KR20020092774A - A composition for preserving against decay and for protecting against insects - Google Patents

Abstract

PURPOSE: To obtain an antiseptic and insect proof agent composition having both characteristics of safety for humans and animals and adaptability to the environment possessed by a natural material and effectiveness against wood detroying fungi or wood eating insect pests possessed by a chemical agent. CONSTITUTION: This antiseptic and insect proof agent composition is obtained by formulating an adduct of a terpene compound to a maleic anhydride with a natural antiseptic and insect proof ingredient. α-Terpinene is preferably applied as the terpene compound. At least one ingredient of hinokitiol, tannin, turpineol, obacunone, limonene, kihadanin, terpineol, azadiradione, pulegone, taxifolin, quercetin, naringenin, myricetin, menthol, citronellal, camphene, p-menthane, a 3,8-diol, benzoic acid, benzaldehyde, cadinol, perillaldehyde, cineole, α-pinene, β-pinene and longifolene is applied as the natural antiseptic and insect proof ingredient.

Description

Preservative and Insect Repellent Composition {A COMPOSITION FOR PRESERVING AGAINST DECAY AND FOR PROTECTING AGAINST INSECTS}

The present invention relates to an antiseptic and insect repellent composition used to prevent the damage caused by the generation of fungi, such as wood fungi, termite, wood insects, etc., or to prevent damage caused in advance.

Conventionally, preservatives and insect repellents used for preventing or controlling pests or pests of wood have been prescribed a chemical agent. Chemical agents are characterized by excellent fast-acting properties, inexpensiveness, and ease of use.

These chemicals are used by spraying or spraying at a rate of 300 ml (m) per m ² on the entire surface of wood within 1 m from the top of the base of the floor. In addition, a continuous footing, a footing, and the surface of the parquet soil around the pipe are treated with a strip of 1 liter (liter) per meter with a width of 20 cm, or a bathroom, kitchen, entrance, kitchen door, 3ℓ (liter) per 1m ² is used in the form of cotton in the part where concrete is used such as toilet.

Recently, however, a number of chemical hypersensitivity, volatile organic compound (VOC) problems, acute toxicity, and intoxication caused by these chemical agents have been aggravated.

On the other hand, there is a movement to use natural preparations as a gentler medicine to the human body. Natural preparations include cypress oil, cypress oil, vinegar liquor, and moonshine (alpinaia speciosa).

However, these natural drugs have excellent effects at the moment, but are generally used because of their reputation for being almost ineffective and superstitious. Or, even if it is effective, if the odor is strong and scattered under the floor, it is unpleasant for people living in the living space, and sometimes it may cause health problems.

Therefore, there is no effective effect in terms of efficacy and health of the human body in the currently used chemical or natural medicine.

The present invention has been made in view of such a conventional problem, and has both antiseptic properties such as safety for humans and animals with natural materials, adaptability to the environment, and effectiveness against wood fungi or wood food pests possessed by chemical agents. And an insect repellent composition.

In order to achieve the above object, the present invention is to provide an antiseptic and insect repellent composition formed by blending a natural antiseptic and insect repellent component with maleic anhydride adduct of a terpene compound.

Summary of the Invention The gist of the present invention is to use a component derived from nature and to combine them, so that it is possible to exhibit a high degree of antiseptic and insect repellent effect that could not be achieved alone.

Conventional natural preparations are merely extracts from plants that have already been dissolved in a variety of components, such as cypress oil and cypress oil. However, the active ingredient dissolved in natural extract essential oils is not only very small, but each has only an independent effect. Moreover, since most of them are volatile and volatilized and lost in a short time, the sustainability of the effect cannot be expected.

In the present invention, by effectively combining the components that have already been extracted and purified alone, an enhancement, that is, a synergistic effect, which could not be achieved by the sole components alone was achieved. Moreover, the development of antiseptic and insect repellent compositions that combine both fast-acting and sustained properties has been achieved.

In the antiseptic and insect repellent composition of the present invention, the terpene compound used as a raw material of the maleic anhydride adduct of the terpene compound as the active ingredient is a compound generally contained in plant essential oils obtained from leaves, stems, roots, and fruits of plants.

Herein, the terpene is generally a polymer of isoprene (C ₅ H ₈ ), and a monoterpene (C ₁₀ H ₁₆ ), a sesqui terpene (C ₁₅ H ₂₄ ), and a diterpene (C ₂₀ H ₃₂ ) And the like. Terpene compounds are compounds having these as a basic skeleton.

The terpene compound may be chain-shaped, ring-shaped. Specific examples thereof include, for example, mycene, allocymen, ocimene, α-pinene, β-pinene, dipentene, limonene, α-phellandrene, α-terpinene, and γ-terpinene. Terpinolene, 1,8-cineol, 1,4-cineol, α-terpineol, β-terpineol, γ-terpineol, campene, tricyclene, sabinene , Paramentadienes, karens, etc. are mentioned, It is not limited to these. Of these, α-terpinene, Milsen, allocymen and limonene are preferably used, and α-terpinene is particularly preferably used.

α-terpinene is a component derived from nature having the structure represented by the following [Formula 1], and is a monoterpene extracted from a Japanese basil or apiaceae, and also used as a flavoring tea tree oil. A softening ingredient is included and such oils are widely used as medicines. It is also used as a curry spice.

[Formula 1]

In addition, the maleic anhydride adduct of (alpha)-terpinene has the structure shown by following [Formula 2].

[Formula 2]

The addition reaction product of the terpene compound and maleic anhydride is usually obtained by reacting in the presence of a catalyst or catalyst. When the terpene compound is a compound having conjugated double bonds, it is a Diels-Alder reaction, so the reaction proceeds only by heating in the absence of a catalyst and the adduct. Is obtained.

However, when a terpene compound is a nonconjugated system, it is made to react normally in presence of an acidic catalyst. The acid catalyst at that time includes sulfuric acid, hydrochloric acid, phosphoric acid, polyphosphoric acid, hydroxyl, acetic acid, heteropoly acid, acidic clay, activated clay, acidic cation exchange resin, and the like, but is not limited thereto.

Reaction temperature is 0-250 degreeC normally, and it is preferable that it is 50-200 degreeC. If it is less than 0 degreeC, reaction progresses slowly, and when it exceeds 250 degreeC, since side reactions, such as superposition | polymerization, become remarkable, it is not preferable.

Natural preservative and insect repellent components used in the present invention include, for example, hinokithiol, tannin, terpineol, obaknon, limonene, chidanine, terpineol, azadiradione, pregon, taxoxyline, Quercetin, naringenin, myricetin, menthol, citronellal, camphor, p-mentene, 3,8-diol, benzoic acid, benzaldehyde, cardinol, peryl aldehyde, cineol, α-pinene, β-pinene, longipolene Etc. are preferable, but they are not limited to these. In addition, the antiseptic and insect repellent composition of this invention contains at least 1 component of these natural antiseptic and insect repellent components. Among these natural antiseptic and insect repellent components, hinokithiol is particularly preferably used.

The terpene compound used as a raw material of the antiseptic and insect repellent composition of the present invention has a slight insect repellent effect, and its sustainability is greatly extended by forming an adduct with maleic anhydride.

However, the insect repellent effect of the maleic anhydride adduct of the terpene compound is slightly insufficient in practical use, and by mixing other natural components therein, an effect that exceeds the effect possessed by both is exerted.

The blending ratio of the maleic anhydride adduct of the terpene compound used in the antiseptic and insect repellent composition of the present invention and the natural antiseptic and insect repellent component is usually a natural antiseptic and insect repellent component with respect to 1 part by weight of the maleic anhydride adduct of the terpene compound. Is 0.1-2.0 weight part, and it is preferable when it is 0.2-0.5 weight part. If the natural antiseptic and insect repellent components are less than 0.1 part by weight, the effect of the effect is shortened, and it is not preferable.

In addition, to the antiseptic and insect repellent composition of the present invention, a diluent solvent derived from nature can be added to enhance the antiseptic and insect repellent effect.

As the diluting solvent, gum turpentine (refined essential oil of rosin), longipolene, pine oil, limonene, cineol, terpineol are preferably used, but not limited thereto. Among these diluent solvents, rubber terepin and long gifolene are particularly preferably used.

The blending ratio of these diluents is preferably from 2.0 to 98.9 parts by weight, and from 3.0 to 98.8 parts by weight based on 1 part by weight of the maleic anhydride adduct of the terpene compound. If the diluent is less than 2.0 parts by weight, the dilution of the natural antiseptic and insect repellent compositions is difficult and undesirable. If the diluent is more than 98.9 parts by weight, the effective amount of the antiseptic and insect repellent compositions cannot be diluted.

A water-soluble drug can also be obtained by mix | blending surfactant with the antiseptic and insect repellent composition of this invention.

In this case, the ratio of the surfactant to be blended is usually 5.0 to 20.0 parts by weight with respect to 1 part by weight of maleic anhydride adduct of the terpene compound, and preferably, 10.0 to 15.0 parts by weight can be achieved by adding an agent.

As a usage form of the antiseptic and insect repellent composition of the present invention, for example, the antiseptic and insect repellent composition may be mixed with a porous particulate matter to obtain a particulate drug having antiseptic and insect repellent properties.

Examples of the porous particulate matter include natural or artificial zeolites, sepiolites, fine particles of volcanic pumice stone, activated carbon, silicon earth, silica gel, and the like. no.

It is preferable that 5.0-20.0 weight part of antiseptic and insect repellent compositions are mixed with 8.0 to 15.0 weight part with respect to the said particulate-form chemical | medical agent normally with respect to 100 weight part of porous particulate matter.

The antiseptic and insect repellent compositions of the present invention have a remarkable effect in preventing the damage caused by the occurrence of wood fungi and the invasion of wood pests, or to control the damage already occurred.

Wood fungi include, for example, antrodia sinuosa, ginkgo leaf velvet mushroom (paxillus panuoides), liver mushrooms (pycnoporus coccineus), cloud mushrooms (trametes versicolor), fomitopsis palustris, etc. Can be mentioned. Wood pests include termites, lyctidae, wood beetle, comb-beard beetle (anobiidae), and beaver (siricidae).

In addition, the antiseptic and insect repellent compositions of the present invention are excellent antiseptic and insect repellent compositions having excellent safety for humans and animals and less environmental impact by applying natural materials.

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described concretely, this invention is not limited to this embodiment at all.

EXAMPLE

Examples 1-6

1.0 parts by weight of maleic anhydride adduct of α-terpinene (manufactured by Yashara Chemical Co., Ltd .: product name TM-60, purity 98%) with hinokithiol (manufactured by Osaka Organic Synthetic Co., Ltd., purity: 98%) 0.10, 0.25 and 0.50 weight part was mixed, and terpene essential oil was added and dissolved in the remainder. As terpene-based oils, rubber terepin and longipolene (both manufactured by Yashara Chemical Co., Ltd.) were used.

As a comparative example, the maleic anhydride adduct of (alpha) -terpinene alone is 1.0 weight part of the acetone solution, 0.25 weight part of the acetone solution of hinokithiol, rubber terepine alone, and long gifolene alone.

1 ml (ml) of each drop was dropped on a filter paper of 9 cm in diameter, dried for 3 days, then placed inside a 9 cm diameter chalet, and 1 ml (ml) of purified water was dropped dropwise, and then house termites were dropped. Fifty ants were put in and left in a constant temperature and humidity chamber at a temperature of 28 ° C. and a relative humidity of 85% for three days to observe the health status of house termites.

The results were as shown in the following [Table 1]. In the table, the reaction rate (%) is a value derived from the formula "((Number of dead bugs x 1 + number of anesthetic bugs x 0.7 + number of convulsion bugs x 0.3) ÷ total test bugs] x 100"), and the mortality rate ( %) Is a numerical value derived from the formula ((number of dead bugs ÷ total test bugs) x 100), and the concentration (%) is the weight blending ratio of each component when the total amount of the compound composition is 100. .

TABLE 1

Use pharmaceutical density(%) Test result (% reaction rate /% mortality) Day 1 Day 2 3rd day Example 1 Terpinene Maleic Acid + Hinokithiol 1.0 + 0.10 70/35 90/50 100/100 Example 2 Terpinenemaleic Acid + Hinokithiol 1.0 + 0.25 85/35 90/50 100/100 Example 3 Terpinenemaleic Acid + Hinokithiol 1.0 + 0.50 90/50 100/100 100/100 Example 4 Terpinenemaleic Acid + Hinokithiol 1.0 + 0.10 85/40 95/90 100/100 Example 5 Terpinenemaleic Acid + Hinokithiol 1.0 + 0.25 95/90 100/100 100/100 Example 6 Terpinenemaleic Acid + Hinokithiol 1.0 + 0.50 90/65 100/100 100/100 Comparative Example 1 Terpinene Maleic Acid 1.0 0/0 0/0 30/0 Comparative Example 2 Hinoki Thiol 0.25 25/0 30/0 55/15 Comparative Example 3 Rubber terepin 100 0/0 0/0 0/0 Comparative Example 4 Longipolin 100 0/0 0/0 30/0

Examples 1-3: Using rubber terepine as a diluting solvent

Examples 4-6: Longipolene is used as a diluting solvent

Terpinene Maleic acid: Yashara Chemical Co., Ltd. Product: TM-60, Purity 98%

Hinoki thiol: product made by Osaka Organic Synthetic Co., Ltd., purity 98%

Comparing Examples 1 to 6 and Comparative Examples 1 to 4, it can be easily confirmed that the addition of the hinokithiol to the maleic anhydride adduct of α-terpinene results in a synergistic effect far exceeding the respective effects alone. .

Examples 7-8

0.25 parts by weight of hinokithiol (product of Osaka Organic Synthetics, 98%) by 1.0 part by weight of maleic anhydride adduct of α-terpinene (product of Yashara Chemical Co., Ltd .: product name TM-60, purity 98%), Prepare 15.0 parts by weight of a nonionic anionic surfactant and balance the remaining rubber terepine or long gifolene (all of which are manufactured by Yashara Chemical Co., Ltd.), and Japan Wood Conservation Association Standard No. 13 (for soil treatment). The test was carried out according to the ant control efficacy test method and the indoor efficacy test method. The results were as shown in Table 2 below.

TABLE 2

Use pharmaceutical Solvent used Termite penetration length (mm) Remarks Example 7 Terpinenemaleic Acid + Hinokithiol Rubber terepin 5 Conformity Example 8 Terpinenemaleic Acid + Hinokithiol Longipolin 3 Conformity Comparative Example 5 Terpinene 1.0% Acetone 50 Non-compliance Comparative Example 6 Terpinene 2.0% Acetone 50 Non-compliance Comparative Example 7 Hinokithiol 0.25% Acetone 50 Non-compliance Comparative Example 8 Hinokithiol 0.50% Acetone 50 Non-compliance Comparative Example 9 - Rubber terepin 50 Non-compliance Comparative Example 10 - Longipolin 50 Non-compliance Comparative Example 11 - water 50 Non-compliance

Terpinene Maleic acid: Yashara Chemical Co., Ltd. Product: TM-60, Purity 98%

Hinoki thiol: product made by Osaka Organic Synthetic Co., Ltd., purity 98%

Through the above results, it was confirmed that the antiseptic and insect repellent composition of the present invention has excellent insect repellent effect against white ants.

Examples 9-10

0.25 parts by weight of hinokithiol (product of Osaka Organic Synthetic Co., Ltd., purity: 98%) to 1.0 part by weight of maleic anhydride adduct of α-terpinene (product of Yashara Chemical Co., Ltd .: product name TM-60, purity 98%) Antiseptic effect according to Japanese Wood Conservation Association Standard No. 1 (Indoor antiseptic effect test method of surface preservative wood preservative) which was dissolved in rubber terepene or long gifolene (all of Yasuhara Chemical Co., Ltd.) The test was conducted. The results were as shown in Table 3 below.

TABLE 3

Use pharmaceutical density(%) % Mass loss (With or without weather operation) Pomitopsis Fallustris Cloud Mushroom Example 9 Terpinene Maleic Acid + Hinokithiol 1.0 + 0.25 2.3 / 1.8 1.6 / 1.4 Example 10 Terpinenemaleic Acid + Hinokithiol 1.0 + 0.25 2.2 / 1.5 1.4 / 1.3 Comparative Example 12 Terpinene Maleic Acid 1.0 25.4 / 23.6 18.5 / 17.4 Comparative Example 13 Terpinene Maleic Acid 2.0 24.6 / 22.8 16.3 / 15.1 Comparative Example 14 Hinoki Thiol 0.25 14.3 / 6.8 13.7 / 4.3 Comparative Example 15 Hinoki Thiol 0.50 12.8 / 2.9 11.5 / 2.7 Comparative Example 16 No treatment - 38.6 29.5

Example 9 Rubber Terepin as Diluent

Example 10 Longipolene as Diluent

Terpinene Maleic acid: Yashara Chemical Co., Ltd. Product: TM-60, Purity 98%

Hinoki thiol: product made by Osaka Organic Synthetic Co., Ltd., purity 98%

Through the above results, it was confirmed that the antiseptic and insect repellent composition of the present invention has excellent antibacterial effect and weather resistance against wood fungi.

Examples 11-12

0.25 parts by weight of hinokithiol (product of Osaka Organic Synthetic Co., Ltd., purity: 98%) to 1.0 part by weight of maleic anhydride adduct of α-terpinene (product of Yashara Chemical Co., Ltd .: product name TM-60, purity 98%) Ant in accordance with the Japanese Wood Conservation Association Standard No. 11 (Indoor Ant Control Effect Test Method of Surface Preservative Wood Preservative). A control efficacy test was conducted. The results were as shown in Table 4 below.

TABLE 4

Use pharmaceutical density % Mass loss Weatherproof operation Weatherproof operation Example 11 Terpinenemaleic Acid + Hinokithiol 1.0 + 0.25 2.8 2.3 Example 12 Terpinenemaleic Acid + Hinokithiol 1.0 + 0.25 2.6 2.2 Comparative Example 17 Terpinene Maleic Acid 1.0 23.4 19.5 Comparative Example 18 Terpinene Maleic Acid 2.0 16.4 12.7 Comparative Example 19 Hinoki Thiol 0.25 15.3 2.9 Comparative Example 20 Hinoki Thiol 0.50 10.3 2.3 Comparative Example 21 No treatment - 27.4

Example 11 Use of Rubber Terepin as Diluent

Example 12 Longipolene as Diluent

Terpinene Maleic acid: Yashara Chemical Co., Ltd. Product: TM-60, Purity 98%

Hinoki thiol: product made by Osaka Organic Synthetic Co., Ltd., purity 98%

Through the above results, it was confirmed that the antiseptic and insect repellent composition of the present invention has excellent antiseptic effect and weather resistance.

Examples 13-14

0.25 parts by weight of hinokithiol (manufactured by Osaka Organic Synthetics, 98%) by 1.0 part of maleic anhydride adduct of α-terpinene (product of Yashara Chemical Co., Ltd .: product name TM-60, purity 98%) Ant in accordance with the Japanese Wood Conservation Association Standard No. 11 (Outdoor Ant Control Effect Test Method of Surface Preservative Wood Preservative). A control efficacy test was conducted. The results are shown in [Table 5].

TABLE 5

Use pharmaceutical density(%) Test result Example 13 Terpinenemaleic Acid + Hinokithiol 1.0 + 0.25 2 years no charge Example 14 Terpinenemaleic Acid + Hinokithiol 1.0 + 0.25 2 years no charge Comparative Example 22 Terpinene Maleic Acid 1.0 There was discomfort within six months Comparative Example 23 Terpinene Maleic Acid 2.0 There was discomfort within six months Comparative Example 24 Hinoki Thiol 0.25 There was a discomfort within one year Comparative Example 25 Hinoki Thiol 0.50 There was a discomfort within two years Comparative Example 26 No treatment - There was disorganization within three months

Example 13: Use of rubber terepine as diluent

Example 14 Longipolene as Diluent

Terpinene Maleic acid: Yashara Chemical Co., Ltd. Product: TM-60, Purity 98%

Hinoki thiol: product made by Osaka Organic Synthetic Co., Ltd., purity 98%

Through the above results, it was confirmed that the antiseptic and insect repellent composition of the present invention has excellent ant control effect even outdoors.

Examples 15-18

0.25 parts by weight of hinokithiol (manufactured by Osaka Organic Synthetics, 98%) by 1.0 part by weight of maleic anhydride adduct of α-terpinene (product of Yashara Chemical Co., Ltd .: product name TM-60, purity 98%), 15.0 parts by weight of the nonionic anionic surfactant and the remainder of the mixture of rubber terepin or longifolene (all manufactured by Yashara Chemical Co., Ltd.), and 10.0 parts by weight of maleic anhydride of α-terpinene. The weight parts were mixed, and 87.5 parts by weight of rubber terepine or long gifolene was added thereto, and the mixture was dissolved in zeolite (3 to 5 mm) so as to have a weight ratio of 1: 9, respectively. The ant control efficacy test was carried out in accordance with No. 13 (Method for testing ant control effectiveness and soil effect test method for soil ant control agent). The results are shown in Table 6 below.

TABLE 6

Use pharmaceutical density(%) Test result Example 15 Terpinenemaleic Acid + Hinokithiol 1.0 + 0.25 2 years of no complaints Example 16 Terpinenemaleic Acid + Hinokithiol 1.0 + 0.25 2 years of no complaints Example 17 Terpinenemaleic Acid + Hinokithiol 1.0 + 0.25 There was no discomfort for two years Example 18 Terpinenemaleic Acid + Hinokithiol 1.0 + 0.25 There was no discomfort for two years Comparative Example 27 Terpinene Maleic Acid 1.0 There was discomfort within six months Comparative Example 28 Terpinene Maleic Acid 2.0 There was discomfort within six months Comparative Example 29 Hinoki Thiol 0.25 There was a discomfort within one year Comparative Example 30 Hinoki Thiol 0.50 There was a discomfort within one year Comparative Example 31 No treatment - There was disorganization within three months

Examples 15 and 17: Rubber Terepin as Diluent

Example 16, 18: Longipolene was used as diluent

Examples 15 and 16: Surfactant Formulated

Example 17, 18: Mixing in Zeolite

Terpinene maleic acid: Yashara Chemical Co., Ltd. product. Formerly TM-60,

Hinoki thiol: product made by Osaka Organic Synthesis Co., Ltd. Purity 98%

Through the above results, it was confirmed that the antiseptic and insect repellent composition of the present invention has excellent ant control effect indoors.

The antiseptic and insect repellent compositions of the present invention have a remarkable effect in the prevention of damage caused by the generation of wood fungi, invasion of wood pests, or the prevention of damage already occurring. For example, it has a wide range of effects on wood pests such as Antrodia cynuosa and ginkgo velvet velvet mushrooms, white ants such as house termites, and woody wood pests.

In addition, the antiseptic and insect repellent composition of the present invention is an antiseptic and insect repellent composition having excellent safety for humans and animals and less environmental impact by applying natural materials.

Moreover, the antiseptic and insect repellent compositions of the present invention are inexpensive and insect repellent compositions that are inexpensive and easy to handle when used.

Claims (4)

The antiseptic and insect repellent composition formed by mix | blending natural antiseptic and insect repellent components with the maleic anhydride adduct of a terpene compound. The antiseptic and insect repellent composition according to claim 1, wherein the maleic anhydride adduct of the terpene compound is a maleic anhydride adduct of α-terpinene. The natural antiseptic and insect repellent component according to claim 1 or 2, wherein the natural preservatives and insect repellents are hinokithiol, tannin, terpineol, obaknon, limonene, chidanine, terpineol, aza diradion, pregon and taxoxyline. , Quercetin, naringenin, myrcetin, menthol, citronellal, camphor, p-mentene, 3,8 diol, benzoic acid, benzaldehyde, cardinol, peryl aldehyde, cineol, α-pinene, β-pinene, longgiolene Antiseptic and insect repellent composition, characterized in that at least one component. The antiseptic and insect repellent composition according to any one of claims 1 to 3, wherein at least one component of rubber terepin, longopolene, fine oil, limonene, cineol and terpineol is used as the diluting solvent.