DE2929920A1 - FRAGRANT ANTI-INSECT AGENT, IN PARTICULAR INSECT POWDER - Google Patents

Description

T 51 922

Applicant : IDEMITSU KOSAN COMPANY LIMITED No. 1-1, 3-chome, Marunouchi, Chiyoda-ku, Tokyo, Japan

Fragrant anti-insect preparations, in particular insect powder

The invention relates to a new anti-insect agent, in particular a new insect powder; it specifically relates to an anti-insect agent, particularly insect powder, for clothes, as well a method for repelling or repelling insects and for killing insects, in particular for protection can be applied to clothes.

Anti-insect repellants, especially insect powder, for clothes, such as naphthalene, camphor, and p-dichlorobenzene, have been around for a long time known. p-dichlorobenzene, which is currently the largest part of the anti- Insect repellant market is an organic chlorine compound with a relatively high toxicity and a peculiar disgusting odor. Aldrin and Dieldrin that too organic chlorine compounds are known as anti-insect repellants, which are used in fiber treatment, however, the application of these anti-insect agents is currently in Japan banned because of its toxicity. Naphthalene and camphor are similar to p-dichlorobenzene in terms of insect repellency or inferior to insect repellency. This results in,

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that an anti-insect repellent, especially insect powder, for Clothes that are non-toxic to human body, have no peculiar offensive smell, and are excellent Has insect repellency or repellency, has not yet been available.

In view of the above-described disadvantages of the known Anti-insect repellants, especially insect powder, for clothes, intensive and extensive research has been carried out, to find a compound that occurs in nature, i. e. represents a naturally occurring product that, because it is non-toxic, safe, fragrant and has a great insect repellant effect.

It has now been found according to the invention that 1-carvone these Conditions suffice. The aim of the present invention is in particular to provide a fragrant anti-insect agent, in particular Insect powder to indicate which contains 1-carvone as an effective component.

1-Carvone is a compound of the formula given below, which is a main component of spearmint oil and is widely used as a spice for food and dentifrices.

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The 1-carvone used in the invention includes pure and the relatively pure compound as well as raw (roughly) cleaned Substances. 1-Carvone can also be used when included in a composition containing this compound contains as the main component, such as a natural purified oil, a mixed spice, a mixed perfume and a mixture of 1-carvone and linalool and / or anethole.

1-Carvone can be used on its own, but it is usually used in the form of a mixture with other substances For example, 1-carvone, 'since it is in the form of an oily Substance present can be used in the following form: A material such as "silica gel, cotton and filter-. paper, absorbs an appropriate amount of 1-carvone and then contains and wraps it in cloth, Japanese paper or some other material « According to another embodiment of the invention a sublimable substance such as adamantane, endotrimethylene norbomane, Camphor, cyclododecane, and mixtures thereof, as carriers used with an insecticidal amount of 1-carvone. It is also possible, if desired and / or if necessary fragrant anti-insect products, especially insect powder, add some antioxidant (e.g. quinones, aromatic amines, aldehyde amines, phenols and the like). To make a Preparation containing a sublimable substance carrier and Contains 1-carvone, the following methods can be used: The sublimable substance is formed into an appropriate form and then it is made to absorb 1-carvone,

amounts

or alternatively, the two substances are mixed together appropriately mixed and the resulting mixture is then

melted by heating, then shaped into the appropriate shape and allowed to solidify.

As a sublimable substance, camphor can be used alone, however, it is conveniently combined with another sublimable substance such as adamantane so that it is converted into 1-carvone incorporated and firmly retained in it.

In the production of the fragrant anti-insect emitting ice according to the invention, in particular insect powder, the amount of 1-carvone, which is to be used and the proportion in which it is to be mixed with other components are dependent on the intended use and the application sites (size of the effective area and tightness or tightness of the room).

According to the invention, an effective protection against insects which are harmful to clothes, such as the common Japanese hide beetle (Attagenus japonicus), cabinet beetles (Anthrenus _v ^T erbasci), the casemaking clothes moth (Tinea pellionella), webbing- '. Clothes moth (Tineola bisselliella) and wallpaper moth (carpet beetle larva) (Trichophage t'apetzella) ₇ can be achieved. In addition, the anti-insect agent of the present invention is characterized in that 1-carvone is derived from a natural substance, is safe because it is non-toxic, and has an aromatic odor. It can also be used as an insecticide because 1-carvone kills insects that are harmful to clothes. If 1-carvone is present as an effective component on a sublimable carrier substance, the insect repellent or repellent effect can also be maintained with a constant strength over a long period of time.

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away, i.e. the rate of volatilization the effective component can be kept constant. In addition, when the effective component is on a sublimable one Carrier substance is located, the end of the insect repellent or repulsion effect can be assessed visually.

Figures 1 through 3 of the accompanying drawings are diagrams illustrating the ability of sublimable carriers to retain 1-carvone.

The invention is illustrated in more detail by the following examples, but without being limited to it.

example 1

0.3 g of cotton were impregnated with a mixture of 1 g of 1-carvone and 5 ml of tetrahydrofuran, and the cotton so impregnated in this way was allowed to stand at room temperature for 5 hours and thereby dried to remove tetrahydrofuran. Under use of the insect repellent produced in this way (Insect powder) was subjected to an insect repellancy test using the procedure described below carried out:

In the middle of a polyvinyl chloride jar (30 cm 21 cm χ 4.5 cm) was a plate made of aluminum foil with a diameter of 9 cm and a thickness of 0.3 cm arranged to which 1 g of muslin and the above-described anti-insect repellent (insect powder) were applied. Thereafter 20 larvae of the cabinet beetle (Anthrenus verbasci)

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introduced into the vessel. Then the vessel was covered with a cover vessel made of polyvinyl chloride (33 cm × 27 cm × 6 cm), which was placed in a constant temperature, constant humidity device. The number of insects which entered the above plate to eat the muslin was counted every day for a period of 5 days. The cover vessel had a hole 0.8 cm in diameter through which the insects could breathe sufficiently. The number of insects that entered the bait plate and the number of those that died during the 5 days, are given in Table I below.

Example 2

An anti-insect repellent (insect powder) was prepared under the same conditions as in Example 1, this time however, a spearmint oil was used in place of 1-carvone, and the test was carried out in the same manner as in Example 1 carried out ,, The results are given in Table I.

Reference example 1

The test was carried out under the same conditions as in Example 1, but this time no anti-insect agent (Insect powder) was used. The results are given in Table I.

Comparative example 1

Under the same conditions as in Example 1, an

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ti insect repellant (insect powder) produced, this time being but was used as an effective component of the same camphor, and the test was carried out in the same manner as in Example 1. The results are given in Table I.

Example 3

4 g of an anti-insect repellent (insect powder) was prepared by mixing 2 parts by weight of 1-carvone with 100 parts by weight a mixture of endotrimethylene norbornane and adamantane (mixing ratio of the former to the latter = 8: 2, based on weight). Using this anti-insect repellent (Insect powder), the insect repellent test was carried out in the same manner as in Example 1. The results are given in Table I.

Example 4

Under the same conditions as in Example 3, an anti-insect repellent (Insect powder), but this time 4 parts by weight of spearmint oil instead of 2 parts by weight 1-carvone were used, and the insect repellent test was carried out in the same manner as in Example 1 carried out. The results are given in Table I.

Reference example 2

The test was carried out in the same way as in Example 3, this time a mixture of endotrimethylene norbornane and adamantane (with the same mixing ratio as in

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Example 3, weight = 4 g) used without the addition of 1-carvone which is the effective component of the anti-insect repellent acted. The results are given in Table I.

Comparative example 2

Under the same conditions as in Example 3, a Anti-insect repellants (insect powder) produced, this time being however, camphor as an effective component instead of 1-carvone was used and the test was carried out in the same manner as in Example 3. The results are in the table I stated.

Table I. .Day 3rd day 4th day 5 .Day number of 20th 20th 20th 20th dead insect
ten ² ) example Number of insects which
entered the bait plate ^) 11 10 9 10 0 Reference example l 1st day 2 0 2 2 2 1 See example 1 20th 3 3 3 3 17th example 1 7th 19th 19th 19th 19th 15th Example 2 0 17th 16 17th 18th 1 Reference example 2 0 0 3 4th 4th 1 See example 2 18th 4th 5 5 5 14th Example 3 10 13th Example 4 0 0

Average value of the measurements taken 5 χ a day The insects did not starve because they were more than 7 days

can survive even "when" they are not given bait.

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Example 5

Cotton was impregnated with a solution obtained by dissolving 0.5 ml of linalool and 0.5 ml of 1-carvone in 5 ml of tetrahydrofuran, and the tetrahydrofuran was then volatilized at room temperature. Using the anti-insect agent thus prepared, an insect repellent test was carried out using the following method:

A vessel made of polyvinyl chloride (20 cm × 50 cm × 5 cm) was divided into a left and a right compartment (20 cm × 25 cm × 5 cm) by inserting a. Partition plate in the center of the jar, and 1 g of muslin (wool) and the above anti-insect repellent were placed in the left compartment. A 1.5 cm diameter hole was also drilled in the partition plate to provide a passage. Thereafter, 10 larvae of 60-day-old Japanese common hide beetles (Attagenus japonicus) were placed on both sides of the passage. Subsequently, the left compartment was covered with a plastic lid and the right compartment was covered with a wire mesh and the insect repellent test was started. The outer air flow was directed from right to left. During the test, the vessel was kept in a constant temperature and constant humidity device at a temperature of 30 ± 3 ^° C. and a humidity of 65 ± 3%. The amount of test clothing (muslin) eaten by insects during the test period of 7 days was determined. The results are given in Table II below.

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Example 6

An anti-insect repellent was made under the same conditions prepared as in Example 5, but this time using anethole instead of linalool, and the test was carried out in carried out in the same manner as in Example 5. The results are given in Table II.

Example 7

An anti-insect repellent was made under the same conditions prepared as in Example 5, but this time using a spearmint oil instead of 1-carvone, and the test was carried out in the same manner as in Example 5. The results are given in Table II.

Example 8

The test was carried out in the same manner as in Example 5, this time 20 (30 day old) larvae of casemaking clothes moths (Tinea pellionella) instead of the common Japanese ones Hide-beetles (Attagenus japonicus) were used. The results are given in Table II.

Example 9

An anti-insect repellent was used under the same conditions as in Example 5 but this time anethole instead of linalool and 20 (30 days old) larvae of casemaking clothes moths (Tinea pellionella) instead of habitual

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Japanese hide beetle (Attagenus japonicus) was used, and the test was carried out in the same manner as in Example 5 carried out. The results are given in Table II.

Example 10

An anti-insect repellent was prepared under the same conditions as in Example 5, this time a spearmint oil instead of 1-carvone and 20 (30 day old) larvae of casemaking clothes moth (Tinea pellionella) instead of ordinary ones Japanese hide beetles (Attagenus japonicus) were used, and the test was carried out on "the same way as in Example 5 carried out. The results are given in Table II.

Reference example 3

An anti-insect repellent was obtained under the same conditions as in Example 5 except that 1.0 ml of linalool was used this time were used as the effective component thereof, and the test was carried out in the same manner as in Example 5. The results are given in Table II.

Reference example 4

An anti-insect repellant was prepared under the same conditions as in Example 5, this time using 1.0 ml of 1-carvone as an effective component of the same and 20 (30 day old) larvae of case-making clothes moth (Tinea pellionella) instead of the

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common Japanese hide beetle (Attagenus japonicus) used and the test was carried out in the same manner as in Example 5. The results are in the table II stated.

Comparative example 3

The test was carried out under the same conditions as in Example 5, but this time no anti-insect agent was used. The results are given in Table II.

Comparative example 4

The test was carried out under the same conditions as in Example 5, except that this time no anti-insect agent and 20 Casemaking clothes moth larvae (30 days old) (Tinea pellionella) instead of the common Japanese hide beetles (Attagenus japonicus). The results are in given in Table II.

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4h table II

5 Effective component 0.5
0.5 0.5
0.5 1.0 ml
ml insect eaten
Quantity (ag) example 6th
7th 1-carvone
Linalool 1-carvone 0.5
Anethole 0.5
Spearmint
oil 0.5
Linalool 0.5 0.5
0.5 1.0 ml
ml
ml
ml O example
example 8th 1-carvone
Linalool Spearmint
oil 0.5
Linalool 0.5 ml
ml More common yes
panicked hide-
Beetle (Attagenus
japonicus) 0
0 example 9 1-carvone
Anethole Linalool ml
ml 1 example 10 1-carvone ml
ml Casemaking KIei
dermoth (tinea
pellionella) 3 example 3 ml 2 Reference
example 4th ml More common yes
panicked hide-
Beetle 2 Reference
example Comparison Casemaking clothes
dermotte 6th example 3
Comparison
example 4 More common yes 56 panicked hide-
Beetle
Casemaking KIei
dermotte 43

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Example 11

100 parts by weight of camphor with a predetermined amount of 1-carvone was added, were heated to a temperature of 180 C and melted. The melted mixture was in a test tube by cooling the same from the bottom immediately solidified. Then became the one containing the solidified mixture Test tube left with its mouth facing down for a day. After a day, the presence or absence became the liquid flowing down from the solidified mixture is checked. The results are in the next given below in Table III. This experiment enables the ability of the liquid to produce 1-carvone to be determined withhold when camphor is used as a carrier for 1-carvone.

Reference example 5

The procedure carried out in Example 11 was repeated, this time using 100 parts by weight of p-dichlorobenzene instead of Camphor was used and heated until liquid at 90C. The results are given in Table III.

Reference example 6

The procedure described in Reference Example 5 was repeated, this time using naphthalene instead of p-dichlorobenzene was used. The results are given in Table III. As can be seen from the table, p-dichlorobenzene is to camphor in terms of the ability to retain 1-carvone, far inferior.

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^{A (o} 292992Q

Table III

Sublimable substance 1-carvone (parts by weight) 100 parts by weight 5 10 15 20

Fighter O O O X p-dichlorobenzene O X X X naphthalene O O O X

o: The substance has a retention capacity (no liquid flows downwards)

x: The substance has no retention capacity (liquid flows downwards).

Example 12

100 parts by weight of camphor to which 4 parts by weight of 1-carvone are added were heated to a temperature of 180 C and melted. The melted mixture was in a metal mold (42 mm in diameter and 16 mm in height) was poured and solidified. The one with it obtained molded body was sublimed in a stream of air at room temperature and the change in weight of the molded body and the change in the concentration of 1-carvone in the molded article were determined. The results are in the figure 1 of the accompanying drawings. This experiment makes it possible to determine the ability of camphor to ger of 1-carvone to retain the 1-carvone.

The indicated concentration values were obtained by conversion the concentration of 1-carvone in the shaped body

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sublimation, assuming that the concentration at the time of shaping, i.e. on the first day of sublimation, 100 was.

Example 13

A mixture of 70 parts by weight of camphor, 20 parts by weight Adamantane and 10 parts by weight of endotrimethylene norbomane were heated to 160 ° C. and melted and added to the mixture 4 parts by weight of 1-carvone were added. This molten mixture was prepared in exactly the same manner as in Example 12 treated. The results are shown in Figure 2 of the accompanying drawings.

Reference example 7

The same procedure as in Example 12 was followed except that this time the camphor was replaced with naphthalene and this was heated to 90 C and melted. The results are shown in Figure 3 of the accompanying drawings.

As can be seen from the results in Figs. 1 to 3, naphthalene is to camphor in terms of the ability to 1-carvone hold back, far inferior, i.e. naphthalene sublimes very slowly and 1-carvone evaporates quickly. Therefore volatilized most of the 1-carvon from the mixture thereof until the weight loss of the mixture reaches 20%.

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L e r s e i t e

Claims (4)

T 51 922 applicant; IDEMITSU KOSAN COMPANY LIMITED No. 1-1, 3-chome, Marunouchi, Chiyoda-ku, Tokyo, Japan Patent pending 1. Fragrant anti-insect repellant, especially insect powder, characterized in that it is 1-carvone contains. 2 «anti-insect agent according to claim 1, characterized in that that the 1-carvone is on a sublimable carrier substance is located. 3, anti-insect agent according to claim 2, characterized in, that the sublimable substance is adamantane, endotrimethylene norboraan, Camphor, cyclododecane or a mixture thereof. 4. Anti-insect agent according to one of claims 1 to 3, characterized in that it is a clothing anti-insect agent, especially a clothes insect powder. Ö09S8S / 092Ö