000 or less and a low molecular weight of a polymerization degree of 2 to 7 mer, and is generally a liquid or a high viscosity liquid. It can be isolated by ordinary distillation, and it has repellent properties by itself. The average molecular weight can be measured by the last method or the viscosity method, but gel permeation chromatography GLP (Gelpermeation Chomatograp
hy), and it can be separated and sorted accurately. In general, the terpene oligomer is preferably dissolved and dispersed in 1 part of the monomer in 1 to 10 parts of activated clay or acid clay and an appropriate amount of solvent and polymerized at about 100 to 150 ° C. When using the Friedel-Crafts type catalyst, the molecular weight is
It is easy to form high molecular weight polymers of 1000 or less, and it is advisable to polymerize at around 30 ° C for a short time. Alternatively, the high polymer may be pyrolyzed,
It can also be obtained by contacting the warmed strongly acidic cation exchange resin particles with a warmed monomer solution. An oligomer can also be obtained by telomerization in the presence of a substance having a large chain transfer constant, for example, telogen.
The oligomers preferably used in the present invention are listed below.

Pinene Oligomer (Component No. 15): β-Pinene 50% Toluene Solution Add β-Pinene 1% Aluminum Chloride
Stirred at 30-35 ° C for 2 hours, filtered, washed with water, dehydrated, and fractionated to remove the solvent. 2% Approximately 20%, trimer approximately 70%, tetramer or higher polymer approximately 10% blend.

Dipentene oligomer (Component No. 16): dipentene 0.5% aluminum chloride is added to a toluene solution of 50% dipentene and stirred at 30 to 35 ° C for 2 hours to obtain a dimer of about 40% and a trimer of about 50%. Viscous liquid of about 10% polymer and monomer.

Camphuene Oligomer (Component No. 17): Strongly charged cation-type ion-exchange resin particle layer kept at about 70 ° C, with a length of 30 cm, the canfuen solution heated at 70 ° C was flowed down at a rate of 4 ml / min. , Cold alkali, wash with water, fractional distillation, boiling point 148 ~ 151 ℃
A dimer of about 95% and a trimer of about 5% obtained by collecting a fraction of / 4 mmHg.

Aloocimene Oligomer (Component No. 18): Pyrolysed high molecular weight aloocimene polymer and collecting distillate at 210-315 ℃ about 5% monomer, about 70% dimer, about 25 trimer %.

Pinene dipentene cooligomer (component No. 19): 1% by weight of aluminum chloride was added to a mixture of 1 part of α-pinene, 1.5 parts of β-pinene and 2.5 parts of dipentene, and the mixture was heated at 30 to 35 ° C. for 2 hours.
A co-oligomer having a viscosity of about 100 cps at 80 ° C obtained by stirring for an hour.

Camphuen Nopol Co-oligomer (Component No. 20): Obtained by adding 5 wt% of acid clay of terpene monomer to 50% solution of 1 part of camphor and 1 part of nopol, and stirring at 120 ° C for 5 hours for rectification A cooligomer with a viscosity of 165 cps at 80 ° C.

Myrcene Pineneco Oligomer (Component No. 21): Myrcene 2
An oligomer having a viscosity of 145 cps at 80 ° C. obtained by adding 5% by weight of activated clay of a terpene monomer to a 50% toluene solution of 1 mol of β-pinene.

The pest repellent composition of the present invention is a terpenoid compound monomer exemplified by the above components No. 1 to No. 14 and components No. 15 to N.
O.21 and the like are used in combination with terpene oligomers and / or cooligomers. The oligomers are the most rational in addition to those described in this description, in consideration of repellent efficacy and price. It is also possible to get things.

As described above, the composition of the present invention comprises a terpenoid compound monomer and its low-polymerization compound and / or low-copolymerization compound as active ingredients. In order to reinforce the effect of the active ingredient, a higher ketone, Pest repellents such as sulfate terpene component, dialkyl toluamide, dialkyl phthalate, polybutene, polyisobutene, and raw rubber may be added.

Examples of higher ketones that can be used in the present invention include nonylphenyl ketone, acetophenone, cyclohexanone, isophorone, and the like, and green leaf alcohol, green leaf aldehyde,
Cinnamon alcohol and cinnamon aldecht can also be used as having the same function. In addition, mainly Pinus elliottii En
An oil component, that is, a sulfate terpene separated from a cooking liquid of a glow material or a Pinus palustris Mill material) chip during the production of cellulose can be economically advantageously used. This oil consists of about 60% α-pinene and 15-20% β-pinene, as well as the various terpenoids, ferrandrene, sedrene, longifolene, borneol, p-cymene, fuencor, terpinen-4-ol, and methylcavicol. .

The polybutene, polyisobutene or raw rubber that can be used in the composition of the present invention can be selected from those having any degree of polymerization as long as it can impart tackiness to the composition, and
It is also an advantage of the present invention that a pest repellent composition that is characteristic of an insect repellent such as dialkyltoluamide and dialkylphthalate can be obtained. In addition, other repellent components such as atraquinone, dihydroanthraquinone, diphenyl ether,
Geraniol, thiuram, creosote, cyclohexylimide, acrylic compound, tetrahydrocapsaicin, capsaicin, selenium compound, etc. can be used together.

Further, the composition of the present invention contains one or more pesticide components such as fuention, fenitrothion or diazinon, a drin agent, and a carbamate which have an insect repellent action, and agrochemical components such as bactericides, herbicides and plant growth regulators. In combination, those pesticide components or medicinal insecticidal components are highly effective because the terpenoid compound, which is the active ingredient of the composition of the present invention, has a high solubility and a relatively high boiling point. It And the pesticide bioactive effect of so-called pesticide components such as insecticide, sterilization, weeding, plant growth regulator, pigment,
Animal repellency can be synergized to give a very useful composition.

The pest repellent composition of the present invention can be used in the form of powder, granules, wettable powders, liquids, emulsions, pastes, gels, fumigants and aerosols. In addition, the repellent property is a phenomenon due to the negative running property, but it may act as a positive running property, that is, an attractant depending on the animal species at a certain threshold value of concentration. This point must be sufficiently pre-tested to achieve its purpose. Further, the composition is impregnated with a liquid material in a natural or synthetic resin, fixed on a non-woven tape, cured with tolylene diisocyanate, methylenebis (4-phenylisocyanate), an acrylic prepolymer, a urethane prepolymer, Benzylidene sorbitol, 12-hydroxystearic acid,
Gel modeling can be performed with an amino acid gelling agent, paraffin wax, synthetic resin, functional oligomer, or the like.
These can be a composition that not only acts as a pest repellent but also gives humans an aroma.

Examples of the pest repellent composition of the present invention will be given below.

〔Example〕

Example 1 Granules 84 parts of natural pumice stone (average particle size 1.5 mm) was rotatably oil-absorbed with 15 parts of the component mixture liquid of the following Table 1, and 1 part of inorganic silicate fine powder was coated, and repellent granules. To get

Example 2. Emulsion 92 parts of the liquid mixture of the ingredients shown in Table 2 below was added with polyoxyethylene (n
= 20) 5.6 parts of nonylphenyl ether and 2.4 parts of calcium dodecylbenzene sulfonate are mixed and dissolved to obtain a repellent emulsion.

Example 3. Aerosol Agent A repellent aerosol is obtained by filling a pressure resistant aerosol container with 360 ml of a 50% aqueous emulsion containing 50% of the emulsion containing the ingredients shown in Table 3 below and liquefied petroleum gas.

Example 4. Repellent tape 3 parts of 50% polymethacryl emulsion polymerization liquid was added to 90 parts of the component liquid mixture shown in Table 4 below and mixed, and 6 parts of tolylene diisocyanate (TDI) was added to this solution to give a thickness. 1mm, width 5cm and non-woven tape (30% cotton, 20% polyester, nylon fiber)
50%) and the repellent compatible resin content is 70% so as to be dip coated and then cured to obtain a repellent tape.

Example 5 Adhesive Emulsion To 50 parts of the compounded solution shown in Table 5 below, 15 parts of polybutene (average molecular weight of about 2350), 5 parts of polyoxyethylene (n = 5) lauryl ester, 15 parts of acetophenone, and 15 parts of xylene were added. , Get a sticky emulsion.

Example 6 Gel Agent To 90 parts of a liquid mixture of the ingredients shown in Table 6 below, 1 part of dibenzylidene sorbitol, 2 parts of dimethylformamide and 7 parts of 12-hydroxystearic acid were heated to about 65 to 70 ° C. and dissolved. After cooling, a repellent gel is obtained.

Example 7. Dust 10 parts of the liquid mixture of the ingredients shown in Table 7 below, 10 parts of pearlite fine powder having an average particle size of 100 mμ and 80 kaolin fine powder having an average particle size of 40 mμ
The parts are mixed to obtain a repellent powder.

Example 8 Adhesive Paste Agent A sulfate terpene solution (15% pinene, 14% terpineol, 11% dipetene, 5% anethole, 4% ferrandrene, 2% sedrene, 6% borneol) was added to 50 parts of the component liquid mixture shown in Table 8 below. , P-Cymen 3%, Longhihoren 4
%, Other terpene hydrocarbons 36%) 15 parts, raw rubber 2 parts and polyoxyethylene (n = 5) lauryl ether 5 parts are added and dissolved, and 3 parts of polyacrylic water-absorbing resin fine powder are suspended in water 25 Add parts to obtain an adhesive paste.

Example 9. Insecticidal and bactericidal animal repellent emulsion 50 parts of the following component combination solutions, 10 parts of pesticide active ingredients, 5 parts of dimethylskilloxide and 20 parts of kerosene were uniformly dissolved,
Polyoxyethylene (n = 11) nonyl phenyl ether
12 parts and 3 parts of calcium dodecylbenzene sulfonate are added to obtain an insecticidal and bactericidal pest repellent composition emulsion.

Sample No. 36 can be used as a natural product control agent, Nos. 37 and 38 can be used as house-toxic insecticides, and No. 39 can be used as a persistent bactericidal repellent.

Example 10. Pest repellent paint 30 parts of the component mixture liquid of Table 10 below, vinyl propionate resin
15 parts, bioactive agent 5 parts, methyl isobutyl ketone 10 parts,
20 parts of toluene and 20 parts of xylene are uniformly dissolved to obtain a pest repellent paint.

These are coating compositions having insecticidal properties and strong repellency. .

Example 11. Bird repellent sol agent 40 parts of the component combination liquid of Table 11 below, 5 parts of insecticidal component, 4 parts of paraffin wax were heated to homogenize, and this was stirred in 50 parts of an aqueous solution in which 1 part of polyvinyl alcohol was dissolved. While being added, it is dispersed uniformly to obtain a bird repellent sol.

These can be used as repellent sol agents for strong pigeons, crows and sparrows.

Example 12. Synthetic Resin Body Containing Pest Repellent 40 parts of the component mixture liquid of the following Table 12 and 60 parts of synthetic resin are mixed and heated to homogeneity, and a sheet is formed by radiation molding or heating roll as a wire covering.

These are compositions having a strong repellency against harmful animals such as mice, cockroaches, and ants.

Example 13. Pest repellent gel agent 25 parts of the gel agent was added to 75 parts of the component mixture liquid of Table 13 below, heated to homogenize, and dispensed and cooled in a wide-mouth 100-500 ml polyethylene bottle having a diameter of about 3 cm. To obtain a gel.

When these are opened and installed in closed-type telegraph devices (connection terminal boxes, telephones, etc.), computers, food vending machines, etc., they can prevent feeding damage or nesting of flies, cockroaches, ants, etc. for a long period of time.

Example 14. Feeding damage preventing seed dressing agent To 17 parts of silicic acid anhydride was added to 33 parts of the terpene component liquid in Table 14 below, and the mixture was pulverized. To this, 25 parts of anhydrous gypsum and 25 parts of kaolin were added and mixed to give a dressing agent. To get

These dressings are 2% of soybean or corn seeds
If the seedlings are dressed with water, it is possible to completely prevent missing strains due to feeding damage such as sparrows, crows, and pigeons until germination.

The effect of the pest repellent composition of the present invention will be described in the following test examples.

Test Example 1. (Dog) Test method: Two dogs (Separd hybrid 1 and a half years old) were fasted for about 1 day, and commercially available rice was fed with the test sample evenly spread and adhered, and the elapsed time And investigate the remaining food intake.

Approximately 100 g of commercially cooked rice was placed in a circular plastic container having a diameter of 25.2 cm and a height of 7 cm, and was lightly loosened to make it uniform, and sample Nos. 1 to 6 of Example 1 were used.
6.5 g of the composition of the present invention are uniformly dispersed. For each sample material, the capacity of the empty container, the rice, and the sample to be tested was measured in advance, and after a certain period of time, the residual rate (corresponding to the repelling rate) of the amount of sample rice was calculated. However, about 100 g of untreated cooked rice was administered every 3 days, and comparison was made with the test number section. The results are shown in Table 15 below.

As shown in the above table, the composition of the present invention showed a remarkable repellent effect on dogs.

Test Example 2. (Cat) Test method: Two permuse cat hybrids (cats about 3 years old and 1.5 years old) were fasted in a metal cage of about 2 m ³ for about 1 day, and commercially available cat food (tuna meat boiled crushed). Product) about 95g in diameter 2
The repellent composition of the present invention of Sample Nos. 7 to 11 of Example 2 and Nos. 12-1 and No. 12 were placed in a circular plastic container having a height of 5 cm and a height of 7 cm.
Add 7 ml of 8-fold diluted solution of the control composition of -2 uniformly. The residual rate of the cat food in each container is measured at regular intervals. However, about 95 g of the untreated food was administered every 3 days, and comparison was made with the sample number section. The results are shown in Table 16.

As described above, the control di-1-P-menthene and the mixed preparation thereof with poly-1-P-menthene have almost no repellent effect on cats.

Test Example 3. (Dog, cat, etc.) A polyethylene bag containing about 1 kg of garbage (the content of about 1 and aerosol sample Nos. 13 to 17 of Example 3 about 50 ml per bag)
After spray coating, the untreated bag was left alone in the dust-filling area where wild dogs and stray cats appeared, and the untreated area was broke in 8 hours overnight, but the aerosol-treated bags of Nos. 13-17 were for 5 days. The bag remained without being broken, and its repellent effect was remarkable. In addition, there was almost no smell of raw garbage, and even the aroma was felt.

Test Example 4. (Boar) In a chestnut garden where wild boars appear and disappear, a test area of 4 × 10 m, a height of about 30 cm above the ground, and a repellent tape of sample number No. 18 to 22. The sample and untreated tape were applied. About 2 kg of sweet potatoes were buried near the surface of the ground in each center, and after a certain period of time, the remaining amount of each was weighed to measure the repellent rate. The results are shown in Table 17.

As described above, almost all sweet potatoes in the treated area remained without being eaten, and a remarkable repellent effect was observed in the untreated tape area.

Test Example 5. (Antelope) A test was conducted on the effects of Sample Nos. 23 to 25 of Example 5 at a hinoki plantation in the area where the Japanese antelope was heavily damaged by feeding damage.

In December, 250 ml of 50 times water diluted to 50-100 above the ground per tree
It was sprayed on cm trunks and the extent of damage was investigated in June of the following year (211 days after spraying), and the results shown in Table 18 were obtained.

As described above, the composition of the present invention was able to minimize damage by avoiding antelope.

Test Example 6. (Hare) A second-year-old cypress seedling reforestation test was conducted in a forestry area of 4 years with 50 trees per ward to avoid damage by the hare. Sample Nos. 7 to 11 of Example 2 and control repellent emulsions No. 12-1 and No. 12-2
Approximately 125 ml of 50 times liquid was sprayed on about 50 cm above the ground, and the number of damage caused by feeding damage was measured after 3, 6 and 12 months, and the damage rate was observed to obtain the results shown in Table 19.

From the above results, the composition of the present invention, No. 12-1 and No. 12-2
It is considered that the hares are more repellent than the control product of 1. and the results can be expected sufficiently.

Test Example 7 (rat) Test method: 70 cm long, 50 cm wide, 10 cm high with corrugated wire mesh lid
10 mice aged 5 weeks were placed in the aluminum cage of. After fasting for about 1 day, about 6 g of the gel samples No. 26 to 28 and No. 29 gel of Example 6 were applied to about 30 g of commercially available mouse food (diameter 1 cm, length 3 cm). Separately, the untreated hood (30 g) was placed in a corrugated wire mesh recess, and the residual rate was measured at regular intervals. In addition, about 30 g of untreated feed was given every 3 days for testing. The results are shown in Table 20.

As described above, the composition of the present invention is obviously superior to the control gel of No. 29 (di-1-P-menthene gel) in rats.

Test Example 9. (Snake) Approximately 3 g each of aerosol sample Nos. 13 to 15 of Example 3 is sprayed on chicken chicks having a body weight of about 45 g. 10 treated samples and 2 silver hubs having a body length of about 80 cm were placed in a glass circular container having a diameter of 1 m and a height of 20 cm, and 48 hours later, the prey repellent rate was investigated. The results are shown in Table 21.

As described above, the composition of the present invention has a remarkable repellency against snakes.

Test example 10. (Pigeon) Test method: Put two adult pigeons in a wire net of 1 m x 3 m x 2 m, and about 1
They were fasted daily and 40 g of corn pieces were placed and fed. 10 g of the sample Nos. 30 to 32 of Example 7 were mixed with each other. The repellent rate was calculated by weighing the remaining amount of each container at regular time intervals. However, about 40 g of untreated feed was administered every 3 days and compared with the sample number group. The results are shown in Table 22.

As described above, the composition of the present invention exhibits a remarkable repellent effect on pigeons.

Test Example 11, (crow) Test method: Three 1-year-old crows were tested in a cage having a wire mesh of 1 m x 3 m x 2 m. Fasted for about 1 day and mixed with corn fines of about 2 mm so as to have 4% of the repellent composition of Sample Nos. 7 to 11 and Control No. 12-1 of Example 2, 6 g x 6 cm of 40 g of each feed. It was put into a food container of No. 1 and tested. No treatment 6
It was placed in a cage together with 0 g, and the residual rate was measured at regular intervals. It should be noted that 40 g of untreated feed was administered every 3 days and compared with the sample number group. The results are shown in Table 23.

From the above results, the composition of the present invention was
From the effect of o.12-1 (di-1-P-menthene emulsion), a high residual effect on crows was obtained.

Test Example 12. (Pigeon) Sample numbers No. 33 to 3 of the adhesive paste agent of Example 8 on the balcony of 2 × 3 m and the handrails on which pigeons constantly fly and are contaminated.
5% 20% water dispersion emulsion was applied, 100 g of corn fines were placed on the veranda floor, and the residual material of the bait was weighed over time, the repelling rate (%) was measured, and the results in Table 24 were obtained. It was

From the above results, it was confirmed that the composition of the present invention has a high repellent effect on pigeons.

Test Example 13. (Cockroach) A round glass container having a diameter of 1 m and a height of 20 cm is laid with cut rice straw at the bottom of 2 cm, and 10 black cockroach females, male adults and 10 larvae are placed therein,
2 ml of 10-fold water diluted with sample Nos. 7 to 11 of Example 2 was added to 10 × 1.
Drop onto the center of a 2 cm paper filter. After air-drying, make a corrugated fold celter so that there are 3 mountains, put it in a test glass container,
After 8 hours, 24 hours, and 48 hours, the number of solids collected in each cellter was measured, and the results shown in Table 25 were obtained.

From the above results, it showed a strong repellent property against cockroaches.

Test Example 14. (Yes termite) Two-way expedition red pine sapwood (with 3 to 5 annual rings of 10 mm) was prepared into a size of 20 mm x 20 mm x 20 mm to prepare a test piece. The emulsion of Example 2 was immersed in a 1% aqueous emulsion of Sample No. 9 for 10 minutes, and then naturally dried for 10 days to obtain a treated test piece.

Next, in a glass container with a diameter of 110 mm and a height of 150 mm (capacity 1400 ml), put 400 g of quartz sand that had been sterilized by dry heat at 105 ° C for 2 hours in advance, and add 100 ml of sterilized water, and then treated and untreated test pieces. Was set up, and 50 yellow termites (48 worker ants and 2 soldier ants) were put into this. After 48 hours, the number of termites gathered in the treated and untreated test pieces was measured, but they were not gathered in the test part at all, and 42 untreated pieces were observed, which clearly showed repellent effect.

Test Example 15. (Tick) No. 3 of the insecticidal animal repellent emulsion of Example 9 on a filter paper of 5 cm x 5 cm.
6-38 100 times water diluted solution to 0.125 ml (50 m
l / m ² ) Spray. After air-drying, fold in dusts of 0.1 g of Dust mites, fold them in half, wrap them in a box, and seal them with tape. After 24 hours, the bag was opened, and the number of total resident and dead insects was examined with a magnifying glass to obtain the results shown in Table 26.

From the above results, it was revealed that the composition of the present invention has excellent repellent insecticidal activity.

Test Example 16. (Slugs and snails) Field soil is evenly spread to a thickness of about 2 cm in a glass circular container having a diameter of 20 cm, and three slugs and snails are put therein. To this, sample numbers No. 36 to 3 of the insecticidal animal repellent emulsion of Example 9 were added.
Insert cabbage 2 cm x 3 cm slices and untreated pieces dipped in 8 times 50 times diluted water. After 27 hours, the weight of each test piece was weighed and the residual rate was used as the repellent amount.

From the above results, it is clear that the composition of the present invention has a strong repellency against slugs and snails.

Test Example 17. (Blue mold, housefly) 0.125 ml (50 ml / m) of 200 times water emulsion of Sample No. 39 of the bactericidal animal repellent emulsion of Example 9 was applied to a 5 cm x 5 cm veneer plate.
² (Spray and air-dry. Transfer this to a glass container with a diameter of 20 cm and a height of 10 cm, anesthetize 10 adult houseflies, and after 3 hours, set the number of insects on the test piece and untreated piece for 3 minutes. Upon investigation, there were 2 anti-58 animals each, and a repellent effect was observed.
When 0.2 ml of blue mold spore suspension was sprayed on this test piece and post-cultured at 30 ° C. saturation temperature, blue mold was generated on one surface of the untreated veneer plate piece, but completely blue mold was generated on the test sample piece. There was no.

Test Example 18. (Mice) A 10 cm × 10 cm test piece of nylon mesh having a mesh size of 2 cm is dip-coated on the pest repellent paint sample Nos. 40 to 42 of Example 10 for 10 minutes. After 24 hours of air-drying, an artificial diet for rats having a diameter of about 1.2 cm and a length of 3 cm was wrapped, and the untreated net-containing feed was tested at the same time as one latte 6 months old. The results are shown in Table 28.

Example 19. (Spodoptera litura) Test method: Four pots of summer oranges (30 cm in height) planted in pots were placed on a turntable, and the insecticidal repellent emulsion sample Bungou No. 36-38 was diluted 500 times with water. Spray 50 ml of liquid.
After air-drying, 3 leaves were placed in a polyethylene cup 10 cm in height and 4.5 cm in height, and 10 third-instar larvae of Spodoptera litura were released.
The mortality rate after 24 hours was calculated. Also, 15 days after the spray treatment, the test was repeated 15 days after leaving it in the field, and the residual effect was obtained. The results shown in Table 29 were obtained. As a control, emulsions prepared by using xylene in place of the terpenoid in the compositions No. 36 to 38 were designated No. 36 (control) to 38 (control), respectively.

From the above results, it became clear that the insect repellent of the present invention is a composition having a large residual effect.

[Effects of the Invention] The pest repellent composition of the present invention is composed of a natural terpenoid monomer having low human-toxicity and a terpenoid oligomer or cooligomer that is naturally metabolized in a natural plant body in view of its constituent materials. In fact, it is never fatal to humans or animals and is not involved in the core of life. It is said that coexistence of living creatures in the natural world is achieved only by the repellent phenomenon function that imparts a negative running property to the target animal. Especially when used as a material related to food production, the significance of its nontoxicity and extremely low toxicity is important.

Claims (5)

[Claims] 1. A pest repellent composition comprising a terpenoid compound monomer and this low polymerization compound and / or this low copolymerization compound. 2. The terpenoid compound monomer is β-myrcene, aloocimene, citral, linalool, limonene, dipentene, terpinene, terpineol, anethole, pinene, nopol, camphor, nopyracetate and isobornylacetate. A pest repellent composition. 3. The pest repellent composition according to claim 1, wherein the low-polymerization compound or low-copolymerization compound has a weight average molecular weight of 1,000 or less. 4. The repellent composition according to claim 1, wherein a higher ketone, a sulfate terpene component (ferrandrene, cedrene, carene, longifolene, borneol, p-cymene, fencor, terpinen-4-ol, methylcabicol), dialkyl are used. Toluamide, dialkyl phthalate,
A pest repellent composition comprising one or more pest repellent components consisting of polybutene, polyisobutene and raw rubber in combination. 5. A pest repellent composition comprising the repellent composition according to claim 1 in combination with one or more agrochemical components consisting of insecticide, bactericidal, herbicidal and plant growth regulators.