AU2019250325B2 - Flying Insect Pest Repellent Product and Method for Repelling Flying Insect Pest - Google Patents

Abstract

Provided is a flying-noxious-insect-repellent product in which a silicone rubber has improved molding workability, mechanical properties, etc. The flying-noxious-insect-repellent product also has excellent ability to volatilize flying-noxious-insect-repellent fragrance components and excellent flying-noxious-insect-repelling effects. A flying-noxious-insect-repellent product that comprises a silicone rubber molded body that has a hardness of no more than 50 degrees and a flying-noxious-insect-repellent fragrance composition that is retained in the silicone rubber molded body. The silicone rubber molded body is a cured product of an addition-type liquid silicone rubber composition. The flying-noxious-insect-repellent fragrance composition contains, as flying-noxious-insect-repellent fragrance components, (a) a terpene hydrocarbon compound and/or a terpene ketone compound, (b) an ester compound, and (c) a terpene alcohol compound, the ratio {(X+Y)/Z} of the total of the amount X of (a) and the amount Y of (b) to the amount Z of (c) being 0.2–4.0.

Description

DESCRIPTION FLYING INSECT PEST REPELLENT PRODUCT AND METHOD FOR REPELLING FLYING INSECT PEST TECHNICAL FIELD

[0001] The present invention relates to a flying insect

pest repellentproduct whichis amolded silicone rubber article

having a hardness of not more than 50 degrees, the molded rubber

article holding a flying insect pest repellent fragrance

composition containinga flyinginsectpest repellent fragrance

component with the flying insect pest repellent fragrance

composition being held in interstices in a molecular structure

of the rubber constituting the molded silicone rubber article,

and a method for repelling flying insect pests using this flying

insect pest repellent product.

BACKGROUND ART

[0002] Repellents containing DEET (N,N-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 ofrepelling flyinginsectpests. However, users hesitate or avoid using insecticidal components which vaporize at room temperature in not a few situations.

[00031 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

flyinginsect pest repellent containing anaturalessentialoil

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, aliphatichydrocarbons such as hexane, kerosene, and paraffin, aromatic hydrocarbons, and ethers.

[00051 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, 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 is 2-10% by

mass. These repellents are advertisedasbeingnaturalandsafe,

but are not necessarily satisfactory, because their repellent

effects are inferior in terms of sustainability.

[00061 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.

[00081 Incidentally, silicone rubber is known for its good adsorptivity and gas permeability, stable physicalproperties, and good ability to discharge fragrance materials. Because of such properties, air fresheners which are silicone rubber containing a fragrance material are commercially sold. In incorporating a fragrance material into a silicone rubber, generally, (i) a millable-type silicone rubber composition containing a silicone compound or (ii) a liquid silicone rubber composition containing a liquid silicone polymer is mixed with the fragrance material, followed by vulcanization

(cross-linking) using a reaction aid such as sulfur, an additive,

etc. However, the fragrance materialeasily separates from the

silicone 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

the reaction aid during molding. Therefore, it has been

difficult to obtain amolded article having fragrance and stable

physical properties.

[00091 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.

[0010] As mentioned above, a molded silicone rubber

article is prepared by curing and molding (i) a millable-type

silicone rubber composition containing a silicone compound or

(ii) a liquid silicone rubber composition containing a silicone

compound. Furthermore, the liquid silicone rubber composition

(II) includes two kinds: addition-type and condensation-type.

In the development of a useful flying insect pest repellent

product utilizing a silicone rubber, the presentinventors used

a molded silicone rubber article, which is a cured product of

(I) a millable-type silicone rubber composition or (II) a liquid

silicone rubber composition, and considered the compatibility

between this andvarious flyinginsect pest repellent fragrance

compositions. Consequently, they found that, by adopting a

mixture of (m) a specific acetic acid ester compound and (n)

a monoterpene-based alcohol and/or an aromatic alcohol having

10 carbon atoms as a repellant composition, a flying insect pest

repellent fragrance component is finely vaporized and

discharged from the molded silicone rubber article to thereby

exert an excellent flying insect pest repellent effect over a

predetermined period (Patent Document 6).

[0011] The flying insect pest repellent product of Patent

Document 6 was excellent in performance to repel flying insect

pests, but had problems in molding workability and mechanical

properties such as occurrence of burr during molding and poor

mold release property due to the complex shape of the flying

insect pest repellent product, etc. when the millable-type

silicone rubber composition (I) was used as a raw material.

Therefore, the present inventors decided to further consider

addition-type liquid silicone rubber compositions as the liquid

silicone rubber composition (II) as a raw material for a molded

silicone rubber article in detail. Incidentally, Japanese

Patent No. 5053114 (Patent Document 7) discloses a repellant

silicone rubber composition containing an oxime-type liquid

silicone rubber composition, which is one of condensation-type

liquid silicone rubber compositions, and acrinathrin. However,

the composition did not serve as a reference since generation

of by-products is inevitable in condensation-types, and

acrinathrin does not vaporize and discharge and thus has

completely different characteristics from those of flying

insect pest repellent fragrance components.

CITATION LIST PATENT LITERATURE

[0012]

Patent Document 1: Japanese Unexamined Patent

Application Publication No. 2002-173407

Patent Document 2: Japanese Unexamined Patent

Application Publication No. 2003-201203

Patent Document 3: Japanese Unexamined Patent

Application Publication No. S61-289002

Patent Document 4: Japanese Unexamined Patent

Application Publication No. H08-311216

Patent Document 5: Japanese Unexamined Patent

Application Publication No. 2011-26462

Patent Document 6: Japanese Patent No. 5832649

Patent Document 7: Japanese Patent No. 5053114

SUMMARY OF INVENTION TECHNICAL PROBLEM

[0013] Thus, there has been a situation where, in order

to attain a flying insect pest repellent product having a

further more excellent flying insect pest repellent effect by

using a molded silicone rubber article which is a cured product

of an addition-type liquid silicone rubber composition and

improving the molding workability and mechanical properties of

the molded silicone rubber article, and finding a flying insect

pest repellent fragrance composition having high compatibility

with the molded silicone rubber article, it is absolutely

necessary to conduct various tests, and there is no other choice

but to repeat trial and error.

[0014] With the above problems in mind, the present invention has been made. It is an object to the present invention to provide a flying insect pest repellent product which utilizes the properties of a silicone rubber and has improvedmoldingworkability, mechanicalproperties , etc., and which has an excellent ability to vaporize and discharge a flying insect pest repellent fragrance component and has an excellent repellent effect on flying insect pests, and a method for repelling flying insect pests.

SOLUTION TO PROBLEM

[0015] The present invention has found that the following

configurations have a good effect in order to achieve the above

object.

[0016] (1) A flying insect pest repellent product which

is a molded silicone rubber article having a hardness of not

more than50 degrees, the moldedsilicone rubber article holding

a flyinginsectpest 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

constituting the molded silicone rubber article, wherein

the molded silicone rubber article is a cured product of

an addition-type liquid silicone rubber composition including

(A) a methylvinylpolysiloxane, (B) a

methylhydrogenpolysiloxane as a cross-linking silicone polymer, (C) a platinum compound as a reaction catalyst, (D) a reinforcing filler, and (E) a reaction suppressing agent, the flying insect pest repellent fragrance composition includes the following (a), (b) and (c) as the flying insect pest repellent fragrance component:

(a) at least one terpene-based hydrocarbon compound

selected from the group consisting of limonene, pinene,

camphene and terpinene, and/or at least one terpene-based

ketone compound selected from the group consisting of carvone,

pulegone, menthone, camphor and piperitone,

(b) at least one ester compound selected from the group

consisting of benzyl acetate, p-t-butylcyclohexyl acetate,

menthyl acetate, linalyl acetate, benzyl benzoate, allyl

hexanoate, allyl heptanoate and allyl octanoate, and

(c) at least one terpene-based alcohol compound selected

from the group consisting of linalool, terpineol, menthol,

dihydromyrcenol, citronellol and geraniol, and

a content ratio {(X + Y) / Z} of a content X of the

terpene-based hydrocarbon compound and/or the terpene-based

ketone compound (a) and a content Y of the ester compound (b)

in total to a content Z of the terpene-based alcohol compound

(c) in the flying insect pest repellent fragrance composition

has been set to 0.2 to 4.0.

[00171 (2) The flyinginsectpest repellentproduct of (1),

wherein the molded silicone rubber article is a secondary vulcanized product in which a low molecular weight siloxane has been decreased.

[0018] (3) The flying insect pest repellent product of (1)

or (2), wherein the reinforcing filler includes a

siloxane-modified silica.

[0019] (4) The flying insect pest repellent product of any

one of (1) to (3), wherein the flying insect pest repellent

fragrance composition further contains, as the flying insect

pest repellent fragrance component, (d) at least one fragrance

selected from the group consisting of styralyl acetate,

o-t-butylcyclohexyl acetate, citronellyl acetate, phenethyl

acetate, geranyl acetate, cinnamyl acetate, tricyclodecenyl

acetate, anisyl acetate, allylcyclohexyl acetate,

allylcyclohexyl propionate, allylisobutyloxy acetate,

allyl-n-amyloxy acetate, allylcyclohexyloxy acetate,

allylphenoxy acetate, phenethyl alcohol, borneol, eugenol,

nerol, ethyllinalool, thymol, p-menthane-3,8-diol, 1,8-cineol,

diphenyloxide, citronellal, damascone, cis-jasmone and

dihydrojasmone.

[0020] (5) The flying insect pest repellent product of any

one of (1) to (4), wherein the flying insect pest repellent

fragrance composition is substantially free from citral.

[0021] (6) The flying insect pest repellent product of any

one of (1) to (5), wherein an average amount of vaporization

and discharge of the flying insect pest repellent fragrance component from the surface of the molded silicone rubber article is 0.04 to 0.9 mg/cm 2.h.

[0022] (7) The flying insect pest repellent product of (6),

wherein the molded silicone rubber article is a ring-shaped

molded rubber article including an elastic ring, which is put

around or attached to a portion of a human body or an object,

or a band-shaped molded rubber article capable of forming an

elastic ring, which is put around or attached to a portion of

a human body or an object, by joining ends together or causing

the ends to be close to each other.

[0023] (8) The flying insect pest repellent product of (7)

, wherein the flying insect pest repellent fragrance component

is vaporized and discharged over 5 to 15 hours in a state that

the ring is put around or attached to the portion of the human

body or the object.

[0024] (9) The flying insect pest repellent product of (7)

or (8), wherein the ring has a contour of a graphic shape or

a figure.

[0025] (10) A method for repelling flying insect pests

using the flying insect pest repellent product of any one of

(1) to (9), the method including:

vaporizing and discharging the flying insect pest

repellent fragrance component from a surface of the molded

rubber article.

ADVANTAGEOUS EFFECTS OF INVENTION

[0026] According to the flying insect pest repellent

product and the method for repelling flying insect pest of the

present invention, since a flying insect pest repellent

fragrance composition containing a specific flying insect pest

repellent fragrance component is held by a molded silicone

rubber article which is a cured product of an addition-type

liquid silicone rubber composition, the molding workability,

mechanical properties, etc. of said molded silicone rubber

article are improved, and the ability to vaporize and discharge

the flying insect pest repellent fragrance components and the

repellent effect on flying insect pests are further more

excellent than those of conventional products. Therefore, the

usefulness of said product and method is extremely high.

BRIEF DESCRIPTION OF DRAWINGS

[0027]

Fig. 1 is a schematic view of a ring-shaped molded rubber

article. Fig. 1 (a) shows the ring molded rubber article as

it is not attached, and Fig. 1 (b) shows the ring molded rubber

article as it is attached to a wrist, respectively;

Fig. 2 is an external view of a band-shaped molded rubber

article. Fig. 2 (a) shows the band-shapedmolded rubber article

as it is not attached, and Fig. (b) shows the band-shaped molded

rubber article as it is attached to a wrist, respectively.

DESCRIPTION OF EMBODIMENTS

[0028] The 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 willbe described together with the flyinginsect pest

repellent product. Note that the present invention is not

intended to be limited to configurations described in the

embodiments described below.

[0029] The flying insect pest repellent product of the

present invention includes a molded silicone rubber article

which is a cured product of an addition-type liquid silicone

rubber composition andhas ahardness ofnotmore than 50 degrees

(may hereinafter be abbreviated to a "molded rubber article"),

and holds a flying insect pest repellent fragrance composition

containing 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.

[0030] The addition-type liquid silicone rubber

composition contains (A) a methylvinylpolysiloxane, (B) a

methylhydrogenpolysiloxane as a cross-linking silicone

polymer, (C) a platinum compound as a reaction catalyst, (D)

a reinforcing filler, and (E) a reaction suppressing agent.

There are a one-pack type addition-type liquid silicone rubber

composition, and a two-pack type addition-type liquid silicone

rubber composition, in which two liquids are mixed during the

curing and molding of the silicone rubber, and either of which

can be used.

[0031] Examples of the methylvinylpolysiloxane (A)

include those of types (A-1) to (A-3) mentioned below, which

have vinylgroups, whichare involvedin acrosslinking reaction,

on both terminals of a molecular chain and/or side chains of

a molecular chain.

[0032] Type (A-1): methylvinylpolysiloxanes having vinyl

groups on both terminals of a molecular chain, such as a

dimethylpolysiloxane in which both terminals of a molecular

chain are capped by dimethylvinylsiloxane groups, a

methylalkylpolysiloxane in which both terminals of a molecular

chain are capped with dimethylvinylsiloxane groups, a

dimethylsiloxane-methylphenylsiloxane copolymer in which both

terminals of a molecular chain are capped with

dimethylvinylsiloxane groups, and a

dimethylsiloxane-methylalkylsiloxane copolymer in which both

terminals of a molecular chain are capped with

dimethylvinylsiloxane groups.

[0033] Type (A-2): methylvinylpolysiloxanes having vinyl

groups on side chains of a molecular chain and having no vinyl

groups on both terminals of the molecular chain, such as a methylvinylpolysiloxane in which both terminals of a molecular chain are capped with trimethylsiloxy groups, a methylvinylsiloxane-dimethylsiloxane copolymer in which both terminals of a molecular chain are capped with trimethylsiloxy groups, and a methylvinylsiloxane-methylphenylsiloxane copolymer in which both terminals of a molecular chain are capped with trimethylsiloxy groups.

[0034] Type (A-3): methylvinylpolysiloxanes having vinyl

groups on both terminals of a molecular chain and side chains

of the molecular chain.

[0035] In the addition-type liquid silicone rubber

composition, type (A-1) or type (A-3) is generally used as the

methylvinylpolysiloxane (A), and it is more preferable to use

type (A-1) and type (A-2) in combination from the viewpoint of

improving mold release property. The content of the

methylvinylpolysiloxane (A) in the addition-type liquid

silicone rubber composition is preferably 50 to 80% by mass.

[0036] The methylhydrogenpolysiloxane (B) acts as a

crosslinking agent for the methylvinylpolysiloxane (A). That

is, a hydrosilylation reaction of the hydrogen atoms bound to

the silicon atoms in the methylhydrogenpolysiloxane (B) with

the vinyl groups in the methylvinylpolysiloxane (A) occurs to

cure the addition-type liquid silicone rubber composition by

cross-linking. Examples of such methylhydrogenpolysiloxane

(B) include a methylhydrogenpolysiloxane in which both terminals of a molecular chain are capped with trimethylsiloxy groups, a dimethylsiloxane-methylhydrogensiloxane copolymer in which both terminals of a molecular chain are capped with trimethylsiloxy groups, a methylphenylsiloxane-methylhydrogensiloxane copolymer in which both terminals of a molecular chain are capped with trimethylsiloxy groups, a dimethylpolysiloxane in which both terminals of a molecular chain are capped with dimethylhydrogensiloxy groups, a methylhydrogenpolysiloxane in which both terminals of a molecular chain are capped with dimethylhydrogensiloxy groups, and a dimethylsiloxane-methylhydrogensiloxane copolymer in which both terminals of a molecular chain are capped with dimethylhydrogensiloxy groups, etc. It is necessary that the content of the methylhydrogenpolysiloxane (B) in the addition-type liquid silicone rubber composition is in an amount such that the hydrogen atoms bonded to the silicon atoms in the methylhydrogenpolysiloxane (B) with respect to 1 mol of the vinyl groups bonded to the silicon atoms in the methylvinylpolysiloxane (A) is in the range of 0.5 to 3 mol, and is preferably 5 to 15% by mass.

[0037] The platinum compound (C) acts as a hydrosilylation

reaction catalyst to accelerate a hydrosilylation reaction of

the hydrogen atoms bonded to the silicon atoms in the

methylhydrogenpolysiloxane (B) to the vinyl groups in the methylvinylpolysiloxane (A). Examples of such platinum compound (C) include compounds that are well-known as hydrosilylation reaction catalysts such as platinum black, a platinum-supported alumina powder, a platinum-supported silica powder, a platinum-supported carbon powder, chloroplatinic acid, a complex of chloroplatinic acid and an olefin, a complex of chloroplatinic acid and a diketone, and a complex of chloroplatinic acid and

1,3-divinyltetramethyldisiloxane. A catalytic amount is

sufficient as the content of the platinum compound (C) in the

addition-type liquid silicone rubber composition, and the

amount is preferably 0.01 to 1.0% by mass so as to suppress an

increase in the costs of the flying insect pest repellent

product.

[00381 The reinforcing filler (D) makes the addition-type

liquid silicone rubber composition viscous to improve the

molding workability, improve the mechanical properties of the

molded silicone rubber article, and eventually improve the mold

release property from a mold. Examples of such reinforcing

filler (D) include fumed silica (dry process silica),

precipitated silica (wet process silica), light calcium

carbonate, fumed titanium oxide, carbon black, etc., and a

siloxane-modified silica obtained by imparting hydrophobicity

to a surface of a dry process silica or a wet process silica

by using a surface treating agent such as hexamethyldisilazane

(HMDS), polydimethylsiloxane (PDMS) or dimethyldichlorosilane

(DDS) is specifically preferable. The content of the

reinforcing filler (D) in the addition-type liquid silicone

rubber composition can be suitably preset with consideration

for the viscosity of the addition-type liquid silicone rubber

composition and the mechanical properties of the molded

silicone rubber article, etc., and is preferably 10 to 50% by

mass.

[00391 The reaction suppressing agent (E) prevents the

addition-type liquid silicone rubber composition from curing

at an ordinary temperature, and allows the composition to be

cured during heating. Examples of such reaction suppressing

agent (E) include 3-methyl-1-butyne-3-ol,

3,5-dimethyl-1-hexyne-3-ol, 1-ethynylcyclohexanol, propargyl

alcohol, etc. The content of the reaction suppressing agent

(E) in the addition-type liquid silicone rubber composition is

preferably 0.001 to 0.1% by mass.

[0040] The addition-type liquid silicone rubber

composition used in the present invention may contain, besides

the above-mentioned components (A) to (E), bulking fillers such

as calcined silica micropowder, microsilicate powder,

pulverized quartz, cristobalite powder, titanium oxide powder

and magnesium oxide powder, and may appropriately include

well-known additives such as pigments, heat-resistant agents,

flame retarders, non-crosslinkable silicone oils, antibacterial agents and anti-mold agents.

[0041] The addition-type liquid silicone rubber

composition can be cured and molded by a well-known molding

apparatus and amoldingmethod. As the cure-molding apparatus,

a compression molding machine, a transfer molding machine and

an injection molding machine, etc. used in a general method for

molding a liquid silicone rubber composition can be used. At

this time, if the temperature for curing the liquid silicone

rubber composition is too low, the curing rate is slow and the

producibility is lowered, whereas if the curing temperature is

too high, the mechanical strength of the molded silicone rubber

article is lowered. Therefore, the cure temperature is

preferably 50 to 2400C, more preferably 120 to 2100C.

[0042] Incidentally, it is also possible to control the

amount of vaporization and discharge of the flying insect pest

repellent fragrance composition, which is added later, by

adjusting the crosslinking density of the cured product of the

addition-type liquid silicone rubber composition, or by

adjusting the contents of a reinforcing filler and a bulking

filler, which are used as the additives for the addition-type

liquid silicone rubber composition, or the content of a

non-crosslinkable silicone oil.

[0043] The molded silicone rubber article obtained by

curing and molding the addition-type liquid silicone rubber

composition are stable in view of physical properties, whereas itis known that, in the case where lowmolecular weight siloxane components, etc. remain in the molded rubber article, these may adversely affect the physical properties and may cause yellowing in the molded rubber article itself. Furthermore, the process of the consideration on the flying insect pest repellent flavor material component by the present inventors has revealed that there are flavor materials that are labile to the effects of components remaining in a molded rubber article, such as citral. Therefore, it is preferable that the molded silicone rubber article used in the present invention is a secondary vulcanized product in which low molecular weight siloxanes have been reduced by undergoing a post cure treatment

(secondary vulcanization treatment) after the curing by using

an oven, etc. for about 1 to 15 hours at a temperature of 160

to 2400C, preferably for about 2 to 7 hours at a temperature

of 190 to 2200C. It was found that, by undergoing the post cure

treatment, the molded rubber article can further be stabilized

in view of physical properties to suppress not only the

yellowing or browning of the molded rubber article itself but

also the yellowing or browning which can occur due to an

interaction with the flavor material.

[0044] The molded silicone rubber article has physical

properties that it is excellent in gas permeability and it is

excellent in ability to adsorb and discharge fragrance

materials. This is considered to 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. Specifically, if the hardness of the molded rubber article is not more than

50 degrees, the molecular structure of the silicone rubber does

not become excessively dense, and thus the fragrance molecules

easily enter into interstices of the molecular structure of the

rubber. If the hardness of the molded rubber article is more

than 50 degrees, the silicone rubber has a very dense molecular

structure, and therefore, it becomes difficult for fragrance

molecules to enter interstices of the molecular structure of

the rubber, which does not conform with the gist of the present

invention. 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.

[0045] The present invention is characterized by that it

has attained a flying insect pest repellent product in which

the molding workability, mechanical properties, etc. have been

improved by using the molded rubber article obtained as above

which is a cured product of an addition-type liquid silicone

rubber composition andhas ahardness ofnotmore than50 degrees,

and which has a more excellent repellent effect on flying insect

pests than those of conventional products by finding an optimal flying insect pest repellent fragrance composition for said molded rubber article. In Japanese Patent No. 5832649 (Patent

Document 6), the present inventors disclosed that, in the case

where a molded rubber article of both (I) a cured product of

a millable-type silicone rubber composition, and (II) a cured

product of a liquid silicone rubber composition were used, a

mixture containing (m) a specific acetic acid ester compound

and (n) a monoterpene-based alcohol and/or an aromatic alcohol

having 10 carbon atoms was preferable as a flying insect pest

repellent fragrance composition which has compatibility to

these cured products.

[0046] Thereafter, the present inventors continued

further consideration on (II) a molded rubber article which is

a cured product of an addition-type liquid silicone rubber

composition among liquid silicone rubber compositions, and

consequently found that, unlike the case of Patent Document 6,

a specific flying insect pest repellent fragrance component is

the optimum in view of compatibility with a molded rubber

article which is a cured product of the addition-type liquid

silicone rubber composition, and achieved the flying insect

pest repellent product of the present invention.

[0047] The flying insect pest repellent fragrance

composition used in the flying insect pest repellent product

ofthe presentinvention contains substantiallynoinsecticidal

component, and contains a fragrance component as a flyinginsect pest repellent component. Such a fragrance component is referred to as a "flying insect pest repellent fragrance component." The flying insect pest repellent fragrance composition contains, as the flying insect pest repellent fragrance component, a component (a), a component (b) and a component (c) mentioned below.

[0048] Examples of the component (a) include

terpene-based hydrocarbon compounds such as limonene, pinene,

camphene and terpinene, and/or terpene-based ketone compounds

such as carvone, pulegone, menthone, camphor and piperitone.

These terpene-based hydrocarbon compounds and/or

terpene-based ketone compounds may be used alone or in

combination.

[0049] Examples of the component (b) include ester

compounds such as benzyl acetate, p-t-butylcyclohexyl acetate,

menthyl acetate, linalyl acetate, benzyl benzoate, allyl

hexanoate, allyl heptanoate and allyl octanoate. These ester

compounds may be used alone or in combination.

[0050] Examples of the component (C) include

terpene-based alcohol compounds such as linalool, terpineol,

menthol, dihydromyrcenol, citronellol and geraniol. These

terpene-based alcohol compounds may be used alone or in

combination.

[0051] It was recognized from the results of the intensive

studies by the present inventors that, when a content ratio { (X

+ Y) / Z} of a content X of the component (a) and a content Y

of the component (b) in total to a content Z of the component

(c) is set to 0.2 to 4.0, preferably 0.78 to 1.8 in the flying

insect pest repellent product of the present invention, the

components conform with the molded rubber article which is a

cured product of the addition-type liquid silicone rubber

composition, and an excellent vaporizing and discharging

ability and an excellent flying insect pest repellant result

can be obtained.

[0052] The flying insect pest repellent fragrance

composition may further contain a component (d) mentionedbelow

as the flying insect pest repellent fragrance component.

[0053] Examples of the component (d) include fragrances

such as styralyl acetate, o-t-butylcyclohexyl acetate,

citronellyl acetate, phenethyl acetate, geranyl acetate,

cinnamyl acetate, tricyclodecenyl acetate, anisyl acetate,

allylcyclohexyl acetate, allylcyclohexyl propionate,

allylisobutyloxy acetate, allyl-n-amyloxy acetate,

allylcyclohexyloxy acetate, allylphenoxy acetate, phenethyl

alcohol, borneol, eugenol, nerol, ethyllinalool, thymol,

p-menthane-3,8-diol, 1,8-cineol, diphenyloxide, citronellal,

damascone, cis-jasmone and dihydrojasmone. These fragrances

maybeused alone orin combination. Incidentally, sincecitral

has a possibility to be affected by the residual components in

the molded rubber article to cause a problem of coloring, it is preferable that the flying insect pest repellent fragrance composition is substantially free from citral in the flying insect pest repellent product of the present invention.

[0054] The following various essential oils containing the

above fragrance components such as jasmine oil, neroli oil,

peppermint oil, lavender oil, bergamot oil, orange oil,

geranium oil, petitgrain oil, lemon oil, citronella oil,

cinnamon oil, eucalyptus oil, lemon eucalyptus oil and thyme

oil, etc. may be suitably added to the flying insect pest

repellent fragrance composition. Since such essential oils

contain the components (a) , (b) and (c) mentioned above, it is

also possible to supply the components (a), (b) and (c) to the

flying insect pest repellent fragrance composition so that a

stronger flying insect pest repellent effect is exerted, by

adjusting the contents of the essential oils.

[0055] The flying insect pest repellent fragrance

composition preferably further contains a repellent effect

sustaining component during the 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.

[0056] Specificexamples of the above glycoland/or glycol

ether (followedby 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 glycolethers may be used alone or in combination.

The blend ratio of the glycol and/or glycol ether to the flying

insect pest repellent fragrance materialis suitably about 0.2

10.

[0057] 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 insecticidalcomponent

include empenthrin, profluthrin, transfluthrin, and

metofluthrin, which are members of the family of pyrethroids

which vaporize and discharge at an ordinary 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.

[00581 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 flyinginsect pest repellent fragrance

compositionmaybe encapsulatedintomicrocapsules or entrapped

into a cyclodextrin, 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.

[00591 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. These solvents may be used alone or

in combination. 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.

[00601 The flying insect pest repellent fragrance

composition mentioned above is added to a molded rubber article

which is a cured product of an addition-type liquid silicone

rubber composition andhas ahardness ofnotmore than50 degrees,

followedby apredetermined treatment, so that the molded rubber

article holds the flying insect pest repellent fragrance

composition, whereby the flying insect pest repellent product

of the present invention is completed. By allowing the flying

insect pest repellent fragrance component to discharge from the

surface of the molded silicone rubber article 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.

[0061] 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 placedin 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 under stirring. 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.

[0062] The amount (amount of retention) 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 ofuse of the flyinginsect 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 5-15 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 15-30 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.

[00631 The shape and specification of the molded rubber

article are explained below. As the shape of the molded rubber

article, a ring shape, a band-shape, a small strip sheet-shape,

etc. can be suitably adopted, and the molded rubber article is

preferably constituted as a ring-shaped molded rubber article

including an elastic ring, which is put around or attached to

a portion of a human body or an object, or a band-shaped molded

rubber article capable of forming an elastic ring, which is put

around or attached to a portion of a human body or an object,

by joining ends together or causing the ends to be close to each

other.

[0064] In the ring-shaped molded rubber article and the

band-shaped molded rubber article holding the flying insect

pest repellent fragrance composition, when the ring 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,

the flying insect pest repellent fragrance component is

gradually vaporized and discharged from the surface of the ring-shaped molded rubber article and the band-shaped 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 amount of vaporization and discharge of the flying insect pest repellent fragrance component (the average amount of vaporization and discharge per a unit surface area) is preferably 0.04-0.9 mg/cm 2 .h over the surface area of the entire molded rubber article in order to maintain that vaporization and discharge performance. If the average amount 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 amount ofvaporization and discharge

of the flying insect pest repellent fragrance component is less

than 0.04 mg/cm2 .h, the flying insect pest repellent effect is

not sufficient. If the average amount 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 compositionwhichis heldin 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 amount 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/cm 2.h.

[00651 As the ring-shaped molded rubber article, a

string-shaped article withalinked surrounding (wire diameter:

1 to 3 mm, length: about 10 to 20 cm) so that the molded rubber

article is easily put around or attached to a portion of a human

body such as a wrist or an ankle or the above-mentioned object,

and is preferably formed into a graphic shape or a figure. Fig.

1 shows a schematic view of the ring-shaped molded rubber

article 1. Fig. 1 (a) shows the ring molded rubber article 1

as it is not attached, and Fig. 1 (b) shows the ring molded rubber

article 1as it is attached to awrist 2. The ring-shapedmolded

rubber article 1 has an elastic ring, which is put around or

attached to a portion of a human body or an object. As shown

in Fig. 1 (a), the contour of the ring has a contour of graphic

shape or a figure. Examples of the graphic shape or a figure

include, but are naturally not limited to, animals, insects,

vehicles and alphabets. It is preferable that the ring-shaped

molded rubber article 1 has an original shape which stretches

or shrinks when a part of the article is extended and attached

to a wrist, an ankle, etc. so as to form an attached state in

which at least 20%, preferably 30% of said part is distant from

the skin of the wrist or ankle. This is because not only the gap portion contributes to the improvement of the vaporization and discharge of the repellant fragrance component but also it is desirable to prevent the repellant fragrance component, even it is a fragrance component, from contacting with the skin, to the extent possible. Fig. 1 (b) shows a gap portion 3, which has been formedby distancing apart of the molded rubber article

1 from the wrist 2.

[00661 Although the main portion of the ring-shaped molded

rubber article is a graphic shape or a figure formed from one

string-shaped article, it is also preferable to form branched

portion(s) by forming branch(es) from one or more portion(s)

of this string-shaped article molded rubber article to form

additional accessories. By doing so, decorativeness is

imparted, and the weight of the molded rubber article can be

increased to thereby increase the amount of the flying insect

pest repellent fragrance component held by the molded rubber

article, which leads to an advantage that the number of the

flying insect pest repellent products of the present invention

to be put to a wrist, an ankle, etc. can be decreased. The shape

and size of each accessory are not specifically limited as long

as the ability of this portion to vaporize and discharge the

fragrance component is not excessively greater or smaller than

that of the main portion having a graphic shape or a figure.

[0067] The band-shaped molded rubber article is not

specifically limited as long as the shape before use is a band-shape, and is easily used at a size with a width of about

0.5 to 2.0 cm, a length of about 10 to 25 cm and a thickness

of about 1 to 3 mm. For example, it is preferable that the

band-shaped molded rubber article is of a shape having a

band-shaped portion formed by a row ofparts eachhaving at least

one void and a void-surrounding portion surrounding said void,

and joint portions that are configured to join the ends of the

band-shaped portion together or causing the ends to be close

to each other to form an elastic ring, which is put around or

attached to a portion of a human body or an object, or a shape

having a band-shaped portion having at least one projection on

one end, and a joint portion configured to fit the projection

therein to form an elastic ring, which is put around or attached

to a portion of a human body or an object. The band-shaped

portion serves as a main material (main body) of the molded

rubber article. The band-shaped portion can retain elasticity

which is equivalent or more than that of a molded rubber article

which has been simply formed into a string shape, and has no

problem in view of strength. The joint portion is configured

to change the shape of the molded rubber article (flying insect

pest repellent product) before use, which has a band-shape, to

a ring-shape upon use, and temporary fix the shape. Since the

size of the formed ring can be adjusted by the joint portion,

the state of attachment to a portion of a human body or an object

can be suitably 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 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 the skin of a wrist, an ankle, etc., with a gap between the molded rubber article and the skin being maximized.

A preferable constitution of the joint portion include a

specification in which a plurality of receiving portions is

disposed on one end of a band-shaped portion (or the other end)

and one or more projection(s) is/are disposed on the other end

(or the one end). Specifically, for example, the joint portion

can be designed by disposing three to seven circular

thorough-holes as receivingportions along the lengthdirection

so that a T-shaped projection disposed on the other end is set

in either of the thorough-holes to form a ring. Alternatively,

the joint portion can be designed by disposing six to ten

circular thorough-holes as receiving portions along the length

direction so that two to four projections disposed on another

end are set in the thorough-holes to form a ring.

[00681 The voids present in the band-shaped portion

generate a diffusing airflow to contribute to the improvement of vaporization and discharge performance. The sizes and shapes of the voids in the band-shaped portion 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, need to be determined, taking these factors into account. It is preferable that the sizes of the voids are set so as to satisfy

0.05 S1/ S2 0.6, where Si represents the total area of the

voids, and S 2 represents the area of the entire molded rubber

article (including Si), as measured when the molded rubber

article is in an unstretched state, for example. If the value

of SI/S 2 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 Si/S 2

exceeds 0.6 (i.e., the area percentage of the voids with respect

to the molded rubber article exceeds 60%), it is probable that

aproblemis causedin the strengthof the moldedrubber article.

[00691 The voids may each be shaped such that a contour

thereofhas 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 U-shaped 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.

[0070] It is preferable that the band-shapedmolded rubber

article has elasticity so that when an elastic ring, which is

put around or attached to a portion of a human body or an object,

is formed, an attached state in which at least 20%, preferably

30% of saidportion is distant from the skin ofawrist, an ankle,

etc. is formed.

[0071] An example of a band-shaped molded rubber article

100 including a band-shaped portion 10 and a joint portion 20,

which is used as the flying insect pest repellent product of

the presentinvention, is shownin Fig.2. Fig. 2 is an external

view of the band-shaped molded rubber article 100. Fig. 2 (a)

shows the band-shaped molded rubber article 100 as it is not

attached, and Fig. 2 (b) shows the band-shaped molded rubber

article 100 as it is attached to a wrist H by linking the both

ends of the band-shaped molded rubber article 100. In the

band-shaped molded rubber article 100, a plurality of portions

1A each having a void having a contour fashioned after a star

are connected in a row.

[0072] Examples of the flying insect pest repellent

product include a wrist ring, a wrist band, etc. using the

ring-shaped molded rubber article and the band-shaped molded

rubber article mentioned above. 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 watchstrap so that the moldedrubber article canbe 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. Such combination of the molded rubber article and the

accommodation portion can be applied to not only flying insect

pest repellentproducts forhumanbodies, but also flyinginsect

pest repellent products of various forms such as place-type

flying insect pest repellent products for use in spaces in

vehicles, etc., suspending-type flying insect pest repellent

products, etc., as long as the vaporization and discharge

performance of the flying insect pest repellent fragrance

component is ensured.

[0073] When one to five of the flyinginsect pest repellent

products of the present invention thus obtained are attached

to a site such as awrist or an ankle, in aroomsuchas an entrance,

a kitchen, a bathroom, a living room, or a bedroom, a space such

as a warehouse or a 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 component 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

[0074] The Examples of the flying insect pest repellent

product of present invention are explained below.

[0075] [Example 1]

As a two-pack type addition-type liquid silicone rubber

composition, silicone rubber composition liquids 1 and 2 were

prepared at the following formulations, and the prepared

silicone rubber composition liquids 1 and 2 were mixed at room

temperature, and the mixture was cured at 1400C by using an injection moldingmachine to mold the mixture into a string ring shape fashioned after a figure of an animal (wire diameter: about 2 mm, weight: 1.6 g, hardness: 32 degree). After the molding, the molded article was put into an oven and subjected to a post cure treatment at 2100C for 5 hours to give a molded silicone rubber article.

Silicone rubber composition liquid 1

Component (A): a methylvinylpolysiloxane in which both

terminals of a molecular chain are capped with

dimethylvinylsiloxane groups 63% by mass

Component (C): a complex of chloroplatinic acid and

1,3-divinyltetramethyldisiloxane 0.05% by mass

Component (D): a siloxane-modified silica (using HMDS as

a surface treating agent) 20% by mass

Bulking filler: a microsilicate powder 16.95% by mass

Silicone rubber composition liquid 2

Component (A): a methylvinylpolysiloxane in which both

terminals of a molecular chain are capped with

dimethylvinylsiloxane groups 63% by mass

Component (B): a methylhydrogenpolysiloxane in which

both terminals of a molecular chain are capped with

trimethylsiloxy groups 7.6% by mass

Component (D): a siloxane-modified silica (using HMDS as

a surface treating agent) 20% by mass

Component (E): 1-ethynylcyclohexanol 0.05% by mass

Bulking filler: microsilicate powder 9.35% by mass

[0076] A flying insect pest repellent fragrance

composition was prepared by the following formulation. This

flying insect pest repellent fragrance composition was free

from citral as a flying insect pest repellent fragrance

component, and had a content ratio { (X + Y) / Z} of a content

X of the component (a) to a content Y of the component (b) in

total to a content Z of the component Z of 1.1.

- Flying insect pest repellent fragrance composition (30

mg per one molded rubber article)

Component (a): 1-carvone 14.3% by mass (4.3 mg)

Component (b): benzyl acetate 7.0% by mass (2.1 mg)

p-t-Butylcyclohexyl acetate 4.0% by mass (1.2 mg)

Benzyl benzoate 6.7% by mass (2.0 mg)

Allyl heptanoate 5.7% by mass (1.7 mg)

Component (c): linalool 10.3% by mass (3.1 mg)

Terpineol 9.7% by mass (2.9 mg)

Dihydromyrcenol 8.3% by mass (2.5 mg)

Geraniol 4.7% by mass (1.4 mg)

Component (d): styralyl acetate, thymol and

p-menthane-3,8-diol 12.6% by mass (3.8 mg) in total

Repellent effect sustaining component: dipropylene

glycol 16.7% by mass (5.0 mg)

[0077] One hundred pieces of string ring-shaped molded

silicone rubber articles were put into a sealed container equipped with a spraying apparatus, and the flying insect pest repellent fragrance composition prepared was sprayed by using this spraying apparatus so that the amount of adsorption per one molded rubber article was 30 mg (25.0 mg as the flying insect pest repellent fragrance component). After sufficient stirring, 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 having a wrist-ring shape and an effective sustained period of about 10 hours (Example 1) were obtained. In addition, alternatively, a molded silicone rubber article having a hardness of 80 degrees was separately tested in a similar manner. However, the flying insect pest repellent fragrance composition was adsorbed in only a small amount, and therefore, the flying insect pest repellent of the present invention was not obtained.

[0078] The flyinginsect pest repellent product ofExample

1 had an average amount of vaporization and discharge of the

flying insect pest repellent fragrance component of 0.35

mg/cm 2.h (from the time when the use was initiated to 2 hours

after the initiation of use) over the entire surface area, and

when the product was put around a wrist, about 44% of the wrist

ring was distant from the skin of the wrist. When the

experimenter stayed outdoors with two pieces of the flying insect pest repellent products of Example 1 worn on either wrist

(two 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.

[0079] [Examples 2 to 10 and Comparative Examples 1 to 5]

A string ring-shaped molded rubber article, which is a

cured product of an addition-type liquid silicone rubber

composition, was formed by molding according to Example 1,

except that the components (A) and (D) of the addition-type

liquid silicone rubber composition were changed to the

composition shown in Table 1, and allowing the molded rubber

article to adsorb a flying insect pest repellent fragrance

composition, of which composition is shown in Table 2, to give

the flying insect pest repellent product of the present

invention (Examples 2 to 10) . In Table 1, "A-1" is a

dimethylpolysiloxane in which both terminals of a molecular

chain are capped with dimethylvinylsiloxane groups, "A-2" is

a methylvinylpolysiloxane in which both terminals of a

molecular chain are capped with trimethylsiloxy groups, and

"A-3" is a methylvinylpolysiloxane in which both terminals of

amolecular chain are cappedwithdimethylvinylsiloxane groups.

Furthermore, "Siloxane-modified silica P" is a

siloxane-modified silica subjected to a surface treatment by

using HMDS, and "Siloxane-modified silica Q" is a

siloxane-modified silica subjected to a surface treatment by

using PDMS.

[0080] [Table 1]

Addition-type liquid silicone rubber composition Postcure

Component (A) (% by mass) Component (D) (% by mass)

2 A-3 63 Siloxane-modified silica P 20 Conducted

A-i 43 A-2 20 Fumed silica 20 Conducted 3

4 A-3 63 Siloxane-modifiedsilicaQ 20 Conducted

5 A-3 63 Siloxane-modified silica P 20 Conducted

6 A-3 63 Siloxane-modified silica P 20 Notconducted

7 A-3 63 Silica 20 Conducted

8 A-3 63 Silica 20 Conducted

9 A-3 63 Silica 20 Notconducted

10 A-3 63 Silica 20 Not conducted

1 20 A-3 Mi6abe-type 63 silicone rubber composition Silica 20 Conducted Not conducted E 2 A-3 63 Silica 20 Not conducted

4 A-3 63 Silica 20 Not conducted

o 5 A-3 63 Silica 20 Not conducted

[0081] [Table 2]

0 0 0 0

E) -N

r0 a) c I I (U >

0 co

a 0

4-, Oco o 00 00 00 00 0 - 41- ~ r- r-: r-: r- r C: C) C

cl ( l r- r- r- r- r- m0 m0 04 C4 CN (Ni CN C(N m

-a

00 0 0 0

coC -uca0 Q 0 0 I

2 EOCW > e 1 --'.r co 00 :E C.1 CD) cn)-CL Z a- z~ 0. C. -.

N m- 0LO C- ( 240 ,*- ur d0 00d0 d,:> a) )

l r_ a 0Cu

C) 0 0 S) -E Co

41 CD S~ _j) IV 2j r- LO -r CO )4 4-o C4 ) , C 04 C4 ) Coq 4 C* 4 t 4 C C

41 (n 4)

4-, 4) a) 4 0 +

4) 4)ID4 a 'o m 4Z x +

C E C- 41 N N 0 NO0 NQ O N ) - 1 C ))C 0OC C C CC LL 4 cuO4C L'C 4 t cct ) a .t ~U ~ 0 Cc cCc Cc Cc )

M CL -,a x-0 -0 x -0 x -Ox 5 x Ox (

0 c~>C 3~ 'C >. C > > r > -C: >.c > 2NN 4 N N N N N N N N a) a)i CO44=, Co

CNC MN LN 0cu MN (N cN co

) W) 0 C ) 0 0 0) 4) 0) 0) 0~ 0) 0 >: C C C _r -C O_ > C C-CC.C 4.0 CL -- 4E ) 4-' 41 1 4-'

(N 00 W~ a)) (0 00 a)-

saldwu4X3

[0082] A string ring-shaped molded rubber article (a cured

product of a millable-type silicone rubber composition) was

formed into the same shape as that of Example 1, and this molded

rubber article was allowed to adsorb a flying insect pest

repellent fragrance composition, of which composition is shown

in Table 3, to give a flying insect pest repellent product which

was out of the scope of the present invention (Comparative

Example 1) Furthermore, a string ring-shaped molded rubber

article (a cured product of an addition-type liquid silicone

rubber composition) was formed by molding according to Example

1, except that the components (A) and (D) were changed to the

composition shown in Table 1, and the molded rubber article was

allowed to adsorb a flying insect pest repellent fragrance

composition, of which composition is shown in Table 3, to give

a flyinginsect pest repellent product whichwas out ofthe scope

of the present invention (Comparative Examples 2 to 5).

[0083] [Table 3]

LO cc c

0N co c co 0 6 CC

0

-o0 0 0 0 0 41) ID (D a) a)

00 00 00 00 0 E) 0 a)4) V1 W 0 Cn C C C C E E i I I I 4a 0 00 w co co co

N C -'-* 0 Q, -r-'P c ' Icr- DC mtr- C o 2 a 0

o : c 00 C C u a o. o. o o (a - o C: - C: r I 4- C: 0 O ) cuEw Ci

0O a- C r- r- ~r'

(0

a0C 0 0 m V 3 N. N 0N 0 N

o O NQ NO NOM -0' C -x x x -0x ~ a- >Z >C -5,-2 - >4-C C 00N _ N~ - N - N cE c > c> c > c:> 30 D a)= 0= V LL oo mm< c X CN? CN? C'J U?

0 V 0 0 0

+J 4 4) +)

O 0D V D a)) __ oIt - c'~i Cc l U

seidwEX3GAi;2JedW09

[0084] For the flying insect pest repellent products of

Examples 2 to 10 and the flying insect pest repellent products

of Comparative Examples 1 to 5 obtained as above, the following

evaluations and tests were carried out. [1] Evaluation of the

molding workability of the molded rubber article, [2]

Evaluation of the mold release property of the molded rubber

article, [3] Evaluation of the coloring on the surface of the

molded rubber article, [4] Test on the flying insect pest

repellent effect, and [5] Tests for measuring the amount of

vaporization and discharge of the flying insect pest repellent

fragrance component.

[0085] [1] Evaluation of the molding workability of the

molded rubber article

The molding workability of the molded rubber article used

in the flying insect pest repellent product was evaluated by

the following four scales: © (very good), 0 (good), A (poor)

and X (very poor).

[0086]

[2] Evaluation of the mold release property of the molded rubber

article

The mold release property of the molded rubber article

used for the flying insect pest repellent product was evaluated

by the following four scales: © (very good), 0 (good), A

(poor) and X (very poor).

[0087]

[3] Evaluation of the coloring on the surface of the molded

rubber article

The presence or absence of coloring on the surface of the

molded rubber article in the flying insect pest repellent

product was evaluated by the following four scales: © (no

coloring was observed), 0 (slight coloring was observed), A

(coloring was observed: yellowing) and X (coloring was

observed: brown spots).

[00881 [4] Test on the flying insect pest repellent effect

In a testing room (about 6 M3 ), two plastic cups (about

1 L) with no lid, which were therefore open, were placed side

by side. A Culex pipiens pallens attractant and a specimen

flying insect pest repellent product were placed in one

(treatment zone) of the two cups, and only the Culex pipiens

pallens attractant was placed in the other plastic cup (control

zone). At two hours after the initiation of use, and at seven

hours after the initiation of use, about 50 adults of Culex

pipiens pallens (female) were released in the room. The number

ofinsects entering aplasticcupin each zone was counted. The

flying insect pest repellency rate was calculated by:

Flying insect pest 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

[00891

[5] Test for measuring the amount of the vaporization and

discharge of the flying insect pest repellent fragrance

component

The weight of the flying insect pest repellent product

was measured at the time when the use was initiated, at two hours

after the initiation of use, and at seven hours after the

initiation of use, and based on the amounts of weight loss, the

average amounts of vaporization and discharge per unit surface

area and unit time from the time when the use was initiated to

two hours after the initiation of use, and from two hours after

the initiation of use to seven hours after the initiation of

use were calculated.

[00901 The results of the evaluation and tests are shown

in Table 4.

[0091] [Table 4]

Average amount of Mold Presence Flying insect pest vaporization and Molding release or absence repellency rate (%) discharge workability property of coloring (mg/cm h) 2h later 7h later 0~2h 2-7h 2 0 ©0 © 100 100 0.40 0.35 3 ©-0 ©0 96 93 0.37 0.32 4 © ©0 © 94 91 0.34 0.28 5 © ©~0 © 95 86 0.42 0.27 E 6 ©~0 0 0 93 84 0.39 0.23 wU 7 0- 0 0 0_0 90 83 0.38 0.25 8 0-0 0 @_-0 89 81 0.37 0.261 9 0 0 0-A 87 80 0.34 0.22 10 0 0 0 95 87 0.40 0.26 1 A A 0 87 79 0.35 0.18 -T 2 0 0 0-A 75 58 0.30 0.21 3 0 0 0-A 62 47 0.24 0.16 4 0 0 0-A 66 50 0.23 0.14 0 5 0 0 0-A 71 56 0.29 0.17

[0092] As a result of the tests, in the flying insect pest

repellentproducts ofExamples 2 to 10 (amolded silicone rubber

articles which is a cured product of an addition-type liquid

silicone rubber composition, holding a flying insect pest

repellent fragrance composition containing specific flying

insect pest repellent fragrance components), when the average

amounts of vaporization and discharge from the time when the

use was initiated to two hours after the initiation of use and

from two hours after the initiation of use to seven hours after

the initiation of use, and the flying insect pest repellency

rates at two hours after the initiation of use and at seven hours

after the initiation ofuse were verified, it was confirmed that

a satisfying flying insect pest repellent effect with an excellent ability to vaporize and discharge the flying insect pest repellent fragrance component was exerted. The specific flying insect pest repellent fragrance component used herein contained (a) a terpene-based hydrocarbon compound and/or a terpene-based ketone compound, (b) an ester compound, and (c) a terpene-based alcohol compound, wherein a content ratio { (X

+ Y) / Z} ofacontentXofthe terpene-basedhydrocarbon compound

and/or terpene-based ketone compound (a) and a content Y of the

ester compound (b) in total to a content Z of the terpene-based

alcohol compound (c) was adjusted to 0.2 to 4.0. On the other

hand, the flying insect pest repellent products being free from

either of the components (a), (b) and (c) as the specific flying

insect pest repellent fragrance component (Comparative

Examples 2 to 4), and the flying insect pest repellent product

in which the content ratio of those components was out of the

range defined in the present invention (Comparative Example 5)

had a poor ability to vaporize and discharge the flying insect

pest repellent fragrance component and a poor repellent effect.

Furthermore, the flying insect pest repellent products of

Examples 2 to 10, which contained a molded silicone rubber

article being a cured product of an addition-type liquid

silicone rubber composition, were superior in molding

workability and mold release property to those of the flying

insect pest repellent product of Comparative Example 1, which

contained amolded silicone rubber article being acuredproduct of a millable-type silicone rubber composition.

[00931 It was confirmed that the flying insect pest

repellent products of Examples 2 to 4 containing the repellent

effect sustaining component were able to stably sustain the

repellent effect even seven hours after the initiation of use.

Furthermore, it was confirmed that the mold release property

was improvedin Example 3, in which (A-1) a dimethylpolysiloxane

in which both terminals of a molecular chain are capped with

dimethylvinylsiloxane groups and (A-2) a

methylvinylpolysiloxane in which both terminals of a molecular

chain are capped with trimethylsiloxy groups were in

combination as the component (A) of the addition-type liquid

silicone rubber composition. Furthermore, it was confirmed

that Examples 2 and 4 to 6were excellentinmoldingworkability,

and thus use of a siloxane-modified silica as the component (D)

of the addition-type liquid silicone rubber composition was

effective for improving the moldingworkability. Furthermore,

citral was incorporated as a flying insect pest repellent

fragrance component in both the flying insect pest repellent

product of Example 8 and the flying insect pest repellent

product of Example 9, and the degree of coloring was suppressed

more in Example 8, in which the molded silicone rubber article

was subjected to a post cure treatment, than that in Example

9. It was confirmed from this fact that molded silicone rubber

article can be stabilized in terms of physical properties and the problem of coloring can be improved by subjecting the molded silicone rubber article to a post cure treatment.

[0094] [Examples 11 to 16]

An addition-type liquid silicone rubber composition was

cured according to Example 5, andmolded into a string ring shape.

After the molding, the product wasputinto an oven and subjected

to a post cure treatment under various conditions shown in Table

5 to give amolded silicone rubber article. The obtained molded

rubber article was allowed to adsorb a flying insect pest

repellent fragrance composition according to Example 5 to give

the flying insect pest repellent product of the present

invention (Examples11to 16). The flyinginsectpest repellent

product of Example 11 was the same as the flying insect pest

repellent product of Example 5. The flying insect pest

repellent products of Examples 11 to 16 obtained were subjected

to [4] Test on the flying insect pest repellent effect, and [5]

Test on the amount of vaporization and discharge of the flying

insect pest repellent fragrance component mentioned above (the

details of the test results are omitted), and it was confirmed

that either of the products had an excellent vaporization and

discharge ability and an excellent flying insect pest repellent

effect which were similar to those of the flying insect pest

repellent product ofExample 5. Furthermore, the flyinginsect

pest repellent products of Examples 11 to 16 were subjected to

[1] evaluation of the molding workability (including the post cure treatment workability) of the molded rubber article and

[3] evaluation of the coloring on the surface of the molded

rubber article mentioned above. The results of the evaluation

are shown in Table 5.

[0095] [Table 5]

Conditions for post cure treatment Molding Presence workability or absence Treatment Treatment time (h) of coloring temperature (C) 11 210 5 © © 12 190 4 © © a 13 160 7 © 0 E X 14 240 2 © 0 15 140 10 0 A 16 260 2 0 x

[0096] As a result of the evaluation, all of the flying

insectpestrepellentproducts ofExamples11to14 specifically

had very excellent molding workability of the molded rubber

article, and the coloring on the surface of the molded rubber

article was suppressed to a certain extent or more. That is,

it was confirmed that the molded silicone rubber article was

changed to a secondaryvulcanizedproductin whichlowmolecular

weight siloxanes had been decreased by the post cure treatment.

Specifically, in the flying insect pest repellent products of

Examples 11 and 12, in which the treatment temperature for the

post cure treatment was 190 to 210°C and the treatment time was

4 to 5 hours, the molded rubber article had very excellent

molding workability, whereas coloring was not observed at all on the surface of the molded rubber article.

[0097] On the other hand, coloring was observed on the

surface of the molded rubber article in the flying insect pest

repellent product of Example 15, in which the treatment

temperature for the post cure treatment was lower than 1600C,

and thus it is considered that the decreasing of the low

molecular weight siloxane by the post cure treatment was

insufficient. In the flying insect pest repellent product of

Example 16, in which the treatment temperature for the post cure

treatment was higher than 2400C, yellowing occurred on the

molded rubber article itself. However, the molding

workability of the molded rubber article was fine and there was

no significant problem in practical use also in these flying

insect pest repellent products of Examples 15 and 16.

[0098] Accordingly, in the case where the flying insect

pest repellent product of the present invention is subjected

to a post cure treatment, the treatment conditions are

considered that a preferable treatment temperature is 160 to

2400C, and a more preferable temperature is 190 to 2200C, with

consideration for the actual the treatment conditions together

with the evaluation results mentioned above. Furthermore, it

is considered that a preferable treatment time is about 1 to

15 hours, and a more preferable treatment time is about 2 to

7 hours.

[0099] [Example 17]

An addition-type liquid silicone rubber composition was

preparedby the following formulation, and this silicone rubber

composition was cured by using an injection molding machine at

1300C to formparts eachhaving avoidhaving a contour fashioned

after a star, and seven pieces of the parts were linked together

to constitute a band-shaped portion, and joint portions (six

circular through-holes (female portions) at one end thereof,

and a T-shapedprojectingportion at the other end thereof) were

provided to the ends of the band-shaped body to form a

band-shaped molded rubber article (length: 20 cm, weight: 3.6

g, hardness: 34 degrees, ratio (Si / S2) of total surface area

of voids (S1) with respect to total surface area of molded rubber

article (S2): 0.35). After the molding, this molded rubber

article was put into an oven, and subjected to a post cure

treatment at 2200C for 7 hours.

- Addition-type liquid silicone rubber composition

Component (A) : a methylvinylpolysiloxane in which both

terminals of a molecular chain are capped with

dimethylvinylsiloxane groups 67% by mass

Component (B): a

dimethylsiloxane-methylhydrogensiloxane copolymer in which

both terminals of a molecular chain are capped with

trimethylsiloxy groups 8.3% by mass

Component (C): a complex of chloroplatinic acid and an

olefin 0.04% by mass

Component (D): a siloxane-modified silica (using DDS as

a surface treating agent) 15% by mass

Component (E): 3-Methyl-1-butyne-3-ol 0.08% by mass

Bulking filler: Microsilicate powder 9.58% by mass

[0100] A flying insect pest repellent fragrance

composition was prepared by the following formulation. This

flying insect pest repellent fragrance composition was free

from citral as the flying insect pest repellent fragrance

component, and had a content ratio { (X + Y) / Z} of a content

X of the component (a) to a content Y of the component (b) in

total to a content Z of the component Z of 1.2.

- Flying insect pest repellent fragrance composition (90 mg per

one molded rubber article)

Component (a): menthone 6.4% by mass (5.8 mg)

$-damascone 4.1% by mass (3.7 mg)

Component (b): menthyl acetate 9.2% by mass (8.3 mg)

benzyl benzoate 7.8% by mass (7.0 mg)

allyl octanoate 8.5% by mass (7.7 mg)

Component (c): linalool 9.0% by mass (8.1 mg)

1-Menthol 11.4% by mass (10.3 mg)

Citronellol 3.7% by mass (3.3 mg)

Geraniol 5.4% by mass (4.9 mg)

Component (d): Allylcyclohexyloxy acetate,

ethyllinalool, 1,8-cineol 14.5% by mass in total (13.1 mg)

Repellent effect sustaining component: Tripropylene glycol monomethyl ether 20.0% by mass (18.0 mg)

[0101] Ninety (90) mg of the above-mentioned flying insect

pest repellent fragrance composition (72 mgas the flyinginsect

pest repellent fragrance component) was poured onto a part of

the outer surface oftheband-shapedmoldedrubber article. The

molded rubber article was allowed to stand under sealing for

two days to allow the flying insect pest repellent fragrance

composition to permeate evenly in the entirety of the molded

rubber article to give an flying insect pest repellent product

of the present invention having an effective sustention time

of about 12 hours (Example 17).

[0102] The flyinginsect pest repellent product ofExample

17 was put around a wrist with the T-shaped projecting portion

provided to one end of the band-shaped 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

flyinginsectpest repellentproduct ofExample 17 hadexcellent

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 the flying insect pest repellent

product of Example 17 was equivalent to that of three pieces

of string-shaped products. Therefore, it is sufficient to put a single piece of this product around a wrist to use. Thus, this product was very practical, and the experimenter was not annoyed by flying insect pests such as mosquitoes and small flies over a use period of about 12 hours.

[0103] [Example 18]

The one-pack type addition-type liquid silicone rubber

composition used in Example 17 was formed by curing a small strip

sheet-like molded rubber article (diameter: 3 cm, thickness:

1.2 mm, surface area of one surface: 7.1 cm 2 ). Fifty (50) mg

of the flying insect pest repellent fragrance composition used

in Example 17 (40 mg as the flying insect pest repellent

fragrance component) was poured onto a part of the surface of

the obtained molded rubber article, and allowed to stand under

sealing for two days to allow the flying insect pest repellent

fragrance composition to permeate uniformly in the entirety of

the molded rubber article. This was accommodated in a plastic

accommodation portion having a ring shape (diameter: 3.5 cm)

and having a front surface portion and a rear surface portion

each having a circular hole at the center (diameter: 2.7 cm),

said front and rear surface portions being integrally molded

via a hinge portion, to give an in-car flying insect pest

repellent product of the present invention having an effective

sustention time of 10 hours (Example 18).

[0104] When the flying insect pest repellent product of

Example 18 was used by hanging in a car, the average amount of vaporization and discharge of the flying insect pest repellent fragrance component from the time when the use was initiated to five hours after the initiation of use was 0.32 mg/cm 2-h.

Furthermore, the product was able toprevent flyinginsectpests

such as mosquitoes and small flies from entering into the car

over approximately ten hours.

INDUSTRIAL APPLICABILITY

[0105] The flying insect pest repellent product of the

present invention can be used for the purpose of controlling

not only flying insect pests but also a wide variety of insect

pests.

REFERENCE SIGNS LIST

[0106] 1 Ring-shaped molded rubber article

100 Band-shaped molded rubber article

Claims (10)

CLAIMS What is claimed is:

1. A flying insect pest repellent product which is a

molded silicone rubber article having a hardness of not more

than 50 degrees, the molded silicone 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

constituting the molded silicone rubber article, wherein

the molded silicone rubber article is a cured product of

an addition-type liquid silicone rubber composition comprising

(A) a methylvinylpolysiloxane, (B) a

methylhydrogenpolysiloxane as a cross-linking silicone

polymer, (C) a platinum compound as a reaction catalyst, (D)

a reinforcing filler, and (E) a reaction suppressing agent,

the flying insect pest repellent fragrance composition

comprises the following (a), (b) and (c) as the flying insect

pest repellent fragrance component:

(a) at least one terpene-based hydrocarbon compound

selected from the group consisting of limonene, pinene,

camphene and terpinene, and/or at least one terpene-based

ketone compound selected from the group consisting of carvone, pulegone, menthone, camphor and piperitone,

(b) at least one ester compound selected from the group

consisting of benzyl acetate, p-t-butylcyclohexyl acetate,

menthyl acetate, linalyl acetate, benzyl benzoate, allyl

hexanoate, allyl heptanoate and allyl octanoate, and

(c) at least one terpene-based alcohol compound selected

from the group consisting of linalool, terpineol, menthol,

dihydromyrcenol, citronellol and geraniol, and

a content ratio {(X + Y) / Z} of a content X of the

terpene-based hydrocarbon compound and/or the terpene-based

ketone compound (a) and a content Y of the ester compound (b)

in total to a content Z of the terpene-based alcohol compound

(c) in the flying insect pest repellent fragrance composition

has been set to 0.2 to 4.0.

2. The flying insect pest repellent product according

to claim 1, wherein the molded silicone rubber article is a

secondary vulcanized product in which a low molecular weight

siloxane has been decreased.

3. The flying insect pest repellent product according

to claim 1 or 2, wherein the reinforcing filler comprises a

siloxane-modified silica.

4. The flying insect pest repellent product according to any one of claims 1 to 3, wherein the flying insect pest repellent fragrance composition further contains, as the flying insect pest repellent fragrance component, (d) at least one fragrance selected from the group consisting of styralyl acetate, o-t-butylcyclohexyl acetate, citronellyl acetate, phenethyl acetate, geranyl acetate, cinnamyl acetate, tricyclodecenyl acetate, anisyl acetate, allylcyclohexyl acetate, allylcyclohexylpropionate, allylisobutyloxy acetate, allyl-n-amyloxy acetate, allylcyclohexyloxy acetate, allylphenoxy acetate, phenethyl alcohol, borneol, eugenol, nerol, ethyllinalool, thymol, p-menthane-3,8-diol, 1,8-cineol, diphenyloxide, citronellal, damascone, cis-jasmone and dihydrojasmone.

5. The flying insect pest repellent product according

to any one of claims 1 to 4, wherein the flying insect pest

repellent fragrance composition is substantially free from

citral.

6. The flying insect pest repellent product according

to any one of claims 1 to 5, wherein an average amount of

vaporization and discharge of the flying insect pest repellent

fragrance component from the surface of the molded silicone

rubber article is 0.04 to 0.9 mg/cm 2.h.

7. The flying insect pest repellent product according

to claim 6, wherein the molded silicone rubber article is a

ring-shaped molded rubber article comprising an elastic ring,

which is put around or attached to a portion of a human body

or an object, or a band-shaped molded rubber article capable

of forming an elastic ring, which is put around or attached to

a portion of a human body or an object, by joining end portions

together or causing the end portions to be close to each other.

8. The flying insect pest repellent product according

to claim 7, wherein the flying insect pest repellent fragrance

component is vaporized and discharged over 5 to 15 hours in a

state that the ring is put around or attached to the portion

of the human body or the object.

9. The flying insect pest repellent product according

to claim 7 or 8, wherein the ring has a contour of a graphic

shape or a figure.

10. A method for repelling flying insect pests using

the flying insect pest repellent product according to any one

of claims 1 to 9, the method comprising:

vaporizing and discharging the flying insect pest

repellent fragrance component from the surface of the molded

rubber article.