JPS64364B2 - - Google Patents

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Publication number
JPS64364B2
JPS64364B2 JP59090183A JP9018384A JPS64364B2 JP S64364 B2 JPS64364 B2 JP S64364B2 JP 59090183 A JP59090183 A JP 59090183A JP 9018384 A JP9018384 A JP 9018384A JP S64364 B2 JPS64364 B2 JP S64364B2
Authority
JP
Japan
Prior art keywords
granules
esoprophos
esoprofos
abietic acid
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.)
Expired
Application number
JP59090183A
Other languages
Japanese (ja)
Other versions
JPS60237008A (en
Inventor
Kaoru Chiba
Yukinobu Murata
Yoshihiko Nabeya
Shinji Yonemura
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.)
Hokko Chemical Industry Co Ltd
Original Assignee
Hokko Chemical Industry 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 Hokko Chemical Industry Co Ltd filed Critical Hokko Chemical Industry Co Ltd
Priority to JP9018384A priority Critical patent/JPS60237008A/en
Publication of JPS60237008A publication Critical patent/JPS60237008A/en
Publication of JPS64364B2 publication Critical patent/JPS64364B2/ja
Granted legal-status Critical Current

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  • Agricultural Chemicals And Associated Chemicals (AREA)

Description

【発明の詳細な説明】[Detailed description of the invention]

(イ) 発明の目的 産業上の利用分野 本発明は、農業上、特に農薬粒剤の製造業の分
野において利用しうる新規な発明に関する。より
詳しくは、本発明は有効成分として、以下に示す
エソプロホスを含有する粒状農薬組成物におい
て、当該有効成分の経時的安定化を図り、哺乳動
物に対する経皮毒性を軽減化するための改良技術
に関するものである。 エソプロホス O―エチル S,S―ジプロピ
ルホスホロジチオエート 従来の技術 エソプロホスの粒剤中における経時変化を抑え
る物質として、アルキレンまたはポリアルキレン
グリコールを添加する方法が知られている(米国
特許第2970080号明細書)。また、エソプロホスに
植物油であるボイルアマニ油またはアマニ油と、
プロピレングリコールを同時に添加することによ
り、脱臭と安定化がはかられ、人畜の皮膚に対す
る毒性が軽減されることについて開示されている
(特公昭57−5201号公報)。 一方、アビエチン酸は、ラツカー、ワニスなど
塗料、乳酸・酪酸・酵母などの成長促進剤、防菌
剤あるいは、メチルエステルルなどにして、ゴ
ム、ワニス、合成樹脂の溶剤とし金属塩として紙
のサイズ用などに用いられる。 発明が解決しようとする問題点 エソプロホスは、既にジヤガイモシストセンチ
ユウ、サツマイモネコブセンチユウをはじめとす
る各種センチユウ類、コガネムシ、ハリガネム
シ、カイガラムシ類などに効果を有することが公
知の土壌殺虫殺線虫剤である。しかし、エソプロ
ホスは粒剤化すると、有効成分の経時変化が非常
に大きい。したがつて、もし、農薬で通常なされ
ている2年間の有効成分量を保証するには、粒剤
を製造する際にエソプロホスの仕込量を大幅に増
やす必要がある。ところが、それによつて、もと
もとエソプロホスは人畜に対する経皮毒性が高い
ので、粒剤の製剤時や散粒時に、より一層の危険
性が増し、一方では、作物に対して薬害を与える
原因となる。また仕込量を増やせばコスト高とな
るため経済的にも非常に不利となる。また、経時
変化によつて生じた多量の分解物が作物に対して
薬害を与えるなどの悪影響も懸念される。 また、エソプロホスは哺乳動物に対する経皮毒
性が非常に強く、この製剤の取扱いには厳重な注
意が必要である。 このような現状に対し、従来のいずれの技術で
も、エソプロホスの粒剤中の安定化および経皮毒
性の軽減化について満足のいくものはない。 本発明は、このような事情に鑑み、従来の技術
に代りエソプロホスが長期間(最低2年間)に亘
り経時的に変化することなく安定で、しかも経皮
毒性のない新しいタイプのエソプロホス粒剤を提
供することにある。 (ロ) 発明の構成 問題を解決するための手段 本発明者らは、粒剤にした場合のエソプロホス
の安定化、およびエソプロホス粒剤の哺乳動物に
対する経皮毒性を軽減化する技術について鋭意研
究した。その結果、アビエチン酸
〔abieticoacid:シルビン酸(cylvic acid)とも
いう〕を添加することにより、エソプロホスの経
時変化を顕著に抑制すると同時に、経皮毒性を大
幅に軽減化することを見出し、本発明に至つた。 本発明のアビエチン酸は、高純度品はもちろ
ん、アビエチン酸を含有するロジンまたはトール
油なども使用できる。 本発明で使用するアビエチン酸の配合量は、粒
剤中に0.1%(重量%)以上あれば効果を発揮す
るが、効果と経済性の両面から考えると0.1〜5
%が望ましい。 作 用 本発明のアビエチン酸をエソプロホス粒剤に添
加すると、常温で2年間貯蔵してもエソプロホス
の分解率を1%以下に減らすことが可能となる。
また、経皮毒性を顕著に軽減化することができ
る。また、アビエチン酸を添加しても、エソプロ
ホスの前記した本来有する生物効果を損なうこと
もない。 本発明の調製法は特に限定されることはなく、
通常の農薬粒剤を調製する方法でよい。例えば、
次の方法で調製できる。 調製法 1 あらかじめエソプロホスを含浸させた粒状鉱物
質担体に、有機溶剤(例えばメタノールなど)で
溶かした本発明のアビエチン酸を噴霧吸着させ、
乾燥して粒剤を得る。 調製法 2 あらかじめ有機溶剤(例えばメタノールなど)
にエソプロホスと本発明のアビエチン酸を同時に
溶かしたものを、粒状鉱物質担体に噴霧吸着さ
せ、乾燥して粒剤を得る。 調製法 3 エソプロホス、鉱物質担体、結合剤などに本発
明のアビエチン酸を加えて混合したのち、水を加
えて混練後、押し出し造粒機または転動造粒機な
どで造粒する。乾燥、整粒して粒剤を得る。 本発明で使用する鉱物質担体としては、農薬製
剤で用いられるものはいずれも使用できる。例え
ば、クレー、珪藻土、タルク、ベントナイト、ア
タパルジヤイト、バーミキユライト、ゼオライ
ト、軽石、セルロースパウダー、ホワイトカーボ
ンなどが挙げられ、粒状鉱物質担体を使用する場
合は、これらの鉱物質を適当な粒径に揃えたもの
でもよく、通常の造粒法によつて調製した有効成
分の含有されない空粒剤でもよい。 以下に、本発明を具体的に説明するために実施
例を挙げるが、本発明はこれらの例示のみに限定
されるものではない。なお、実施例中で部とある
のはすべて重量部である。 実施例1 (調製法1) 粒状アタパルジヤイト(14〜48メツシユ)94部
に、エソプロホス5部を噴霧吸着させる。次いで
アビエチン酸5%メタノール溶液20部を噴霧吸着
させ、乾燥後、エソプロホスとして5%含有する
粒剤を得る。 実施例2 (調製法2) 粒状ゼオライト(14〜48メツシユ)94部に、エ
ソプロホス12.5%およびアビエチン酸2.5%を同
時に含むメタノール溶液40部を噴霧吸着させ、乾
燥後、エソプロホスとして5%含有する粒剤を得
る。 実施例3 (調製法3) エソプロホス5部、ホワイトカーボン3部、ク
レー91部にアビエチン酸1部を加えて混合し、水
15部を加えて混練したのち、押し出し造粒機にて
造粒する。次いで乾燥、整粒(14〜48メツシユ)
し、エソプロホスとして5%含有する粒剤を得
る。 (ハ) 発明の効果 本発明の有用性を証するために試験例をあげ
る。 なお、実施例1〜3より本発明のアビエチン酸
を除いて調製したものを対照例1〜3とし、以下
の方法で調製した試料を対照例4とした。 〔対照例4の調製法〕 特公昭57−5201号公報記載のエソプロホス粒剤 あらかじめエソプロホス5部、アマニ油1部お
よびプロピレングリコール2.5部を相溶させたも
のを、粒状アタパルジヤイト(14〜48メツシユ)
91.5部に噴霧吸着させ、エソプロホスとして5%
含有する粒剤を得る。 試験例1 虐待による有効成分の経時変化 実施例に準じて調製した試料50gを140ml容マ
ヨネーズ瓶に入れ、栓をして、45℃の恒温器内に
放置した。放置30日後(常温で1年間貯蔵したこ
とに相当)、60日後(同2年間に相当)に取り出
し、試料中のエソプロホス含有量をGC(ガスクロ
マトグラフイー)にて分析し、虐待する前の含有
量に対する分解率(%)を算出した。結果を第1
表に示す。
(a) Field of industrial application of the invention The present invention relates to a novel invention that can be used in agriculture, particularly in the field of manufacturing agricultural chemical granules. More specifically, the present invention relates to an improved technique for stabilizing the active ingredient over time and reducing transdermal toxicity to mammals in a granular agricultural chemical composition containing esoprophos shown below as an active ingredient. It is something. Esoprophos O-ethyl S,S-dipropyl phosphorodithioate Conventional technology A method of adding alkylene or polyalkylene glycol as a substance to suppress changes over time in granules of esoprophos is known (US Pat. No. 2,970,080). Specification). In addition, boiled linseed oil or linseed oil, which is a vegetable oil, is added to esoprofos,
It is disclosed that by adding propylene glycol at the same time, deodorization and stabilization can be achieved and toxicity to the skin of humans and animals can be reduced (Japanese Patent Publication No. 57-5201). On the other hand, abietic acid can be used as paints such as lacquer and varnish, growth promoters such as lactic acid, butyric acid, and yeast, and antibacterial agents, and as a solvent for rubber, varnish, and synthetic resins, such as methyl ester, and as a metal salt for paper size. It is used for various purposes. Problems to be Solved by the Invention Esoprophos is a soil insecticide and nematocide that is already known to be effective against various nematodes, including Gypsum nematode and Sweet potato nematode, as well as scarab beetles, scarab beetles, scale insects, etc. It is. However, when esoprofos is made into granules, the active ingredient changes significantly over time. Therefore, in order to guarantee the amount of active ingredients for two years, which is usually the case with agricultural chemicals, it is necessary to significantly increase the amount of esoprophos used when manufacturing granules. However, because of this, esoprofos has high dermal toxicity to humans and livestock, so it becomes even more dangerous when it is formulated into granules or dispersed, and on the other hand, it causes chemical damage to crops. In addition, increasing the amount of preparation increases the cost, which is economically disadvantageous. There is also concern that large amounts of decomposed products produced over time may cause harmful effects to crops, such as phytotoxicity. Furthermore, esoprofos has very strong dermal toxicity to mammals, and strict care is required when handling this preparation. In response to the current situation, none of the conventional techniques is satisfactory in stabilizing esoprofos in granules and reducing transdermal toxicity. In view of these circumstances, the present invention provides a new type of esoprofos granules that are stable over a long period of time (at least 2 years) without changing over time, and are non-dermal toxic, in place of the conventional technology. It is about providing. (b) Means for solving the structural problems of the invention The present inventors have conducted extensive research on stabilizing esoprofos when made into granules and on techniques for reducing the transdermal toxicity of esoprophos granules to mammals. . As a result, it was discovered that by adding abietic acid (also called cylvic acid), the temporal change of esoprofos can be significantly suppressed, and at the same time, the transdermal toxicity can be significantly reduced. I've reached it. As the abietic acid of the present invention, not only high-purity products but also rosin or tall oil containing abietic acid can be used. The amount of abietic acid used in the present invention is effective if it is 0.1% (weight%) or more in the granules, but from the viewpoint of both effectiveness and economy, it is 0.1 to 5%.
% is desirable. Effect When the abietic acid of the present invention is added to esoprofos granules, it becomes possible to reduce the decomposition rate of esoprofos to 1% or less even when stored at room temperature for 2 years.
Further, transdermal toxicity can be significantly reduced. Furthermore, even if abietic acid is added, the above-mentioned inherent biological effects of esoprofos will not be impaired. The preparation method of the present invention is not particularly limited,
A conventional method for preparing pesticide granules may be used. for example,
It can be prepared by the following method. Preparation method 1 Abietic acid of the present invention dissolved in an organic solvent (for example, methanol, etc.) is sprayed and adsorbed onto a granular mineral carrier impregnated with esoprophos in advance,
Dry to obtain granules. Preparation method 2 Organic solvent (e.g. methanol, etc.)
A solution in which esoprophos and the abietic acid of the present invention are simultaneously dissolved is sprayed and adsorbed onto a granular mineral carrier and dried to obtain granules. Preparation Method 3 After adding and mixing the abietic acid of the present invention to esoprofos, a mineral carrier, a binder, etc., water is added and kneaded, followed by granulation using an extrusion granulator or a rolling granulator. Dry and sieve to obtain granules. As the mineral carrier used in the present invention, any carrier used in agricultural chemical formulations can be used. Examples include clay, diatomaceous earth, talc, bentonite, attapulgite, vermiculite, zeolite, pumice, cellulose powder, white carbon, etc. When using a granular mineral carrier, these minerals should be adjusted to an appropriate particle size. They may be prepared in the same way, or they may be empty granules containing no active ingredient prepared by a normal granulation method. Examples are given below to specifically explain the present invention, but the present invention is not limited to these examples. In addition, all parts in the examples are parts by weight. Example 1 (Preparation method 1) 5 parts of esoprophos is sprayed and adsorbed onto 94 parts of granular attapulgite (14 to 48 mesh). Next, 20 parts of a 5% abietic acid methanol solution is adsorbed by spraying, and after drying, granules containing 5% esoprophos are obtained. Example 2 (Preparation method 2) 94 parts of granular zeolite (14 to 48 mesh) was sprayed and adsorbed with 40 parts of a methanol solution containing 12.5% esoprophos and 2.5% abietic acid at the same time, and after drying, granules containing 5% esoprophos were obtained. get the agent. Example 3 (Preparation method 3) 1 part of abietic acid was added to 5 parts of esoprophos, 3 parts of white carbon, and 91 parts of clay, mixed, and mixed with water.
After adding 15 parts and kneading, the mixture is granulated using an extrusion granulator. Next, drying and grading (14 to 48 mesh)
Granules containing 5% esoprofos are obtained. (c) Effect of the invention Test examples will be given to prove the usefulness of the present invention. In addition, the samples prepared by removing the abietic acid of the present invention from Examples 1 to 3 were designated as Control Examples 1 to 3, and the samples prepared by the following method were designated as Control Example 4. [Preparation method of Comparative Example 4] Esoprophos granules described in Japanese Patent Publication No. 57-5201 A mixture of 5 parts of esoprophos, 1 part of linseed oil, and 2.5 parts of propylene glycol was mixed with granular attapulgite (14 to 48 mesh).
Spray adsorb to 91.5 parts, 5% as esoprophos
Obtain granules containing: Test Example 1 Changes in active ingredients over time due to abuse 50 g of a sample prepared according to the example was placed in a 140 ml mayonnaise bottle, the bottle was capped, and the bottle was left in a thermostat at 45°C. After 30 days (equivalent to storage at room temperature for 1 year) and 60 days (equivalent to 2 years), the sample was taken out and the esoprophos content in the sample was analyzed using GC (gas chromatography) to determine the content before abuse. The decomposition rate (%) relative to the amount was calculated. Results first
Shown in the table.

【表】 試験例2 マウスによる経皮毒性試験 パツチテスト絆創膏のガーゼ部(直径1.5cm)
を蒸留水で湿し、実施例に準じて調製した試料
(マウス1Kgに対しエソプロホスとして50mg)を
塗布する。そして、これをマウスの脱毛した皮膚
に貼付し、経時的に死亡数を観察した。本試験に
供したマウスは1試料当り5匹である。 結果を第2表に示す。
[Table] Test Example 2 Dermal toxicity test using mice Gauze part of patch test bandage (diameter 1.5cm)
moisten with distilled water, and apply a sample prepared according to the example (50 mg of esoprophos per 1 kg of mouse). This was then applied to the depilated skin of mice, and the number of deaths was observed over time. Five mice were used for each sample in this test. The results are shown in Table 2.

【表】 試験例3 トマトのサツマイモネコブセンチユウ
に対する防除効果 実施例に準じて調製した試料の所定量を、1/50
00アールポツトに入れたサツマイモネコブセンチ
ユウ汚染土壌に施用し、均一に混和した。混和
後、トマト種子5粒を播種して散水し、温室内に
放置した。播種20日後に、発芽して生育したトマ
ト苗を抜き取り、根部のネコブ発現程度を調べ、
防除価(%)を求めた。 なお、ネコブ発現程度の評価および防除価は以
下の方法で求めた。 ネコブ発現程度 0:無 1:僅 2:少 3:中 4:多 5:激 防除価(%)=(1−処理区の平均ネコブ発現程度
/無処理区の平均ネコブ発現程度)×100 本試験は、1区1ポツト、5反復で行つた。結
果を第3表に示す。
[Table] Test Example 3 Control effect of tomato on sweet potato nematode
It was applied to soil contaminated with sweet potato knotweed in a 00R pot and mixed uniformly. After mixing, five tomato seeds were sown, watered, and left in a greenhouse. 20 days after sowing, the tomato seedlings that had germinated and grown were pulled out and the degree of Nekobu expression in the roots was examined.
The control value (%) was determined. In addition, the evaluation of the level of Nekobu expression and the control value were determined by the following method. Degree of occurrence of Nekobub 0: None 1: Slight 2: Slight 3: Medium 4: High 5: Extremely Control value (%) = (1 - Average degree of Nekobuki in the treated area/Average degree of Nekob in the non-treated area) x 100 trees The test was conducted with 1 pot per section and 5 repetitions. The results are shown in Table 3.

【表】 註2) ロジンおよびトール油の添加量は、 ロジ
ンまたはトール油としての添加量である。
[Table] Note 2) The amount of rosin and tall oil added is the amount added as rosin or tall oil.

Claims (1)

【特許請求の範囲】[Claims] 1 有効成分として、O―エチル S,S―ジプ
ロピルホスホロジチオエートを含有する粒状農薬
において、アビエチン酸を添加してなることを特
徴とする粒状農薬組成物。
1. A granular agricultural chemical composition comprising O-ethyl S,S-dipropyl phosphorodithioate as an active ingredient and abietic acid added thereto.
JP9018384A 1984-05-08 1984-05-08 Granular composition of agricultural chemical Granted JPS60237008A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP9018384A JPS60237008A (en) 1984-05-08 1984-05-08 Granular composition of agricultural chemical

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP9018384A JPS60237008A (en) 1984-05-08 1984-05-08 Granular composition of agricultural chemical

Publications (2)

Publication Number Publication Date
JPS60237008A JPS60237008A (en) 1985-11-25
JPS64364B2 true JPS64364B2 (en) 1989-01-06

Family

ID=13991371

Family Applications (1)

Application Number Title Priority Date Filing Date
JP9018384A Granted JPS60237008A (en) 1984-05-08 1984-05-08 Granular composition of agricultural chemical

Country Status (1)

Country Link
JP (1) JPS60237008A (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI124101B (en) 2012-05-14 2014-03-14 Hankkija Maatalous Oy Modified tall oil fatty acid
FI124918B (en) 2013-05-14 2015-03-31 Hankkija Maatalous Oy tall oil fatty acids
FI125051B (en) * 2013-10-24 2015-05-15 Hankkija Oy Tall oil fatty acid
BR112016010803B8 (en) 2013-11-13 2021-09-14 Forchem Oy Resin acid based food supplement and non-therapeutic use of a resin acid based food supplement
JP7412692B2 (en) * 2020-06-05 2024-01-15 株式会社エナジーフロント Antibacterial porous membrane and antibacterial coating material using it

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53135933A (en) * 1972-08-25 1978-11-28 Mobil Oil Low toxic odorless organic sulfurized phosphoric compound composition
JPS5566596A (en) * 1978-08-08 1980-05-20 Sumitomo Chem Co Ltd Agent for controlling rice blast by applying to water surface or soil
JPS5788102A (en) * 1980-11-21 1982-06-01 Mitsui Toatsu Chem Inc Agricultural fungicide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53135933A (en) * 1972-08-25 1978-11-28 Mobil Oil Low toxic odorless organic sulfurized phosphoric compound composition
JPS5566596A (en) * 1978-08-08 1980-05-20 Sumitomo Chem Co Ltd Agent for controlling rice blast by applying to water surface or soil
JPS5788102A (en) * 1980-11-21 1982-06-01 Mitsui Toatsu Chem Inc Agricultural fungicide

Also Published As

Publication number Publication date
JPS60237008A (en) 1985-11-25

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