TWI563915B - Volatile chemicalcontaining structure - Google Patents
Volatile chemicalcontaining structure Download PDFInfo
- Publication number
- TWI563915B TWI563915B TW101144534A TW101144534A TWI563915B TW I563915 B TWI563915 B TW I563915B TW 101144534 A TW101144534 A TW 101144534A TW 101144534 A TW101144534 A TW 101144534A TW I563915 B TWI563915 B TW I563915B
- Authority
- TW
- Taiwan
- Prior art keywords
- mass
- volatile
- volatile agent
- component
- insect
- Prior art date
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Catching Or Destruction (AREA)
Description
本發明係關於一種將含有揮發性藥劑之樹脂形成為特定之立體結構的含有揮發性藥劑之結構體。 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.
於住宅中,窗戶或正門等成為害蟲之侵入口。作為針對此之抑制害蟲自侵入口侵入之方法,考慮於該等場所配置防蟲器具。 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.
作為此種防蟲器具之例,已知有使揮發性之防蟲劑保持於網狀物上,將其收納至具有開放窗之容器中之防蟲器具,或將保持有揮發性藥劑之網狀物嵌入框架構件中之防蟲器具(參照專利文獻1)等。 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.
此處,該防蟲器具包括於聚烯烴等樹脂中含有揮發性之防蟲成分之樹脂成形體,隨著時間經過使防蟲成分揮發而使害蟲無法侵入該製品或者其周圍。作為此種製品,不僅蚊帳或防蟲網等用作害蟲對策之製品成為對象,管或電纜等外包裝、或樹脂纖維製品所有亦成為對象。 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.
例如於專利文獻2中,記載有製作包括聚烯烴系樹脂,百滅寧或四氟苯菊酯(transfluthrin)等害蟲防除劑,及非晶矽石等非晶性無機載體之樹脂組合物之母料的主旨(0033~0035);另外藉由擠出成形或射出成形等將以聚烯烴系樹脂作為基本樹脂而混練者製成各種成形體之主旨(0036)等。 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.
又,於專利文獻3中,表示有將美特寧(於文獻中化學式 1(下述式(1))中,R1為H,R2為-CH=CHCH3,R3為甲氧基甲基)、丙氟菊酯(於上述化學式1(下述式(1))中,R1及R2與美特寧相同,R3為甲基)等擬除蟲菊酯化合物用作害蟲防除用樹脂成形體之防蟲成分之例。 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.
進而,於專利文獻4中,記載有含有蒸散性塑化劑及滲出促進劑之樹脂組合物,以改善防蟲用樹脂組合物之揮發性。又,於專利文獻4及5中,作為殺蟲活性化合物,列舉有四氟苯菊酯(transfluthrin)(專利文獻3[0011])。 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]).
專利文獻1;日本專利特開2006-314284號公報 Patent Document 1; Japanese Patent Laid-Open No. 2006-314284
專利文獻2:日本專利特開2008-106232號公報 Patent Document 2: Japanese Patent Laid-Open Publication No. 2008-106232
專利文獻3:日本專利特開2007-77069號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. 2007-77069
專利文獻4:日本專利3858929號公報 Patent Document 4: Japanese Patent No. 3858929
專利文獻5:日本專利特開2001-192309號公報 Patent Document 5: Japanese Patent Laid-Open Publication No. 2001-192309
然而,專利文獻1之防蟲器具懸掛於窗戶或正門等而使用之情形較多,於該情形時,有感覺防蟲器具為障礙,感 覺礙眼之情況。對此,考慮到藉由縮小防蟲器具整體之大小,並減薄厚度,而減少防蟲器具之存在感之方法。 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.
然而,為了縮小防蟲器具整體之大小,並減薄厚度,必需縮小防蟲器具內之保持有防蟲劑之網狀物,其結果,伴隨著防蟲劑之揮發量之減少,防蟲效果會降低。 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.
又,於將保持有揮發性藥劑之網狀物收納至容器中使用之情形時,揮發性藥劑自網狀物之表面揮發,但若網狀物之總表面積中與容器之內壁接觸之部分較多,則有揮發性藥劑之揮發受到阻礙而揮發量降低,附著於內壁之揮發性藥劑引起容器之污染之可能性。 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.
然而,該問題於除防蟲劑以外,使用忌避劑、芳香劑、抗菌劑等揮發性藥劑之情形時,亦有產生揮發量之降低或污染等同樣之問題之情況。 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.
進而,將四氟苯菊酯或美特寧等用作防蟲成分,於如專利文獻2般製造與細粉末載體混合並與樹脂混練之顆粒時,若欲使該等防蟲成分成為高濃度,則有自顆粒之滲出(滲出)較多,黏膩而變得難以用於成形之問題。 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.
因此,本發明之目的在於即便縮小含有揮發性藥劑之結構體整體之大小,亦確保表面積而抑制揮發性藥劑之揮發量降低,並且,儘量減少結構體整體之表面積中會與容器之內壁接觸之部分,避免阻礙揮發性藥劑之揮發,同時防止容器之污染,又,其目的在於關於使用供於樹脂成形體之製造之四氟苯菊酯或美特寧等之樹脂顆粒,使其容易適應性地調整滲出,並成形。 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.
本發明係藉由使用一種含有揮發性藥劑之結構體,而解決上述問題,該含有揮發性藥劑之結構體係將棒狀體形成為波狀而製成波狀體,藉由使複數根波狀體於其頂部彼此交叉並接合而構成之立體結構體,且上述立體結構體係使用含有具有揮發性之揮發性藥劑之樹脂組合物而形成,所捏合之上述揮發性藥劑可滲出至上述立體結構體之表面並自該表面揮發。 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.
又,本發明於製造上述含有揮發性藥劑之結構體時,將作為防蟲成分之四氟苯菊酯、美特寧及丙氟菊酯中之至少1種用作揮發性藥劑,將乙烯-乙酸乙烯酯共聚物用作揮發性藥劑及細粉末載體一起混練之樹脂,若需要,則主要進而調配低密度聚乙烯(LDPE,low density polyethylene)等聚烯烴系樹脂,並且,於使用四氟苯菊酯之情形時,亦含有防晶體析出成分,以適當量混合該等並製造含有防蟲成分之樹脂顆粒。通常混練於其中加入有聚烯烴系樹脂者而製成樹脂組合物,將其成形為含有揮發性藥劑之結構體,藉此解決上述問題。 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.
再者,即便於美特寧或丙氟菊酯作為防晶體析出成分而起作用之情形時,於調配比之計算時亦以防蟲成分而計算。 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.
首先,對於本發明中使用之揮發性藥劑樹脂顆粒(含有防蟲成分之樹脂顆粒)進行說明。根據本發明,藉由使其與5質量%以上、50質量%以下之乙烯-乙酸乙烯酯共聚物 進行混合,可於適度之範圍內抑制所獲得之顆粒之滲出。於使用於常溫下為液狀之美特寧或丙氟菊酯之情形時,亦必需調整滲出,關於在常溫下為晶質之四氟苯菊酯,由於若欲提高樹脂中之濃度,則有於本發明之目標下,伴隨滲出而晶體於顆粒之表面析出之虞,故而本發明之作用效果尤其於使用四氟苯菊酯之情形時更有用。由於若完全未發生滲出則亦不產生防蟲成分之揮發,故而不希望完全地抑制滲出,藉由於上述範圍內含有成為滲出調整樹脂之乙烯-乙酸乙烯酯共聚物,控制顆粒形態時之滲出。並且,將該顆粒用作母料,關於藉由擠出成形或射出成形等而獲得之成形體,亦可確保揮發所需之滲出。再者,於將乙烯-乙酸乙烯酯共聚物設為上述範圍之後,亦可使用其他樹脂而實現樹脂添加量之調整,作為此種樹脂,較佳為與乙烯-乙酸乙烯酯共聚物之親和性較高之LDPE。 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.
作為於10質量%以上、30質量%以下之範圍內含有之細粉末載體,可使用如白碳般之微晶矽石等、與四氟苯菊酯或美特寧等不發生反應、且表面積較寬之細粉末。該細粉末載體載持防蟲成分並抑制黏膩,其結果,與樹脂一起混練而獲得之顆粒亦成為整體變得不易黏膩,可較佳地用作母料者。 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.
另一方面,於防蟲成分中使用四氟苯菊酯之情形時,可於1質量%以上、20質量%以下之範圍內含有防晶體析出成分。所謂該防晶體析出成分,係具有抑制於常溫下為晶質之四氟苯菊酯於表面析出之效果之成分。可用作該防晶體 析出成分之化合物為於常溫下為液狀之二元酸酯化合物、芳香族酯化合物、高級脂肪酸酯化合物、除四氟苯菊酯以外之擬除蟲菊酯化台物、擬除蟲菊酯用增效劑等,該等可使用一種或混合複數種而使用。其中,較佳為包含丁二酸二丁酯等二元酸酯化合物。又,與此同時,亦可使用作為擬除蟲菊酯化合物之酚丁滅寧,使用作為擬除蟲菊酯用增效劑之N-(2-乙基己基)-雙環[2,2,1]-七-5-烯-2,3-二甲醯亞胺,更提高防止晶體析出之效果。又,於使用美特寧之情形時,具有不僅作為防晶體析出成分,可加強防蟲作用之優點。 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.
藉由該等之組合可含有於顆粒之防蟲成分之含量例如於四氟苯菊酯或丙氟菊酯之情形時為20質量%以上、60質量%以下,於美特寧之情形時為10質量%以上、50質量%以下。將以該含有率獲得之含有防蟲成分之樹脂顆粒作為母料,包含15質量%以上、80質量%以下,剩餘包括低密度聚乙烯(LDPE)等聚烯烴系樹脂之樹脂組合物係藉由擠出成形或射出成形其他樹脂成形,提供使防蟲成分適度地揮發且防蟲效果優異之含有揮發性藥劑之結構體者。 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.
由於本發明之含有揮發性藥劑之結構體係使用波狀體而形成,故而與大致平面之網狀物之情形相比,於一定範圍內之表面積增大。因此,即便縮小整體之大小,亦可確保可揮發揮發性藥劑之表面積,並可保持揮發性藥劑之揮發量。 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.
又,由於成為立體結構,故而可減少與容器接觸之含有揮發性藥劑之結構體之部分,並可抑制藉由與容器之內壁接觸而產生之揮發性藥劑之揮發量降低或容器之污染。 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.
進而,由於本發明之顆粒抑制作為防蟲成分之四氟苯菊酯、美特寧或丙氟菊酯之過度之滲出,又於四氟苯菊酯之情形時亦抑制晶體之析出,故而於製造樹脂成形體時作為母料不黏膩,可較佳地使用。 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.
又,由於成為該母料之顆粒含有20~30質量%以上之高濃度之作為防蟲成分之四氟苯菊酯、美特寧或丙氟菊酯,故而亦可提高由使用該顆粒之樹脂組合物形成的含有揮發性藥劑之結構體之防蟲成分濃度,並可獲得防蟲效果之持續時間較長之樹脂成形體。 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.
本發明之含有揮發性藥劑之結構體包括組合有將棒狀體形成為波狀而製成波狀體者之結構體。 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.
作為該波狀體,可列舉如圖1(a)所示之包括矩形波之波狀體11、或如(b)所示之包括正弦曲線等曲線之波狀體12等。又,作為包括矩形波之波狀體,並不限於如圖1(a)所示之包括折曲部為直角附近之矩形波之波狀體11,亦可為如(c)所示之包括折曲部之角度為銳角之矩形波之波狀體13,或雖未圖示,但包括折曲部之角度為鈍角之矩形波之波狀體。 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.
藉由使用該等波狀體,與使用直線狀之棒狀體相比,可較多地取得存在於特定之體積內之棒狀體之表面積,並可 更增加揮發性藥劑之揮發量。該等之中,若使用包括矩形波之波狀體,則製成含有揮發性藥劑之結構體時,於特定之體積內,可更增大整體之表面積,變得更有效率。 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.
上述波狀體藉由使其複數根於其頂部彼此交叉並接合,而構成立體結構體。然而,所謂上述頂部,係指於將上述波狀體於長度方向移動時,該變化量自正向負、及自負向正變化之部位,即,表示上述波狀體之各波之振幅方向之最大振幅的場所。並且,將上述變化量自正向負變化之頂部稱為第1頂部,將上述變化量自負向正變化之頂部稱為第2頂部。 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.
具體而言,上述結構體可藉由使1個波狀體之作為一個振幅方向之頂點之部分的第1頂部(圖1(a)之11a,圖1(b)之12a)與其他波狀體之第1頂部(11a、12a)接合並交叉,又,使於與上述一個頂部相反方向具有振幅之作為另一個頂部之第2頂部(圖1(a)之11b,圖1(b)之12b)與其他波狀體之第2頂部(11b、12b)接合並交叉而構成。 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.
作為此種立體結構體之具體例,可列舉圖2(a)所示之立體結構體。其為使用圖1(a)所示之波狀體作為波狀體,於頂部使2根波狀體大致直角地交叉者。再者,周圍部根據與立體結構體之強度、形狀、外部容器等之關係適宜地決定。 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.
作為使用圖1(b)之波狀體,於頂部使2根波狀體大致直角地交叉並接合之立體結構體之具體例,可列舉具有圖2(b)所示之部分之立體結構體。 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). .
於頂部交叉之波狀體之數量可為2根,亦可為3根或4根,亦可為5根以上。作為交叉之波狀體之數量為3根之例,可列舉具有圖2(c)所示之部分之立體結構體。 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.
其次,作為上述立體結構體,可列舉進而配置加強材料並接合之立體結構體。於該加強材料中不含有揮發性藥劑之情形時,可進一步增加存在於特定之體積內的棒狀體之表面積,並且,亦可提高立體結構體之強度。 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.
具體而言,可列舉利用包括直線狀之棒狀體之加強材料加強1個含有頂部之面中所包含之至少2個頂部彼此之立體結構體等。所謂該含有頂部之面,係構成上述立體結構體之面,係指配置頂部之面。 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.
作為該立體結構體之例,可列舉於圖2(a)所示之立體結構體,配置有包括直線狀之棒狀體之加強材料14的圖3(a)~(g)或圖4(a)~(c)所示之立體結構體。該立體結構體係於除兩端緣部及兩側緣部之第1頂部11a以外之全部第1頂部11a上,自該第1頂部11a,朝向接近於其之4個第1頂部11a,配置上述加強構件14並接合者。 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.
圖3(a)表示該立體結構體之平面圖,圖3(b)表示側視圖,圖3(c)表示c-c剖面圖,圖3(d)表示d-d剖面圖。進而,圖3(e)表示端視圖,圖3(f)表示f-f剖面圖,圖3(g)表示g-g剖面圖。 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.
進而又,圖4(a)表示該立體結構體之立體圖,圖4(b)表示(a)之前視圖,即與圖3(a)同一之圖。並且,圖4(c)表示c-c剖面圖。 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.
如上所述,圖3(a)~(g)或圖4(a)~(c)所示之立體結構體雖然僅於包含第1頂部11a之含有頂部之面配置有加強材料14,但是並不限於此,亦可為如圖4(d)所示,於包含第1頂部11a之含有頂部之面及包含第2頂部11b之含有頂部之面兩者配置有加強材料14者。又,配置有加強材料14之場所可不為除上述兩端緣部及兩側緣部之頂部(第1頂部或第2頂部)以外之全部頂部(第1頂部或第2頂部)之間,根據上述揮發性藥劑之揮發量或強度,亦可為部分之頂部(第1頂部或第2頂部)之間。 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).
然而,構成波狀體之棒狀體之粗細、或波狀體之波之週期、振幅之寬度、加強材料14之配置之程度等只要依據所獲得之立體結構體之使用場所、使用目的、揮發量等任意地設定即可。例如,於圖4(a)所示之立體結構體中,於配置於更狹小之場所之情形時,可製成如圖5(a)所示,縮窄立體結構體之寬度,作為代替增厚厚度者,又,於貼於紗窗等上使用之情形時,可製成如圖5(b)所示,減薄厚度,並且,於周圍部配置有加強構件者。 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.
進而又,亦可為如圖6所示,變更圖1(a)所示之立體結構體之第1頂部11a或第2頂部11b之形狀者,例如,將圖6所示之十字狀變更為口字狀者。即便將十字狀變更為口字狀,亦只是變更上述複數個波狀體之交叉部之形狀者。再者,該變更只要不損害本發明之效果,並不限定於變化成口字狀。 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.
藉由此種形狀之變更,尤其是將第1頂部11a或第2頂部 11b之形狀自十字狀變更為口字狀,於重疊本發明之含有揮發性藥劑之結構體時,就該含有揮發性藥劑之結構體具有之彈性之關係而言,可防止鄰接之含有揮發性藥劑之結構體相互嵌合,並可節省拉開兩者之工夫,有助於生產效率之提高。 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.
作為具有此種口字狀之頂部的含有揮發性藥劑之結構體之例,可列舉:於第1頂部11a設置有口字狀之頂部,圖7(a)(b)所示之含有揮發性藥劑之結構體;於第2頂部11b設置有口字狀之頂部,圖8(a)(b)所示之含有揮發性藥劑之結構體;於第1頂部11a及第2頂部11b兩者設置有口字狀之頂部,圖9(a)(b)所示之含有揮發性藥劑之結構體等。 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.
構成上述立體結構體之樹脂組合物為於樹脂中含有包含防蟲成分之揮發性藥劑之組合物,並且,為可揮發所含有之上述揮發性藥劑之組合物,通常,使用含有揮發性藥劑之樹脂顆粒而製造。其次,對該顆粒進行詳述。 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.
具體而言,係使作為揮發性藥劑之防蟲成分載持於細粉末載體,使其與樹脂一起混練之含有防蟲成分之樹脂顆粒,又,於防蟲成分為四氟苯菊酯之情形時,為含有防晶體析出成分者。可將該顆粒用作母料,將視需要於其中進而混合追加之樹脂並進行混練者作為樹脂組合物成為製造各種樹脂成形體時之材料。本發明之含有防蟲成分之樹脂顆粒係可於該形態下進行傳輸、保存,抑制於其間發生滲出、晶體析出等者。 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.
作為上述樹脂,於直接、或使用後述之載體時,若可使所含有之上述揮發性藥劑逐漸地自表面揮發,則並無特別限定。例如可列舉:分支低密度聚乙烯(LDPE)、線性低密度聚乙烯(LLDPE)等聚乙烯(PE);聚丙烯(PP)等聚烯烴系樹脂;或者,該等與羧酸酯(乙酸乙烯酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯等)之聚烯烴系共聚物等。該羧酸酯對控制揮發性藥劑自樹脂表面之揮發較為有效,一般具有羧酸酯之相對於聚烯烴系樹脂之調配比率越高則揮發性藥劑之滲出之速度越延遲的傾向。於本發明中,可較佳地使用羧酸酯相對於聚烯烴系樹脂1~35重量%調配之乙烯-乙酸乙烯酯共聚物(EVA,Ethylene Vinyl Acetate)或乙烯-甲基丙烯酸甲酯共聚物(EMMA,Ethylene Methyl Methacrylate)等。 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.
又,可使用調整聚烯烴系共聚物與烯烴之均聚物之含有比率並混合之聚合物摻合物,亦可視需要含有苯乙烯系彈性體等其他高分子化合物。 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.
再者,所謂上述羧酸酯,係表示不飽和羧酸酯或甲酸乙烯酯。 Further, the above-mentioned carboxylic acid ester means an unsaturated carboxylic acid ester or a vinyl formate.
尤其是,於本發明中,特佳為包含乙烯-乙酸乙烯酯共聚物(乙烯-乙酸乙烯酯樹脂)。乙烯-乙酸乙烯酯共聚物不僅具有作為構成顆粒之樹脂成分之功能,亦對四氟苯菊酯、美特寧及丙氟菊酯,作為滲出調整劑而起作用。於上述防蟲成分為四氟苯菊酯或丙氟菊酯之情形時,該乙烯-乙酸乙烯酯共聚物之調配量可相對於顆粒整體含有5質量 %以上,較佳為含有10質量%以上,更佳為15質量%以上。於未達5質量%時,於顆粒狀態下抑制滲出之效果變得不充分。另一方面,上限較佳為50質量%以下,更佳為45質量%以下。其原因在於,若過多,則有即便於將顆粒作為母料與其他樹脂混合而獲得之樹脂成形體中,亦過分抑制滲出,過分降低作為本來之目標的上述防蟲成分之揮發之防蟲效果之虞。再者,於上述防蟲成分為美特寧之情形時,由於同樣之理由適當為5質量%以上、35質量%以下。又,於上述防蟲成分為將美特寧作為主體與其他化合物混合之情形時,較佳為10質量%以上、35質量%以下。 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.
又,共聚物中之乙烯單元與乙酸乙烯酯單元之數量比較佳為90:10~70:30。其原因在於,若乙酸乙烯酯單元過少,則物性變得與聚乙烯幾乎不變,且變得幾乎無法期待於本發明中所必需之滲出調整效果。另一方面,若乙酸乙烯酯單元過多則變得不易成形為顆粒狀。 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.
上述乙烯-乙酸乙烯酯共聚物之熔體質量流率(MFR,Melt mass-flow rate)較佳為5 g/10 min以上、50 g/10 min以下。若MFR過小,則有變得無法期待作為滲出調整劑之效果之虞,若MFR過大,則有變得無法忽視對顆粒之物性造成之影響之虞。 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.
進而又,為了調整顆粒之重量或調整物性,除上述乙烯-乙酸乙烯酯共聚物(EVA)以外,亦可含有上述聚烯烴系樹脂,就與乙烯-乙酸乙烯酯共聚物之親和性而言,較佳為聚乙烯,於成形性方面,尤佳為低密度聚乙烯,具體而 言為分支低密度聚乙烯(LDPE)、鏈狀低密度聚乙烯(LLDPE)。 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).
上述防晶體析出成分為可抑制四氟苯菊酯之晶體於顆粒表面析出之成分,具體而言,可使用於常溫下為液狀之二元酸酯化合物、芳香族酯化合物、高級脂肪酸酯化台物、除四氟苯菊酯其本身以外之擬除蟲菊酯化合物、擬除蟲菊酯用增效劑等。該等可單獨使用,亦可併用複數種。 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.
於上述防晶體析出成分中,較佳為二元酸酯化合物。尤其是,沸點為200~330℃之二元酸酯化合物的防止晶體析出之效果較高,例如可例示丁二酸二丁酯、葡萄糖酸二丁酯、己二酸二乙酯、鄰苯二甲酸二乙酯等,但並不限定於該等。 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.
又,作為上述擬除蟲菊酯化合物,例如可使用酚丁滅寧或者美特寧、或該兩者。由於若該等與上述二元酸酯化合物併用,則防止晶體析出之效果進一步提高,故而較佳。 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.
所謂上述擬除蟲菊酯用增效劑,係於與擬除蟲菊酯併用時可增強擬除蟲菊酯之殺蟲效力者,具體而言,代表為N-(2-乙基己基)-雙環[2,2,1]-七-5-烯-2,3-二甲醯亞胺或胡椒基丁氧化物等。該等上述擬除蟲菊酯用增效劑亦可藉由與上述二元酸酯化合物併用,而提高防止晶體析出之效果。 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.
上述防晶體析出成分較佳為相對於顆粒整體含有1質量%以上、20質量%以下。由於二元酸酯化合物尤其有效,故而只要將其作為主體適宜地組合其他防晶體析出成分而使用即可。 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.
於包含上述防蟲成分之含有揮發性藥劑之樹脂顆粒中,除該等成分以外,於不失去包含上述防蟲成分之揮發性藥劑之效果,並且,不失去上述樹脂或防晶體析出成分之滲出或晶體析出之抑制效果之範圍內,亦可包含其他添加物,例如樹脂穩定劑或著色劑等。 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.
以上述結構及混合比製造含有揮發性藥劑之樹脂顆粒時之程序並無特別限定。例如可列舉如下程序:首先混合上述防蟲成分與上述細粉末載體,之後加入乙烯-乙酸乙烯酯共聚物及若需要加入其他聚烯烴系樹脂等,與上述防晶體析出成分一起混練。 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.
若包含上述防蟲成分之揮發性藥劑為於常溫下有效成分揮發者,則並無特別限定,可使用防蟲劑、忌避劑、芳香劑、除臭劑、防黴劑、抗菌劑等。 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.
作為上述防蟲成分,可列舉:四氟苯菊酯、美特寧、烯炔菊酯、丙氟菊酯、丙烯菊酯、炔呋菊酯、炔丙菊酯、苄呋菊酯、胺菊酯、酚丁滅寧、天然除蟲菊酯等擬除蟲菊酯系殺蟲成分;二氯松、撲滅松、馬拉松等有機磷系殺蟲成分;烯蟲酯、烯蟲乙酯等昆蟲成長控制劑等;其中,較佳為選自四氟苯菊酯、美特寧、烯炔菊酯、丙氟菊酯之擬除蟲菊酯系殺蟲成分。於該等化合物中,有存在基於不對稱碳或不飽和鍵之光學異構物或幾何異構物之情況,當然該等之各自單獨或者任意之混合物亦包含於本發明中。 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.
上述美特寧及丙氟菊酯於常溫下為液狀,另一方面,四氟苯菊酯有晶質。由於四氟苯菊酯具有晶質,故而於本發 明中較理想為與防晶體析出成分之併用。 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.
作為上述忌避劑,可列舉:N,N-二乙基甲苯醯胺(DEET)、鄰苯二甲酸二甲酯、鄰苯二甲酸二丁酯、2-乙基-己二醇、丁二酸二丁酯、對薄荷烷-3,8-二醇等。 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.
作為上述芳香劑,可列舉:香茅油、甜橙油、檸檬油、萊姆油、柚子油、薰衣草油、薄荷油、桉葉油、茉莉油、檜油、綠茶精油、檸檬烯、α-蒎烯、沈香醇、香葉草醇、苯乙醇、戊桂皮醛、乙酸芐酯等。 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.
作為上述除臭劑,於揮發性者中可列舉:扁柏葉油、扁柏油、竹萃取物、善燃草萃取物、桐油或丙酮酸乙酯、丙酮酸苯乙酯等丙酮酸酯等。 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.
作為上述防黴劑,可列舉:2-正辛基-4-異噻唑啉-3-酮、異丙基甲基苯酚、鄰苯基苯酚等。 Examples of the antifungal agent include 2-n-octyl-4-isothiazolin-3-one, isopropylmethylphenol, and o-phenylphenol.
作為上述抗菌劑,可列舉:檜木醇、四氫沈香醇、丁香酚、香茅醛、異硫氰酸烯丙酯等。 Examples of the antibacterial agent include eucalyptus alcohol, tetrahydro eugenol, eugenol, citronellal, and allyl isothiocyanate.
於上述含有揮發性藥劑之樹脂顆粒中,視需要,可併用被稱為滑石、氧化鋁、矽石、白碳之微晶矽石或細粉末矽酸、矽藻土、沸石類、黏度礦物、木粉等細粉末載體,亦可進而適宜地調配著色劑、穩定劑、抗靜電劑等。若使用細粉末載體,則可於顆粒內載持上述防蟲成分等揮發性藥劑,又,可於第一階段調製於樹脂中高濃度地含有揮發性藥劑之母料,於第二階段採用進而使用樹脂稀釋至特定濃度而獲得之樹脂組合物之製造步驟,較為便利。又,亦有產生自樹脂組合物內部至表面部之連通氣泡,內部之揮發 性藥劑變得容易滲出至表面之情況。 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.
作為顆粒中之防蟲成分含量,於使用美特寧之情形時,可於顆粒整體之10質量%以上、50質量%以下之範圍內含有,尤其更佳為15質量%以上、35質量%以下之範圍。又,於使用四氟苯菊酯或丙氟菊酯之情形時,可於顆粒整體之20質量%以上、60質量%以下之範圍內含有,尤其更佳為30質量%以上、50質量%以下之範圍。即便於防蟲成分為任一者之情形時,若過少則於用作母料時亦必需相應大量地準備,於製造上成為非有效。另一方面,若過多則有即便藉由構成本發明之其他成分,亦無法再抑制滲出及晶體析出,顆粒黏膩而於保存或傳輸、成形時出現障礙之虞。再者,於併用複數種化合物作為防蟲成分之情形時,較佳為將該等合計之含有率為60質量%以下。 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.
於使用上述細粉末載體之情形時,其使用量可為相對於顆粒整體量為10質量%以上,上限可為至多30質量%。若少於10質量%,則保持揮發性藥劑之性能低劣,母料之製造變得困難。又,有作為載體過少而無法再載持上述防蟲成分,上述防蟲成分之滲出變得過大之虞。另一方面,若多於30質量%,則有對立體結構體之強度或揮發性藥劑之滲出性造成影響,與後述樹脂之調配比方面,變得難以維持作為顆粒之形態之情況。進而,由於成為亦包含於使用顆粒之成形品中,故而若過多則亦有對防蟲製品之物性造成影響之虞。 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.
又,上述細粉末載體之大小較佳為數目平均粒徑為1 μm 以上、30 μm以下,更佳為5 μm以上、20 μm以下。若數目平均粒徑超過30 μm,則由於即便以上述範圍之含有率存在,表面積亦不足,故而作為載體變得不易載持上述防蟲成分,所獲得之顆粒變得容易黏膩。另一方面,未達1 μm之微粒子實際上較難,由於物性較大地變化故而不佳。 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.
本發明之含有揮發性藥劑之結構體可藉由對將上述含有揮發性藥劑之顆粒作為母料,通常於其中加入聚烯烴系樹脂而獲得之樹脂組合物進行射出成形等,從而成形。該射出成形條件可考慮使用之樹脂之種類、各成分之調配比率等,於周知之條件下進行。 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.
作為於此處使用之聚烯烴系樹脂,例如可較佳地使用低密度聚乙烯。其原因在於,與上述含有揮發性藥劑之樹脂顆粒中所包含之乙烯-乙酸乙烯酯共聚物之親和性良好,而且由於熔解溫度較低,故而成形時,可最小限地防止由溫度所引起之防蟲成分之揮發、分解損失。又,於該成形時,於不使上述防蟲成分變質,並且,於不超過必要地阻礙揮發之範圍內亦可包含其他添加物。 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.
上述樹脂組合物中之揮發性藥劑之含量根據使用之揮發性藥劑之種類、樹脂之種類、使用環境、使用時間等適宜地決定。雖然有使用時間越長越提高揮發性藥劑之含量之必要,但是適當為於1~20質量%之範圍內設定。若未達1質量%,則難以確保奏效所需之藥量,另一方面,若超過20質量%,則有捏合揮發性藥劑之後之成形變得困難,進而產生揮發性藥劑過剩地滲出至樹脂表面而容易發生黏膩 之障礙之情況。 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.
成形方法並無特別限定,可用於擠出成形、射出成形、加壓成形、真空成形等,尤其可較佳地利用於擠出成形或射出成形。 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.
作為與聚烯烴系樹脂等追加樹脂之混合比率,若含有揮發性藥劑之樹脂顆粒為15質量%以上、80質量%以下,聚烯烴系樹脂為20質量%以上、85質量%以下,則可於所獲得之樹脂成形體中包含適當量之上述防蟲成分而賦予適度之揮發性。 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.
由於上述樹脂組合物之上述揮發性藥劑滲出至含有揮發性藥劑之結構體之表面,並自該表面揮發,故而若手接觸該含有揮發性藥劑之結構體,則有揮發性藥劑附著於手上之虞。因此,較佳為將本發明之含有揮發性藥劑之結構體收納至容器中使用。該容器只要有手不易接觸內部之含有揮發性藥劑之結構體,並且,揮發性藥劑容易揮發之程度之孔(開放孔)即可,並無特別限定。又,較佳為,根據使用用途,該容器具有可懸掛、貼於紗窗等上之結構。 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.
再者,本發明之含有揮發性藥劑之結構體亦具有與網形狀相比更堅固,於製造步驟中可順利地進行收納至容器中之優點。 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.
本發明之含有揮發性藥劑之結構體藉由收納至上述容器中,並懸掛、貼於紗窗等上、靜置,可根據使用之揮發性藥劑,用作防蟲劑、驅蟲劑、芳香劑、除臭劑等。 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.
本發明之由使用含有防蟲成分之樹脂顆粒之樹脂組合物 而製造之含有揮發性藥劑之結構體對多個以昆蟲類為首之節肢動物,具體而言,赤家蚊、地下家蚊、白紋伊蚊等蚊類;蚋、蠓類;蠅類;蝶蠅類;衣蛾類等發揮基於殺蟲效果或忌避效果之優異之防蟲效果。 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.
以下,使用實施例更具體地表示本發明。再者,本發明只要不超過其主旨,並不限定於以下實施例。 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.
首先,作為結構體研究,對本發明之含有揮發性藥劑之結構體進行研究。 First, as a structure study, a structure containing a volatile drug of the present invention was studied.
使用由圖4(a)所示之立體結構體形成之含有揮發性藥劑之結構體進行實驗。 The experiment was carried out using a structure containing a volatile agent formed of the three-dimensional structure shown in Fig. 4 (a).
首先,於120~140℃下混練作為揮發性藥劑之四氟苯菊酯(住友化學股份有限公司製造)50重量份、白碳(EVONIK公司製造:Carplex # 80,平均粒徑:15 μm)18重量份、乙烯-乙酸乙烯酯共聚物(東曹股份有限公司製造:Ultrasen710,共聚物中之乙酸乙烯酯之含有率:28%)20重量份、及LDPE(旭化成股份有限公司:Suntec LDM6520)12重量份,製造顆粒狀母料。 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.
繼而,於120~140℃下混練所獲得之顆粒100重量份與上述LDPE300重量份後,對所獲得之樹脂組合物進行射出成形,獲得包括圖4(a)所示之立體結構體之含有揮發性藥劑之結構體(10 g)。 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).
構成該立體結構體之棒狀體及加強材料14之剖面為約 1.3 mm×1.3 mm之正方形,構成該立體結構體之波狀體之第1頂部11a與第2頂部11b之間的距離為10 mm,第1頂部11a及第2頂部11b之長度均設為8 mm。又,將含有揮發性藥劑之結構體整體之大小設為95 mm×160 mm×12 mm。該含有揮發性藥劑之結構體之表面積為29900 mm2。 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 .
將所獲得之含有揮發性藥劑之結構體懸掛於室內,於25℃、風速0.5 m之條件下,測定揮發性藥劑之揮發量以及揮發時間。揮發量以及揮發時間之測定方法藉由隨時間測定含有揮發性藥劑之結構體之重量而進行。 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.
其結果,揮發時間為大約200天,總時間之平均之揮發量為5.8 mg/天。 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.
對於結構體研究實施例1中所獲得之樹脂組合物進行射出成形,獲得筒狀且網眼為菱形之網狀物(4.8 g)。該網狀物具有外徑0.7 mm之粗細,網眼為4 mm×4 mm,將筒狀壓平時之整體之大小為80 mm×150 mm(切割,於一面擴大時之寬窄相當於160 mm×150 mm),為實施例1之大小之約2倍。該含有揮發性藥劑之結構體之表面積為20400 mm2。 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 .
將所獲得之網狀物以與實施例1相同之方式進行,測定揮發性藥劑之揮發量以及揮發時間。 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.
其結果,揮發時間為大約200天,總時間之平均之揮發量為2.9 mg/天,預想為了獲得與本發明之含有揮發性藥劑之結構體同等之揮發量,有必要相當程度增大網狀物,或者加重重量,並於製品設計上伴隨著困難。 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.
如上所述,可明確如下情況:結構體研究實施例1之含有揮發性藥劑之結構體之揮發量與結構體研究比較例1之揮發量相比為約2倍,就表面積之對比而言其揮發量之增大超過預想地顯著,進而,藉由減少與容器接觸之結構體之部分,亦可抑制藉由與容器之內壁接觸而產生之揮發性藥劑之揮發量降低或容器之污染。 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.
繼而,作為成分研究,對本發明之含有防蟲成分之樹脂顆粒之成分進行研究。再者,由於以下有11個實施例、3個比較例,故而於以下不稱為「成分研究實施例」或「成分研究比較例」,簡稱為「實施例」、「比較例」。 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".
首先,對使用之藥劑進行說明。 First, the agent to be used will be described.
.四氟苯菊酯(住友化學股份有限公司製造:Biosurin) . Tefluthrin (manufactured by Sumitomo Chemical Co., Ltd.: Biosurin)
.美特寧(住友化學股份有限公司製造:Eminence) . Metlin (manufactured by Sumitomo Chemical Co., Ltd.: Eminence)
.微晶矽石(EVONIK公司製造:Carplex # 80,白碳,平均粒徑:15 μm) . Microcrystalline vermiculite (manufactured by EVONIK: Carplex # 80, white carbon, average particle size: 15 μm)
.乙烯-乙酸乙烯酯共聚物(東曹股份有限公司製造:U1trasen710,乙烯:乙酸乙烯酯單元比=72:28,以下記為「EVA-A」) . Ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation: U1trasen710, ethylene: vinyl acetate unit ratio = 72:28, hereinafter referred to as "EVA-A")
.乙烯-乙酸乙烯酯共聚物(東曹股份有限公司製造:Ultrasen541,乙烯:乙酸乙烯酯單元比=90:10,以下記為「EVA-B」) . Ethylene-vinyl acetate copolymer (manufactured by Tosoh Corporation: Ultrasen 541, ethylene: vinyl acetate unit ratio = 90:10, hereinafter referred to as "EVA-B")
.低密度聚乙烯(旭化成股份有限公司製造:Suntec LDM6520,以下記為「LDPE-A」) . Low-density polyethylene (manufactured by Asahi Kasei Co., Ltd.: Suntec LDM6520, hereinafter referred to as "LDPE-A")
.低密度聚乙烯(日本聚乙烯股份有限公司製造:NOVATEC LDLJ802,以下記為「LDPE-B」) . Low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd.: NOVATEC LDLJ802, hereinafter referred to as "LDPE-B")
.丁二酸二丁酯(SHIONO FINESSE股份有限公司製造) . Dibutyl succinate (manufactured by SHIONO FINESSE Co., Ltd.)
.酚丁滅寧(住友化學股份有限公司製造:SUMITHRIN) . Phenol dingning (manufactured by Sumitomo Chemical Co., Ltd.: SUMITHRIN)
以於下述記載之混合比,於防蟲成分、微粒子載體、乙烯-乙酸乙烯酯共聚物、及四氟苯菊酯之情形時混合防晶體析出成分、及其他樹脂。作為混合時之程序,首先,使防蟲成分.四氟苯菊酯36重量份載持於白碳16重量份之後,使用Technovel股份有限公司製造:雙軸擠出成形機,於120~140℃下於其中混練乙烯-乙酸乙烯酯共聚物(EVA-A)40重量份、防晶體析出成分.丁二酸二丁酯3.2重量份、及LDPE(LDPE-A)4.8重量份並進行擠出成形,製造直徑3mm、長度5mm之含有防蟲成分之樹脂顆粒。關於該顆粒,測定滲出及晶體之析出之有無。 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.
將顆粒約10g加入直徑7cm之玻璃培養皿中,蓋上均勻擴大之後蓋而密封。於40℃下保存7天後,以目視觀察滲出至顆粒之表面之油脂上浮之狀況,利用下述基準進行評價。 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.
無油脂上浮:○,表面發光之程度:△,清晰之油脂上浮:× No grease floating: ○, the degree of surface luminescence: △, clear grease floating: ×
關於用於上述滲出測定方法之試樣,於25℃下保存7天 後,以目視觀察晶體析出之狀況,利用下述基準進行評價。 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.
無由晶體析出所引起之變白:○,稍有變白:△,針狀晶體析出:× No whitening caused by crystal precipitation: ○, slightly whitened: △, needle crystal precipitation: ×
於120~140℃下混練上述含有防蟲成分之樹脂顆粒100重量份與LDPE(LDPE-B)300重量份(包含著色劑顆粒10重量份)之後,投入至射出成形機中,獲得包括圖4(a)~(c)所示之立體結構體之含有揮發性藥劑之結構體(10g)。 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).
構成該立體結構體之矩形波狀體1(1a、1b)及加強材料2之剖面為約1.3mm×1.3mm之正方形,構成該立體結構體之矩形波狀體1之第1頂部1a與第2頂部1b之間之距離為10mm,第1頂部1a及第2頂部1b之長度均設為8mm。又,將含有揮發性藥劑之結構體整體之大小設為95mm×160mm×12mm。 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.
將所獲得之含有揮發性藥劑之結構體懸掛於室內,於25℃、風速0.5m之條件下,測定揮發性藥劑之揮發量以及揮發時間。揮發量以及揮發時間之測定方法藉由隨時間測定含有揮發性藥劑之結構體之重量而進行。 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.
其結果,揮發時間為大約130天,總時間之平均之揮發量為5.8mg/天。 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.
依照上述<顆粒之製造方法>製造表1所示之組成之含有防蟲成分之樹脂顆粒,關於該等顆粒,測定滲出及晶體之析出之有無。將結果合併而示於表1。 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.
試驗之結果,含有包括四氟苯菊酯、美特寧及丙氟菊酯中之至少1種之防蟲成分,細粉末載體,及乙烯-乙酸乙烯酯共聚物之本發明之含有防蟲成分之樹脂顆粒未觀察到過度之滲出,又關於四氟苯菊酯顆粒未達到由晶體析出所引起之變白現象亦成為障礙之程度,表現出良好之狀態。再者,認定作為防晶體析出成分,如丁-二酸二丁酯之類之二元酸酯化合物有較十四烷酸異丙酯(高級脂肪酸酯化合物) 防止晶體析出之效果更優異之傾向。 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.
另一方面,如比較例所示,即便缺少特定之防蟲成分、細粉末載體、及乙烯-乙酸乙烯酯共聚物中之任一者,於滲出以及晶體析出之方面亦會產生問題。 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.
依照上述<成形體之製造>,對表2所示之樹脂組合物進行擠出成形,調製筒狀且網眼為菱形之防蟲網(4.8 g)。該網狀物具有外徑0.7 mm之粗細,網眼為4 mm×4 mm,將筒狀壓平時之整體之大小為80 mm×150 mm。 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.
將2個防蟲網懸掛於室內,於25℃、風速0.5 m之條件下,測定防蟲成分之揮發量以及揮發時間。揮發量以及揮發時間之測定方法係藉由隨時間測定防蟲網之重量而進行。將結果合併而示於表2。 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.
防蟲網a及防蟲網e表現出如目標之平均揮發量以及揮發時間。另一方面,認定雖然實施例3及實施例6之顆粒未產生滲出以及晶體析出之問題,但是使用該等而製造之防蟲網b及防蟲網d由於乙烯-乙酸乙烯酯共聚物、或者細粉末載體之調配量稍多,故而有揮發量稍許降低之傾向。相 反,防蟲網c起因於乙烯-乙酸乙烯酯共聚物之調配量較低而變得容易滲出,表現出揮發量稍增加之傾向。 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‧‧‧波狀體 11‧‧‧Wave
11a‧‧‧第1頂部 11a‧‧‧1st top
11b‧‧‧第2頂部 11b‧‧‧2nd top
12‧‧‧波狀體 12‧‧‧Wave
12a‧‧‧第1頂部 12a‧‧‧1st top
12b‧‧‧第2頂部 12b‧‧‧2nd top
13‧‧‧波狀體 13‧‧‧Wave
14‧‧‧加強材料 14‧‧‧Enhanced materials
圖1(a)係表示波狀體之例之前視圖,(b)係表示波狀體之其他例之前視圖,(c)係表示波狀體之其他例之前視圖。 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.
圖2(a)係表示立體結構體之例之立體圖,(b)係表示立體結構體之其他例之局部放大圖,(c)係表示立體結構體之其他例之局部放大圖。 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.
圖3(a)係表示立體結構體之例之前視圖,(b)係(a)之側視圖,(c)係(a)之c-c剖面圖,(d)係(a)之d-d剖面圖,(e)係(a)之端視圖,(f)係(a)之f-f剖面圖,(g)係(a)之g-g剖面圖。 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).
圖4(a)係圖3(a)之立體圖,(b)係(a)之前視圖,(c)係(b)之c-c剖面圖,(d)係(a)所示之立體結構體之其他例,係於包含第1頂部之含有頂部之面及包含第2頂部之含有頂部之面設置有加強材料之情形相當於立體結構體(c)之位置的剖面圖。 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.
圖5(a)係表示立體結構體之其他例之立體圖,(b)係表示立體結構體之其他例之立體圖。 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.
圖6係表示立體結構體之頂部之形狀的變更之例的立體圖。 Fig. 6 is a perspective view showing an example of a change in the shape of the top of the three-dimensional structure.
圖7(a)係表示立體結構體之其他例之自正面側之立體圖,(b)係(a)之自背面側之立體圖。 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).
圖8(a)係表示立體結構體之其他例之自正面側之立體圖,(b)係(a)之自背面側之立體圖。 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).
圖9(a)係表示立體結構體之其他例之自正面側之立體圖,(b)係(a)之自背面側之立體圖。 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‧‧‧波狀體 11, 12‧‧‧ wavy
12a‧‧‧第1頂部 12a‧‧‧1st top
12b‧‧‧第2頂部 12b‧‧‧2nd top
Claims (13)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011285408 | 2011-12-27 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201325453A TW201325453A (en) | 2013-07-01 |
TWI563915B true TWI563915B (en) | 2017-01-01 |
Family
ID=49224523
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW101144534A TWI563915B (en) | 2011-12-27 | 2012-11-28 | Volatile chemicalcontaining structure |
Country Status (1)
Country | Link |
---|---|
TW (1) | TWI563915B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1239401A (en) * | 1997-07-10 | 1999-12-22 | 地球制药株式会社 | Pesticide applicator |
CN1933726A (en) * | 2004-09-13 | 2007-03-21 | 大日本除虫菊株式会社 | Medicine volatilizer |
CN101516986A (en) * | 2006-09-29 | 2009-08-26 | 住友化学株式会社 | Polymer composition, process for producing fiber and the fiber |
-
2012
- 2012-11-28 TW TW101144534A patent/TWI563915B/en active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1239401A (en) * | 1997-07-10 | 1999-12-22 | 地球制药株式会社 | Pesticide applicator |
CN1933726A (en) * | 2004-09-13 | 2007-03-21 | 大日本除虫菊株式会社 | Medicine volatilizer |
CN101516986A (en) * | 2006-09-29 | 2009-08-26 | 住友化学株式会社 | Polymer composition, process for producing fiber and the fiber |
Also Published As
Publication number | Publication date |
---|---|
TW201325453A (en) | 2013-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6071940B2 (en) | Insect repellent-containing resin pellets and insect repellent products using the same | |
JP6028078B2 (en) | Control material for controlling adult mosquitoes | |
JP6408091B2 (en) | Drug volatilizer | |
US20090326064A1 (en) | Pesticidal composition | |
JP5937933B2 (en) | Drug volatilizer | |
JP2010193817A (en) | Volatile chemical and insect pest control method using the same | |
JP2006256997A (en) | Insect pest-controller and mosquito-controller | |
TWI563915B (en) | Volatile chemicalcontaining structure | |
JP3336714B2 (en) | Insect repellent resin composition | |
JP5959280B2 (en) | Transfluthrin-containing resin pellets and insect-proof products using the same | |
JP2736433B2 (en) | Sustained-release pest repellent | |
JP2019041591A (en) | Resin product | |
JPH02191201A (en) | Sustained release repellent for insect pest | |
JPH11349407A (en) | Vermin repelling agent | |
JP2016123389A (en) | Three-dimensional structure containing volatile chemical | |
JP2016123390A (en) | Three-dimensional structure containing volatile chemical | |
JP2019071904A (en) | Three-dimensional structure containing volatile chemical | |
JP2023101180A (en) | Chemical volatilization device |