JPH0741402A - Chemical-sustained-release resin molding and its production - Google Patents

Chemical-sustained-release resin molding and its production

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Publication number
JPH0741402A
JPH0741402A JP15968293A JP15968293A JPH0741402A JP H0741402 A JPH0741402 A JP H0741402A JP 15968293 A JP15968293 A JP 15968293A JP 15968293 A JP15968293 A JP 15968293A JP H0741402 A JPH0741402 A JP H0741402A
Authority
JP
Japan
Prior art keywords
drug
resin
release
weight
parts
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.)
Pending
Application number
JP15968293A
Other languages
Japanese (ja)
Inventor
Takashi Chinuki
高志 千貫
Tomomi Sato
友美 佐藤
Tatsuhiro Nagamatsu
龍弘 永松
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
Original Assignee
Sumitomo Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Priority to JP15968293A priority Critical patent/JPH0741402A/en
Publication of JPH0741402A publication Critical patent/JPH0741402A/en
Pending legal-status Critical Current

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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)

Abstract

PURPOSE:To obtain a chemical-sustained-release resin molding capable of holding a large amount of chemical without bleeding it and W releasing it at a constant rate. CONSTITUTION:A resin composition composed of 10-0 pts.wt. thermoplastic resin such as a polyolefin-based resin and 50 to 400 pts.wt., preferably 70 to 200 pts.wt. filler, preferably calcium carbonate is uniaxially or biaxially stretched by a factor of 1.1 to 10. With the resultant porous resin molding, a chemical (e.g. an insecticide, a repellent, a germicide, a fungicide or a perfume) is admixed in an amount of >= saturation dissolution in the resin, thus affording the objective chemical sustained-release resin molding. As the method for admixing the chemical, addition to the resin composition before molding, coating or immersion of the molding before stretching or immersion of the porous molding is used. For controlling the release rate of the chemical-sustained-release resin molding within a more preferable range, in the case where the molding is a sheet or a film, at least one side thereof is coated with a chemical- permeable thermoplastic resin composition layer. In the case of a rod-shaped molding, the outer periphery of the rod-shaped molding is coated therewith.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は薬剤徐放樹脂成形体およ
びその製造方法に関する。さらに詳しくは、薬剤を大量
に保持することを特徴とする薬剤徐放樹脂成形体および
その製造方法に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a drug sustained-release resin molding and a method for producing the same. More specifically, the present invention relates to a sustained-release drug-molded resin product characterized by holding a large amount of a drug and a method for producing the same.

【0002】[0002]

【従来の技術】熱可塑性樹脂に薬剤を均一に混練した樹
脂組成物からなる成型体から薬剤を徐放する方法が従来
より知られており、この方法では、時間の経過により樹
脂成形体表面から環境へ薬剤が放出され、樹脂中の薬剤
量が低下していくのに伴い、薬剤の放出速度が低下する
ので、一定速度の薬剤の放出を維持することは困難であ
った。また、樹脂と相溶する薬剤量は、樹脂、薬剤の選
定によっても異なるが、通常は熱可塑性樹脂に対しては
0.1〜5重量%程度と低く、長期の放出が期待できな
いものであった。樹脂組成物に例えば飽和溶解度以上の
多量の薬剤を配したとしても、その場合は薬剤のブリー
ドがおっこたり、初期に薬剤が大量に放出されたりする
ためにやはり薬剤の安定した放出という点では十分なも
のではないという問題があった。
2. Description of the Related Art A method of gradually releasing a drug from a molded product composed of a resin composition in which a drug is uniformly kneaded with a thermoplastic resin has been known in the past. Since the rate of drug release decreases as the amount of drug in the resin decreases as the drug is released into the environment, it has been difficult to maintain a constant rate of drug release. The amount of the drug compatible with the resin varies depending on the selection of the resin and the drug, but is usually as low as about 0.1 to 5% by weight with respect to the thermoplastic resin, and long-term release cannot be expected. It was For example, even if a large amount of the drug having a saturated solubility or more is arranged in the resin composition, in that case, the drug bleeds, or the drug is released in a large amount in the initial stage, so that the drug is still released in a stable manner. There was a problem that it was not enough.

【0003】[0003]

【発明が解決しようとする課題】本発明者らは、ブリー
ドさせずに大量の薬剤を含有し、かつ一定速度での放出
が可能である薬剤徐放化方法について鋭意研究を続けて
きた。その結果、樹脂と充填剤、該樹脂に対する飽和溶
解量以上の薬剤からなる樹脂組成物を一軸または二軸に
延伸して多孔質化することにより、薬剤の大量保持と一
定速度の放出性能を持つ薬剤徐放樹脂成形体が得られる
ことを見いだし本発明に至った。
DISCLOSURE OF THE INVENTION The present inventors have conducted extensive studies on a sustained-release method for a drug, which contains a large amount of drug without bleeding and can be released at a constant rate. As a result, a resin composition composed of a resin, a filler, and a drug having a saturated dissolution amount or more with respect to the resin is uniaxially or biaxially stretched to make it porous, so that a large amount of drug can be retained and a constant rate of release performance The present invention has been completed by finding that a drug-releasing resin molded product can be obtained.

【0004】[0004]

【課題を解決するための手段】すなわち、本発明は、 1.熱可塑性樹脂100重量部、充填剤50〜400重
量部よりなる樹脂組成物を一軸または二軸に1.1〜1
0の倍率で延伸して得られる多孔質樹脂成形体に熱可塑
性樹脂に対する飽和溶解度以上の量の薬剤を含有してな
る薬剤徐放樹脂成形体、 2.熱可塑性樹脂100重量部、充填剤50〜400重
量部および熱可塑性樹脂に対する飽和溶解度以上の量の
薬剤からなる樹脂組成物を一軸または二軸に1.1〜1
0の倍率で延伸して多孔質化することを特徴とする薬剤
徐放樹脂成形体の製造方法、 3.熱可塑性樹脂100重量部と充填剤50〜400重
量部からなる樹脂組成物を、薬剤に浸漬または薬剤を塗
布した状態で一軸または二軸に1.1〜10倍に延伸し
て多孔質化することを特徴とする薬剤徐放樹脂成形体の
製造方法、 4.熱可塑性樹脂100重量部、充填剤50〜400重
量部よりなる樹脂組成物を一軸または二軸に1.1〜1
0の倍率で延伸して得られる多孔質樹脂成形体に熱可塑
性樹脂に対する飽和溶解量以上の量の薬剤を含有させる
ことを特徴とする薬剤徐放樹脂成形体の製造方法、を提
供するものである。
That is, the present invention is as follows. A resin composition comprising 100 parts by weight of a thermoplastic resin and 50 to 400 parts by weight of a filler is uniaxially or biaxially 1.1 to 1
1. A drug sustained-release resin molded product, which comprises a porous resin molded product obtained by stretching at a draw ratio of 0 and containing an amount of a drug having a saturated solubility or higher in a thermoplastic resin. A resin composition comprising 100 parts by weight of a thermoplastic resin, 50 to 400 parts by weight of a filler, and a drug in an amount equal to or more than the saturated solubility in the thermoplastic resin is uniaxially or biaxially 1.1 to 1
2. A method for producing a drug sustained-release resin molded product, which comprises stretching at a ratio of 0 to make it porous. A resin composition consisting of 100 parts by weight of a thermoplastic resin and 50 to 400 parts by weight of a filler is uniaxially or biaxially stretched 1.1 to 10 times in a state of being immersed in the drug or coated with the drug to make it porous. 3. A method for producing a drug sustained-release resin molded product, which is characterized by: A resin composition comprising 100 parts by weight of a thermoplastic resin and 50 to 400 parts by weight of a filler is uniaxially or biaxially 1.1 to 1
To provide a method for producing a drug sustained-release resin molded product, characterized in that a porous resin molded product obtained by stretching at a draw ratio of 0 contains a drug in an amount equal to or more than a saturated dissolution amount in a thermoplastic resin. is there.

【0005】本発明に用いる熱可塑性樹脂としては、例
えば、低密度ポリエチレン、高密度ポリエチレン、ポリ
プロピレン、ポリブテン等のα−オレフィンホモポリマ
ー、炭素数3〜18のα−オレフィン類から選ばれた少
なくとも一種のα−オレフィンとエチレンとの共重合
体、プロピレンとエチレンおよび/またはブテン−1と
の共重合体、エチレンと酢酸ビニルおよび/またはアク
リル酸エステル・メタアクリル酸エステル類などエチレ
ン性不飽和結合を有する有機カルボン酸誘導体との共重
合体などのポリオレフィン系樹脂が挙げられる。これら
は単独あるいは2種類以上用いることができる。これら
樹脂のうち、特に炭素数3〜8のα−オレフィン類から
選ばれた少なくとも一種のα−オレフィンとエチレンと
の共重合体が充填剤配合時の強度の点から好ましく、熱
可塑性樹脂成分の少なくとも20重量%以上が炭素数4
〜8のα−オレフィン類から選ばれた少なくとも一種の
α−オレフィンとエチレンとの共重合体である線状低密
度ポリエチレンであって、密度0.870〜0.915
g/cm3 のものが低温での延伸加工性の点からさらに
好ましい。
The thermoplastic resin used in the present invention is, for example, at least one selected from α-olefin homopolymers such as low density polyethylene, high density polyethylene, polypropylene and polybutene, and α-olefins having 3 to 18 carbon atoms. Of α-olefin and ethylene, copolymers of propylene and ethylene and / or butene-1, ethylene and vinyl acetate and / or ethylenic unsaturated bonds such as acrylic acid ester / methacrylic acid ester Examples thereof include polyolefin resins such as a copolymer with an organic carboxylic acid derivative. These may be used alone or in combination of two or more. Among these resins, a copolymer of ethylene with at least one α-olefin selected from α-olefins having 3 to 8 carbon atoms is preferable from the viewpoint of strength at the time of compounding the filler, and is a thermoplastic resin component. At least 20% by weight or more has 4 carbon atoms
A linear low density polyethylene which is a copolymer of ethylene with at least one α-olefin selected from α-olefins having a density of 0.870 to 0.915.
Those having g / cm 3 are more preferable from the viewpoint of drawability at low temperature.

【0006】本発明において、熱可塑性樹脂100重量
部に対する充填剤の量は通常、50〜400重量部であ
る。充填剤の量が50重量部未満の場合は、延伸後に多
孔質化した樹脂成体に占める微細孔の全体積が不十分で
あり、400重量部を超える場合は、加工性が悪化する
ために好ましくない。特に、加工安定性の面から、充填
剤は70〜200重量部が好ましい。
In the present invention, the amount of the filler is usually 50 to 400 parts by weight based on 100 parts by weight of the thermoplastic resin. When the amount of the filler is less than 50 parts by weight, the total volume of the fine pores occupying the resin body made porous after stretching is insufficient, and when it exceeds 400 parts by weight, the workability is deteriorated, which is preferable. Absent. Particularly, from the viewpoint of processing stability, the filler is preferably 70 to 200 parts by weight.

【0007】本発明で用いられる充填剤の例として、炭
酸カルシウム、炭酸マグネシウム、炭酸バリウムなどの
炭酸塩、硫酸バリウム、硫酸マグネシウム、硫酸カルシ
ウムなどの硫酸塩、リン酸マグネシウム、リン酸カルシ
ウムなどのリン酸塩、水酸化マグネシウム、水酸化アル
ミニウムなどの水酸化物、アルミナ、シリカ、酸化マグ
ネシウム、酸化カルシウム、酸化亜鉛、酸化チタンなど
の酸化物、塩化亜鉛、塩化鉄、塩化ナトリウムなどの塩
化物、アルミニウム粉、ゼオライト、シラス、白土、珪
藻土、タルク、カーボンブラック、火山灰などの無機充
填剤や木粉、パルプ粉などのセルロース系粉末、ナイロ
ン粉末、ポリカーボネート粉末、ポリプロピレン粉末、
ポリ4─メチルペンテン−1粉末などの合成樹脂系粉
末、活性炭、キトサン粉末、キチン粉末、でん粉などの
有機充填剤を挙げることができ、これらは単独または組
み合わせて使用される。薬剤徐放樹脂成形体の柔軟性、
外観などの点から充填剤としては炭酸カルシウムが特に
好ましい。充填剤は、平均粒径が1〜100μmの充填
剤が分散性にすぐれ、均質な多孔質体が得られるので薬
剤徐放樹脂成形体からの薬剤の放出速度が均一になるこ
とから好ましく用いられる。
Examples of the filler used in the present invention include carbonates such as calcium carbonate, magnesium carbonate and barium carbonate, sulfates such as barium sulfate, magnesium sulfate and calcium sulfate, and phosphates such as magnesium phosphate and calcium phosphate. Hydroxides such as magnesium hydroxide and aluminum hydroxide, oxides such as alumina, silica, magnesium oxide, calcium oxide, zinc oxide and titanium oxide, chlorides such as zinc chloride, iron chloride and sodium chloride, aluminum powder, Inorganic fillers such as zeolite, shirasu, clay, diatomaceous earth, talc, carbon black, and volcanic ash, and wood powder, cellulose powder such as pulp powder, nylon powder, polycarbonate powder, polypropylene powder,
Mention may be made of synthetic resin powders such as poly-4-methylpentene-1 powder and organic fillers such as activated carbon, chitosan powder, chitin powder and starch, which may be used alone or in combination. Flexibility of drug sustained-release resin molding,
From the viewpoint of appearance and the like, calcium carbonate is particularly preferable as the filler. The filler is preferably used because the filler having an average particle diameter of 1 to 100 μm has excellent dispersibility and a homogeneous porous body can be obtained, so that the drug release rate from the drug sustained-release resin molded product becomes uniform. .

【0008】本発明の薬剤徐放樹脂成形体は、熱可塑性
樹脂に対する飽和溶解度量以上の薬剤を保持することが
できる。薬剤の量の上限は、用いる熱可塑性樹脂、薬
剤、充填剤の量と種類によりことなり、特に限定されな
いが、あまりに多すぎるとブリードアウトしてしまうこ
とになるので、上限は通常熱可塑性樹脂100重量部に
対して350重量部程度まである。本発明の多孔質化し
た薬剤徐放樹脂成形体は、延伸して得られるミクロボイ
ド(微細孔)よりなるものであり、該ミクロボイドは非
独立孔であり、貫通孔を有し、その中に薬剤が存在して
いるので、熱可塑性樹脂の飽和溶解量以上の量の薬剤が
樹脂成型体中に存在しても表面でのブリードアウト現象
を呈することはない。ここで言う熱可塑性樹脂に対する
飽和溶解量とは、樹脂を該薬剤に浸漬した時に該樹脂が
吸収し得る該薬剤の最大量のことであり(本発明では、
便宜上23℃で測定した値を意味する)。該薬剤が23
℃で固体である場合には該樹脂と該薬剤を加熱融解させ
た状態で混合し、23℃に冷却して放置したときに、該
薬剤が樹脂内部あるいは樹脂表面にて結晶化をおこさず
に該樹脂中に均一に分散し得る最大量のことである。
The drug sustained-release resin molded product of the present invention can hold a drug having a saturated solubility or more in a thermoplastic resin. The upper limit of the amount of the drug depends on the amounts and types of the thermoplastic resin, the drug, and the filler to be used, and is not particularly limited, but if the amount is too large, bleed out occurs, so the upper limit is usually the thermoplastic resin 100. It is up to about 350 parts by weight with respect to parts by weight. The porous drug sustained-release resin molded product of the present invention comprises microvoids (fine pores) obtained by stretching, and the microvoids are non-independent pores and have through-holes, and the drug is contained therein. Therefore, even if the amount of the chemical agent equal to or more than the saturated dissolution amount of the thermoplastic resin is present in the resin molded body, the bleed-out phenomenon on the surface does not occur. The saturated dissolution amount with respect to the thermoplastic resin referred to here is the maximum amount of the drug that can be absorbed by the resin when the resin is immersed in the drug (in the present invention,
For convenience, it means the value measured at 23 ° C.). The drug is 23
When it is a solid at ℃, the resin and the drug are mixed in a state of being heated and melted, and when the drug is cooled to 23 ° C. and left to stand, the drug does not crystallize inside the resin or on the resin surface. It means the maximum amount that can be uniformly dispersed in the resin.

【0009】本発明の薬剤徐放樹脂成形体は、目的に応
じて種々の薬剤を徐放化できるので、本発明で用いられ
る薬剤は特に限定されないが、用いることのできる薬剤
としては、防虫剤、防黴剤、忌避剤、殺菌剤、防錆剤、
芳香剤および植物から得られた精油等からなる群から任
意に選ばれた少なくとも一つ以上の薬剤があげられる。
ここで言う薬剤とは、有効活性成分またはその製剤のこ
とである。さらに具体的に本発明において用いられる薬
剤を例示すると、防虫剤としては、ペルメトリン、アレ
スリン、d−アレスリン、dd−アレスリン、プラレス
リン、サイフェノトリン、d−フェノトリン、d−レス
メトリン、エンペントリン、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、ベンフルスリン、テラ
レスリン、フェノトリン等のピレスロイド系殺虫剤、フ
ェニトロチオン、ジクロルボス、ナレド、フェンチオ
ン、シアホス、クロルピリホス、ダイアジノン、カルク
ロホス等の有機燐系殺虫剤、メトキシジアゾン等の殺虫
剤、プロポクスル、フェノブカーブ、カルバリル等のカ
ーバメート系殺虫剤、ピリプロキシフェン、メソプレ
ン、ヒドロプレン、ジフルベンズロン、シロマジン、フ
ェノキシカーブ、ルフェニュロン(CGA18459
9)等の昆虫成育調節物質が挙げられる。これら、防虫
剤の効果を高める化合物としては、ピペロニルブトキサ
イド、MGK264、オクタクロロジプロピルエーテル
等が挙げられ、上記防虫剤と併用することができる。害
虫等の忌避剤としては、ジエチルトルアミド、ジブチル
フタレート等が挙げられる。 防黴剤としては、デヒド
ロ酢酸、4−イソプロピル−m−クレゾール、フタル酸
ベンジルn−ブチル、イソチオシアン酸アリル等が挙げ
られる。殺菌剤としては、クレゾール、レゾルシン等が
挙げられる。植物精油としては、ヒノキ精油、ヒバ精
油、月桃精油、カラシ抽出油、ワサビ抽出油等が挙げら
れ、これら植物精油類には芳香作用の他に防虫、防黴等
の活性も有するものもあるので、その薬効および活性に
より芳香剤としてのみならず防虫剤、防黴剤としても使
用できる場合がある。
Since the drug sustained-release resin molded product of the present invention can release various drugs depending on the purpose, the drug used in the present invention is not particularly limited, but the drug that can be used is an insect repellent. , Antifungal agent, repellent, bactericide, rust inhibitor,
At least one or more agents arbitrarily selected from the group consisting of aromatic agents and essential oils obtained from plants and the like can be mentioned.
The drug as used herein refers to an active ingredient or its preparation. More specifically, examples of the drug used in the present invention include insect repellents such as permethrin, allethrin, d-allethrin, dd-allethrin, plaresulin, cyphenothrin, d-phenothrin, d-resmethrin, enpentrin, fenvalerate, and phen. Pyrethroid insecticides such as propasulin, cyhalothrin, cyfluthrin, etofenprox, tralomethrin, benfluthrin, terralesulin, and phenothrin, organophosphorus insecticides such as fenitrothion, dichlorvos, naredo, fenthion, siaphos, chlorpyrifos, diazinon, and calclofos, methoxydiazo. Insecticides such as benzene, propoxur, fenobucarb, carbamate insecticides such as carbaryl, pyriproxyfen, mesoprene, hydroprene, diflubenz Down, cyromazine, phenoxy curve, Rufenyuron (CGA18459
Insect growth regulators such as 9). Examples of these compounds that enhance the effect of the insect repellent include piperonyl butoxide, MGK264, octachlorodipropyl ether and the like, which can be used in combination with the above insect repellent. Examples of pest repellents include diethyltoluamide, dibutyl phthalate and the like. Examples of the mildew-proofing agent include dehydroacetic acid, 4-isopropyl-m-cresol, benzyl n-butyl phthalate, and allyl isothiocyanate. Examples of the bactericide include cresol and resorcin. Examples of plant essential oils include hinoki cypress essential oil, hiba essential oil, moon peach essential oil, mustard extract oil, wasabi extract oil, and the like.Some of these plant essential oils also have activities such as insect repellent and mildew proof in addition to aroma action. Therefore, depending on its medicinal effect and activity, it may be used not only as an aromatic agent but also as an insect repellent or a fungicide.

【0010】本発明における薬剤徐放樹脂成形体を得る
通常の実施態様の一つの方法として、まず、熱可塑性樹
脂と充填剤および熱可塑性樹脂に対する飽和溶解度以上
の量の薬剤に、必要に応じては分散剤や安定剤などを加
えてロール型またはバンバリー型の混練機あるいは一軸
または二軸押出機などを用いる通常の方法で混合あるい
は混練して組成物を得る。次いでこの組成物を通常、厚
さ30μm〜10mmのシート形状や径が30μm〜1
0mmの棒状体に成形し、成形加工したものを通常、1
0〜140℃の範囲で,より好ましくは20〜140℃
の範囲で一軸または二軸に1.1〜10倍の倍率で延伸
することにより薬剤徐放樹脂成形体を得るものである。
樹脂組成によって好ましい延伸温度は異なるが、延伸温
度が10℃未満だと延伸時の安定性が好ましくなく、1
40℃を越える温度だとミクロボイドが発生しにくいた
め好ましくない。延伸方法としては、一軸延伸の場合は
通常ロール延伸や引き抜きダイを用いた延伸方法が用い
られる。二軸延伸の場合は同時二軸延伸でも可能である
し、縦方向の延伸を行なった後に横方向を延伸する逐次
二軸延伸でも可能である。延伸倍率は、通常、1.1〜
10倍の範囲である。延伸倍率が1.1倍未満では、気
孔率(樹脂成形体の単位重量当たりの微細孔の全体積の
割合)が低くなり、延伸後の樹脂成形体内部において、
樹脂からブリードアウトした薬剤を安定的に存在させる
ことができなくなる。一方、10倍を越える場合には樹
脂が破断してしまったり、必要以上に微細孔の径が大き
くなるために上記範囲の倍率の延伸が好ましい。延伸し
て得られた成形体はそのまま使用することができるが、
必要によりアニーリングして後収縮を抑えることも行わ
れる。アニーリングの温度は、延伸温度と樹脂の融点と
の間が好ましい。
As one of the ordinary methods for obtaining the drug sustained-release resin molded product of the present invention, first, a thermoplastic resin, a filler, and a drug in an amount equal to or more than the saturated solubility in the thermoplastic resin are added, if necessary. Is mixed or kneaded with a dispersant, a stabilizer and the like by a usual method using a roll type or Banbury type kneader or a single-screw or twin-screw extruder to obtain a composition. Then, this composition is usually used in the form of a sheet having a thickness of 30 μm to 10 mm and a diameter of 30 μm to 1 mm.
It is usually molded into a rod-shaped body of 0 mm and molded into 1
In the range of 0 to 140 ° C, more preferably 20 to 140 ° C
By uniaxially or biaxially stretching at a ratio of 1.1 to 10 times within the above range, a drug sustained-release resin molded body is obtained.
The preferred stretching temperature varies depending on the resin composition, but if the stretching temperature is less than 10 ° C, the stability during stretching is unfavorable.
If the temperature exceeds 40 ° C, microvoids are less likely to occur, which is not preferable. As the stretching method, in the case of uniaxial stretching, a roll stretching method or a stretching method using a drawing die is usually used. In the case of biaxial stretching, simultaneous biaxial stretching is possible, or sequential biaxial stretching in which transverse stretching is carried out after longitudinal stretching is possible. The draw ratio is usually 1.1-
The range is 10 times. When the draw ratio is less than 1.1 times, the porosity (the ratio of the total volume of the fine pores per unit weight of the resin molded body) becomes low, and the inside of the resin molded body after stretching is
The drug bleeding out from the resin cannot be stably present. On the other hand, if it exceeds 10 times, the resin will be broken or the diameter of the fine pores will be unnecessarily increased, so stretching at a draw ratio in the above range is preferable. The molded product obtained by stretching can be used as it is,
If necessary, annealing is also performed to suppress post-shrinkage. The annealing temperature is preferably between the stretching temperature and the melting point of the resin.

【0011】薬剤が液体である場合、薬剤をそのまま用
いるか、あるいは揮発性または不揮発性の溶剤で希釈し
て延伸前の樹脂組成物の調製に用いることができ、薬剤
が固体である場合には、薬剤をそのまま樹脂および充填
剤と混合して延伸することも可能であり、薬剤を揮発性
または不揮発性の溶剤に溶解させて用いることもでき
る。また、薬剤が熱加工により揮散または分解するなど
の理由により、予め樹脂と充填剤に薬剤を混合できない
場合には、熱可塑性樹脂と充填剤、必要に応じて分散剤
や安定剤などをロール型またはバンバリー型の混練機あ
るいは一軸または二軸押出機などを用いる通常の方法で
混合あるいは混練して組成物を得る。次いでこの組成物
を通常30μm〜10mmのシート形状や径が30μm
〜10mmの棒状体に成形加工したものを、薬剤または
薬剤を揮発性の溶剤に溶解させた液に浸漬するかまたは
棒状体に薬剤またはその溶液を塗布した状態で延伸する
ことによって薬剤徐放樹脂成形体が得られる。この方法
では、延伸の際に形成されるミクロボイド(微細孔)中
に薬剤が取り込まれてゆくことにより目的とする薬剤徐
放樹脂成形体が得られる。また、本発明の薬剤徐放樹脂
成形体は、熱可塑性樹脂100重量部、充填剤50〜4
00重量部よりなる樹脂組成物を1.1〜10の倍率で
延伸して得られる多孔質樹脂成形体を薬剤またはその溶
液に浸漬するかまたは薬剤またはその溶液を多孔質樹脂
成形体に滴下して熱可塑性樹脂に対する飽和溶解量以上
の量の薬剤を含有させる方法で製造することもできる。
When the drug is a liquid, it can be used as it is or diluted with a volatile or non-volatile solvent to prepare a resin composition before stretching. When the drug is a solid, it can be used. Alternatively, the drug may be mixed as it is with the resin and the filler and stretched, or the drug may be dissolved in a volatile or non-volatile solvent before use. In addition, if the chemicals cannot be mixed with the resin and the filler in advance because the chemicals are volatilized or decomposed by heat processing, the thermoplastic resin and the filler, and if necessary, the dispersant and the stabilizer are roll type. Alternatively, a composition is obtained by mixing or kneading by a usual method using a Banbury type kneader or a single-screw or twin-screw extruder. Then, this composition is usually used in a sheet shape of 30 μm to 10 mm and a diameter of 30 μm
A drug sustained-release resin obtained by forming a rod-shaped body having a diameter of 10 mm into a drug or a liquid in which the drug is dissolved in a volatile solvent, or stretching the rod-shaped product with the drug or its solution applied. A molded body is obtained. In this method, the drug sustained-release resin molded product of interest is obtained by incorporating the drug into the microvoids (fine pores) formed during stretching. The drug sustained-release resin molded product of the present invention comprises 100 parts by weight of a thermoplastic resin and 50 to 4 fillers.
A porous resin molding obtained by stretching a resin composition consisting of 100 parts by weight at a ratio of 1.1 to 10 is immersed in a drug or a solution thereof, or the drug or a solution thereof is dropped into the porous resin molding. It can also be produced by a method in which a drug is contained in an amount equal to or more than the saturated dissolution amount in the thermoplastic resin.

【0012】本発明の薬剤徐放樹脂成形体において、薬
剤の放出速度をより好ましい範囲にコントロールするた
めに、熱可塑性樹脂100重量部、充填剤50〜400
重量部および熱可塑性樹脂に対する飽和溶解度量以上の
薬剤からなる樹脂組成物の少なくとも片面に熱可塑性樹
脂組成物を配してなる樹脂組成物を一軸または二軸に
1.1〜10の倍率で延伸することによっても得られ
る。同様の目的のため、薬剤とこれを含有する多孔質樹
脂成形体からなる薬剤徐放樹脂成形体の少なくとも片面
に、薬剤が透過可能な熱可塑性樹脂組成物層をラミネー
トなどの方法で貼合することによっても薬剤徐放樹脂成
形体を得ることができる。棒状体の薬剤徐放性樹脂成形
体を製造する場合には、熱可塑性樹脂100重量部、充
填剤50〜400重量部および熱可塑性樹脂に対する飽
和溶解量以上の量の薬剤からなる樹脂組成物の外周部に
薬剤が透過可能な熱可塑性樹脂組成物層を配してなる樹
脂組成物を1.1〜10の倍率で延伸することにより薬
剤徐放樹脂成形体を得ることができる。または棒状の薬
剤徐放性樹脂成形体を、溶剤に熱可塑性樹脂を溶解させ
た溶液に浸漬し、引き上げた後で溶剤を蒸発させること
によって熱可塑性樹脂を棒状体の外周部に配することが
できる。
In the drug sustained-release resin molding of the present invention, in order to control the drug release rate within a more preferable range, 100 parts by weight of a thermoplastic resin and 50 to 400 fillers are used.
A resin composition obtained by arranging a thermoplastic resin composition on at least one side of a resin composition consisting of parts by weight and a drug having a saturated solubility in a thermoplastic resin or more, is uniaxially or biaxially stretched at a ratio of 1.1 to 10 It can also be obtained by doing. For the same purpose, a drug-permeable thermoplastic resin composition layer is attached to at least one surface of a drug sustained-release resin molded product comprising a drug and a porous resin molded product containing the drug by a method such as lamination. Also by this, a drug sustained-release resin molded product can be obtained. In the case of producing a rod-shaped drug sustained-release resin molded product, a resin composition comprising 100 parts by weight of a thermoplastic resin, 50 to 400 parts by weight of a filler, and a drug in an amount equal to or more than a saturated dissolution amount with respect to the thermoplastic resin. A drug-controlled release resin molded product can be obtained by stretching a resin composition having a thermoplastic resin composition layer permeable to a drug on the outer peripheral portion thereof at a ratio of 1.1 to 10. Alternatively, the rod-shaped drug sustained-release resin molded article may be immersed in a solution in which a thermoplastic resin is dissolved in a solvent, and the thermoplastic resin may be disposed on the outer peripheral portion of the rod-shaped object by evaporating the solvent after pulling up. it can.

【0013】かかる目的のために配される熱可塑性樹脂
組成物としては、例えば、低密度ポリエチレン、高密度
ポリエチレン、ポリプロピレン、ポリブテン等のα−オ
レフィンホモポリマー、炭素数3〜18のα−オレフィ
ン類から選ばれた少なくとも一種のα−オレフィンとエ
チレンとの共重合体、プロピレンとエチレンおよび/ま
たはブテン−1との共重合体などの熱可塑性樹脂単独ま
たはこれらの2種以上の混合物が用いられる。あるい
は、これらの熱可塑性樹脂と、炭酸カルシウム、炭酸マ
グネシウム、炭酸バリウムなどの炭酸塩、硫酸バリウ
ム、硫酸マグネシウム、硫酸カルシウムなどの硫酸塩、
リン酸マグネシウム、リン酸カルシウムなどのリン酸
塩、水酸化マグネシウム、水酸化アルミニウムなどの水
酸化物、アルミナ、シリカ、酸化マグネシウム、酸化カ
ルシウム、酸化亜鉛、酸化チタンなどの酸化物、塩化亜
鉛、塩化鉄、塩化ナトリウムなどの塩化物、アルミニウ
ム粉、ゼオライト、シラス、白土、珪藻土、タルク、カ
ーボンブラック、火山灰などの無機充填剤や木粉、パル
プ粉などのセルロース系粉末、ナイロン粉末、ポリカー
ボネート粉末、ポリプロピレン粉末、ポリ−4−メチル
ペンテン−1粉末などの合成樹脂系粉末、でん粉キト
酸、キチン粉末、活性炭などの有機充填剤との混合物で
あってもよい。かかる樹脂または樹脂と充填剤よりなる
熱可塑性樹脂組成物層は、薬剤の透過を全く遮るもので
はなく、薬剤を透過させる性質をもつものであり、樹脂
の種類、樹脂層の厚さ、充填剤の選択により薬剤の透過
の速度を制御して薬剤の徐放速度を調節することができ
る。
Examples of the thermoplastic resin composition arranged for such purpose include, for example, α-olefin homopolymers such as low density polyethylene, high density polyethylene, polypropylene and polybutene, and α-olefins having 3 to 18 carbon atoms. A thermoplastic resin such as a copolymer of at least one α-olefin selected from ethylene and ethylene, a copolymer of propylene and ethylene and / or butene-1 or a mixture of two or more thereof is used. Alternatively, with these thermoplastic resins, calcium carbonate, magnesium carbonate, carbonates such as barium carbonate, barium sulfate, magnesium sulfate, sulfates such as calcium sulfate,
Phosphates such as magnesium phosphate and calcium phosphate, hydroxides such as magnesium hydroxide and aluminum hydroxide, alumina, silica, oxides such as magnesium oxide, calcium oxide, zinc oxide and titanium oxide, zinc chloride, iron chloride, Chlorides such as sodium chloride, aluminum powder, zeolite, shirasu, clay, diatomaceous earth, talc, carbon black, inorganic fillers such as volcanic ash and wood powder, cellulose powder such as pulp powder, nylon powder, polycarbonate powder, polypropylene powder, It may be a mixture with a synthetic resin powder such as poly-4-methylpentene-1 powder, starch chito acid, chitin powder, or an organic filler such as activated carbon. Such a resin or a thermoplastic resin composition layer comprising a resin and a filler does not completely block the permeation of the drug but has the property of allowing the drug to permeate. The type of resin, the thickness of the resin layer, the filler The rate of drug permeation can be controlled by controlling the selection of the above to control the sustained release rate of the drug.

【0014】[0014]

【発明の作用】本発明で用いる薬剤がある程度の蒸気圧
(1×10-5〜1×102 mmHg)を有する場合、薬
剤は成形体中の樹脂部分および表面に露出しているミク
ロボイドからの蒸散により放出される。樹脂部分につい
ては初期の状態では該樹脂の飽和溶解量存在しており、
薬剤の放出が始まると樹脂成型体の放出面と内部との間
に濃度勾配が生じるが、ミクロボイド中に薬剤が多量に
存在しているためミクロボイド中から樹脂部分へ薬剤の
供給がおこり、やがて平衡状態に達する。この平衡状態
はミクロボイド中の薬剤がなくなるまで持続するため、
その間の放出速度は一定速度となる。かなり低い蒸気圧
(1×10-5mmHgより低い蒸気圧)の薬剤の場合、
樹脂成型体表面からの蒸散による薬剤の放出は極めて微
量であるが、樹脂やミクロボイドの表面から薬剤を接触
により直接に吸着するか、あるいは媒体を通しての間接
的に吸着することにより樹脂やミクロボイドの表面の薬
剤が失われ、表面濃度が低下すると、上記の場合と同様
に、ミクロボイドから薬剤の供給が行われ、表面濃度は
一定に保たれることになり、実質的に薬剤の徐放量を一
定とすることができる。
When the drug used in the present invention has a certain vapor pressure (1 × 10 −5 to 1 × 10 2 mmHg), the drug is removed from the resin portion in the molded article and the microvoids exposed on the surface. It is released by evaporation. Regarding the resin portion, the saturated dissolution amount of the resin is present in the initial state,
When drug release begins, a concentration gradient occurs between the release surface and the inside of the resin molding, but since there is a large amount of drug in the microvoids, the drug is supplied from the microvoids to the resin part and eventually equilibrates. Reach the state. This equilibrium state continues until the drug in the microvoids is exhausted,
During that time, the release rate is constant. For drugs with a fairly low vapor pressure (vapor pressures below 1 × 10 −5 mmHg),
The amount of drug released from the surface of the resin molded body due to evaporation is extremely small, but the drug is directly adsorbed from the surface of the resin or microvoids by contact or indirectly adsorbed through a medium, and thus the surface of the resin or microvoids. When the drug is lost and the surface concentration decreases, the drug is supplied from the microvoids and the surface concentration is kept constant, as in the above case, and the sustained release amount of the drug is substantially constant. can do.

【0015】[0015]

【発明の効果】本発明の薬剤徐放樹脂成形体は大量の薬
剤の保持に優れ、一定速度または一定量での薬剤の放出
に向いているという点から、防虫剤、防黴剤、殺菌剤、
防錆剤、芳香剤および植物から得られた精油などの薬剤
の薬剤徐放樹脂成形体として極めて有用であり、用いる
薬剤の性質により、本発明の樹脂成形体は、防虫、防
黴、殺菌、防錆のため、あるいは芳香剤として使用する
ことができる。
INDUSTRIAL APPLICABILITY The drug sustained-release resin molded product of the present invention is excellent in retaining a large amount of drug, and is suitable for releasing the drug at a constant rate or at a constant amount. ,
Anti-rust agent, aromatic and extremely useful as a drug sustained-release resin molded product of a drug such as essential oil obtained from plants, due to the nature of the drug used, the resin molded product of the present invention, insect repellent, mildew-proof, sterilization, It can be used for rust prevention or as a fragrance.

【0016】[0016]

【実施例】以下、実施例により詳細に説明するが、本発
明はこれによって限定されるものではない。なお、実施
例および比較例に示した物性の測定法および効力評価試
験の方法は以下の通りである。 飽和溶解量:熱可塑性樹脂を50×50×0.5mm
に成形したシートを23℃の薬剤に浸漬し、ある一定時
間後に樹脂への薬剤の吸収が飽和に達した時点での吸収
された薬剤量の単位樹脂重量当たりに対する量を飽和溶
解量としたものである。 薬剤放出量:薬剤徐放樹脂成形体からの薬剤の放出量
は、該薬剤徐放樹脂成形体を4cm×10cmの大きさ
の試験片(放出面積:80cm2 )として40℃の恒温
槽中に吊るし、成形体中の薬剤の減量を重量変化により
調べ、下式により各試験片からの薬剤の蒸散率を求めて
表3、4および図1〜3に示した。 蒸散率(%)=(一定期間後の放出薬剤量)÷(初期の
薬剤量)×100 ブリードアウト性:薬剤徐放樹脂成形体表面への薬剤
のブリードアウトの有無は目視により観察し評価した。 効力評価試験方法 a)初期効力評価 供試虫:チャバネゴキブリ(Blattella germanica)成
虫(性比=1); イエシロアリ(Coptotermers formosanus);職蟻 ノミ(Ctenocephalides felis)
EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. The methods for measuring physical properties and the efficacy evaluation tests shown in Examples and Comparative Examples are as follows. Saturated dissolution amount: Thermoplastic resin 50 x 50 x 0.5 mm
The sheet formed into a sheet was dipped in a drug at 23 ° C, and the amount of drug absorbed per unit weight of resin when the absorption of the drug into the resin reached saturation after a certain period of time was taken as the saturated dissolution amount. Is. Drug release amount: The drug release amount from the drug sustained-release resin molded product was measured by using the drug sustained-release resin molded product as a test piece having a size of 4 cm × 10 cm (release area: 80 cm 2 ) in a constant temperature bath at 40 ° C. The amount of the drug in the molded article was hung and examined by changing the weight, and the transpiration rate of the drug from each test piece was determined by the following formula and shown in Tables 3 and 4 and FIGS. Evaporation rate (%) = (amount of drug released after a certain period of time) / (initial amount of drug) x 100 Bleed-out property: The presence or absence of bleed-out of the drug on the surface of the drug sustained-release resin molding was visually observed and evaluated. . Efficacy evaluation test method a) Initial efficacy evaluation Specimens: German cockroach (Blattella germanica) adult (sex ratio = 1); Yellow termite (Coptotermers formosanus); Worker fleas (Ctenocephalides felis)

【0017】試験方法:各供試薬剤徐放樹脂成形体上
に、供試虫1群10頭を放ち、120分間所定時間毎に
ノックダウン虫数を観察しKT50(供試虫の50%が
ノックダウンするのに要する時間)を求めた。また、ゴ
キブリでは3日後、シロアリでは1日後、ノミでは1日
後に致死を観察し、致死率(%)を求めた。各3反復実
施した。表3に結果を示す。なお、各試験に用いた薬剤
徐放樹脂成形体の大きさは以下の通りである。 対ゴキブリ(15×15cm) 対シロアリ(7.5×7.5cm) 対ノミ (7.5×7.5cm)
Test method: 10 test insects in a group of 10 were released on each resin agent sustained-release resin molded product, and the number of knockdown insects was observed every 120 minutes at a predetermined time. KT50 (50% of the test insects was The time required to knock down) was calculated. In addition, lethality was observed after 3 days in cockroaches, 1 day after in termites, and 1 day after in fleas, and the lethality rate (%) was calculated. Each was repeated 3 times. The results are shown in Table 3. The size of the drug sustained-release resin molding used in each test is as follows. Against cockroaches (15 x 15 cm) Against termites (7.5 x 7.5 cm) Against fleas (7.5 x 7.5 cm)

【0018】b)効力持続性評価 試験方法:各供試薬剤徐放樹脂成形体の表面をエタノー
ルを含漬させたガーゼにてこすり、薬剤徐放樹脂成形体
表面の薬剤を拭き取った後、室温下で1日放置してエタ
ノールを完全に揮散させるとともに薬剤徐放樹脂成形体
表面の薬剤濃度を安定化させ初期効力評価と同様の試験
を行なった。表4に結果を示す。
B) Evaluation of persistence of efficacy Test method: Rubbing the surface of each of the reagent controlled release resin moldings with gauze impregnated with ethanol to wipe off the drug on the surface of the drug controlled release resin molding, and then at room temperature. The test was conducted in the same manner as in the initial efficacy evaluation by allowing the solution to stand for one day under the conditions to completely volatilize ethanol and stabilize the drug concentration on the surface of the drug sustained-release resin molded product. The results are shown in Table 4.

【0019】(実施例1)熱可塑性樹脂として線状低密
度ポリエチレン(住友化学工業(株)製、商品名:エク
セレンVL VL200)100重量部と充填剤として
炭酸カルシウム(白石カルシウム(株)製、商品名:ホ
ワイトンSSB(赤))120重量部と、薬剤としてエ
ンペントリン(住友化学工業(株)製、商品名:ベーパ
ースリン)55重量部をバンバリーミキサーによって1
20℃で5分間混練して樹脂組成物を得た。 この樹脂
組成物を押出機によりTダイ成形により厚さ1mmのシ
ートとし、このシートをロール延伸機により50℃で一
軸(MD)方向に4倍に延伸し薬剤徐放樹脂成形体を得
た。得られた薬剤徐放樹脂成形体は、加工性は良好であ
り、薬剤徐放樹脂成形体表面への薬剤のブリードアウト
がなく優れた性能を有していた。
Example 1 100 parts by weight of linear low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200) as a thermoplastic resin and calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd.) as a filler, Trade name: Whiten SSB (red) 120 parts by weight and Empentrin (Sumitomo Chemical Co., Ltd., trade name: Vaporthrin) 55 parts by weight as a medicine by using a Banbury mixer 1
The resin composition was obtained by kneading at 20 ° C. for 5 minutes. This resin composition was formed into a sheet having a thickness of 1 mm by T-die molding using an extruder, and this sheet was stretched at a temperature of 50 ° C. by a factor of 4 in a uniaxial (MD) direction to obtain a drug sustained-release resin molded body. The obtained drug sustained-release resin molded product had good processability and had excellent performance without bleeding out of the drug on the surface of the drug sustained-release resin molded product.

【0020】(実施例2)薬剤としてフェノトリン(住
友化学工業(株)製、商品名:スミスリン)を使用した
こと以外は、実施例1と同様な方法で薬剤徐放樹脂成形
体を得た。この薬剤徐放樹脂成形体は、加工性は良好で
あり、薬剤徐放樹脂成形体表面への薬剤のブリードアウ
トがなく優れた性能を有していた。
Example 2 A drug sustained-release resin molding was obtained in the same manner as in Example 1, except that phenothrin (Sumitomo Chemical Co., Ltd., trade name: Smithlin) was used as the drug. The drug sustained-release resin molded article had good processability and had excellent performance without bleeding out of the drug on the surface of the drug sustained-release resin molded article.

【0021】(実施例3)熱可塑性樹脂として線状低密
度ポリエチレン(住友化学工業(株)製、商品名:エク
セレンVL VL200)20重量部と線状低密度ポリ
エチレン(住友化学工業(株)製、商品名:スミカセン
α CS3003)60重量部と低密度ポリエチレン
(住友化学工業(株)製、商品名:スミカセン F20
8−0)20重量部を用いたこと以外は実施例1と同様
な方法で薬剤徐放樹脂成形体を得た。この薬剤徐放樹脂
成形体は、加工性は良好であり、薬剤徐放樹脂成形体表
面への薬剤のブリードアウトがなく優れた性能を有して
いた。
(Example 3) 20 parts by weight of linear low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200) as a thermoplastic resin and linear low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd.) , Trade name: Sumikasen α CS3003) 60 parts by weight and low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., Trade name: Sumikasen F20
8-0) A drug sustained-release resin molding was obtained in the same manner as in Example 1 except that 20 parts by weight was used. The drug sustained-release resin molded article had good processability and had excellent performance without bleeding out of the drug on the surface of the drug sustained-release resin molded article.

【0022】(実施例4)熱可塑性樹脂として線状低密
度ポリエチレン(住友化学工業(株)製、商品名:エク
セレンVL VL200)100重量部と充填剤として
炭酸カルシウム(白石カルシウム(株)製、商品名:ホ
ワイトンSSB(赤))120重量部とをバンバリーミ
キサーによって120℃で5分間混練して樹脂組成物を
得た。この樹脂組成物を押出機によりTダイ成形し、厚
さ1mmのシートとし、得られたシートをエンペントリ
ン液中に浸漬した状態でロール延伸機により50℃で一
軸方向に4倍に延伸し薬剤徐放樹脂成形体を得た。シー
ト表面に付着した薬剤を拭き取り、この薬剤徐放樹脂成
形体中のエンペントリンの含有量を測定したところ、4
5重量部であった。この薬剤徐放樹脂成形体は、加工性
は良好であり、薬剤徐放樹脂成形体表面への薬剤のブリ
ードアウトがなく優れた性能を有していた。
Example 4 100 parts by weight of linear low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200) as a thermoplastic resin and calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd.) as a filler, 120 parts by weight of product name: Whiten SSB (red) was kneaded with a Banbury mixer at 120 ° C. for 5 minutes to obtain a resin composition. This resin composition was subjected to T-die molding by an extruder to form a sheet having a thickness of 1 mm, and the obtained sheet was immersed in an empentryin solution and stretched 4 times in a uniaxial direction at 50 ° C. by a roll stretching machine to gradually release the drug. An extruded resin molding was obtained. The drug adhering to the surface of the sheet was wiped off, and the content of empentrin in the drug sustained-release resin molded product was measured.
It was 5 parts by weight. The drug sustained-release resin molded article had good processability and had excellent performance without bleeding out of the drug on the surface of the drug sustained-release resin molded article.

【0023】(実施例5)実施例1で得られた多孔質体
の両面に熱可塑性樹脂として低密度ポリエチレン(住友
化学工業(株)製、商品名:スミカセン G801)を
ラミネート加工により50μmの厚みで配し、薬剤徐放
樹脂多層体を得た。得られた薬剤徐放樹脂多層体は、薬
剤徐放樹脂成形体表面への薬剤のブリードアウトがなく
優れた性能を有していた。
(Example 5) Low density polyethylene (Sumitomo Chemical Co., Ltd., trade name: Sumikasen G801) as a thermoplastic resin was laminated on both sides of the porous body obtained in Example 1 to a thickness of 50 μm. To obtain a drug sustained-release resin multilayer body. The obtained drug sustained-release resin multilayer body had excellent performance without bleeding out of the drug on the surface of the drug sustained-release resin molded product.

【0024】(実施例6)実施例1で得られた多孔質体
の両面に熱可塑性樹脂として線状低密度ポリエチレン
(住友化学工業(株)製、商品名:エクセレンVL V
L200)をラミネート加工により50μmの厚みで配
し、薬剤徐放樹脂成形体を得た。得られた薬剤徐放樹脂
成形体は、薬剤徐放樹脂成形体表面への薬剤のブリード
アウトがなく優れた性能を有していた。
Example 6 A linear low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL V) as a thermoplastic resin on both sides of the porous body obtained in Example 1
L200) was laminated to a thickness of 50 μm to obtain a drug sustained-release resin molded body. The obtained drug sustained-release resin molded product had excellent performance without bleeding out of the drug onto the surface of the drug sustained-release resin molded product.

【0025】(実施例7)ロール延伸の際の延伸温度を
室温(23℃)としたこと以外は、実施例1と同様な方
法で薬剤徐放樹脂成形体を得た。得られた薬剤徐放樹脂
成形体は、加工性は良好であり、薬剤徐放樹脂成形体表
面への薬剤のブリードアウトがなく優れた性能を有して
いた。
(Example 7) A drug sustained-release resin molding was obtained in the same manner as in Example 1 except that the stretching temperature during roll stretching was room temperature (23 ° C). The obtained drug sustained-release resin molded product had good processability and had excellent performance without bleeding out of the drug on the surface of the drug sustained-release resin molded product.

【0026】(実施例8)充填剤の配合量を150重量
部、薬剤の配合量を135重量部とし、ロール延伸の際
の延伸温度を室温(23℃)としたこと以外は、実施例
1と同様な方法で薬剤徐放樹脂成形体を得た。得られた
薬剤徐放樹脂成形体は、加工性は良好であり、薬剤徐放
樹脂成形体表面への薬剤のブリードアウトがなく優れた
性能を有していた。
Example 8 Example 1 was repeated except that the amount of the filler was 150 parts by weight, the amount of the drug was 135 parts by weight, and the stretching temperature during roll stretching was room temperature (23 ° C.). A drug sustained-release resin molded product was obtained in the same manner as in (1). The obtained drug sustained-release resin molded product had good processability and had excellent performance without bleeding out of the drug on the surface of the drug sustained-release resin molded product.

【0027】(実施例9)可塑性樹脂として線状低密度
ポリエチレン(住友化学工業(株)製、商品名:エクセ
レンVL VL200)40重量部と線状低密度ポリエ
チレン(住友化学工業(株)製、商品名:スミカセンα
FZ201−0)60重量部とし、充填剤として炭酸
カルシウム(白石カルシウム(株)製、商品名:ホワイ
トンSSB(赤))150重量部とし、薬剤としてヒノ
キ精油(紀州ヒノキ屋(株)製)135重量部を用い、
ロール延伸の際の温度を室温(23℃)としたこと以外
は実施例1と同様な方法で薬剤徐放樹脂成形体を得た。
得られた薬剤徐放樹脂成形体は、加工性は良好であり、
薬剤徐放樹脂成形体表面への薬剤のブリードアウトがな
く優れた性能を有していた。
Example 9 40 parts by weight of linear low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200) as a plastic resin and linear low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd.) Product Name: Sumikasen α
FZ201-0) 60 parts by weight, calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: Whiten SSB (red)) 150 parts by weight as a filler, and Hinoki essential oil (manufactured by Kishu Hinokiya Co., Ltd.) as a drug. Using 135 parts by weight,
A drug sustained-release resin molded body was obtained in the same manner as in Example 1 except that the temperature during roll stretching was room temperature (23 ° C.).
The obtained drug sustained-release resin molded product has good processability,
There was no bleed-out of the drug on the surface of the drug sustained-release resin molded product, and it had excellent performance.

【0028】(実施例10)充填剤の配合量を150重
量部とし、薬剤としてイソチオシアン酸アリル(ミドリ
十字(株)製、商品名:ワサオーロ)を用い、ロール延
伸の際の延伸温度を室温(23℃)としたこと以外は、
実施例4と同様な方法で薬剤徐放樹脂成形体を得た。こ
の薬剤徐放樹脂成形体100重量部中のイソチオシアン
酸アリルの含有量は65重量部であった。得られた薬剤
徐放樹脂成形体の表面には薬剤のブリードアウトが生じ
ず、良好な薬剤徐放体であった。
(Example 10) The blending amount of the filler was 150 parts by weight, allyl isothiocyanate (Midori Cross Co., Ltd., trade name: Wasa Auro) was used as a drug, and the stretching temperature at the time of roll stretching was room temperature ( 23 ° C) except that
A drug sustained-release resin molded body was obtained in the same manner as in Example 4. The content of allyl isothiocyanate in 100 parts by weight of the drug sustained-release resin molded product was 65 parts by weight. Bleed-out of the drug did not occur on the surface of the obtained drug-controlled release resin molded product, and the drug-controlled release product was good.

【0029】(実施例11)薬剤としてピリプロキシフ
ェン(住友化学工業(株)製、商品名:スミラブ)を3
重量部と、d−アレスリン(住友化学工業(株)製、商
品名:ピナミンフォルテ)を40重量部配合した事以外
は、実施例1と同様な方法で薬剤徐放樹脂成形体を得
た。得られた薬剤徐放樹脂成形体は、加工性は良好であ
り、薬剤徐放樹脂成形体表面への薬剤のブリードアウト
がなく優れた性能を有していた。
Example 11 Pyriproxyfen (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilab) was used as a drug.
A drug sustained-release resin molded product was obtained in the same manner as in Example 1, except that 40 parts by weight of d-allethrin (manufactured by Sumitomo Chemical Co., Ltd., trade name: Pinamine Forte) was blended. . The obtained drug sustained-release resin molded product had good processability and had excellent performance without bleeding out of the drug on the surface of the drug sustained-release resin molded product.

【0030】(実施例12)薬剤としてピリプロキシフ
ェン(住友化学工業(株)製、商品名:スミラブ)を3
重量部と、メトキシジアゾン(住友化学工業(株)製、
商品名:エレミック)を40重量部配合した事以外は、
実施例1と同様な方法で薬剤徐放樹脂成形体を得た。得
られた薬剤徐放樹脂成形体は、加工性は良好であり、薬
剤徐放樹脂成形体表面への薬剤のブリードアウトがなく
優れた性能を有していた。
Example 12 Pyriproxyfen (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumilab) was used as a drug.
Parts by weight and methoxydiazone (Sumitomo Chemical Co., Ltd.,
Product name: ELEMIC)
A drug sustained-release resin molded body was obtained in the same manner as in Example 1. The obtained drug sustained-release resin molded product had good processability and had excellent performance without bleeding out of the drug on the surface of the drug sustained-release resin molded product.

【0031】(実施例13)熱可塑性樹脂として線状低
密度ポリエチレン(住友化学工業(株)製、商品名:ス
ミカセンα FZ201−0)を100重量部と充填剤
として炭酸カルシウム(白石カルシウム(株)製、商品
名:ホワイトンSSB(赤))150重量部と薬剤とし
てピリプロキシフェンを3重量部と、フェノトリン36
重量部およびN-(2-ethylhexyl)-8,9,10-trinorborn-5-e
ne-2,3-dicarboximideを72重量部配合し、ロール延伸
の際の延伸温度を室温(23℃)としたこと以外は、実
施例1と同様な方法で薬剤徐放樹脂成形体を得た。得ら
れた薬剤徐放樹脂成形体は、加工性は良好であり、薬剤
徐放樹脂成形体表面への薬剤のブリードアウトがなく優
れた性能を有していた。
(Example 13) 100 parts by weight of linear low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumikasen α FZ201-0) as a thermoplastic resin and calcium carbonate as a filler (Shiraishi Calcium Co., Ltd. ), Trade name: Whiten SSB (red)) 150 parts by weight, 3 parts by weight of pyriproxyfen as a drug, and phenothrin 36
Parts by weight and N- (2-ethylhexyl) -8,9,10-trinorborn-5-e
A drug sustained-release resin molding was obtained in the same manner as in Example 1 except that 72 parts by weight of ne-2,3-dicarboximide was blended and the stretching temperature during roll stretching was room temperature (23 ° C.). . The obtained drug sustained-release resin molded product had good processability and had excellent performance without bleeding out of the drug on the surface of the drug sustained-release resin molded product.

【0032】(比較例1)熱可塑性樹脂として線状低密
度ポリエチレン(住友化学工業(株)製、商品名:エク
セレンVL VL200)100重量部と充填剤として
炭酸カルシウム(白石カルシウム(株)製、商品名:ホ
ワイトンSSB(赤))40重量部と、薬剤としてエン
ペントリン(住友化学工業(株)製、商品名:ベーパー
スリン)55重量部をバンバリーミキサーによって12
0℃で5分間混練して樹脂組成物を得た。この樹脂組成
物を押出機によりTダイ成形により厚さ1mmのシート
とし、このシートをロール延伸機により50℃で一軸方
向に4倍に延伸し薬剤徐放樹脂成形体を得た。得られた
薬剤徐放樹脂成形体は多孔質化度が低いために内部から
エンペントリンがブリードアウトして実用に至らないも
のであった。
(Comparative Example 1) 100 parts by weight of linear low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200) as a thermoplastic resin and calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd.) as a filler, Brand name: Whiten SSB (red) 40 parts by weight and Empentrin (Sumitomo Chemical Co., Ltd., product name: Vaporthrin) 55 parts by weight as a drug are mixed with a Banbury mixer 12
A resin composition was obtained by kneading at 0 ° C. for 5 minutes. This resin composition was formed into a sheet having a thickness of 1 mm by T-die molding with an extruder, and this sheet was stretched uniaxially by 4 times at 50 ° C. with a roll stretching machine to obtain a drug sustained-release resin molded body. Since the obtained drug-releasing resin molded product had a low degree of porosity, empentrin bleeded out from the inside, which was not practical.

【0033】(比較例2)熱可塑性樹脂として線状低密
度ポリエチレン(住友化学工業(株)製、商品名:エク
セレンVL VL200)100重量部と充填剤として
炭酸カルシウム(白石カルシウム(株)製、商品名:ホ
ワイトンSSB(赤))450重量部と、薬剤としてエ
ンペントリン(住友化学工業(株)製、商品名:ベーパ
ースリン)55重量部をバンバリーミキサーによって1
2℃で5分間混練して樹脂組成物を得た。この樹脂組成
物を押出機によりTダイ成形により厚さ1mmのシート
とし、このシートをロール延伸機により50℃で一軸方
向に4倍の延伸を試みたが、破断してしまい薬剤徐放樹
脂成形体を得ることができなかった。
(Comparative Example 2) 100 parts by weight of linear low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200) as a thermoplastic resin and calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd.) as a filler, Brand name: Whiten SSB (red)) 450 parts by weight and Empentrin (Sumitomo Chemical Co., Ltd., product name: Vaporthrin) 55 parts by weight as a drug are mixed with a Banbury mixer 1
A resin composition was obtained by kneading at 2 ° C. for 5 minutes. This resin composition was formed into a sheet having a thickness of 1 mm by T-die molding with an extruder, and this sheet was tried to be stretched 4 times in a uniaxial direction at 50 ° C. with a roll stretching machine, but it broke and was gradually released into a drug-release resin molding. I couldn't get a body.

【0034】(比較例3)延伸処理を施さなかったこと
以外は実施例1と同様な方法で樹脂組成物の厚さ1mm
のシートを得た。得られたシートは多孔質化していない
ために内部からエンペントリンがブリードアウトして実
用に至らないものであった。
Comparative Example 3 A resin composition having a thickness of 1 mm was prepared in the same manner as in Example 1 except that the stretching treatment was not performed.
Got a sheet of. Since the obtained sheet was not made porous, empentrin bleeded out from the inside, which was not practical.

【0035】(比較例4)熱可塑性樹脂として線状低密
度ポリエチレン(住友化学工業(株)製、商品名:エク
セレンVL VL200)100重量部と充填剤として
炭酸カルシウム(白石カルシウム(株)製、商品名:ホ
ワイトンSSB(赤))120重量部と、薬剤としてエ
ンペントリン(住友化学工業(株)製、商品名:ベーパ
ースリン)55重量部をバンバリーミキサーによって1
20℃で5分間混練して樹脂組成物を得た。 この樹脂
組成物を押出機によりTダイ成形により厚さ1mmのシ
ートとし、このシートをロール延伸機により50℃で一
軸方向に12倍に延伸を試みたが破断してしまい、薬剤
徐放樹脂成形体を得ることができなかった。
(Comparative Example 4) 100 parts by weight of linear low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200) as a thermoplastic resin and calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd.) as a filler, Trade name: Whiten SSB (red) 120 parts by weight and Empentrin (Sumitomo Chemical Co., Ltd., trade name: Vaporthrin) 55 parts by weight as a medicine by using a Banbury mixer 1
The resin composition was obtained by kneading at 20 ° C. for 5 minutes. This resin composition was formed into a sheet having a thickness of 1 mm by T-die molding with an extruder, and this sheet was tried to be stretched 12 times in a uniaxial direction at 50 ° C. with a roll stretching machine, but it broke, resulting in drug sustained release resin molding. I couldn't get a body.

【0036】(実施例14)熱可塑性樹脂として線状低
密度ポリエチレン(住友化学工業(株)製、商品名:エ
クセレンVL VL200、エンペントリン飽和溶解量
2.3重量%)100重量部と充填剤として炭酸カルシ
ウム(白石カルシウム(株)製、商品名:ホワイトンS
SB(赤))120重量部と、薬剤としてエンペントリ
ン(住友化学工業(株)製、商品名:ベーパースリン、
20℃での蒸気圧6.5×10-4mmHg)40重量部
をバンバリーミキサーによって120℃で5分間混練し
て樹脂組成物を得た。この樹脂組成物を押出機によりT
ダイ成形により厚さ1mmのシートとし、このシートを
ロール延伸機により50℃で一軸方向に4倍に延伸し薬
剤徐放樹脂成形体を得た。得られた薬剤徐放樹脂成形体
からの薬剤放出量を測定したところ、第3表および図1
に示す様に単位時間当たりの薬剤放出量が一定にコント
ロールされており、非常に良好な薬剤徐放樹脂成形体で
あった。
Example 14 As a thermoplastic resin, 100 parts by weight of linear low-density polyethylene (Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200, saturated dissolution amount of empentrin 2.3% by weight) and 100 parts by weight of filler Calcium carbonate (Shiraishi Calcium Co., Ltd., trade name: Whiten S
SB (red) 120 parts by weight, and as a drug, Enpentrin (Sumitomo Chemical Co., Ltd., trade name: Vaporthrin,
40 parts by weight of vapor pressure 6.5 × 10 −4 mmHg) at 20 ° C. was kneaded with a Banbury mixer at 120 ° C. for 5 minutes to obtain a resin composition. This resin composition was processed into T by an extruder.
A sheet having a thickness of 1 mm was formed by die molding, and the sheet was stretched uniaxially by 4 times at 50 ° C. by a roll stretching machine to obtain a drug sustained-release resin molded body. The amount of drug released from the obtained drug sustained-release resin molded product was measured, and Table 3 and FIG.
As shown in (3), the drug release amount per unit time was controlled to be constant, and it was a very good drug sustained-release resin molded product.

【0037】(実施例15)実施例14で得られた多孔
質体の両面に熱可塑性樹脂として低密度ポリエチレン
(住友化学工業(株)製、商品名:スミカセン G80
1)をラミネート加工により50μmの厚みで配し、薬
剤徐放樹脂成形体を得た。この薬剤徐放樹脂成形体は第
3表および図1に示す通り優れた性能を有していた。
(Example 15) Low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumikasen G80) as a thermoplastic resin on both surfaces of the porous body obtained in Example 14
1) was laminated with a thickness of 50 μm to obtain a drug sustained-release resin molded body. The drug sustained-release resin molded product had excellent performance as shown in Table 3 and FIG.

【0038】(実施例16)実施例14で得られた多孔
質体の両面に熱可塑性樹脂として線状低密度ポリエチレ
ン(住友化学工業(株)製、商品名:エクセレンVL
VL200)をラミネート加工により50μmの厚みで
配し、薬剤徐放樹脂成形体を得た。この薬剤徐放樹脂成
形体は第3表および図1に示す通り優れた性能を有して
いた。
(Example 16) Linear low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL) on both sides of the porous body obtained in Example 14 as a thermoplastic resin.
VL200) was laminated to have a thickness of 50 μm to obtain a drug sustained-release resin molded body. The drug sustained-release resin molded product had excellent performance as shown in Table 3 and FIG.

【0039】(実施例17)実施例14で得られた多孔
質体の両面に熱可塑性樹脂として高密度ポリエチレン
(昭和電工(株)製、商品名:ショウレックス505
0)をラミネート加工により80μmの厚みで配し、薬
剤徐放樹脂成形体を得た。この薬剤徐放樹脂成形体は第
3表および図1に示す通り優れた性能を有していた。
(Example 17) High density polyethylene (made by Showa Denko KK, trade name: Shorex 505) as a thermoplastic resin on both sides of the porous body obtained in Example 14
0) was laminated to a thickness of 80 μm to obtain a drug sustained-release resin molding. The drug sustained-release resin molded product had excellent performance as shown in Table 3 and FIG.

【0040】(実施例18)熱可塑性樹脂として線状低
密度ポリエチレン(住友化学工業(株)製、商品名:エ
クセレンVL VL200、イソチオシアン酸アリルの
飽和溶解量4.5重量%)100重量部と充填剤として
炭酸カルシウム(白石カルシウム(株)製、商品名ホワ
イトンSSB(赤))150重量部とをバンバリーミキ
サーによって120℃で5分間混練して樹脂組成物を得
た。この樹脂組成物を押出機によりTダイ成形し、厚さ
1mmのシートとし、得られたシートをイソチオシアン
酸アリル(ミドリ十字(株)製、商品名:ワサオーロ、
20℃における蒸気圧4mmHg)液中に浸漬した状態
でロール延伸機により室温下(23℃)に一軸方向に4
倍に延伸し薬剤徐放樹脂成形体を得た。さらにこの薬剤
徐放樹脂成形体の両面に熱可塑性樹脂として低密度ポリ
エチレン(住友化学工業(株)製、商品名:スミカセン
F208−0)をラミネート加工により50μmの厚
みで配し、薬剤徐放樹脂成形体を得た。この薬剤徐放樹
脂成形体は第4表および図2に示す通り優れた性能を有
していた。
Example 18 As a thermoplastic resin, 100 parts by weight of linear low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200, saturated dissolution amount of allyl isothiocyanate 4.5% by weight) was used. 150 parts by weight of calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name Whiten SSB (red)) as a filler was kneaded with a Banbury mixer at 120 ° C. for 5 minutes to obtain a resin composition. This resin composition was T-die molded by an extruder to form a sheet having a thickness of 1 mm, and the obtained sheet was allyl isothiocyanate (Midori Cross Co., Ltd., trade name: Wasauro,
4mm uniaxially at room temperature (23 ° C) with a roll stretching machine while immersed in liquid at 20 ° C vapor pressure 4mmHg)
It was stretched twice to obtain a drug sustained-release resin molded product. Furthermore, low-density polyethylene (Sumitomo Chemical Co., Ltd., trade name: Sumikasen F208-0) as a thermoplastic resin was laminated on both sides of this drug sustained-release resin molded product by lamination to a thickness of 50 μm, A molded body was obtained. The drug sustained-release resin molded product had excellent performance as shown in Table 4 and FIG.

【0041】(実施例19)両面に配する熱可塑性樹脂
として高密度ポリエチレン(昭和電工(株)製、商品
名:ショウデックス5050)を用いたこと以外は実施
例18と同様にしてこの薬剤徐放樹脂成形体は第4表お
よび図3に示す通り優れた性能を有していた。
(Example 19) This example was prepared in the same manner as in Example 18 except that high-density polyethylene (Showa Denko KK, trade name: SHOWDEX 5050) was used as the thermoplastic resin on both sides. The resin-release molded product had excellent performance as shown in Table 4 and FIG.

【0042】(比較例5)熱可塑性樹脂として線状低密
度ポリエチレン(住友化学工業(株)製、商品名:エク
セレンVL VL200)100重量部と充填剤として
炭酸カルシウム(白石カルシウム(株)製、商品名:ホ
ワイトンSSB(赤))40重量部と、薬剤としてエン
ペントリン(住友化学工業(株)製、商品名:ベーパー
スリン)40重量部をバンバリーミキサーによって12
0℃で5分間混練して樹脂組成物を得た。この樹脂組成
物を押出機によりTダイ成形により厚さ1mmのシート
とし、このシートをロール延伸機により50℃で一軸方
向に4倍に延伸し薬剤徐放樹脂成形体を得た。得られた
薬剤徐放樹脂成形体は多孔質化が低いために内部からエ
ンペントリンがブリードアウトして実用に適さないもの
であった。
(Comparative Example 5) 100 parts by weight of linear low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200) as a thermoplastic resin and calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd.) as a filler. Brand name: Whiten SSB (red) 40 parts by weight and Empentrin (Sumitomo Chemical Co., Ltd., product name: Vaporthrin) 40 parts by weight as a medicine are mixed with a Banbury mixer 12
A resin composition was obtained by kneading at 0 ° C. for 5 minutes. This resin composition was formed into a sheet having a thickness of 1 mm by T-die molding with an extruder, and this sheet was stretched uniaxially by 4 times at 50 ° C. with a roll stretching machine to obtain a drug sustained-release resin molded body. The obtained drug-releasing resin molded product was not suitable for practical use because the penetrin bleeded out from the inside because of low porosity.

【0043】(比較例6)熱可塑性樹脂として線状低密
度ポリエチレン(住友化学工業(株)製、商品名:エク
セレンVL VL200)100重量部と充填剤として
炭酸カルシウム(白石カルシウム(株)製、商品名:ホ
ワイトンSSB(赤))450重量部と、薬剤としてエ
ンペントリン(住友化学工業(株)製、商品名:ベーパ
ースリン)40重量部をバンバリーミキサーによって1
20℃で5分間混練して樹脂組成物を得た。この樹脂組
成物を押出機によりTダイ成形により厚さ1mmのシー
トとし、このシートをロール延伸機により50℃で一軸
方向に4倍の延伸を試みたが、破断してしまい薬剤徐放
樹脂成形体を得ることができなかった。
Comparative Example 6 100 parts by weight of linear low density polyethylene (Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200) as a thermoplastic resin and calcium carbonate (Shiraishi Calcium Co., Ltd.) as a filler, Brand name: Whiten SSB (red) (450 parts by weight) and Empentrin (Sumitomo Chemical Co., Ltd., product name: Vaporthrin) 40 parts by weight as a drug are mixed with a Banbury mixer.
The resin composition was obtained by kneading at 20 ° C. for 5 minutes. This resin composition was formed into a sheet having a thickness of 1 mm by T-die molding with an extruder, and this sheet was tried to be stretched 4 times in a uniaxial direction at 50 ° C. with a roll stretching machine, but it broke and was gradually released into a drug-release resin molding. I couldn't get a body.

【0044】(比較例7)延伸処理を施さなかったこと
以外は実施例14と同様な方法で樹脂組成物の厚さ1m
mのシートを得た。得られたシートは多孔質化していな
いために内部からエンペントリンがブリードアウトして
実用に至らないものであった。
(Comparative Example 7) A resin composition having a thickness of 1 m was prepared in the same manner as in Example 14 except that the stretching treatment was not performed.
m sheets were obtained. Since the obtained sheet was not made porous, empentrin bleeded out from the inside, which was not practical.

【0045】(比較例8)熱可塑性樹脂として線状低密
度ポリエチレン(住友化学工業(株)製、商品名:エク
セレンVL VL200)100重量部と充填剤として
炭酸カルシウム(白石カルシウム(株)製、商品名:ホ
ワイトンSSB(赤))120重量部と、薬剤としてエ
ンペントリン(住友化学工業(株)製、商品名:ベーパ
ースリン)40重量部をバンバリーミキサーによって1
20℃で5分間混練して樹脂組成物を得た。この樹脂組
成物を押出機によりTダイ成形により厚さ1mmのシー
トとし、このシートをロール延伸機により50℃で一軸
方向に12倍に延伸を試みたが破断してしまい、薬剤徐
放樹脂成形体を得ることができなかった。
(Comparative Example 8) 100 parts by weight of linear low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200) as a thermoplastic resin and calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd.) as a filler, Trade name: 120 parts by weight of Whiten SSB (red) and 40 parts by weight of empentryn (Sumitomo Chemical Co., Ltd., trade name: Vaporthrin) as a drug with a Banbury mixer
The resin composition was obtained by kneading at 20 ° C. for 5 minutes. This resin composition was formed into a sheet having a thickness of 1 mm by T-die molding with an extruder, and this sheet was tried to be stretched 12 times in a uniaxial direction at 50 ° C. with a roll stretching machine, but it broke, resulting in drug sustained release resin molding. I couldn't get a body.

【0046】(比較例9)薬剤の配合量を2重量部とし
た以外は実施例14と同様にして薬剤徐放樹脂成形体を
得た。得られた薬剤徐放樹脂成形体からの薬剤放出量を
測定したところ、第3表および図1に示す様に単位時間
当たりの薬剤放出量が経時的に減少してしまった。
Comparative Example 9 A drug sustained release resin molding was obtained in the same manner as in Example 14 except that the compounding amount of the drug was 2 parts by weight. When the drug release amount from the obtained drug sustained-release resin molded product was measured, the drug release amount per unit time decreased with time as shown in Table 3 and FIG.

【0047】(比較例10)熱可塑性樹脂として、エチ
レン−メチルメタクリレート共重合体(住友化学工業
(株)製、商品名:アクリフト WH202、エンペン
トリン飽和溶解量14重量%)100重量部、薬剤とし
てエンペントリン15重量部バンバリーミキサーによっ
て120℃で5分間混練して樹脂組成物を得た。この樹
脂組成物を押出機によりTダイ成形により厚さ1mmの
シートとし、薬剤徐放樹脂成形体を得た。得られた薬剤
徐放樹脂成形体からの薬剤放出量を測定したところ、第
3表および図1に示す様に単位時間当たりの薬剤放出量
が経時的に減少してしまった。
(Comparative Example 10) 100 parts by weight of an ethylene-methyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Acryft WH202, saturated dissolution amount of empentrin 14% by weight) as a thermoplastic resin, and empentrin as a drug. A resin composition was obtained by kneading with 15 parts by weight Banbury mixer at 120 ° C. for 5 minutes. This resin composition was formed into a sheet having a thickness of 1 mm by T-die molding using an extruder to obtain a drug sustained-release resin molded body. When the drug release amount from the obtained drug sustained-release resin molded product was measured, the drug release amount per unit time decreased with time as shown in Table 3 and FIG.

【0048】(実施例20)熱可塑性樹脂として線状低
密度ポリエチレン(住友化学工業(株)製、商品名:エ
クセレンVL VL200、フェノトリン飽和溶解量
2.2重量%)100重量部と充填剤として炭酸カルシ
ウム(白石カルシウム(株)製、商品名:ホワイトンS
SB(赤))120重量部と、薬剤としてフェノトリン
(住友化学工業(株)製、商品名:スミスリン)22重
量部をバンバリーミキサーによって120℃で5分間混
練して樹脂組成物を得た。この樹脂組成物を押出機によ
りTダイ成形により厚さ1mmのシートとし、このシー
トをロール延伸機により50℃で一軸方向に4倍に延伸
し薬剤徐放樹脂成形体を得た。得られた薬剤徐放樹脂成
形体は、表面への薬剤のブリードアウトがなく、また表
5および表6に示す様にノックダウン効果および殺虫効
果の初期効力および持続性が非常に高く、接触型薬剤の
徐放化方法として非常に優れている。
Example 20 100 parts by weight of linear low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200, saturated dissolution amount of phenothrin 2.2% by weight) as a thermoplastic resin and a filler Calcium carbonate (Shiraishi Calcium Co., Ltd., trade name: Whiten S
SB (red) 120 parts by weight and phenothrin (Sumitomo Chemical Co., Ltd., trade name: Smithlin) 22 parts by weight as a drug were kneaded with a Banbury mixer at 120 ° C. for 5 minutes to obtain a resin composition. This resin composition was formed into a sheet having a thickness of 1 mm by T-die molding with an extruder, and this sheet was stretched uniaxially by 4 times at 50 ° C. with a roll stretching machine to obtain a drug sustained-release resin molded body. The obtained drug-releasing resin molded product had no bleed-out of the drug on the surface, and as shown in Tables 5 and 6, the knockdown effect and the insecticidal effect were very high in initial efficacy and persistence, and the contact type It is an excellent method for sustained release of drugs.

【0049】(実施例21)実施例20で得られた多孔
質体の両面に熱可塑性樹脂として低密度ポリエチレン
(住友化学工業(株)製、商品名:スミカセン G80
1)をラミネート加工により各50μmの厚みで配し、
薬剤徐放樹脂成形体を得た。得られた薬剤徐放樹脂成形
体は、表面への薬剤のブリードアウトはもちろんなく、
また表5および表6に示す様にノックダウン効果および
殺虫効果の初期効力および持続性が非常に高く、薬剤の
徐放化方法として非常に優れている。
(Example 21) Low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumikasen G80) as a thermoplastic resin on both surfaces of the porous body obtained in Example 20.
1) is laminated to a thickness of 50 μm each,
A drug release resin molding was obtained. The obtained drug sustained-release resin molded product had no bleed-out of the drug on the surface,
Further, as shown in Tables 5 and 6, the knockdown effect and the insecticidal effect have very high initial efficacy and sustainability, and are very excellent as a method for sustained release of a drug.

【0050】(実施例22)実施例20で得られた多孔
質体の両面に熱可塑性樹脂として線状低密度ポリエチレ
ン(住友化学工業(株)製、商品名:エクセレンVL
VL200)をラミネート加工により各50μmの厚み
で配し、薬剤徐放樹脂成形体を得た。得られた薬剤徐放
樹脂成形体は、表面への薬剤のブリードアウトはもちろ
んなく、また表5および表6に示す様にノックダウン効
果および殺虫効果の初期効力および持続性が非常に高
く、薬剤の徐放化方法として非常に優れている。
Example 22 Linear low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL) as a thermoplastic resin on both surfaces of the porous body obtained in Example 20.
VL200) was laminated to a thickness of 50 μm to obtain a drug sustained-release resin molding. The obtained drug sustained-release resin molded product had no bleed-out of the drug on the surface, and as shown in Tables 5 and 6, the knockdown effect and the insecticidal effect were very high in initial efficacy and persistence. Is an excellent method for the sustained release of

【0051】(実施例23)実施例20で得られた多孔
質体の両面に熱可塑性樹脂として高密度ポリエチレン
(昭和電工(株)製、商品名:ショウレックス505
0)をラミネート加工により各80μmの厚みで配し、
薬剤徐放樹脂成形体を得た。得られた薬剤徐放樹脂成形
体は、表面への薬剤のブリードアウトがなく、また表5
および表6に示す様にノックダウン効果および殺虫効果
の初期効力および持続性が非常に高く、薬剤の徐放化方
法として非常に優れていることが判った。
(Example 23) High density polyethylene (manufactured by Showa Denko KK, trade name: Shorex 505) as a thermoplastic resin on both sides of the porous body obtained in Example 20.
0) is laminated to a thickness of 80 μm each,
A drug release resin molding was obtained. The obtained drug sustained-release resin molded product had no bleed-out of the drug on the surface, and Table 5
Also, as shown in Table 6, it was found that the knockdown effect and the insecticidal effect were very high in initial efficacy and persistence, and were extremely excellent as a method for sustained-release of a drug.

【0052】(比較例11)熱可塑性樹脂として線状低
密度ポリエチレン(住友化学工業(株)製、商品名:エ
クセレンVL VL200)100重量部と充填剤とし
て炭酸カルシウム(白石カルシウム(株)製、商品名:
ホワイトンSSB(赤))40重量部と、薬剤としてフ
ェノトリン(住友化学工業(株)製、商品名:スミスリ
ン)40重量部をバンバリーミキサーによって120℃
で5分間混練して樹脂組成物を得た。この樹脂組成物を
押出機によりTダイ成形により厚さ1mmのシートと
し、このシートをロール延伸機により50℃で一軸方向
に4倍に延伸し薬剤徐放樹脂成形体を得た。得られた薬
剤徐放樹脂成形体は多孔質化が低いために内部からフェ
ノトリンがブリードアウトして実用に至らないものであ
った。
(Comparative Example 11) 100 parts by weight of linear low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200) as a thermoplastic resin and calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd.) as a filler, Product name:
40 parts by weight of Whiten SSB (red) and 40 parts by weight of phenothrin (Sumitomo Chemical Co., Ltd., trade name: Smithlin) as a drug are treated with a Banbury mixer at 120 ° C.
Was kneaded for 5 minutes to obtain a resin composition. This resin composition was formed into a sheet having a thickness of 1 mm by T-die molding with an extruder, and this sheet was stretched uniaxially by 4 times at 50 ° C. with a roll stretching machine to obtain a drug sustained-release resin molded body. Since the obtained drug-releasing resin molded product had low porosity, phenothrin bleeded out from the inside, which was not practical.

【0053】(比較例12)熱可塑性樹脂として線状低
密度ポリエチレン(住友化学工業(株)製、商品名:エ
クセレンVL VL200)100重量部と充填剤とし
て炭酸カルシウム(白石カルシウム(株)製、商品名:
ホワイトンSSB(赤))450重量部と、薬剤として
フェノトリン(住友化学工業(株)製、商品名:スミス
リン)40重量部をバンバリーミキサーによって120
℃で5分間混練して樹脂組成物を得た。この樹脂組成物
を押出機によりTダイ成形により厚さ1mmのシートと
し、このシートをロール延伸機により50℃で一軸方向
に4倍の延伸を試みたが、破断してしまい薬剤徐放樹脂
成形体を得ることができなかった。
(Comparative Example 12) 100 parts by weight of linear low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200) as a thermoplastic resin and calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd.) as a filler, Product name:
450 parts by weight of Whiten SSB (red) and 40 parts by weight of phenothrin (Sumitomo Chemical Co., Ltd., trade name: Smithlin) as a drug were used in 120 by a Banbury mixer.
The resin composition was obtained by kneading at 5 ° C. for 5 minutes. This resin composition was formed into a sheet having a thickness of 1 mm by T-die molding with an extruder, and this sheet was tried to be stretched 4 times in a uniaxial direction at 50 ° C. with a roll stretching machine, but it broke and was gradually released into a drug-release resin molding. I couldn't get a body.

【0054】(比較例13)延伸処理を施さなかったこ
と以外は実施例20と同様な方法で樹脂組成物の厚さ1
mmのシートを得た。得られたシートは多孔質化してい
ないために内部からフェノトリンがブリードアウトして
実用に至らないものであった。
Comparative Example 13 A resin composition having a thickness of 1 was prepared in the same manner as in Example 20 except that the stretching treatment was not performed.
A sheet of mm was obtained. Since the obtained sheet was not made porous, phenothrin bleeded out from the inside, which was not practical.

【0055】(比較例14)熱可塑性樹脂として線状低
密度ポリエチレン(住友化学工業(株)製、商品名:エ
クセレンVL VL200)100重量部と充填剤とし
て炭酸カルシウム(白石カルシウム(株)製、商品名:
ホワイトンSSB(赤))120重量部と、薬剤として
フェノトリン(住友化学工業(株)製、商品名:スミス
リン)40重量部をバンバリーミキサーによって120
℃で5分間混練して樹脂組成物を得た。この樹脂組成物
を押出機によりTダイ成形により厚さ1mmのシートと
し、このシートをロール延伸機により50℃で一軸方向
に12倍に延伸を試みたが破断してしまい、薬剤徐放樹
脂成形体を得ることができなかった。
(Comparative Example 14) 100 parts by weight of linear low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200) as a thermoplastic resin and calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd.) as a filler. Product name:
120 parts by weight of Whiten SSB (red) and 40 parts by weight of phenothrin (Sumitomo Chemical Co., Ltd., trade name: Smithlin) as a drug were used in 120 by a Banbury mixer.
The resin composition was obtained by kneading at 5 ° C. for 5 minutes. This resin composition was formed into a sheet having a thickness of 1 mm by T-die molding with an extruder, and this sheet was tried to be stretched 12 times in a uniaxial direction at 50 ° C. with a roll stretching machine, but it broke, resulting in drug sustained release resin molding. I couldn't get a body.

【0056】(比較例15)薬剤の配合量を2重量部と
した以外は実施例20と同様にして薬剤徐放樹脂成形体
を得た。得られた薬剤徐放樹脂成形体は、表面への薬剤
のブリードアウトはなかったが、表5および表6に示す
様にノックダウン効果および殺虫効果が非常に低かっ
た。
Comparative Example 15 A drug sustained release resin molding was obtained in the same manner as in Example 20 except that the compounding amount of the drug was 2 parts by weight. The obtained drug sustained-release resin molded product had no bleed-out of the drug on the surface, but as shown in Tables 5 and 6, the knockdown effect and the insecticidal effect were very low.

【0057】(比較例16)熱可塑性樹脂として、エチ
レン−メチルメタクリレート共重合体(住友化学工業
(株)製、商品名:アクリフト WH202、フェノト
リン飽和溶解量15重量%)100重量部、薬剤として
フェノトリン15重量部バンバリーミキサーによって1
20℃で5分間混練して樹脂組成物を得た。この樹脂組
成物を押出機によりTダイ成形により厚さ1mmのシー
トとし、薬剤徐放樹脂成形体を得た。得られた薬剤徐放
樹脂成形体は表面への薬剤のブリードアウトはなかった
が、第5表および第6表に示す様にノックダウン効果お
よび殺虫効果が非常に低かった。
Comparative Example 16 As a thermoplastic resin, 100 parts by weight of ethylene-methyl methacrylate copolymer (Sumitomo Chemical Co., Ltd., trade name: Acryft WH202, phenothrin saturated dissolution amount 15% by weight), and phenothrin as a drug 1 by 15 parts by weight Banbury mixer
The resin composition was obtained by kneading at 20 ° C. for 5 minutes. This resin composition was formed into a sheet having a thickness of 1 mm by T-die molding using an extruder to obtain a drug sustained-release resin molded body. The obtained drug-releasing resin molded product did not bleed out the drug to the surface, but as shown in Tables 5 and 6, the knockdown effect and insecticidal effect were very low.

【0058】(比較例17)熱可塑性樹脂として、塩化
ビニル(住友化学工業(株)製、商品名:スミリット
Sx−13F)100重量部、可塑剤としてDOA43
重量部、薬剤としてフェノトリン25重量部をロール混
練にて5分間混練して樹脂組成物を得た。この樹脂組成
物を押出機によりTダイ成形により厚さ1mmのシート
とし、薬剤徐放樹脂成形体を得た。得られた薬剤徐放樹
脂成形体は表面への薬剤のブリードアウトはなく、表5
に示す様に初期効力は高かったが、表6に示す様に効力
持続性が非常に低かった。
(Comparative Example 17) As a thermoplastic resin, vinyl chloride (manufactured by Sumitomo Chemical Co., Ltd., trade name: Smilit)
Sx-13F) 100 parts by weight, DOA43 as a plasticizer
By weight, 25 parts by weight of phenothrin as a drug was kneaded by roll kneading for 5 minutes to obtain a resin composition. This resin composition was formed into a sheet having a thickness of 1 mm by T-die molding using an extruder to obtain a drug sustained-release resin molded body. The obtained drug sustained-release resin molded product had no drug bleed-out on the surface, and
The initial efficacy was high as shown in Table 1, but the persistence of efficacy was very low as shown in Table 6.

【0059】(実施例24)熱可塑性樹脂として線状低
密度ポリエチレン(住友化学工業(株)製、商品名:エ
クセレンVL VL200)100重量部と充填剤とし
て炭酸カルシウム(白石カルシウム(株)製、商品名:
ホワイトンSSB(赤))450重量部と、薬剤として
エンペントリン(住友化学工業(株)製、商品名:ベー
パースリン)55重量部をバンバリーミキサーによって
120℃で5分間混練して樹脂組成物を得た。この樹脂
組成物を押出機により径1mmのストランドとし、この
ストランドを口孔600μmの引き抜きダイを用いて2
3℃で一軸方向に4倍の延伸し薬剤徐放樹脂成形体を得
た。
Example 24 100 parts by weight of linear low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200) as a thermoplastic resin and calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd.) as a filler, Product name:
450 parts by weight of Whiten SSB (red) and 55 parts by weight of empentryn (Sumitomo Chemical Co., Ltd., trade name: Vaporthrin) as a drug are kneaded with a Banbury mixer at 120 ° C. for 5 minutes to obtain a resin composition. It was This resin composition was formed into a strand having a diameter of 1 mm by an extruder, and the strand was cut with a drawing die having a 600 μm opening.
A drug sustained-release resin molded product was obtained by uniaxially stretching 4 times at 3 ° C.

【0060】(実施例25)熱可塑性樹脂として線状低
密度ポリエチレン(住友化学工業(株)製、商品名:エ
クセレンVL VL200)100重量部と充填剤とし
て炭酸カルシウム(白石カルシウム(株)製、商品名:
カルライトSA)100重量部をバンバリーミキサーに
よって120℃で5分間混練して樹脂組成物を得た。こ
の樹脂組成物を押出機により、Tダイ成形により厚さ
1.6mmのシートとしこのシートをロール延伸機によ
り23℃で一軸方向に4倍の延伸し多孔質樹脂成形体シ
ートを得た。得られたシートをイソチオシアン酸アリル
(ミドリ十字(株)製、商品名:ワサオーロ、20℃に
おける蒸気圧4mmHg)液中に浸漬し、イソチオシア
ン酸アリルの吸収量を経時的に測定した。浸漬開始30
分後に一定重量に達したのでシートを引き上げ表面に付
着したイソチオシアン酸アリルを拭きとって薬剤徐放樹
脂成形体を得た。
Example 25 100 parts by weight of linear low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL200) as a thermoplastic resin and calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd.) as a filler, Product name:
100 parts by weight of Callite SA) was kneaded with a Banbury mixer at 120 ° C. for 5 minutes to obtain a resin composition. This resin composition was formed into a sheet having a thickness of 1.6 mm by T-die molding with an extruder, and this sheet was stretched 4 times uniaxially at 23 ° C. with a roll stretching machine to obtain a porous resin molded sheet. The obtained sheet was immersed in an allyl isothiocyanate (manufactured by Midori Cross Co., Ltd., trade name: Wasauro, vapor pressure 4 mmHg at 20 ° C.) liquid, and the absorption amount of allyl isothiocyanate was measured with time. Start soaking 30
Since the weight reached a certain value after a minute, the sheet was pulled up and the allyl isothiocyanate adhering to the surface was wiped off to obtain a drug sustained-release resin molded body.

【0061】 [0061]

【0062】 [0062]

【0063】 [0063]

【0064】樹脂A:線状低密度ポリエチレン(住友化
学工業(株)製、商品名:エクセレンVL VL20
0,コモノマー:ブテン−1,密度0.900g/cm
3 ) 樹脂B:線状低密度ポリエチレン(住友化学工業(株)
製、商品名:スミカセンα CS3003,コモノマ
ー:ヘキセン−1,密度0.933g/cm3 ) 樹脂C:低密度ポリエチレン(住友化学工業(株)製、
商品名:スミカセン F208−0,密度0.933g
/cm3 ) 樹脂D:低密度ポリエチレン(住友化学工業(株)製、
商品名:スミカセン G801) 樹脂E:線状低密度ポリエチレン(住友化学工業(株)
製、商品名:スミカセンα FZ201−0,コモノマ
ー:ヘキセン−1,密度0.912g/cm3 ) 樹脂F:エチレン−メチルメタクリレート共重合体(住
友化学工業(株)製、商品名:アクリフト WH20
2) 樹脂G:高密度ポリエチレン(昭和電工(株)製、商品
名:ショウレックス5050) 樹脂H:塩化ビニル(住友化学工業(株)製、商品名:
スミリット Sx−13F) 充填剤:炭酸カルシウム(白石カルシウム(株)製、商
品名:ホワイトンSSB(赤))、*印は炭酸カルシウ
ム(白石カルシウム(株)製、商品名:カルライトS
A) 薬剤a:エンペントリン(住友化学工業(株)製、商品
名:ベーパースリン) 薬剤b:フェノトリン(住友化学工業(株)製、商品
名:スミスリン) 薬剤c:ヒノキ精油(紀州ヒノキ屋製) 薬剤d:イソチオシアン酸アリル(ミドリ十字(株)
製、商品名:ワサオーロ) 薬剤e:ピリプロキシフェン(住友化学工業(株)製、
商品名:スミラブ) 薬剤f:d−アレスリン(住友化学工業(株)製、商品
名:ピナミンフォルテ) 薬剤g:メトキシジアゾン(住友化学工業(株)製、商
品名:エレミック) 薬剤h:MGK264
Resin A: Linear low-density polyethylene (manufactured by Sumitomo Chemical Co., Ltd., trade name: Excellen VL VL20)
0, comonomer: butene-1, density 0.900 g / cm
3 ) Resin B: Linear low density polyethylene (Sumitomo Chemical Co., Ltd.)
Product name: Sumikasen α CS3003, comonomer: hexene-1, density 0.933 g / cm 3 ) Resin C: low density polyethylene (Sumitomo Chemical Co., Ltd.,
Product name: Sumikasen F208-0, density 0.933g
/ Cm 3 ) Resin D: Low density polyethylene (manufactured by Sumitomo Chemical Co., Ltd.,
Product name: Sumikasen G801) Resin E: Linear low density polyethylene (Sumitomo Chemical Co., Ltd.)
Made, trade name: Sumikasen α FZ201-0, comonomer: hexene-1, density 0.912 g / cm 3 ) Resin F: ethylene-methyl methacrylate copolymer (Sumitomo Chemical Co., Ltd. make, trade name: Acryft WH20
2) Resin G: High-density polyethylene (Showa Denko KK, trade name: Shorex 5050) Resin H: Vinyl chloride (Sumitomo Chemical Co., Ltd., trade name:
Smilit Sx-13F) Filler: calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: Whiten SSB (red)), * indicates calcium carbonate (manufactured by Shiraishi Calcium Co., Ltd., trade name: Callite S)
A) Drug a: Empentrin (Sumitomo Chemical Co., Ltd., trade name: Vaporthrin) Drug b: Phenotrin (Sumitomo Chemical Co., Ltd., trade name: Smith Lin) Drug c: Hinoki essential oil (Kishu Hinokiya) Drug d: allyl isothiocyanate (Midori Cross Co., Ltd.)
Made, trade name: Wasauro) Drug e: Pyriproxyfen (Sumitomo Chemical Co., Ltd.,
Trade name: Sumilab) Drug f: d-allethrin (Sumitomo Chemical Co., Ltd., trade name: Pinamine Forte) Drug g: Methoxydiazone (Sumitomo Chemical Co., Ltd., trade name: Elemic) Drug h: MGK264

【0065】加工性、ブリードアウトの評価 実施例1−3、5、6、14−17、20−23は空気
中で50℃で、実施例4では薬剤中で50℃で、実施例
7−13、18、19、24,25は空気中/23℃
で、4倍の倍率で延伸した結果、加工性は良好であり、
得られた製品からのブリードアウトは見られなかった。
Evaluation of processability and bleed-out Examples 1-3, 5, 6, 14-17, 20-23 were carried out at 50 ° C. in air, and in Example 4 at 50 ° C. in drug, Example 7- 13, 18, 19, 24, 25 are in air / 23 ° C
As a result of stretching at a magnification of 4 times, the workability is good,
No bleed out was seen from the resulting product.

【0066】 [0066]

【0067】 [0067]

【0068】 [0068]

【0069】 [0069]

【0070】 [0070]

【0071】[0071]

【図面の簡単な説明】[Brief description of drawings]

【図1】実施例14−17および比較例9、10(表
3)の薬剤の経時的蒸散率を表わす。
FIG. 1 shows the transpiration rate of the agents of Examples 14-17 and Comparative Examples 9 and 10 (Table 3) over time.

【図2】実施例18(表4)の薬剤の経時的蒸散率を表
わす。
FIG. 2 shows the transpiration rate of the drug of Example 18 (Table 4) over time.

【図3】実施例19(表4)の薬剤の経時的蒸散率を表
わす。
FIG. 3 shows the transpiration rate with time of the drug of Example 19 (Table 4).

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 // B29K 105:16 (31)優先権主張番号 特願平5−7463 (32)優先日 平5(1993)1月20日 (33)優先権主張国 日本(JP) (31)優先権主張番号 特願平5−122431 (32)優先日 平5(1993)5月25日 (33)優先権主張国 日本(JP)─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location // B29K 105: 16 (31) Priority claim number Japanese Patent Application No. 5-7463 (32) Priority Sundaira 5 (1993) January 20 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 5-122431 (32) Priority Date 5 (1993) May 25 (33) Priority Claiming country Japan (JP)

Claims (12)

【特許請求の範囲】[Claims] 【請求項1】熱可塑性樹脂100重量部、充填剤50〜
400重量部よりなる樹脂組成物を一軸または二軸に
1.1〜10の倍率で延伸して得られる多孔質樹脂成形
体に熱可塑性樹脂に対する飽和溶解量以上の量の薬剤を
含有してなる薬剤徐放樹脂成形体。
1. A thermoplastic resin 100 parts by weight and a filler 50 to 50 parts by weight.
A porous resin molding obtained by uniaxially or biaxially stretching a resin composition consisting of 400 parts by weight at a ratio of 1.1 to 10 contains a drug in an amount equal to or more than a saturated dissolution amount in a thermoplastic resin. Drug sustained release resin molding.
【請求項2】薬剤徐放樹脂成形体がフィルムまたはシー
トである請求項1記載の薬剤徐放樹脂成形体。
2. The drug sustained-release resin molded article according to claim 1, wherein the drug sustained-release resin molded article is a film or a sheet.
【請求項3】薬剤徐放樹脂成形体が棒状体である請求項
1記載の薬剤徐放樹脂成形体。
3. The drug sustained-release resin molded article according to claim 1, wherein the drug sustained-release resin molded article is a rod-shaped body.
【請求項4】請求項2の薬剤徐放樹脂成形体の少なくと
も片面に薬剤が透過可能な熱可塑性樹脂組成物層を配し
てなる薬剤徐放樹脂成形体。
4. A drug sustained-release resin molded product comprising a drug-permeable thermoplastic resin composition layer arranged on at least one surface of the drug sustained-release resin molded product according to claim 2.
【請求項5】請求項3の薬剤徐放樹脂成形体の外周部に
薬剤が透過可能な熱可塑性樹脂組成物層を配してなる薬
剤徐放樹脂成形体。
5. A drug sustained-release resin molded product comprising a drug-permeable thermoplastic resin composition layer on the outer periphery of the drug sustained-release resin molded product according to claim 3.
【請求項6】熱可塑性樹脂が、ポリオレフィン系樹脂で
あり、薬剤が防虫剤、忌避剤、殺菌剤、防黴剤あるいは
芳香剤の何れか一つ以上の薬剤であり、充填剤が炭酸カ
ルシウムである請求項1〜5のいづれか一に記載の薬剤
徐放樹脂成形体。
6. The thermoplastic resin is a polyolefin resin, the drug is one or more of an insect repellent, a repellent, a bactericide, a fungicide, and an aromatic, and the filler is calcium carbonate. 6. The drug sustained-release resin molded product according to any one of claims 1 to 5.
【請求項7】薬剤がピレスロイド系殺虫剤、メトキシジ
アゾン、ピリプロキシフェンからなる群から選ばれた少
なくとも一つ以上の防虫剤である請求項6記載の薬剤徐
放樹脂成形体。
7. The controlled drug release molded article according to claim 6, wherein the drug is at least one insect repellent selected from the group consisting of pyrethroid insecticides, methoxydiazone, and pyriproxyfen.
【請求項8】ポリオレフィン系樹脂が、エチレンと、C
3 −C18のα−オレフィン類から選ばれた少なくとも一
種のα−オレフィンとの共重合体である請求項6または
7記載の薬剤徐放樹脂成形体。
8. The polyolefin resin is ethylene and C
The drug-controlled release resin molded article according to claim 6 or 7, which is a copolymer with at least one α-olefin selected from 3- C 18 α-olefins.
【請求項9】熱可塑性樹脂100重量部、充填剤50〜
400重量部および熱可塑性樹脂に対する飽和溶解度以
上の量の薬剤からなる樹脂組成物を一軸または二軸に
1.1〜10の倍率で延伸して多孔質化することを特徴
とする薬剤徐放樹脂成形体の製造方法。
9. A thermoplastic resin 100 parts by weight and a filler 50 to 50 parts by weight.
A drug sustained-release resin comprising a resin composition comprising 400 parts by weight and an amount of a drug having a saturated solubility or higher with respect to a thermoplastic resin, which is uniaxially or biaxially stretched at a ratio of 1.1 to 10 to be porous. Method for manufacturing molded body.
【請求項10】熱可塑性樹脂100重量部と充填剤50
〜400重量部からなる樹脂組成物を、薬剤に浸漬また
は薬剤を塗布した状態で一軸または二軸に1.1〜10
倍に延伸して多孔質化することを特徴とする薬剤徐放樹
脂成形体の製造方法。
10. A thermoplastic resin 100 parts by weight and a filler 50.
The resin composition consisting of ˜400 parts by weight is uniaxially or biaxially 1.1 to 10 in the state of being dipped in the chemical or coated with the chemical.
A method for producing a drug sustained-release resin molded product, which comprises stretching twice and making it porous.
【請求項11】熱可塑性樹脂100重量部、充填剤50
〜400重量部よりなる樹脂組成物を一軸または二軸に
1.1〜10の倍率で延伸して得られる多孔質樹脂成形
体に熱可塑性樹脂に対する飽和溶解度以上の量の薬剤を
含有させることを特徴とする薬剤徐放樹脂成形体の製造
方法。
11. A thermoplastic resin 100 parts by weight and a filler 50.
To 400 parts by weight of a resin composition uniaxially or biaxially stretched at a ratio of 1.1 to 10 to contain a drug in an amount equal to or higher than its saturated solubility in a thermoplastic resin. A method for producing a characterized drug sustained-release resin molded product.
【請求項12】熱可塑性樹脂100重量部、充填剤50
〜400重量部からなる樹脂組成物を一軸または二軸に
1.1〜10の倍率で延伸して得られる多孔質樹脂成形
体に、ピレスロイド系殺虫剤、メトキシジアゾン、ピリ
プロキシフェンからなる群から選ばれた少なくとも一つ
以上の防虫剤を熱可塑性樹脂への飽和溶解度以上の量含
有せしめてなる薬剤徐放樹脂成形体を使用することを特
徴とする害虫防除方法。
12. A thermoplastic resin 100 parts by weight and a filler 50.
To 400 parts by weight of a resin composition uniaxially or biaxially stretched at a ratio of 1.1 to 10, and a group consisting of a pyrethroid insecticide, methoxydiazone, and pyriproxyfen. A method for controlling insect pests, which comprises using a drug sustained-release resin molded product containing at least one or more insect repellents selected from the above, in an amount of saturated solubility or higher in a thermoplastic resin.
JP15968293A 1992-07-06 1993-06-29 Chemical-sustained-release resin molding and its production Pending JPH0741402A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP15968293A JPH0741402A (en) 1992-07-06 1993-06-29 Chemical-sustained-release resin molding and its production

Applications Claiming Priority (11)

Application Number Priority Date Filing Date Title
JP17813992 1992-07-06
JP4-178139 1992-07-06
JP29569092 1992-11-05
JP30361992 1992-11-13
JP5-7463 1993-01-20
JP746393 1993-01-20
JP12243193 1993-05-25
JP5-122431 1993-05-25
JP4-303619 1993-05-25
JP4-295690 1993-05-25
JP15968293A JPH0741402A (en) 1992-07-06 1993-06-29 Chemical-sustained-release resin molding and its production

Related Child Applications (1)

Application Number Title Priority Date Filing Date
JP2003029268A Division JP2003313337A (en) 1992-07-06 2003-02-06 Method for manufacturing molded body of drug slowly releasing resin

Publications (1)

Publication Number Publication Date
JPH0741402A true JPH0741402A (en) 1995-02-10

Family

ID=29554543

Family Applications (2)

Application Number Title Priority Date Filing Date
JP15968293A Pending JPH0741402A (en) 1992-07-06 1993-06-29 Chemical-sustained-release resin molding and its production
JP2003029268A Pending JP2003313337A (en) 1992-07-06 2003-02-06 Method for manufacturing molded body of drug slowly releasing resin

Family Applications After (1)

Application Number Title Priority Date Filing Date
JP2003029268A Pending JP2003313337A (en) 1992-07-06 2003-02-06 Method for manufacturing molded body of drug slowly releasing resin

Country Status (1)

Country Link
JP (2) JPH0741402A (en)

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* Cited by examiner, † Cited by third party
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WO1995017819A1 (en) * 1993-12-28 1995-07-06 Rengo Co., Ltd. Controlled-release ait preparation, process for producing the same, and use thereof
KR100363766B1 (en) * 2000-06-30 2002-12-06 삼성종합화학주식회사 A Producing Method of Mothproof Film
KR100465176B1 (en) * 1997-06-27 2005-05-18 삼성토탈 주식회사 Manufacturing method of breathable film
JP2005139329A (en) * 2003-11-07 2005-06-02 Sumika Color Kk Olefinic resin pellet in double layered structure for insect-proof resin composition
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