JP5980131B2 - Insecticide for clothing - Google Patents

Description

The present invention relates to an insect repellent for clothing.

Conventionally, various insect repellents have been put to practical use mainly for chiffons, drawers, closets, and clothing storage boxes in order to protect textile products from garment pests such as moths, cutworms, and stains. As its active ingredients, sublimable insect repellents such as p-dichlorobenzene and naphthalene were used in the past, but safety problems and strong irritating odors were pointed out, and room temperature volatile pyrethroid insecticides such as empentrin and profluthrin Has become the mainstream. The latter pyrethroid insecticidal component is an effective component that is odorless and exhibits a high amount of insecticidal effect against clothing pests, and is excellent in safety and highly useful.
In recent years, consumer needs have diversified, and there is a tendency to actively perfume treatment spaces and clothing using insect repellents that have some fragrance rather than odorlessness. .

Against this background, some proposals have been made to use natural essential oils and perfume ingredients having insect repellent effects and aromatic properties as insect repellent ingredients.
For example, JP-A-50-24436 discloses linalool, anethole, menthol, cinnamic aldehyde, thymol, eugenol, and JP-B-57-5761 discloses anethole, eugenol, anisaldehyde dimethyl acetal, p-isopropylanisole, isocabebitol, In JP-A-7-112907, 1,4-diethoxybenzene is linalool, geraniol, borneol, nerolidol, nerol, α-terpineol, perilaldehyde, citral, camphor, α-ionone, 1,8-cineol, linalool oxide. Alternatively, it is described that citral diethyl acetal is used as an active ingredient of an insect repellent. In addition, in Japanese Patent No. 4311773, attention is paid to a hatching inhibitor of clothing pests, and it is considered that if the migration from eggs to larvae is suppressed, food damage caused by clothing pests can be prevented, and linalol and geranio are used as egg hatching inhibitors. Numerous terpene compounds have been proposed, such as thiol, citronellal, allyl heptanoate and neryl acetate.
However, these are not necessarily suitable as a fragrance as an insect repellent for clothing, such as too strong incense, and those that satisfy the insect repellent effect have not yet been recognized.

Japanese Patent Laid-Open No. 50-24436 Japanese Patent Publication No.57-5761 JP-A-7-112907 Japanese Patent No. 4311773

An object of this invention is to provide the insect repellent for clothes which contains the fragrance | flavor component which can give the fragrance suitable for clothing which the insect repellent activity with respect to clothes pest was not known conventionally as an active ingredient.

The present invention has been found that the following constitution has an excellent effect for achieving the above-mentioned object.
(1) As an insect repellent active ingredient,
Calixol, hedion, iso-E super, 3,7-dimethyl-1-octanol, 4-isopropylcyclohexanol, 2-cyclohexylidene-2-phenylacetonitrile, estragole, 3,7-dimethyl-2,6-nonadiene An insect repellent for clothing comprising one or more fragrance components selected from nitrile and 3-methyl-5-phenyl-1-pentanol .
(2) The insect repellent for clothing according to claim 1, wherein the insect repellent activity is activity against squid and carp.
(3) As an insect repellent active ingredient,
The insect repellent for clothing according to (1) or (2), comprising one or more perfume ingredients selected from iso-E super, estragole and 3,7-dimethyl-1-octanol.
(4) An insect repellent for clothing imparted with a fungicidal effect, characterized by containing one or more perfume ingredients according to (3).

The active ingredient of the insect repellent for clothing of the present invention is known as a fragrance component, but it is not known at all to have activity against clothing pests, has excellent fragrance as a fragrance, and also has antifungal activity. Therefore, its practicality is extremely high.

The insect repellent for clothing of the present invention is an insect repellent active ingredient,
Calixol (ethyl-2-methyl-6-pentyl-4-oxocyclohexyl-2-enecarboxylate: hereinafter referred to as Compound 1),
Headion (methyl dihydrojasmonate: hereinafter referred to as Compound 2),
Iso-E super (2-acetyl-2,3,8,8-tetramethyloctaline: hereinafter referred to as compound 3),
3,7-dimethyl-1-octanol (hereinafter referred to as compound 4),
4-isopropylcyclohexanol (apo patchone: hereinafter referred to as compound 5),
2-cyclohexylidene-2-phenylacetonitrile (referred to as compound 6)
Estragole (hereinafter referred to as Compound 7),
3,7-dimethyl-2,6-nonadienenitrile (lemonile: hereinafter referred to as compound 8) and phenylhexanol (3-methyl-5-phenyl-1-pentanol: hereinafter referred to as compound 9)
1 type or 2 types or more of fragrance | flavor components chosen from are contained, It is characterized by the above-mentioned.

Reports on the action of these compounds on insects
Compounds 3, 5, 6, 8, and 9 are not found in the range examined,
Compound 1 is described as a repellent component against bed bugs in US Patent Application Publication No. 2012/0046359.
Further, Compound 2 is used as a tick control component in JP-A No. 2002-356404, as a mosquito repellent component in JP-A No. 05-208902, and as a flushing-out component of cockroaches in JP-A No. 2002-326903. Is described.
Compound 4 is described as an active ingredient for attracting mites in JP-A-10-117657. Further, Compound 7 also has a report as a flushing-out component of cockroaches in JP-A No. 2002-326903. However, the insecticidal activity of these compounds against clothing pests, particularly moths and moths, has not been known to date.
As a result of screening various fragrance ingredients for use in insect repellents for clothing, the present inventors have found that the above compounds can be used as active ingredients for insect repellents for clothes because of the insect repellent activity against clothing pests. It is.

In addition, the insect repellent effect referred to in the present invention includes not only the insecticidal effect of clothing pests against larvae and adults, but also the comprehensive effect including the repellent effect and the effect of preventing invasion and eating damage to clothing, etc. .
In addition, these compounds have optical isomers and geometric isomers based on asymmetric carbon, and these and single mixtures thereof are also included in the present invention.

In addition to the above insect repellent active ingredient, the insect repellent for clothing of the present invention is blended with a room temperature volatile pyrethroid insecticide and another insect repellent active perfume ingredient to enhance the insect repellent effect and to be used for aroma scent. You can also.
Examples of the room temperature volatile pyrethroid insecticide include empentrin, transfluthrin, metfurthrin, profluthrin and the like.
Further, as other perfume ingredients having insect repellent activity, terpineol, citronellal, citral, terpineol, citronellol, geraniol, nerol, linalool, dihydrolinalool, tetrahydrolinalool, dihydromyrsenol, menthol, borneol, isoborneol, etc. Examples include, but are not limited to, terpene aldehydes such as dimethyloctanal, terpene ketones such as carvone, dihydrocarvone, pregon, and menthone. Also, plant essential oils containing these components, such as citronella oil, cinnamon oil, eucalyptus oil, lemon eucalyptus oil, hiba oil, lavender oil, orange oil, grapefruit oil, cedarwood oil, geranium oil, thyme white oil, peppermint oil Etc. may be blended.

Since some of the insect repellent active ingredients of the present invention also have a fungicidal effect as described later, in addition to the insect repellent effect, they are also effective for preventing the occurrence of fungus in a drape or drawer with increased humidity. If necessary, an antifungal component such as 2-phenylphenol (OPP) or 4-isopropyl-3-methylphenol (IPMP) may be appropriately blended. Further, an antibacterial component, a sterilizing component, a deodorizing component, a stabilizer such as BHT, a pH adjuster, a colorant, and the like may be appropriately blended, or, for example, green leaf alcohol or green leaf called “green fragrance” An aldehyde can be added to give a relaxing effect when the storage is opened.

In the present invention, liquid, gel, solid, sheet-like materials prepared with insect repellent active ingredients according to the needs of the usage scene are applied as various forms of insect repellents for clothing.
In preparing a liquid clothing pest repellent, in addition to water, alcohol solvents such as ethanol and isopropanol, glycol solvents such as 1,3-butylene glycol, propylene glycol and dipropylene glycol, diethylene glycol monobutyl ether, Various solvents such as glycol ether solvents such as propylene glycol monomethyl ether, aliphatic hydrocarbon solvents, and surfactants (solubilizers) are used as appropriate.
Surfactants include polyoxyethylene hydrogenated castor oil, polyoxyethylene higher alkyl ether (polyoxyethylene lauryl ether, polyoxyethylene oleyl ether), polyoxyethylene higher fatty acid ester, polyoxyethylene polyoxypropylene alkyl ether, etc. Nonionic surfactants and higher alkylamine oxide surfactants such as laurylamine oxide, stearylamine oxide, amidopropyldimethylamine oxide lauryl, and the like can be exemplified.
Further, examples of the gelling agent used for preparing the gel-like body include carrageenan, xanthan gum, gellan gum, gelatin, aluminum octylate, 12-hydroxystearic acid and the like.

In addition to the liquid or gel-like shape, when the insect repellent active ingredient of the present invention is impregnated or held in a solid carrier, it can be produced by being housed in a breathable case or bag. And what is necessary is just to install this insect repellent for a chiffon, a drawer | drawer, a closet, and a clothing storage box, and to volatilize an active ingredient from a solid support | carrier. Solid carriers include fiber carriers such as pulp, linter and rayon, beads or foam made of cellulose (regenerated cellulose), inorganic porous carriers such as silicate, silica and zeolite, sublimable carriers such as trioxane and adamantane, etc. Can be given. As the fibrous carrier, a mat or sheet having a thickness of about 1 to 3 mm is easy to use. On the other hand, in the case of cellulose beads, a deodorizing effect can be imparted by adding charcoal thereto.

Examples of the breathable case at that time include a plastic container having an opening, and examples of the breathable bag include a non-woven bag, a cotton bag, and a net case. In the case of the latter nonwoven bag, the material of the nonwoven fabric is not particularly limited, and examples thereof include polyester (PET), polyethylene (PE), polypropylene (PP), polyamide, polylactic acid, rayon, and the like. Alternatively, a laminated product such as polyester or polypropylene / rayon laminated with paper (partially adsorbing an active ingredient and its volatilization amount can be adjusted secondarily) or a blended product may be used. Absent. In addition, the shape and configuration of the non-woven bag can also be determined as appropriate. For example, both sides may be made of a breathable non-woven fabric of the above material, or one side is a breathable non-woven fabric of the above material and the other side is small. What stuck together the plastic film which may have many holes may be used.

The compounding amount of the insect repellent active ingredient relative to the total amount of the insect repellent for clothing of the present invention varies depending on the form of the preparation, but it is appropriate to set it to about 0.001 g to 1 g per one insect repellent for clothing. For example, in the case of a chiffon or a closet, it is easy to use 1 to 3 of the insect repellent for clothing, and in the case of a drawer or a clothing storage box, the number of applications may be set as appropriate. If the amount is less than the lower limit of the blending amount, the desired insect-repellent effect may be insufficient. On the other hand, if it is blended more than necessary, it may cause problems such as a sticky feeling and is not practical.

When the insect repellent for clothing thus obtained is placed in a close-sealed space such as a chiffon, drawer, closet or clothing storage box, the active ingredients are volatilized from various impregnated carriers, and the moths, moths, chicks of sims As well as clothing pests such as scallops, stag beetles, indoor dust mites such as mite mites, leopard mites, dust mites, claw mites, scallops, hornworms, cockroaches, ants, mosquitoes, moths, chironomids, flies, butterflies It has a practical insect repellent effect against various pests such as mosses and is extremely practical.

Next, the insect repellent for clothing of the present invention will be described in more detail based on specific examples.
(Insect repellent effect test 1)
A PP nonwoven fabric of 5 × 10 cm was impregnated with 1 mL of a 20-fold diluted solution of ethanol as a test fragrance component. After air-drying, the fragrance component-impregnated nonwoven fabric was folded in half, and two sides were heat sealed to form a 5 × 5 cm bag. In this bag, a 4 × 4 cm wool cloth was placed, and 15 moth larvae were also placed. The other side of the bag was similarly heat-sealed and allowed to stand in a sealed container of about 6 L. After standing for 5 days, the bag was opened, and the mortality of the larvae and the degree of damage of the woolen cloth were observed and evaluated.
Evaluation was performed according to the following criteria.

The degree of damage is
−: No damage to damage +: Damage caused by shaving of woolen wool is observed but not penetrated ++: Damage to damage is found and there is a through hole +++: Massive damage is recognized, multiple or large Overall evaluation with through-holes
A: There is no food damage and the death rate is 50% or more.
○: Even if there is food damage, it is not penetrating and the death rate is 50% or more.
Δ: Even if there is a food damage, it is not penetrating and the death rate is less than 50%.
X: There is a feeding damage or a death rate of 30% or less.

As a result of the test, the insect repellent active ingredient used in the present invention showed superior efficacy to terpineol and other perfume ingredients, which have been reported to have an insect repellent effect, with regard to the lethal effect against moth larvae and the effect of preventing food damage.

(Insect repellent effect test 2)
A 10 × 10 cm filter paper was impregnated with 1 mL of a 10-fold diluted solution of ethanol as a test fragrance component.
Twenty moth larvae were placed on a 5 × 5 cm wool cloth laid on the bottom of a cylindrical closed container (capacity: about 6 L). The filter paper impregnated with the fragrance after air drying was fixed to the back of the container lid so as to hang, and then the container was sealed with this lid and allowed to stand. After standing for 5 days, the lid was opened, and the mortality of the larvae in the container and the degree of damage of the wool were observed and evaluated.
Evaluation was performed according to the following criteria.
The degree of damage is
−: No damage to damage +: Damage caused by shaving of woolen wool is observed but not penetrated ++: Damage to damage is found and there is a through hole +++: Massive damage is recognized, multiple or large Comprehensive evaluation with a through-hole was shown by the following criteria.
A: There is no food damage and the death rate is 50% or more.
○: Even if there is food damage, it is not penetrating and the death rate is 50% or more.
Δ: Even if there is a food damage, it is not penetrating and the death rate is less than 50%.
X: There is a feeding damage or a death rate of 30% or less.

As a result of the test, the insect repellent active ingredient used in the present invention showed superior efficacy to citral and other perfume ingredients, which have been reported to have an insect repellent effect, in terms of the lethal and damaging effects on moth larvae.

(Anti-mold test)
Scrape off the fungi containing spores of Cladosporium cladosporioides, Penicillium citrinum and Alternaria alternata grown on potato dextrose agar medium, in sterile water Each mold spore suspension was dispersed.
Next, a 6 mm diameter paper disk inoculated with 10 μL of the above-described mold spore suspension was placed in the center of a petri dish having a diameter of 55 mm and a height of 12 mm that had been hardened with 5 ml of potato dextrose agar medium.
Inside the cylindrical closed container (capacity: about 6 L) with a diameter of 20 cm and a height of 20 cm, this petri dish is turned upside down without a lid so that the surface of the medium is not blocked, and the height of about 3 cm from the bottom of the closed container It was placed on the gantry so that it was in the right position. Moreover, in order to raise the humidity in a container, the beaker containing 50 mL of water was installed in the bottom face of the airtight container.
The filter paper impregnated with 1 mL of the test fragrance component in 10 × 10 cm filter paper was fixed to the back of the lid of the sealed container so as to hang, and then the container was sealed with this lid and allowed to stand. These operations were operated as aseptically as possible.
After standing for 5 days, the sealed container lid was opened, and the growth state of the mold on the petri dish medium was observed.
In the evaluation, the growth diameter of the mold colony in the untreated section when the non-medicine filter paper was hung in the sealed container was measured, and the ratio was defined as 100%.

As a result of the test, the insect repellent active ingredient used in the present invention exhibited a fungicidal effect superior to that of citral, which has been reported to have a fungicidal effect.

[Example: insect-proof mat type]
An insect repellent mat was prepared by impregnating a pulp paper having an area of 90 cm ² and a thickness of 1 mm with the combination and amount of the fragrance component described in Table 4, and the adjusted mat was stored in a polyester plastic case having an opening, An insect repellent for clothing of the present invention was produced.
A wool blanket was placed in a costume case measuring 50 cm long × 40 cm wide × 25 cm high (about 50 L) until about the eighth minute, and one insecticide for clothing was placed on the top of the blanket. Similarly, a clothes case of the same size in which only a wool blanket was placed and no insect repellent was installed was designated as an untreated section.
Four net cages containing 10 moth larvae and a 5 cm × 5 cm wool cloth were placed in the costume case, and the degree of damage of the wool cloth was determined according to the following after one week.

−: No damage to the food +: Damage caused by shaving of the woolen fabric is observed but not penetrated ++: Damage to the food is found and there is a through hole +++: Excessive food damage is recognized, or multiple or There are large through holes

As a result of the test, it was shown that the insect repellent active ingredient used in the present invention exhibits a sufficient effect of preventing damage from moth larvae when used alone or in combination as in Examples 1 to 19. This effect is not all shown in the case of a perfume component, and since it was not recognized in known perfume components such as dihydrojasmon (Comparative Example 1) and farnesol (Comparative Example 2), the insect repellent active ingredient according to the present invention The effectiveness of the insect repellent for clothing using was demonstrated.

[Example: insect-proof bead type]
The combination and amount of insect repellents described in Examples 1, 4, 6, 11, 13, and 17 in Table 4 were added to about 4 g of charcoal-blended cellulose beads having an average particle size of 3 mm (charcoal content: 50 mass%). 6 mg of active ingredient and green tea extract, and 20 mg of propylene glycol are contained, and the beads are stored in a bag (6 × 9 cm) made of a paper laminated polyester nonwoven fabric with air permeability on both sides to prepare the insect repellent for clothing of the present invention. did. Two pieces of this insect repellent were placed on a clothing case measuring 50cm in length, 40cm in width, and 25cm in height (about 50L) after putting the clothing up to about the eighth minute. Volatilized and for about 3 months, it was not affected by clothing pests such as iga, koiga, himemekaobushimushi, himemarukatsushimushi. Moreover, no mold was observed on the clothing, and a moderate fragrance was imparted, which was extremely practical.

The present invention can be used not only for clothing insect repellents but also in a wide range of pest repellent fields.

Claims (4)

As an insect repellent active ingredient,
Calixol, hedion, iso-E super, 3,7-dimethyl-1-octanol, 4-isopropylcyclohexanol, 2-cyclohexylidene-2-phenylacetonitrile, estragole, 3,7-dimethyl-2,6-nonadiene An insect repellent for clothing comprising one or more fragrance components selected from nitrile and 3-methyl-5-phenyl-1-pentanol . The insect repellent for clothing according to claim 1, wherein the insect repellent activity is activity against squid and carp. As an insect repellent active ingredient,
The insect repellent for clothing according to claim 1 or 2, comprising one or more perfume ingredients selected from iso-E super, estragole and 3,7-dimethyl-1-octanol. An insect repellent for clothing imparted with an antifungal effect, comprising one or more flavoring ingredients according to claim 3.