JP2001279033A - Resin composition and molded article - Google Patents
Resin composition and molded articleInfo
- Publication number
- JP2001279033A JP2001279033A JP2000098709A JP2000098709A JP2001279033A JP 2001279033 A JP2001279033 A JP 2001279033A JP 2000098709 A JP2000098709 A JP 2000098709A JP 2000098709 A JP2000098709 A JP 2000098709A JP 2001279033 A JP2001279033 A JP 2001279033A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- resin composition
- insecticidal
- insecticidal compound
- compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、殺虫性化合物を配
合したポリオレフィン系樹脂組成物および該樹脂組成物
からなる成形体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin composition containing an insecticidal compound and a molded article comprising the resin composition.
【０００２】[0002]
【従来の技術】従来より、樹脂中に殺虫性化合物を含有
してなる樹脂組成物を成形した成形体は、殺虫性化合物
の蒸散あるいは殺虫性化合物の成形体表面へのにじみ、
いわゆるブリードにより殺虫性化合物を成形体から徐放
し、長期間にわたって殺虫性化合物のもつ性能を発揮さ
せるものとして広い分野で使用されている。例えば、愛
玩動物のノミ取り首輪、家畜のダニ駆除耳札、蚊帳、浄
化層内でのハエ等駆除目的の殺虫樹脂製剤、等が広い分
野で使用されている。ここでブリードとは、成形体を構
成する樹脂中への飽和溶解量を超える量（過飽和量）の
殺虫性化合物が成形体中に保持されている場合に生じ、
成形体中の過飽和分（＝殺虫性化合物の配合量−殺虫性
化合物の成形体を構成する樹脂中への飽和溶解量）の殺
虫性化合物が時間と共に成形体表面へ移行する現象であ
り、殺虫性化合物を成形体表面から長期にわたって徐放
する方法として有効である。しかし、飽和溶解量を超え
る量の殺虫性化合物が配合された樹脂組成物から得られ
る成形体の場合、殺虫性化合物の樹脂への飽和溶解量は
一定であるため、過飽和量の殺虫性化合物は経時的に成
形体表面にブリードし、殺虫性化合物の成形体からのブ
リード開始時期をコントロールすることは通常困難であ
る。また、過飽和量の殺虫性化合物は、成形体を密閉状
態で保存していても経時的に放出されるため、保存中の
殺虫性化合物のブリ−ドより、成形体使用時の殺虫効果
の持続性が損われるという問題があった。このような殺
虫性化合物含有樹脂成形体を製造後、使用時まで殺虫性
化合物の成形体からのブリードを抑え、使用開始から速
やかに殺虫性化合物をブリードさせる方法について種々
検討されてきたが、特開平９−７７９０８号公報におい
て、蒸気圧が殺虫性化合物と比較して高い蒸散性を有す
る可塑剤を上記樹脂成形体に加えることにより、殺虫性
化合物の放出を制御できると開示されている。2. Description of the Related Art Conventionally, a molded article obtained by molding a resin composition containing a pesticidal compound in a resin is liable to evaporate the pesticidal compound or bleed onto the surface of the molded article.
It is used in a wide range of fields as a so-called bleed, which releases a pesticidal compound from a molded article gradually and exerts the performance of the pesticidal compound over a long period of time. For example, flea-removing collars for pets, mite-killing ear tags for livestock, mosquito nets, insecticidal resin preparations for controlling flies and the like in a purification layer, and the like are widely used. Here, the bleed occurs when an amount of the insecticidal compound exceeding the saturated dissolution amount in the resin constituting the molded body (supersaturated amount) is held in the molded body,
This is a phenomenon in which the supersaturated component (= the compounding amount of the insecticidal compound−the saturated dissolution amount of the insecticidal compound in the resin constituting the molded product) in the molded product is transferred to the surface of the molded product with time, and the insecticide is a phenomenon. This is effective as a method for releasing the active compound from the surface of the molded article over a long period of time. However, in the case of a molded article obtained from a resin composition containing an insecticide compound in an amount exceeding the saturated dissolution amount, since the saturated dissolution amount of the insecticide compound in the resin is constant, the supersaturated amount of the insecticidal compound is It is usually difficult to bleed onto the surface of the molded article with the passage of time and control the timing of bleeding of the insecticidal compound from the molded article. Further, since the supersaturated amount of the insecticidal compound is released over time even when the molded article is stored in a closed state, the insecticidal effect at the time of using the molded article can be maintained more than the bleeding of the insecticidal compound during storage. There was a problem that the property was impaired. After manufacturing such a resin molded article containing an insecticidal compound, various methods have been studied for suppressing bleeding of the insecticide compound from the molded article until use, and for bleeding the insecticide compound immediately from the start of use. Japanese Unexamined Patent Publication No. Hei 9-77908 discloses that the release of an insecticidal compound can be controlled by adding a plasticizer having a higher vapor pressure than the insecticide compound to the resin molded article.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、特開平
９−７７９０８号公報における方法では、基材樹脂がポ
リエチレン樹脂やポリプロピレン樹脂のようなポリオレ
フィン系樹脂であるような場合には、殺虫性化合物の放
出の制御は不十分であった。本発明は、殺虫性化合物の
ブリード開始時期を制御でき、殺虫性化合物の利用率が
向上した殺虫性化合物含有ポリオレフィン系樹脂組成物
を提供することを目的とする。However, in the method disclosed in Japanese Patent Application Laid-Open No. 9-77908, when the base resin is a polyolefin resin such as a polyethylene resin or a polypropylene resin, the release of the insecticidal compound is prevented. Was inadequately controlled. An object of the present invention is to provide an insecticidal compound-containing polyolefin resin composition in which the bleeding start time of an insecticidal compound can be controlled and the utilization rate of the insecticidal compound is improved.
【０００４】[0004]
【課題を解決するための手段】このようなことから、本
発明者らはポリオレフィン系樹脂を基材樹脂として用い
た場合においても、密閉状態で保存している期間中には
殺虫性化合物がブリードせず、密閉状態を解除した成形
体の使用開始とともに殺虫性化合物がブリードする成形
体を開発すべく検討の結果、該成形体を与える樹脂組成
物を開発し、該樹脂組成物を成形することにより得られ
る成形体が、該成形体の保存中には殺虫性化合物がブリ
ードせず、成形体の使用開始とともに殺虫性化合物がブ
リードする成形体となることを見出し本発明に至った。In view of the above, the present inventors have found that even when a polyolefin-based resin is used as a base resin, the insecticidal compound bleeds during storage in a sealed state. As a result of studying to develop a molded product in which the insecticidal compound bleeds together with the start of use of the molded product in which the sealed state was released, a resin composition that gives the molded product was developed, and the resin composition was molded. Found that the insecticidal compound did not bleed during storage of the molded article, and became a molded article in which the insecticidal compound bleed when the molded article was used.
【０００５】すなわち本発明は、ポリオレフィン系樹脂
と、ピレスロイド化合物、有機リン化合物、カーバメー
ト化合物、ネオニコチノイド化合物および昆虫成長制御
化合物から選ばれた１種以上の殺虫性化合物（以下、殺
虫性化合物とする）と、置換基を有していてもよい炭素
数が７〜１７である脂肪族炭化水素（以下、脂肪族炭化
水素とする）を1種以上含有する樹脂組成物であって、
殺虫性化合物を該殺虫性化合物のポリオレフィン系樹脂
への飽和溶解量の１．１倍以上、かつ置換基を有してい
てもよい炭素数が７〜１７である脂肪族炭化水素を殺虫
性化合物の２０重量％以上含有することを特徴とする樹
脂組成物および該樹脂組成物からなる成形体に関するも
のである。That is, the present invention relates to a polyolefin resin and one or more insecticidal compounds selected from pyrethroid compounds, organophosphorus compounds, carbamate compounds, neonicotinoid compounds and insect growth controlling compounds (hereinafter referred to as insecticidal compounds and And a resin composition containing one or more aliphatic hydrocarbons having 7 to 17 carbon atoms which may have a substituent (hereinafter, referred to as aliphatic hydrocarbons),
The insecticide compound is obtained by dissolving an aliphatic hydrocarbon having 7 to 17 carbon atoms which may have a substituent at least 1.1 times the saturated solubility of the insecticide compound in the polyolefin-based resin. The present invention relates to a resin composition characterized by containing not less than 20% by weight of a resin composition and a molded article made of the resin composition.
【０００６】[0006]
【発明の実施の形態】本発明の樹脂組成物は、ポリオレ
フィン系樹脂、殺虫性化合物、および脂肪族炭化水素の
少なくとも３種類の成分からなり、その組成は、殺虫性
化合物を該殺虫性化合物のポリオレフィン系樹脂への飽
和溶解量の１．１倍以上、脂肪族炭化水素を殺虫性化合
物の２０重量％以上含有するものである。BEST MODE FOR CARRYING OUT THE INVENTION The resin composition of the present invention comprises at least three kinds of components: a polyolefin resin, an insecticidal compound, and an aliphatic hydrocarbon. It contains 1.1% or more of the saturated amount dissolved in the polyolefin-based resin and 20% by weight or more of the aliphatic pesticidal compound.
【０００７】本発明の樹脂組成物中において、殺虫性化
合物の量が該殺虫性化合物のポリオレフィン系樹脂への
飽和溶解量の１．１倍より少ない場合、成形体としたと
きのブリード量が少なく、十分な効果が得られない。よ
って殺虫性化合物の配合量としては、該殺虫性化合物の
ポリオレフィン系樹脂への飽和溶解量の１．１倍以上で
あり、好ましくは１．２倍以上、さらに好ましくは１．
５倍以上である。樹脂組成物中に含有される殺虫性化合
物量の上限は特にないが、必要以上にその量が多すぎて
も成形体の保存中に殺虫性化合物のブリードが起こりや
すくなるため、通常は該殺虫性化合物のポリオレフィン
系樹脂への飽和溶解量の１０倍以下である。In the resin composition of the present invention, when the amount of the pesticidal compound is less than 1.1 times the saturated solubility of the pesticidal compound in the polyolefin resin, the amount of bleed in a molded article is small. , The sufficient effect cannot be obtained. Therefore, the compounding amount of the insecticidal compound is 1.1 times or more, preferably 1.2 times or more, and more preferably 1.times. Or more of the saturated solubility of the insecticide compound in the polyolefin resin.
5 times or more. The upper limit of the amount of the insecticidal compound contained in the resin composition is not particularly limited, but bleeding of the insecticidal compound is likely to occur during storage of the molded article even if the amount is excessively large. 10 times or less the saturated solubility of the reactive compound in the polyolefin resin.
【０００８】ここで殺虫性化合物のポリオレフィン系樹
脂への飽和溶解量とは、以下のような方法で求められ
る。適宜の大きさ、例えば長さ５ｃｍ、幅５ｃｍ、厚さ
５００μｍのポリオレフィン系樹脂シートの重量を測定
し、次いで２３℃の条件下で殺虫性化合物溶液に浸漬す
る。浸漬開始から数時間毎にシートを殺虫性化合物溶液
から取り出して表面に付着した殺虫性化合物溶液を拭き
取った後、シート重量を測定し、以下の手順でこのポリ
オレフィン系樹脂に対する殺虫性化合物の飽和溶解度を
決定する。[0008] Here, the saturated dissolution amount of the insecticidal compound in the polyolefin resin is determined by the following method. A polyolefin resin sheet having an appropriate size, for example, a length of 5 cm, a width of 5 cm, and a thickness of 500 μm is measured, and then immersed in a pesticidal compound solution at 23 ° C. After taking out the sheet from the pesticidal compound solution every several hours from the start of immersion and wiping off the pesticidal compound solution attached to the surface, the sheet weight was measured, and the saturation solubility of the pesticidal compound in the polyolefin resin was determined by the following procedure. To determine.
【０００９】浸漬前のシート重量をＷ0とする。浸漬開
始からｔ1時間後（ただし、０＜ｔ1≦１２）に１回目の
シート重量測定を行ない、このときのシート重量を
Ｗ1、溶解度をＤ1とする［Ｄ1＝１００×（Ｗ1−Ｗ0）
／Ｗ0］。浸漬開始からｔ2時間後（ただし、１２＜
ｔ2）に２回目のシート重量測定を行なう。浸漬開始か
らｔn時間後のｎ回目（ただし、ｎは２以上の整数）の
シート重量測定におけるシート重量をＷn、溶解度をＤn
とすると、Ｄnは以下の式で求められる。 Ｄn（％）＝１００×（Ｗn−Ｗ0）／Ｗ0 浸漬開始後ｔn-1時間経過した時から浸漬開始後ｔn時間
経過した時までの間の単位時間あたりの溶解度変化量を
Ｅnとすると、Ｅnは以下の式で表わされる。 Ｅn＝（Ｄn−Ｄn-1）／（ｔn−ｔn-1） Ｅnが下式を満たすこととなった時点での溶解度Ｄnを、
飽和溶解度と定義する。 １００×Ｅn／Ｅ1≦１ 上式中、Ｅ1は、式：Ｅ1＝Ｄ1／ｔ1で定義される。The sheet weight before immersion is W 0 . After t 1 hour from the start of immersion (however, 0 <t 1 ≦ 12), the first sheet weight measurement is performed, and the sheet weight at this time is W 1 and the solubility is D 1 [D 1 = 100 × (W 1 -W 0)
/ W 0 ]. After t 2 hours from the start of immersion (however, 12 <
At t 2 ), a second sheet weight measurement is performed. In the n-th (n is an integer of 2 or more) sheet weight measurement t n hours after the start of immersion, the sheet weight is W n , and the solubility is D n.
Then, D n is obtained by the following equation. D n (%) = 100 × (W n −W 0 ) / W 0 Solubility change per unit time from the time t n-1 hours after the start of immersion to the time t n hours after the start of the immersion the When E n, E n is expressed by the following equation. E n = a (D n -D n-1) / (t n -t n-1) Solubility D n at the time the E n becomes to satisfy the following formula,
Defined as saturation solubility. 100 × E n / E 1 ≦ 1 In the above formula, E 1 is defined by the formula: E 1 = D 1 / t 1 .
【００１０】殺虫性化合物を２種類以上混合して使用す
る場合、当該殺虫性化合物の混合物が２３℃において液
体である場合には、該殺虫性化合物混合溶液にポリオレ
フィン系樹脂シートを浸漬し、上記した方法と同様にし
て該殺虫性化合物混合溶液のポリオレフィン系樹脂に対
する飽和溶解度を決定する。When a mixture of two or more pesticidal compounds is used, if the mixture of pesticidal compounds is liquid at 23 ° C., a polyolefin resin sheet is immersed in the mixed solution of pesticidal compounds, In the same manner as described above, the saturated solubility of the insecticidal compound mixed solution in the polyolefin resin is determined.
【００１１】使用する殺虫性化合物が２３℃で固体であ
る場合には、２３℃における飽和溶解度は次のような方
法で決定する。ポリオレフィン系樹脂１００重量部に対
して、殺虫性化合物を例えば５重量部添加し、溶融混練
した後、プレスしてシート状とする。該シートを２３℃
で一日放置した後、シート表面を拭き取り、拭き取り前
後でのシート重量を比較する。拭き取りによってシート
重量が減少した場合には、このポリオレフィン系樹脂に
対する該殺虫性化合物の飽和溶解度は５重量％未満であ
ると判断する。次に殺虫性化合物添加量を５重量部未
満、例えば４重量部として同様の操作を行なう。シート
表面の拭き取りによってシート重量が減少しなかった場
合には、このポリオレフィン系樹脂に対する該殺虫性化
合物の飽和溶解度は４重量％以上５重量％未満である。
さらに厳密な飽和溶解度を求める必要がある場合には、
殺虫性化合物添加量を４重量部以上、例えば４．５重量
部添加して同様の操作を行なう。殺虫性化合物を４重量
部添加したものが、拭き取りによってシート重量が減少
した場合は、さらに殺虫性化合物添加量を減らして同様
の操作を行なう。このように殺虫性化合物添加量を調整
しながら溶融混練、プレス、表面拭き取りの操作を繰り
返す。拭き取りによってシート重量が減少しなくなった
ときの最大殺虫性化合物添加量と、拭き取りによってシ
ート重量が減少するときの最小殺虫性化合物添加量とか
ら、飽和溶解度を求めることができる。When the pesticidal compound used is a solid at 23 ° C., the saturation solubility at 23 ° C. is determined by the following method. For example, 5 parts by weight of an insecticidal compound is added to 100 parts by weight of the polyolefin-based resin, melt-kneaded, and then pressed to form a sheet. 23 ° C
After one day, the sheet surface is wiped off, and the sheet weight before and after wiping is compared. When the sheet weight is reduced by wiping, it is determined that the saturated solubility of the pesticidal compound in the polyolefin resin is less than 5% by weight. Next, the same operation is performed with the addition amount of the insecticidal compound being less than 5 parts by weight, for example, 4 parts by weight. When the sheet weight is not reduced by wiping the sheet surface, the saturated solubility of the insecticidal compound in the polyolefin resin is 4% by weight or more and less than 5% by weight.
If you need a more exact saturation solubility,
The same operation is performed by adding 4 parts by weight or more, for example, 4.5 parts by weight of the insecticidal compound. If the weight of the sheet is reduced by wiping the sheet to which 4 parts by weight of the pesticidal compound has been added, the same operation is performed by further reducing the amount of the pesticidal compound added. The operations of melt-kneading, pressing and wiping the surface are repeated while adjusting the amount of the insecticidal compound thus added. The saturation solubility can be determined from the maximum amount of the insecticidal compound added when the sheet weight is not reduced by wiping and the minimum amount of the insecticidal compound when the sheet weight is reduced by the wiping.
【００１２】殺虫性化合物を２種類以上混合して使用
し、かつ当該殺虫性化合物の混合物が２３℃において固
体である場合には、上述した方法と同様に、当該殺虫性
化合物の混合物をポリオレフィン系樹脂に溶融混練して
シートを作製し、該シート表面を拭き取り、拭き取り前
後のシート重量変化を調べる方法によって、飽和溶解度
を求めることができる。When a mixture of two or more pesticidal compounds is used and the mixture of the pesticidal compounds is solid at 23 ° C., the mixture of the pesticidal compounds is converted to a polyolefin-based compound in the same manner as described above. Saturation solubility can be determined by a method in which a sheet is prepared by melt-kneading with a resin, the surface of the sheet is wiped, and changes in sheet weight before and after wiping are examined.
【００１３】本発明の樹脂組成物中における脂肪族炭化
水素の含量は、該樹脂組成物中に含有される殺虫性化合
物量の２０重量％以上である。脂肪族炭化水素の含量
が、殺虫性化合物量の２０重量％よりも少ない場合、樹
脂組成物もしくは該樹脂組成物からなる成形体を保存中
に殺虫性化合物のブリードを抑えることが困難となる。
また、樹脂組成物中に含有される脂肪族炭化水素量の上
限は特になく、その配合量によっても殺虫性化合物のブ
リード開始時期をコントロールすることができる。しか
し樹脂組成物中に液体成分が多い場合は、成形が困難と
なるため、通常、殺虫性化合物と脂肪族炭化水素の液体
成分を合わせて、樹脂組成物中の６０重量％以下である
ことが好ましい。The content of the aliphatic hydrocarbon in the resin composition of the present invention is at least 20% by weight based on the amount of the insecticidal compound contained in the resin composition. When the content of the aliphatic hydrocarbon is less than 20% by weight of the amount of the insecticidal compound, it becomes difficult to suppress the bleeding of the insecticidal compound during storage of the resin composition or a molded article made of the resin composition.
The upper limit of the amount of the aliphatic hydrocarbon contained in the resin composition is not particularly limited, and the bleeding start time of the insecticidal compound can be controlled by the amount thereof. However, when the liquid composition is large in the resin composition, molding becomes difficult. Therefore, usually, the total of the liquid components of the insecticidal compound and the aliphatic hydrocarbon is 60% by weight or less in the resin composition. preferable.
【００１４】本発明に適用されるポリオレフィン系樹脂
としては、たとえば高密度ポリエチレン、低密度ポリエ
チレン、線状低密度ポリエチレン、超低密度ポリエチレ
ン、エチレンと炭素数３以上のα−オレフィンとの共重
合体等のポリエチレン樹脂、プロピレン単独重合体、プ
ロピレンと炭素数４以上のα−オレフィンとのランダム
共重合体やブロック共重合体、エチレン−メチルメタク
リレート共重合体、エチレン−酢酸ビニル共重合体、エ
チレン−アクリル酸共重合体、エチレン−酢酸ビニル−
メチルメタクリレート共重合体等のエチレン性不飽和結
合を有するカルボン酸誘導体とエチレンとの共重合体、
ポリビニルアルコール、ポリ酢酸ビニル等の樹脂、ポリ
ブタジエン、ポリイソプレン、スチレン−ブタジエン共
重合体等のゴム、環状オレフィンからなる重合体、およ
びその水素添加物石油樹脂、ロジン樹脂、クマロン−イ
ンデン樹脂、テルペン樹脂等が挙げられる。これらポリ
オレフィン系樹脂は単独で使用してもよいし、２種以上
を混合して使用してもよく、使用する殺虫性化合物の種
類や用途に適したものを選択することができる。Examples of the polyolefin resin applicable to the present invention include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, and a copolymer of ethylene and an α-olefin having 3 or more carbon atoms. Such as polyethylene resin, propylene homopolymer, random copolymer or block copolymer of propylene and an α-olefin having 4 or more carbon atoms, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate copolymer, ethylene- Acrylic acid copolymer, ethylene-vinyl acetate-
A copolymer of ethylene and a carboxylic acid derivative having an ethylenically unsaturated bond such as a methyl methacrylate copolymer,
Resins such as polyvinyl alcohol and polyvinyl acetate, rubbers such as polybutadiene, polyisoprene and styrene-butadiene copolymers, polymers composed of cyclic olefins, and hydrogenated petroleum resins, rosin resins, cumarone-indene resins, terpene resins And the like. These polyolefin-based resins may be used alone or in combination of two or more, and a resin suitable for the kind and application of the insecticidal compound to be used can be selected.
【００１５】本発明で使用される殺虫性化合物として
は、ピレスロイド化合物、有機リン化合物、カーバメー
ト化合物、ネオニコチノイド化合物および昆虫成長制御
化合物が使用される。ピレスロイド化合物の例として
は、ペルメトリン、アレスリン、プラレスリン、サイフ
ェノトリン、フェノトリン、レスメトリン、エムペント
リン、フェンバレレート、フェンプロパスリン、シハロ
トリン、サイフルトリン、エトフェンプロクス、トラロ
メスリン、エスビオスリン、トランスフルスリン、テラ
レスリン等がある。有機リン化合物の例としては、フェ
ニトロチオン、フェンチオン、シアノホス、クロルピリ
ホス、ダイアジノン、カルクロホス、サリチオン等があ
る。カーバメート化合物の例としては、メトキサジアゾ
ン、プロポクスル、カルバリル、フェノブカルブ等があ
る。ネオニコチノイド化合物の例としては、イミダクロ
プリド、アセタミプリド、ニテンピラム等がある。昆虫
成長制御化合物の例としては、メトプレン、ピリプロキ
シフェン等がある。殺虫性化合物の中には光学活性体を
含むものもあるが、これらも本発明に含まれることは勿
論である。殺虫性化合物はそれぞれ単独で使用してもよ
いし、２種類以上混合して使用することもできる。ま
た、殺虫性化合物に加えピペロニルブトキサイド、ＭＧ
Ｋ−２６４等の殺虫剤の効力増強剤を加えて使用するこ
ともできる。As the insecticidal compounds used in the present invention, pyrethroid compounds, organophosphorus compounds, carbamate compounds, neonicotinoid compounds and insect growth controlling compounds are used. Examples of pyrethroid compounds include permethrin, arrestrin, pralethrin, cyphenothrin, phenothrin, resmethrin, empentrin, fenvalerate, fenpropathrin, cyhalothrin, cyfluthrin, etofenprox, tralomethrin, esbiosrin, transfluthrin, terralesrin and the like. Examples of the organic phosphorus compound include fenitrothion, fenthion, cyanophos, chlorpyrifos, diazinon, carclofos, salicion, and the like. Examples of carbamate compounds include methoxadiazone, propoxur, carbaryl, fenobcarb and the like. Examples of neonicotinoid compounds include imidacloprid, acetamiprid, nitenpyram and the like. Examples of insect growth controlling compounds include methoprene, pyriproxyfen and the like. Some pesticidal compounds contain an optically active substance, and these are of course included in the present invention. The pesticidal compounds may be used alone or in combination of two or more. In addition to insecticidal compounds, piperonyl butoxide, MG
An insecticide potency enhancer such as K-264 may be added for use.
【００１６】本発明に使用される脂肪族炭化水素として
は、直鎖状脂肪族炭化水素、分岐を有する脂肪族炭化水
素、不飽和結合を有する脂肪族炭化水素等が挙げられ
る。また、本発明に使用される置換基を有する脂肪族炭
化水素における置換基としては、クロロ、ブロモ等のハ
ロゲンが挙げられる。このようなハロゲン化炭化水素の
典型的な例として、１−クロロオクタン、２−クロロオ
クタン、１−ブロモオクタン、１−ブロモデカン、１−
ブロモドデカン等が挙げられる。本発明に使用される脂
肪族炭化水素としては、炭素数が７〜１７である脂肪族
飽和炭化水素を用いることが好ましく、さらに好ましく
は炭素数が８〜１２である脂肪族飽和炭化水素であり、
直鎖状脂肪族飽和炭化水素であることがより好ましい。
具体的には、ｎ−ヘプタン、ｎ−オクタン、ｎ−デカ
ン、ｎ−ドデカン等である。脂肪族炭化水素は単独で使
用してもよいし、２種以上混合して使用してもよい。Examples of the aliphatic hydrocarbon used in the present invention include a linear aliphatic hydrocarbon, a branched aliphatic hydrocarbon, and an aliphatic hydrocarbon having an unsaturated bond. Examples of the substituent in the substituted aliphatic hydrocarbon used in the present invention include halogen such as chloro and bromo. Typical examples of such halogenated hydrocarbons include 1-chlorooctane, 2-chlorooctane, 1-bromooctane, 1-bromodecane,
Bromodecane and the like can be mentioned. As the aliphatic hydrocarbon used in the present invention, it is preferable to use an aliphatic saturated hydrocarbon having 7 to 17 carbon atoms, more preferably an aliphatic saturated hydrocarbon having 8 to 12 carbon atoms. ,
More preferably, it is a linear aliphatic saturated hydrocarbon.
Specific examples include n-heptane, n-octane, n-decane, n-dodecane and the like. Aliphatic hydrocarbons may be used alone or in combination of two or more.
【００１７】本発明の樹脂組成物には、殺虫性化合物お
よび脂肪族炭化水素以外に必要に応じて、殺虫性化合物
の成形体表面へのにじみ出しを促進するブリード促進
剤、殺虫性化合物のブリ−ド後、動物体上で殺虫性化合
物の拡散をし易くする展着剤等の他、充填剤、酸化防止
剤、顔料等を適宜配合することができる。The resin composition of the present invention may further contain a bleeding accelerator which promotes oozing of the pesticidal compound onto the surface of the molded article, if necessary, in addition to the pesticidal compound and the aliphatic hydrocarbon. After the addition, fillers, antioxidants, pigments, etc., as well as a spreading agent or the like that facilitates the diffusion of the insecticidal compound on the animal body can be appropriately blended.
【００１８】本発明の殺虫性化合物、脂肪族炭化水素の
樹脂への配合方法は特に限定されるものではなく、原料
を例えばバンバリーミキサー、押出機等の混合機を用い
て混合後、ペレット状の樹脂組成物とすることができ
る。また、ポリオレフィン系樹脂を粉末状としたもの
に、殺虫性化合物、脂肪族炭化水素をスーパーミキサー
等を用いて混合し、粉末状の樹脂組成物とすることもで
きる。ポリオレフィン系樹脂を粉砕する方法についても
特に限定するものではないが、例えば冷凍粉砕法が挙げ
られる。The method of compounding the insecticidal compound and the aliphatic hydrocarbon of the present invention into a resin is not particularly limited. For example, the raw materials are mixed using a mixer such as a Banbury mixer or an extruder, and then mixed into pellets. It can be a resin composition. In addition, a powdery resin composition can be obtained by mixing a polyolefin-based resin in powder form with an insecticidal compound and an aliphatic hydrocarbon using a supermixer or the like. The method for pulverizing the polyolefin-based resin is not particularly limited, either.
【００１９】本発明の樹脂組成物を用いて成形した成形
体は、成形体中に含有される脂肪族炭化水素が蒸散しな
い密閉状態での保存期間中は成形体中に含有される過飽
和量の殺虫性化合物がその表面にブリードせず、長期間
の保存が可能である。また、包装を解除すると脂肪族炭
化水素が蒸散し、これによって初めて殺虫性化合物のブ
リードが開始される。すなわち、殺虫性化合物のブリー
ド開始時期をコントロールすることができる。The molded article molded using the resin composition of the present invention has a supersaturated amount contained in the molded article during a storage period in a closed state in which the aliphatic hydrocarbon contained in the molded article does not evaporate. The pesticidal compound does not bleed on its surface and can be stored for a long time. Also, when the packaging is released, the aliphatic hydrocarbons evaporate, which starts bleeding of the insecticidal compound for the first time. That is, the bleeding start time of the insecticidal compound can be controlled.
【００２０】本発明の成形体の形状はそれぞれの使用形
態、目的に応じて適宜選定され、例えば、動物用首輪、
イヤータッグ、メダル等の用途に応じて、立体状、平面
状、棒状、等の種々の形状に加工したり、ネット、繊
維、不織布、シート、フィルム等の形状に加工して使用
することができる。The shape of the molded article of the present invention is appropriately selected according to the form of use and purpose.
Depending on the application such as ear tags and medals, it can be processed into various shapes such as three-dimensional, flat, rod, etc., or processed into nets, fibers, non-woven fabrics, sheets, films, etc. and used. .
【００２１】また、使用形態や目的に応じて、本発明の
樹脂組成物から成る層を含有する多層構成の成形体とし
て使用することもできる。例えば、ある殺虫性化合物を
含有する本発明の樹脂組成物から成る層と、これとは異
なる殺虫性化合物を含有する本発明の樹脂組成物から成
る層とを多層にして使用することもできるし、殺虫性化
合物を含まない樹脂層や皮革等と本発明の樹脂組成物か
ら成る層とを多層化して使用することも可能である。Further, depending on the use form and purpose, it can be used as a multilayered molded article containing a layer composed of the resin composition of the present invention. For example, a layer composed of the resin composition of the present invention containing a certain pesticidal compound and a layer composed of the resin composition of the present invention containing a different pesticidal compound can be used as a multilayer. It is also possible to use a resin layer or leather containing no pesticidal compound and a layer composed of the resin composition of the present invention in multiple layers.
【００２２】上記成形体は、本発明の樹脂組成物を通常
の成形方法、例えば射出成形、押出し成形、プレス成
形、スラッシュ（粉末）成形等の公知の成形方法で容易
に製造され、また、使用時の力学的物性の改善、活性化
合物の成形体表面の高濃度化、あるいは加工成形性の向
上等の目的に応じて、適宜多層押出し成形、多色射出成
形、複合紡糸、押出しラミネート成形等の従来知られて
いる種々の方法で加工して成形体とすることができる。The above-mentioned molded article is easily produced by a known molding method such as injection molding, extrusion molding, press molding, slush (powder) molding, etc., of the resin composition of the present invention. Depending on the purpose of improving the mechanical properties at the time, increasing the concentration of the active compound surface of the active compound, or improving the processability, multi-layer extrusion molding, multicolor injection molding, composite spinning, extrusion lamination molding, etc. It can be processed by various conventionally known methods to obtain a molded body.
【００２３】[0023]
【発明の効果】本発明の成形体は、該成形体中に含有さ
れる脂肪族炭化水素が蒸散しない密閉状態での保存期間
中は成形体中に含有される過飽和量の殺虫性化合物が成
形体表面にブリードせず、長期間の保存が可能である。
そして包装を解除すると脂肪族炭化水素が蒸散し、殺虫
性化合物のブリードが開始される。すなわち本発明の成
形体では、殺虫性化合物のブリード開始時期をコントロ
ールすることができる。そのため、殺虫性化合物の利用
率を向上させることができる。According to the present invention, the supersaturated insecticidal compound contained in the molded article is formed during the storage period in a closed state in which the aliphatic hydrocarbon contained in the molded article does not evaporate. It can be stored for a long time without bleeding on the body surface.
When the package is released, the aliphatic hydrocarbon evaporates, and bleeding of the insecticidal compound is started. That is, in the molded article of the present invention, the bleeding start time of the insecticidal compound can be controlled. Therefore, the utilization rate of the insecticidal compound can be improved.
【００２４】[0024]
【実施例】以下、実施例をあげて本発明をさらに詳しく
説明するが、本発明はこれらに限定されるものではな
い。なお、実施例中で使用したポリオレフィン系樹脂、
殺虫性化合物および脂肪族炭化水素は以下のとおりであ
る。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The polyolefin resin used in the examples,
The pesticidal compounds and the aliphatic hydrocarbons are as follows.
【００２５】ポリオレフィン系樹脂 ポリエチレン（デュポン ダウ エラストマー ジャパ
ン(株)製、商品名：エンゲージ８２００、ＥＧと略） エチレン−メタクリル酸メチル共重合体（住友化学工業
（株）製、 商品名：アクリフトＷＫ４０２（ＭＭＡ含量２５ｗｔ
％）、ＷＫと略）殺虫性化合物 ｄ−フェノトリン （住友化学工業（株）製 ピレスロ
イド化合物、商品名：スミスリン、ＳＵＭと略） ピリプロキシフェン（住友化学工業（株）製 昆虫成長
制御化合物、商品名：スミラブ、ＳＬＶと略） 脂肪族炭化水素 ｎ−ドデカン （キシダ化学（株）製）Polyolefin resin Polyethylene (manufactured by Dupont Dow Elastomer Japan KK, trade name: Engage 8200, abbreviated as EG) Ethylene-methyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: ACLIFT WK402 ( MMA content 25wt
%), Abbreviated as WK) Insecticidal compound d-phenothrin (a pyrethroid compound manufactured by Sumitomo Chemical Co., Ltd., trade name: abbreviated as Smithrin, SUM) pyriproxyfen (an insect growth control compound manufactured by Sumitomo Chemical Co., Ltd., product) Name: Sumilab, abbreviated as SLV) Aliphatic hydrocarbon n-dodecane (manufactured by Kishida Chemical Co., Ltd.)
【００２６】飽和溶解度測定 プラストグラフ（循環オイル温度＝１２０℃）で溶融混
練したポリオレフィン系樹脂（ＥＧ３７．５ｇ、ＷＫ１
２．５ｇ）を１２０℃でプレス成形して長さ５ｃｍ、幅
５ｃｍ、厚さ５００μｍのシートを作製し、この重量を
精秤した。このシートと、２３℃に調整した殺虫性化合
物混合物（ＳＵＭ／ＳＬＶ＝８６．２／１３．８重量
％：２３℃では液体）とを用いて、前記方法により、こ
の殺虫性化合物混合物の該シートに対する飽和溶解度を
求めた。殺虫性化合物混合物のポリオレフィン系樹脂に
対する飽和溶解度は、１０．０％であった。Measurement of saturation solubility Polyolefin resin melt-kneaded by plastograph (circulating oil temperature = 120 ° C.) (EG 37.5 g, WK1
2.5 g) was pressed at 120 ° C. to form a sheet having a length of 5 cm, a width of 5 cm and a thickness of 500 μm, and the weight was precisely weighed. Using this sheet and the pesticidal compound mixture adjusted to 23 ° C. (SUM / SLV = 86.2 / 13.8% by weight: liquid at 23 ° C.), the sheet of the pesticidal compound mixture is obtained by the above-mentioned method. Was determined. The saturated solubility of the pesticidal compound mixture in the polyolefin resin was 10.0%.
【００２７】［実施例１］プラストグラフ（循環オイル
温度＝１２０℃）で溶融混練したポリオレフィン系樹脂
（ＥＧ２４．３ｇ、ＷＫ８．１ｇ）に、殺虫性化合物
（ＳＵＭ６．５５ｇ、ＳＬＶ１．０５ｇ）と脂肪族炭化
水素（１０ｇ）とを混合した液体を滴下し、滴下終了後
１２０℃で５分間攪拌し、樹脂組成物を得た。得られた
樹脂組成物を１２０℃でプレス成形して長さ７．５ｃ
ｍ、幅５．５ｃｍ、厚さ３ｍｍのシートを作製してアル
ミ製トレーにのせ、トレーごと重量を天秤を用いて精秤
した。このシートを２３℃に設定したオーブン内に３日
間開放条件でトレーにのせた状態で放置した後、表面に
ブリードした成分およびトレーに付着した成分を、紙
（株式会社クレシア製、商品名キムタオル）で拭き取
り、拭き取った後のシート重量をトレーを含めて精秤し
た。拭き取り前後の重量変化から、開放条件下でのブリ
ード量を測定した。同時に、同じ処方で同じサイズのシ
ートをアルミホイルで密封した状態で、２３℃、3日間
のエージングを実施した後、天秤で精秤した。シート表
面にブリードした成分とアルミホイルに付着した成分と
を、上記と同様の方法で拭き取った後再度シートをアル
ミホイルに包んで精秤し、拭き取り前後の重量変化から
密封条件下でのブリード量を測定した。これらの結果を
表１に示した。Example 1 A polyolefin resin (EG 24.3 g, WK 8.1 g) melt-kneaded with a plastograph (circulating oil temperature = 120 ° C.) was mixed with an insecticidal compound (SUM 6.55 g, SLV 1.05 g) and fat. A liquid mixed with an aromatic hydrocarbon (10 g) was added dropwise, and after completion of the addition, the mixture was stirred at 120 ° C. for 5 minutes to obtain a resin composition. The obtained resin composition is press-molded at 120 ° C. to have a length of 7.5 c.
A sheet having a width of 5.5 m, a width of 5.5 cm and a thickness of 3 mm was prepared and placed on an aluminum tray, and the weight of the entire tray was precisely weighed using a balance. After leaving this sheet placed on a tray in an oven set at 23 ° C. for 3 days under open conditions, the component bleeding on the surface and the component adhering to the tray were removed from paper (Crecia Co., Ltd., Kim Towel). And the sheet weight after the wiping was precisely measured including the tray. The amount of bleed under open conditions was measured from the weight change before and after wiping. At the same time, after aging at 23 ° C. for 3 days while sealing sheets of the same formulation and the same size with aluminum foil, the sheets were precisely weighed with a balance. After wiping the component bleeding on the sheet surface and the component adhering to the aluminum foil in the same manner as above, wrap the sheet again in aluminum foil and weigh it accurately. Was measured. The results are shown in Table 1.
【００２８】［比較例１］実施例１と同様にＥＧを３
０．４ｇとＷＫを１０．１ｇとを溶融混練したところ
に、ＳＵＭ８．２ｇとＳＬＶ１．３ｇとの混合液体を滴
下した後さらに混練し、樹脂組成物を製造した。実施例
１と同様の操作を行い、開放条件および密封条件で、２
３℃、３日間のエージングを実施し、ブリード量を測定
した。これらの結果を表１に示した。[Comparative Example 1] As in Example 1, EG was 3
A mixed liquid of 8.2 g of SUM and 1.3 g of SLV was dropped and kneaded after melting and kneading 0.4 g and 10.1 g of WK to produce a resin composition. The same operation as in Example 1 was performed.
Aging was performed at 3 ° C. for 3 days, and the amount of bleed was measured. The results are shown in Table 1.
【００２９】[0029]
【表１】 [Table 1]
【００３０】比較例１に比べて実施例１では、開放状態
では多量のブリードが認められ、密封条件ではわずかな
量のブリードしか認められなかった。密封保存後のシー
トの外観も良好であった。比較例１では、開放条件でブ
リードは認められるものの、密封条件でも多量のブリー
ドが認められ、密封保存後のシートの外観は不良であ
り、アルミホイルへの付着が多かった。In Example 1, as compared with Comparative Example 1, a large amount of bleed was observed in the open state, and only a small amount of bleed was observed in the sealed condition. The appearance of the sheet after the sealed storage was also good. In Comparative Example 1, although bleeding was observed under the open condition, a large amount of bleeding was observed even under the sealed condition, and the appearance of the sheet after the sealed storage was poor, and the adhesion to the aluminum foil was large.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ａ０１Ｎ 47/40 Ａ０１Ｎ 47/40 Ｚ 51/00 51/00 53/00 53/00 Ｂ 57/00 57/00 Ｂ Ｃ０８Ｋ 5/00 Ｃ０８Ｋ 5/00 Ｃ０８Ｌ 101/00 Ｃ０８Ｌ 101/00 (72)発明者 中田 博紀 大阪府高槻市塚原２丁目10番１号 住友化 学工業株式会社内 (72)発明者 羽山 賢三 大阪府大阪市中央区久太郎町１丁目９番28 号 住化ライフテク株式会社内 Ｆターム(参考） 4H011 AC01 AC06 AC08 BA01 BB04 BB06 BB09 BB11 BB13 BB15 BB17 BC01 BC19 DA01 DH02 4J002 AA011 BB031 BB051 BB061 BB071 BB081 EG006 EL066 ET006 EW006 FD186 Continuation of the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (reference) A01N 47/40 A01N 47/40 Z 51/00 51/00 53/00 53/00 B 57/00 57/00 B C08K 5/00 C08K 5/00 C08L 101/00 C08L 101/00 (72) Inventor Hiroki Nakata 2-10-1 Tsukahara, Takatsuki-shi, Osaka Sumitomo Chemical Industries, Ltd. (72) Inventor Kenzo Hayama Osaka, Osaka 1-9-28 Kutaro-cho, Chuo-ku, Sumitomo-ku F-term (reference) in Sumika Lifetech Co., Ltd.
Claims (10)
合物、有機リン化合物、カーバメート化合物、ネオニコ
チノイド化合物および昆虫成長制御化合物から選ばれた
１種以上の殺虫性化合物と、置換基を有していてもよい
炭素数が７〜１７である脂肪族炭化水素を1種以上含有
する樹脂組成物であって、殺虫性化合物を該殺虫性化合
物のポリオレフィン系樹脂への飽和溶解量の１．１倍以
上、かつ置換基を有していてもよい炭素数が７〜１７で
ある脂肪族炭化水素を殺虫性化合物の２０重量％以上含
有することを特徴とする樹脂組成物。1. A polyolefin resin, at least one insecticidal compound selected from a pyrethroid compound, an organic phosphorus compound, a carbamate compound, a neonicotinoid compound and an insect growth controlling compound, and A resin composition containing one or more aliphatic hydrocarbons having a good carbon number of 7 to 17, wherein the pesticidal compound is at least 1.1 times the saturated solubility of the pesticidal compound in the polyolefin resin, A resin composition comprising an aliphatic hydrocarbon having 7 to 17 carbon atoms which may have a substituent, in an amount of 20% by weight or more of the insecticidal compound.
ことを特徴とする請求項１に記載の樹脂組成物。2. The resin composition according to claim 1, wherein the insecticidal compound is a pyrethroid compound.
を特徴とする請求項１に記載の樹脂組成物。3. The resin composition according to claim 1, wherein the insecticidal compound is an organic phosphorus compound.
ことを特徴とする請求項１に記載の樹脂組成物。4. The resin composition according to claim 1, wherein the insecticidal compound is a carbamate compound.
あることを特徴とする請求項１に記載の樹脂組成物。5. The resin composition according to claim 1, wherein the insecticidal compound is a neonicotinoid compound.
ことを特徴とする請求項１に記載の樹脂組成物。6. The resin composition according to claim 1, wherein the insecticidal compound is an insect growth controlling compound.
７である脂肪族炭化水素が、炭素数が７〜１７である脂
肪族飽和炭化水素であることを特徴とする請求項１に記
載の樹脂組成物。7. A compound having 7 to 1 carbon atoms which may have a substituent.
The resin composition according to claim 1, wherein the aliphatic hydrocarbon having 7 is an aliphatic saturated hydrocarbon having 7 to 17 carbon atoms.
素が、炭素数が８〜１２である脂肪族飽和炭化水素であ
ることを特徴とする請求項７に記載の樹脂組成物。8. The resin composition according to claim 7, wherein the aliphatic saturated hydrocarbon having 7 to 17 carbon atoms is an aliphatic saturated hydrocarbon having 8 to 12 carbon atoms.
素が、直鎖状脂肪族飽和炭化水素であることを特徴とす
る請求項８に記載の樹脂組成物。9. The resin composition according to claim 8, wherein the aliphatic saturated hydrocarbon having 8 to 12 carbon atoms is a linear aliphatic saturated hydrocarbon.
物を成形してなる成形体。10. A molded article obtained by molding the resin composition according to claim 1.
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| JP2000098709A JP4448595B2 (en) | 2000-03-31 | 2000-03-31 | Resin composition and molded body |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000098709A JP4448595B2 (en) | 2000-03-31 | 2000-03-31 | Resin composition and molded body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001279033A true JP2001279033A (en) | 2001-10-10 |
| JP4448595B2 JP4448595B2 (en) | 2010-04-14 |
Family
ID=18613166
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|---|---|---|---|
| JP2000098709A Expired - Fee Related JP4448595B2 (en) | 2000-03-31 | 2000-03-31 | Resin composition and molded body |
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| WO2008004711A3 (en) * | 2006-07-07 | 2008-09-04 | Sumitomo Chemical Co | Insect controlling material |
| WO2011077592A1 (en) * | 2009-12-25 | 2011-06-30 | Sumitomo Chemical Company, Limited | Polymer composition and molded articles shaped of the same |
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| WO2011077594A1 (en) * | 2009-12-25 | 2011-06-30 | Sumitomo Chemical Company, Limited | Polymer composition and molded articles shaped of the same |
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| WO2011145667A1 (en) * | 2010-05-19 | 2011-11-24 | Sumitomo Chemical Company, Limited | Pest control material |
| AP3632A (en) * | 2010-05-19 | 2016-03-08 | Sumitomo Chemical Co | Pest control material |
| JP2012006868A (en) * | 2010-06-24 | 2012-01-12 | Nix Inc | Small animal controlling resin composition |
| JP2013133405A (en) * | 2011-12-26 | 2013-07-08 | Sumitomo Chemical Co Ltd | Insect repellent resin composition and use thereof |
| JP2013231130A (en) * | 2012-04-27 | 2013-11-14 | Sumika Life Tech Co Ltd | Double layered pellet for insect-proof resin and insect-proof product obtained therefrom |
| JP2015020968A (en) * | 2013-07-18 | 2015-02-02 | 大日本除蟲菊株式会社 | Medicinal agent vaporization body with flavor |
| JP2016047611A (en) * | 2014-08-27 | 2016-04-07 | 未来工業株式会社 | Synthetic resin pipe |
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