AU2017241474B2

AU2017241474B2 - Flying insect pest repellent product and method for repelling flying insect pest

Info

Publication number: AU2017241474B2
Application number: AU2017241474A
Authority: AU
Inventors: Tomomi Iwamoto; Yumi Kawajiri; Koji Nakayama; Taiji Ono; Ryoko Ukita
Original assignee: Dainihon Jochugiku Co Ltd
Current assignee: Dainihon Jochugiku Co Ltd
Priority date: 2016-03-31
Filing date: 2017-03-27
Publication date: 2019-09-12
Anticipated expiration: 2037-03-27
Also published as: TW201735788A; CN108601344A; KR20180100642A; AU2017241474A1; JPWO2017170362A1; WO2017170362A1; JP6617194B2; KR102083252B1; HK1254831A1

Abstract

Provided are a flying pest insect repelling product and a flying pest insect repelling method having excellent repelling effect against flying pest insects while leveraging the characteristics of a silicone rubber. In the flying pest insect repelling product 100, a flying pest insect repelling aroma composition containing a flying pest insect repelling aroma component is held in a rubber molded body having a hardness of 45 or less and containing a silicone rubber, the flying pest insect repelling aroma composition being held in an inserted state into gaps within the molecular structure of the rubber constituting the rubber molded body. The rubber molded body is provided with: a band body 10 comprising parts containing at least one hollow shape and an outer contour portion surrounding the hollow shape; and a linking portion 20 for linking or bringing closer to one another the end portions of the band body 10 to form a stretchable ring portion wherethrough a portion of a human body or an object is inserted or fitted. The flying pest insect repelling product 100 is configured in such a manner that the flying pest insect repelling aroma component volatilizes from the surface of the rubber molded body.

Description

DESCRIPTION

FLYING INSECT PEST REPELLENT PRODUCT AND METHOD FOR REPELLING FLYING INSECT PEST

TECHNICAL FIELD [0001]

The present invention relates to flying insect pest repellent products and methods for repelling flying insect pests .

BACKGROUND ART [0002]

Repellents containing DEET (Ν,Ν-diethyl toluamide) are conventionally commonly applied to the skin surface in order to repel flying insect pests such as mosquitoes, black flies, chironomids, flies, etc. However, DEET is somewhat less volatile than typical fragrance components, and therefore, cannot be expected to provide a spatial repellent effect. Meanwhile, insecticidal components which vaporize at room temperature, such as empenthrin, which is a member of the family of pyrethroids, can be vaporized and diffused into space to achieve the effect of repelling flying insect pests. However, users hesitate or avoid using insecticidal components which vaporize at room temperature in not a few situations.

[0003]

Therefore, several attempts to use volatile natural essential oils, or components thereof, as a repellent component have been proposed.

For example it is well known that citronella oil, or citronellal, which is a major component thereof, has a repellent effect on mosquitoes. In the United States of America, candles containing citronella oil as an active component are on the market. However, the method of causing citronellal to spread into space by means of heat of the candle is not efficient in vaporizing or diffusing citronellal, and therefore, has not a practical repellent effect.

[0004]

Japanese Unexamined Patent Application Publication No.

2002-173407 (Patent Document 1) describes a flying insect pest repellent containing a natural essential oil selected from citronella oil, and in addition, orange oil, cassia oil, etc., as an active component. Patent Document 1 also describes various examples of a solvent for use in a liquid formulation, including alcohols such as methyl alcohol and ethyl alcohol, esters such as diethyl phthalate and isopropyl myristate, aliphatic hydrocarbons such as hexane, kerosene, and paraffin, aromatic hydrocarbons, and ethers.

[0005]

In addition, Japanese Unexamined Patent Application Publication No. 2003-201203 (Patent Document 2) describes a volatile insect pest repellent composition containing, as an insect pest repellent component (A) , citronellal, and one or more selected from terpineol, menthol, limonene, geraniol, citronellol, camphene, etc., where the content of citronellal in the insect pest repellent component (A) is 2-10% by mass. These repellents are advertised as being natural and safe, but are not necessarily satisfactory, because their repellent effects are inferior in terms of sustainability.

[0006]

Moreover, Japanese Unexamined Patent Application Publication No. S61-289002 (Patent Document 3) proposes a repellent for arthropods, mollusks, and reptiles containing glycol ethers as an active component. Patent Document 3 states that glycol ethers have a good repellent effect on cockroaches and ticks. However, the effect is in no way sufficient. In addition, Patent Document 3 does not mention any repellent effect on flying insect pests.

[0007]

Thus, there is not yet a known useful fragrance composition for repelling flying insect pests, that is aimed at achieving a flying insect pest repellent effect, and in addition to this, an improved sustainability of fragrance. There is demand for the development of such a composition. [0008]

Incidentally, silicone rubber is known for its good adsorptivity and gas permeability, stable physical properties, and good ability to discharge fragrance materials. Because of such properties, air fresheners which are silicone rubber containing a fragrance material are commercially sold.

Silicone rubber containing a fragrance material is typically produced by mixing a silicone compound or liquid silicone with the fragrance material, followed by linking) using a vulcanizing agent such as sulfur, an additive, etc .

However, the fragrance material easily separates from the rubber polymer or the additive during kneading, and moreover, a chemical change such as decomposition or degeneration occurs in the fragrance material due to heat or sulfur during molding.

Therefore, it has been difficult to obtain a molded article having fragrance and stable physical properties.

As a means for solving the above problems, Japanese

Unexamined Patent

Application

Publication No. H08-311216 (Patent Document 4) and Japanese

Unexamined Patent Application

Publication No. 2011-26462 (Patent Document 5) employ a method of adding a fragrance material to silicone rubber after molding instead of kneading silicone rubber together with a fragrance material before molding.

However, neither of these documents mentions compatibility between the nature of the fragrance composition and silicone rubber.

Therefore, it is not unclear that the techniques of these documents are applicable to the flying insect pest repellent fragrance composition, which has different functionality.

CITATION LIST

PATENT LITERATURE [0010]

Patent

Document

Japanese

Unexamined

Patent

Application Publication No.

2002-173407

Patent

Document

Japanese

Unexamined

Patent

Application Publication No.

2003-201203

Patent

Document

3:

Japanese

Unexamined

Patent

Application Publication No.

Patent

Document

Japanese

Unexamined

Patent

Application Publication No.

Patent

Document

5:

Japanese

Unexamined

Patent

Application Publication No.

2011-26462

SUMMARY OF INVENTION

TECHNICAL PROBLEM [0011]

Thus, there has been a situation where, in order to develop a useful flying insect pest repellent product using silicone rubber, it is necessary to find a flying insect pest repellent fragrance composition which has a high repellent effect and good compatibility with silicone rubber, through trial and error, and conduct various tests.

[0012]

With the above problems in mind, the present invention has been made. It is an object to the present invention to provide a product and method for repelling flying insect pests which have a good repellent effect on flying insect pests while utilizing properties of silicone rubber.

SOLUTION TO PROBLEM [0013]

The present invention has found that the following configurations have a good effect in order to achieve the above object.

[0014] insect pest repellent product which is a molded rubber article containing silicone rubber and having a hardness of not more than degrees, the molded rubber article holding a flying insect pest repellent fragrance composition containing a flying insect pest repellent fragrance component with the flying insect pest repellent fragrance composition being held in interstices in a molecular structure of the rubber of the molded rubber article, wherein the molded rubber article includes :

a band-shaped body including parts linked together, each part including at least one void and a void-surrounding portion surrounding the at least one void;

and a joint portion configured to join opposite ends of the band-shaped body together or cause the opposite ends to be close to each other, so that the molded rubber article forms an elastic ring, which is put around or attached to a portion of a human body or an object, and the flying insect pest repellent fragrance component is vaporized and discharged from a surface of the molded rubber article .

[0015] (2) The flying insect pest repellent product of (1), wherein

	when	the molded rubber	article	is	not	stretched, the
molded	rubber article	satisfies
	0.05	< Si/ S₂ <	0.6
where	Si	represents	a total	area	of	the	voids,	and S₂
represents	an area	of the	entire	molded	rubber	article

(including Si) , as measured when the molded rubber article is laid flat.

[0016] (3) The flying insect pest repellent product of (1) or (2), wherein the joint portion includes a plurality of female portions provided at one end portion of the band-shaped body, and a projecting portion provided at the other end portion of

the band-shaped body	and configured to adjust	a size	of	the
ring.
[0017]
	(4) The flying	insect	pest repellent product of	any	one
of (1)	-(3), wherein
	when the ring	is put	around or attached	to the	portion

of the human body or the object, the flying insect pest repellent fragrance component is vaporized and discharged over

5-15 hours.

[0018] (5)

The flying insect pest repellent product of (4) , wherein the flying insect pest repellent fragrance component is

vaporized	and	discharged at an	average	rate of 0.05-1.0
mg/cm²-h over	an entire surface	area of	the molded	rubber
article .
[0019]
(6)	The	flying insect pest	repellent	product of	any one

of (1)-(5), wherein the flying insect pest repellent fragrance composition contains, as the flying-insect pest repellent fragrance component, a component (a) and a component (b), the component (a) is a single acetic acid ester compound or a mixture of acetic acid ester compounds, the acetic acid ester compounds being represented by:

CHa-COO-Rl (I) where R1 is an alcohol residue having 6-12 carbon atoms, and the component (b) is a monoterpene alcohol and/or an aromatic alcohol having 10 carbon atoms.

[0020] (7) The flying insect pest repellent product of (6), wherein the flying insect pest repellent fragrance composition further contains, as the component (a) , a single allyl ester compound or a mixture of allyl ester compounds, the allyl ester compounds being represented by:

R2-CH₂-COO-CH₂-CH=CH₂ where R2 is an alkyl, alkoxy, cycloalkyl, or cycloalkoxy group having

4-7 carbon atoms, or a phenoxy group, and acetic [0021] the component (a) is at least one selected from the acid ester compounds and the allyl ester compounds.

(8) The flying insect pest repellent product of (6) or the blend ratio of the component (a) to the component (b) is 0.1-2.0.

[0022] (9) The flying insect pest repellent product of any one the acetic acid ester compound is at least one selected from the group consisting of p-tert-butylcyclohexyl acetate, o-tert-butylcyclohexyl acetate, p-tert-pentylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, phenylethyl acetate, styralyl acetate, anisyl acetate, cinnamyl acetate, terpinyl acetate, dihydroterpinyl acetate, linalyl acetate, ethyllinalyl acetate, citronellyl acetate, geranyl acetate, neryl acetate, bornyl acetate, and isobornyl acetate .

[0023] (10) The flying insect pest repellent product of any one of (7)-(9), wherein the allyl ester compound is at least one selected from the group consisting of allyl hexanoate, allyl heptanoate, allyl octanoate, allyl n-amyloxyacetate, allyl cyclohexylacetate, allyl cyclohexyloxyacetate, and allyl phenoxyacetate .

[0024] (11) The flying insect pest repellent product of any one of (6)-(10), wherein the monoterpene alcohol and/or the aromatic alcohol having 10 carbon atoms are at least one selected from the group consisting of terpineol, geraniol, dihydromyrcenol, borneol, menthol, citronellol, nerol, linalool, ethyl linalool, thymol, eugenol, and p-menthane-3,8-diol.

[0025] (12) The flying insect pest repellent product of any one of (6)-(11), wherein the flying insect pest repellent fragrance composition further contains a glycol and/or glycol ether having a vapor pressure of 0.2-20 Pa at 20°C as a repellent effect sustaining component for the flying insect pest repellent fragrance component during vaporization and discharge.

[0026] (13) The flying insect pest repellent product of (12), wherein the glycol and/or the glycol ether are at least one selected from the group of consisting of benzyl glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butylene glycol, hexylene glycol, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, and tripropylene glycol monomethyl ether.

[0027] (14) The flying insect pest repellent product of (12) or (13), wherein the glycol is dipropylene glycol.

[0028] (15) The flying insect pest repellent product of any one of (1)-(14), wherein the voids each have a contour of a graphic shape or a figure .

[0029] molded rubber hardness of flying insect pest article containing not more than repellent product which is silicone degrees, rubber and having the molded rubber article holding a flying insect pest repellent fragrance composition containing a flying insect pest repellent fragrance component with the flying insect pest repellent fragrance composition being held in interstices in a molecular structure of the rubber of the molded rubber article, wherein the molded rubber article includes: a band-shaped body including at least one projecting portion at one end thereof;

and a joint portion configured such that the projecting portion is fitted thereinto, so that the molded rubber article forms an elastic ring, which is put around or attached to a portion of a human body or an object, and the flying insect pest repellent fragrance component is vaporized and discharged from a surface of the molded rubber article .

[0030] (17) A method for repelling a flying insect pest using the flying insect pest repellent product of any one of (1)- (16), the method comprising:

vaporizing and discharging the flying insect pest repellent fragrance component from a surface of the molded rubber article.

ADVANTAGEOUS EFFECTS OF INVENTION [0031]

The flying insect pest repellent product and flying insect pest repellent method of the appropriately vaporize and discharge repellent fragrance component from a containing silicone rubber and having present invention can a flying insect pest molded rubber article a hardness of not more than 45 degrees, and therefore, have an excellent flying insect pest repellent effect for a predetermined period of time. The molded rubber article includes a band-shaped body having parts linked together, each part having at least one void and a void-surrounding portion surrounding the void, and therefore, can have elasticity equivalent to or better than that of a string-shaped molded rubber article. The vaporization and discharge performance per unit weight of the flying insect pest repellent fragrance component of the molded rubber article is comparable to that of a string-shaped molded rubber article, and therefore, a single piece of the present invention has vaporization and discharge performance equivalent to that of several string-shaped molded rubber articles. Thus, the flying insect pest repellent product and flying insect pest repellent method of the present invention are excellent in terms of efficiency and convenience. The molded rubber article also includes a joint portion which is configured to join opposite ends of the band-shaped body together or cause the opposite ends to be close to each other, so that the molded rubber article forms an elastic ring, which is put around or attached to a portion of the human body or an object. Therefore, by adjusting a size of the ring, the attachment to the portion of the human body or the object can be appropriately adjusted. Furthermore, when a component which has fragrance is used as the flying insect pest repellent fragrance material, the flying insect pest repellent product and flying insect pest repellent method of the present invention can sustain the initial fragrance type over a long period of time, and therefore, are highly useful.

BRIEF DESCRIPTION OF DRAWINGS [0032] [FIG. 1] FIG. 1 is an external view of a molded silicone rubber article which has parts linked together, each part having a void whose contour has a star shape. FIG. 1(a) shows the molded silicone rubber article as it is not attached. FIG. 1(b) shows the molded silicone rubber article as it is attached to a wrist.

[FIG. 2] FIG. 2 is an external view of a molded silicone rubber article as it is not attached, that has parts linked together, each part having a void whose contour is in the shape of a pigeon.

[FIG. 3] FIG. 3 is an external view of a molded silicone rubber article as it is not attached, that has parts linked together, each part having a void whose contour is in the shape of an angel.

[FIG. 4] FIG. 4 is an external view of a molded silicone rubber article as it is not attached, that has a plurality of projecting portions which can be fitted into a joint portion.

DESCRIPTION OF EMBODIMENTS [0033]

Embodiments of a flying insect pest repellent product according to the present invention will now be described. A method for repelling flying insect pests according to the present invention will be described together with the flying insect pest repellent product. Note that the present invention is not intended to be limited to configurations described in the embodiments described below and the accompanying drawings. [0034]

The flying insect pest repellent product of the present invention is a molded rubber article which contains silicone rubber and has a hardness of not more than 45 degrees (may hereinafter be abbreviated to a molded rubber article), and holds a fragrance composition for repelling flying insect pests (hereinafter also referred to as a flying insect pest repellent fragrance composition), that contains a fragrance component for repelling flying insect pests (hereinafter also referred to as a flying insect pest repellent fragrance component). A specific type of flying insect pest repellent fragrance component suitable for the molded rubber article is used. The flying insect pest repellent fragrance component will be described in detail below.

[0035]

Silicone rubber, which is used in the molded article, has good gas permeability and stable physical properties, and good ability to adsorb and discharge fragrance materials. This may be because fragrance materials, the molecular structure of which has a carbon backbone, easily enter interstices of the three-dimensionally cross-linked molecular structure of the rubber. In order to utilize the properties of silicone rubber, it is preferable to adjust the hardness of the molded rubber article to not more than 45 degrees. For example, a silicone rubber having a hardness of not more than 45 degrees is used as a material for the molded rubber article. As a result, the finished molded rubber article has a hardness of not more than 45 degrees. If the hardness of the molded rubber article is not more than 45 degrees, the silicone rubber does not have very dense molecular structure, and therefore, fragrance molecules easily enter interstices of the molecular structure of the rubber. Note that the hardness of the molded rubber article is measured using a method or device compliant with Japanese Industrial Standards (JIS K6253). In the present invention, the hardness of the molded rubber article is measured using a durometer compliant with the above standards.

[0036]

Any of the types of silicone rubber, such as room temperature curable type, thermosetting type, condensation type, and addition type, can be used. Typically, a silicone compound or liquid silicone is vulcanized (cross-linked) using a vulcanizing agent such as sulfur, an additive such as silica, etc., and is molded. Note that, by adjusting the cross-link density of silicone rubber, or by adjusting the amount of a silicone oil or filler which is used and added as an additive, the rate of vaporization and discharge of a flying insect pest repellent fragrance composition which is subsequently added, can be controlled.

[0037]

The molded rubber article used in the present invention may contain other types of rubber. For example, the molded rubber article containing fluorinated rubber in addition to silicone rubber is expected to have improved durability.

[0038]

The molded rubber article used in the present invention includes: a band-shaped body including parts linked together, each part including at least one void and a void-surrounding portion which surrounds the void; and a joint portion which is configured to join opposite ends of the band-shaped body together or cause the opposite ends to be close to each other, so that the molded rubber article forms an elastic ring, which is put around or attached to a portion of the human body or an object. Alternatively, the molded rubber article used in the present invention includes: a band-shaped body having at least one projecting portion at one end thereof; and a joint portion which is configured such that the projecting portion is fitted thereinto, so that the molded rubber article forms an elastic ring, which is put around or attached to a portion of the human body or an object. The band-shaped body is a main part (main body) of the molded rubber article. The band-shaped body can have elasticity equivalent to or better than when the molded rubber article is in the shape of a string, and have sufficient strength. The joint portion is used to change the shape of the molded rubber article (flying insect pest repellent product) from the band (before use) to the ring (in use), and temporarily fix the ring shape. The joint portion can be used to adjust a size of the ring thus formed so that the attachment of the molded rubber article to a portion of the human body or an object can be appropriately adjusted. For example, when the molded rubber article is put around or attached to a portion of the human body or an object, then if the molded rubber article moves more than necessary and therefore feels uncomfortably loose, the joint portion may be adjusted to fasten the molded rubber article somewhat more firmly. Meanwhile, if the user desires to avoid direct contact between the skin and the molded rubber article containing just a fragrance component to the extent possible, the joint portion may be adjusted such that the molded rubber article is loosely attached to a wrist, ankle, etc., with a gap between the molded rubber article and the skin being maximized. In a preferable example configuration of the joint portion, a plurality of female portions are provided at one end portion (or the other end portion) of the band-shaped body, and one or more projecting portions are provided at the other end portion (or one end portion). Specifically, for example, three to seven circular through-holes may be disposed as female portions in the longitudinal direction, and a T-shaped projecting portion may be provided at the opposite end portion. This molded rubber article may form a ring when the T-shaped projecting portion is fitted into any of the through holes. Alternatively, six to ten circular through-holes may be disposed as female portions in the longitudinal direction, and two to four projecting portions may be provided at the opposite end portion. This molded rubber article may form a ring when the two to four projecting portions are fitted into two to four of the six to ten through-holes.

[0039]

The opposite ends of the band-shaped body are joined together or disposed close to each other by the joint portion so that the molded rubber article forms a ring, which is put

around	or attached to	a portion of	the human body	such	as a
wrist	or ankle, or an	object such	as the	handle,	etc .,	of a
buggy,	etc., the handlebars, etc.,	of a	bicycle,	etc .,	the

handle, etc., of a handbag, rucksack, bag, etc., a chinstrap, or a shoelace. In this situation, the flying insect pest repellent fragrance component is gradually vaporized and discharged from the surface of the molded rubber article. For example, when the flying insect pest repellent product is configured to sustain the vaporization and discharge state over 5-15 hours, the average rate of vaporization and discharge of the flying insect pest repellent fragrance component is preferably 0.05-1.0 mg/cm²-h over the surface area of the entire molded rubber article in order to maintain that vaporization and discharge performance. If the average rate of vaporization and discharge of the flying insect pest repellent fragrance component is within this range, the bleeding of the flying insect pest repellent fragrance component in the molded rubber article stably smoothly proceeds over 5-15 hours, preferably 8-12 hours. If the average rate of vaporization and discharge of the flying insect pest repellent fragrance component is less than 0.05 mg/cm²-h, the flying insect pest repellent effect is not sufficient. If the average rate of vaporization and discharge of the flying insect pest repellent fragrance component exceeds 1.0 mg/cm²-h, the sustained period of the repellent effect may decrease, or the amount of the flying insect pest repellent fragrance component or the flying insect pest repellent fragrance composition which is held in the molded silicone rubber article may be excessively large, so that the surface is likely to become wet and sticky. Note that, in the present invention, the average rate of vaporization and discharge refers to an average value calculated over a period of time during which the rate of vaporization and discharge is at least 0.02 mg/cm²-h.

[0040]

The molded rubber article used in the present invention has a feature that the vaporization and discharge performance per unit weight thereof is comparable to that of a molded rubber article which is molded in the shape of a string. String-shaped molded rubber articles and flat plate (solid) band-shaped molded rubber articles have heretofore been commonly used, and it has been considered that the former is superior to the latter in vaporization and discharge performance per unit weight. Therefore, it had been predicted that the molded rubber article used in the present invention would have intermediate vaporization and discharge performance per unit weight, compared to string-shaped molded rubber articles and flat plate band-shaped molded rubber articles.

The result of tests surprisingly demonstrated that the molded rubber article used in the present invention has substantially the same vaporization and discharge performance per unit weight of string-shaped molded rubber articles. Although the reason for this finding is not clear, it is considered that the voids provided in the parts generate diffused air flow, which contributes to an improvement in vaporization and discharge performance.

Therefore, the molded rubber article used in the present invention alone can acquire vaporization and discharge performance equivalent to what is acquired by several string-shaped molded rubber articles. Therefore, the molded rubber article used in the present invention can be used to provide a flying insect pest repellent product which is advantageous in terms of efficiency and convenience.

[0041]

The shape of the molded rubber article used in the present invention before use is not limited as long as it is in the shape of a band, and it is easy to use if the width is about 0.5-2.0 cm, the length is about 10-25 cm, and the thickness is about 1-3 mm. The sizes and shapes of the voids in the band-shaped body have influence on the vaporization and discharge performance of the flying insect pest repellent fragrance component from the molded rubber article, and in addition, the elasticity and strength of the molded rubber article, and therefore, may be determined, taking these factors into account.

[0042]

When the molded rubber article is not stretched, the sizes of the voids preferably satisfy 0.05 d Si/ S2 0.6, more preferably 0.2 < Si/ S2 0.5, where Si represents the total area of the voids, and S2 represents the area of the entire molded rubber article (including Si) , as measured when the molded rubber article is laid flat, for example. If the value of S1/S2 is less than 0.05 (i.e., the area percentage of the voids with respect to the molded rubber article is less than 5%), the vaporization and discharge performance per unit weight of the molded rubber article is lower than that of a string-shaped molded rubber article. If the value of S1/S2 exceeds 0.6 (i.e., the area percentage of the voids with respect to the molded rubber article exceeds 60%), the molded rubber article is likely to have insufficient strength.

[0043]

The voids may each be shaped such that a contour thereof has a graphic shape or a figure. Examples of the graphic shape or figure include, but are not limited to, animals, insects, vehicles, and alphabets. Some of the voids may be provided with a bottom to have a recessed or concave shape having a Ushaped cross-section. This can increase the weight of the molded rubber article and thereby increase the amount of the flying insect pest repellent fragrance component contained therein while the design of the voids is kept. Note that a branch portion extending from a void-surrounding portion surrounding a void may be formed so that the molded rubber article has more variety in terms of figure or design.

[0044]

FIGS. 1-4 show examples of the molded rubber article 100 including the band-shaped body 10 and the joint portion 20 which is used as the flying insect pest repellent product 100 of the present invention. FIG. 1 is an external view of a molded silicone rubber article 100 which has parts 1A linked together, each part 1A having a void whose contour has a star shape. FIG. 1(a) shows the molded silicone rubber article 100 as it is not attached. FIG. 1(b) shows the molded silicone rubber article 100 as it is attached to a wrist H with the opposite ends of the molded silicone rubber article 100 being joined together. FIG. 2 is an external view of a molded silicone rubber article 100 as it is not attached, that has parts IB linked together, each part IB having a void whose contour is in the shape of a pigeon. FIG. 3 is an external view of a molded silicone rubber article 100 as it is not attached, that has parts IC linked together, each part IC having a void whose contour is in the shape of an angel. FIG.

is an external view of a molded silicone rubber article 100 as it is not attached, that has a plurality of projecting portions 30 which can be fitted into the joint portion 20.

[0045]

The flying insect pest repellent fragrance composition used in the flying insect pest repellent product of the present invention contains substantially no insecticidal component, and contains a fragrance component as a flying insect pest repellent component. Such a fragrance component is referred to as a flying insect pest repellent fragrance component. The flying insect pest repellent fragrance component contains the following components (a) and (b) .

[0046]

The component (a) is, for example, a single acetic acid ester compound or a mixture of acetic acid ester compounds, the acetic acid ester compounds being represented by:

CHa-COO-Rl (I) where R1 is an alcohol residue having 6-12 carbon atoms.

The component (b) is, for example, a monoterpene alcohol and/or an aromatic alcohol having 10 carbon atoms.

[0047]

Of the flying insect pest repellent fragrance components, a single allyl ester compound or a mixture of allyl ester compounds may be additionally contained as the component (a), the allyl ester compounds being represented by:

R2-CH₂-COO-CH₂-CH=CH₂ (II) where R2 is an alkyl, alkoxy, cycloalkyl, or cycloalkoxy group having 4-7 carbon atoms, or a phenoxy group. In this case, the component (a) is at least one selected from the acetic acid ester compounds and the allyl ester compounds.

[0048]

The flying insect pest repellent fragrance composition preferably further contains a glycol and/or glycol ether having a vapor pressure of 0.2-20 Pa at 20°C as a repellent effect sustaining component during vaporization and discharge of the flying insect pest repellent fragrance component.

[0049]

The amount of the flying insect pest repellent fragrance component or the flying insect pest repellent fragrance composition which is added to (held in) the molded rubber article may be suitably determined based on the purpose of use or period of use of the flying insect pest repellent product, and the type or specification of the molded rubber article, etc. For example, in the case of a repellent product which is used for 8-12 hours at a time, the weight of the product is typically about 1.0-5.0 g, and the flying insect pest repellent fragrance component which is held is suitably within the range of 20-200 mg (i.e., 0.4-20% by mass) per molded rubber article.

[0050]

Also, according to the result of tests conducted by the present inventors described below, it was found that the vaporization and discharge state of the flying insect pest repellent fragrance component from the molded rubber article is affected by the prescription of the flying insect pest repellent fragrance composition. For the flying insect pest repellent fragrance composition used in the present invention, the glycol and/or glycol ether which are blended as a repellent effect sustaining component during vaporization and discharge, significantly contribute to stabilization of vaporization and discharge of the fragrance component from the molded silicone rubber article. On the other hand, in the case of the flying insect pest repellent fragrance composition which does not contain a glycol and/or a glycol ether, it was found that the amount of the composition which is vaporized and discharged during an early period tends to be somewhat greater (eventually, the sustained period might be less than 5 hours, and the average rate of vaporization and discharge might exceed 1.0 mg/cm²-h) .

[0051]

The flying insect pest repellent fragrance component contained in the flying insect pest repellent fragrance composition used in the flying insect pest repellent product of the present invention will be specifically described.

[0052]

Specific examples of the acetic acid ester compound represented by the general formula (I) which is the component (a) , of the flying insect pest repellent fragrance components, include p-tert-butylcyclohexyl acetate, o-tert-butylcyclohexyl acetate, p-tert-pentylcyclohexyl acetate, tricyclodecenyl acetate, benzyl acetate, phenylethyl acetate, styralyl acetate, anisyl acetate, cinnamyl acetate, terpinyl acetate, dihydroterpinyl acetate, linalyl acetate, ethyllinalyl acetate, citronellyl acetate, geranyl bornyl acetate, and isobornyl acetate.

acetate, neryl acetate,

These acetic acid ester compounds may be used alone or in combination.

[0053]

The specific examples of the allyl ester compound represented by the general formula (II) which is the component (a), of the flying insect pest repellent fragrance components, include allyl hexanoate, allyl heptanoate, allyl octanoate, allyl isobutyloxyacetate, allyl n-amyloxyacetate, allyl cyclohexylacetate, allyl cyclohexylpropionate, allyl cyclohexyloxyacetate, and allyl phenoxyacetate. These allyl ester compounds may be used alone or in combination. Also, these allyl ester compounds may be used in combination with any of the acetic acid ester compounds.

[0054]

Specific examples of the monoterpene alcohol and/or the aromatic alcohol having 10 carbon atoms which are the component (b) , of the flying insect pest repellent fragrance components, include terpineol, geraniol, dihydromyrcenol, borneol, menthol, citronellol, nerol, linalool, ethyl linalool, thymol, eugenol, and p-menthane-3,8-diol. These monoterpene alcohols and/or aromatic alcohols having 10 carbon atoms may be used alone or in combination.

[0055]

In the flying insect pest repellent product of the present invention, the components the flying insect pest repellent fragrance components are preferably used in conjunction with each other.

In this case, the results of the extensive study conducted by the present inventors demonstrated that if the blend ratio of the component (a) to the component (b) is set to 0.1-2.0, a particularly good flying insect pest repellent effect is achieved.

[0056]

In the flying insect pest repellent product of the present invention, the following additives may be suitably added as a flying insect pest repellent fragrance component, in addition to the above fragrance components: for example, ester compounds such as benzyl benzoate, cinnamyl formate, and geranyl formate; monoterpene hydrocarbons such as limonene; monoterpene ketones such as menthone, carvone, pulegone, camphor, and damascone; monoterpene aldehydes such as citral, citronellal, neral, and perillaldehyde; phenylethyl alcohol;

diphenyl oxide; indol aroma (dihydroindenyl-2,4-dioxane); etc.

Moreover, the following various essential oils containing the above fragrance components may be suitably added: for example, jasmine oil, neroli oil, peppermint oil, bergamot oil, orange

oil, geran	ium oil, petitgrain	oil,	lemon oil,	citronella oil,
lemongrass	oil, cinnamon oil,	eucalyptus oil,	lemon eucalyptus
oil, thyme	oil, etc.
[0057]
In	the flying insect	pest	repellent	product of the

present invention, the flying insect pest repellent fragrance composition held by the molded rubber article preferably further contains a repellent effect sustaining component during vaporization and discharge of the flying insect pest repellent fragrance component. The repellent effect sustaining component is, for example, a glycol and/or glycol ether having a vapor pressure of 0.2-20 Pa at 20°C. Such a glycol and/or glycol ether are exemplified as a solvent together with ethanol, isopropanol, lamp oil, etc., in Patent Document 2. Also, Patent Document 3 states that such a glycol and/or glycol ether has a good repellent effect on cockroaches and ticks, but does not mention an effect on flying insect pests. Therefore, the present inventors were the first to find that the above glycol and/or glycol ether not only serve as a solvent, but also have the action of specifically sustaining

the repellent effect of	the	flying	insect	pest	repellent
fragrance	material, and	when	a flying	insect	pest	repellent
fragrance	material which	can	provide fragrance	is	used, also

allows the flying insect pest repellent fragrance material to sustain the initial fragrance type.

[0058]

Specific examples of the above glycol and/or glycol ether (followed by the vapor pressure at 20°C) include propylene glycol (10.7 Pa), dipropylene glycol (1.3 Pa), tripropylene glycol (0.67 Pa), diethylene glycol (3 Pa), triethylene glycol (1 Pa), 1,3-butylene glycol, hexylene glycol (6.7 Pa), benzyl glycol (2.7 Pa), diethylene glycol monobutyl ether (3 Pa) , dipropylene glycol monobutyl ether, and tripropylene glycol monomethyl ether. Of them, dipropylene glycol is preferable to the object of the present invention. Note that the above glycols and/or glycol ethers may be used alone or in combination. The blend ratio of the glycol and/or glycol ether to the flying insect pest repellent fragrance material is suitably about 0.05-5.

[0059]

The flying insect pest repellent fragrance composition may be blended with other functional components unless the advantages of the present invention are impaired. Examples of other functional components include insecticidal components, deodorant components, and antibacterial and antifungal components. Examples of the insecticidal component include empenthrin, profluthrin, transfluthrin, and metofluthrin, which are members of the family of pyrethroids which vaporize at room temperature. When an insecticidal component is blended, the amount of the insecticidal component is preferably limited to as small an amount as possible because of the spirit of the present invention. A representative example of the deodorant component is an extract of a plant selected from Poaceae, Theaceae, Ginkgoaceae, Oleaceae, Moraceae, Rutaceae, Malpighiaceae, and Ebenaceae. Also, leaf alcohol, leaf aldehyde, etc., which are called green odor, may be added to impart a relaxing effect. These functional components may be used alone or in combination.

[0060]

The flying insect pest repellent fragrance composition may be optionally suitably blended with a solvent, surfactant, solubilizer, dispersant, stabilizer, pH adjuster, colorant, etc., unless the advantages of the present invention are impaired. Also, the flying insect pest repellent fragrance composition may be encapsulated into microcapsules or several of the flying insect pest repellent fragrance components may be bound together into a cyclodextrin-like structure, so that the flying insect pest repellent fragrance composition can be stabilized or the vaporization and discharge performance of the flying insect pest repellent fragrance component can be adjusted.

[0061]

Examples of the solvent used in formulation of the flying insect pest repellent product include water, lower alcohols such as ethanol and isopropanol, ketone solvents, ester solvents, and hydrocarbon solvents such as normal paraffin and isoparaffin. Examples of the surfactant include non-ionic surfactants such as polyoxyethylene hydrogenated castor oil, polyoxyethylene higher alkyl ethers (polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, etc.), polyoxyethylene alkyl phenyl ethers, polyoxyethylene higher fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerin fatty acid esters, and polyoxyethylene polyoxypropylene alkyl ethers, and higher alkyl amine oxide surfactants such as lauryl amine oxide, stearyl amine oxide, and lauric acid amide propyldimethylamine oxide. These surfactants may be used alone or in combination. [0062]

The above flying insect pest repellent fragrance composition is added to a molded rubber article containing silicone rubber and having a hardness of not more than 45 degrees, followed by a predetermined treatment, so that the molded rubber article holds the flying insect pest repellent fragrance composition, whereby the production of the flying insect pest repellent product of the present invention is completed. By using the flying insect pest repellent product of the present invention, the flying insect pest repellent method of the present invention can be carried out.

[0063]

The flying insect pest repellent fragrance composition can be added to the molded rubber article using a conventionally known suitable technique. For example, if the molded rubber article has a large surface area, the molded rubber article is caused to carry or support the flying insect pest repellent fragrance composition by a solution dispensing technique or an application technique. If the molded rubber article has a small surface area, a large number of the molded rubber articles are placed in a closed container, and the flying insect pest repellent fragrance composition and, optionally, a solvent are added to the container by spraying or dropping, and allowed to permeate the molded rubber articles. Alternatively, the molded rubber article may be immersed in a solution of the flying insect pest repellent fragrance composition for a suitable period of time. Alternatively, the molded rubber article containing a high concentration of the flying insect pest repellent fragrance composition and the non-treated molded rubber article are placed together in a closed container, and allowed to stand for a suitable period of time so that the concentration of the fragrance composition is caused to be uniform in the entire molded rubber article. The flying insect pest repellent product can be manufactured using these techniques.

[0064]

The amount of the flying insect pest repellent fragrance composition which is contained in the flying insect pest repellent product of the present invention may be suitably determined based on the purpose of use or period of use of the flying insect pest repellent product, and the type or specifications of the molded rubber article, etc. For example, in the case of the flying insect pest repellent product which is used for 8-12 hours at a time, about 20-200 mg of the flying insect pest repellent fragrance composition is preferably contained per molded rubber article. In the case of the flying insect pest repellent product which is used for 1530 days, the weight of the product is preferably about 2-10 g, and about 100-2000 mg of the flying insect pest repellent fragrance composition is preferably contained per molded rubber article, for example.

[0065]

According to the flying insect pest repellent product of the present invention, the molded rubber article itself may be a flying insect pest repellent product. Examples of the flying insect pest repellent product include a wrist ring and a wrist band. The flying insect pest repellent product may also be in the form of a watch strap. In this case, an accommodation portion for accommodating a small piece of molded rubber article may be formed in a portion of the watch strap so that the molded rubber article can be replaced with a new one. Note that, in this case, the flying insect pest repellent product has the advantage of allowing the molded rubber article not to be in direct contact with the skin of the arm.

[0066]

When one to five of the flying insect pest repellent products of the present invention thus obtained are attached to a site such as a wrist or ankle, in a room such as a front door, kitchen, bathroom, living room, or bedroom, space such as a warehouse or car, a garden, or the open air as required, the flying insect pest repellent product provides a good flying insect pest repellent effect on flying insect pests such as mosquitoes (Culicidae including Culex pipiens pallens, Culex pipiens molestus, Aedes albopictus, etc.), black flies (Simuliidae), chironomids (Chironomidae), flies (Brachycera), small flies (Drosophilidae, Phoridae, etc.), drain flies (Psychodidae), tineid moths (Tineidae), etc., over a predetermined period of time. When a flying insect pest repellent fragrance material which can provide fragrance is used, the initial fragrance type is sustained over a predetermined period of time without being changed. In addition, the present product contains substantially no insecticidal component, and therefore, can be used by users who do not like to use insecticides, without hesitation, and therefore, the practical utility is considerably high.

Examples [0067]

To demonstrate the effectiveness of the flying insect pest repellent product of the present invention, the following examples and comparative examples were carried out.

[0068] (Example 1)

A flying insect pest repellent fragrance composition of the present invention was formulated which contained: 10.2% by mass of benzyl acetate and 3.5% by mass of tricyclodecenyl acetate as an acetic acid ester compound represented by the general formula (I) which is the component (a) of the flying insect pest repellent fragrance component; 10.2 % by mass of dihydromyrcenol and 6.8% by mass of geraniol as a monoterpene alcohol and/or an aromatic alcohol having 10 carbon atoms which are the component (b) of the flying insect pest repellent fragrance component; 40.1% by mass of dipropylene glycol as a repellent effect sustaining component; and further 29.2% by mass of other flying insect pest repellent fragrance materials (including 5.4% by mass of eucalyptus oil and 6.9% by mass of benzyl benzoate). The blend ratio of the component (a) to the component (b) in this flying insect pest repellent fragrance composition was 0.81.

[0069]

A silicone compound was used to form a molded rubber article (length: 20 cm, weight: 3.1 g, hardness: 32, and ratio (S1/S2) of the total area (Si) of the voids to the area (S2) of the entire molded rubber article: 0.29) having a band-shaped body configured by seven parts linked together, each part having a void whose contour is star-shaped, and a joint portion provided at either end of the band-shaped body (six circular through-holes (female portions) at one end thereof, and a T-shaped projecting portion at the other end thereof). Next, 0.1 g of the above flying insect pest repellent fragrance composition was injected into an external surface of the molded rubber article at one site thereof. The molded rubber article was allowed to stand in a closed space for two days so that the flying insect pest repellent fragrance composition permeated uniformly the entire molded rubber article. As a result, a flying insect pest repellent product of the present invention which had an effective sustained period of about 12 hours was obtained.

[0070]

The flying insect pest repellent product (molded rubber was put around a wrist with the Tshaped projecting portion provided at one end of the bandshaped body being fitted into one of the circular throughholes provided at the other end so that the band-shaped body formed a ring.

At that time, this product had excellent elasticity and therefore was easily handled. In addition, the size of the ring of this product was conveniently adjusted so that the band-shaped molded rubber article was attached to a wrist with the band-shaped molded rubber article being prevented from moving on the wrist very much. The vaporization and discharge performance of this product was equivalent to that of three string-shaped products. Therefore, a single piece of this product put around a wrist was sufficiently effective. Thus, this product was very practical, and the experimenter was not annoyed by flying insect pests such as mosquitoes and small flies over about 12 hours.

(Example 2) [0071]

A flying insect pest repellent fragrance composition of the present invention was formulated which contained: 9.5% by mass of p-tert-butylcyclohexyl acetate and 3.7% by mass of phenylethyl acetate as an acetic acid ester compound represented by the general formula (I) which is the component (a) of the flying insect pest repellent fragrance component; 4.8% by mass of allyl heptanoate as an allyl ester compound represented by the general formula (II) which is the component (a); 15.3% by mass of terpineol, 9.1% by mass of geraniol, and 10.5% by mass of linalool as an monoterpene alcohol and/or an aromatic alcohol having 10 carbon atoms which are the component (b) of the flying insect pest repellent fragrance component; 27.6% by mass of dipropylene glycol as a repellent effect sustaining component; and 19.5% by mass of other flying insect pest repellent fragrance materials (including 7.9% by mass of limonene and 6.4% by mass of benzyl benzoate). In this flying insect pest repellent fragrance composition, the blend ratio of the component (a) to the component (b) was 0.52.

[0072]

A vulcanizing agent was added to liquid silicone, followed by molding, to form a molded rubber article (length: 23 cm, weight: 3.6 g, hardness: 37, and ratio (S1/S2) of the total area (Si) of the voids to the area (S2) of the entire molded rubber article: 0.35) having a band-shaped body configured by eight parts linked together, each part having a void whose contour is in the shape of a pigeon, and a joint portion provided at either end of the band-shaped body (five circular through-holes (female portions) at one end thereof, and a T-shaped projecting portion at the other end thereof). A hundred of the molded rubber articles were placed in a closed container equipped with a spray device. The flying insect pest repellent fragrance composition was sprayed over the molded rubber articles using the spray device in an amount such that the amount of the composition which was adsorbed by each molded rubber article was 94 mg (68 mg of the flying insect pest repellent fragrance component). The molded rubber articles were allowed to stand for one day so that the flying insect pest repellent fragrance composition permeated uniformly the entire molded rubber articles. As a result, flying insect pest repellent products of the present invention which had an effective sustained period of about 10 hours, were obtained. Note that, alternatively, a molded silicone rubber article having a hardness of 80 degrees was tested in a similar manner. However, the flying insect pest repellent fragrance composition was adsorbed in only a small amount, and therefore, such a molded silicone rubber article was not applicable to the present invention.

[0073]

The flying insect pest repellent product (molded rubber article) thus obtained was put around a wrist with the Tshaped projecting portion provided at one end of the bandshaped body being fitted into one of the circular through holes provided at the other end so that the band-shaped body formed a ring. At that time, the size of the ring was adjusted such that the molded rubber article was somewhat loosely attached to the wrist with the molded rubber article, i.e., the molded rubber article was not firmly fastened. When the experimenter stayed outdoors with this product worn on either wrist (one for each wrist) , the experimenter was not annoyed by flying insect pests such as mosquitoes and small flies over about 10 hours, so that a practical repellent effect was demonstrated. Also, it was fun to wear the product having a figure of an animal, and fragrance still having the initial fragrance type wafted in space around the body, so that the experimenter also enjoyed a pleasantly fresh smell.

[0074] <Sustainability Evaluation Test 1>

As in Example 1, a flying insect pest repellent fragrance composition was formulated which contained: 12 mg of styralyl acetate as an acetic acid ester compound represented by the general formula (I) which is the component (a) of the flying insect pest repellent fragrance component; 28 mg of geraniol as a monoterpene alcohol and/or an aromatic alcohol having 10 carbon atoms which are the component (b) of the flying insect pest repellent fragrance component; and each repellent effect sustaining component, and can be used in the flying insect pest repellent product of the present invention. A sustainability evaluation test 1 described below was conducted on the flying insect pest repellent fragrance composition thus obtained. In this test, the knockdown activity against adults of Culex pipiens pallens (female (?)) was used as an index for sustainability evaluation.

[0075]

Several pieces of specimen reagent-treated filter paper were formulated by impregnated filter paper having a diameter of 15 cm with 0.5 mL of acetone solution (specimen reagent) containing 70 mg of the flying insect pest repellent fragrance material and respective repellent effect sustaining components, followed by air drying. A plastic cylinder (inner diameter: 20 cm, and height: 43 cm) was installed, in which one of the prepared pieces of specimen reagent-treated filter paper was then placed. A 12-mesh wire mesh was provided on top of the plastic cylinder to separate upper and lower spaces. A second cylinder (inner diameter: 20 cm, and height: 20 cm) in which 20 specimen adults of Culex pipiens pallens were released was placed on top of the plastic cylinder. A third cylinder (inner diameter: 20 cm, and height: 43 cm) was placed on top of the second cylinder. The number of specimen insects which were knocked down as time passed was counted to obtain a value KT50 (a time it takes to knock down half of the specimen insects). Note that, in order to evaluate the sustainability of each specimen reagent, two pieces of specimen reagenttreated filter paper, i.e., specimen reagent-treated filter paper immediately after air drying (0 hours in Table 1), and specimen reagent-treated filter paper which had been placed in another room for four hours for vaporization and discharge after air drying (4 hours in Table 1), were tested. The results of the sustainability evaluation test 1 are shown in 5 Table 1.

[0076]

Table 1

	Repellent effect sustaining component in specimen reagent	Vapor pressure (Pa/20°C)	KT₅₀ (min)
0 h	4 h
Glycol/glycol ether	1	Tripropylene glycol	0.67	62.7	101.4
2	Triethylene glycol	1	75.6	117.9
3	Dipropylene glycol	1.3	19.0	42.6
4	Benzyl glycol	2.7	42.3	75.7
5	Diethylene glycol	3	38.1	76.8
6	Hexylene glycol	6.7	59.6	82.3
7	Propylene glycol	10.7	36.2	59.5
8	Diethylene glycol monobutyl ether	3	23.4	50.2
Other compounds	1	Myristate isopropyl	0.012	82.8	> 120
2	Neochiozol	2.7	86.9	> 120
3	Isobutyl alcohol	1200	32.5	> 120
4	—	—	36.1	> 120

[0077]

According to the results of Table 1, it was demonstrated that a glycol and/or glycol ether having a vapor pressure of 0.2-20 Pa at 20°C has the action of sustaining the knockdown effect, i.e., is useful as a repellent effect sustaining component. Note that the comparison between ethylene glycols and propylene glycols showed that the latter is generally preferable. In contrast to this, myristate isopropyl and

Neochiozol, which are not a glycol or a glycol ether, had a poor knockdown effect sustaining action even though the vapor pressure was within the range of 0.2-20 Pa at 20°C.

[0078]

Based on	the	results	of	Table 1, a	sustainability
evaluation	test	similar to	that	described	above was	next
conducted	on benzyl	glycol	and	dipropylene	glycol,	where
different	types	and	amounts	of flying insect	pest repellent
fragrance 2 . [0079]	components	were used	. The results are shown in	Table

Table 2

	Repellent effect sustaining component	Flying-insect pest repellent fragrance materials	KT₅₀ (min)
(a)	(b)	(a)/(b)	0 h	4 h
(a) and (b)	1 2	Benzyl glycol 75mg	Benzyl acetate 10mg	Menthol 40mg	0.25	41.6	47.8
Benzyl acetate 2mg	Menthol 45mg	0.05	54.3	62.1
3 4 5	Dipropylene glycol 75mg	Benzyl acetate 10mg	Thymol 40mg	0.25	22.7	36.5
Benzyl acetate 2mg	Thymol 45mg	0.04	37.4	43.2
Benzyl acetate 38mg	Thymol 15mg	2.5	35.8	41.6
(a) or (b)	1 2	Benzyl glycol 75mg	Benzyl acetate 10mg	—	—	61.9	79.2
—	Menthol 40mg	—	83.7	102.3
3 4	Dipropylene glycol 75mg	Benzyl acetate 10mg	—	—	44.8	68.4
—	Thymol 40mg	—	65.0	110.7

[0080]

According to the results of Table 2, it was found that the repellent effect sustaining component used in the present invention has a more efficient knockdown effect sustaining action when an acetic acid ester compound represented by the general formula (I) which is the component (a) of the flying insect pest repellent fragrance component, and a monoterpene alcohol and/or an aromatic alcohol having 10 carbon atoms which are the component (b) of the flying insect pest repellent fragrance component, are used in combination, and the blend ratio of the component (a) to the component (b) is 0.04-2.5.

[0081] (Examples 3-11)

As in Example 1, a silicone compound was used to form seven band-shaped molded rubber articles having the following void contours, specifications, etc.

• Void contour: star, pigeon, angel, flower, clover, notebook, and rose • Length: 20-24 cm • Weight: 2.9-3.8 g • Hardness: 30-39 • Ratio (S1/S2) of the total area (Si) of the voids to the area (S2) of the entire molded rubber article: 0.08-0.53 [0082]

Next, the above seven molded rubber articles, one for each type, were placed in an aluminum bag whose inner surface was coated with polyester film, and 0.56 g of a flying insect pest repellent fragrance composition containing a flying insect pest repellent fragrance material shown in in Table 3 (an average of 0.08 g per article) was injected into the aluminum bag through an opening of the bag. The bag was sealed and allowed to stand for 7-10 days. As a result, the flying insect pest repellent fragrance composition was uniformly distributed in the entire bag. A flying insect pest repellent product of the present invention was obtained which had an effective sustained period of about 8-12 hours.

[0083]

In a testing room (about 6 m³) , two plastic cups (about

L) with no lid, which were therefore open, were placed side by side. A Drosophilidae attractant and a specimen flying insect pest repellent product were placed in one (treatment zone) of the two cups, and only the Drosophilidae attractant was placed in the other plastic cup (control zone). After five hours of use, adults of Drosophilidae (the number of them was about 100) were released in the room. The number of insects entering a plastic cup in each zone was counted. The repellency rate was calculated by:

repellency rate = [(the number of insects entering the control zone - the number of insects entering the treatment zone)/the number of insects entering the control zone] x 100 [0084]

Table 3

\	Repellent effect sustaining component	Flying-insect pest repellent fragrance materials	Area ratio Cs/sp	Vaporization and discharge rate (mg/cm -h)	Repellency rate
(a)	(b)	(a)/(b)
	3	Dipropylene glycol	40mg	Benzyl acetate Tricyclodecenyl acetate	11mg 4m g	Dihydromyrcenol Geraniol	10mg 7mg	0.88	0.28	0.17	100
	4	Benzyl glycol	24mg	p-tert-butylcyclohexyl acetate Allyl heptanoate	10mg 5mg	Terpineol Linalool Eugenol	15mg 11 mg 9mg	0.43	0.42	0.31	100
	5	Dipropylene glycol	26mg	Styralyl acetate	18mg	Terpineol	21mg	0.86	0.37	0.26	100
Examples	6	Dipropylene glycol	26mg	Styralyl acetate	18mg	Terpineol	21 mg	0,86	0.08	0.07	83
	Triethylene glycol	20mg	Benzyl acetate	1.7mg	Geraniol Nerol	18mg 6mg	0.07	0,19	0.29	87
	8	Diethylene glycol monobutyl ether	18mg	Cinnamyl acetate Allyl heptanoate	10mg 8.7 mg	p~menthane-3,8-dioi Borneol	6mg 2mg	2.3	0.53	0.21	90
	9	-	Styralyl acetate	18mg	Terpineol	21 mg	0,86	0.25	0.20	79
	10	PEG^1?	36mg	Styralyl acetate	18mg	Terpineol	21mg	0.36	0,31	0.14	71
	11	PPGME ^!>	30mg	Styralyl acetate	I8mg	Terpineol	21 mg	0.86	0.27	0.23	80
:amples	1	Dipropylene glycol	26mg	Styralyl acetate	18mg	Terpineol	21 mg	0.86	0.28	0.02	35
rative ex	2	Dipropylene glycol	26mg	Styralyl acetate	18mg	Terpineol	21 mg	0.86	(Flat plate)	0.04	42
Q. E O	3	Dipropylene glycol	16mg		Mint oil	20mg		-	0.30	0.26	33

1) PEG: Polyethylene glycol Vapor pressure: < 0,01 Pa/20^cC

2) PPGME: Polypropylene glycol monomethyl ether Vapor pressure: 1660 Pa/ZO^C * Molded silicone rubber article having a hardness of 80 degrees [0085]

The flying insect pest repellent product of the present invention was a band-shaped molded silicone rubber article equipped with voids having a hardness of not more than 45 degrees, that holds a flying insect pest repellent fragrance composition containing a flying insect pest repellent fragrance component and preferably additionally a repellent effect sustaining component, with the average rate of vaporization and discharge of the flying insect pest repellent fragrance component being preferably 0.05-1.0 mg/cm²-h over the surface area of the entire molded rubber article when the flying insect pest repellent product was put on a portion of the human body, such as a wrist or an ankle, with the joint

6 portions provided at opposite ends of the band-shaped body being fitted together to form a ring.

[0086]

According to the results of Table 3, it was demonstrated that the flying insect pest repellent product of the present invention has a good flying insect pest repellent effect in the test after five hours of vaporization and discharge. Also, when an acetic acid ester compound represented by the general formula (I) which is the component (a) of the flying insect pest repellent fragrance component, and/or an allyl ester compound represented by the general formula (II) which is the component (a) of the flying insect pest repellent fragrance component, and a monoterpene alcohol and/or an aromatic alcohol having 10 carbon atoms which are the component (b) of the flying insect pest repellent fragrance component, were used in combination, and the blend ratio of the component (a) to the component (b) was 0.1-2.0, the repellent effect sustaining component had a more efficient action, and not only the repellency rate but also the fragrance sustainability were satisfactory.

[0087]

Note that if, as in Example 6, the average rate of vaporization and discharge was about 0.07 mg/cm²-h, the repellent effect was slightly reduced. Also, if, as in Examples 9-11, the glycol and/or glycol ether repellent effect sustaining component was not blended, or if any, the vapor pressure thereof at 20°C was not within the range of 0.2-20 Pa, the repellent effect was slightly reduced (it may be considered that, in Examples 9 and 11, the flying insect pest repellent fragrance component had been excessively vaporized and discharged until the test was conducted after five hours of vaporization and discharge, so that the repellent effect was not sufficiently sustained) . In Examples 6 and 9-11, the repellent effect was about twice as high as those of the comparative examples corresponding to conventional flying insect pest repellent products, and therefore, was practically effective .

[0088]

In contrast to this, in Comparative Example 1 in which a molded silicone rubber article having a hardness of more than 45 degrees was used, the repellent effect was low. The flat plate band-shaped molded rubber article not having a void of Comparative Example 2 had a low vaporization and discharge efficiency and repellent effect compared to Example 6. This suggests that the presence of the voids generates diffused air flow and thereby contributes to an improvement in the vaporization and discharge efficiency. Furthermore, in

Comparative Example 3 in which mint oil, which is not considered to be a flying insect pest repellent fragrance material, was used, the repellent effect was not sufficient.

[0089]

Thus, it was demonstrated that the flying insect pest repellent product of the present invention includes: a bandshaped body including parts linked together, each part including at least one void and a void-surrounding portion which surrounds the void; and a joint portion which is configured to join opposite ends of the band-shaped body together or cause the opposite ends to be close to each other, so that the molded rubber article forms an elastic ring, which is put around or attached to a portion of the human body or an object, in which a flying insect pest repellent fragrance component, and preferably a repellent effect sustained component, are vaporized and discharged from the surface of the molded rubber article, and therefore, the product is highly practically useful.

[0090]

The flying insect pest repellent product of the present invention further includes, at an end portion of the bandshaped body, a joint portion which is configured to form an elastic ring, which is put around or attached to a portion of the human body or an object, a size of the ring being adjustable. Therefore, when the molded rubber article is put around or attached to a portion of the human body or an object, then if the molded rubber article moves more than necessary and therefore feels uncomfortably loose, the joint portion may be adjusted to fasten the molded rubber article somewhat more firmly. Meanwhile, if the user desires to avoid direct contact with the molded rubber article containing just a fragrance component, to the extent possible, the joint portion may be adjusted such that the molded rubber article is loosely attached to a wrist, ankle, etc., with a gap between the molded rubber article and the skin being maximized. Thus, the attachment of the flying insect pest repellent product of the present invention to a wrist, etc., can be appropriately adjusted, resulting in high convenience.

INDUSTRIAL APPLICABILITY [0091]

The flying insect pest repellent product and method of the present invention can be used for the purpose of controlling a wide variety of insect pests including flying insect pests.

REFERENCE SIGNS LIST [0092]

10	BAND-SHAPED BODY
20	JOINT PORTION
30	PROJECTING PORTION
100	MOLDED SILICONE RUBBER ARTICLE	(FLYING INSECT
REPELLENT PRODUCT)
H	WRIST

Claims

2017241474 16 Aug 2019

1. A flying insect pest repellent product which is a

5 molded rubber article containing silicone rubber and having a hardness of not more than 45 degrees, the molded rubber article holding a flying insect pest repellent fragrance composition containing a flying insect pest repellent fragrance component with the flying insect pest repellent fragrance composition .0 being held in interstices in a molecular structure of the rubber of the molded rubber article, wherein the molded rubber article includes: a band-shaped body including parts linked together, each part including at least one void and a void-surrounding portion surrounding the at least .5 one void; and a joint portion configured to join opposite ends of the band-shaped body together or cause the opposite ends to be close to each other, so that the molded rubber article forms an elastic ring, which is put around or attached to a portion of a human body or an object,

20 the flying insect pest repellent fragrance component is vaporized and discharged from a surface of the molded rubber article, and when the molded rubber article is not stretched, the molded rubber article satisfies:

25 0.08 < S1/S2 < 0.53

2017241474 16 Aug 2019 where Si represents a total area of the voids, and S2 represents an area of the entire molded rubber article (including Si) , as measured when the molded rubber article is laid flat.

5 2. The flying insect pest repellent product of claim 1, wherein the joint portion includes a plurality of female portions provided at one end portion of the band-shaped body, and a projecting portion provided at the other end portion of the

.0 band-shaped body and configured to adjust a size of the ring. 3. The flying insect pest repellent product of claim 1 or 2, wherein when the ring is put around or attached to the portion

.5 of the human body or the object, the flying insect pest repellent fragrance component is vaporized and discharged over 5-15 hours.
4. The flying insect pest repellent product of claim 3, wherein

20 the flying insect pest repellent fragrance component is vaporized and discharged at an average rate of 0.05-1.0 mg/cm².h over an entire surface area of the molded rubber article.
5. The flying insect pest repellent product of any one

25 of claims 1-4, wherein

2017241474 16 Aug 2019 the flying insect pest repellent fragrance composition contains, as the flying-insect pest repellent fragrance component, a component (a) and a component (b), the component (a) is a single acetic acid ester compound

5 or a mixture of acetic acid ester compounds, the acetic acid ester compounds being represented by:

CHa-COO-Rl (I) where R1 is an alcohol residue having 6-12 carbon atoms, and the component (b) is a monoterpene alcohol and/or an aromatic .0 alcohol having 10 carbon atoms.
6. The flying insect pest repellent product of claim 5, wherein the flying insect pest repellent fragrance composition .5 further contains, as the component (a), a single allyl ester compound or a mixture of allyl ester compounds, the allyl ester compounds being represented by:

R2-CH₂-COO-CH₂-CH=CH₂ (II) where R2 is an alkyl, alkoxy, cycloalkyl, or cycloalkoxy group 20 having 4-7 carbon atoms, or a phenoxy group, and the component (a) is at least one selected from the acetic acid ester compounds and the allyl ester compounds.
7. The flying insect pest repellent product of claim 5 25 or 6, wherein

2017241474 16 Aug 2019 the blend ratio of the component (a) to the component (b) is 0.1-2.0 .
8. The flying insect pest repellent product of any one

5 of claims 5-7, wherein the acetic acid ester compound is at least one selected from the group consisting of p-tert-butylcyclohexyl /clohexyl acetate, o-tert-butylcyclohexyl acetate, p-tertpentylcyclohexyl acetate, tricyclodecenyl acetate, benzyl .0 acetate, phenylethyl acetate, styralyl acetate, anisyl acetate, cinnamyl acetate, terpinyl acetate, dihydroterpinyl acetate, linalyl acetate, ethyllinalyl acetate, citronellyl acetate, geranyl acetate, neryl acetate, bornyl acetate, and isobornyl acetate .

.5
9. The flying insect pest repellent product of any one of claims 6-8, wherein the allyl ester compound is at least one selected from the group consisting of allyl hexanoate, allyl heptanoate, allyl 20 octanoate, allyl n-amyloxyacetate, allyl cyclohexylacetate, allyl cyclohexyloxyacetate, and allyl phenoxyacetate.
10. The flying insect pest repellent product of any one of claims 5-9, wherein

25 the monoterpene alcohol and/or the aromatic alcohol having 10 carbon atoms are at least one selected from the group

2017241474 16 Aug 2019 consisting of terpineol, geraniol, dihydromyrcenol, borneol, menthol, citronellol, nerol, linalool, ethyl linalool, thymol, eugenol, and p-menthane-3,8-diol.

5 11. The flying insect pest repellent product of any one of claims 5-10, wherein the flying insect pest repellent fragrance composition further contains a glycol and/or glycol ether having a vapor pressure of 0.2-20 Pa at 20°C as a repellent effect sustaining .0 component for the flying insect pest repellent fragrance component during vaporization and discharge.

12. The flying insect pest repellent product of claim
11, wherein .5 the glycol and/or the glycol ether are at least one selected from the group of consisting of benzyl glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3butylene glycol, hexylene glycol, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, and tripropylene 20 glycol monomethyl ether.
13. The flying insect pest repellent product of claim 11 or 12, wherein the glycol is dipropylene glycol.

2017241474 16 Aug 2019
14. The flying insect pest repellent product of any one of claims 1-13, wherein the voids each have a contour of a graphic shape or a figure .
15. A method for repelling a flying insect pest using the flying insect pest repellent product of any one of claims 1-14, the method comprising:

vaporizing and discharging the flying insect pest .0 repellent fragrance component from a surface of the molded rubber article.