TWI698177B - Flying insect pest repellent product and method for repelling flying insect pest - Google Patents

Abstract

The subject of the present invention is to provide a flying insect repellent product that improves the molding workability and mechanical properties of silicone rubber, and has excellent flying insect repellent fragrance ingredients and excellent flying insect repellent effects. The solution of the present invention is a flying pest repellent product, which is a flying pest repellent product of a silicone rubber molded body with a hardness of less than 50 degrees to keep flying pests repellent fragrance composition. The silicone rubber molding system is added to a molded liquid polymer The hardened material of the silicone rubber composition, the flying insect repellent fragrance composition, as the flying insect repellent fragrance ingredient, contains (a) terpene-based hydrocarbon compounds and/or terpene-based ketone compounds, (b) ester compounds, and (c) The terpene-based alcohol compound, the total of the blending amount X of (a) and the blending amount Y of (b), and the blending ratio {(X+Y)/Z} of the blending amount Z of (c) are set at 0.2～4.0.

Description

Flying pest repellent products and flying pest repellent methods

The present invention relates to a silicone rubber molded body with a hardness of less than 50 degrees, and a flying pest repellent fragrance composition containing flying pest repellent fragrance ingredients is maintained in a state of entering the gap of the molecular structure of the rubber constituting the silicone rubber molded body The flying pest repellent product and the flying pest repellent method using the flying pest repellent product.

In the past, for flying insects such as mosquitoes, gnats, chironomid, flies, etc., a common method was to apply a repellent containing DEET (N,N-diethyl toluidine) on the skin surface. However, when acetone is compared with ordinary fragrance ingredients, the volatility is a little low, so the space repellent effect cannot be expected. On the other hand, volatile insecticidal ingredients at room temperature, such as Empenthrin, which is a pyrethroid system, evaporate in space. Although it can achieve the deterrent effect on flying pests, it is avoided in many cases. Use of volatile insecticidal ingredients at room temperature.

Therefore, as a repellent ingredient, several proposals have tried to use volatile natural essential oils or their components. For example, it is well known that citronella oil or its main component citronellal shows a deterrent effect against mosquitoes, and candles containing citronella oil as an active ingredient are commercially available in the United States. However, the method of using the heat of the candle to release citronellal has poor volatilization efficiency and cannot exert its practical avoidance effect.

In addition, Japanese Unexamined Patent Publication No. 2002-173407 (Patent Document 1) describes in addition to citronella oil, a flying pest repellent that uses natural essential oils selected from orange oil and cassia seed oil as active ingredients as an effective ingredient. The solvent of the liquid includes alcohols such as methyl alcohol and ethyl alcohol, esters such as diethyl phthalate and isopropyl myristate, and aliphatic hydrocarbons such as hexane, kerosene, and paraffin. , Aromatic hydrocarbons, ethers, etc.

In addition, Japanese Unexamined Patent Publication No. 2003-201203 (Patent Document 2) discloses a pest repellent volatile composition, which contains citronellal as a pest repellent ingredient and is selected from terpineol, menthol, limonene, and geraniol. One or more of citronellol, camphene, etc. The content of citronellal in pest repellent ingredients is 2-10% by mass. However, although these repellents have noticed natural product positioning and doubts about safety, their repellent effects continue to deteriorate and are not always satisfactory.

Furthermore, Japanese Patent Application Laid-Open No. 61-289002 (Patent Document 3) proposes "a repellent for arthropods, molluscs, and reptiles containing glycol ethers as active ingredients". Although Patent Document 3 describes that glycol ethers exhibit an excellent deterrent effect against cockroaches and mites, the effect cannot be said to be sufficient, and there is no mention of the deterrent effect of flying insects.

In this way, the flying insect repellent effect, and in addition, the useful flying insect repellent fragrance composition whose goal is the continuous improvement of fragrance is not yet known, and its development is being sought.

However, it is known that silicone rubber is excellent in adsorbability and gas permeability, has stable physical properties, and has excellent fragrance dispersion. Commercially available fragrances that take advantage of such properties and contain fragrances in silicone rubber. When perfume is contained in silicone rubber, mix it with a compound silicone rubber composition that usually contains (I) a silicone compound (Compound), or a liquid containing (II) a liquid silicone polymer The silicone rubber composition and fragrance are vulcanized (crosslinked) using reaction aids such as sulfur and additives. However, it is easy to cause the separation of fragrance and silicone rubber polymer or additives during kneading, and as a result of chemical changes such as heat during molding and decomposition and denaturation of fragrance due to reaction aids, it is difficult to obtain aromatic and physical properties. Stable forming body.

Therefore, as a means to solve this problem, Japanese Unexamined Patent Publication No. 8-311216 (Patent Document 4) or Japanese Unexamined Patent Application Publication No. 2011-26462 (Patent Document 5) are not used to knead fragrance before molding of silicone rubber. Instead, it is a method of adding perfume after the silicone rubber is formed. However, these documents do not mention the properties of the fragrance composition and the suitability of silicone rubber at all, and it is not necessarily suitable for flying pest repellent fragrance compositions with different functions.

As mentioned above, the silicone rubber molding system is cured and molded (I) a kneaded silicone rubber composition containing a silicone compound, or (II) a liquid silicone rubber composition. In addition, (II) liquid silicone rubber composition has two types of addition type and condensation type. The inventors of the present invention used (I) mixing silicone rubber composition or (II) liquid silicone rubber composition hardened product, namely, polysilicone rubber to develop useful flying pest repellent products. The silicone rubber molded body was studied for its suitability with various flying insect repellent fragrance compositions. As a result, it was found that as a repellent composition, by using a mixture of (m) a specific acetate compound and (n) a monoterpene-based alcohol and/or an aromatic alcohol with 10 carbon atoms, flying pests can avoid the fragrance ingredients from poly The silicone rubber molded body evaporates well and exhibits an excellent flying pest repellent effect over a specified period of time (Patent Document 6).

Although the flying insect repellent product of Patent Document 6 has excellent performance in repelling flying insects, when the (I) kneaded silicone rubber composition is used as a raw material, it is due to the complicated shape of the flying insect repellent product , During molding, burrs or deterioration of mold release properties, etc., have problems for molding workability and mechanical properties. Therefore, the inventors of the present invention, as a raw material for silicone rubber moldings, conducted further detailed studies on (II) addition molding in the liquid silicone rubber composition. Still, Japanese Patent No. 5053114 (Patent Document 7) discloses a repellent silicone rubber composition in which an oxime type liquid silicone rubber composition is blended with Ananin (Acrinathrin), which is one of the condensation types, However, since the formation of condensed by-products cannot be avoided, and Ananin is non-volatile and completely different from the characteristics of flying pest repellent fragrance ingredients, it cannot be used as a reference. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2002-173407 A [Patent Document 2] JP 2003-201203 A [Patent Document 3] Japanese Patent Application Publication No. 61-289002 [Patent Document 4] Japanese Patent Application Laid-Open No. 8-311216 [Patent Document 5] JP 2011-26462 A [Patent Document 6] Japanese Patent No. 5832649 Specification [Patent Document 7] Japanese Patent No. 5053114 Specification

[The problem to be solved by the invention]

In this way, it has been discovered that the use of the hardened product of the addition-molded liquid silicone rubber composition, that is, the silicone rubber molded body, improves its molding workability and mechanical properties, and is highly compatible with the flying pest repellent fragrance composition. Flying pest repellent products that exert a more excellent flying pest repellent effect are indispensable for the implementation of various tests, and there are situations where repeated trials have to be repeated.

The present invention was completed in view of the above-mentioned problems to provide a method that makes full use of the properties of silicone rubber, and improves its molding workability and mechanical properties, and the volatility of the fragrance ingredients and the repellent effect on flying pests. Excellent flying insect repellent products and flying insect repellent methods are the purpose. [Means to solve the problem]

The present invention has found that the following constitution exerts excellent effects in order to achieve the above-mentioned object.

(1) A flying pest repellent product, which is a silicone rubber molded body with a hardness of less than 50 degrees, and a flying pest repellent fragrance composition containing flying pest repellent fragrance ingredients is used to form the aforementioned silicone rubber molded body A product that keeps the gaps in the molecular structure of rubber from flying insects, It is characterized in that the aforementioned polysiloxane rubber molded body contains (A) methyl vinyl polysiloxane, (B) methyl hydrogen polysiloxane as a cross-linked polysiloxane polymer, and (C) as a reaction catalyst. The cured product of the liquid silicone rubber composition of the addition-molded liquid silicone rubber composition of (D) reinforcing filler and (E) reaction inhibitor, The aforementioned flying pest repellent fragrance composition, as the aforementioned flying pest repellent fragrance ingredient, contains the following (a), (b) and (c): (a) At least one terpene-based hydrocarbon compound selected from the group consisting of limonene, pinene, camphene, and terpinene and/or selected from carvone, pulerone, menthone, camphor and pepper At least one terpene-based ketone compound in the group consisting of ketones (Piperitone), (b) Selected from benzyl acetate, pt-butylcyclohexyl acetate, menthol acetate, linalyl acetate, benzyl benzoate, allyl hexanoate, alkene At least one ester compound in the group consisting of propyl heptanoate and allyl octanoate, (c) At least one terpene alcohol compound selected from the group consisting of linalool, terpineol, menthol, dihydromyrcenol, citronellol and geraniol The total of (a) the blending amount X of terpene-based hydrocarbon compounds and/or terpene-based ketone compounds and the blending amount Y of (b) ester compounds in the aforementioned flying pest repellent fragrance composition, and (c) terpene The blending ratio {(X+Y)/Z} of the blending amount Z of the alcohol compound is set to 0.2 to 4.0.

(2) The flying pest repellent product described in (1), wherein the aforementioned silicone rubber molding system reduces the secondary vulcanized rubber of low molecular weight silicone.

(3) The flying pest repellent product as described in (1) or (2), wherein the aforementioned reinforcing filler contains silicone modified silica.

(4) The flying insect repellent product described in any one of (1) to (3), wherein the flying insect repellent fragrance composition is used as the flying insect repellent fragrance ingredient and further contains (d) selected from the group consisting of sulfa Acetate, ot-butylcyclohexyl acetate, citronellyl acetate, phenethyl acetate, geranyl acetate, cinnamyl acetate, tricyclodecenyl acetate , Anisyl acetate, allyl cyclohexyl acetate, allyl cyclohexyl propionate, allyl isobutoxy acetate, allyl n-pentoxy acetate, allyl Cyclohexyloxyacetate, allylphenoxyacetate, phenethyl alcohol, borneol, eugenol, nerol, ethyllinalool, thymol, p-menthane-3, 8-diol, 1,8-cineole, diphenyl oxide, citronellal, damascone, cis-jasmone, and dihydrojasmone are fragrances of at least one kind.

(5) The flying insect repellent product described in any one of (1) to (4), wherein the flying insect repellent fragrance composition does not substantially contain citral.

(6) The flying insect repellent product described in any one of (1) to (5), wherein the average volatility of the flying insect repellent fragrance ingredient from the surface of the silicone rubber molded body is 0.04 to 0.9 mg/cm ² •h.

(7) The flying insect repellent product described in (6), wherein the silicone rubber molding system has a ring-shaped rubber molded body inserted or worn on a part of the human body or a stretchable ring of an object, or combined Or it is close to the ends to form a belt-shaped rubber molded body that can be inserted or worn on a part of a human body or a stretchable ring of an object.

(8) The flying insect repellent product described in (7), which is attached to the ring part to be inserted or worn on a part of the human body or the object, and the flying insect repellent fragrance ingredient volatilizes for 5-15 hours.

(9) The flying pest repellent product as described in (7) or (8), wherein the ring part has the outline of a figure or character.

(10) A flying pest repellent method, which uses the flying pest repellent product described in any one of (1) to (9), characterized in that the surface of the rubber molded body is Flying pests avoid volatilization of fragrance ingredients. [Invention Effect]

According to the flying insect repellent product and the flying insect repellent method of the present invention, the hardened product of the liquid silicone rubber composition, namely the silicone rubber molded body, is used to maintain the flying insect repellent fragrance containing the specific flying pest repellent fragrance ingredient The composition improves the molding workability and mechanical properties of the silicone rubber molded body, and the volatility of the flying insect repellent fragrance ingredient is more excellent than the conventional products, so it is useful Extremely high.

Hereinafter, the flying pest repellent product of the present invention will be described. The flying pest repellent method of the present invention is also described in the description of the flying pest repellent product. However, the present invention is not intentionally limited to the configuration described in the embodiment described below.

The flying insect repellent product of the present invention is a hardened product of an addition-molded liquid silicone rubber composition, a silicone rubber molded body with a hardness of less than 50 degrees (hereinafter, sometimes referred to as "rubber molded body") , Keep the flying insect repellent fragrance composition containing flying insect repellent fragrance ingredients. Flying insect repellent fragrance ingredients are used for specific types of rubber moldings. The details of the fragrance ingredients to avoid flying insects will be described later.

The addition type liquid polysiloxane rubber composition contains (A) methyl vinyl polysiloxane, (B) methyl hydrogen polysiloxane as cross-linked polysiloxane polymer, and (C) as the reaction catalyst Medium platinum compound, (D) reinforcing filler and (E) reaction inhibitor. When the addition-molded liquid silicone rubber composition is one-component, it can be used even if it is mixed with two-components during curing and molding of silicone rubber.

(A) Methyl vinyl polysiloxanes include the following (A-1) to (A-3) having vinyl groups participating in the crosslinking reaction at both ends of the molecular chain and/or the side chain of the molecular chain Type.

Type (A-1): Dimethylpolysiloxane with both ends of the molecular chain blocked by dimethylvinylsiloxane, and methylalkane with both ends of the molecular chain blocked by dimethylvinylsiloxane -Based polysiloxanes, dimethylsiloxane•methylphenylsiloxane copolymers with both ends of the molecular chain blocked by dimethylvinylsiloxane, and copolymers with both ends of the molecular chain blocked by dimethylvinylsiloxane The oxyalkyl-blocked dimethylsiloxane•methylalkylsiloxane copolymer, etc. have vinyl groups at both ends of the molecular chain.

Type (A-2): Methyl vinyl polysiloxane with both ends of the molecular chain blocked by trimethylsiloxy groups, and methyl vinylsiloxane with both ends of the molecular chain blocked by trimethylsiloxy groups• Dimethylsiloxane copolymers and methylvinylsiloxane and methylphenylsiloxane copolymers in which both ends of the molecular chain are blocked by trimethylsiloxy groups, etc. have vinyl groups in the side chain of the molecular chain and Those without vinyl groups at both ends of the molecular chain.

(A-3) Type: Those with vinyl groups at both ends of the molecular chain and side chains of the molecular chain.

For addition molding liquid silicone rubber composition, (A) methyl vinyl polysiloxane is generally used (A-1) or (A-3), but from the viewpoint of improving mold release See, it is more preferable to use the (A-1) type and the (A-2) type in combination. The blending amount of (A) methyl vinyl polysiloxane in the addition type liquid silicone rubber composition is preferably 50 to 80% by mass.

(B) Methyl hydrogen polysiloxane is used as the crosslinking agent of (A) methyl vinyl polysiloxane. That is, the silicon atom in (B) methyl hydrogen polysiloxane is bonded with hydrogen atom, and the vinyl group in (A) methyl vinyl polysiloxane undergoes a hydrosilylation reaction, and crosslinking makes The addition-molded liquid silicone rubber composition hardens. Examples of (B) methyl hydrogen polysiloxane include methyl hydrogen polysiloxane in which both ends of the molecular chain are blocked by trimethylsiloxy groups, and both ends of the molecular chain are blocked by trimethylsiloxy groups. Blocked dimethylsiloxane•methylhydrosiloxane copolymer, methylphenylsiloxane•methylhydrosiloxane copolymer with both ends of the molecular chain blocked by trimethylsiloxane groups, molecular chain Dimethylpolysiloxane whose two ends are blocked by dimethylhydrosiloxane, methylhydrosiloxane whose molecular chain is blocked by dimethylhydrosiloxane, and both ends of molecular chain are blocked by dimethyl Dimethylsiloxane•Methylhydrosiloxane copolymer, etc. blocked by hydrosilyl alkoxy. The blending amount of (B) methyl hydrogen polysiloxane in the addition type liquid polysiloxane rubber composition is less than that of the silicon atom-bonded vinyl group in (A) methyl vinyl polysiloxane. Ears, it is necessary that (B) the amount of hydrogen atoms bonded to silicon atoms in methyl hydrogen polysiloxane is in the range of 0.5 to 3 mol, preferably 5 to 15% by mass.

(C) Platinum compounds are used as catalysts for the hydrosilylation reaction to promote the bonding of hydrogen atoms to the silicon atoms in (B) methyl hydrogen polysiloxanes (A) in methyl vinyl polysiloxanes Hydrosilylation of vinyl groups. Examples of such (C) platinum compounds include platinum black, platinum-supported alumina powder, platinum-supported silica powder, platinum-supported carbon powder, chloroplatinic acid, and chloroplatinic acid. Hydrosilylation reactions with olefin complexes, chloroplatinic acid and diketone complexes, and chloroplatinic acid and 1,3-divinyltetramethyldisiloxane complexes, etc. Catalyst well-known compound. The blending amount of the platinum compound (C) in the addition-molded liquid silicone rubber composition is sufficient as the amount of the catalyst. In order to suppress the increase in the price of the flying insect repellent product, it is preferably 0.01-1.0% by mass.

(D) Reinforcing filler is to make the addition molding liquid silicone rubber composition into viscosity, improve the molding workability, and improve the mechanical properties of the silicone rubber molded body, thereby enhancing the mold release performance. As such (D) reinforcing fillers, for example, fumed silica (dry silica), precipitated silica (wet silica), light calcium carbonate, gas Fumed titanium oxide, carbon black, etc., especially on the surface of dry process silica or wet process silica, use hexamethyldisilazane (HMDS), polydimethylsiloxane ( Surface treatment agents such as PDMS) and dimethyldichlorosilane (DDS) are better to modify silicon dioxide with hydrophobic siloxanes. The blending amount of (D) reinforcing filler in the addition-molding liquid silicone rubber composition can be considered appropriate by considering the viscosity of the addition-molding liquid silicone rubber composition and the mechanical properties of the silicone rubber molding. The setting is preferably 10-50% by mass.

(E) The reaction inhibitor becomes to prevent the hardening of the addition-molded liquid silicone rubber composition at room temperature and can harden when heated. Examples of such (E) reaction inhibitors include 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, and 1-ethynyl ring Hexanol, propynyl alcohol, etc. The blending amount of the (E) reaction inhibitor in the addition-molded liquid silicone rubber composition is preferably 0.001 to 0.1% by mass.

The addition-molding liquid silicone rubber composition used in the present invention, in addition to the above-mentioned components (A) to (E), can be used as a bulking filler, for example, it can be blended with calcined silica fine powder and fine silicon powder , Pulverized quartz, Cristobalite powder, titanium oxide powder, magnesium oxide powder, etc., or can be appropriately blended with pigments, heat-resistant agents, flame retardants, non-crosslinkable silicone oils, antibacterial agents, and mildew Well-known additives such as agents.

The addition-molded liquid silicone rubber composition can be hardened and molded by a well-known molding device and molding method. As a curing molding device, it can be used in compression molding machines, conveyor molding machines, injection molding machines, etc., which are commonly used in the molding method of liquid silicone rubber composition. At this time, if the curing temperature of the liquid silicone rubber composition is too low, the curing speed will slow down and productivity will decrease. On the other hand, if the curing temperature is too high, the mechanical strength of the silicone rubber molded body will be reduced. Therefore, the curing temperature is preferably 50 to 240°C, more preferably 120 to 210°C.

Furthermore, by adjusting the crosslinking density of the hardened substance of the addition type liquid polysiloxane rubber composition, or as a reinforcing filler or augmenting filler used as an additive of the addition type liquid polysiloxane rubber composition, Or adjust the amount of non-crosslinkable silicone oil added, and also control the volatile amount of the flying pest repellent fragrance composition added later.

Although the silicone rubber molded body of the cured, molded and added liquid silicone rubber composition has stable physical properties, it is known that low-molecular-weight silicone components, etc. remain in the rubber molded body, and such affected physical properties are known Adverse effects on the above, or the rubber molding itself may cause yellowing. In addition, in the process of research on the ingredients of the fragrance repellent against flying insects by the present inventors, it became clear that there are fragrances that are susceptible to the residual components in the rubber molded body like citral. Therefore, the silicone rubber molded body used in the present invention is preferably implemented at a temperature of 160-240°C for about 1-15 hours, preferably at a temperature of 190-220°C, by using an oven or the like after curing. The post-hardening treatment (secondary vulcanization treatment) for about 2-7 hours reduces the secondary vulcanization of low-molecular-weight silicone. The post-curing treatment makes the physical properties of the rubber molded body more stable. It is believed that not only the yellowing or browning of the rubber molded body itself can be suppressed, but also the yellowing or browning caused by the interaction with the fragrance. .

Silicone rubber molded body has excellent gas permeability and excellent fragrance absorption and emission characteristics. This is believed to be because the main chain of the molecular structure of the fragrance is made of carbon, and the fragrance molecules easily enter the gap of the molecular structure of the rubber that undergoes three-dimensional crosslinking. Especially when the hardness of the rubber molded body is less than 50 degrees, since the molecular structure of silicone rubber is too dense, the fragrance molecules are likely to enter the gaps of the molecular structure of the rubber. When the hardness of the rubber molded body exceeds 50 degrees, the molecular structure of the rubber molded body becomes too dense, and it is difficult for perfume molecules to enter the gaps of the molecular structure of the rubber, which is not suitable for the purpose of the present invention. Still, the hardness of the rubber molded body is measured by a method or device in accordance with the Japanese Industrial Standards (JIS K6253). In the present invention, a durometer suitable for the above specifications is used to measure the hardness of the rubber molded body.

The characteristic of the present invention is that the hardened product of the addition-molded liquid silicone rubber composition obtained in this way, by using a rubber molded body with a hardness of 50 degrees or less, improves the molding workability and mechanical properties, and the rubber The molded body is to find the most suitable flying insect repellent fragrance composition, and the repellent effect on the flying insects is compared with the previous products, and a more excellent flying insect repellent product is realized. The inventors of the present invention disclosed in Japanese Patent No. 5832649 (Patent Document 6) the use of (I) a cured product of a kneaded silicone rubber composition and (II) a cured product of a liquid silicone rubber composition. In the case of the two rubber moldings, as a flying pest repellent fragrance composition with these compatibility, it contains (m) a specific acetate compound and (n) a monoterpene alcohol and/or a carbon number 10 fragrance A mixture of group alcohols is a good idea.

Then, the inventors of the present invention targeted the rubber molded body of the liquid silicone rubber composition, which is an addition-molded hardened product. As a result of further research, they found that it is different from the case of Patent Document 6. The flying insect repellent fragrance ingredient is most suitable for the compatibility with the hardened product of the addition-molded liquid silicone rubber composition, that is, the rubber molded body, and finally reaches the flying insect repellent product of the invention.

The flying pest repellent fragrance composition used in the flying pest repellent product of the present invention does not substantially use insecticidal components, but uses the fragrance ingredients as flying pest repellent components. Such fragrance ingredients are called "flying pest repellent fragrance ingredients". The flying insect repellent fragrance composition, as the flying insect repellent fragrance ingredient, contains the following components (a), (b) and (c).

The component (a) includes terpene-based hydrocarbon compounds such as limonene, pinene, camphene, and terpinene, and/or terpene-based ketones such as carvone, pulene, menthone, camphor, and piperonone Compound. These terpene-based hydrocarbon compounds and/or terpene-based ketone compounds can be used alone or in any combination.

The component (b) includes benzyl acetate, pt-butylcyclohexyl acetate, menthol acetate, linalyl acetate, benzyl benzoate, and allyl hexanoic acid. Ester, allyl heptanoate and allyl caprylate and other ester compounds. These ester compounds can be used alone or in any combination.

(C) Component includes terpene-based alcohol compounds such as linalool, terpineol, menthol, dihydromyrcenol, citronellol, and geraniol. These terpene-based alcohol compounds can be used alone or in any combination.

In the flying pest repellent product of the present invention, it is determined by the inventors’ diligent research that the total amount of (a) component X and (b) component Y is combined with (c) component When the blending ratio {(X+Y)/Z} of the blending amount Z is set at 0.2-4.0, preferably at 0.78-1.8, a hardened product with addition-molded liquid silicone rubber composition is obtained, namely The rubber molded body is suitable, and has excellent volatility and flying pest repellent results.

The flying insect repellent fragrance composition, as the flying insect repellent fragrance ingredient, may further contain the following component (d).

(D) Component includes threonyl acetate, ot-butylcyclohexyl acetate, citronellyl acetate, phenethyl acetate, geranyl acetate, and cinnamyl acetate Ester, tricyclodecenyl acetate, anisyl acetate, allyl cyclohexyl acetate, allyl cyclohexyl propionate, allyl isobutoxy acetate, allyl n -Pentyloxyacetate, allylcyclohexyloxyacetate, allylphenoxyacetate, phenethyl alcohol, borneol, eugenol, nerol, ethyllinalool, 100 Among them is phenol, p-menthane-3,8-diol, 1,8-cineole, diphenyl oxide, citronellal, damascone, cis-jasmone and dihydrojasmone, etc. spices. These fragrances can be used alone or in any combination. Furthermore, since citral is affected by the remaining components in the rubber molded body and may cause coloring problems, the flying insect repellent product of the present invention preferably does not substantially contain citral in the flying insect repellent fragrance composition.

Various essential oils containing the above-mentioned fragrance ingredients, such as jasmine oil, neroli oil, peppermint oil, lavender oil, bergamot oil, orange oil, geranium oil, petitgrain oil, and lemon oil, can be appropriately added to the flying pest repellent fragrance composition. , Citronella oil, cinnamon oil, eucalyptus oil, lemon eucalyptus oil, thyme oil, etc. Since such essential oils contain the above-mentioned components (a), (b) and (c), the addition amount of essential oils can be adjusted to supplement (a) components, ( b) component and (c) component, exert a stronger effect of avoiding flying pests.

In the flying insect repellent fragrance composition, it is preferable to further contain a component for sustaining the repellent effect when the flying insect repellent fragrance component volatilizes. The so-called repellent effect lasting component is, for example, glycol and/or glycol ether with a vapor pressure of 0.2-20 Pa at 20°C.

Specific examples of the above-mentioned glycol and/or glycol ether (and the vapor pressure at 20°C) include propylene glycol (10.7Pa), dipropylene glycol (1.3Pa), tripropylene glycol (0.67Pa), and diethylene glycol (3Pa), triethylene glycol (1Pa), 1,3-butanediol, hexanediol (6.7Pa), benzyldiol (2.7Pa), diethylene glycol monobutyl ether (3Pa), two Propylene glycol monobutyl ether and tripropylene glycol monomethyl ether, among them, dipropylene glycol is suitable for the purpose of the present invention. Furthermore, the above-mentioned glycol and/or glycol ether can be used alone or in any combination. The blending ratio of the flying pest repellent fragrance ingredient relative to glycol and/or glycol ether is about 0.2 to 10 times.

In the flying pest repellent fragrance composition, as long as it does not impede the effect of the present invention, other functional components may be blended. As other functional components, for example, insecticidal components, deodorizing components, antibacterial and antibacterial components, etc. can be cited. Examples of the insecticidal ingredients include normal temperature pyrethrin-based pyrethrin, Profluthrin, Transfluthrin, and Metofluthrin. When the insecticidal ingredient is blended, it is preferable to keep it as a trace amount according to the purpose of the present invention. As deodorant ingredients, representative plant extracts selected from the grass family, the camellia family, the ginkgo family, the slender family, the moraceae, the rutaceae, the tiger tail family, and the persimmon family. In addition, green leaf alcohol or green leaf aldehyde called "green fragrance" may be added to give a relaxing effect. These functional components can be used alone or in any combination.

In the flying pest repellent fragrance composition, as long as it does not impede the effects of the present invention, if necessary, solvents, surfactants, solubilizers, dispersants, stabilizers, pH adjusters, colorants, etc. can be appropriately blended . In addition, for example, by microencapsulation or cyclodextrinization of the flying pest repellent fragrance composition, it is also possible to try to stabilize the flying pest repellent fragrance composition, or to adjust the volatility of the flying pest repellent fragrance component.

Examples of solvents used in the preparation of flying insect repellent products include lower alcohols such as water, ethanol and isopropanol, ketone solvents, ester solvents, and hydrocarbon solvents such as normal paraffin or isoparaffin. These solvents can be used alone or in any combination. As the surfactant, for example, polyoxyethylene hardened castor oil, polyoxyethylene higher alkyl ethers (polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, etc.), polyoxyethylene alkyl phenyl ethers , Polyoxyethylene higher fatty acid esters, polyoxyethylene sorbitol fatty acid esters, polyoxyethylene glycerol fatty acid esters, polyoxyethylene polyoxypropylene alkyl ether and other nonionic surfactants, lauryl amine oxide , Stearyl amine oxide, lauric acid amine propyl dimethyl amine oxide and other advanced alkyl amine oxide surfactants. These surfactants can be used alone or in any combination.

By adding the above-mentioned flying insect repellent fragrance composition to the hardened product of the addition-molded liquid silicone rubber composition and having a hardness of less than 50 degrees, the silicone rubber molded body is subjected to the specified treatment to treat the rubber molded body Keep the flying pest repellent fragrance composition, and complete the flying pest repellent product of the present invention. Furthermore, by using the flying insect repellent product of the present invention, the flying insect repellent fragrance component is volatilized from the surface of the silicone rubber molded body, and the flying insect repelling method of the present invention can be implemented.

As a method of adding the flying pest repellent fragrance composition to the rubber molded body, a conventionally known method can be suitably adopted. For example, when the surface area of the rubber molded body is large, the flying insect repellent fragrance composition is carried by a liquid medicine dispensing method or a coating method. When the surface area of the rubber molded body is small, put a large number of rubber molded bodies into a closed container, where the flying pest repellent fragrance composition is added with a solvent if necessary, sprayed or dripped, and soaked in the rubber molded body while stirring. Furthermore, the rubber molded body is immersed in the liquid of the flying pest repellent fragrance composition for an appropriate time, or the rubber molded body containing the flying pest repellent fragrance composition and the untreated rubber molded body are mixed in a closed container at a high concentration and placed By passing through the entire rubber molded body at an appropriate time and averaging the concentration of the fragrance composition, it is also possible to produce flying insect repellent products.

The blending amount (retention amount) of the flying pest repellent fragrance composition in the flying pest repellent product of the present invention is appropriately determined by the use of the flying pest repellent product, the period of use, and the type or specifications of the rubber molded body. can. For example, in the case of a flying insect repellent product that is used for 5 to 15 hours per time, it is preferable to blend about 20 to 200 mg of flying insect repellent fragrance composition per rubber molded body. In the case of using the flying insect repellent product for 15 to 30 days, it is preferable to set the weight of the product to about 2 to 10 g, and to blend about 100 to 2000 mg of the flying insect repellent fragrance composition for each rubber molded body.

Hereinafter, the shape and specifications of the rubber molded body will be described. As the shape of the rubber molded body, a ring shape, a band shape, a small sheet shape, etc. can be appropriately adopted, but the rubber molded body is preferably a ring having a stretchable ring portion inserted or worn on a part of the human body or an object. Shaped rubber molded body, or combined with or close to the ends, can be inserted into or worn on a part of the human body or a belt-shaped rubber molded body that can be stretched to an object.

To keep flying pests away from the ring-shaped rubber molded body and the band-shaped rubber molded body of the fragrance composition, the ring is inserted or worn on a part of the human body such as the wrist or ankle, or the handles of off-road vehicles, bicycles, etc., bags, backpacks, When holding objects such as handbags, straps such as hats, shoes, etc., slowly volatilize flying insect repellent fragrance ingredients from the surface of the ring-shaped rubber molded body and the belt-shaped rubber molded body. For example, in the case of flying insect repellent products whose volatile state lasts for 5-15 hours, in order to maintain the volatility, the average volatile amount of flying insect repellent fragrance ingredients from the surface of the rubber molded body (average volatile amount per unit surface area) , Preferably 0.04～0.9mg/cm ² •h. When the average volatilization amount of the flying pest repellent fragrance component is within this range, the release of the flying pest repellent fragrance component in the rubber molded body lasts 5 to 15 hours, preferably 8 to 12 hours, and smoothly proceeds. When the average volatilization amount of flying insect repellent fragrance ingredients is less than 0.04mg/cm ² •h, the flying insect repellent effect is insufficient. When the average volatility of flying pest repellent fragrance ingredients exceeds 1.0mg/cm ² •h, the duration of the repellent effect will be shortened, or the retention of flying pest repellent fragrance ingredients or flying pest repellent fragrance compositions in the silicone rubber molded body will change Too large, and there is the possibility of sticky on the surface. In addition, in the present invention, the so-called average volatilization amount is a value obtained for a time zone showing a volatilization amount of 0.02 mg/cm ² •h or more.

As a ring-shaped rubber molded body, a string-shaped body (wire diameter: 1 to 3 mm, length: about 10 to about 10 mm) that connects the surroundings is used so that it can be easily inserted or worn on a part of the human body such as the wrist or ankle or the aforementioned objects. About 20cm), it is preferable to use those that form graphics or characters. FIG. 1 is a schematic diagram of an annular rubber molded body 1. Fig. 1(a) shows a ring-shaped rubber molded body 1 when it is not worn, and Fig. 1(b) shows a state where the ring-shaped rubber molded body 1 is worn on a wrist 2. The ring-shaped adult rubber body 1 is provided with a stretchable ring part that is inserted or worn on a part of the human body or an object. The outline of the ring is shown in Figure 1(a) with the outline of figures or characters. Examples of graphics or characters include animal series, insect series, vehicle series, letter series, etc., but of course they are not limited to these. The original shape of the annular rubber molded body 1 is preferably expanded when a part of it is worn on the wrist or ankle, etc., with at least 20%, preferably 30% of this part being separated from the skin of the wrist or ankle, etc. Way stretcher. This is because the partitioned part not only helps to avoid the increase in the volatility of fragrance ingredients, although it is a fragrance ingredient, it is desirable to avoid contact with the skin as much as possible. Fig. 1(b) shows the partition 3 formed by partitioning a part of the rubber molded body 1 from the wrist 2.

Although the ring-shaped rubber molded body is composed of a figure or character formed by a rope-shaped body as the main part, the rubber molded body can be branched from one or several positions of the rope-shaped body to form a branch to form an accessory accessory Way. By how to give decorativeness and increase the weight of the rubber molded body and maintain the amount of flying insect repellent fragrance ingredients, it can reduce the number of flying insect repellent products of the present invention worn on the wrist or ankle. advantage. The shape or size of the accessory is not particularly limited if the volatility of the fragrance component of this part is not too large or too small compared with the main part of the graphics or characters.

As the belt-shaped rubber molded body, if the shape before use is belt-shaped, it is not particularly limited, but it is easy to have 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 use, for example, it is preferable to have the shape of a belt-shaped part and a connecting part, the belt-shaped part is formed by connecting parts including at least one hollow and a shell part surrounding the hollow, and the connecting part is connected to or close to the belt-shaped part The ends of each other form a stretchable loop that is inserted or worn on a part of the human body or an object, or the belt-shaped portion has at least one protrusion on one end side, and the joint is inserted by the protrusion to form an insertion Or worn on a part of the human body or on the stretchable ring of an object. The belt-shaped part is the main material (body) of the rubber molded body. Compared with a rubber molded body that is formed into a rope shape alone, the belt-shaped part can maintain the same or more stretchability and has no problem in strength. The bonding part is the one that temporarily fixes the belt-shaped rubber molded body before use (flying pest repellent product) into a ring during use. With the joining part, since the size of the formed ring part can be adjusted, the bonding state with a part of the human body or an object can be appropriately adjusted. For example, when the rubber molded body is inserted into or worn on a part of the human body or an object, if the rubber molded body is disliked to move more than necessary, the joint can be adjusted so that the degree of contraction becomes slightly stronger. On the other hand, even though it is a fragrance ingredient, if it is desired to avoid contact with the skin as much as possible, it is also possible to gently adjust the combination so that the rubber molded body can be worn as far as possible from the skin of the wrist or ankle. unit. As a preferable structure of the coupling portion, a specification in which a plurality of receiving portions are provided on one end side (or the other end side) of the belt-shaped portion, and one or more protruding portions are provided on the other end side (or one end side) can be cited. Specifically, for example, as the receiving portion, 3 to 7 circular through holes can be arranged along the longitudinal direction, and any one of them can be fitted with a T-shaped protrusion provided on the other end side to form a ring portion Way design. Or as a receiving part, 6 to 10 circular through holes can be arranged along the length direction, and 2 to 4 protrusions provided on one end side are inserted into the through holes to form a ring.

Existing in the middle of the band to generate diffuse air flow, which helps to increase volatility. The size or shape of the hollow part of the band, in addition to the volatility of the flying insect repellent fragrance ingredients from the rubber molded body, also affects the elasticity or strength of the rubber molded body, so it is necessary to consider these factors to determine . The size of the hollow, for example, when the rubber molded body is in a non-contracting state, it is preferable to set the total area occupied by the hollow as S ₁ in a plan view, and the total area (including S ₁ ) of the rubber molded body to be S ₂ When it is set to satisfy 0.05≦S ₁ /S ₂ ≦0.6. When the value of S ₁ /S ₂ is less than 0.05 (that is, the ratio of the hollow area to the rubber molded body is less than 5%), the volatile energy per unit weight of the rubber molded body is less than that of the rubber molded body formed into a rope . On the other hand, when the value of S ₁ /S ₂ exceeds 0.6 (that is, the ratio of the hollow area to the rubber molded body exceeds 60%), there is a possibility that the strength of the rubber molded body may cause problems.

Examples of hollow shapes include those whose outlines are formed into figures or character shapes. Examples of figures or character shapes include animal series, insect series, vehicle series, letter series, etc., but of course they are not limited to these. Furthermore, for some hollows, this filling can also be changed to a concave shape. By doing so, the design of the hollow can be maintained, the weight of the rubber molded body can be increased, and the filling amount of the fragrance ingredient to avoid flying insects can be increased. Still, it is okay to form branch parts extending outward from the outer shell part enclosing the hollow in a manner that imparts character or design.

When the belt-shaped rubber molded body forms a stretchable loop that is inserted or worn on a part of the human body or an object, it is preferable to form at least 20% of the loop, preferably 30%, to be separated from the skin of the wrist or ankle. Stretcher in an open way of putting on state.

An example of a belt-shaped rubber molded body 100 provided with a belt-shaped portion 10 and a joint portion 20 used as the flying pest repellent product of the present invention is shown in FIG. 2. FIG. 2 is an external view of a band-shaped rubber molded body 100. FIG. Fig. 2(a) shows the band-shaped rubber molded body 100 when it is not worn, and Fig. 2(b) shows the band-shaped rubber molded body 100 worn on the wrist H by combining the two ends of the band-shaped rubber molded body 100. To the belt-shaped rubber molded body 100, a plurality of parts 1A imitating a star shape are connected as a hollow outline.

Examples of flying insect repellent products include wrist rings and bracelets using the above-mentioned annular rubber molded body and band-shaped rubber molded body. In addition, the flying insect repellent product may be formed into a watchband shape. In this case, a storage portion for storing small pieces of rubber moldings may be formed in a part thereof, so that the rubber moldings can be replaced by themselves. In this case, the rubber molded body has the advantage of not directly contacting the skin of the wrist. Such a combination of rubber molded body and storage body, as long as the volatility of the fragrance ingredients is ensured to avoid flying pests, it can be used not only for humans, but also for mounting and hanging types used in spaces such as cars. Fly pest repellent products.

The flying pest repellent product of the present invention obtained in this way can be used in spaces such as entrances, kitchens, toilets, living rooms, bedrooms, etc., warehouses, cars, etc., or in courtyards, outdoors, on wrists or ankles, etc. It is necessary to wear 1 to 5 for use. For mosquitoes such as Culex pipiens pallens, house mosquitoes, Aedes albopictus, gnats, chironomids, flies, fruit flies (fruit flies, fleas, etc.), Flying pests such as butterflies, flies, clothes moths, etc., exert excellent flying pest repellent effects for a specified period of time. Moreover, when using aromatic flying insect repellent fragrance ingredients, the initial fragrance does not deteriorate and lasts for a specified period, and because this product does not contain insecticidal ingredients, it can be used even for people who do not like to use insecticides. No resistance to use, so its practicality is extremely high. [Example]

Hereinafter, examples of the flying pest repellent product of the present invention will be described.

[Example 1] As a two-component addition-molded liquid silicone rubber composition, one and two silicone rubber compositions were prepared using the following methods, and the prepared silicone rubber composition 1 and 2 Mix at room temperature and use an injection molding machine to harden at 140°C to form a string loop that imitates animal characters (wire diameter: about 2mm, weight: 1.6g, hardness: 32 degrees). After molding, it was placed in an oven and subjected to post-curing treatment at 210°C for 5 hours to obtain a silicone rubber molded body. • 1 part of silicone rubber composition (A) Component: Methyl vinyl polysiloxane with both ends of the molecular chain blocked by dimethyl vinyl silicone 　63% by mass (C) Component: a complex of chloroplatinic acid and 1,3-divinyltetramethyldisiloxane 　0.05% by mass (D)Component: Silicone modified silicon dioxide (using HMDS as surface treatment agent) 　 20% by mass Incremental filler: microsilica powder 　 16.95 mass% • 2 liquids of silicone rubber composition (A) Component: Methyl vinyl polysiloxane with both ends of the molecular chain blocked by dimethyl vinyl silicone 　63% by mass (B) Component: Methyl hydrogen polysiloxane with both ends of the molecular chain blocked by trimethylsilyloxy groups 　7.6% by mass (D)Component: Silicone modified silicon dioxide (using HMDS as surface treatment agent) 　 20% by mass (E) Component: 1-ethynyl cyclohexanol 　0.05 mass% Incremental filler: micro silica powder 　9.35 mass%

Prepare the flying pest repellent fragrance composition in the following ways. This flying insect repellent fragrance composition is a flying insect repellent fragrance ingredient, and does not contain citral, the total of the blending amount of (a) component X and the blending amount of (b) component Y, and the blending amount of (c) component The blending ratio of Z {(X+Y)/Z} is 1.1. •Flying pest repellent fragrance composition (30mg per rubber molded body) (a) Ingredient: l-carvone 　 14.3% by mass (4.3 mg) (b) Component: Benzyl acetate "7.0% by mass (2.1 mg) p-t-butylcyclohexyl acetate 　4.0% by mass (1.2mg) Benzyl benzoate 　 6.7% by mass (2.0 mg) Allyl heptanoate 　5.7 mass% (1.7mg) (c) Component: Linalool 　 10.3% by mass (3.1 mg) Terpineol 　9.7% by mass (2.9mg) Dihydromyrcenol　8.3% by mass (2.5mg) Geraniol 　 4.7% by mass (1.4 mg) (d) Ingredients: threonyl acetate, thymol, p-menthane-3,8-diol "12.6 mass% (3.8 mg) in total Repellent effect lasting ingredient: Dipropylene glycol 　 16.7% by mass (5.0 mg)

Put 100 string-shaped silicone rubber moldings into a closed container with a spray device. Using the above spray device, the prepared flying pest repellent fragrance composition will absorb 30mg per rubber molded body. (As a flying insect repellent fragrance ingredient, 25.0mg). After being fully stirred, it was left for 1 day to make the flying insect repellent fragrance composition uniformly permeate the entire rubber molded body to obtain the flying insect repellent product of the present invention (Example 1) in the form of a wrist ring and an effective duration of about 10 hours. Still, other methods are also tried for the silicone rubber molded body with a hardness of 80 degrees, but the flying insect repellent fragrance composition only adsorbs a little, and the flying insect repellent product of the present invention cannot be obtained.

In the flying pest repellent product of Example 1, the average volatilization amount of the flying pest repellent fragrance ingredient per full surface area is 0.35mg/cm ² •h (from the start of use to 2 hours after the start of use), when worn on the wrist, it is About 44% of the wrist ring is separated from the skin of the wrist. When the flying pest repellent products of Example 1 were rolled up on the left and right wrists and went out, it took about 10 hours without disturbing flying pests such as mosquitoes or fruit flies, confirming the practical repellent effect. In addition, by attaching animal characters to the body to enjoy the childishness, and to directly diffuse the fragrance of the initial fragrance in the space around the body, you can also enjoy a comfortable freshness.

[Examples 2 to 10, Comparative Examples 1 to 5] Except that the components (A) and (D) of the addition type liquid silicone rubber composition are changed to the composition shown in Table 1, the other according to Example 1, the curing of the addition type liquid silicone rubber composition The object is a string-shaped rubber molded body, and the flying insect repellent fragrance composition shown in Table 2 is adsorbed to obtain the flying insect repellent product of the present invention (Examples 2-10). Still, in Table 1, "A-1" refers to dimethylpolysiloxane with both ends of the molecular chain blocked by dimethylvinylsiloxane, and "A-2" refers to both ends of the molecular chain blocked by trimethyl Methyl vinyl polysiloxane blocked by silanoxy group, "A-3" is methyl vinyl polysiloxane blocked by dimethyl vinyl siloxane at both ends of the molecular chain. In addition, "Silicone Modified Silicon Dioxide P" is a siloxane modified silicon dioxide that uses HMDS for surface treatment, and "Silicone Modified Silicon Dioxide Q" is a siloxane that uses PDMS for surface treatment. Modified silicon dioxide.

The hardened product of the kneaded silicone rubber composition, that is, the string-shaped rubber molded body was formed into the same shape as in Example 1. The flying pest repellent fragrance composition shown in Table 3 was adsorbed to obtain a Flying pest repellent product outside the scope of the present invention (Comparative Example 1). In addition, the components (A) and (D) of the addition-molded liquid silicone rubber composition were changed to the composition shown in Table 1. Others were formed in accordance with Example 1 for curing of the addition-molded liquid silicone rubber composition The object is a string-shaped rubber molded body, and the flying insect repellent fragrance composition shown in Table 3 is adsorbed to obtain flying insect repellent products outside the scope of the present invention (Comparative Examples 2 to 5).

For the flying insect repellent products of Examples 2 to 10 and the flying insect repellent products of Comparative Examples 1 to 5, [1] evaluation of molding workability of rubber moldings, [2] evaluation of mold release properties of rubber moldings Evaluation, [3] Evaluation of coloration on the surface of rubber moldings, [4] Flying insect repellent effect test, and [5] Flying insect repellent fragrance component volatile content test.

[1] Evaluation of molding workability of rubber molding The molding workability of the rubber molded body used in the flying insect repellent product was evaluated in four stages of ◎ (very good), ○ (good), △ (bad) and × (very bad).

[2] Evaluation of mold release properties of rubber moldings The mold releasability of the rubber molded body used in flying insect repellent products was evaluated in four stages: ◎ (very good), ○ (good), △ (bad), and × (very bad).

[3] Evaluation of the coloration on the surface of the rubber molded body The coloring on the surface of the rubber molded body of the flying insect repellent product can be divided into four stages: ◎ (no coloring), ○ (only slightly coloring), △ (coloring: yellowing) and × (coloring: brown stains) Evaluation.

[4] The flying pest repellent effect test was conducted in a test room (about 6m ³ ) with 2 uncovered open plastic cups (about 1L). Put the C. pipiens adult attractor and the test flying pest repellent product (treatment area) in one plastic cup, and put only the C. pipiens adult attractor (no treatment area) in another plastic cup. 2 hours after use and 7 hours after use, put about 50 Culex pipiens adult (female) in the room, count the invading insects in the two plastic cups, and calculate the flying insect repellent rate according to the following formula. Flying pest repellent rate (%)=[(number of invading insects in untreated area-number of invading insects in treated area)/number of invading insects in untreated area]×100

[5] Determination of the volatile content of the ingredients of the repellent fragrances from flying insects The weight of the flying insect repellent product is measured at the start of use, 2 hours after use, and 7 hours after use. Based on the weight loss, calculate from the start of use to 2 hours after the start of use, and from the start of use 2 hours to The average volatilization amount of fragrance ingredients per unit of surface area per unit time of flying pest repellent after 7 hours of use.

Table 4 shows the results of the evaluation and test.

As a result of the test, the flying insect repellent products of Examples 2 to 10 (in addition to the hardened product of the liquid silicone rubber composition, that is, the silicone rubber molded body, maintain the flying insect repellent fragrance containing the specific flying insect repellent fragrance ingredient Composition), verify the average volatilization from the start of use to 2 hours after the start of use and 2 hours from the start of use to 7 hours after the start of use, and the flying pest repellent rate after 2 hours from the start of use and 7 hours after the start of use At the time, it was confirmed that the volatility of the flying insect repellent fragrance ingredients is excellent, and it exerts a satisfying flying insect repellent effect. Here, the so-called specific flying insect repellent fragrance ingredient means containing (a) terpene-based hydrocarbon compound and/or terpene-based ketone compound, and (b) ester compound, and (c) terpene-based alcohol compound, and (c) ) The blending amount Z of the terpene-based alcohol compound is blended with respect to the blending amount of (a) the blending amount of the terpene-based hydrocarbon compound and/or the terpene-based ketone compound X and (b) the blending amount Y of the ester compound The combined ratio {(X+Y)/Z} is adjusted to 0.2～4.0. In this regard, the flying insect repellent product (Comparative Examples 2 to 4) that does not contain any of the specific flying insect repellent fragrance ingredients (a), (b), and (c) and the blending ratio of these components The flying insect repellent product (Comparative Example 5) within the specified range of the present invention is one whose volatility and repellent effect of the flying insect repellent fragrance components have deteriorated. In addition, the silicone rubber molded body is the hardened product of the addition-molded liquid silicone rubber composition, that is, the flying pest repellent products of Examples 2 to 10, and the silicone rubber molded body is a mixed silicone rubber composition Compared with the flying insect repellent product of Comparative Example 1, the cured product of the object is the one with excellent molding workability and mold release.

It was confirmed that the flying pest repellent products of Examples 2 to 4 in which the repellent effect lasting component was blended were stable and continued the repellent effect even 7 hours after the start of use. In addition, as the component (A) of the addition type liquid polysiloxane rubber composition, the (A-1) molecular chain both ends of the dimethyl polysiloxane blocked by dimethyl vinyl siloxane groups are used together with (A-2) Example 3 of methyl vinyl polysiloxane with both ends of the molecular chain blocked by trimethylsilyloxy groups, confirming that the mold releasability is improved. In addition, the series of Examples 2, 4 to 6 are excellent in molding workability. As the (D) component of the addition-molding liquid silicone rubber composition, it was confirmed that the use of silicone-modified silica is effective in improving molding workability. . In addition, the flying pest repellent product of Example 8 and the flying pest repellent product of Example 9 are both used as flying pest repellent fragrance ingredients. Although citral is blended, the silicone rubber molded body of Example 8 is post-hardened. Example 9 further suppressed the degree of coloration. It can be confirmed that the post-curing treatment of the silicone rubber molded body can stabilize the physical properties of the silicone rubber molded body and improve the coloring problem.

[Examples 11-16] According to Example 5, the addition type liquid silicone rubber composition was hardened to form a string ring. After molding, it was placed in an oven, and post-hardening treatment was performed under various conditions shown in Table 5 to obtain a silicone rubber molded body. The resulting rubber molded body was adsorbed by the flying insect repellent fragrance composition according to Example 5 to obtain the flying insect repellent product of the present invention (Examples 11-16). The flying pest repellent product of Example 11 is the same as the flying pest repellent product of Example 5. For the flying insect repellent products of Examples 11-16 obtained, when the aforementioned [4] flying insect repellent effect test and [5] flying insect repellent fragrance component volatile amount measurement test were performed, the details of the test results are omitted, but confirmation Both exhibited the same level of excellent volatility and flying pest repellent effect as the flying pest repellent product of Example 5. Furthermore, for the flying pest repellent products of Examples 11-16, the aforementioned [1] Evaluation of the molding workability (including post-curing workability) of the rubber molded body and [3] Evaluation of the coloration on the surface of the rubber molded body . The results of the evaluation are shown in Table 5.

As a result of the evaluation, in particular, the molding workability of the rubber moldings of the flying pest repellent products of Examples 11-14 is very good, and the coloration on the surface of the rubber moldings is also suppressed above a certain level. That is, it was confirmed that the silicone rubber molded body was post-cured to become a secondary vulcanized rubber with reduced molecular weight silicone. The most important thing is that the post-hardening treatment temperature is 190～210℃, and the treatment time is 4～5 hours. The flying insect repellent products of Examples 11 and 12 have excellent molding workability of rubber molded bodies, but they are better than rubber. No coloration was observed on the surface of the molded body.

On the other hand, the flying pest repellent product of Example 15 in which the treatment temperature of the post-hardening treatment is less than 160°C, because coloration is observed on the surface of the rubber molded body, it is considered that the reduction of low-molecular-weight silicones by the post-hardening treatment is insufficient full. The flying pest repellent product of Example 16 in which the post-hardening treatment temperature exceeds 240°C is the yellowing of the rubber molded body itself. However, even in the flying pest repellent products of Example 15 and Example 16, the molding workability of the rubber molded body is good, and there is no major problem in practical use.

From the above, for the flying pest repellent product of the present invention, when the post-hardening treatment is carried out, the treatment conditions are considered to be 160～240℃, and the more preferable temperature is 190～ when considering the above evaluation results and actual treatment conditions. 220°C. Furthermore, it is considered that the preferable treatment time is about 1 to 15 hours, and the more preferable treatment time is about 2 to 7 hours.

[Example 17] The liquid silicone rubber composition was prepared by adding the following methods, and the silicone rubber composition was cured at 130°C using an injection molding machine to form a hollow outline. Connecting 7 parts imitating a star shape, constituted A belt-shaped part, and a belt-shaped rubber molded body (with 6 circular through holes (receiving part) on one end side and T-shaped protrusion part on the other end side) formed at both ends of the belt-shaped part ( Length: 20 cm, weight: 3.6 g, hardness: 34 degrees, the ratio (S1/S2) of the total area (S1) occupied by the hollow to the total area (S2) of the rubber molded body (S1/S2): 0.35). After molding, this rubber molded body was placed in an oven and subjected to a post-curing treatment at 220°C for 7 hours. •Additional liquid silicone rubber composition (A) Component: Methyl vinyl polysiloxane with both ends of the molecular chain blocked by dimethyl vinyl siloxane 　 67% by mass (B) Component: Dimethylsiloxane•Methylhydrosiloxane copolymer with both ends of the molecular chain blocked by trimethylsilyloxy groups 　8.3% by mass (C)Component: A complex of chloroplatinic acid and olefin 　0.04% by mass (D)Component: Silicone modified silicon dioxide (using DDS as a surface treatment agent) 　15% by mass (E) Component: 3-methyl-1-butyn-3-ol "0.08% by mass Incremental filler: microsilica powder "9.58% by mass

Prepare the flying pest repellent fragrance composition in the following ways. This flying insect repellent fragrance composition is used as a flying insect repellent fragrance ingredient, does not contain citral, and is blended with component (c) relative to the total amount of the blending amount X of component (a) and the blending amount Y of component (b) The blending ratio {(X+Y)/Z} of the total amount Z is 1.2. •Flying pest repellent fragrance composition (90mg per rubber molded body) (a) Ingredient: Menthone "6.4% by mass (5.8mg) β-Turketone (Damascone) 　 4.1% by mass (3.7 mg) (b) Ingredient: Menthol acetate "9.2% by mass (8.3 mg) Benzyl benzoate 　7.8% by mass (7.0mg) Allyl caprylate 　 8.5% by mass (7.7 mg) (c) Component: Linalool 9.0% by mass (8.1 mg) l-menthol 　 11.4% by mass (10.3 mg) Citronellol 　 3.7% by mass (3.3 mg) Geraniol 5.4% by mass (4.9mg) (d) Ingredients: Allylcyclohexyloxyacetate, ethyllinalool, 1,8-cineole, 14.5% by mass (13.1mg) in total Repellent effect lasting ingredient: Tripropylene glycol monomethyl ether 　 20.0% by mass (18.0 mg)

On one of the outer surfaces of the belt-shaped rubber molded body, 90 mg of the above-mentioned flying insect repellent fragrance composition (as the flying insect repellent fragrance ingredient, 72 mg) was added. Placed under airtight for 2 days, the flying insect repellent fragrance composition was uniformly permeated into the entire rubber molded body, and the flying insect repellent product of the present invention with an effective duration of about 12 hours (Example 17) was obtained.

Wrap the flying pest repellent product of Example 17 on the wrist, and form a loop by inserting the T-shaped protrusion provided on the other end of the belt into one of the circular through holes provided on one end of the belt. unit. At this time, the flying pest repellent product of Example 17 is easy to handle due to its excellent stretchability. In addition, adjusting the size of the ring can be in a state where the band-shaped rubber molded body does not move much on the wrist. Since the volatility energy of the flying pest repellent product of Example 17 is equivalent to 3 points of the rope-shaped product, it is sufficient to wear one of this product on the wrist. In this way, this product is very practical, and it will not be bothered by flying insects such as mosquitoes or fruit flies during the use period of about 12 hours.

[Example 18] The one-liquid addition molding liquid silicone rubber composition used in Example 17 was cured to form a small sheet-like rubber molded body (diameter: 3 cm, thickness: 1.2 mm, single-sided surface area : 7.1cm ² ). Add 50mg of the flying pest repellent fragrance composition used in Example 17 (as a flying pest repellent fragrance ingredient, 40mg) on one of the positions on the surface of the resulting rubber molded body, and place it under airtight for 2 days to make the flying pest repellent fragrance composition The substance permeates the entire rubber molded body uniformly. Put this in a ring shape (diameter: 3.5cm), and place the front face and the back face with a circular cavity (diameter: 2.7cm) in the center through the hinge part, and store them in an integral plastic storage body to obtain an effective duration The flying pest repellent product of the present invention was used in the vehicle for about 10 hours (Example 18).

When the flying insect repellent product of Example 18 was suspended in a car for use, the average volatility of the flying insect repellent fragrance ingredients from the start of use to 5 hours after the start of use was 0.32 mg/cm ² •h, and further, about It takes 10 hours to prevent flying insects such as mosquitoes or fruit flies from invading the car. [Industrial availability]

The flying pest repellent product of the present invention is not only used for flying pests, but can also be used for the purpose of repelling a wide range of pests.

1‧‧‧Annular rubber molding 1A‧‧‧Parts 2‧‧‧Wrist 3‧‧‧Partition 10‧‧‧Strip 20‧‧‧Joint 100‧‧‧belt shaped rubber molding

[Fig. 1] Fig. 1 is a schematic diagram of a ring-shaped rubber molded body, respectively showing (a) the ring-shaped rubber molded body when it is not worn, and (b) the ring-shaped rubber molded body worn on the wrist. [Figure 2] Figure 2 is an external view of a belt-shaped rubber molded body, showing (a) the belt-shaped rubber molded body when it is not worn, and (b) the belt-shaped rubber molded body worn on the wrist.

Claims (10)

A flying insect repellent product, which is a silicone rubber molded body with a hardness of less than 50 degrees, and a flying insect repellent fragrance composition containing flying pest repellent fragrance ingredients to enter the molecules of the rubber constituting the aforementioned silicone rubber molded body The flying insect repellent product that maintains the state of the structure gap is characterized in that the aforementioned silicone rubber molded body contains (A) methyl vinyl polysiloxane, and (B) methyl as a cross-linked polysiloxane polymer Hydrogen polysiloxane, (C) platinum compound as a reaction catalyst, (D) reinforcing filler, and (E) hardened product of a liquid polysiloxane rubber composition of a reaction inhibitor to prevent flying insects. The fragrance composition, as the aforementioned flying pest repellent fragrance ingredient, contains the following (a), (b) and (c): (a) selected from the group consisting of limonene, pinene, camphene and terpinene At least one terpene-based hydrocarbon compound and/or at least one terpene-based ketone compound selected from the group consisting of carvone, pulerone, menthone, camphor and pipertone (Piperitone), (b) Selected from benzyl acetate, pt-butylcyclohexyl acetate, menthol acetate, linalyl acetate, benzyl benzoate, allyl hexanoate, allyl heptanoate At least one ester compound in the group consisting of acid ester and allyl caprylate, (c) selected from linalool, terpineol, menthol, dihydromyrcenol, citronellol and geraniol (A) Terpene-based hydrocarbon compound of at least one kind of terpene-based alcohol compound in the group consisting of alcohol in the aforementioned flying pest repellent fragrance composition And/or the blending ratio of the blending amount X of the terpene-based ketone compound and the blending amount Y of (b) the ester compound and the blending ratio of the blending amount Z of (c) the terpene-based alcohol compound {(X+Y )/Z} is set at 0.2~4.0. Such as the flying pest repellent product of claim 1, wherein the aforementioned silicone rubber molding system reduces the secondary vulcanized rubber of low molecular weight silicone. For example, the flying pest repellent product of claim 1 or 2, wherein the aforementioned reinforcing filler contains siloxane-modified silicon dioxide. For example, the flying insect repellent product of claim 1 or 2, wherein the flying insect repellent fragrance composition is used as the flying insect repellent fragrance ingredient, and further contains (d) selected from threonyl acetate and ot-butylcyclohexyl ethyl Ester, citronellyl acetate, phenethyl acetate, geranyl acetate, cinnamyl acetate, tricyclodecenyl acetate, anisyl acetate, allyl ring Hexyl acetate, allyl cyclohexyl propionate, allyl isobutoxy acetate, allyl n-pentoxy acetate, allyl cyclohexyloxy acetate, allyl Phenoxy acetate, phenethyl alcohol, borneol, eugenol, nerol, ethyl linalool, thymol, p-menthane-3,8-diol, 1,8-eucalyptus oil A fragrance of at least one of the group consisting of phenol, diphenyl oxide, citronellal, Damascone, cis-jasmone and dihydrojasmone. Such as the flying insect repellent product of claim 1 or 2, wherein the flying insect repellent fragrance composition system does not substantially contain citral. Such as the flying insect repellent product of claim 1 or 2, wherein the average volatile amount of the flying insect repellent fragrance ingredient from the surface of the silicone rubber molded body is 0.04~0.9mg/cm ² ‧h. Such as the flying pest repellent product of claim 6, wherein the aforementioned silicone rubber molding system is provided with a ring-shaped rubber molded body inserted into or worn on a part of the human body or a stretchable ring of an object, or combined with or near the end With each other, it can form a belt-shaped rubber molded body that is inserted or worn on a part of a human body or a stretchable ring of an object. For example, the flying insect repellent product of claim 7 is attached to the ring to be inserted into or worn on a part of the human body or the aforementioned object, and the flying insect repellent fragrance ingredient volatilizes for 5 to 15 hours. For example, the flying pest repellent product of claim 7, wherein the aforementioned ring part is provided with an outline of graphics or characters. A flying pest repellent method, which uses the flying pest repellent product of any one of claims 1-9, which is characterized in that the flying pest repellent fragrance ingredient is volatilized from the surface of the rubber molded body.

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