KR100991165B1 - Composition of anti-rodent and method of preparing the same - Google Patents

Abstract

The present invention relates to a snow-repellent resin molding composition that prevents damage caused by rodents such as rats, and includes red pepper extract containing capsaicin, garlic extract containing allicin, onion extract, and allyl isothiocyanate as active ingredients. The microcapsules filled with these compounds to prevent contamination due to the pungent taste and irritation of the compound by microencapsulating a sulfide composition comprising a mustard and / or horseradish extract and a ginger extract containing vanylyl ketones. Incorporation in the resin enables to adequately block strong pungent taste and irritation, and is characterized by preventing noise damage by rodents, dogs, cats and other wild animals.

Rodents, capsaicin, allicin, wildlife killing, microcapsules

Description

Deposition agent composition and its manufacturing method {Composition of anti-rodent and method of preparing the same}

The present invention relates to a snow-repellent resin molding composition that prevents damage caused by rodents such as rats, and includes red pepper extract containing capsaicin, garlic extract containing allicin, onion extract, and allyl isothiocyanate as active ingredients. The microcapsules filled with these compounds to prevent contamination due to the pungent taste and irritation of the compound by microencapsulating the mixed extract composition consisting of mustard and / or horseradish extract and ginger extract containing vanillyl ketones It is possible to properly block strong pungent taste and irritation by containing it in, characterized in that it prevents the damaging damage by rodents, dogs, cats and other wild animals.

Rodents and other animals damage agriculture and forestry, enter buildings, apartments, homes, food warehouses, factories, electrical equipment and facilities, telecommunications facilities, package, wires, telephone lines, signal and communication cables, computer devices, etc. Several types of repellents have been proposed as one effective way to prevent crushing, and cycloheximide, ZAC (zinc dimethyl dithiocarbamate and cyclohexylamine complexes) actually used in these repellents. And trialkyltin compounds are known as repellents used in natural and synthetic resin products. In particular, cycloheximide, an antibiotic discovered in 1950, is widely used due to its excellent preventive effects against rodents and other animals, but because it is an antibiotic, it is expensive, relatively toxic, and human Since they taste little, they are practically limited because of safety concerns, such as the risk that infants can lick household electrical cords treated with the material. In addition, cycloheximide is very water soluble and easily decomposed at high temperatures, so it is known to make it into microcapsules and to incorporate such microcapsules into articles such as wire shells in order to minimize their harmful effects in actual use. National Patent Publication No. 112932/1974).

While the cycloheximide has an excellent effect in preventing damaging damage by rodents and other animals, it is expensive, relatively toxic and hardly tasted by humans, and because of its high water solubility and ease of decomposition at high temperatures. In order to solve the problem of being susceptible to various environmental factors in the manufacturing process, more useful and safe modifications of the material and improvement of the material which can be used in a wide range of fields mentioned above using food ingredients obtained from nature. Mixed extracts containing the active ingredients of pepper, garlic, onion, ginger, mustard and / or horseradish, which are used as insect repellents, biocontrol agents, rodents and other animal repellents while developing methods for producing modified varieties. A composition consisting of these mixed extracts The present invention is based on the fact that a resin molding composition consisting of microcapsules containing capsaicin or a red pepper extract containing capsaicin and garlic extract containing allicin are mixed at an appropriate ratio to have an excellent eradication effect than a composition used as an insect repellent. It was completed.

The pepper contains a capsaicin component represented by the following formula (1), which can be used as a repellent of animals such as mammals, birds, and insects, and a repellent prepared from capsaicin as a raw material. It can be used to protect vegetables and grains from insects as well as protective agents such as furniture and furniture, and was published in 1992 by the US Environmental Protection Agency as REDFACTS.

[Formula 1]

(1)

(One)

Wherein R is an alkyl, alkynyl or alkenyl group, each group having 7 to 12 carbon atoms.

Among the capsaicin compounds of the general formula (1), preferred are capsaicin compounds in which R in general formula (1) has 7 to 10 carbon atoms. Some of these examples are shown below:

R = CH ₃ (CH ₂ ) ₆ (caprylic acid vanylamide),

R = CH ₃ (CH ₂ ) ₇ (nonyl acid vanylylamide),

R = CH ₃ (CH ₂ ) ₈ (decyl acid vanylylamide),

R = (CH ₃ ) ₂ CH (CH ₂ ) ₅ (nordihydrocapsaicin I),

R = (CH ₃ ) ₂ CH (CH ₂ ) ₆ (dihydrocapsaicin),

R = (CH ₃ ) ₂ CH (CH ₂ ) ₇ (homodihydrocapsaicin I),

R = CH ₃ CH ₂ CH (CH ₃ ) (CH ₂ ) ₄ (nordihydrocapsaicin II),

R = CH ₃ CH ₂ CH (CH ₃ ) (CH ₂ ) ₆ (Homodihydrocapsaicin II),

R = (CH ₃ ) ₂ CHCH = CH (CH ₂ ) ₄ (capsaicin),

R = (CH ₃ ) ₂ CHCH ₂ CH = CH (CH ₂ ) ₄ (homocapsaicin I) and

R = CH ₃ CH ₂ CH (CH ₃ ) CH = CH (CH ₂ ) ₄ (homocapsaicin II).

Allicin (allicin) used with the capsaicin is extracted from Garlic as a compound having the following formula (2), it can be used to protect vegetables, fruits, seeds, etc. from algae, insects It is also known from REDFACTS published by the US Environmental Protection Agency.

[Formula 2]

(2)

(2)

Many studies have been conducted to use these natural extracts as a repellent for animals and insects. As a result, there are Japanese Patent Application Laid-Open No. 64-83006 and Japanese Patent Laid-Open No. 3-7554. Lactones extracted from skin and cinnamon are mixed and used to prepare pest repellent and to be used for packing foods. Japanese Patent Application Laid-Open Nos. 59-53497, 62-61562, and 63-41495, Japanese Patent Application Laid-Open No. 1-213291, Japanese Patent Application Laid-open No. 3-41011, and the like disclose a technique for mixing insect extracts and yukari extract as insect repellents. Techniques for using alcohol glycosides, phenol glycosides, nitrile glycosides, mustard oil glycosides, cyclopentene glycosides and the like as pest repellents are known.

Examples of using allicin mentioned above include Japanese Patent Application Laid-Open No. Hei 4-5211 and US Pat. No. 5,705,152. These are known for techniques for sterilizing and insecticidal compositions, and capsaicin is known. Japanese Patent Laid-Open No. 7-10703, Japanese Patent Laid-Open No. 7-41407, and U.S. Patent No. 5,674,496. These include capsaicin stored in microcapsules and used as an additive to synthetic resins to combat animals, capsaicin and other compounds. Enumerate techniques for combating animals and insects by mixing them.

In addition, Korean Patent Publication No. 96-9493 discloses a technique for containing an allicin-containing component and a capsaicin-containing component in a breathable container and used as a repellent such as rice worms.

On the other hand, Korean Patent Laid-Open Publication No. 04-26874 discloses a technique for using a composition containing onion extract as a main component to combat the cat as a cat repellent.

Ginger's spice is composed of shogaol, ginger, and gingeryl vanillyl ketones, which are known to have bactericidal and antimicrobial properties, and glycosides such as sinigrin and Mustard and / or horseradish containing an aryl isocyanate-based material is known in Korea Patent Publication No. 01-49278 that has a insect repellent, antibacterial function and is used as a grain quality preservative.

However, there is no known technique in which a composition prepared by mixing the above-mentioned natural extracts is used to prevent noise damage by rodents, dogs, cats and other wildlife. Therefore, the inventors of the present invention consist of extracts containing the active ingredients of red pepper, garlic, onion, ginger, mustard and / or wasabi to prepare a composition of the compounding ratio having an elevated effect by using the respective effects and to prepare these mixed extracts The microencapsulation prevents the active ingredient from being contaminated and prepares the resin molding composition and has completed the present invention to have excellent repellency for animals.

Accordingly, it is an object of the present invention to provide a snow remover composition which prevents sonic damage by rodents and other animals.

Another object of the present invention is a pepper extract containing capsaicin, garlic extract containing allicin, onion extract, mustard and / or horseradish extract containing allyl isothiocyanate as an active ingredient and ginger extract containing vanillyl ketones. It is to provide a microcapsule comprising a.

Another object of the present invention is to provide a resin molding composition comprising a microcapsule containing a mixed extract prepared by combining the natural extract.

In order to achieve the above object, the present invention provides a snow-depositing composition that prevents damage to the mouth by rodents and other animals.

Hereinafter, the configuration of the present invention will be described in detail.

Pepper extract containing the capsaicin compound, which is a hot ingredient of red pepper, as a main component can be obtained in the following manner.

Dried and powdered peppers are prepared using alcohol solvents (e.g. methanol and ethanol), ether solvents (e.g. ethyl ether), ketone solvents (e.g. acetone), aromatic solvents (e.g. benzene), chlorine solvents (e.g. : Dichloroethane and chloroform), or other suitable solvent, and after filtering, the filtrate is heated in a reduced pressure evaporator to remove the solvent to obtain a red pepper extract. Chromatography of the extract using a silica gel or alumina column can give a pepper extract containing a high concentration of capsaicin compound.

Garlic extract is 30% to 80% by weight of garlic juice obtained by pressing the washed well garlic and 1% to 20% by weight of garlic oil obtained by distilling the garlic juice 10% to 50% by weight food starch syrup It can be prepared by mixing with. Garlic extract loses its unique fragrance due to the change of allicin component during heat processing such as steaming. Garlic juice obtained during processing by pressing garlic contains about 0.3% of allicin component. It is difficult to exert its functions, and the garlic juice contains a large amount of water, so it is difficult to mix the capsaicin-containing pepper extract with oil components, so the garlic juice 30% to 80% by weight and garlic juice 1% to 20% by weight of the garlic oil obtained by distilling is mixed with 10% to 50% by weight of food starch.

Onion varieties are divided into round and flat round scales, red and yellow scales, and white ones. Also, depending on taste, they are divided into mono onions and spicy onions. The onion used in the present invention may be used in any variety, but it is preferable to use a spicy onion.

In the present invention, the scales of the onion are used, the scales contain compounds such as propyl disulfide, allyl sulfide and the like to emit a unique smell. On the other hand, these components physiologically promote the secretion of digestive juices and have effects such as excitement, sweating, and diuresis. In addition, the scales contain minerals such as calcium and phosphoric acid together with various vitamins, and also have the effect of removing harmful substances in the blood.

In addition, according to another configuration of the present invention, the rodent repellent composition containing the onion extract according to the present invention is

a) A process for sorting the scales of onions of a predetermined size or more harvested:

b) removing the outer membrane from the scales of the selected onion (膜質: translucent like thin paper);

c) washing the stem of the onion from which the membrane is removed;

d) a pulverizing step of crushing the scales of the washed onion with a grinder after drying; And

e) characterized in that it is prepared by the step consisting of the process of crushing the pulverized liquid obtained from the crushing process to a mesh of a predetermined mesh or more.

In addition, ginger, mustard and / or horseradish extracts, which is another component of the present invention, are ground with these plant raw materials and extracted with alcoholic solvents (e.g. methanol and ethanol) and the crude alcohol extracts are ether solvents (e.g. ethyl ether). Extracted with ketone solvents (e.g. acetone), aromatic solvents (e.g. benzene), chlorine solvents (e.g. dichloroethane and chloroform), or other suitable solvents and filtered, and the filtrate is heated in a reduced pressure evaporator to remove the solvent. Thereby obtaining ginger, mustard and / or horseradish extracts.

In the composition for prevention of wetting by rodent animals used in the present invention, the red pepper extract containing the capsaicin compound as an active ingredient is 10% by weight to 65% by weight, preferably 50% by weight. Prepared from 10% to 40% by weight of garlic extract containing allicin, 10% to 30% by weight of onion extract, 5% to 30% by weight of mustard and / or horseradish extract, 10% to 30% by weight of ginger extract Can be. The mixed composition of the plant extract is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight based on the total amount of the resin molding composition. By considering various restrictions depending on the form of use, the concentration can be appropriately determined from the above range in view of efficiency and economy.

Known methods can be used to incorporate microcapsules filled with the mixed extract in a resin. For example, a method of directly adding and mixing microcapsules to resin materials and additives (e.g., plasticizers, pigments, etc.) and shaping the mixture, or when preparing and molding the masterbatch containing the mixed extract in advance, Mention may be made of dilution of this masterbatch with the resinous material to the desired concentration.

Encapsulation techniques that can be used in the present invention are not limited and various known techniques can be used. For example, after dissolving the wall raw material in the composition containing the complex extract to be microencapsulated, the solution is dispersed in an insoluble dispersion medium (usually water) and an appropriate reactant soluble in the dispersion medium is added to the dispersion with stirring, and Methods using interfacial polymerization techniques to form capsule walls that encapsulate the core material by reacting on the surface of dispersed particles, or on-site to form capsule walls with wall material supplied from dispersed particles or dispersion media on the surface of dispersed particles Mention may be made of methods using polymerization techniques. Other known encapsulation techniques can also be used, such as coacervation, in-air-phase microencapsulation methods, and the like.

As a wall material for in-liquid microencapsulation, urea resins, melamine resins, guanimine resins, phenol resins, polyamides, polyureas, polyurethanes, polyesters, gelatins and the like can be used. These react with monomers, low molecular weight prepolymers, crosslinking agents, polymerization initiators and the like. As the air-containing encapsulating wall material, polyvinyl alcohol, polyacrylic acid, cellulose acetate, polymethacrylate, and the like can be used. These materials may be used alone or in combination.

It has been found that the use of melamine resin as capsule wall material can enhance the repellent effect on animals. In particular, microcapsules can be prepared according to in situ polymerization techniques by using melamine and formaldehyde or precondensates thereof (methylolmelamine) as acidic starting materials under acidic conditions. This method is merely an example, and other methods and other wall materials may be appropriately used depending on the method of use, various conditions, economics, and other factors.

Microcapsule formulations that can be used in the present invention are usually prepared in powder form, consisting of a composition containing at least 1% by weight, preferably 5 to 80% by weight of the mixed extract. To prepare these powders, they may be dried by various methods such as spray drying, multistage hot air drying, vacuum drying and the like.

The weight ratio of the core material to the wall material of the microcapsules may be generally 1: 0.01 to 1:10, preferably 1: 0.1 to 1: 2, but is not limited to the above range.

The average particle diameter of the microcapsules can be changed as desired, and is usually adjusted to about 1 to 150 mu m. In order to maximize the effect of preventing noise damage by animals, it is preferable that 90% or more of the microcapsules are manufactured to have a particle size of 5 to 100 μm (average particle size is 15 to 50 μm).

The microencapsulation process is generally carried out by (1) dispersing the mixed composition consisting of capsaicin compounds or red pepper extracts containing them as a main component and garlic, onion, ginger, mustard and / or horseradish extract in water and (2) the mixed extracts. And forming two polymer walls around the dispersed particles of the composition containing the polymer. The particle diameter can be adjusted by the viscosity of the core material, the dispersion temperature, the spraying device, the rotation speed of the stirrer obtained in the apparatus, the dispersion time, the type or amount of the dispersant, and the like. For example, to obtain 1 liter of microcapsule dispersion having an average particle diameter in the above-mentioned range using a 1 liter mixer (manufactured by Matsushita Electric Co., Ltd., MX-M2), 20 to 50 ° C and 1000 to It can be dispersed for 5 minutes at 1500 rpm. In addition, in order to obtain 1 liter of the microcapsule dispersion having an average particle diameter in the above range using a 1 liter round bottom flask equipped with a stirring blade of 7 cm length, the microcapsules were mixed at 50 to 85 ° C. and 500 to 700 rpm for 30 minutes. Can be encapsulated (dispersed). If the rotational speed which forms the polymer wall is less than the rotational speed at the time of dispersion, this rotational speed does not affect the particle diameter much.

In order to obtain the microcapsules of the present invention, any kind of capsaicin compounds of the general formula (1) may be used as the core substance. That is, the manufacturing method of a capsaicin compound is not limited to any specific method. In the present invention, a method for preparing a capsaicin compound was prepared using the method described in Korean Patent No. 250159.

An overview of the method of preparing the microcapsules has already been mentioned, but will be described in detail as follows.

First, the interfacial polymerization method will be described.

The fat-soluble wall raw material A is dissolved in a hydrophobic core material containing a capsaicin compound and a composition consisting of the above extracts, and water and auxiliaries such as dispersants are added to the solution. The resulting mixture is stirred at predetermined stirring conditions to form a system in which a solution of hydrophobic core material and fat soluble wall raw material A is dispersed in a predetermined particle diameter on water. While stirring the system, an aqueous solution of water-soluble wall raw material B is added thereto to allow the two wall raw materials to react at the interface of the dispersed particles and the water phase to form a polymer capsule wall that is insoluble to both the core material and the water phase and is hydrophobic. Microcapsules containing the core material are prepared (single step microencapsulation).

Multistage microencapsulation may be employed to minimize the amount of capsaicin compound and mixed extract remaining unencapsulated. A slightly water soluble, high solubility in the mixed extract composition and in which the fat soluble wall raw material C is dissolved is added to the microencapsulated system by itself or after the solvent is dispersed in water and the water soluble wall raw material D is added to Reaction under conditions and temperature conditions again produces a polymer wall (two step microencapsulation). Repeat this process several times to efficiently microencapsulate the red pepper extract containing the capsaicin compound remaining unmicroencapsulated and the mixed extract and to minimize the amount of the capsaicin compound and the mixed extract remaining unmicroencapsulated (multistage micro Encapsulation).

The fat soluble wall raw materials A and C and the water soluble wall raw materials B and D may be different or the same respectively. Examples of these are as follows.

As examples of fat-soluble wall raw materials, mention may be made of polyisocyanates, polyvalent carboxylic acid chlorides and polyvalent sulfonic acid chlorides. For example, they are hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, toluene diisocyanate, xylene diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl diisocyanate, sebacoyl dichloride , Didifoyl dichloride, azeloyl dichloride, terephthaloyl dichloride, trimesoyl dichloride and benzenesulfonyl dichloride.

As examples of water soluble wall raw materials, mention may be made of polyhydric amines and polyhydric compounds. For example these are ethylene diamine, hexamethylene diamine, phenylene diamine, diethylene triamine, triethylene tetraamine, piperazine, ethylene glycol, butanediol, hexanediol and polyethylene glycol.

In-situ polymerization method is demonstrated.

The in situ polymerization method dissolves the wall raw material in the red pepper extract containing the capsaicin compound and the hydrophobic core material or water containing the mixed extract, and disperses the hydrophobic core material in the water, thereby providing an interface between the dispersed particles and the water phase. In the process, microcapsules are prepared by forming insoluble polymer walls on the hydrophobic core material and water. This method is different from the interfacial polymerization method. In the present invention, the red pepper extract containing the capsaicin compound and the microcapsules of the composition consisting of the mixed extract prepared in water (single step microencapsulation method), (1) high solubility to the capsaicin compound and the mixed extract And disperse the hydrophobic core material in this system, or (2) the high solubility and slightly water soluble solvent of the capsaicin compound and the mixed extract, in this system. By adding the water-soluble wall raw material F to this system by itself or in the form of an aqueous solution, at the interface between the dispersed particles and the water phase, a polymer wall insoluble to the hydrophobic core material and water is formed (two-step microencapsulation method). ). This process is repeated several times to effectively microencapsulate the red pepper extract containing the capsaicin compound, which remains unencapsulated, and the mixed extract, thereby minimizing the amount of capsaicin compound and the mixed extract remaining unencapsulated (multistage microencapsulation). method).

Examples of wall raw materials E and F are as follows. As the fat-soluble wall raw material E, a substance which forms a polymer by a radical polymerization reaction (for example, acrylate, methacrylate, vinyl acetate, styrene, divinylbenzene, ethylene dimethacrylate, etc.) is used. As the water-soluble wall raw material F, a substance which forms a polymer by condensation polymerization (for example, urea / formalin, melamine / formalin, phenol / formalin, etc.) is preferable.

The type and amount of wall raw material used in the present invention is selected according to the type of core material and the purpose of using the microcapsules. In the present invention, a multistage microencapsulation method combining a surface polymerization method and an in situ polymerization method can be adopted.

As adjuvants for use in microencapsulation, there are dispersants for dispersing hydrophobic core substances in water. More specifically, natural polysaccharides such as acacia gum, sodium alginate, locust bean gum and xanthan gum; Semisynthetic polysaccharides such as carboxymethyl cellulose and methyl cellulose; And synthetic polymers such as polyvinyl alcohol, alone or in the form of mixtures. The amount of the dispersant used is usually 0.01 to 10.0%, preferably 0.1 to 3.0% with respect to the suspension composition when microencapsulation is performed. Polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, alkylphenyl condensate ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylamino ethers, polyoxyethylene alkylamides, polyoxyethylene polyoxypropylene block polymers, One or more surfactants such as polyoxyethylene vegetable oil ether, sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester are used. The amount of the surfactant to be used is usually 10% or less, preferably 3% or less with respect to the dispersion. When the core material for microcapsules is prepared by dissolving the capsaicin compound in a solvent, ethers such as butyl ether and ethylvinyl ether; Aliphatic or aromatic hydrocarbons such as heptane and xylene; Halogenated hydrocarbons such as dichloromethane and trichloroethane; Mineral oils such as machine oils; Vegetable oils; And one or more solvents selected from solvents mainly used as plasticizers for resins such as phthalates, adipates, phosphates, maleates and low molecular weight epoxy compounds. As other adjuvants, anti-molding agents and specific gravity regulators, and stabilizers and pH regulators for some capsaicin compounds can be added to the core material and / or water phase.

The resin containing the microcapsules filled with the composition consisting of the capsaicin compound and the mixed extract as a core substance in the resin molding composition and the molded article (product) thereof of the present invention is not limited to a specific form. Various resins such as semisynthetic resins, pure synthetic resins, natural resins, synthetic rubbers, copolymer resins and plastic alloys obtained by mixing or grafting two or more resins can be used. These types of resins can be used alone or in combination.

Nitrocellulose, acetylcellulose, cellulose propionate, methyl cellulose, ethyl cellulose, carboxymethyl cellulose and the like can be mentioned as examples of the semisynthetic resin in the composition of the present invention. Examples of compliant thermoplastic resins are polyethylene, polystyrene, polypropylene, methacryl resin, vinyl chloride resin, polyamide resin, polo resin, silicone resin, polycarbonate, polyether resin and the like. Examples of thermosetting resins that can be used in the present invention include phenol resins, furfural resins, xylene resins, urea resins, melamine resins, guanamine resins, unsaturated polyester resins, diallyl phthalate resins, alkyd resins, futan resins, aniline resins, Epoxy resins, polyurethane resins, polyimide resins and the like can be mentioned. Synthetic rubbers that can be used in the compositions of the present invention include rubbers in diene form, olefin form, acrylic form, silicone form, fluorine form and other forms. Examples of natural resins are copal resins, rosin, natural rubbers and vulcanized natural rubbers. The form of the resin most preferably used for the purposes of the present invention is a compatible thermoplastic or easy to process thermoplastic rubber. The resin may be added with suitable auxiliaries such as plasticizers, stabilizers, flame retardants, lubricants, colorants, fillers, antioxidants, ultraviolet absorbers and the like to improve the molding processability and stability of the composition. In addition, the composition may be treated with pest control agents, plant control agents and the like so that the composition has an additional effect upon use.

Typical usage of the resin molded article (product) of the present invention is as follows.

1) articles consisting mainly of thermoplastics; Cables for electrical and optical communications, power transmission, etc .; Mixed with electrical equipment and wiring cords.

2) Processing in furniture fixtures, interior and exterior materials for buildings, containers, hoses, pipes, plates, packages, packaging materials, etc.

3) Thread treatment in textile products.

4) Treatment on various types of tapes and sheets, and their application (by attachment, winding, etc.) to articles (mechanical parts, devices, wood, etc.) that are to be protected from damage caused by animals.

5) Sealants and various resin-based paste-like products and dough to close entrances for rodents and other animals to buildings, etc.

Resin molding composition of the mixed extract composition consisting of capsicin compound or capsaicin as the main component, red pepper extract, garlic, onion, ginger, mustard and / or horseradish extract according to the present invention in order to prevent damaging by rodents or other animals And the molded articles thereof have an increased effect, with each effect added to prevent noise damage by animals. In particular, a capsaicin compound microencapsulated with a melamine resin film and a composition consisting of the mixed extract has a high effect. The effect is particularly high when microcapsules having a particle size of at least 90% having a particle diameter of 5 to 100 mu m (average particle diameter is 15 to 50 mu m) are used.

In addition, the composition of the present invention has good molding processability due to excellent water resistance and heat resistance, the reduction in efficiency during the molding process is very small, and can maintain a constant efficiency for a long time. In addition, molded articles (products) from compositions comprising resins are noticeably reduced in spicy taste and irritability to humans and are easier to handle.

As a microcapsule resin molding composition containing a mixed extract consisting of capsicum compound containing capsaicin compound, pepper extract, garlic extract, onion extract, ginger extract, mustard and / or horseradish extract, The prepared rodent damping sheet can be installed easily and inexpensively and can exert the effect of preventing the damaging damage caused by rodents and other animals by increasing the effect by the composite composition of each component extract.

The present invention will be described in more detail with reference to Examples. (In the following description, all parts are by weight unless otherwise indicated.)

[ Example  1] red pepper extract and Capsaicin  Preparation of compounds

1000 g of dried red pepper is placed in a soxhlet apparatus and extracted with acetone as a solvent for 1 hour to obtain a reddish brown mixture. The reddish brown mixture is vacuum distilled in a vacuum distillation until there is no acetone, and the solvent is removed. An extract was obtained. The capsaicin compound represented by Formula 1 used in the present invention was prepared by the following method.

The present invention provides a capsaicin compound of the following general formula (1) by condensing a compound of the following general formula (2) with a vanylylamine or a salt thereof in a solvent, if necessary, in the presence of an acid binder; In this state, the starting materials required for microencapsulation (eg encapsulating agent) are placed in the same reactor; Also provided is a method for preparing a capsaicin compound and its microcapsules, comprising preparing the microcapsules by an oil spray system in water:

(2)

(2)

Wherein R is an alkyl group, an alkenyl group or an alkynyl group and each group has 7 to 12 carbon atoms and Hal is a halogen atom.

[ Example  2] Preparation of Garlic Extract

2,000 g of garlic was pressed to obtain 200 g of garlic juice, 100 g of the obtained garlic juice was fractionated and distilled at 220 ° C. to 225 ° C. to obtain 11.5 g of garlic oil, followed by mixing and stirring 70 g of the garlic juice and 5 g of garlic oil syrup. 100 g of garlic extract having a viscosity of 1,500 to 1,700 cps was prepared.

[ Example  3] Preparation of Onion Extract

About 10kg of the scales of onions harvested above a certain size are selected, and after removing the outer membrane from the scales of the onions, the water is washed with water and dried. The scales of the washed onions were pulverized with a mixer to obtain a pulverized liquid, and the pulverized liquid was pressed with a mesh of 200 mesh to obtain 5.5 kg of onion juice. 500 ml of water was added to about 2.5 kg of the obtained onion juice and then homogenized with mild stirring to prepare a composition according to the present invention.

[ Example  4] Preparation of Mustard and / or Wasabi Extract

1000 g of finely ground mustard and / or horseradish were immersed in 2 L of methanol for 2 days, and then the methanol extract obtained by filtration was evaporated under reduced pressure to remove the solvent, and extracted three times with 200 mL of hexane or chloroform to evaporate under reduced pressure. Or 100 g of wasabi extract was obtained.

Preparation of ginger extract was obtained in the same manner as in Example 4 was used in the present invention.

[ Example  5] Capsaicin  Microencapsulation of Mixed Extract Compositions Composed of Compound and / or Red Pepper Extract, Garlic, Onion, Ginger, Mustard, and / or Horseradish Extracts

10 parts of the mixed extract composition consisting of 50% by weight of capsaicin compound and / or red pepper extract, 20% by weight garlic extract, 10% by weight onion extract, 15% by weight ginger extract, 5% by weight mustard and / or horseradish extract and Millionate MR- 10 parts of 400 (manufactured by Nippon Urethane Co., Ltd.) was dissolved in 75 parts of dioctyl phthalate, and the solution was mixed with polyvinyl alcohol [Gosenol GH-17 (The Nippon Synthetic Chemical) while stirring at 650 rpm for 10 minutes using the above-described mixer. Industry Co., Ltd.)] was dispersed in 300 g of a 1% aqueous solution to prepare an O / W emulsion. At this time, 2.5 g of ethylenediamine and 2.5 g of diethylenetriamine were dissolved in 95 g of water, and the solution was added dropwise to the emulsion with stirring at 250 rpm to allow them to react for 3 hours at 60 ° C., thus having a polyurea wall and suspended in water. Microcapsules (average particle diameter: 49 μm) were prepared. The suspension was dried with a spray dryer to obtain microcapsules containing 10% by weight of a capsaicin compound and / or a mixed extract composition consisting of red pepper extract, garlic, onion, ginger, mustard and / or horseradish extract, respectively. 2 parts of these microcapsules were added to 98 parts of vinyl compound SE-24 (manufactured by Mitsui Toatsu Chemical Inc.), and the mixture was subjected to rolling treatment in the same manner as in Comparative Example 1 to obtain capsaicin compound and / or pepper extract, garlic, onion, A 1 mm thick polyvinyl chloride sheet containing 0.2% of a mixed extract composition consisting of ginger, mustard, and / or horseradish extracts was obtained.

[ Example  6]

Dissolve 10 parts of vanylylamide and 20 parts of sebacoyl chloride in 65 parts of dioctyl phthalate and disperse this solution in 200 parts of 1% aqueous solution of Gasenol GH-17 while stirring at 1200 rpm for 10 minutes using the above-described mixer. O / W emulsions were prepared. At this time, 5 parts of ethylenediamine, 5 parts of diethylenetriamine and 10 parts of sodium hydroxide were dissolved in 80 parts of water, and the solution was added dropwise to the emulsion while stirring at 250 rpm to induce the reaction and the reaction was continued at 3O < 0 > C for 3 hours. Microcapsules with amide walls and suspended in water were prepared.

95% of the prepared microcapsules had a particle diameter of 5 to 100 µm and an average particle diameter of 23 µm. The suspended microcapsules were dried using a spray dryer to obtain microcapsules each containing 10% nonyl acid vanillylamide. 2 parts of these microcapsules were added to 98 parts of vinyl compound SE-24 and the mixture was subjected to rolling treatment in the same manner as in Comparative Example 1 to obtain a 1 mm thick polyvinyl chloride sheet containing 0.2% of nonyl acid vanylylamide. .

[ Example  7]

10 parts dioctyl adipate mixed extract composition consisting of 50% by weight of capsaicin compound and / or red pepper extract, 15% by weight garlic extract, 10% by weight onion extract, 15% by weight ginger extract, 10% by weight mustard and / or horseradish extract Dissolved in 70 parts and added to 200 parts of a 3% aqueous solution of pH 4.5 prepared by dissolving styrene-maleic anhydride resin and a small amount of sodium hydroxide in water, and then using a mixer (1 liter) at 25 ° C. and 1200 rpm. Stir for 5 minutes to form an O / W emulsion. Then, 35 parts of a 50% aqueous solution of Sumilez Resin 613 (melamine-formaldehyde prepolymer, manufactured by Sumitomo Chemical Co., Ltd.) was added dropwise to the emulsion while stirring at 250 rpm, and the mixture was continuously stirred at 70 ° C. for 3 hours to form a melamine resin capsule wall. And prepared microcapsules suspended in water. 92% of the prepared microcapsules had a particle diameter of 5 to 100 µm and an average particle diameter of 28 µm.

The prepared microcapsules were dried and mixed with vinyl compound SE-24, followed by rolling the mixture in accordance with Comparative Example 1 to obtain a capsaicin compound and / or a red pepper extract, garlic, onion, ginger, mustard and / or horseradish extract. A 1 mm thick polyvinyl chloride sheet containing 0.2% of the mixed extract composition was prepared.

[ Example  8]

10 parts mixed extract composition consisting of 50% by weight of capsaicin compound and / or red pepper extract, 25% by weight garlic extract, 10% by weight onion extract, 10% by weight ginger extract, 5% by weight mustard and / or horseradish extract and dioctyl phthalate Dissolve this in 65 parts and disperse this solution in 200 parts of a 3% aqueous solution of styrene-maleic anhydride resin and a small amount of sodium hydroxide (pH 4.5), and then totally a round-bottom flask (1 liter with 7 cm long stirring blades). ) Was stirred at 85 ° C. and 700 rpm for 30 minutes to prepare an O / W emulsion. 50 parts of 50% aqueous solution of this melamine-formaldehyde prepolymer Sumilez Resion 613 (manufactured by Sumitomo Chemical Co., Ltd.) was added dropwise to the emulsion with stirring at 350 rpm. Stirring at 70 ° C. for 3 hours yielded microcapsules with melamine resin capsule walls suspended in water. 94% of these microcapsules had a particle diameter of 5 to 100 µm and an average particle diameter of 23 µm.

The microcapsules thus prepared were dried and added to the vinyl compound SE-24, followed by rolling in the same manner as in Comparative Example 1 to capsaicin compound and / or red pepper extract, garlic, onion, ginger, mustard and / or horseradish extract. A 1 mm thick polyvinyl chloride sheet containing 0.2% of the mixed extract composition was prepared.

[ Example  9]

The same procedure as in Example 4 was conducted except that the dispersion conditions were changed (dispersed at 1000 rpm) to prepare microcapsules having a melamine resin wall and suspended in water. 86% of these microcapsules had a particle diameter of 5 to 100 µm and an average particle diameter of 10 µm. The prepared microcapsules were dried and added to the vinyl compound SE-24, followed by rolling in the manner of Comparative Example 1 to obtain 50% by weight of capsaicin compound and / or red pepper extract, 20% by weight of garlic extract, 10% by weight of onion extract, ginger A 1 mm thick polyvinyl chloride sheet containing 0.2% of a mixed extract composition consisting of 15% by weight of the extract and 5% by weight of mustard and / or horseradish extract was prepared.

[ Example  10]

Microcapsules suspended in water with melamine resin walls were prepared according to the same process as in Example 4 except that the dispersion conditions were varied (dispersed at 500 rpm). 72% of these microcapsules had a particle diameter of 5 to 100 mu m and an average particle diameter of 65 mu m. The microcapsules thus obtained were dried and added to the vinyl compound SE-24, followed by rolling the mixture according to the method of Comparative Example 1 to obtain 50% by weight of capsaicin compound and / or red pepper extract, 20% by weight of garlic extract, and onion extract 10. A 1 mm thick polyvinyl chloride sheet containing 0.2% of the mixed extract composition consisting of 5% by weight, 15% by weight of ginger extract, 5% by weight of mustard and / or horseradish extract was prepared.

[ Control  One]

99.8 parts of commercially available vinyl compound (vinyl compound SE-24) containing a plasticizer, pigment, etc., 50% by weight of capsaicin compound and / or red pepper extract, 20% by weight of garlic extract, 10% by weight of onion extract, 15% by weight of ginger extract , 0.2 parts of a mixed extract composition consisting of 5% by weight of mustard and / or horseradish extract and using a heated pressure roll (Model NS-105 (J) W, manufactured by Nishimura Machinery Co., Ltd.) at 10.degree. The mixture was hot rolled for minutes to give a 1 mm thick polyvinyl chloride sheet containing 0.2% of the mixed extract composition.

[ Control  2]

0.6 parts of methanol extract of red pepper containing 35% capsaicin compound was added to 99.4 parts of vinyl compound SE-24, and the mixture was rolled in the same manner as in Comparative Example 1 to obtain 1 mm thick polyvinyl chloride containing 0.2% of capsaicin compound. A sheet was obtained.

[ Control  3]

0.2 part of the mixed extract composition consisting of capsaicin compound and / or red pepper extract 50%, garlic extract 20%, onion extract 10%, ginger extract 15%, mustard and / or horseradish extract 5% by weight vinyl compound SE- 24% of a mixed extract composition comprising red pepper extract, garlic, onion, ginger, mustard and / or horseradish extract, which was added to 99.8 parts and subjected to rolling treatment of the mixture in the same manner as in Comparative Example 1, containing the capsaicin compound as a main component A 1 mm thick polyvinyl chloride sheet containing was obtained.

[ Control  4]

In the same manner as in Comparative Example 1, only vinyl compound SE-24 was hot-rolled to prepare a 1 mm thick polyvinyl chloride sheet.

[Test Example 1-1] Effects of Preventing Sound Damage by Rodents

[Test Methods]

Each of the sheets obtained in Control Example 1, Control Example 2, Control Example 3, Control Example 4 and Example 8 was cut to a size of 75 × 150 mm. This was folded in duplicate, two loaves of solid food of rodents were placed in it, and the specimens were prepared by dipping a stapler on three edges. Each of the specimens thus prepared was placed in a cage with three rodents weighing about 300 g and left overnight in this state, and the area of the sheet damaged by the rodents was examined. Specimens using the sheets obtained in one of Control Examples 1-4 and Example 8 were placed in each cage and tested in five cages for each specimen.

[Table 1] Measurement result of prevention of noise damage by rodents

Sound Damage Area (cm2) Psalter Our number One 2 3 4 5 Average Control One 0 0.15 0.2 0 0 0.06 Control 2 0 0.1 0 0.4 0 0.10 Control 3 0.05 0 0.2 0 0.2 0.09 Control 4 14.0 9.0 20.0 9.0 19.2 11.87 Example 8 0 0 0 0 0 0

The specimen of Example 8 showed an excellent effect in preventing noise damage compared to the specimen of the control example and showed high practical applicability. It is noteworthy that the sheet containing the microcapsules made from the composition consisting of the mixed natural extract prepared in Example 8 was not damaged at all. In the control case, the food in the psalms was consumed in each cage.

[Test Example 1-2] Effect of preventing sound damage by rodents

[Test method] Using the sheets obtained in Examples 6 to 10 and Comparative Example 4, the specimens prepared in the same manner as in Test Example 1-1 were placed in individual cages (in each cage containing three rodents). 1 specimen per day), which was left alone for one day, and the area of each sheet injured by rodents was examined.

[Table 2] Survey on the area of noise damage by rodents

Sound Damage Area (cm2) Psalter Our number One 2 3 4 5 Average Example 6 0.9 3.9 0.1 1.0 2.3 1.64 Example 7 0 0.02 0 0 0.1 0.02 Example 8 0 0 0 0 0 0 Example 9 0 0.1 0.1 0.2 0.3 0.14 Example 10 0.1 1.0 0 0.3 0.1 0.3 Control 4 12.3 19.0 22.0 14.6 8.9 15.36

Each of the specimens of Examples 6 to 10 exhibited excellent anti-damage damage effect and high practical applicability compared to the specimen of Comparative Example 4. It is noteworthy that the microcapsules with melamine walls prepared in Examples 7, 8, 9 and 10 showed a higher anti-damage effect than the microcapsules with polyamide walls prepared in Example 6. In addition, the microcapsules prepared in Examples 7 and 8, in which the particle diameter of 5% or more and 90% or more and the average particle diameter is 15 to 50 µm, the examples of Examples 9 and 10, in which the particle diameter and the average particle diameter are not limited to the above ranges. It showed a better sound damage prevention effect than the prepared microcapsules. Microcapsules containing the mixed extract composition of the present invention consisting of red pepper extract, garlic extract, onion extract, ginger extract, mustard and / or horseradish extract as a main component of the capsaicin compound prepared in Example 6 The resin molding compositions showed excellent effects.

[Test Example 2-1] Spicy taste and skin irritation test for humans

[Test Methods]

[Spicy]

A sensory test for pungent taste was conducted by allowing the tester to lick the components used to prepare the sheets and sheets obtained in the individual examples or controls, namely capsaicin compound, nonyl acid vanylylamide and the mixed extract composition of the present invention. When each plant extract was placed at the tip of the tongue, each tester felt spicy throughout the mouth, but when the sheet containing the microcapsules prepared in Example 1 was licked, all testers felt only a little spicy.

[Skin irritation]

A 3 cm <2> piece of each sheet was attached to the inside of the arm of the investigator while a small amount (about 1 mg) of each of the components was applied to a similar portion and the irritation felt by each tester for 2 hours after application was examined. As a result, there was a tingling irritation at the application of each plant component extract, but the microcapsules made of the composition of the present invention prepared by mixing red pepper, garlic, onion, ginger, mustard and / or horseradish extract obtained in Example 1 I did not feel any irritation in the sheet.

Claims (8)

delete Red pepper extract containing 10 to 65% by weight of the capsaicin compound of the general formula (1) as a core material, 10-40% by weight garlic extract containing allicin, 10-30% by weight of onion extract, mustard and / or horseradish extract 5 to 30% by weight of the composite extract mixed with ginger extract 10 to 30% by weight as a microcapsule resin for preventing damage to the animal, characterized in that containing 0.01 to 10% by weight relative to the total weight of the resin molding Molding composition.

(One) Wherein R is an alkyl, alkynyl or alkenyl group, each group having 7 to 12 carbon atoms. The resin molding composition of claim 2, wherein the microcapsules have a particle diameter of 5 to 100 μm or more and an average particle diameter of the microcapsules is 15 to 50 μm. 4. The resin molding composition according to claim 3, wherein the microcapsules are melamine resin. The resin molding composition according to any one of claims 2 to 4, wherein the resin is a thermoplastic resin. The resin molded product obtained by shape | molding the resin molding composition of Claims 2-4 with an electric wire, a cable, a hose, a pipe, a sheet, or a board. The method according to any one of claims 2 to 4, wherein the red pepper extract, garlic extract, onion extract, mustard and / or wasabi extract, ginger extract contained in the complex extract is obtained by organic solvent extraction method Resin molding composition. The method of claim 7, wherein The organic solvent is a resin molding composition, characterized in that methanol, ethanol or acetone.