JP6823225B2 - Flying pest repellent products and flying pest repellent methods - Google Patents

Description

In the present invention, in a silicone rubber molded body having a hardness of 50 degrees or less, a flying pest repellent fragrance composition containing a flying pest repellent fragrance component is held in a state of being inserted into a gap in the molecular structure of the rubber constituting the silicone rubber molded body. The present invention relates to a flying pest repellent product and a flying pest repellent method using the flying pest repellent product.

Conventionally, a method of applying a repellent containing DEET (N, N-diethyltoluamide) to the skin surface against flying pests such as mosquitoes, silkworms, chironomids, and flies has been widely used. However, DEET cannot be expected to have a spatial repellent effect because it is somewhat less volatile than ordinary fragrance components. On the other hand, it is possible to volatilize a room temperature volatilizing insecticidal component, for example, pyrethroid empentrin, into the space to realize a repellent effect against flying pests, but the use of a room temperature volatilizing insecticidal component is rarely avoided. Does exist.

Therefore, some attempts have been proposed to use volatile natural essential oils as repellent components and their composition components. For example, it is well known that citronella oil and its main component, citronellal, have a repellent effect on mosquitoes, and candles containing citronella oil as an active ingredient are commercially available in the United States. However, the method of dissipating citronellal using the heat of the candle has poor volatilization efficiency of citronellal and cannot produce a practical repellent effect.

Further, Japanese Patent Application Laid-Open No. 2002-173407 (Patent Document 1) describes a flying pest repellent containing a natural essential oil selected from orange oil, cassia oil and the like as an active ingredient in addition to citronella oil, and is used as a liquid preparation. As a solvent for this, alcohols such as methyl alcohol and ethyl alcohol, esters such as diethyl phthalate and isopropyl myristate, aliphatic hydrocarbons such as hexane, kerosine and paraffin, aromatic hydrocarbons, ethers and the like. , Various types are listed.

In addition, Japanese Patent Application Laid-Open No. 2003-201003 (Patent Document 2) contains citronellal and one or more selected from tarpineol, menthol, limonene, geraniol, citronellol, camphene and the like as pest repellent components. Disclosed is a pest repellent volatilization composition in which the content of citronellal in the pest repellent component is 2 to 10% by mass. However, although these repellents claim to be naturally produced and give consideration to safety, their repellent effects are inferior in sustainability and are not always satisfactory.

Further, Japanese Patent Application Laid-Open No. 61-289002 (Patent Document 3) proposes "a repellent for arthropods, mollusks and reptiles containing glycol ethers as an active ingredient". Patent Document 3 describes that glycol ethers have an excellent repellent effect on cockroaches and mites, but the effect is far from sufficient, and the repellent effect on flying pests is mentioned at all. Absent.

As described above, a useful flying pest repellent fragrance composition aiming at the effect of repelling flying pests and further improving the persistence of fragrance is not yet known, and its development is required.

By the way, it is known that silicone rubber is excellent in adsorptivity and gas permeability, is physically stable, and is excellent in fragrance divergence. Taking advantage of these properties, air fresheners containing a fragrance in silicone rubber are commercially available. When the fragrance is contained in the silicone rubber, usually, (I) a miraculous silicone rubber composition containing a silicone compound or (II) a liquid silicone rubber composition containing a liquid silicone polymer and the fragrance are mixed and mixed with sulfur or the like. Vulcanization (crosslinking) is performed using a reaction aid, an additive, or the like. However, separation of the fragrance and the silicone rubber polymer or the additive is likely to occur during kneading, and further, as a result of causing chemical changes such as decomposition and modification of the fragrance by the heat during molding and the reaction aid, the fragrance has aroma. Moreover, it was difficult to obtain a molded product having stable physical properties.

Therefore, as a means for solving such a problem, in JP-A-8-31216 (Patent Document 4) and JP-A-2011-26462 (Patent Document 5), the fragrance is not kneaded before the silicone rubber molding. A method of adding a fragrance after molding silicone rubber is adopted. However, these documents make no mention of the properties of the fragrance composition and its compatibility with silicone rubber, and do not necessarily apply to functionally different flying pest repellent fragrance compositions.

As described above, the silicone rubber molded body is prepared by curing and molding (I) a miraculous silicone rubber composition containing a silicone compound or (II) a liquid silicone rubber composition. Further, there are two types of (II) liquid silicone rubber compositions, an addition type and a condensation type. In developing a useful flying insect repellent product using silicone rubber, the present inventors have (I) a miraculous silicone rubber composition or (II) a cured product of a liquid silicone rubber composition, which is a silicone rubber molded product. Was used to examine the compatibility of this with various flying pest repellent fragrance compositions. As a result, by adopting a mixture containing (m) a specific acetic acid ester compound and (n) a monoterpene alcohol and / or an aromatic alcohol having 10 carbon atoms as the repellent composition, the flying pest repellent fragrance component is made of silicone. It has been found that it volatilizes well from the rubber molded body and exerts an excellent effect of repelling flying insects over a predetermined period (Patent Document 6).

The flying pest repellent product of Patent Document 6 was excellent in performance of repelling flying pests, but (I) when a miraculous silicone rubber composition was used as a raw material, the flying pest repellent product was complicated. Due to the shape, burrs are generated during molding and the mold releasability is poor, and there are problems in molding workability and mechanical properties. Therefore, the present inventors have decided to proceed with a more detailed study on the addition type of the (II) liquid silicone rubber composition as a raw material for the silicone rubber molded product. Japanese Patent No. 5053114 (Patent Document 7) discloses a repellent silicone rubber composition obtained by blending acrinathrin with an oxime type liquid silicone rubber composition which is a kind of condensation type. The formation of by-products is unavoidable, and acrinathrin is non-volatile and has completely different properties from the flying pest repellent fragrance component, so it was not useful as a reference.

JP-A-2002-173407 JP-A-2003-201003 JP-A-61-289002 Japanese Unexamined Patent Publication No. 8-31216 Japanese Unexamined Patent Publication No. 2011-26462 Japanese Patent No. 5823649 Japanese Patent No. 5053114

As described above, by using the silicone rubber molded product which is a cured product of the additive liquid silicone rubber composition, the molding workability and mechanical properties thereof are improved, and a flying pest repellent fragrance composition having high compatibility with the molded product is obtained. After finding out, in order to realize a flying pest repellent product that has an even better effect of repelling flying pests, it was indispensable to carry out various tests, and trial and error had to be repeated.

The present invention has been made in view of the above problems, and while making the best use of the characteristics of silicone rubber, improving its molding workability, mechanical properties, etc., as well as the volatilization performance of flying pest repellent fragrance components and repelling against flying pests. An object of the present invention is to provide a flying pest repellent product having excellent effects and a flying pest repellent method.

The present invention has found that the following configuration exerts an excellent effect in achieving the above object.

(1) In a silicone rubber molded body having a hardness of 50 degrees or less, the flying pest repellent fragrance composition containing a flying pest repellent fragrance component is held in a state of being inserted into a gap in the molecular structure of the rubber constituting the silicone rubber molded body. It is a flying pest repellent product that has been used.
The silicone rubber molded product includes (A) methylvinylpolysiloxane, (B) methylhydrogenpolysiloxane as a crosslinked silicone polymer, (C) a platinum compound as a reaction catalyst, (D) a reinforcing filler, and (E). ) A cured product of an additive-type liquid silicone rubber composition containing a reaction inhibitor.
The flying pest repellent fragrance composition contains the following (a), (b), and (c) as the flying pest repellent fragrance component.
(A) At least one terpene hydrocarbon compound selected from the group consisting of limonene, pinene, camphene, and terpinene, and / or at least one terpene compound selected from the group consisting of carboxylic, pregon, menthone, camphor, and piperiten. Ketone compound,
(B) At least one ester compound selected from the group consisting of benzyl acetate, pt-butylcyclohexyl acetate, menthyl acetate, linalyl acetate, benzyl benzoate, allyl hexanoate, allyl heptanoate, and allyl octanoate.
(C) Containing at least one terpene alcohol compound selected from the group consisting of linalool, terpineol, menthol, dihydromilsenol, citronellol, and geraniol.
The total of (a) the total amount X of the terpene hydrocarbon compound and / or the terpene ketone compound and (b) the amount Y of the ester compound in the flying pest repellent fragrance composition, and (c) the terpene alcohol compound. A flying pest repellent product in which the compounding ratio {(X + Y) / Z} with the compounding amount Z is set to 0.2 to 4.0.

(2) The flying pest repellent product according to (1), wherein the silicone rubber molded product is a secondary vulcanized product in which low molecular weight siloxane is reduced.

(3) The flying pest repellent product according to (1) or (2), wherein the reinforcing filler contains siloxane-modified silica.

(4) The flying pest repellent fragrance composition contains (d) styralyl acetate, ot-butylcyclohexyl acetate, citronellyl acetate, phenethyl acetate, geranyl acetate, cinnamyl acetate, and tri as the flying pest repellent fragrance component. Cyclodecenyl acetate, anisyl acetate, allylcyclohexyl acetate, allylcyclohexylpropionate, allylisobutyloxyacetate, allyl n-amyloxyacetate, allylcyclohexyloxyacetate, allylphenoxyacetate, phenethyl alcohol, borneol, eugenol, nerol, It further contains at least one fragrance selected from the group consisting of ethyllinalol, timol, p-menthan-3,8-diol, 1,8-cineol, diphenyloxide, citronellal, damascon, cis-jasmon, and dihydrojasmon ( The flying pest repellent product according to any one of 1) to (3).

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

(6) The average amount of volatilization of the flying pest repellent fragrance component from the surface of the silicone rubber molded product is 0.04 to 0.9 mg / cm ² · h, any one of (1) to (5). Flying pest repellent products described in.

(7) The silicone rubber molded body is an annular rubber molded body having a stretchable ring portion into which a part of the human body or an object is inserted or mounted, or a part of the human body or a part of the human body in which ends are bonded or brought close to each other. The flying pest repellent product according to (6), which is a strip-shaped rubber molded body capable of forming a stretchable ring portion into which an object is inserted or mounted.

(8) The flying pest repellent product according to (7), wherein the flying pest repellent fragrance component volatilizes over 5 to 15 hours with a part of the human body or the object inserted or attached to the ring portion.

(9) The flying pest repellent product according to (7) or (8), wherein the ring portion has a graphic or character contour.

(10) A method for repelling flying pests using the flying pest repellent product according to any one of (1) to (9).
A method for repelling flying pests by volatilizing the flying pest repellent fragrance component from the surface of the rubber molded body.

According to the flying pest repellent product and the flying pest repellent method of the present invention, a flying pest repellent fragrance composition containing a specific flying pest repellent fragrance component in a silicone rubber molded product which is a cured product of the additive liquid silicone rubber composition. In addition to improving the molding workability and mechanical properties of the silicone rubber molded product, the volatilization performance of the flying pest repellent fragrance component and the repellent effect against flying pests are even better than those of conventional products. The usefulness is extremely high.

FIG. 1 is a schematic view of an annular rubber molded body, showing (a) an annular rubber molded body when not attached, and (b) an annular rubber molded body attached to the wrist, respectively. FIG. 2 is an external view of the strip-shaped rubber molded body, showing (a) a strip-shaped rubber molded body when not attached, and (b) a strip-shaped rubber molded body attached to the wrist, respectively.

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

The flying pest repellent product of the present invention is a cured product of an add-on liquid silicone rubber composition and flies to a silicone rubber molded product having a hardness of 50 degrees or less (hereinafter, may be abbreviated as "rubber molded product"). A flying pest repellent fragrance composition containing a pest repellent fragrance component is retained. As the flying pest repellent fragrance component, a specific type suitable for the rubber molded product is used. Details of the flying pest repellent fragrance component will be described later.

The additive liquid silicone rubber composition includes (A) methylvinylpolysiloxane, (B) methylhydrogenpolysiloxane as a crosslinked silicone polymer, (C) a platinum compound as a reaction catalyst, (D) a reinforcing filler, and (E) Contains a reaction inhibitor. The addition-type liquid silicone rubber composition includes a one-component type and a two-component type in which two agents are mixed at the time of curing and molding the silicone rubber, and any of them can be used.

Examples of the methyl vinyl polysiloxane (A) include the following types (A-1) to (A-3) having a vinyl group involved in the cross-linking reaction at both ends of the molecular chain and / or the side chain of the molecular chain. ..

(A-1) Type: Dimethylpolysiloxane having both ends of the molecular chain sealed with a dimethylvinylsiloxane group, methylalkylpolysiloxane having both ends of the molecular chain sealed with a dimethylvinylsiloxane group, and dimethylvinylsiloxane having both ends of the molecular chain. Dimethylsiloxane / methylphenylsiloxane copolymer sealed with a group, and dimethylsiloxane / methylalkylsiloxane copolymer having both ends of the molecular chain sealed with a dimethylvinylsiloxane group, etc. having vinyl groups at both ends of the molecular chain ..

(A-2) Type: Methylvinylpolysiloxane with both ends of the molecular chain sealed with a trimethylsiloxy group, a methylvinylsiloxane / dimethylsiloxane copolymer with both ends of the molecular chain sealed with a trimethylsiloxy group, and both molecular chains. A polymer having a vinyl group on the side chain of the molecular chain, such as a methylvinylsiloxane / methylphenylsiloxane copolymer whose ends are sealed with a trimethylsiloxy group, and no vinyl group at both ends of the molecular chain.

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

In the addition type liquid silicone rubber composition, the (A-1) type or the (A-3) type is generally used for the (A) methyl vinyl polysiloxane, but it is said that the mold releasability is improved. From the viewpoint, it is more preferable to use the (A-1) type and the (A-2) type together. The blending amount of (A) methyl vinyl polysiloxane in the addition type liquid silicone rubber composition is preferably 50 to 80% by mass.

(B) Methylhydrogenpolysiloxane acts as a cross-linking agent for (A) methylvinylpolysiloxane. That is, the silicon atom-bonded hydrogen atom in (B) methylhydrogenpolysiloxane undergoes a hydrosilylation reaction with the vinyl group in (A) methylvinylpolysiloxane, and the addition-type liquid silicone rubber composition is cured by cross-linking. Examples of such (B) methylhydrogenpolysiloxane include methylhydrogenpolysiloxane having both ends of the molecular chain sealed with a trimethylsiloxy group, and dimethylsiloxane / methyl having both ends of the molecular chain sealed with a trimethylsiloxy group. Hydrogen siloxane copolymer, methylphenylsiloxane / methylhydrogensiloxane copolymer with both ends of the molecular chain sealed with trimethylsiloxy groups, dimethylpolysiloxane with both ends of the molecular chain sealed with dimethylhydrogensiloxy groups, molecules Examples thereof include methylhydrogenpolysiloxane having both ends of the chain sealed with a dimethylhydrogensiloxy group, and a dimethylsiloxane / methylhydrogensiloxane copolymer having both ends of the molecular chain sealed with a dimethylhydrogensiloxy group. The blending amount of (B) methylhydrogenpolysiloxane in the additive liquid silicone rubber composition is (B) in methylhydrogenpolysiloxane with respect to 1 mol of silicon atom-bonded vinyl group in (A) methylvinylpolysiloxane. The amount of the hydrogen atom bonded to the silicon atom needs to be in the range of 0.5 to 3 mol, preferably 5 to 15% by mass.

The platinum compound (C) acts as a hydrosilylation reaction catalyst and promotes the hydrosilylation reaction of the silicon atom-bonded hydrogen atom in (B) methylhydrogenpolysiloxane to the vinyl group in (A) methylvinylpolysiloxane. .. Examples of such a platinum compound (C) include platinum black, platinum-supported alumina powder, platinum-supported silica powder, platinum-supported carbon powder, platinum chloride acid, a complex of platinum chloride acid and an olefin, and platinum chloride acid. Examples of compounds known as hydrosilylation reaction catalysts such as a complex of diketone and diketone and a complex of platinum chloride and 1,3-divinyltetramethyldisiloxane can be mentioned. The amount of the platinum compound (C) to be blended in the addition type liquid silicone rubber composition is sufficient in the amount of the catalyst, and is 0.01 to 1.0% by mass in order to suppress an increase in the price of the flying pest repellent product. Is preferable.

(D) The reinforcing filler makes the additive liquid silicone rubber composition viscous to improve molding workability, improves the mechanical properties of the silicone rubber molded product, and thus improves the mold releasability from the mold. .. Examples of such (D) reinforcing filler include fumed silica (dry silica), precipitated silica (wet silica), light calcium carbonate, fumed titanium oxide, carbon black, and the like, and in particular, dry silica. A siloxane-modified silica obtained by imparting hydrophobicity to the surface of legal silica or wet method silica using a surface treatment agent such as hexamethyldisilazane (HMDS), polydimethylsiloxane (PDMS), or dimethyldichlorosilane (DDS). preferable. The blending amount of the (D) reinforcing filler in the additive-type liquid silicone rubber composition can be appropriately set in consideration of the viscosity of the additive-type liquid silicone rubber composition, the mechanical properties of the silicone rubber molded product, and the like. , 10 to 50% by mass is preferable.

The reaction inhibitor (E) prevents the addition-type liquid silicone rubber composition from curing at room temperature, and makes it possible to cure when heated. Examples of such (E) reaction inhibitor include 3-methyl-1-butyne-3-ol, 3,5-dimethyl-1-hexin-3-ol, 1-ethynylcyclohexanol, propargyl alcohol and the like. Can be mentioned. The blending amount of the reaction inhibitor (E) in the addition type liquid silicone rubber composition is preferably 0.001 to 0.1% by mass.

In addition to the above-mentioned components (A) to (E), the additive-type liquid silicone rubber composition used in the present invention can be used as an additional filler, for example, calcined silica fine powder, fine silica powder, crushed quartz, or Christovalite powder. Titanium oxide powder, magnesium oxide powder and the like may be blended, and well-known additives such as pigments, heat-resistant agents, flame-retardant agents, non-crosslinkable silicone oils, antibacterial agents and antifungal agents may be blended as appropriate.

The addition type liquid silicone rubber composition can be cured and molded by a well-known molding apparatus and molding method. As the curing molding apparatus, a compression molding machine, a transfer molding machine, an injection molding machine, or the like used in a normal liquid silicone rubber composition molding method can be used. At this time, if the curing temperature of the liquid silicone rubber composition is too low, the curing rate becomes slow and the productivity decreases, while if the curing temperature is too high, the mechanical strength of the silicone rubber molded body decreases, so that it is cured. The temperature is preferably 50 to 240 ° C, more preferably 120 to 210 ° C.

The amount of the reinforcing filler, the bulking filler, or the non-crosslinkable silicone oil added to adjust the cross-linking density of the cured product of the additive-type liquid silicone rubber composition or as an additive of the additive-type liquid silicone rubber composition. It is also possible to control the amount of volatilization of the flying pest repellent fragrance composition to be added later by adjusting.

The silicone rubber molded product obtained by curing and molding the additive liquid silicone rubber composition is physically stable, but if low molecular weight siloxane components or the like remain in the rubber molded product, these may adversely affect the physical properties. , It is known that the rubber molded body itself may cause yellowing. In addition, in the process of studying the flying pest repellent fragrance component by the present inventors, it was clarified that there is a fragrance that is easily affected by the residual component in the rubber molded body such as citral. Therefore, the silicone rubber molded product used in the present invention is post-cured at a temperature of 160 to 240 ° C. for about 1 to 15 hours, preferably at a temperature of 190 to 220 ° C. for about 2 to 7 hours after curing. It is preferable that the secondary vulcanized product has a reduced amount of low molecular weight siloxane by subjecting it to a treatment (secondary vulcanization treatment). It is recognized that the post-cure treatment not only makes the rubber molded body more stable in physical properties and suppresses yellowing or browning of the rubber molded body itself, but also suppresses yellowing or browning that may occur due to interaction with the fragrance. Was done.

The silicone rubber molded product has excellent gas permeability and excellent adsorption and divergence of fragrance. It is considered that this is because the main chain of the molecular structure of the fragrance is composed of carbon, and the fragrance molecule easily enters the gap of the molecular structure of the rubber in which the fragrance molecule is three-dimensionally crosslinked. In particular, when the hardness of the rubber molded product is 50 degrees or less, the molecular structure of the silicone rubber does not become too dense, so that the fragrance molecules easily enter the gaps in the molecular structure of the rubber. If the hardness of the rubber molded body exceeds 50 degrees, the molecular structure of the rubber molded body becomes too dense, and it becomes difficult for the fragrance molecules to enter the gaps in the molecular structure of the rubber, which does not conform to the gist of the present invention. The hardness of the rubber molded product is measured by a method or apparatus conforming to the Japanese Industrial Standards (JIS K6253). In the present invention, the hardness of the rubber molded product is measured using a durometer conforming to the above standards.

The feature of the present invention is to improve molding workability, mechanical properties, etc. by using a cured product of the additive liquid silicone rubber composition thus obtained and having a hardness of 50 degrees or less. By finding the optimum flying pest repellent fragrance composition for a rubber molded product, we have realized a flying pest repellent product whose repellent effect against flying pests is even better than that of conventional products. In Patent No. 5823649 (Patent Document 6), the present inventors have described both rubber molded bodies, which are (I) a cured product of a mirable type silicone rubber composition and (II) a cured product of a liquid silicone rubber composition. When used, as a flying pest repellent fragrance composition compatible with these, a mixture containing (m) a specific acetate compound and (n) a monoterpene-based alcohol and / or an aromatic alcohol having 10 carbon atoms is preferable. It was disclosed that it was.

After that, as a result of further studies by the present inventors on a rubber molded product which is an addition-type cured product among (II) liquid silicone rubber compositions, a specific flight is different from the case of Patent Document 6. It has been found that the pest repellent fragrance component is optimal in compatibility with a rubber molded product which is a cured product of the additive liquid silicone rubber composition, and the flying pest repellent product of the present invention has been achieved.

The flying pest repellent fragrance composition used in the flying pest repellent product of the present invention does not substantially use an insecticidal component, and uses the fragrance component as a flying pest repellent component. Such a fragrance component is referred to as a "flying pest repellent fragrance component". The flying pest repellent fragrance composition contains the following components (a), (b), and (c) as the flying pest repellent fragrance component.

Examples of the component (a) include terpene hydrocarbon compounds such as limonene, pinene, camphene, and terpinene, and / or terpene ketone compounds such as carboxylic, pregon, menthone, camphor, and piperitone. These terpene-based hydrocarbon compounds and / or terpene-based ketone compounds may be used alone or in any combination.

Examples of the component (b) include ester compounds such as benzyl acetate, pt-butylcyclohexyl acetate, menthyl acetate, linalyl acetate, benzyl benzoate, allyl hexanoate, allyl heptanoate, and allyl octanoate. These ester compounds may be used alone or in any combination.

Examples of the component (c) include terpene-based alcohol compounds such as linalool, terpineol, menthol, dihydromilsenol, citronellol, and geraniol. These terpene-based alcohol compounds may be used alone or in any combination.

In the flying pest repellent product of the present invention, the total of the blending amount X of the component (a) and the blending amount Y of the component (b) and the blending ratio of the blending amount Z of the component (c) {(X + Y) / Z } Is set to 0.2 to 4.0, preferably 0.78 to 1.8, and is compatible with a rubber molded body which is a cured product of an add-on liquid silicone rubber composition, and has excellent volatilization performance and flight. It was confirmed from the results of diligent research by the present inventors that pest repellent results were obtained.

The flying pest repellent fragrance composition may further contain the following component (d) as a flying pest repellent fragrance component.

As the component (d), styralyl acetate, ot-butylcyclohexyl acetate, citronellyl acetate, phenethyl acetate, geranyl acetate, cinnamyl acetate, tricyclodecenyl acetate, anisyl acetate, allylcyclohexyl acetate, allylcyclohexyl Propionate, allylisobutyloxyacetate, allyl n-amyloxyacetate, allylcyclohexyloxyacetate, allylphenoxyacetate, phenethyl alcohol, borneol, eugenol, nerol, ethyllinalol, timol, p-menthan-3,8-diol, 1 , 8-Cineol, diphenyloxide, citronellal, damascon, cis-jasmon, dihydrojasmon and the like. These fragrances may be used alone or in any combination. Since citral may cause a coloring problem due to the influence of residual components in the rubber molded body, the flying pest repellent product of the present invention does not substantially contain citral in the flying pest repellent fragrance composition. Is preferable.

The flying pest repellent fragrance composition includes various essential oils containing the above fragrance components, for example, jasmine oil, neroli oil, peppermint oil, lavender oil, bergamot oil, orange oil, geranium oil, petitgrain oil, lemon oil, citronella oil. , Cinnamon oil, eucalyptus oil, lemon eucalyptus oil, thyme oil and the like may be added as appropriate. Since such essential oils contain the above-mentioned components (a), (b), and (c), the amount of the essential oils added can be adjusted to make a flying pest repellent fragrance composition ( It is also possible to supplement the a) component, the (b) component, and the (c) component to exert a stronger effect of repelling flying pests.

It is preferable that the flying pest repellent fragrance composition further contains a component that sustains the repellent effect at the time of volatilization of the flying pest repellent fragrance component. The repellent effect lasting component is, for example, glycol and / or glycol ether having a vapor pressure of 0.2 to 20 Pa at 20 ° C.

Specific examples of the above glycol and / or glycol ether (with steam pressure at 20 ° C.) include propylene glycol (10.7 Pa), dipropylene glycol (1.3 Pa), tripropylene glycol (0.67 Pa), and diethylene glycol. (3Pa), triethylene glycol (1Pa), 1,3-butylene glycol, hexylene glycol (6.7Pa), benzyl glycol (2.7Pa), diethylene glycol monobutyl ether (3Pa), dipropylene glycol monobutyl ether, and tri. Propylene glycol monomethyl ether is mentioned, and among them, dipropylene glycol is suitable for the object of the present invention. The above-mentioned glycol and / or glycol ether may be used alone or in any combination. The appropriate blending ratio of glycol and / or glycol ether to the flying pest repellent fragrance component is about 0.2 to 10 times.

The flying pest repellent fragrance composition may contain other functional ingredients as long as the effects of the present invention are not impaired. Examples of other functional components include insecticidal components, deodorant components, sterilizing / antibacterial components, and the like. Examples of the insecticidal component include empentrin, profluthrin, transfluthrin, and metoflutrin, which are pyrethroids that volatilize at room temperature. When the insecticidal component is blended, it is preferable to keep the amount as small as possible in light of the gist of the present invention. As the deodorant component, a plant extract selected from Gramineae, Theaceae, Ginkgoaceae, Oleaceae, Moraceae, Rutaceae, Malpighiaceae, and Ebenaceae is typical. It is also possible to add a green leaf alcohol, a green leaf aldehyde, or the like called "green scent" to impart a relaxing effect. These functional ingredients may be used alone or in any combination.

The flying pest repellent fragrance composition may contain a solvent, a surfactant, a solubilizer, a dispersant, a stabilizer, a pH adjuster, a colorant, as necessary, as long as the effects of the present invention are not impaired. Etc. may be appropriately blended. Further, by microencapsulating or cyclodextrinizing the flying pest repellent fragrance composition, for example, the flying pest repellent fragrance composition may be stabilized or the volatility of the flying pest repellent fragrance component may be adjusted. Is also possible.

Examples of the solvent used for preparing the flight pest repellent product include water, lower alcohols such as ethanol and isopropanol, ketone solvents, ester solvents, and hydrocarbon solvents such as normal paraffin and isoparaffin. These solvents may be used alone or in any combination. Examples of the surfactant include polyoxyethylene hydrogenated castor oil, polyoxyethylene higher alkyl ethers (polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, etc.), polyoxyethylene alkylphenyl ethers, and polyoxyethylene higher fatty acids. Nonionic surfactants such as esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene polyoxypropylene alkyl ethers, laurylamine oxide, stearylamine oxide, lauric acid amidopropyldimethylamine Higher alkylamine oxide-based surfactants such as oxides can be mentioned. These surfactants may be used alone or in any combination.

The above-mentioned flying pest repellent fragrance composition is added to a silicone rubber molded product which is a cured product of an additive liquid silicone rubber composition and has a hardness of 50 degrees or less, and is subjected to a predetermined treatment to give the rubber molded body a flying pest repellent fragrance. By retaining the composition, the flying pest repellent product of the present invention is completed. Then, by using the flying pest repellent product of the present invention and volatilizing the flying pest repellent fragrance component from the surface of the silicone rubber molded product, the flying pest repellent method of the present invention can be carried out.

As a method for adding the flying pest repellent fragrance composition to the rubber molded product, a conventionally known method can be appropriately adopted. For example, when the surface area of the rubber molded product is large, the flying pest repellent fragrance composition is supported by a chemical solution dispensing method or a coating method. When the surface area of the rubber molded product is small, a large number of rubber molded products are placed in a closed container, and a flying pest repellent fragrance composition is added thereto together with a solvent as necessary, sprayed or dropped, and the rubber molded product is stirred. Infiltrate into. Further, the rubber molded product is immersed in the liquid of the flying pest repellent fragrance composition for an appropriate time, or the rubber molded product containing the flying pest repellent fragrance composition in a high concentration and the untreated rubber molded product are placed in a closed container. It is also possible to produce a flying pest repellent product by a method of averaging the concentration of the fragrance composition over the entire rubber molded product by mixing the mixture and leaving it for an appropriate time.

The blending amount (retention amount) of the flying pest repellent fragrance composition in the flying pest repellent product of the present invention may be appropriately determined depending on the intended use, the period of use, the type of the rubber molded body, the specifications thereof, and the like. Good. For example, in the case of a flying pest repellent product that is used for 5 to 15 hours at a time, it is preferable to blend about 20 to 200 mg of a flying pest repellent fragrance composition per rubber molded product. In the case of a flying pest repellent product that is used for 15 to 30 days, for example, it is preferable that the product weight is about 2 to 10 g and a flying pest repellent fragrance composition of about 100 to 2000 mg is blended per rubber molded body.

Hereinafter, the shape and specifications of the rubber molded body will be described. As the shape of the rubber molded body, an annular shape, a strip shape, a small piece sheet shape or the like can be appropriately adopted, but the rubber molded body includes a stretchable ring portion into which a part or an object of the human body is inserted or attached. It is preferably configured as an annular rubber molded body or a strip-shaped rubber molded body capable of forming a stretchable ring portion into which a part or an object of a human body is inserted or attached by connecting or bringing the ends close to each other.

The annular rubber molded body and the band-shaped rubber molded body that retain the flying pest repellent fragrance composition have a ring portion of a part of the human body such as a wrist or ankle, or a handle such as a buggy or a bicycle, a bag, a rucksack, or a bag. When inserted or attached to an object such as a handle, a hat, a shoe, or the like, the flying pest repellent fragrance component gradually volatilizes from the surface of the annular rubber molded body and the band-shaped rubber molded body. For example, in the case of a flying pest repellent product whose volatilization state lasts for 5 to 15 hours, the average volatilization amount (unit surface area) of the flying pest repellent fragrance component from the surface of the rubber molded body in order to maintain such volatilization performance. The average volatilization amount per unit) is preferably 0.04 to 0.9 mg / cm ² · h. When the average volatilization amount of the flying pest repellent fragrance component is within this range, the bleeding of the flying pest repellent fragrance component in the rubber molded body proceeds stably and smoothly for 5 to 15 hours, preferably 8 to 12 hours. .. If the average volatilization amount of the flying pest repellent fragrance component is less than 0.04 mg / cm ² · h, the flying pest repellent effect is insufficient. If the average volatilization amount of the flying pest repellent fragrance component exceeds 1.0 mg / cm ² · h, the duration of the repellent effect will be shortened, or in the silicone rubber molded body of the flying pest repellent fragrance component or the flying pest repellent fragrance composition. There is a possibility that the holding amount of the material becomes excessive and the surface becomes sticky. In the present invention, the average volatilization amount is defined as an average value for a time group showing a volatilization amount of 0.02 mg / cm ² · h or more.

The annular rubber molded body is a single string-like body (wire diameter: 1 to 3 mm, length: 1 to 3 mm, length: 1 to 3 mm) connected around the body so that it can be easily inserted or attached to a part of the human body such as a wrist or ankle or the above-mentioned object. It is about 10 to 20 cm), and preferably a figure or a character is used. FIG. 1 is a schematic view of the annular rubber molded body 1. FIG. 1A shows the annular rubber molded body 1 when not attached, and FIG. 1B shows the state in which the annular rubber molded body 1 is attached to the wrist 2. The annular rubber molded body 1 includes a stretchable ring portion into which a part or an object of a human body is inserted or attached. The contour of the ring has a graphic or character profile, as shown in FIG. 1 (a). Examples of figures or characters include, but are not limited to, animal series, insect series, vehicle series, alphabet series, and the like. When a part of the original shape of the annular rubber molded body 1 is expanded and attached to the wrist, ankle, etc., at least 20%, preferably 30% of the portion is formed in a state of being separated from the skin of the wrist, ankle, etc. It is preferable that the material expands and contracts so as to do so. This is because not only the separated portion contributes to the improvement of volatilization of the repellent fragrance component, but it is desirable to avoid contact with the skin as much as possible even though it is a fragrance component. FIG. 1B shows a separation portion 3 formed by separating a part of the rubber molded body 1 from the wrist 2.

The main part of the annular rubber molded body is a figure or character formed from one string-shaped body, and the rubber molded body is branched from one or several places of the string-shaped body to form a branched portion. However, the attached accessories may be configured. By doing so, the decorativeness is imparted, the weight of the rubber molded body is increased, and the amount of the flying pest repellent fragrance component held can be increased. As a result, the flying pest repellent product of the present invention to be attached to the wrist, ankle, etc. It has the advantage of reducing the number. The shape and size of the accessory are not particularly limited as long as the fragrance component volatilization property of this part is not excessive or too small as compared with the figure or the main part of the character.

The strip-shaped rubber molded body is not particularly limited as long as the shape before use is strip-shaped, but the size thereof is about 0.5 to 2.0 cm in width, about 10 to 25 cm in length, and 1 to 1 in thickness. A material of about 3 mm is easy to use. For example, a band-shaped portion in which at least one hollow and an outer shell portion surrounding the hollow are connected and the ends of the strip-shaped portion are joined or brought close to each other to form a part of the human body or a part of the human body. A shape having a joint portion forming an expandable ring portion into which an object is inserted or mounted, or a band-shaped portion having at least one protrusion on one end side and a part of the human body by fitting the protrusion. Alternatively, a shape including a joint portion forming a stretchable ring portion into which an object is inserted or mounted is preferable. The strip-shaped portion serves as the main material (main body) of the rubber molded body. The strip-shaped portion can maintain elasticity equal to or higher than that of a rubber molded body simply molded into a string shape, and there is no problem in terms of strength. The joint portion is a band-shaped rubber molded body (flying pest repellent product) before use, which is temporarily fixed by changing it into an annular shape at the time of use. Since the size of the formed ring portion can be adjusted by the connecting portion, the state of adhesion to a part of the human body or an object can be appropriately adjusted. For example, if you do not want the rubber molded body to move more than necessary when you insert or attach it to a part or object of the human body, you can adjust the joint so that the degree of tightening is somewhat stronger. Good. On the other hand, even if it is a fragrance component, if you want to avoid direct contact with the skin as much as possible, loosely adjust the joint so that the rubber molded body is attached as far as possible from the skin such as the wrist and ankle. Is also possible. A preferable configuration of the connecting portion includes a specification in which a plurality of receiving portions are provided on one end side (or the other end side) of the strip-shaped portion and one or a plurality of protrusions are provided on the other end side (or one end side). Specifically, for example, 3 to 7 round through holes are arranged along the length direction as a receiving portion, and a T-shaped protrusion provided on the other end side is fitted into any of them. It can be designed to form a ring. Alternatively, 6 to 10 round through holes are arranged as receiving portions along the length direction, and 2 to 4 protrusions provided on one end side are fitted into the through holes to form a ring portion. Can be designed as

The hollow existing in the band-shaped portion creates a diffused air flow and contributes to the improvement of volatility. The size and shape of the hollow band-shaped part affect not only the volatilization performance of the flying pest repellent fragrance component from the rubber molded body, but also the elasticity and strength of the rubber molded body, so it is necessary to determine these factors in consideration. There is. Regarding the size of the hollow, for example, when the rubber molded body is in a non-stretchable state, the total area occupied by the hollow is S ₁ and the total area (including S ₁ ) of the rubber molded body is S ₂ in a plan view. When this is done, it is preferable that 0.05 ≤ S ₁ / S ₂ ≤ 0.6 is set. When the value of S ₁ / S ₂ is less than 0.05 (that is, the hollow area ratio to the rubber molded body is less than 5%), the volatilization performance per unit weight of the rubber molded body is formed into a string shape. It will not reach the body. On the other hand, if the value of S ₁ / S ₂ is more than 0.6 (that is, the hollow area ratio to the rubber molded body is more than 60%), there is a possibility that the strength of the rubber molded body may be problematic.

Examples of the hollow shape include those whose contour is configured to have a figure or character shape. Examples of the figure or character shape include, but are not limited to, animal series, insect series, vehicle series, alphabet series, and the like. Further, some of the hollows can be filled in and modified into a concave shape. By doing so, it is possible to increase the weight of the rubber molded product and increase the filling amount of the flying pest repellent fragrance component while maintaining the hollow design. Of course, it is also possible to form a branch portion extending outward from the outer shell portion surrounding the hollow to give character and design.

In a band-shaped rubber molded body, when a part or an object of a human body is inserted or attached to form a stretchable ring portion, at least 20%, preferably 30% of the ring portion is separated from the skin such as a wrist or ankle. It is preferable that the material expands and contracts so as to form a mounted state.

FIG. 2 shows an example of a band-shaped rubber molded body 100 provided with a band-shaped portion 10 and a connecting portion 20 used as the flying pest repellent product of the present invention. FIG. 2 is an external view of the strip-shaped rubber molded body 100. FIG. 2A shows a strip-shaped rubber molded body 100 when not attached, and FIG. 2B shows a strip-shaped rubber molded body 100 attached to the wrist H by connecting both ends of the strip-shaped rubber molded body 100. In the strip-shaped rubber molded body 100, a plurality of parts 1A imitating a star are connected as a hollow contour.

Examples of the flight pest repellent product include the above-mentioned annular rubber molded product, and a wrist ring, wrist band, etc. using the strip-shaped rubber molded product. In addition, the flying pest repellent product can be configured in the shape of a watch band. In this case, a storage portion for storing a small piece of rubber molded body can be formed in a part thereof so that the rubber molded body can be replaced freely. It is possible. In this case, there is an advantage that the rubber molded body does not come into direct contact with the skin of the arm. Such a combination of the rubber molded body and the stored body is a mounting type or a hanging type used not only for the human body but also for spaces such as in a car as long as the volatilization performance of the flying pest repellent fragrance component is secured. It can be applied to various forms of flying pest repellent products.

The flying pest repellent product of the present invention thus obtained can be used in spaces such as entrances, kitchens, toilets, living rooms, bedrooms, warehouses, cars, etc., and in gardens, outdoors, wrists, ankles, etc. Mosquitoes such as Culex pipiens, London Underground mosquito, and Black fly, flies, flies, flies (Psychodidae, flies, etc.), butterfly flies, and squid, by attaching 1 to 5 to the flight as needed. It exerts an excellent repellent effect on flying pests such as mosquitoes over a predetermined period of time. When an aromatic flying pest repellent fragrance component is used, the initial fragrance tone does not deteriorate and lasts for a predetermined period of time, and since this product does not substantially contain an insecticidal component, it is an insecticide. Even people who do not like to use it can use it without any resistance, so its practicality is extremely high.

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

[Example 1]
As a two-component additive liquid silicone rubber composition, one and two silicone rubber compositions are prepared according to the following formulation, and the prepared silicone rubber compositions and two are mixed at room temperature and injected. It was cured at 140 ° C. using a molding machine to form a string ring shape (wire diameter: about 2 mm, weight: 1.6 g, hardness: 32 degrees) imitating an animal character. After molding, it was placed in an oven and post-cured at 210 ° C. for 5 hours to obtain a silicone rubber molded product.
-Silicone rubber composition 1 liquid (A) component: Methylvinylpolysiloxane with both ends of the molecular chain sealed with dimethylvinylsiloxane groups 63% by mass
Component (C): Complex of chloroplatinic acid and 1,3-divinyltetramethyldisiloxane 0.05% by mass
Component (D): Siloxane-modified silica (HMDS is used as a surface treatment agent) 20% by mass
Increased filler: fine silica powder 16.95% by mass
-Silicone rubber composition 2 liquid (A) component: Methylvinylpolysiloxane with both ends of the molecular chain sealed with a dimethylvinylsiloxane group 63% by mass
Component (B): Methylhydrogenpolysiloxane with both ends of the molecular chain sealed with a trimethylsiloxy group 7.6% by mass
Component (D): Siloxane-modified silica (HMDS is used as a surface treatment agent) 20% by mass
(E) Ingredient: 1-ethynylcyclohexanol 0.05% by mass
Increased filler: fine silica powder 9.35% by mass

A flying pest repellent fragrance composition was prepared according to the following formulation. This flying pest repellent fragrance composition does not contain citral as a flying pest repellent fragrance component, and is the sum of the blending amount X of the component (a) and the blending amount Y of the component (b), and the blending amount of the component (c). The blending ratio with Z {(X + Y) / Z} was 1.1.
・ Flying pest repellent fragrance composition (30 mg per rubber molded product)
(A) Ingredient: l-Carvone 14.3% by mass (4.3 mg)
(B) Ingredient: Benzyl acetate 7.0% by mass (2.1 mg)
pt-Butyl Cyclohexyl Acetate 4.0% by Mass (1.2 mg)
Benzyl benzoate 6.7% by mass (2.0 mg)
Allyl heptanoate 5.7% by mass (1.7 mg)
(C) Ingredient: Linalool 10.3% by mass (3.1 mg)
Terpineol 9.7% by mass (2.9 mg)
Dihydromilsenol 8.3% by mass (2.5 mg)
Geraniol 4.7% by mass (1.4 mg)
(D) Ingredients: styralyl acetate, thymol, p-menthane-3,8-diol Total 12.6% by mass (3.8 mg)
Repellent effect lasting ingredient: Dipropylene glycol 16.7% by mass (5.0 mg)

100 string-ring-shaped silicone rubber molded bodies were placed in a closed container equipped with a spraying device, and the flying pest repellent fragrance composition prepared using the above spraying device was adsorbed by the amount of adsorption per rubber molded body. It was sprayed to 30 mg (25.0 mg as a flying pest repellent fragrance component). After sufficiently stirring, the product is left for 1 day to uniformly permeate the entire rubber molded body with the flying pest repellent composition, and is in a wristling form and has an effective duration of about 10 hours. Example 1) was obtained. Separately, a silicone rubber molded product having a hardness of 80 degrees was similarly tested, but the flying pest repellent fragrance composition adsorbed only a small amount, and the flying pest repellent product of the present invention could not be obtained.

The average volatilization amount of the flying pest repellent fragrance component in the flying pest repellent product of Example 1 per total surface area was 0.35 mg / cm ² · h (from the start of use to 2 hours after the start of use) and was worn on the wrist. At that time, about 44% of the wrist ring was separated from the skin of the wrist. When two flying pest repellent products of Example 1 were wrapped around the left and right wrists and went out, a practical repellent effect was confirmed without being bothered by flying pests such as mosquitoes and flies for about 10 hours. It was. In addition, by wearing an animal character, you can enjoy the playfulness, and the space around your body has the fragrance of the initial scent, so you can enjoy the refreshing feeling.

[Examples 2 to 10, Comparative Examples 1 to 5]
The components (A) and (D) of the additive-type liquid silicone rubber composition are changed to the compositions shown in Table 1, and the others are string rings which are cured products of the additive-type liquid silicone rubber composition according to Example 1. A rubber molded product in the shape of a shape was molded, and the flying pest repellent fragrance composition shown in Table 2 was adsorbed on the molded rubber molded product to obtain the flying pest repellent product of the present invention (Examples 2 to 10). In Table 1, "A-1" is a dimethylpolysiloxane having both ends of the molecular chain sealed with a dimethylvinylsiloxane group, and "A-2" is a methyl having both ends of the molecular chain sealed with a trimethylsiloxy group. It is a vinyl polysiloxane, and "A-3" is a methyl vinyl polysiloxane in which both ends of the molecular chain are sealed with a dimethylvinylsiloxane group. Further, "siloxane-modified silica P" is siloxane-modified silica surface-treated with HMDS, and "siloxane-modified silica Q" is siloxane-modified silica surface-treated with PDMS.

A string ring-shaped rubber molded product, which is a cured product of a mirable type silicone rubber composition, is formed in the same shape as in Example 1, and the flying pest repellent fragrance composition shown in Table 3 is adsorbed on the rubber molded product to repel flying pests. A flying pest repellent product (Comparative Example 1) outside the range of Further, the components (A) and (D) of the additive-type liquid silicone rubber composition are changed to the compositions shown in Table 1, and the others are cured products of the additive-type liquid silicone rubber composition according to Example 1. A string ring-shaped rubber molded body was molded, and the flying pest repellent fragrance composition shown in Table 3 was adsorbed on the rubber molded body to obtain a flying pest repellent product (Comparative Examples 2 to 5) outside the scope of the present invention. ..

Regarding the obtained flying pest repellent products of Examples 2 to 10 and the flying pest repellent products of Comparative Examples 1 to 5, [1] evaluation of molding workability of the rubber molded body, and [2] releasability of the rubber molded body. , [3] Evaluation of coloring on the surface of the rubber molded body, [4] Test of repellent effect on flying pests, and [5] Test on measurement of volatilization amount of fragrance component repelling flying pests.

[1] Evaluation of molding workability of rubber molded product The molding workability of the rubber molded product used for the flying pest repellent product was evaluated as ◎ (very good), ○ (good), △ (inferior), and × (very good). It was evaluated on a four-point scale (inferior).

[2] Evaluation of mold releasability of rubber molded product The mold releasability of the rubber molded product used in the flying pest repellent product was evaluated as ◎ (very good), ○ (good), △ (inferior), and × (very good). It was evaluated on a four-point scale (inferior).

[3] Evaluation of coloring on the surface of the rubber molded product The presence or absence of coloring on the surface of the rubber molded product of the flying pest repellent product was determined by ◎ (no coloring), 〇 (slightly colored), △ (colored: yellowing), and It was evaluated on a four-point scale of × (colored: brown stain).

[4] Flying pest repellent effect test Two open plastic cups (about 1 L) without lids were installed in the test room (about 6 m ³ ). One plastic cup contained an adult Culex pipiens attractant and a test flying pest repellent product (treated plot), and the other plastic cup contained only an adult Culex pipiens attractant (untreated plot). Approximately 50 adult Culex pipiens (female) were released indoors 2 hours after the start of use and 7 hours after the start of use, the invaders invading the plastic cups in both sections were counted, and the flight pest repellent rate was calculated according to the following formula.
Flying pest repellent rate (%) = [(Number of invaders in untreated plot-Number of invaders in treated plot) / Number of invaders in untreated plot] x 100

[5] Measurement test of volatilization amount of flying pest repellent fragrance component The weight of the flying pest repellent product is measured at the start of use, 2 hours after the start of use, and 7 hours after the start of use, and at the start of use based on the amount of weight loss. From 2 hours after the start of use and from 2 hours after the start of use to 7 hours after the start of use, the average volatilization amount of the flying pest repellent fragrance component per unit surface area and unit time was calculated.

The evaluation and test results are shown in Table 4.

As a result of the test, the flying pest repellent product of Examples 2 to 10 (the flying pest repellent fragrance composition containing a specific flying pest repellent fragrance component is held in the silicone rubber molded product which is a cured product of the additive liquid silicone rubber composition. The average volatilization amount from the start of use to 2 hours after the start of use and from 2 hours after the start of use to 7 hours after the start of use, and the flight between 2 hours after the start of use and 7 hours after the start of use. When the pest repellent rate was verified, it was confirmed that the flying pest repellent fragrance component had excellent volatilization performance and had a satisfactory flying pest repellent effect. Here, the specific flying pest repellent fragrance component contains (a) a terpene-based hydrocarbon compound and / or a terpene-based ketone compound, (b) an ester compound, and (c) a terpene-based alcohol compound, and The total amount of (a) terpene-based hydrocarbon compound and / or terpene-based ketone compound compounding amount X and (b) ester compound compounding amount Y to (c) terpene-based alcohol compound compounding amount Z {( X + Y) / Z} is adjusted to 0.2 to 4.0. On the other hand, flying pest repellent products (Comparative Examples 2 to 4) that do not contain any of the components (a), (b), and (c), which are specific flying pest repellent fragrance components, and their formulations. The flying pest repellent product (Comparative Example 5) having a ratio outside the specified range of the present invention was inferior in the volatilization performance and the repellent effect of the flying pest repellent fragrance component. Further, in the flying insect repellent products of Examples 2 to 10 in which the silicone rubber molded product is a cured product of the additive liquid silicone rubber composition, Comparative Example 1 in which the silicone rubber molded product is a cured product of the miraculous silicone rubber composition. Compared with the flying pest repellent product, it was excellent in molding workability and mold releasability.

It was confirmed that the flying pest repellent products of Examples 2 to 4 containing the repellent effect lasting component can stably maintain the repellent effect even after 7 hours from the start of use. Further, as the component (A) of the additive liquid silicone rubber composition, dimethylpolysiloxane in which both ends of the (A-1) molecular chain are sealed with a dimethylvinylsiloxane group and trimethylsiloxy at both ends of the (A-2) molecular chain. In Example 3 in which the methylvinyl polysiloxane sealed with a group was used in combination, it was confirmed that the releasability was improved. Further, Examples 2, 4 to 6 have excellent molding workability, and the use of siloxane-modified silica as the component (D) of the additive liquid silicone rubber composition is effective in improving the molding workability. It was confirmed that. Further, the flying pest repellent product of Example 8 and the flying pest repellent product of Example 9 both contained citral as a flying pest repellent fragrance component, but in Example 8 in which the silicone rubber molded body was post-cured, The degree of coloring was suppressed as compared with Example 9. From this, it was confirmed that the problem of coloring can be improved by physically stabilizing the silicone rubber molded product by post-curing the silicone rubber molded product.

[Examples 11 to 16]
The addition type liquid silicone rubber composition was cured according to Example 5 and molded into a string ring shape. After molding, it was placed in an oven and post-cured under various conditions shown in Table 5 to obtain a silicone rubber molded product. The flying pest repellent fragrance composition of the present invention was adsorbed on the obtained rubber molded body according to Example 5 to obtain the flying pest repellent products (Examples 11 to 16). The flying pest repellent product of Example 11 is the same as the flying pest repellent product of Example 5. The above-mentioned [4] flying pest repellent effect test and [5] flying pest repellent fragrance component volatilization amount measurement test were carried out on the obtained flying pest repellent products of Examples 11 to 16, and the details of the test results are as follows. Although omitted, it was confirmed that all of them have excellent volatilization performance and a flying pest repellent effect comparable to those of the flying pest repellent product of Example 5. Further, with respect to the flying pest repellent products of Examples 11 to 16, the above-mentioned [1] evaluation of molding workability (including post-cure treatment workability) of the rubber molded product and [3] evaluation of coloring on the surface of the rubber molded product Was done. The evaluation results are shown in Table 5.

As a result of the evaluation, in particular, the flying pest repellent products of Examples 11 to 14 were all excellent in molding workability of the rubber molded body, and the coloring on the surface of the rubber molded body was suppressed to a certain extent or more. .. That is, it was confirmed that the silicone rubber molded product was a secondary vulcanized product in which low-molecular-weight siloxane was reduced by post-cure treatment. In particular, the flying pest repellent products of Examples 11 and 12 having a post-cure treatment temperature of 190 to 210 ° C. and a treatment time of 4 to 5 hours are extremely excellent in molding workability of the rubber molded product. However, no coloring was observed on the surface of the rubber molded product.

On the other hand, in the flying pest repellent product of Example 15 in which the treatment temperature of the post-cure treatment was less than 160 ° C., the surface of the rubber molded body was colored, so that the reduction of low molecular weight siloxane by the post-cure treatment was insufficient. It is probable that there was. In the flying pest repellent product of Example 16 in which the treatment temperature of the post-cure treatment exceeded 240 ° C., the rubber molded body itself was yellowed. However, also in these flying pest repellent products of Examples 15 and 16, the molding workability of the rubber molded product was good, and there was no major problem in practical use.

From the above, when the post-cure treatment is performed on the flying pest repellent product of the present invention, the treatment conditions are more preferably 160 to 240 ° C. in consideration of the practical treatment conditions together with the above evaluation results. The temperature is considered to be 190-220 ° C. Further, 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]
An additive liquid silicone rubber composition is prepared according to the following formulation, and this silicone rubber composition is cured at 130 ° C. using an injection molding machine, and seven parts that imitate stars as hollow contours are joined together to form a strip-shaped portion. (Length: 20 cm, length: 20 cm,) having joints (six round through holes (receiving parts) on one end side and T-shaped protrusions on the other end side) at both ends of the strip-shaped portion. Weight: 3.6 g, hardness: 34 degrees, ratio (S1 / S2): 0.35) of the total area (S1) occupied by the hollow to the total area (S2) of the rubber molded body was molded. After molding, the rubber molded product was placed in an oven and post-cured at 220 ° C. for 7 hours.
-Additional liquid silicone rubber composition (A) component: Methylvinylpolysiloxane 67% by mass in which both ends of the molecular chain are sealed with a dimethylvinylsiloxane group.
Component (B): 8.3% by mass of dimethylsiloxane / methylhydrogensiloxane copolymer having both ends of the molecular chain sealed with a trimethylsiloxy group
Component (C): Complex of chloroplatinic acid and olefin 0.04% by mass
Component (D): Siloxane-modified silica (DDS is used as a surface treatment agent) 15% by mass
(E) Component: 3-Methyl-1-butyne-3-ol 0.08% by mass
Increased filler: fine silica powder 9.58% by mass

A flying pest repellent fragrance composition was prepared according to the following formulation. This flying pest repellent fragrance composition does not contain citral as a flying pest repellent fragrance component, and the blending amount of the component (c), which is the total amount of the blending amount X of the component (a) and the blending amount Y of the component (b). The blending ratio {(X + Y) / Z} with respect to Z was 1.2.
-Flying pest repellent fragrance composition (90 mg per rubber molded product)
(A) Ingredient: Menthone 6.4% by mass (5.8 mg)
β-Damascone 4.1% by mass (3.7 mg)
(B) Ingredient: Mentyl acetate 9.2% by mass (8.3 mg)
Benzyl benzoate 7.8% by mass (7.0 mg)
Allyl octanoate 8.5% by mass (7.7 mg)
(C) Ingredient: 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 (4.9 mg)
(D) Ingredients: allylcyclohexyloxyacetate, ethyllinalool, 1,8-cineole total 14.5% by mass (13.1 mg)
Repellent effect lasting ingredient: Tripropylene glycol monomethyl ether 20.0% by mass (18.0 mg)

90 mg of the above-mentioned flying pest repellent fragrance composition (72 mg as a flying pest repellent fragrance component) was added to one place on the outer surface of the strip-shaped rubber molded body. The flying pest repellent fragrance composition was allowed to stand in a hermetically sealed state for 2 days to uniformly permeate the entire rubber molded body to obtain a flying pest repellent product (Example 17) of the present invention having an effective duration of about 12 hours.

The flying pest repellent product of Example 17 is wrapped around the wrist, and a T-shaped protrusion provided on the other end is fitted into one of the round through holes provided on one end side of the band-shaped portion to form a ring portion. did. At this time, the flying pest repellent product of Example 17 has excellent elasticity and is easy to operate, and the size of the ring portion can be adjusted so that the strip-shaped rubber molded body does not move much on the wrist. It was. Since the volatilization performance of the flying pest repellent product of Example 17 is equivalent to that of three string-type products, it is sufficient to wear one of the products on the wrist. As described above, this product is very practical, and during the period of use for about 12 hours, it was not bothered by flying pests such as mosquitoes and flies.

[Example 18]
The one-component additive liquid silicone rubber composition used in Example 17 was cured to form a small sheet-shaped rubber molded body (diameter: 3 cm, thickness: 1.2 mm, surface area on one side: 7.1 cm ² ). Was molded. 50 mg of the flying pest repellent fragrance composition used in Example 17 (40 mg as a flying pest repellent fragrance component) was poured into one place on the surface of the obtained rubber molded body, and left to stand in a sealed state for 2 days for flying pests. The repellent fragrance composition was uniformly permeated throughout the rubber molded body. This is effectively stored in a plastic storage body that is annular (diameter: 3.5 cm) and has a circular hole (diameter: 2.7 cm) in the center, and the front and rear surfaces are integrally molded via a hinge. A flying pest repellent product of the present invention (Example 18) for in-vehicle use having a duration of about 10 hours was obtained.

When the flying pest repellent product of Example 18 was hung in a vehicle and used, the average volatilization amount of the flying pest repellent fragrance component from the start of use to 5 hours after the start of use was 0.32 mg / cm ² · h, and further. It was possible to prevent flying pests such as mosquitoes and flies from invading the vehicle for about 10 hours.

The flying pest repellent product of the present invention can be used not only for flying pests but also for a wide range of pest control purposes.

1 Circular rubber molded body 100 Band-shaped rubber molded body

Claims (10)

In a silicone rubber molded body having a hardness of 50 degrees or less, a flying pest repellent fragrance composition containing a flying pest repellent fragrance component is held in a state of being inserted into a gap in the molecular structure of the rubber constituting the silicone rubber molded body. It is a flying pest repellent product,
The silicone rubber molded product includes (A) methylvinylpolysiloxane, (B) methylhydrogenpolysiloxane as a crosslinked silicone polymer, (C) a platinum compound as a reaction catalyst, (D) a reinforcing filler, and (E). ) A cured product of an additive-type liquid silicone rubber composition containing a reaction inhibitor.
The flying pest repellent fragrance composition contains the following (a), (b), and (c) as the flying pest repellent fragrance component.
(A) At least one terpene hydrocarbon compound selected from the group consisting of limonene, pinene, camphene, and terpinene, and / or at least one terpene compound selected from the group consisting of carboxylic, pregon, menthone, camphor, and piperiten. Ketone compound,
(B) At least one ester compound selected from the group consisting of benzyl acetate, pt-butylcyclohexyl acetate, menthyl acetate, linalyl acetate, benzyl benzoate, allyl hexanoate, allyl heptanoate, and allyl octanoate.
(C) Containing at least one terpene alcohol compound selected from the group consisting of linalool, terpineol, menthol, dihydromilsenol, citronellol, and geraniol.
The total of (a) the total amount X of the terpene hydrocarbon compound and / or the terpene ketone compound and (b) the amount Y of the ester compound in the flying pest repellent fragrance composition, and (c) the terpene alcohol compound. A flying pest repellent product in which the compounding ratio {(X + Y) / Z} with the compounding amount Z is set to 0.2 to 4.0. The flying pest repellent product according to claim 1, wherein the silicone rubber molded product is a secondary vulcanized product in which low-molecular-weight siloxane is reduced. The flying pest repellent product according to claim 1 or 2, wherein the reinforcing filler contains siloxane-modified silica. The flying pest repellent fragrance composition contains (d) styralyl acetate, ot-butylcyclohexyl acetate, citroneryl acetate, phenethyl acetate, geranyl acetate, cinnamyl acetate, and tricyclodece as the flying pest repellent fragrance component. Nylacetate, anisylacetate, allylcyclohexylacetate, allylcyclohexylpropionate, allylisobutyloxyacetate, allyl n-amyloxyacetate, allylcyclohexyloxyacetate, allylphenoxyacetate, phenethyl alcohol, borneol, eugenol, nerol, ethyllinalol, Claims 1 to further contain at least one fragrance selected from the group consisting of timol, p-menthan-3,8-diol, 1,8-cineol, diphenyloxide, citronellal, damascon, cis-jasmon, and dihydrojasmon. The flying pest repellent product according to any one of 3. The flying pest repellent product according to any one of claims 1 to 4, wherein the flying pest repellent fragrance composition does not substantially contain citral. The flying pest according to any one of claims 1 to 5, wherein the average amount of volatilization of the flying pest repellent fragrance component from the surface of the silicone rubber molded product is 0.04 to 0.9 mg / cm ² · h. Repellent product. The silicone rubber molded body is an annular rubber molded body having a stretchable ring portion into which a part or an object of the human body is inserted or mounted, or a part or an object of the human body is inserted by joining or bringing the ends close to each other. The flying pest repellent product according to claim 6, which is a strip-shaped rubber molded body capable of forming a stretchable ring portion to be attached. The flying pest repellent product according to claim 7, wherein the flying pest repellent fragrance component volatilizes over 5 to 15 hours with a part of the human body or the object inserted or attached to the ring portion. The flying pest repellent product according to claim 7 or 8, wherein the ring portion has a graphic or character contour. A method for repelling flying pests using the flying pest repellent product according to any one of claims 1 to 9.
A method for repelling flying pests by volatilizing the flying pest repellent fragrance component from the surface of the rubber molded body.

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