ABSORPTION PROMOTER, FLYING-INSECT PEST REPELLENT FRAGRANCE-CONTAINING COMPOSITION, AND FLYING-INSECT PEST REPELLENT PRODUCT

Abstract

Provided is an absorption promotor for causing a flying-insect pest repellent fragrance-containing composition with a high repellent effect to be rapidly absorbed into an elastomer molded body. The absorption promotor for causing a flying-insect pest repellent fragrance-containing composition into an elastomer molded body having a hardness of 60 degrees or less includes d-limonene and/or 1,8-cineole as an active ingredient. The absorption promotor is blended preferably in a range of 2.0 to 65% by mass and more preferably 10 to 45% by mass in the flying-insect pest repellent fragrance-containing composition.

Claims

1. An absorption promotor for causing a flying-insect pest repellent fragrance-containing composition to be absorbed into an elastomer molded body having a hardness of 60 degrees or less, comprising d-limonene and/or 1,8-cineole as an active ingredient.

2. The absorption promotor of claim 1, wherein the elastomer molded body is a silicon rubber molded body.

3. The absorption promotor of claim 1, wherein the elastomer molded body is a thermoplastic elastomer molded body.

4. The absorption promotor of claim 3, wherein the thermoplastic elastomer molded body is a styrene-based thermoplastic elastomer molded body or an olefin-based thermoplastic elastomer molded body.

5. The absorption promotor of claim 1, wherein the absorption promotor is blended in a range of 2.0 to 65% by mass in the flying-insect pest repellent fragrance-containing composition.

6. The absorption promotor of claim 5, wherein the absorption promotor is blended in a range of 10 to 45% by mass in the flying-insect pest repellent fragrance-containing composition.

7. The absorption promotor of claim 1, wherein the flying-insect pest repellent fragrance-containing composition contains the following component (a) and component (b), the component (a) being an acetate compound as a single substance or a mixture, represented by general formula (I) below,
CH.sub.3—COO—R1   (I) wherein R1 is an alcohol residue having 6 to 12 carbons, the component (b) being a monoterpene-based alcohol and/or an aromatic alcohol having 10 carbon atoms.

8. The absorption promotor of claim 7, wherein the component (a) is at least one selected from the acetate compound and an allyl ester compound as a single substrate or a mixture, represented by general formula (II) below,
R2—CH.sub.2—COO—CH.sub.2—CH═CH.sub.2   (II) wherein R2 is an alkyl, alkoxy, cycloalkyl, cycloalkoxy, or phenoxy group having 4 to 7 carbon atoms.

9. The absorption promotor of claim 7, wherein a blending ratio of the component (a) to the component (b) in the flying-insect pest repellent fragrance-containing composition is set in a range of 0.2 to 2.0 times.

10. The absorption promotor of claim 7, wherein the acetate 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, menthyl acetate, cinnamyl acetate, terpinyl acetate, dihydroterpinyl acetate, linalyl acetate, ethyl linalyl acetate, citronellyl acetate, geranyl acetate, neryl acetate, bornyl acetate, and isobornyl acetate.

11. The absorption promotor of claim 8, wherein the allyl ester compound is at least one selected from the group consisting of allyl hexanoate, allyl heptanoate, allyl octanoate, allyl n-amyl oxyacetate, allyl cyclohexyl acetate, allyl cyclohexyl oxyacetate, and allyl phenoxyacetate.

12. The absorption promotor of claim 7, wherein the monoterpene-based alcohol and/or the aromatic alcohol having 10 carbon atoms is 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.

13. The absorption promotor of claim 7, wherein the flying-insect pest repellent fragrance-containing composition further contains a glycol and/or a glycol ether having a vapor pressure of 0.2 to 20 Pa at 20° C., as a repellant effect persistence component when a flying-insect pest repellent fragrance is volatilized.

14. The absorption promotor of claim 13, wherein the glycol and/or the glycol ether is at least one selected from the group 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.

15. A flying-insect pest repellent fragrance-containing composition, comprising: a component (a) and a component (b); and d-limonene and/or 1,8-cineole, the component (a) being an acetate compound as a single substance or a mixture, represented by general formula (I) below,
CH.sub.3—COO—R1   (I) wherein R1 is an alcohol residue having 6 to 12 carbons, the component (b) being a monoterpene-based alcohol and/or an aromatic alcohol having 10 carbon atoms.

16. The flying-insect pest repellent fragrance-containing composition of claim 15, wherein the component (a) is at least one selected from the acetate compound and an allyl ester compound as a single substrate or a mixture, represented by general formula (II) below,
R2—CH.sub.2—COO—CH.sub.2—CH═CH.sub.2   (II) wherein R2 is an alkyl, alkoxy, cycloalkyl, cycloalkoxy, or phenoxy group having 4 to 7 carbon atoms.

17. A flying-insect pest repellent product, comprising a flying-insect pest repellent fragrance-containing composition in which the absorption promotor according to claim 1 is blended, the flying-insect pest repellent fragrance-containing composition being held on an elastomer molded body while being embedded in interstices of a molecular structure of the elastomer molded body, the elastomer molded body having a hardness of 60 degrees or less.

18. The flying-insect pest repellent product of claim 17, wherein the elastomer molded body having the hardness of 60 degrees or less is configured such that a flying-insect pest repellent fragrance is volatilized from a surface of the elastomer molded body at a rate (average volatilization amount per unit surface area) of 0.04 to 0.9 mg/cm.sup.2.Math.h.

19. The flying-insect pest repellent product of claim 17, wherein the elastomer molded body having the hardness of 60 degrees or less is a ring-shaped elastomer molded body that includes a stretchable ring-shaped portion which a part of a human body or an object is inserted into or attached to, or a band-shaped elastomer molded body which is capable of forming a stretchable ring-shaped portion by connecting or proximating ends and which a part of a human body or an object is inserted into or attached to.

20. The flying-insect pest repellent product of claim 19, wherein the flying-insect pest repellent fragrance is volatilized over 5 to 15 hours while the part of the human body or object is inserted into or attached to the ring-shaped portion.

Description

EXAMPLES

Example 1

[0099] A flying-insect pest repellent fragrance-containing composition containing an absorption promotor of the present invention was prepared by blending the following components, based on the entire amount of the flying-insect pest repellent fragrance-containing composition (30 mg per silicone rubber molded body): 23.5% by mass (7.1 mg) of d-limonene as the absorption promotor into the silicone rubber molded body; 12.8% by mass (3.8 mg) of benzyl acetate and 4.1% by mass (1.2 mg) of tricyclodecenyl acetate as acetate compounds represented by the general formula (I), which were the components (a) in the flying-insect pest repellent fragrance; 6.7% by mass (2.0 mg) of allyl heptanoate as an allyl ester compound represented by the general formula (II), which was the component (a); 14.0% by mass (4.2 mg) of dihydromyrcenol and 7.6% by mass (2.3 mg) of geraniol as the monoterpene-based alcohol and/or aromatic alcohol having 10 carbon atoms, which are the components (b); 14.6% by mass (4.4 mg) of other flying-insect pest repellent fragrances (including 6.0% by mass of β-pinene and 8.6% by mass of benzyl benzoate); and further 16.7% by mass (5.0 mg)) of dipropylene glycol as the repellent effect persistence component. The blending ratio of the components (a) to the components (b) in this flying-insect pest repellent fragrance-containing composition is 1.09 times.

[0100] One hundred silicone rubber molded bodies (hardness of 35 degrees) having a cord and ring shape were prepared using a silicone compound and then placed in a sealed container equipped with a spraying device. The above-mentioned flying-insect pest repellent fragrance-containing composition was sprayed onto the silicone rubber molded bodies using the spraying device such that its adsorption amount was 30 mg per silicone rubber molded body (25.0 mg as the flying-insect pest repellent fragrance). After sufficiently stirring, the flying-insect pest repellent fragrance-containing composition rapidly penetrated the entire silicone rubber molded bodies until 15 hours elapsed, thereby obtaining a flying-insect pest repellent product of the present invention in the form of a wrist ring and having an effective duration of about 10 hours. The average volatilization amount per entire surface area of flying-insect pest repellent fragrance in this flying-insect pest repellent product was 0.34 mg/cm.sup.2.Math.h (from the start of use to 2 hours later), and about 42% of the wrist ring was separated from the skin of the wrist when it was worn on the wrist.

[0101] When a user wore two of the above-mentioned wrist rings around each wrist and carried them outdoors, the practical repellent effect was confirmed over about ten hours without being bothered by flying-insect pests such as mosquitoes and fruit flies. In addition, the user could enjoy the playfulness by wearing the product with the animal characters and could also enjoy the pleasant freshness of the fragrance that wafted while keeping the initial fragrance tone in a space around the user's body. Aside from this, a similar test was conducted on a silicone rubber molded body having a hardness of 80 degrees, but the flying-insect pest repellent fragrance-containing composition was only slightly adsorbed therein and could not be applied to the present invention.

Examples 2 to 13 and Comparative Examples 1 to 4

[0102] A silicone rubber molded body [length: 20 cm, weight: 3.2 g, and ratio (S.sub.1/S.sub.2) of the total area (S.sub.1) occupied by the hollow to the entire area (S.sub.2) of the silicone rubber molded body: 0.29] was molded using a silicone compound by connecting seven parts having a star-like shape as a hollow outline to constitute a band-shaped body and then providing a binding part at both ends of the band-shaped body (one end having six circular through holes (receptacles) and the other end having T-shaped projections). The hardness of the silicone rubber molded body was adjusted to 31 degrees for each of Examples 2 to 13 and Comparative Examples 1 to 3, and to 62 degrees for Comparative Example 4.

[0103] Then, 90 mg of each of the flying-insect pest repellent fragrance-containing compositions shown in Tables 1 and 2, prepared in accordance with Example 1, was injected and added into one site on the outer surface of the silicone rubber molded body, thereby obtaining a flying-insect pest repellent product. Evaluation tests were conducted on the product for items (1) to (4) below. The results obtained are shown in Table 3. [0104] (1) The liquid-absorption performance of the flying-insect pest repellent fragrance-containing composition into the silicone rubber molded body was evaluated by the following method. [0105] (2) After the flying-insect pest repellent product was sealed and stored at 30° C. for six months, the recovery ratio of the flying-insect pest repellent fragrance was determined. [0106] (3) A flying-insect pest repellent effect test was conducted in accordance with the following method. [0107] (4) A volatilization amount measurement test of the flying-insect pest repellent fragrance was conducted in accordance with the following method.

[Liquid-Absorption Performance Evaluation Test of Flying-Insect Pest Repellent Fragrance-Containing Composition]

[0108] The same silicone compound as the above-mentioned silicone rubber molded body was used to prepare a disk-shaped sheet (of about 1 g) with a thickness of about 2 mm and a diameter of 24 mm for the evaluation test. The sheet was placed in a glass petri dish, and one drop of 20 mg of the sample composition was dripped onto the center of the sheet. The petri dish was covered with a lid and stored at 25° C. Then, the time taken for the sample composition in a liquid state to be almost completely absorbed into the sheet was measured. The evaluation was made based on the following criteria.

[0109] Level 5: Liquid-absorption time of six hours or more and less than eight hours

[0110] Level 4: Liquid-absorption time of eight hours or more and less than 10 hours

[0111] Level 3: Liquid-absorption time of 10 hours or more and less than 15 hours

[0112] Level 2: Liquid-absorption time of 15 hours or more and less than 24 hours

[0113] Level 1: Liquid-absorption time of 24 hours or more

[Recovery Test of Flying-Insect Pest Repellent Fragrance]

[0114] A predetermined amount of flying-insect pest repellent product was sealed in a glass bottle and stored at 30° C. for six months. After returning to room temperature, a flying-insect pest repellent fragrance was extracted from the flying-insect pest repellent product by adding acetone to the glass bottle. The content of the flying-insect pest repellent fragrance was analyzed by gas chromatography for the extracted liquid, and the recovery rate of the flying-insect pest repellent fragrance with respect to the prepared amount thereof was determined.

[Flying-Insect Pest Repellent Effect Test]

[0115] Two open plastic cups (of about 1 L) with no lids were placed in a test chamber (of about 6 m.sup.3). One of the plastic cups contained an attractant for adult Culex pipiens and a sample flying-insect pest repellent product (treated section), while the other plastic cup contained only an attractant for adult Culex pipiens (untreated section). About 50 adult Culex pipiens (♀) were released into the room after two and seven hours of the start of use. Then, the numbers of insects invading both sections of the plastic cups were counted, followed by calculating the flying-insect pest repellent ratio in accordance with the following formula.

Flying-insect pest repellent ratio=[(Number of insects invading the untreated section−Number of insects invading the treated section]/[Number of insects invading the untreated section]×100

[Volatilization Amount Measurement Test of Flying-Insect Pest Repellent Fragrance]

[0116] The weight of the flying-insect pest repellent product was measured at the start of use and after two and seven hours of the start of use. Based on decreases in the weight, the average volatilization amount of flying-insect pest repellent fragrance per unit surface area and unit time was calculated for a period of time from the start of use to two hours after the start of use, as well as for a period of time from two hours to seven hours after the start of use.

TABLE-US-00001 TABLE 1 Flying-insect pest repellent fragrance-containing composition (% by mass) Flying-insect pest repellent fragrance Repellant Component (a) effect Absorption Acetate Allyl ester Component Other fragrance persistence promotor compound compound (b) components (a)/(b) component Exam- 2 d-Limonene 23.5 Benzyl acetate 12.8 Allyl 6.7 Dihydro- 14.0 β-Pinene 6.0 1.09 Dipropylene 16.7 ples heptanoate myrcenol glycol Tricyclodecenyl 4.1 Geraniol 7.6 Benzyl 8.6 acetate benzoate 3 d-Limonene 8.2 Benzyl acetate 12.8 Allyl 6.7 Dihydro- 14.0 β-Pinene 21.3 1.09 Dipropylene 16.7 heptanoate myrcenol glycol Tricyclodecenyl 4.1 Geraniol 7.6 Benzyl 8.6 acetate benzoate 4 d-Limonene 3.4 Benzyl acetate 12.8 Allyl 6.7 Dihydro- 14.0 β-Pinene 26.1 1.09 Dipropylene 16.7 heptanoate myrcenol glycol Tricyclodecenyl 4.1 Geraniol 7.6 Benzyl 8.6 acetate benzoate 5 d-Limonene 42.1 Benzyl acetate 10.8 Allyl 6.7 Dihydro- 12.0 — 1.10 Dipropylene 16.7 heptanoate myrcenol glycol Tricyclodecenyl 4.1 Geraniol 7.6 acetate 6 d-Limonene 23.5 Benzyl acetate 12.8 — Dihydro- 14.0 β-Pinene 12.7 0.78 Dipropylene 16.7 myrcenol glycol Tricyclodecenyl 4.1 Geraniol 7.6 Benzyl 8.6 acetate benzoate 7 d-Limonene 23.5 Benzyl acetate 19.2 Allyl 8.0 Dihydro- 8.4 β-Pinene 4.8 2.57 Dipropylene 16.7 heptanoate myrcenol glycol Tricyclodecenyl 6.2 Geraniol 4.6 Benzyl 8.6 acetate benzoate 8 d-Limonene 23.5 Benzyl acetate 12.8 Allyl 6.7 Dihydro- 14.0 β-Pinene 22.7 1.09 — heptanoate myrcenol Tricyclodecenyl 4.1 Geraniol 7.6 Benzyl 8.6 acetate benzoate 9 1,8-Cineole 14.9 Styralyl acetate 13.7 Allyl 5.3 Terpineol 10.5 Vanillin 13.8 1.41 1,3-Butylene 20.0 hexanoate glycol Menthyl acetate 7.4 Linalool 8.2 Jasmine 6.2 lactone 10 1,8-Cineole 3.6 Styralyl acetate 3.0 Allyl 1.4 Terpineol 21.4 Vanillin 25.1 0.17 1,3-Butylene 20.0 hexanoate glycol Menthyl acetate 2.3 Linalool 17.7 Jasmine 5.5 lactone 11 1,8-Cineole 36.9 Styralyl acetate 12.7 Allyl 5.3 Terpineol 9.5 — 1.44 1,3-Butylene 20.0 hexanoate glycol Menthyl acetate 7.4 Linalool 8.2 12 1,8-Cineole 14.9 Styralyl acetate 13.7 Allyl 5.3 Terpineol 10.5 Vanillin 33.8 1.41 — hexanoate Menthyl acetate 7.4 Linalool 8.2 Jasmine 6.2 lactone 13 1,8-Cineole 57.2 Styralyl acetate 8.7 Allyl 3.5 Terpineol 6.3 — 1.48 1,3-Butylene 15.0 hexanoate glycol Menthyl acetate 4.4 Linalool 4.9

TABLE-US-00002 TABLE 2 Flying-insect pest repellent fragrance-containing composition (% by mass) Flying-insect pest repellent fragrance Repellant Component (a) effect Absorption Acetate Allyl ester Component Other fragrance persistence promotor compound compound (b) components (a)/(b) component Compar- 1 — Benzyl 12.8 Allyl 6.7 Dihydromyrcenol 14.0 β-Pinene 29.5 1.09 Dipropylene 16.7 ative acetate heptanoate glycol Examples Tricyclo- 4.1 Geraniol 7.6 Benzyl 8.6 decenyl benzoate acetate 2 — Styralyl 13.7 Allyl 5.3 Terpineol 10.5 Vanillin 28.7 1.41 1,3-Butyene 20.0 acetate hexanoate glycol Menthyl 7.4 Linalool 8.2 Jasmine 6.2 acetate lactone 3 Xylen 23.5 Benzyl 12.8 Allyl 6.7 Dihydromyrcenol 14.0 β-Pinene 6.0 1.09 Dipropylene 16.7 acetate heptanoate glycol Tricyclo- 4.1 Geraniol 7.6 Benzyl 8.6 decenyl benzoate acetate  4* 1,8- 14.9 Styralyl 13.7 Allyl 5.3 Terpineol 10.5 Vanillin 13.8 1.41 1,3-Butylene 20.0 Cineole acetate hexanoate glycol Menthyl 7.4 Linalool 8.2 Jasmine 6.2 acetate lactone *Silicone rubber molded body having hardness of 62 degrees was used

TABLE-US-00003 TABLE 3 Recovery Liquid- ratio Flying-insect pest Average absorption of fragrance repellent ratio volatilization performance component (%) amount (mg/cm.sup.2 .Math. h) level (%) After 2 h After 7 h 0~2 h 2~7 h Examples 2 4~5 100 100 100 0.41 0.36 3 4 98 96 93 0.37 0.31 4 2~3 95 90 84 0.34 0.29 5 5 99 97 92 0.38 0.32 6 4~5 99 91 85 0.39 0.31 7 4~5 98 92 84 0.38 0.30 8 4~5 98 96 82 0.37 0.23 9 4~5 100 100 97 0.40 0.36 10 2~3 94 90 83 0.34 0.28 11 5 98 95 91 0.37 0.32 12 4~5 98 96 81 0.36 0.24 13 5 97 96 83 0.39 0.28 Comparative 1 1 92 89 76 0.30 0.15 Examples 2 1 91 87 74 0.28 0.16 3 4 89 83 69 0.25 0.13 4 1~2 90 57 38 0.12 0.05

[0117] As a result of the tests, it was confirmed that in Examples 2 to 13, the absorption promotor of the present invention into the silicone rubber modified body, i.e., d-limonene and/or 1,8-cineole blended in the flying-insect pest repellent fragrance-containing composition together with the flying-insect pest repellent fragrance, could accelerate the liquid-absorption rate of the flying-insect pest repellent fragrance-containing composition into the silicone rubber molded body, and contribute to the efficiency of a necessary manufacturing process. Meanwhile, it was also confirmed that the obtained flying-insect pest repellent products had improved quality in a storage state, and exhibited excellent volatilization performance of the flying-insect pest repellent fragrance and satisfactory flying-insect pest repellent effects after two and seven hours of the start of use.

[0118] A composition (Example 4-2) was prepared by changing the content of d-limonene from 3.4% by mass to 2.5% by mass and also changing the content of benzylbenzoate from 8.6% by mass to 9.5% by mass in the flying-insect pest repellent fragrance-containing composition of Example 4 with the contents of other flying-insect pest repellent fragrance components left unchanged. This composition exhibited the absorption performance level, the recovery ratio of fragrance components, the flying-insect pest repellent ratio, and the average volatilization amount which are at the same levels as those in Example 4.

[0119] Further, citronella oil (made in China: 2.6% by mass of d-limonene, 34.4% by mass of citronellal, 24.9% by mass of geraniol, 13.6% by mass of citronellyl acetate and geranyl acetate, and other components) was tested as a flying-insect pest repellent fragrance-containing composition. When compared to Example 4 and Example 4-2, the absorption performance and the recovery ratio of the fragrance components of the citronella oil were almost the same as those of Examples 4 and 4-2, and the flying-insect pest repellent ratio and average volatilization amount thereof were not so different from those of Examples 4 and 4-2.

[0120] Furthermore, ghetto oil (16.6% by mass of 1,8-cineole, 11.5% by mass of terpinen-4-ol, and 7.3% by mass of β-pinene, and other components) was tested as a flying-insect pest repellent fragrance-containing composition. When compared to Example 12, the absorption performance and the recovery ratio of the fragrance components of the ghetto oil were almost the same as those of Example 12, and the flying-insect pest repellent ratio and average volatilization amount thereof were not so different from those of Example 12.

[0121] Thus, it was confirmed that d-limonene and/or 1,8-cineole both were effective as the absorption promotor, regardless of whether they were derived from essential oils or blended as individual components.

[0122] As the flying-insect pest repellent fragrance, a combination of three components, namely, an acetate compound represented by the general formula (I), which was the component (a), an allyl ester compound represented by the general formula (II), which was the component (a), and a monoterpene-based alcohol and/or an aromatic alcohol having 10 carbon atoms, which was the component (b), was the most preferable, and the more excellent flying-insect pest repellent effect was obtained when the ratio of the component (a) to the component (b) was in the range of 0.2 to 2.0. Furthermore, in Examples 2 to 7 and 9 to 11, the blending of the repellent effect persistence component was effective in suppressing the reduction of the flying-insect pest repellent effect in the later stages of use. In contrast, as shown in

[0123] Comparative Examples 1 and 2, when the absorption promotor of the present invention was not blended, the liquid-absorption rate into the silicone rubber molded body in the flying-insect pest repellent fragrance-containing composition became slow, and as a result, there was a risk of decomposition and deterioration of a certain kind of flying-insect pest repellent fragrance on the surface of the silicone rubber molded body, and the flying-insect pest repellent effect in use also became inferior. In Comparative Example 3 in which xylene was used instead of the absorption promoter of the present invention, the liquid-absorption rate became faster, and the silicone rubber molded body was clearly embrittled and unsuitable when compared to Example 2. Furthermore, it was confirmed that as in comparative example 4, when the hardness of the silicone rubber molded body exceeded 60 degrees even in the use of the absorption promoter of the present invention, the liquid-absorption performance was at level 1 to 2, and the flying-insect pest repellent fragrance was difficult to volatilize from the rubber molded body, so that the flying-insect pest repellent effect in use became noticeably inferior.

[0124] Next, instead of the silicone rubber molded body having a hardness of 31 degrees and used in Example 2, the above-mentioned liquid-absorption performance evaluation test was conducted using silicone rubber molded bodies having different hardnesses of 48 degrees, 55 degrees, and 60 degrees. As a result, in the silicone rubber molded body having a hardness of 48 degrees, the liquid-absorption performance was at level 4 to 5, while in the silicone rubber molded bodies having different hardnesses of 55 degrees and 60 degrees, the liquid-absorption performance was at level 3 to 4. From these results, it was confirmed that the hardness of the silicone rubber molded body was preferably 60 degrees or less, and more preferably 50 degrees or less.

Example 14

[0125] A flying-insect pest repellent fragrance-containing composition containing an absorption promotor of the present invention was prepared by blending the following components, based on the entire amount of the flying-insect pest repellent fragrance-containing composition (30 mg per silicone rubber molded body): 15.8% by mass (4.7 mg) of 1,8-cineole as the absorption promotor into the silicon rubber molded body; 10.5% by mass (3.2 mg) of citronellyl acetate and 5.6% by mass (1.7 mg) of p-tert-butylcyclohexyl acetate as acetate compounds, represented by the general formula (I), which were the components (a) in the flying-insect pest repellent fragrance; 7.3% by mass (2.2 mg) of allyl octanoate as an allyl ester compound represented by the general formula (II) which was the component (a); 14.9% by mass (4.5 mg) of menthol and 9.1% by mass (2.7 mg) of thymol as the monoterpene-based alcohol and/or aromatic alcohol having 10 carbon atoms, which were the components (b); 20.1% by mass (6.0 mg) of other flying-insect pest repellent fragrances (including 13.7% by mass of lemongrass oil and 6.4% by mass of benzyl benzoate); and 16.7% by mass (5.0 mg) of dipropylene glycol as a repellent effect persistence component. The blending ratio of the component (a) to the component (b) in the flying-insect pest repellent fragrance-containing composition was 0.98 times.

[0126] A two-component additive liquid silicone rubber composition was cured to form a small piece sheet-shaped silicone rubber molded body (diameter: 3 cm, thickness: 1.2 mm, hardness: 37 degrees, surface area on one side: 7.1 cm.sup.2).

[0127] On the other hand, 30 mg of the above-mentioned flying-insect pest repellent fragrance-containing composition (25 mg as the flying-insect pest repellent fragrance) was injected and added into one site on the surface of the obtained silicone rubber molded body, and the composition was then left under a sealed condition for one day, thereby causing the flying-insect pest repellent fragrance-containing composition to uniformly penetrate the entire silicone rubber molded body.

[0128] This was stored in a plastic storage body [a body obtained by integrally forming a front side portion and a rear side portion via a hinge portion, each of the front and rear side portions being ring-shaped (diameter: 3.5 cm) and including a circular hole (diameter: 2.7 cm) in its center] to thereby obtain a flying-insect pest repellent product of the present invention for the interior of a vehicle with an effective duration of about 10 hours.

[0129] When this product was used while being hung inside the vehicle, the average volatilization amount of flying-insect pest repellent fragrance was 0.28 mg/cm.sup.2.Math.h for a period of time from the start of use to five hours of use, which could prevent flying-insect pests such as mosquitoes, fruit flies, and the like from invading the interior of the vehicle over about 10 hours.

[0130] A composition (Example 14-2) was prepared by changing 15.8% by mass (4.7 mg) of 1,8-cineole to 3.7% by mass (1.1 mg) of d-limonene and 12.1% by mass (3.6 mg) of 1,8-cineole as the absorption promotor in the flying-insect pest repellent fragrance-containing composition of Example 14 with the other components left unchanged. This composition was absorbed into the silicon rubber molded body as rapidly as in Example 14 and also exhibited the average volatilization amount and the flying-insect pest repellent effect which were at the same levels as those in Example 14.

Examples 15 to 22 and Comparative Examples 5 to 9

[0131] A flying-insect pest repellent fragrance-containing composition shown in Table 4 was prepared using a band-shaped thermoplastic elastomer molded body (width: 12 mm, length: 20 cm, thickness: 1.0 mm, weight: 3.0 to 3.5 g) in accordance with Example 1. Then, 100 mg of this composition was injected and added into one site on the outer surface of the thermoplastic elastomer molded body, thereby obtaining a flying-insect pest repellent product.

[0132] After the flying-insect pest repellent products were sealed and stored at 30° C. for six months, the recovery ratio of the flying-insect pest repellent fragrance was determined. In addition, the above-mentioned liquid-absorption performance evaluation test, the flying-insect pest repellent effect test, and the volatilization amount measurement test were conducted on these flying-insect pest repellent products. The results obtained are shown in Table 5.

TABLE-US-00004 TABLE 4 Flying-insect pest repellent fragrance-containing composition (% by mass) Thermo- Flying-insect pest repellent fragrance plastic Component (a) elastomer Allyl (Hardness: Absorption Acetate ester Component degree) promotor compound compound (b) Examples 15 SEBS d- 18.5 Linalyl 15.2 Allyl 7.1 Citronellol 12.9 (41) Limonene acetate cyclohexyl Phenylethyl 3.8 propionate Eugenol 8.4 acetate 16 SEBS d- 18.5 Linalyl 15.2 Allyl 7.1 Citronellol 12.9 (41) Limonene acetate cyclohexy Phenylethyl 3.8 propionate Eugenol 8.4 acetate 17 SEBS d- 18.5 Linalyl 15.2 Allyl 7.1 Citronellol 12.9 (56) Limonene acetate cyclohexyl Phenylethyl 3.8 propionate Eugenol 8.4 acetate 18 SEBS 1,8- 20.3 Benzyl 11.6 Allyl 6.0 Geraniol 18.5 (41) cineole acetate heptanoate Terpinyl 4.7 Ethyl 7.6 acetate linalool 19 TPO-V d- 18.5 Linalyl 15.2 Allyl 7.1 Citronellol 12.9 (36) Limonene acetate cyclohexyl propionate Phenylethyl 3.8 Eugenol 8.4 acetate 20 TPO 1,8- 20.3 Benzyl 11.6 Allyl 6.0 Geraniol 18.5 (36) cineole acetate heptanoate Terpinyl 4.7 Ethyl 7.6 acetate linalool 21 TPEE 1,8- 24.9 Phenylethyl 12.4 Allyl 5.3 Menthol 15.7 (40) cineole acetate octanoate Neryl 5.0 Borneol 9.2 acetate 22 TPO 1,8- 49.3 Benzyl 8.5 Allyl 3.7 Geraniol 12.1 (36) cineole acetate heptanoate Terpinyl 3.8 Ethyl 5.9 acetate linalool Comparative 5 SEBS — Linalyl 15.2 Allyl 7.1 Citronellol 12.9 Examples (41) acetate cyclohexyl propionate Phenylethyl 3.8 Eugenol 8.4 acetate 6 TPO — Benzyl 11.6 Allyl 6.0 Geraniol 18.5 (36) acetate heptanoate Terpinyl 4.7 Ethyl 7.6 acetate linalool 7 TPEE — Phenylethyl 12.4 Allyl 5.3 Menthol 15.7 (40) acetate octanoate Neryl 5.0 Borneol 9.2 acetate 8 SEBS d- 18.5 Linalyl 15.2 Allyl 7.1 Citronellol 12.9 (62) Limonene acetate cyclohexyl Phenylethyl 3.8 propionate Eugenol 8.4 acetate 9 TPO 1,8- 20.3 Benzyl 11.6 Allyl 6.0 Geraniol 18.5 (63) cineole acetate heptanoate Terpinyl 4.7 Ethyl 7.6 acetate linalool Flying-insect pest repellent fragrance Repellant Other effect fragrance persistence components (a)/(b) component Examples 15 Pulegone 12.4 1.22 Dipropylene 16.7 glycol Diphenyl 5.0 oxide 16 Pulegone 12.4 1.22 — Diphenyl 21.7 oxide 17 Pulegone 12.4 1.22 — Diphenyl 21.7 oxide 18 Carvone 11.0 0.85 Dipropylene 16.7 glycol Lemongrass 3.6 oil 19 Pulegone 12.4 1.22 Dipropylene 16.7 glycol Diphenyl oxide 5.0 20 Carvone 11.0 0.85 Dipropylene 16.7 glycol Lemongrass 3.6 oil 21 Damascone 7.5 0.91 Dipropylene 16.7 glycol Eucalyptus 3.3 oil 22 — 0.89 Dipropylene 16.7 glycol Comparative 5 Pulegone 12.4 1.22 Dipropylene 16.7 Examples glycol Diphenyl 23.5 oxide 6 Carvone 27.1 0.85 Dipropylene 16.7 glycol Lemongrass 7.8 oil 7 Damascone 24.5 0.91 Dipropylene 16.7 glycol Eucalyptus 11.2 oil 8 Pulegone 12.4 1.22 Dipropylene 16.7 glycol Diphenyl 5.0 oxide 9 Carvone 11.0 0.85 Dipropylene 16.7 glycol Lemongrass 3.6 oil

TABLE-US-00005 TABLE 5 Recovery Liquid- ratio absorption of fragrance Flying-insect pest Average volatilization performance component repellent ratio (%) amount (mg/cm.sup.2 .Math. h) level (%) After 2 h After 7 h 0~2 h 2~7 h Examples 15 3~4 94 92 84 0.34 0.28 16 3~4 93 90 79 0.31 0.20 17 3 91 89 77 0.28 0.19 18 3~4 94 91 85 0.30 0.26 19 3~4 95 90 84 0.33 0.27 20 3~4 94 91 83 0.31 0.25 21 4~5 95 88 80 0.24 0.15 22 5 95 94 80 0.33 0.20 Comparative 5 1 85 80 65 0.20 0.09 Examples 6 1 87 82 68 0.22 0.11 7 1~2 86 79 61 0.18 0.07 8 1~2 87 60 37 0.12 0.06 9 1~2 86 56 35 0.11 0.04

[0133] Results of the tests in Examples 15 to 22 regarding the absorption promotor of the present invention for the thermoplastic elastomer molded body, i.e., d-limonene and/or 1,8-cineole blended in the flying-insect pest repellent fragrance-containing composition together with the flying-insect pest repellent fragrance, confirmed the followings: the absorption promotor could accelerate the liquid-absorption rate of the flying-insect pest repellent fragrance-containing composition into the thermoplastic elastomer molded body; the absorption promotor contributed to the efficiency of a necessary manufacturing process, as in the silicone rubber molded bodies of Examples 2 to 13; the obtained flying-insect pest repellent products had improved quality in a storage state as the product; the products exhibited excellent volatilization performance of the flying-insect pest repellent fragrance as well as satisfactory flying-insect pest repellent effects, after two and seven hours of the start of use.

[0134] From the comparison between Example 16 and Example 17, it was found that the hardness of the thermoplastic elastomer molded body used in the present invention was preferred to be less than 50 degrees rather than the range of 50 to 60 degrees in order to obtain good liquid-absorption performance. Furthermore, from the comparison between Example 15 and Example 16, the blending of the repellent effect persistence component was effective in suppressing the reduction of the flying-insect pest repellent effect in the later stages of use.

[0135] In contrast, as shown in Comparative Examples 5 to 7, when the absorption promotor of the present invention was not blended, the liquid-absorption rate of the flying-insect pest repellent fragrance-containing composition into the thermoplastic elastomer molded body became slow, and as a result, there was a risk of decomposition and deterioration of a certain kind of flying-insect pest repellent fragrance on the surface of the thermoplastic elastomer molded body, and the flying-insect pest repellent effect in use also became inferior. Furthermore, it was confirmed that as in Comparative Examples 8 and 9, when the hardness of the thermoplastic elastomer molded body exceeded 60 degrees even in the use of the absorption promoter of the present invention, the liquid-absorption performance was at level 1 to 2, and the flying-insect pest repellent fragrance was difficult to volatilize from the thermoplastic elastomer molded body, so that the flying-insect pest repellent effect in use became noticeably inferior.

[0136] Among the materials of the thermoplastic elastomer molded body, SEBS, TPO, and TPO-V were preferable. However, when comparing Examples 2 to 13 using silicone rubber molded bodies with Examples 15 to 22 using thermoplastic elastomer molded bodies, it was confirmed that the silicone rubber molded body was generally superior to the thermoplastic elastomer molded body in terms of the performances, such as the adsorption and dispersion, of the flying-insect pest repellent fragrance-containing composition for the silicone rubber molded body and the thermoplastic elastomer molded body.

INDUSTRIAL APPLICABILITY

[0137] The absorption promotor into the elastomer molded body, the flying-insect pest repellent fragrance-containing composition, and the flying-insect pest repellent product using the flying-insect pest repellent fragrance-containing composition according to the present invention can be utilized not only for flying-insect pests, but also for a wide range of insect pest control purposes.