Flying pest repellent product and flying pest repellent method
阅读说明：本技术 飞行害虫驱避制品及飞行害虫驱避方法 (Flying pest repellent product and flying pest repellent method ) 是由 浮田凉子 岩本友美 大野泰史 川尻由美 中山幸治 于 2019-04-04 设计创作，主要内容包括：本发明提供一种改善硅橡胶的成形作业性、机械特性等,并且飞行害虫驱避香料成分的挥散性能与飞行害虫驱避效果优异的飞行害虫驱避制品。一种飞行害虫驱避制品,其为在硬度50度以下的硅橡胶成形体中保持有飞行害虫驱避香料组合物的飞行害虫驱避制品,硅橡胶成形体为加成型液状硅橡胶组合物的固化物,飞行害虫驱避香料组合物含有(a)萜烯系烃化合物和/或萜烯系酮化合物、(b)酯化合物及(c)萜烯系醇化合物作为飞行害虫驱避香料成分,(a)的配合量X和(b)的配合量Y的合计与(c)的配合量Z的配合比率{(X+Y)/Z}设定在0.2～4.0。(The invention provides a flying pest repellent product which improves the forming operation performance, mechanical characteristics and the like of silicon rubber and has excellent flying pest repellent perfume component volatilization performance and flying pest repellent effect. A flying pest repellent product comprising a silicone rubber molded body having a hardness of 50 degrees or less and a flying pest repellent fragrance composition held therein, wherein the silicone rubber molded body is a cured product of an addition-type liquid silicone rubber composition, and the flying pest repellent fragrance composition contains, as flying pest repellent fragrance components, (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 blending ratio { (X + Y)/Z } of the total of the blending amount X of (a) and the blending amount Y of (b) to the blending amount Z of (c) is set to 0.2 to 4.0.)
1. A flying insect repellent product, wherein a flying insect repellent fragrance composition containing a flying insect repellent fragrance component is held in a silicone rubber molded body having a hardness of 50 ℃ or less in a state of entering into gaps in the molecular structure of the rubber constituting the silicone rubber molded body,
the silicone rubber molded body is a cured product of an addition type liquid silicone rubber composition containing (A) methylvinylpolysiloxane, (B) methylhydrogenpolysiloxane as a crosslinked silicone polymer, (C) a platinum compound as a reaction catalyst, (D) a reinforcing filler, and (E) a reaction inhibitor,
the flying pest repellent fragrance composition contains the following (a), (b) and (c) as the flying pest repellent fragrance components,
(a) a terpene-based hydrocarbon compound selected from at least one of the group consisting of limonene, pinene, camphene and terpinene, and/or a terpene-based ketone compound selected from at least one of the group consisting of carvone, pulegone, menthone, camphor and piperitone;
(b) an ester compound selected from at least one of benzyl acetate, p-tert-butylcyclohexyl acetate, menthyl acetate, linalyl acetate, benzyl benzoate, allyl caproate, allyl heptanoate, and allyl caprylate;
(c) at least one terpene alcohol compound selected from the group consisting of linalool, terpineol, menthol, dihydromyrcenol, citronellol and geraniol,
in the flying pest repellent perfume composition, the ratio of the total of the blending amount X of the terpene hydrocarbon compound and/or terpene ketone compound (a) and the blending amount Y of the ester compound (b) to the blending amount Z of the terpene alcohol compound (c), namely (X + Y)/Z, is set to 0.2-4.0.
2. The flying pest repellent article of claim 1, wherein the silicone rubber shaped body is a secondary vulcanized rubber reduced in low molecular siloxane.
3. The flying pest repellent article of claim 1 or 2, wherein the reinforcing filler comprises silicone modified silica.
4. The flying pest repellent article according to any one of claims 1 to 3, wherein the flying pest repellent fragrance composition further contains (d) as the flying pest repellent fragrance ingredient, and (d) a fragrance selected from at least one of the group consisting of styryl acetate, o-tert-butylcyclohexyl acetate, citronellyl acetate, phenethyl acetate, geranyl acetate, cinnamyl acetate, tricyclodecenyl acetate, anisyl acetate, allyl cyclohexyl propionate, allyl isobutoxy acetate, allyl n-pentoxy acetate, allyl cyclohexyloxy acetate, allyl phenoxyacetate, phenethyl alcohol, borneol, eugenol, nerol, ethyl linalool, thymol, p-menthane-3, 8-diol, 1, 8-eucalyptol, diphenyl ether, citronellal, damascenone, cis-jasmone and dihydrojasmone.
5. The flying pest-repellant article of any one of claims 1-4, wherein the flying pest-repellant fragrance composition is substantially free of citral.
6. The flying insect repellent article according to any one of claims 1 to 5, wherein the average amount of volatilization of the flying insect repellent fragrance component from the surface of the silicone rubber molded body is 0.04mg/cm2·h～0.9mg/cm2·h。
7. The flying pest repellent article of claim 6, wherein the silicone rubber shaped body is: an annular rubber molded body having a stretchable ring portion inserted or attached to a part of a human body or an object; or a band-shaped rubber molding, wherein the end portions are joined or brought close to each other to form an extensible ring portion which is inserted or attached to a part of a human body or an object.
8. The flying pest-repellent article of claim 7, wherein the flying pest-repellent fragrance ingredient continues to be volatilized for 5 to 15 hours in a state where the part of the human body or the object is inserted or mounted on the loop portion.
9. The flying pest repellent article of claim 7 or 8, wherein the loop portion is provided with an outline of a graphic or character.
10. A flying pest repelling method using the flying pest repelling product according to any one of claims 1 to 9, wherein,
allowing the flying pest repellent fragrance component to volatilize from the surface of the rubber molded body.
Technical Field
The present invention relates to a flying pest repellent product in which a flying pest repellent fragrance composition containing a flying pest repellent fragrance component is held in a state of entering into a gap of a molecular structure of rubber constituting a silicone rubber molded body in a silicone rubber molded body having a hardness of 50 degrees or less, and a flying pest repellent method using the flying pest repellent product.
Background
Conventionally, a method of applying a repellent containing an anophelifuge amine (N, N-diethyltoluamide) to a skin surface to flying pests such as mosquitoes, gnats, chironomids, flies, and the like has been widely used. However, the repellent amine has a slightly lower volatility than the conventional perfume components, and therefore a space repellent effect cannot be expected. On the other hand, although it is possible to achieve a repellent effect on flying pests by volatilizing a room temperature volatile insecticidal component, for example, pyrethroid-based empenthrin, the use of a room temperature volatile insecticidal component is often in a concern.
Therefore, several attempts have been made to use volatile natural essential oils and their components as repellent components. For example, citronella oil, citronellal which is a main component thereof, is known to exhibit a repellent effect against mosquitoes, and candles containing citronella oil as an active ingredient have been commercially available in the united states. However, the method of diffusing citronellal by using candle heat has poor volatilization efficiency of citronellal, and thus cannot achieve a practical repellent effect.
In addition, jp 2002-173407 a (patent document 1) describes that a flying pest repellent containing a natural essential oil selected from orange oil, cinnamon oil and the like as an active ingredient in addition to citronella oil is used as a solvent for a liquid agent, and examples thereof include: alcohols such as methanol and ethanol, esters such as diethyl phthalate and isopropyl myristate, aliphatic hydrocarbons such as hexane, kerosene and paraffin, aromatic hydrocarbons, ethers, and the like.
Further, japanese patent application laid-open No. 2003-201203 (patent document 2) discloses an insect repellent volatile composition containing citronellal and one or more selected from terpineol, menthol, limonene, geraniol, citronellol, camphene and the like as an insect repellent component, wherein the content of citronellal in the insect repellent component is 2 to 10 mass%. However, these repellents, while emphasizing natural origin orientation and safety, have not been satisfactory because of their poor persistence of the repellent effect.
In addition, Japanese patent application laid-open No. Sho 61-289002 (patent document 3) proposes "repellents for arthropods, mollusks and reptiles containing glycol ethers as an active ingredient".
As described above, a useful flying pest repellent fragrance composition aiming at the improvement of the flying pest repellent effect and the persistence of fragrance has not been known, and development thereof has been demanded.
However, silicone rubber is known to have excellent adsorption and air permeability, stable physical properties, and excellent fragrance emission. By virtue of this property, fragrances containing perfumes in silicone rubber have been commercially available. When a silicone rubber is used to contain a fragrance, a silicone rubber composition of (I) a kneading type (japanese: ミラブル type) containing an organosilicon compound (japanese: シリコーンコンパウンド) or a liquid silicone rubber composition containing a liquid silicone polymer (II) is usually mixed with a fragrance and vulcanized (crosslinked) using a reaction assistant such as sulfur, an additive, or the like. However, separation of the perfume from the silicone rubber polymer or the additive is likely to occur during kneading, and further, chemical changes such as decomposition and denaturation of the perfume due to heat and a reaction auxiliary agent during molding occur, and as a result, it is difficult to obtain a molded article having aromatic properties and stable physical properties.
Therefore, as means for solving the problems, in japanese patent laid-open nos. 8-311216 (patent document 4) and 2011-26462 (patent document 5), a method of adding a perfume after molding a silicone rubber is adopted instead of kneading the perfume before molding the silicone rubber. However, these documents do not mention the properties of the perfume composition and the suitability for silicone rubber at all, and are not necessarily applicable to flying pest repellent perfume compositions that are functionally different.
As described above, the silicone rubber molded body is prepared by curing and molding (I) a kneading type silicone rubber composition containing an organosilicon compound or (II) a liquid silicone rubber composition. In addition, there are two types of addition type and condensation type in the liquid silicone rubber composition (II). The present inventors used (I) a kneaded silicone rubber composition or (II) a silicone rubber molded body that is a cured product of a liquid silicone rubber composition, and studied the suitability of this molded body with various flying pest repellent fragrance compositions, in developing useful flying pest repellent products using silicone rubber. As a result, it has been found that by using a mixture containing (m) a specific acetate compound and (n) a monoterpene alcohol and/or an aromatic alcohol having 10 carbon atoms as a repellent composition, an airborne pest repellent fragrance component is favorably volatilized from a silicone rubber molded body, and an excellent airborne pest repellent effect is exhibited over a predetermined period of time (patent document 6).
The flying pest repellent product of patent document 6 has excellent performance for repelling flying pests, but when the kneaded silicone rubber composition (I) is used as a raw material, there are problems with respect to molding workability and mechanical properties, such as generation of burrs during molding or deterioration of mold release properties, due to the complicated shape of the flying pest repellent product. Therefore, the present inventors have made further detailed studies on addition molding in the liquid silicone rubber composition (II) as a raw material of the silicone rubber molded body. In the specification of japanese patent No. 5053114 (patent document 7), although a repellent silicone rubber composition is disclosed in which a fluthrin is blended with an oxime type liquid silicone rubber composition which is one of condensation type, the condensation type cannot avoid the formation of by-products, and the fluthrin is non-volatile and has a completely different property from the flying insect repellent fragrance component, and therefore, cannot be referred to.
Prior art documents
Patent document
Patent document 1: japanese patent laid-open publication No. 2002-173407
Patent document 2: japanese patent laid-open publication No. 2003-201203
Patent document 3: japanese laid-open patent publication No. 61-289002
Patent document 4: japanese laid-open patent publication No. 8-311216
Patent document 5: japanese patent laid-open publication No. 2011-26462
Patent document 6: japanese patent No. 5832649 Specification
Patent document 7: japanese patent No. 5053114 Specification
Disclosure of Invention
Problems to be solved by the invention
As described above, it has been found that a silicone rubber molded body which is a cured product of an addition-type liquid silicone rubber composition is used, and the molding workability and mechanical properties thereof are improved, and a flying insect repellent fragrance composition having high suitability for the improvement, and in addition, in order to realize a flying insect repellent product which exhibits a more excellent flying insect repellent effect, it is indispensable to conduct various tests, and there is a situation that trial and error must be repeated.
The present invention has been made in view of the above problems, and an object of the present invention is to provide: a flying pest repellent product which makes full use of the characteristics of silicone rubber, improves the forming operation, mechanical characteristics and the like, and has excellent flying pest repellent fragrance component volatilization performance and flying pest repellent effect; and a flying pest repelling method.
Means for solving the problems
In the present invention, the following configuration is found to exhibit excellent effects for achieving the above object.
(1) A flying insect repellent product, wherein a flying insect repellent fragrance composition containing a flying insect repellent fragrance component is held in a silicone rubber molded body having a hardness of 50 ℃ or less in a state of entering into gaps in the molecular structure of the rubber constituting the silicone rubber molded body,
the silicone rubber molded body is a cured product of an addition type liquid silicone rubber composition containing (A) methylvinylpolysiloxane, (B) methylhydrogenpolysiloxane as a crosslinked silicone polymer, (C) a platinum compound as a reaction catalyst, (D) a reinforcing filler, and (E) a reaction inhibitor,
the flying pest repellent fragrance composition contains the following (a), (b) and (c) as the flying pest repellent fragrance components,
(a) a terpene-based hydrocarbon compound selected from at least one of the group consisting of limonene, pinene, camphene and terpinene, and/or a terpene-based ketone compound selected from at least one of the group consisting of carvone, pulegone, menthone, camphor and piperitone;
(b) an ester compound selected from at least one of benzyl acetate, p-tert-butylcyclohexyl acetate, menthyl acetate, linalyl acetate, benzyl benzoate, allyl caproate, allyl heptanoate, and allyl caprylate;
(c) at least one terpene alcohol compound selected from the group consisting of linalool, terpineol, menthol, dihydromyrcenol, citronellol and geraniol,
in the flying pest repellent perfume composition, the mixing ratio { (X + Y)/Z } of the total of the mixing amount X of the terpene hydrocarbon compound and/or the terpene ketone compound (a) and the mixing amount Y of the ester compound (b) to the mixing amount Z of the terpene alcohol compound (c) is set to 0.2 to 4.0.
(2) The flying pest repellent article according to item (1), wherein the silicone rubber molded body is a secondary vulcanized rubber reduced in low-molecular siloxane.
(3) The flying pest-repellent article according to (1) or (2), wherein the reinforcing filler comprises silicone-modified silica.
(4) The flying pest repellent according to any one of (1) to (3), wherein the flying pest repellent fragrance composition further contains (d) as the flying pest repellent fragrance ingredient, and (d) a fragrance selected from at least one of the group consisting of styryl acetate, o-tert-butylcyclohexyl acetate, citronellyl acetate, phenethyl acetate, geranyl acetate, cinnamyl acetate, tricyclodecenyl acetate, anisyl acetate, allyl cyclohexyl propionate, allyl isobutoxy acetate, allyl n-pentoxy acetate, allyl cyclohexyloxy acetate, allyl phenoxyacetate, phenethyl alcohol, borneol, eugenol, nerol, ethyl linalool, thymol, p-menthane-3, 8-diol, 1, 8-eucalyptol, diphenyl ether, citronellal, damascenone, cis-jasmone and dihydrojasmone.
(5) The flying pest-repellent article according to any one of (1) to (4), wherein the flying pest-repellent perfume composition contains substantially no citral.
(6) The flying insect-repellent article according to any one of (1) to (5), wherein the average amount of the flying insect-repellent fragrance component volatilized from the surface of the silicone rubber molded body is 0.04mg/cm2·h～0.9mg/cm2·h。
(7) The flying pest repellent article according to (6), wherein the silicone rubber molded body is: an annular rubber molded body having a stretchable ring portion inserted or attached to a part of a human body or an object; or a band-shaped rubber molding, wherein the end portions are joined or brought close to each other to form an extensible ring portion which is inserted or attached to a part of a human body or an object.
(8) The flying pest-repellent product according to item (7), wherein the flying pest-repellent fragrance component continues to be volatilized for 5 to 15 hours in a state where the part of the human body or the object is inserted or attached to the loop portion.
(9) The flying pest-repellent article according to (7) or (8), wherein the loop portion has an outline of a figure or a character.
(10) A method for repelling flying insect pests by using the product according to any one of (1) to (9), wherein,
allowing the flying pest repellent fragrance component to volatilize from the surface of the rubber molded body.
Effects of the invention
According to the flying insect repellent product and the flying insect repellent method of the present invention, the molded silicone rubber body which is a cured product of the addition-type liquid silicone rubber composition retains the flying insect repellent fragrance composition containing the specific flying insect repellent fragrance component, and therefore, the molding workability, mechanical properties, and the like of the molded silicone rubber body are improved, and the flying insect repellent fragrance component has a more excellent volatilization performance and a more excellent effect on flying insects than conventional products, and therefore, the present invention has extremely high usefulness.
Drawings
FIG. 1: FIG. 1 is a schematic view of an annular rubber molded body, which shows (a) the annular rubber molded body when not mounted and (b) the annular rubber molded body mounted on a wrist, respectively.
FIG. 2: fig. 2 is an external view of the belt-shaped rubber molded article, which shows (a) the belt-shaped rubber molded article when not attached and (b) the belt-shaped rubber molded article attached to the wrist, respectively.
Detailed Description
Hereinafter, the flying pest repellent of the present invention will be described. The description of the flying pest repelling article is provided together with the description of the flying pest repelling method of the present invention. However, the present invention is not intended to be limited to the configurations described in the embodiments described below.
The flying insect repellent product of the present invention is a cured product of an addition-type liquid silicone rubber composition, and is a product obtained by holding a flying insect repellent fragrance composition containing a flying insect repellent fragrance component in a silicone rubber molded body having a hardness of 50 degrees or less (hereinafter, may be simply referred to as "rubber molded body"). The flying insect repellent fragrance component uses a specific kind of component suitable for the rubber molded body. Details regarding the flying pest repellent fragrance ingredients are described later
The addition-type liquid silicone rubber composition contains (A) methylvinylpolysiloxane, (B) methylhydrogenpolysiloxane as a crosslinked silicone polymer, (C) a platinum compound as a reaction catalyst, (D) a reinforcing filler, and (E) a reaction inhibitor. The addition type liquid silicone rubber composition may be one liquid, or two liquids in which two components are mixed at the time of curing and molding of the silicone rubber.
Examples of the methylvinylpolysiloxane (A) include the following types (A-1) to (A-3) having vinyl groups participating in a crosslinking reaction at both ends of the molecular chain and/or in the side chain of the molecular chain.
Type (A-1): dimethylpolysiloxane having both ends of the molecular chain blocked by dimethylvinylsiloxane, methylalkylpolysiloxane having both ends of the molecular chain blocked by dimethylvinylsiloxane, dimethylsiloxane-methylphenylsiloxane copolymer having both ends of the molecular chain blocked by dimethylvinylsiloxane, and dimethylsiloxane-methylalkylsiloxane copolymer having both ends of the molecular chain blocked by dimethylvinylsiloxane.
(type A-2): examples of the vinyl group-containing silicone resin include methyl vinyl polysiloxane having both molecular chain ends blocked by trimethylsiloxy groups, methyl vinyl siloxane-dimethyl siloxane copolymer having both molecular chain ends blocked by trimethylsiloxy groups, and methyl vinyl siloxane-methylphenyl siloxane copolymer having both molecular chain ends blocked by trimethylsiloxy groups.
(type A-3): having vinyl groups at both ends of the molecular chain and at both sides of the molecular chain side chain.
In the addition type liquid silicone rubber composition, (A) methylvinylpolysiloxane is generally (A-1) type or (A-3) type, but from the viewpoint of improving mold releasability, (A-1) type and (A-2) type are more preferably used in combination. The amount of the methylvinylpolysiloxane (a) added to the addition-type liquid silicone rubber composition is preferably 50 to 80% by mass.
(B) The methylhydrogenpolysiloxane functions as a crosslinking agent for (a) methylvinylpolysiloxane. That is, the hydrogen atom bonded to the silicon atom in the (B) methylhydrogenpolysiloxane and the vinyl group in the (a) methylvinylpolysiloxane undergo a hydrosilylation reaction, and the addition-type liquid silicone rubber composition is cured by crosslinking. Examples of the (B) methylhydrogenpolysiloxane include: methylhydrogenpolysiloxane blocked at both molecular chain ends by trimethylsiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymer blocked at both molecular chain ends by trimethylsiloxy groups, methylphenylsiloxane-methylhydrogensiloxane copolymer blocked at both molecular chain ends by trimethylsiloxy groups, dimethylpolysiloxane blocked at both molecular chain ends by dimethylhydrogensiloxy groups, methylhydrogenpolysiloxane blocked at both molecular chain ends by dimethylhydrogensiloxy groups, dimethylsiloxane-methylhydrogensiloxane copolymer blocked at both molecular chain ends by dimethylhydrogensiloxy groups, and the like. The blending amount of (B) methylhydrogenpolysiloxane in the addition type liquid silicone rubber composition is required to be: the amount of the (B) methylhydrogenpolysiloxane is in the range of 0.5 to 3 mol, preferably 5 to 15 mass%, of Si-bonded hydrogen atoms per 1 mol of Si-bonded vinyl groups in the (A) methylvinylpolysiloxane.
(C) The platinum compound functions as a hydrosilylation catalyst to promote the hydrosilylation reaction of the hydrogen atom bonded to the silicon atom in the (B) methylhydrogenpolysiloxane with the vinyl group in the (a) methylvinylpolysiloxane. Examples of the platinum compound (C) include compounds known as hydrosilylation catalysts, such as platinum black, platinum-supported alumina powder, platinum-supported silica powder, platinum-supported carbon powder, chloroplatinic acid, a complex of chloroplatinic acid with an olefin, a complex of chloroplatinic acid with a diketone, and a complex of chloroplatinic acid with 1, 3-divinyltetramethyldisiloxane. The amount of the platinum compound (C) to be added to the addition-type liquid silicone rubber composition is sufficient as a catalyst amount, and is preferably 0.01 to 1.0 mass% in order to suppress an increase in the price of the flying pest repellent product.
(D) The reinforcing filler makes the addition type liquid silicone rubber composition viscous to improve the molding workability, and improves the mechanical properties of the silicone rubber molded body, thereby improving the releasability from the mold. Examples of the reinforcing filler (D) include fumed silica (dry silica), precipitated silica (wet silica), precipitated calcium carbonate, fumed titanium oxide, and carbon black, and particularly preferred is a silicone-modified silica having a surface treated with a surface treating agent such as Hexamethyldisilazane (HMDS), Polydimethylsiloxane (PDMS), or dimethyldichlorosilane (DDS) to impart hydrophobicity to the surface of the dry silica or the wet silica. The amount of the reinforcing filler (D) to be blended in the addition type liquid silicone rubber composition may be appropriately set in consideration of the viscosity of the addition type liquid silicone rubber composition, the mechanical properties of the silicone rubber molded body, and the like, and is preferably 10 to 50% by mass.
(E) The reaction inhibitor prevents the addition type liquid silicone rubber composition from being cured at normal temperature, and can be cured when heated. Examples of such (E) reaction inhibitors include 3-methyl-1-butyn-3-ol, 3, 5-dimethyl-1-hexyn-3-ol, 1-ethynylcyclohexanol, and propargyl alcohol. The amount of the reaction inhibitor (E) to be added to the liquid silicone rubber composition is preferably 0.001 to 0.1 mass%.
In the addition liquid silicone rubber composition used in the present invention, in addition to the above-mentioned components (a) to (E), as an extender, for example, fired fine silica powder, ground quartz, cristobalite powder, titanium oxide powder, magnesium oxide powder, or the like may be blended, or further, a pigment, a heat-resistant agent, a flame retardant, a non-crosslinkable silicone oil, an antibacterial agent, a fungicide, or the like may be appropriately blended.
The addition type liquid silicone rubber composition can be cured and molded by a known molding apparatus and molding method. As the curing molding apparatus, a compression molding machine, a transfer molding machine, an injection molding machine, and the like used in a general liquid silicone rubber composition molding method can be used. In this case, when the curing temperature of the liquid silicone rubber composition is too low, the curing speed is slow, and the productivity is lowered, while when the curing temperature is too high, the mechanical strength of the silicone rubber molded body is lowered, so the curing temperature is preferably 50 to 240 ℃, and more preferably 120 to 210 ℃.
The amount of the flying pest repellent fragrance composition to be added later can be controlled by adjusting the crosslinking density of the cured product of the addition type liquid silicone rubber composition, or by adjusting the amount of the reinforcing filler or the extender to be used as an additive to the addition type liquid silicone rubber composition, or by adjusting the amount of the non-crosslinkable silicone oil to be added.
A silicone rubber molded product obtained by curing and molding an addition-type liquid silicone rubber composition has stable physical properties, but when a low-molecular siloxane component or the like remains in the rubber molded product, it is known that these components may adversely affect the physical properties or cause yellowing of the rubber molded product itself. In addition, in the course of the studies of the flying insect repellent perfume components by the present inventors, it was found that there is a perfume which is easily affected by the residual components in the rubber molded article, such as citral. Therefore, the silicone rubber molded body used in the present invention is preferably: a secondary vulcanized rubber containing a reduced amount of low-molecular siloxane is obtained by post-curing (secondary vulcanization) at a temperature of 160 to 240 ℃ for about 1 to 15 hours, preferably 190 to 220 ℃ for about 2 to 7 hours using an oven or the like after curing. By performing post-curing treatment, it was confirmed that: the molded rubber product has more stable physical properties, and can inhibit yellowing or browning of the molded rubber product itself, and can also inhibit yellowing or browning due to interaction with a perfume.
The silicone rubber molded body has the characteristics of excellent gas permeability and excellent adsorption and emission of a fragrance. This is considered to be because the main chain of the molecular structure of the perfume is composed of carbon, and the perfume molecules easily enter the gaps of the molecular structure of the three-dimensionally crosslinked rubber. In particular, when the hardness of the rubber molded product is 50 degrees or less, the molecular structure of the silicone rubber is not excessively dense, and therefore, the fragrance molecules easily enter the gaps in the molecular structure of the rubber. When the hardness of the rubber molded product exceeds 50 degrees, the molecular structure of the rubber molded product becomes too dense, and the fragrance molecules are hard to enter the gaps of the molecular structure of the rubber, which is not suitable for the purpose of the present invention. The hardness of the rubber molded article is measured by a method or an apparatus according to japanese industrial standard (JIS K6253). In the present invention, the hardness of the rubber molded article is measured using a durometer satisfying the above-mentioned standard.
The present invention is characterized in that a flying pest repellent product having a more excellent effect on repelling flying pests than conventional products is realized by using a rubber molded body having a hardness of 50 degrees or less, which is a cured product of the addition-type liquid silicone rubber composition obtained in this manner, to improve molding workability, mechanical properties, and the like, and by finding a flying pest repellent fragrance composition most suitable for the rubber molded body. The present inventors have disclosed the following in japanese patent No. 5832649 (patent document 6): when a rubber molded body of both a cured product of (I) the kneading type silicone rubber composition and a cured product of (II) the liquid silicone rubber composition is used, a mixture containing (m) a specific acetate compound and (n) a monoterpene alcohol and/or an aromatic alcohol having 10 carbon atoms is preferable as the flying insect repellent fragrance composition having compatibility with these.
Then, the present inventors have further studied a rubber molded article as an addition-molded cured product out of (II) the liquid silicone rubber composition, and as a result, have found that, unlike the case of patent document 6, a specific flying insect repellent fragrance component is most suitable for compatibility with a rubber molded article as a cured product of an addition-molded liquid silicone rubber composition, and finally have reached the flying insect repellent product of the present invention.
The flying pest repellent perfume composition used in the flying pest repellent article of the present invention does not substantially use an insecticidal component, but uses a perfume component as a flying pest repellent component. Such perfume ingredients are referred to as "flying pest repellent perfume ingredients". The flying pest repellent fragrance composition contains the following components (a), (b) and (c) as flying pest repellent fragrance components.
Examples of the component (a) include: terpene-based hydrocarbon compounds such as limonene, pinene, camphene and terpinene, and/or terpene-based ketone compounds such as carvone, pulegone, menthone, camphor and piperitone. These terpene-based hydrocarbon compounds and/or terpene-based ketone compounds may be used alone or in any combination thereof.
Examples of the component (b) include ester compounds such as benzyl acetate, p-tert-butylcyclohexyl acetate, menthyl acetate, linalyl acetate, benzyl benzoate, allyl caproate, allyl heptanoate, and allyl octanoate. These ester compounds may be used alone or in any combination thereof.
Examples of the component (c) include terpene alcohol compounds such as linalool, terpineol, menthol, dihydromyrcenol, citronellol, and geraniol. These terpene alcohol compounds may be used alone or in any combination thereof.
In the flying pest repellent product of the present invention, as a result of diligent studies by the present inventors, it was confirmed that: when the blending ratio { (X + Y)/Z } of the total of the blending amount X of the component (a) and the blending amount Y of the component (b) to the blending amount Z of the component (c) is set to 0.2 to 4.0, preferably 0.78 to 1.8, the rubber composition is suitable for a rubber molded body which is a cured product of an addition type liquid silicone rubber composition, and excellent volatilization performance and flying pest repelling result are obtained.
The flying pest repellent fragrance composition may further contain the following component (d) as a flying pest repellent fragrance component.
Examples of the component (d) include perfumes such as styryl acetate, o-tert-butylcyclohexyl acetate, citronellyl acetate, phenethyl acetate, geranyl acetate, cinnamyl acetate, tricyclodecenyl acetate, anisyl acetate, allyl cyclohexyl propionate, allyl isobutoxy acetate, allyl n-pentoxy acetate, allyl cyclohexyloxy acetate, allyl phenoxyacetate, phenethyl alcohol, borneol, eugenol, nerol, ethyl linalool, thymol, p-menthane-3, 8-diol, 1, 8-eucalyptol, diphenyl ether, citronellal, damascenone, cis-jasmone, and dihydrojasmone. These perfumes may be used alone or in any combination. In the flying insect pest-repellent product of the present invention, it is preferable that the flying insect pest-repellent fragrance composition does not substantially contain citral, since citral may be affected by residual components in the rubber molded product to cause a problem of coloration.
Various essential oils containing the above-mentioned perfume components, such as jasmine oil, orange flower oil, peppermint oil, lavender oil, bergamot oil, orange oil, geranium oil, orange leaf oil, lemon oil, citronella oil, cinnamon oil, eucalyptus citriodora oil, thyme oil, and the like, may be appropriately added to the flying pest repellent perfume composition. Since such essential oils contain the above-mentioned component (a), (b) and (c), it is also possible to supplement the component (a), (b) and (c) to the flying insect pest-repellent fragrance composition by adjusting the amount of the essential oils added, thereby exerting a stronger flying insect pest-repellent effect.
The flying insect repellent fragrance composition preferably further contains a repellent effect sustaining component for sustaining the repellent effect when the flying insect repellent fragrance component is volatilized. The repellent effect-sustaining component is, for example, a glycol and/or glycol ether having a vapor pressure of 0.2 to 20Pa at 20 ℃.
Specific examples of the above-mentioned diol and/or diol ether (together with the vapor pressure at 20 ℃) include: propylene glycol (10.7Pa), dipropylene glycol (1.3Pa), tripropylene glycol (0.67Pa), diethylene glycol (3Pa), triethylene glycol (1Pa), 1, 3-butanediol, hexanediol (6.7Pa), benzyl glycol (2.7Pa), diethylene glycol monobutyl ether (3Pa), dipropylene glycol monobutyl ether, and tripropylene glycol monomethyl ether, with dipropylene glycol being suitable for the purposes of the present invention. The above-mentioned diols and/or diol ethers may be used alone or in any combination. The blending ratio of the flying pest repellent perfume component to the glycol and/or glycol ether is about 0.2 to 10 times as appropriate.
The flying pest repellent perfume composition may be blended with other functional ingredients as long as the effect of the present invention is not hindered. Examples of the other functional components include an insecticidal component, a deodorant component, and a bactericidal/antibacterial component. Examples of the insecticidal component include pyrethroid-type empenthrin, bifenthrin, transfluthrin, and metofluthrin which volatilize at normal temperature. When the insecticidal component is blended, it is preferable to suppress the amount of the insecticidal component as small as possible in accordance with the purpose of the present invention. The deodorizing component is selected from plant extracts of Gramineae, Theaceae, Ginkgoaceae, Oleaceae, Moraceae, Rutaceae, Saxifragaceae, and Ebenaceae. In addition, a relaxing effect may be imparted by adding a so-called "green fragrance" such as myrtilol or myrobalal. These functional ingredients may be used alone or in combination
In the flying pest repellent fragrance composition, a solvent, a surfactant, a cosolvent, a dispersant, a stabilizer, a pH adjuster, a colorant, and the like may be appropriately blended as necessary as long as the effect of the present invention is not hindered. Further, the flying pest repellent fragrance composition may be microencapsulated or cyclodextrin to stabilize the flying pest repellent fragrance composition or to adjust the volatility of the flying pest repellent fragrance component.
Examples of the solvent used for the preparation of the flying pest repellent product include: lower alcohols such as water, ethanol and isopropanol; ketone solvents, ester solvents, and hydrocarbon solvents such as n-alkanes and iso-alkanes. These solvents may be used alone or in any combination thereof. Examples of the surfactant include: nonionic surfactants such as polyoxyethylene hydrogenated castor oil, polyoxyethylene higher alkyl ethers (e.g., polyoxyethylene lauryl ether and polyoxyethylene oleyl ether), polyoxyethylene alkylphenyl ethers, polyoxyethylene higher fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid glycerides, and polyoxyethylene polyoxypropylene alkyl ether; higher alkylamine oxide-based surfactants such as laurylamine oxide, stearylamine oxide and lauramidopropyldimethylamine oxide. These surfactants may be used alone or in any combination thereof.
The flying insect pest repellent fragrance composition of the present invention is completed by adding the flying insect pest repellent fragrance composition to a silicone rubber molded body having a hardness of 50 degrees or less, which is a cured product of an addition-type liquid silicone rubber composition, and performing a predetermined treatment to hold the flying insect pest repellent fragrance composition on the rubber molded body. Further, the flying insect pest repelling method of the present invention can be carried out by using the flying insect pest repelling product of the present invention to volatilize the flying insect pest repelling fragrance component from the surface of the silicone rubber molded body.
As a method for adding the flying insect repellent fragrance composition to the rubber molded product, conventionally known methods can be suitably used. For example, when the surface area of the rubber molded article is large, the flying insect repellent fragrance composition is carried by a chemical dispensing method or a coating method. When the surface area of the rubber molded article is small, a plurality of rubber molded articles are put into a closed container, and the flying insect repellent fragrance composition is added to the closed container together with a solvent as needed, sprayed or dropped, and the mixture is allowed to permeate the rubber molded article while stirring. Further, the flying insect pest repellent product can also be produced by a method in which a rubber molded body is immersed for an appropriate period of time in a liquid of the flying insect pest repellent fragrance composition, or a rubber molded body containing the flying insect pest repellent fragrance composition at a high concentration and an untreated rubber molded body are mixed in a closed container and left for an appropriate period of time to average the concentration of the fragrance composition over the entire rubber molded body.
The amount of the flying pest-repellent fragrance composition to be incorporated (retained) in the flying pest-repellent article of the present invention may be determined as appropriate depending on the use and the period of use of the flying pest-repellent article, the type of the rubber molded article, the specification thereof, and the like. For example, when the flying insect repellent product is used for 5 to 15 hours per time, it is preferable to blend about 20 to 200mg of the flying insect repellent fragrance composition per rubber molded body. When a flying insect repellent product is used for 15 to 30 days, it is preferable that the product weight is about 2 to 10g and about 100 to 2000mg of the flying insect repellent fragrance composition is added to each rubber molded product.
The shape and specification of the rubber molded product will be described below. As the shape of the rubber molded article, a ring shape, a belt shape, a small sheet shape, or the like can be suitably used, but the rubber molded article is preferably constituted by: an annular rubber molded body having a stretchable ring portion inserted or attached to a part of a human body or an object; or a band-shaped rubber molding, wherein the end portions are joined or brought close to each other to form an extensible ring portion which is inserted or attached to a part of a human body or an object.
A ring-shaped rubber molded article and a belt-shaped rubber molded article holding the flying insect repellent fragrance composition, the ring portion being inserted into or attached to a part of a human body such as a wrist or an ankle; or handles for carts, bicycles, etc.; handles for handbags, backpacks, purses, and the like; in the case of a cap, a shoe or other article such as a belt, the airborne pest repellent fragrance component gradually evaporates from the surface of the annular rubber molded article or the belt-shaped rubber molded article. For example, in the case of a flying insect repellent product in which the state of volatilization continues for 5 to 15 hours, the average amount of flying insect repellent fragrance component volatilized from the surface of the rubber molded body (average amount of volatilized fragrance per unit surface area) is preferably 0.04 to 0.9mg/cm in order to maintain the volatilization performance2H. When the average volatilization amount of the airborne pest repellent perfume component is within this range, the exudation of the airborne pest repellent perfume component into the rubber molded body is stably and smoothly performed for 5 to 15 hours, preferably 8 to 12 hours. The average volatile amount of the flying pest repellent perfume components is less than 0.04mg/cm2And when the flying insect pest repellent is used for h, the flying insect pest repellent effect is insufficient. The average volatile amount of the flying pest repellent perfume component exceeds 1.0mg/cm2When h is used, the duration of the repellent effect becomes short, or the amount of the flying pest repellent fragrance component or the flying pest repellent fragrance composition held in the silicone rubber molded body becomes too large, and there is a possibility that stickiness may occur on the surface. In the present invention, the average volatile amount means 0.02mg/cm2And h or more of the amount of dispersion in the time zone.
The annular rubber molded body is preferably formed into a figure or a character by using 1 string-like body (wire diameter: 1 to 3mm, length: about 10 to 20 cm) connected around the annular rubber molded body so as to be easily inserted or attached to a part of a human body such as a wrist or an ankle or the above-mentioned object. Fig. 1 is a schematic view of an annular rubber molded
The annular rubber molded article may be configured such that a figure or a character formed of 1 string-like body is a main part, and the rubber molded article is branched from 1 position or a plurality of positions of the string-like body to form branched parts to constitute accessories. By setting as above, the amount of the retained flying pest repellent fragrance component can be increased by adding a decorative property and increasing the weight of the rubber molded article, and as a result, there is an advantage that the number of flying pest repellent articles of the present invention to be attached to wrists, ankles, or the like can be reduced. The shape and size of the part are not particularly limited as long as the volatility of the perfume component in the part is not too large or too small as compared with the main part of the figure or character.
The belt-shaped rubber molded article is not particularly limited as long as it is in a belt shape before use, but is easily usable when it has a size of about 0.5 to 2.0cm in width, about 10 to 25cm in length, and about 1 to 3mm in thickness, and for example, it is preferable that: a shape including a band-shaped portion formed by connecting a member including at least one hollow portion and a peripheral portion surrounding the hollow portion, and a coupling portion which forms a stretchable ring portion into which a part of a human body or an object is inserted or attached by coupling or bringing end portions of the band-shaped portion into proximity with each other; alternatively, the band-shaped portion may have at least one protrusion on one end side, and the coupling portion may be configured to form an extensible ring portion into which a part of a human body or an object is inserted or attached by fitting the protrusion. The belt-like portion is a main material (main body) of the rubber molded body. The band-shaped portion can maintain the same or higher elasticity than a rubber molded article molded only into a string shape, and has no problem in strength. The joint is formed by temporarily fixing a rubber molded article (flying insect repellent article) before use in a band shape by changing the article into a ring shape during use. Since the size of the formed loop portion can be adjusted by the joint portion, the contact state with a part of a human body or an object can be appropriately adjusted. For example, when the rubber molded body is inserted or attached to a part of a human body or an object, the degree of locking may be slightly increased by adjusting the coupling portion in a case where the rubber molded body is prohibited from moving more than necessary. On the other hand, even in the case of a perfume component, when it is desired to avoid direct contact with the skin as much as possible, the connecting portion can be adjusted gradually so as to be attached in a state where the rubber molded body is separated from the skin such as the wrist or the ankle as much as possible. A preferable configuration of the coupling portion is a specification in which a plurality of receiving portions are provided on one end side (or the other end side) of the band-shaped portion, and one or more protruding portions are provided on the other end side (or one end side). Specifically, for example, the following can be designed: the receiving portion is provided with 3-7 circular through holes along the length direction, and any one of the through holes can be fitted into a T-shaped protrusion portion provided on the other end side to form a ring portion. Alternatively, the receiving portion may be designed such that 6 to 10 circular through holes are arranged along the longitudinal direction and 2 to 4 protrusions provided on one end side are fitted into the through holes to form a ring portion.
The hollow portion in the belt-like portion generates a diffused airflow, contributing to improvement of volatility. BeltThe size and shape of the hollow portion of the shaped portion have an influence on the stretchability and strength of the rubber molded article in addition to the ability to volatilize the airborne pest repellent fragrance component from the rubber molded article, and therefore it is necessary to determine the size and shape by taking these factors into consideration. Regarding the size of the hollow, for example, when the rubber molded body is in a non-stretched state, it is preferable to set the total area occupied by the hollow as S in a plan view1The whole area of the rubber molding (including S)1) Is defined as S2When it is equal to or less than 0.05, S1/S2The setting is less than or equal to 0.6. S1/S2When the value of (b) is less than 0.05 (that is, the area ratio of the rubber molded article to the hollow is less than 5%), the volatilization performance per unit weight of the rubber molded article is inferior to that of a rubber molded article molded into a string-like shape. On the other hand, S1/S2If the value of (b) exceeds 0.6 (i.e., if the area ratio of the voids in the rubber molded article exceeds 60%), there is a possibility that the strength of the rubber molded article will be deteriorated.
The hollow shape may be configured such that the outline thereof is in the shape of a figure or a character. Examples of the shapes of the figures and characters include animal series, insect series, vehicle series, and letter series, but it is needless to say that the shapes are not limited to these. In addition, the filling can be changed to be concave for some hollows. By such an arrangement, the weight of the rubber molded body can be increased while maintaining the hollow design, and the amount of the airborne pest repellent fragrance component to be filled can be increased. The branch portion extending outward from the outer peripheral portion surrounding the hollow portion may be formed so as to provide a character or design.
In the belt-shaped rubber molded body, it is preferable that: when forming a stretchable loop portion into which a part of a human body or an object is inserted or attached, the loop portion is stretched in an attached state in which at least 20%, preferably 30%, of the loop portion is separated from the skin such as a wrist or an ankle.
Fig. 2 shows an example of a strip-shaped rubber molded
Examples of the flying insect repellent product include wrist rings and wrist bands using the above-described annular rubber molded article and belt-like rubber molded article. In this case, a housing portion for housing the small-piece-shaped rubber molded body may be formed in a part thereof, and the rubber molded body may be replaced freely. In this case, there is an advantage that the rubber molded body does not directly contact the skin of the arm. Such a combination of a rubber molded body and a housing ensures the volatilization performance of the flying insect repellent fragrance component, and is suitable for various types of flying insect repellent products such as a placement type and a hanging type used for a space in a vehicle, not only for human bodies.
The thus obtained flying pest repellent product of the present invention can be used by installing 1 to 5 flying pest repellents in each place such as indoors, such as doorways, kitchens, toilets, living rooms and bedrooms, spaces such as warehouses and cars, or in front of homes and outdoors, such as wrists and ankles, as needed, and thereby exhibits an excellent flying pest repellent effect on flying pests such as culex pipiens, houseflies, aedes albopictus, gnats, chironomids, flies, small flies (fruit flies, flea flies, etc.), butterfly flies, and clothespondback moths for a predetermined period of time. Further, in the case of using an aromatic flying pest repellent perfume component, the initial fragrance is not deteriorated for a predetermined period of time, and the product does not substantially contain an insecticidal component, so that even a person who does not like to use an insecticide cannot resist the use of the product, and thus the usability thereof is extremely high.
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