TWI563915B - Volatile chemicalcontaining structure - Google Patents

Description

Structure containing volatile agents

The present invention relates to a structure containing a volatile agent in which a resin containing a volatile agent is formed into a specific three-dimensional structure.

In the house, the window or the main entrance becomes the intrusion of pests. As a method for suppressing invasion of pests from the intrusion port, it is considered that the insect pest control device is disposed in these places.

As an example of such an insect repellent device, an insect repellent device that holds a volatile insect repellent on a mesh, stores it in a container having an open window, or a net that holds a volatile drug is known. An insect repellent device in which a material is embedded in a frame member (see Patent Document 1) or the like.

Here, the insect repellent device includes a resin molded body containing a volatile insect repellent component in a resin such as polyolefin, and volatilizes the insect repellent component over time to prevent the pest from intruding into the product or its surroundings. As such a product, not only a product for use as a pest control such as a mosquito net or an insect net, but also an outer package such as a tube or a cable or a resin fiber product is also targeted.

For example, Patent Document 2 describes the preparation of a resin composition comprising a polyolefin-based resin, a pest control agent such as chlorpheniramine or transfluthrin, and a resinous inorganic carrier such as amorphous vermiculite. The purpose of the material (0033 to 0035), and the like (0036) and the like, which are obtained by kneading a polyolefin-based resin as a base resin by extrusion molding or injection molding.

Further, in Patent Document 3, it is shown that in the chemical formula 1 (the following formula (1)), R ¹ is H, R ² is -CH=CHCH ₃ , and R ³ is a methoxy group. Methyl), fenfluthrin (in the above Chemical Formula 1 (Formula (1) below), R ¹ and R ^{2 are the} same as Mentinine, R ³ is a methyl group), and the like is a pyrethroid compound used as a pest. An example of the insect-repellent component of the resin molded body for control.

Further, Patent Document 4 describes a resin composition containing a vapor-decomposable plasticizer and an exudation accelerator to improve the volatility of the insect repellent resin composition. Further, in Patent Documents 4 and 5, as the insecticidal active compound, transfluthrin is mentioned (Patent Document 3 [0011]).

Prior technical literature Patent literature

Patent Document 1; Japanese Patent Laid-Open No. 2006-314284

Patent Document 2: Japanese Patent Laid-Open Publication No. 2008-106232

Patent Document 3: Japanese Patent Laid-Open Publication No. 2007-77069

Patent Document 4: Japanese Patent No. 3858929

Patent Document 5: Japanese Patent Laid-Open Publication No. 2001-192309

However, the insect-proof device of Patent Document 1 is often used in a window or a front door, and in this case, there is a feeling that the insect-repellent device is an obstacle. Feeling the situation of the eye. In this regard, a method of reducing the presence of the insect repellent device by reducing the overall size of the insect repellent device and reducing the thickness is considered.

However, in order to reduce the overall size of the insect repellent device and to reduce the thickness, it is necessary to reduce the mesh in which the insect repellent is held in the insect repellent device, and as a result, the insect repellent effect is reduced with the reduction of the volatilization amount of the insect repellent. Will decrease.

Moreover, when the mesh holding the volatile drug is stored in the container, the volatile agent volatilizes from the surface of the mesh, but if the total surface area of the mesh is in contact with the inner wall of the container If the amount is high, the volatilization of the volatile agent is hindered and the amount of volatilization is lowered, and the volatile agent adhering to the inner wall may cause contamination of the container.

However, in the case where a volatile agent such as a repellent, a fragrance, or an antibacterial agent is used in addition to the insect repellent, there are cases where the same problem such as a decrease in the amount of volatilization or contamination is caused.

Further, when tetrafluthrin, meltine or the like is used as an insect-repellent component, when the particles mixed with the fine powder carrier and kneaded with the resin are produced as in Patent Document 2, if the insect-repellent component is to be made highly concentrated However, there is a problem that the oozing (exudation) of the particles is large, and it becomes sticky and becomes difficult to be used for forming.

Accordingly, it is an object of the present invention to ensure a reduction in the amount of volatilization of a volatile drug even when the size of the entire structure containing the volatile agent is reduced, and to minimize contact with the inner wall of the container in the surface area of the entire structure. In part, it is possible to prevent the volatilization of the volatile agent while preventing the contamination of the container, and the purpose thereof is to easily adapt to the use of resin particles such as tetrafluthrin or metinine for the production of the resin molded body. The exudation is adjusted sexually and shaped.

The present invention solves the above problems by using a structure containing a volatile agent, which is formed into a corrugated body by forming a corrugated body into a corrugated body by using a structure containing a volatile agent. a three-dimensional structure formed by crossing and joining the top portions thereof, and the three-dimensional structure system is formed using a resin composition containing a volatile volatile agent, and the kneaded volatile agent can be exuded to the three-dimensional structure. The surface evaporates from the surface.

Further, in the production of the above-described volatile drug-containing structure, at least one of tetrafluthrin, meteline and fenfluthrin which are insect-repellent components is used as a volatile agent, and ethylene is used. The vinyl acetate copolymer is used as a resin in which a volatile agent and a fine powder carrier are kneaded together, and if necessary, a polyolefin resin such as low density polyethylene (LDPE) is mainly blended, and tetrafluorobenzene is used. In the case of pyrethroids, the anti-crystal precipitation component is also contained, and these are mixed in an appropriate amount to produce resin particles containing the insect-repellent component. The above-mentioned problem is usually solved by kneading a resin composition into which a polyolefin resin is added to form a resin composition and molding it into a structure containing a volatile drug.

Further, even when Meitinine or Fenmethrin acts as a crystal precipitation preventing component, it is calculated as an insecticidal component in the calculation of the blending ratio.

First, the volatile drug resin particles (resin particles containing an insecticidal component) used in the present invention will be described. According to the invention, the ethylene-vinyl acetate copolymer is made to be 5% by mass or more and 50% by mass or less By mixing, the oozing of the obtained particles can be suppressed within a moderate range. When it is used in the case of liquid orientin or fifenthrene at a normal temperature, it is necessary to adjust the exudation. Regarding the tetrafluthrin which is crystalline at normal temperature, since it is desired to increase the concentration in the resin, there is Under the object of the present invention, crystals are precipitated on the surface of the particles accompanying bleed, and thus the effects of the present invention are more useful especially in the case of using tetrafluthrin. Since the volatilization of the insect-repellent component does not occur even if bleeding does not occur at all, it is not desirable to completely suppress the bleeding, and the ethylene-vinyl acetate copolymer which is an exudation-adjusting resin is contained in the above range, and the bleeding in the form of particles is controlled. Further, the pellet is used as a master batch, and the molded body obtained by extrusion molding, injection molding, or the like can also ensure bleeding required for volatilization. Further, after the ethylene-vinyl acetate copolymer is in the above range, the amount of addition of the resin may be adjusted by using another resin, and as the resin, affinity with the ethylene-vinyl acetate copolymer is preferred. Higher LDPE.

As the fine powder carrier contained in the range of 10% by mass or more and 30% by mass or less, it is possible to use a microcrystalline vermiculite such as white carbon, which does not react with tetrafluthrin or metinine, and has a surface area. A wider fine powder. The fine powder carrier carries the insect-repellent component and suppresses the stickiness. As a result, the particles obtained by kneading with the resin are also less likely to be sticky as a whole, and can be preferably used as a masterbatch.

On the other hand, when tetrafluthrin is used for the insect-repellent component, the anti-crystal precipitation component can be contained in the range of 1 mass% or more and 20 mass% or less. The anti-crystal precipitation component is a component which suppresses the effect of precipitation of tetrafluthrin which is crystalline at normal temperature on the surface. Can be used as the crystal The compound of the precipitation component is a dibasic acid ester compound, an aromatic ester compound, a higher fatty acid ester compound, a pyrethroid compound other than tetrafluthrin, and a pyrethrum flower which are liquid at normal temperature. As the ester synergist or the like, these may be used alone or in combination of plural kinds. Among them, a dibasic acid ester compound such as dibutyl succinate is preferred. Further, at the same time, phenbutanin which is a pyrethroid compound can be used, and N-(2-ethylhexyl)-bicyclo[2,2, which is a synergist for pyrethroids, can also be used. 1]-seven-5-ene-2,3-dimethylimine, which further enhances the effect of preventing crystal precipitation. Further, in the case of using Meitin, it has an advantage of not only being an anti-crystal precipitation component but also enhancing the insect-repellent action.

The content of the insecticidal component which can be contained in the granules by the combination of these is, for example, in the case of tetrafluthrin or fenfluthrin, it is 20% by mass or more and 60% by mass or less, and in the case of Metlin. 10% by mass or more and 50% by mass or less. The resin pellet containing the insect-repellent component obtained at the content ratio is used as a master batch, and is contained in an amount of 15% by mass or more and 80% by mass or less, and a resin composition containing a polyolefin-based resin such as low-density polyethylene (LDPE) is used. Extrusion molding or injection molding is carried out by molding other resins, and a structure containing a volatile agent which is excellent in volatilization of the insect repellent component and excellent in insect repellent effect is provided.

Since the structural system containing a volatile drug of the present invention is formed using a wavy body, the surface area within a certain range is increased as compared with the case of a substantially planar mesh. Therefore, even if the overall size is reduced, the surface area of the volatile volatile agent can be ensured, and the volatile amount of the volatile agent can be maintained.

Moreover, since it has a three-dimensional structure, it is possible to reduce the portion of the structure containing the volatile drug which is in contact with the container, and it is possible to suppress the decrease in the amount of volatilization of the volatile drug or the contamination of the container by contact with the inner wall of the container.

Further, since the particles of the present invention inhibit excessive exudation of tetrafluthrin, metinine or fifenthrin as an insect-repellent component, and also inhibit precipitation of crystals in the case of tetrafluthrin, When the resin molded body is produced, it is not sticky as a master batch, and can be preferably used.

In addition, since the granules of the master batch contain a high concentration of 20 to 30% by mass or more of tetrafluthrin, metinine or fenthrin as an insect control component, the resin using the granules can also be improved. The concentration of the insecticidal component of the structure containing the volatile agent formed by the composition, and a resin molded body having a long duration of insect control effect can be obtained.

The structure containing a volatile agent of the present invention includes a structure in which a rod-like body is formed into a corrugated shape to form a corrugated body.

Examples of the undulating body include a wavy body 11 including a rectangular wave as shown in Fig. 1 (a), or a wavy body 12 including a curve such as a sinusoid as shown in (b). Further, the wavy body including the rectangular wave is not limited to the wavy body 11 including the rectangular wave in the vicinity of the right angle as shown in FIG. 1(a), and may be included as shown in (c). The wavy body 13 of the rectangular wave whose angle is the acute angle is not shown, but includes a wavy body of a rectangular wave whose angle of the bent portion is an obtuse angle.

By using the undulating bodies, the surface area of the rod-shaped body existing in a specific volume can be obtained more than that of the linear rod-shaped body, and Increase the volatile amount of volatile agents. Among these, when a wavy body including a rectangular wave is used, when a structure containing a volatile drug is prepared, the entire surface area can be increased in a specific volume, and it becomes more efficient.

The undulating body constitutes a three-dimensional structure by causing a plurality of roots to cross and join each other at the top thereof. However, the term "top" refers to a portion where the amount of change changes from positive to negative and from negative to positive when the undulating body is moved in the longitudinal direction, that is, the amplitude direction of each wave of the wavy body. The place of maximum amplitude. Further, the top of the change amount from the positive negative change is referred to as a first top portion, and the top portion where the change amount is changed from negative to positive is referred to as a second top portion.

Specifically, the above-mentioned structure can be formed by the first top portion (11a of FIG. 1(a), 12a of FIG. 1(b)) and other wavy portions in which one wavy body is a part of the apex of one amplitude direction. The first top portion (11a, 12a) of the body is joined and intersected, and the second top portion having the amplitude in the opposite direction to the one top portion is the second top portion (11b of Fig. 1(a), Fig. 1(b) 12b) is formed by joining and intersecting the second top portions (11b, 12b) of the other corrugations.

Specific examples of such a three-dimensional structure include a three-dimensional structure shown in Fig. 2(a). This is to use the wavy body shown in Fig. 1(a) as a wavy body, and the two undulating bodies are crossed at substantially right angles at the top. Further, the surrounding portion is appropriately determined in accordance with the relationship between the strength and shape of the three-dimensional structure, the outer container, and the like.

Specific examples of the three-dimensional structure in which the two corrugated bodies are substantially perpendicularly intersected and joined at the top by using the wavy body of Fig. 1(b) include a three-dimensional structure having a portion shown in Fig. 2(b). .

The number of undulations at the top may be two, three or four, or five or more. Examples of the number of the corrugated bodies that are crossed are three, and a three-dimensional structure having a portion shown in Fig. 2(c) is exemplified.

Next, as the three-dimensional structure, a three-dimensional structure in which a reinforcing material is further disposed and joined is exemplified. When the reinforcing material does not contain a volatile agent, the surface area of the rod body existing in a specific volume can be further increased, and the strength of the three-dimensional structure can also be improved.

Specifically, a three-dimensional structure in which at least two top portions included in one surface including the top portion are reinforced by a reinforcing material including a linear rod-shaped body is exemplified. The surface including the top portion is the surface on which the three-dimensional structure is formed, and refers to the surface on which the top portion is disposed.

Examples of the three-dimensional structure include the three-dimensional structure shown in Fig. 2 (a), and Fig. 3 (a) to (g) or Fig. 4 in which the reinforcing material 14 including the linear rod-shaped body is disposed. The three-dimensional structure shown in a) to (c). The three-dimensional structure system is disposed on all of the first top portions 11a except for the first top portion 11a and the first top portions 11a of the both side edges, from the first top portion 11a toward the four first top portions 11a close thereto. The member 14 is reinforced and joined.

Fig. 3(a) is a plan view showing the three-dimensional structure, Fig. 3(b) is a side view, Fig. 3(c) is a cross-sectional view taken along line c-c, and Fig. 3(d) is a cross-sectional view taken along line d-d. Further, Fig. 3(e) shows an end view, Fig. 3(f) shows a f-f cross-sectional view, and Fig. 3(g) shows a g-g cross-sectional view.

Furthermore, Fig. 4(a) shows a perspective view of the three-dimensional structure, and Fig. 4(b) shows a front view of (a), that is, the same view as Fig. 3(a). 4(c) shows a cross-sectional view of c-c.

As described above, the three-dimensional structure shown in FIGS. 3(a) to (g) or FIGS. 4(a) to 4(c) is provided with the reinforcing material 14 only on the surface including the top portion of the first top portion 11a. The present invention is not limited thereto, and as shown in FIG. 4( d ), the reinforcing material 14 may be disposed on both the top surface including the first top portion 11 a and the top surface including the second top portion 11 b . Further, the place where the reinforcing material 14 is disposed may not be between all the tops (the first top or the second top) except the top end portions and the top edges (the first top or the second top) of the both side edge portions, depending on The volatile amount or strength of the volatile agent may also be between the top portion (the first top or the second top).

However, the thickness of the rod-shaped body constituting the wavy body, the period of the wave of the wavy body, the width of the amplitude, the degree of arrangement of the reinforcing material 14, and the like are determined according to the place of use, the purpose of use, and the volatilization of the obtained three-dimensional structure. The amount can be arbitrarily set. For example, in the case of the three-dimensional structure shown in FIG. 4(a), when it is disposed in a narrower place, the width of the three-dimensional structure can be narrowed as shown in FIG. 5(a). In the case of thick thickness, when it is applied to a screen or the like, it can be made as shown in Fig. 5 (b), and the thickness is reduced, and a reinforcing member is disposed in the peripheral portion.

Further, as shown in FIG. 6, the shape of the first top portion 11a or the second top portion 11b of the three-dimensional structure shown in FIG. 1(a) may be changed. For example, the cross shape shown in FIG. 6 may be changed to Word-shaped person. Even if the cross shape is changed to a square shape, only the shape of the intersection of the plurality of undulating bodies is changed. Further, the change is not limited to the change in the shape of the mouth as long as the effect of the present invention is not impaired.

With this change in shape, especially the first top 11a or the second top The shape of the 11b is changed from a cross shape to a square shape, and when the structure containing the volatile drug of the present invention is superimposed, the volatility of the adjacent structure can be prevented in terms of the elasticity of the structure containing the volatile drug. The structures of the medicaments are fitted to each other, and the labor of both can be saved, which contributes to the improvement of production efficiency.

Examples of the structure containing the volatile drug at the top of the square shape include a top portion having a mouth shape on the first top portion 11a, and a volatile portion as shown in Fig. 7 (a) and (b). a structure of a drug; a top portion having a mouth shape on the second top portion 11b, and a structure containing a volatile drug as shown in Fig. 8 (a) and (b); and being disposed on both the first top portion 11a and the second top portion 11b The top of the mouth shape, the structure containing the volatile agent shown in Fig. 9 (a) and (b), and the like.

The resin composition constituting the three-dimensional structure is a composition containing a volatile drug containing an insect-repellent component in a resin, and is a composition of the volatile drug which is volatilizable, and generally, a volatile drug-containing composition is used. Manufactured from resin pellets. Next, the particles are detailed.

Specifically, the insecticidal component as a volatile drug is carried on a fine powder carrier, and the resin particles containing the insect-repellent component are kneaded together with the resin, and the insect-repellent component is tetrafluthrin. When it is contained, it is a component containing an anti-crystal precipitation component. The granules can be used as a masterbatch, and if necessary, a resin to be mixed and further kneaded as a resin composition can be used as a material for producing various resin molded articles. The resin particles containing the insect-repellent component of the present invention can be transported and stored in this form, and can be prevented from bleeding or crystal precipitation therebetween.

The above-mentioned resin is not particularly limited as long as the volatile agent contained therein is gradually volatilized from the surface when the carrier described later is used. For example, polyethylene (PE) such as branched low density polyethylene (LDPE) or linear low density polyethylene (LLDPE); polyolefin resin such as polypropylene (PP); or these and carboxylate (vinyl acetate) A polyolefin-based copolymer such as ester, methyl methacrylate or ethyl methacrylate. The carboxylic acid ester is effective for controlling the volatilization of the volatile agent from the surface of the resin, and generally, the higher the blending ratio of the carboxylic acid ester to the polyolefin-based resin, the more the rate of bleeding of the volatile drug tends to be delayed. In the present invention, an ethylene-vinyl acetate copolymer (EVA, Ethylene Vinyl Acetate) or an ethylene-methyl methacrylate copolymer prepared by using a carboxylate ester in an amount of 1 to 35% by weight based on the polyolefin resin can be preferably used. (EMMA, Ethylene Methyl Methacrylate), etc.

Further, a polymer blend in which the content ratio of the polyolefin-based copolymer and the homopolymer of the olefin is adjusted and mixed may be used, and other polymer compounds such as a styrene-based elastomer may be contained as needed.

Further, the above-mentioned carboxylic acid ester means an unsaturated carboxylic acid ester or a vinyl formate.

In particular, in the present invention, it is particularly preferred to include an ethylene-vinyl acetate copolymer (ethylene-vinyl acetate resin). The ethylene-vinyl acetate copolymer not only functions as a resin component constituting the particles, but also functions as a bleed-out adjuster for tetrafluthrin, metinine, and fenthrin. In the case where the insect-repellent component is tetrafluthrin or fenfluthrin, the blending amount of the ethylene-vinyl acetate copolymer may be 5 mass with respect to the whole of the pellet. % or more is preferably contained in an amount of 10% by mass or more, and more preferably 15% by mass or more. When the amount is less than 5% by mass, the effect of suppressing bleeding in the state of particles is insufficient. On the other hand, the upper limit is preferably 50% by mass or less, and more preferably 45% by mass or less. The reason for this is that if the particles are too large, the resin molded article obtained by mixing the particles as a masterbatch and other resins excessively suppresses bleeding and excessively reduces the insecticidal effect of the above-mentioned insecticidal component which is the original target. After that. In the case where the insect-repellent component is Metner, it is suitably 5% by mass or more and 35% by mass or less for the same reason. Moreover, when the insecticidal component is a mixture of the metritin and other compounds, it is preferably 10% by mass or more and 35% by mass or less.

Further, the amount of the ethylene unit and the vinyl acetate unit in the copolymer is preferably from 90:10 to 70:30. The reason for this is that if the amount of the vinyl acetate unit is too small, the physical properties become almost unchanged from that of the polyethylene, and the bleeding adjustment effect necessary for the present invention is hardly expected. On the other hand, if the vinyl acetate unit is too large, it becomes difficult to form into a pellet shape.

The melt mass flow rate (MFR, Melt mass-flow rate) of the ethylene-vinyl acetate copolymer is preferably 5 g/10 min or more and 50 g/10 min or less. When the MFR is too small, there is a possibility that the effect as an osmotic adjusting agent cannot be expected, and if the MFR is too large, the influence on the physical properties of the particles cannot be ignored.

Further, in order to adjust the weight of the particles or to adjust the physical properties, the polyolefin-based resin may be contained in addition to the ethylene-vinyl acetate copolymer (EVA), and the affinity with the ethylene-vinyl acetate copolymer may be It is preferably polyethylene, and in terms of formability, it is particularly preferably low density polyethylene, specifically It is branched low density polyethylene (LDPE), chain low density polyethylene (LLDPE).

The anti-crystal precipitation component is a component capable of suppressing precipitation of crystals of tetrafluthrin on the surface of the particles, and specifically, it can be used as a dibasic acid ester compound, an aromatic ester compound, or a higher fatty acid ester which is liquid at normal temperature. a chemical substance, a pyrethroid compound other than tetrafluthrin itself, a synergist for pyrethroids, and the like. These may be used alone or in combination.

Among the above anti-crystal precipitation components, a dibasic acid ester compound is preferred. In particular, the dibasic acid ester compound having a boiling point of 200 to 330 ° C has a high effect of preventing crystal precipitation, and examples thereof include dibutyl succinate, dibutyl gluconate, diethyl adipate, and phthalic acid. Diethyl formate or the like, but is not limited thereto.

Further, as the pyrethroid compound, for example, phenbutanin or metinine, or both, can be used. When these are used in combination with the above-mentioned dibasic acid ester compound, the effect of preventing crystal precipitation is further improved, which is preferable.

The so-called pyrethroid synergist is used to enhance the insecticidal efficacy of pyrethroids when used in combination with pyrethroids, specifically, N-(2-ethylhexyl) - Bicyclo[2,2,1]-hept-5-ene-2,3-dimethylimine or piperonyl butoxide. These synergistic agents for pyrethroids can also be used in combination with the above-described dibasic acid ester compound to enhance the effect of preventing crystal precipitation.

The anti-crystal precipitation component is preferably contained in an amount of 1% by mass or more and 20% by mass or less based on the entire particles. Since the dibasic acid ester compound is particularly effective, it may be used by appropriately combining other anti-crystal precipitation components as a host.

In the resin particles containing the volatile agent containing the insect-repellent component, the effect of the volatile agent containing the insect-repellent component is not lost, and the exudation of the resin or the anti-crystal precipitation component is not lost. Other additives such as a resin stabilizer or a colorant may be contained within the range of the effect of suppressing the precipitation of crystals.

The procedure for producing the resin particles containing the volatile agent in the above structure and mixing ratio is not particularly limited. For example, the above-mentioned insect-repellent component and the fine powder carrier are first mixed, and then an ethylene-vinyl acetate copolymer and, if necessary, another polyolefin-based resin are added, and kneaded together with the above-mentioned anti-crystal precipitation component.

The volatile agent containing the insect-repellent component is not particularly limited as long as the active ingredient is volatilized at normal temperature, and an insecticide, a repellent, a fragrance, a deodorant, a mold inhibitor, an antibacterial agent, or the like can be used.

Examples of the insect-repellent component include tetrafluthrin, meteline, enthrin, fenfluthrin, methrin, fenvalerate, propargyl, fenfenyl, and uranium. Pyrethroid insecticidal components such as ester, phenol butyl chlorpyrifos, natural pyrethrin; organophosphorus insecticidal components such as diclofen, puta pine, marathon; insect growth such as methoprene, methionine A control agent or the like; among them, a pyrethroid-based insecticidal component selected from the group consisting of tetrafluthrin, metinine, enthrin, and fenfluthrin is preferred. Among these compounds, there are cases where optical isomers or geometric isomers based on asymmetric carbon or unsaturated bonds are present, and of course, each of these alone or in any mixture is also included in the present invention.

The above-mentioned metinine and trifluthrin are liquid at normal temperature, and on the other hand, tetrafluthrin has a crystal form. Since tetrafluthrin has a crystalline form, it is in the present hair It is preferable to use in combination with the anti-crystal precipitation component in the Ming Dynasty.

Examples of the repellent include N,N-diethyltoluidine (DEET), dimethyl phthalate, dibutyl phthalate, 2-ethyl-hexanediol, and succinic acid. Dibutyl ester, p-menthane-3, 8-diol, and the like.

Examples of the above-mentioned aromatic agent include citronella oil, orange oil, lemon oil, lime oil, grapefruit oil, lavender oil, peppermint oil, eucalyptus oil, jasmine oil, eucalyptus oil, green tea oil, limonene, and α-蒎. Alkene, linalool, geranyl alcohol, phenylethyl alcohol, penicillin, benzyl acetate, and the like.

Examples of the deodorant include cedar leaf oil, tar tar, bamboo extract, scented grass extract, tung oil or ethyl pyruvate, and pyruvate such as phenylethyl pyruvate.

Examples of the antifungal agent include 2-n-octyl-4-isothiazolin-3-one, isopropylmethylphenol, and o-phenylphenol.

Examples of the antibacterial agent include eucalyptus alcohol, tetrahydro eugenol, eugenol, citronellal, and allyl isothiocyanate.

In the above-mentioned resin particles containing a volatile agent, if necessary, a microcrystalline vermiculite or a fine powder of talc, diatomaceous earth, zeolite, viscosity mineral called talc, alumina, vermiculite or white carbon may be used in combination. A fine powder carrier such as wood powder may be further suitably formulated with a coloring agent, a stabilizer, an antistatic agent, and the like. When a fine powder carrier is used, a volatile agent such as the insecticidal component can be carried in the pellet, and a masterbatch containing a volatile drug in a high concentration in the resin can be prepared in the first stage, and used in the second stage. The production step of the resin composition obtained by diluting the resin to a specific concentration is convenient. In addition, there are also connected bubbles generated from the inside to the surface of the resin composition, and the internal volatilization The sexual agent becomes easy to seep out to the surface.

The content of the insect-repellent component in the granules may be contained in the range of 10% by mass or more and 50% by mass or less, and more preferably 15% by mass or more and 35% by mass or less, based on the total amount of the granules. The scope. In the case of using tetrafluthrin or fenfluthrin, it may be contained in the range of 20% by mass or more and 60% by mass or less based on the entire particles, and more preferably 30% by mass or more and 50% by mass or less. The scope. In other words, when the insect-repellent component is used in any case, if it is too small, it must be prepared in a large amount when it is used as a masterbatch, and it is not effective in manufacturing. On the other hand, if it is too large, even if it constitutes other components of the present invention, it is impossible to suppress bleed out and crystal precipitation, and the particles are sticky and there is a problem in storage, transportation, and molding. In the case where a plurality of compounds are used in combination as an insect-repellent component, the total content of the compounds is preferably 60% by mass or less.

In the case of using the above fine powder carrier, it may be used in an amount of 10% by mass or more based on the total amount of the particles, and the upper limit may be at most 30% by mass. If it is less than 10% by mass, the performance of the volatile agent is kept poor, and the production of the master batch becomes difficult. Further, as the carrier is too small, the insect-repellent component can no longer be carried, and the bleeding of the insect-repellent component becomes excessive. On the other hand, when it is more than 30% by mass, the strength of the three-dimensional structure or the exudation property of the volatile drug may be affected, and it may be difficult to maintain the form of the particles in terms of the mixing ratio of the resin to be described later. Further, since it is also included in the molded article using the granules, if it is too large, it also affects the physical properties of the insect-repellent product.

Further, the size of the fine powder carrier is preferably a number average particle diameter of 1 μm. The above, 30 μm or less, more preferably 5 μm or more and 20 μm or less. When the number average particle diameter exceeds 30 μm, the surface area is insufficient even if it is present in the above range, so that the insect-repellent component is less likely to be carried as a carrier, and the obtained particles are easily sticky. On the other hand, microparticles of less than 1 μm are actually difficult, and are not preferable because of a large change in physical properties.

The volatile drug-containing structure of the present invention can be formed by injection molding or the like of a resin composition obtained by adding the above-mentioned volatile agent-containing particles as a masterbatch and usually adding a polyolefin-based resin thereto. The injection molding conditions can be carried out under well-known conditions in consideration of the kind of the resin to be used, the blending ratio of each component, and the like.

As the polyolefin-based resin used herein, for example, low-density polyethylene can be preferably used. The reason for this is that the affinity with the ethylene-vinyl acetate copolymer contained in the above-mentioned resin particles containing a volatile agent is good, and since the melting temperature is low, the temperature can be minimized during molding. Volatilization and decomposition loss of insect-proof ingredients. Further, at the time of the molding, the insecticidal component is not deteriorated, and other additives may be contained in a range not exceeding the necessity to inhibit volatilization.

The content of the volatile drug in the resin composition is appropriately determined depending on the type of the volatile drug to be used, the type of the resin, the use environment, the use time, and the like. Although it is necessary to increase the content of the volatile drug as the use time is longer, it is suitably set in the range of 1 to 20% by mass. If it is less than 1% by mass, it is difficult to ensure the amount of the drug required for the effect. On the other hand, if it exceeds 20% by mass, the molding after the kneading of the volatile agent becomes difficult, and the volatile agent is excessively exuded to the resin. Surface is prone to stickiness The situation of the obstacles.

The molding method is not particularly limited, and can be used for extrusion molding, injection molding, press molding, vacuum molding, etc., and can be preferably used for extrusion molding or injection molding.

When the ratio of the resin to the additional resin such as the polyolefin resin is 15% by mass or more and 80% by mass or less, and the polyolefin resin is 20% by mass or more and 85% by mass or less, The obtained resin molded body contains an appropriate amount of the above-mentioned insect-repellent component to impart moderate volatility.

Since the volatile agent of the resin composition oozes out to the surface of the structure containing the volatile agent and volatilizes from the surface, if the structure containing the volatile agent is in contact with the hand, the volatile agent adheres to the hand. Hey. Therefore, it is preferred to store the volatile drug-containing structure of the present invention in a container. The container is not particularly limited as long as it has a structure in which the volatile chemical agent is not easily contacted with the inside of the container, and the volatile drug is easily volatilized. Further, it is preferable that the container has a structure that can be hung and attached to a screen or the like depending on the intended use.

Further, the volatile drug-containing structure of the present invention has an advantage that it is stronger than the mesh shape and can be smoothly stored in the container in the production step.

The volatile drug-containing structure of the present invention is stored in the container, suspended, attached to a screen or the like, and allowed to stand, and can be used as an insect repellent, insect repellent, and fragrance according to the volatile agent used. , deodorant, etc.

The resin composition of the present invention using resin particles containing an insect-repellent component The structure containing the volatile agent is a plurality of arthropods headed by insects, specifically, mosquitoes such as Chisato, underground mosquito, Aedes albopictus; cockroaches, cockroaches, flies; butterflies The flies; the clothes moths and the like exert an excellent insect-repellent effect based on the insecticidal effect or the repellent effect.

Example

Hereinafter, the present invention will be more specifically shown by way of examples. In addition, the present invention is not limited to the following examples as long as it does not exceed the gist of the invention.

First, as a structure study, a structure containing a volatile drug of the present invention was studied.

(Structural Research Example 1)

The experiment was carried out using a structure containing a volatile agent formed of the three-dimensional structure shown in Fig. 4 (a).

First, 50 parts by weight of tetrafluorofenthrin (manufactured by Sumitomo Chemical Co., Ltd.) as a volatile agent and white carbon (manufactured by EVONIK: Carplex #80, average particle diameter: 15 μm) were mixed at 120 to 140 °C. Parts by weight, ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation: Ultrasen 710, content of vinyl acetate in the copolymer: 28%) 20 parts by weight, and LDPE (Asahi Kasei Co., Ltd.: Suntec LDM6520) 12 Part by weight, a pelletized masterbatch was produced.

Then, after 100 parts by weight of the granules obtained by kneading at 120 to 140 ° C and 300 parts by weight of the above LDPE, the obtained resin composition is subjected to injection molding to obtain a volatilized product including the three-dimensional structure shown in Fig. 4 (a). The structure of the sexual agent (10 g).

The cross-section of the rod-shaped body and the reinforcing material 14 constituting the three-dimensional structure is a square of about 1.3 mm × 1.3 mm, and the distance between the first top portion 11a and the second top portion 11b constituting the wavy body of the three-dimensional structure is 10 In mm, the lengths of the first top portion 11a and the second top portion 11b are both set to 8 mm. Further, the size of the entire structure containing the volatile drug was set to 95 mm × 160 mm × 12 mm. The structure of the volatile agent-containing structure has a surface area of 29,900 mm ² .

The obtained volatile drug-containing structure was suspended in a room, and the volatile amount and the volatilization time of the volatile drug were measured at 25 ° C and a wind speed of 0.5 m. The method for measuring the amount of volatilization and the time of volatilization is carried out by measuring the weight of the structure containing the volatile agent over time.

As a result, the volatilization time was about 200 days, and the average amount of volatilization of the total time was 5.8 mg/day.

(Structural Study Comparative Example 1)

The resin composition obtained in Structural Study Example 1 was subjected to injection molding to obtain a cylindrical and mesh-shaped mesh (4.8 g). The mesh has an outer diameter of 0.7 mm and a mesh size of 4 mm × 4 mm. When the cylinder is flattened, the overall size is 80 mm × 150 mm (cutting, when the one side is enlarged, the width is equivalent to 160 mm × 150 mm), which is about twice the size of Example 1. The structure of the volatile agent-containing structure has a surface area of 20400 mm ² .

The obtained web was carried out in the same manner as in Example 1, and the amount of volatilization of the volatile drug and the volatilization time were measured.

As a result, the volatilization time was about 200 days, and the average volatile amount of the total time was 2.9 mg/day. It is expected that in order to obtain the same amount of volatilization as the structure containing the volatile agent of the present invention, it is necessary to increase the mesh size considerably. Things, or weight gain, and the difficulty in designing the product.

(result)

As described above, it can be clarified that the amount of volatilization of the structure containing the volatile agent of the structure study example is about 2 times that of the structure of Comparative Example 1 of the structure study, and in terms of surface area comparison The increase in the amount of volatilization is more remarkable than expected, and further, by reducing the portion of the structure in contact with the container, it is possible to suppress a decrease in the amount of volatilization of the volatile drug generated by contact with the inner wall of the container or contamination of the container.

Then, as a component study, the components of the resin particles containing the insect-repellent component of the present invention were investigated. In addition, there are 11 examples and 3 comparative examples below, and therefore, the following are not referred to as "component study examples" or "component study comparison examples", and are simply referred to as "examples" and "comparative examples".

First, the agent to be used will be described.

. Tefluthrin (manufactured by Sumitomo Chemical Co., Ltd.: Biosurin)

. Metlin (manufactured by Sumitomo Chemical Co., Ltd.: Eminence)

. Microcrystalline vermiculite (manufactured by EVONIK: Carplex # 80, white carbon, average particle size: 15 μm)

. Ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation: U1trasen710, ethylene: vinyl acetate unit ratio = 72:28, hereinafter referred to as "EVA-A")

. Ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation: Ultrasen 541, ethylene: vinyl acetate unit ratio = 90:10, hereinafter referred to as "EVA-B")

. Low-density polyethylene (manufactured by Asahi Kasei Co., Ltd.: Suntec LDM6520, hereinafter referred to as "LDPE-A")

. Low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd.: NOVATEC LDLJ802, hereinafter referred to as "LDPE-B")

. Dibutyl succinate (manufactured by SHIONO FINESSE Co., Ltd.)

. Phenol dingning (manufactured by Sumitomo Chemical Co., Ltd.: SUMITHRIN)

<Method of Manufacturing Granules>

In the case of the insecticidal component, the fine particle carrier, the ethylene-vinyl acetate copolymer, and the tetrafluthrin, the anti-crystal precipitation component and other resins are mixed in the mixing ratio described below. As a program when mixing, first, make insect-repellent ingredients. After 36 parts by weight of tetrafluthrin was supported on 16 parts by weight of white carbon, an ethylene-vinyl acetate copolymer (EVA) was kneaded therein at 120 to 140 ° C using a biaxial extrusion molding machine manufactured by Technovel Co., Ltd. -A) 40 parts by weight, anti-crystal precipitation component. 3.2 parts by weight of dibutyl succinate and 4.8 parts by weight of LDPE (LDPE-A) were subjected to extrusion molding to prepare resin particles containing an insect-repellent component having a diameter of 3 mm and a length of 5 mm. Regarding the particles, the presence or absence of bleeding and precipitation of crystals was measured.

<Exudation measurement method>

About 10 g of the granules were placed in a glass petri dish having a diameter of 7 cm, and the lid was evenly enlarged to cover and sealed. After storage at 40 ° C for 7 days, the state of the oil which oozes out to the surface of the granules was visually observed and evaluated by the following criteria.

No grease floating: ○, the degree of surface luminescence: △, clear grease floating: ×

<Method for measuring crystal precipitation>

About the sample used for the above exudation measurement method, stored at 25 ° C for 7 days Thereafter, the state of crystal precipitation was visually observed and evaluated by the following criteria.

No whitening caused by crystal precipitation: ○, slightly whitened: △, needle crystal precipitation: ×

<Manufacture of a molded body>

100 parts by weight of the above-mentioned insecticidal-containing resin particles and 300 parts by weight of LDPE (LDPE-B) (containing 10 parts by weight of the colorant particles) were kneaded at 120 to 140 ° C, and then placed in an injection molding machine to obtain FIG. 4 . A structural body (10 g) containing a volatile agent in the three-dimensional structure shown in (a) to (c).

The rectangular corrugated body 1 (1a, 1b) and the reinforcing material 2 constituting the three-dimensional structure have a square shape of about 1.3 mm × 1.3 mm, and the first top portion 1a and the first portion of the rectangular corrugated body 1 constituting the three-dimensional structure are formed. 2 The distance between the top 1b is 10 mm, and the lengths of the first top 1a and the second top 1b are both set to 8 mm. Further, the size of the entire structure containing the volatile drug was 95 mm × 160 mm × 12 mm.

The obtained volatile drug-containing structure was suspended in a room, and the volatile amount and the volatilization time of the volatile drug were measured at 25 ° C and a wind speed of 0.5 m. The method for measuring the amount of volatilization and the time of volatilization is carried out by measuring the weight of the structure containing the volatile agent over time.

As a result, the volatilization time was about 130 days, and the average amount of volatilization of the total time was 5.8 mg/day.

The resin particles containing the insecticidal component having the composition shown in Table 1 were produced in accordance with the above <Method for Producing Granules>, and the presence or absence of precipitation and crystal precipitation was measured for the particles. The results are combined and shown in Table 1.

As a result of the test, the insect-repellent component comprising at least one of tetrafluthrin, metinine and fenfluthrin, a fine powder carrier, and an ethylene-vinyl acetate copolymer of the present invention contain an insect-repellent component No excessive oozing was observed in the resin particles, and the whitening phenomenon in which the tetrafluthrin particles did not reach the crystal precipitation was also an obstacle and showed a good state. Further, it is considered that as a crystal precipitation preventing component, a dibasic acid ester compound such as dibutyl succinate has a higher isopropyl myristate (higher fatty acid ester compound). The tendency to prevent crystal precipitation is more excellent.

On the other hand, as shown in the comparative example, even if any of the specific insect repellent component, the fine powder carrier, and the ethylene-vinyl acetate copolymer is absent, problems occur in terms of bleeding and crystal precipitation.

The resin composition shown in Table 2 was subjected to extrusion molding in accordance with the above <Production of a molded body> to prepare a tubular insect-resistant net (4.8 g) having a mesh shape and a mesh shape. The mesh has a thickness of 0.7 mm in outer diameter and a mesh size of 4 mm × 4 mm, and the overall size of the cylindrical flat is 80 mm × 150 mm.

Two insect-proof nets were hung in the room, and the volatilization amount and volatilization time of the insect-repellent component were measured at 25 ° C and a wind speed of 0.5 m. The method of measuring the amount of volatilization and the time of volatilization is carried out by measuring the weight of the insect net over time. The results are combined and shown in Table 2.

The insect net a and the insect net e exhibit the average amount of volatilization as the target and the volatilization time. On the other hand, it is considered that although the particles of Example 3 and Example 6 have no problem of bleeding and crystal precipitation, the insect net b and the insect net d manufactured by using these are due to the ethylene-vinyl acetate copolymer, or Since the amount of the fine powder carrier is slightly larger, there is a tendency that the amount of volatilization is slightly lowered. phase On the other hand, the insect repellent net c is likely to bleed out due to the low blending amount of the ethylene-vinyl acetate copolymer, and tends to slightly increase the amount of volatilization.

11‧‧‧Wave

11a‧‧‧1st top

11b‧‧‧2nd top

12‧‧‧Wave

12a‧‧‧1st top

12b‧‧‧2nd top

13‧‧‧Wave

14‧‧‧Enhanced materials

Fig. 1(a) is a front view showing an example of a wavy body, (b) is a front view showing another example of the wavy body, and (c) is a front view showing another example of the wavy body.

2(a) is a perspective view showing an example of a three-dimensional structure, (b) is a partial enlarged view showing another example of the three-dimensional structure, and (c) is a partially enlarged view showing another example of the three-dimensional structure.

Fig. 3(a) is a front view showing an example of a three-dimensional structure, (b) is a side view of (a), (c) is a cc sectional view of (a), and (d) is a dd sectional view of (a), (e) is an end view of (a), (f) is a ff sectional view of (a), and (g) is a gg sectional view of (a).

Fig. 4(a) is a perspective view of Fig. 3(a), (b) is a front view of (a), (c) is a cross-sectional view of cc of (b), and (d) is a solid structure of (a) In another example, a cross-sectional view corresponding to a position of the three-dimensional structure (c) is provided in a case where a reinforcing material is provided on a surface including a top portion of the first top portion and a top surface including the second top portion.

Fig. 5(a) is a perspective view showing another example of the three-dimensional structure, and Fig. 5(b) is a perspective view showing another example of the three-dimensional structure.

Fig. 6 is a perspective view showing an example of a change in the shape of the top of the three-dimensional structure.

Fig. 7(a) is a perspective view showing the other example of the three-dimensional structure from the front side, and Fig. 7(b) is a perspective view from the back side of (a).

Fig. 8(a) is a perspective view showing the other example of the three-dimensional structure from the front side, and Fig. 8(b) is a perspective view from the back side of (a).

Fig. 9(a) is a perspective view showing the other example of the three-dimensional structure from the front side, and Fig. 9(b) is a perspective view from the back side of (a).

11, 12‧‧‧ wavy

12a‧‧‧1st top

12b‧‧‧2nd top

Claims (13)

A structure containing a volatile agent, which is formed into a corrugated body and formed into a corrugated body, and a three-dimensional structure is formed by crossing and joining a plurality of corrugated bodies at the top thereof. The body is formed using a resin composition containing a volatile volatile agent, wherein the kneaded volatile agent can bleed out to the surface of the solid structure and volatilize from the surface. A structure comprising a volatile agent according to claim 1, wherein the wavy system comprises a wavy body of a rectangular wave. The structure containing the volatile agent according to claim 1 or 2, wherein at least the surface including the top surface is at least 2 on the surface including the top surface on which the top surface is disposed and the top surface is disposed The tops are connected to each other by a linear rod-shaped body. The structure containing a volatile drug according to claim 1, wherein the resin composition is a polyolefin resin added to a resin particle containing a volatile drug. The structure containing the volatile agent according to claim 4, wherein the resin particle containing the volatile agent contains at least one insecticidal component including tetrafluthrin, metinine and fenfluthrin, and fine A powder carrier and a resin containing an insecticidal component of an ethylene-vinyl acetate copolymer. The structure containing a volatile agent according to claim 5, wherein the insect-repellent component is tetrafluthrin, and further comprises an anti-crystal precipitation component. The structure containing a volatile drug according to claim 6, wherein the resin particle containing the volatile drug contains 20% by mass or more and 60% by mass or less of tetrafluthrin; and 10% by mass or more and 30% by mass or less; The fine powder carrier; the ethylene-vinyl acetate copolymer of 10% by mass or more and 50% by mass or less; and the crystal precipitation preventing component of 1% by mass or more and 20% by mass or less. The structure containing a volatile agent according to claim 6, wherein the anti-crystal precipitation component is selected from the group consisting of an aromatic ester compound which is liquid at normal temperature, a higher fatty acid ester compound, a dibasic acid ester compound, and a tetrafluorobenzene-containing compound. One or more compounds of pyrethroid compounds other than pyrethroids and synergists for pyrethroids. The structure containing a volatile agent according to claim 8 which contains a dibasic acid ester compound having a boiling point of 200 to 330 ° C as the anti-crystal precipitation component. The structure containing a volatile agent according to claim 9, wherein the dibasic acid ester compound having a boiling point of 200 to 330 ° C is dibutyl succinate. The structure containing a volatile agent according to claim 8, which comprises at least one of metinine and phenbutanin as the pyrethroid compound of the crystal precipitation preventing component. The structure containing a volatile drug according to claim 5, wherein the resin particle containing the volatile agent contains 10% by mass or more and 50% by mass or less of Meitin as the insect-repellent component, and contains 10% by mass or more and 30% by mass. a fine powder carrier of less than %, and An ethylene-vinyl acetate copolymer of 5 mass% or more and 3 mass% or less. An insect-resistant article comprising the structure containing a volatile agent according to any one of claims 1 to 12.