JP7009405B2 - Spreading agent and pesticide formulation for floating pesticide formulation - Google Patents
Spreading agent and pesticide formulation for floating pesticide formulation Download PDFInfo
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Description
本発明は水面浮遊型農薬製剤用拡展剤及び農薬製剤に関する。 The present invention relates to a spreading agent for a water-floating pesticide formulation and an agrochemical formulation.
近年、専業農家の減少、農家の高齢化及び区画整理に伴う大規模圃場の増大が進んでいる背景を受けて、農薬製剤には施用時の省力化が求められている。
例えば、水田等の水が存在する農地へ施用する場合、水田等に入らずに畦畔から投げ込むだけで散布可能な投げ込み型農薬製剤として、水面浮遊型農薬製剤が使用されている。この、水面浮遊型農薬製剤においては、１回の施用で広範囲に防除効果を発現できるよう、高濃度に原体を含有した水面浮遊型農薬製剤が、水面を拡展、拡散する設計の工夫が求められている。
In recent years, with the background that the number of full-time farmers is decreasing, the aging of farmers and the increase of large-scale fields due to land readjustment are progressing, pesticide formulations are required to save labor at the time of application.
For example, when applied to a farmland where water exists such as a paddy field, a water-floating pesticide formulation is used as a throw-in type pesticide formulation that can be sprayed by simply throwing it from the ridge without entering the paddy field or the like. In this water-floating pesticide formulation, the water-floating pesticide formulation containing the drug substance in a high concentration has been devised to expand and diffuse the water surface so that the control effect can be exhibited over a wide range with one application. It has been demanded.
そこで、水面浮遊型農薬製剤の拡展を補助するための薬剤（水面浮遊型農薬製剤用拡展剤）として、アセチレングリコール誘導体（特許文献１）、ポリオキシアルキレンモノアルキルエーテル（特許文献２及び３）及びアルカンジオール誘導体（特許文献４）等が提案されている。 Therefore, acetylene glycol derivatives (Patent Document 1) and polyoxyalkylene monoalkyl ethers (Patent Documents 2 and 3) are used as agents for assisting the spread of water-floating pesticide preparations (spreading agents for water-floating pesticide preparations). ) And an alkanediol derivative (Patent Document 4) and the like have been proposed.
しかしながら、特許文献１～４記載の水面浮遊型農薬製剤用拡展剤は拡展性が十分でなく、農薬施用の更なる省力化の観点から、改善が要望されている。
そこで、本発明は従来技術に比して、拡展性に優れた水面浮遊型農薬製剤用拡展剤を提供することを目的とする。
However, the spreading agents for water-floating pesticide formulations described in Patent Documents 1 to 4 do not have sufficient spreadability, and improvement is required from the viewpoint of further labor saving in the application of pesticides.
Therefore, an object of the present invention is to provide a spreading agent for a water-floating pesticide formulation, which has excellent spreadability as compared with the prior art.
本発明者らはこれらの問題を解決すべく鋭意検討した結果、本発明に到達した。即ち本発明は、下記一般式（１）で表される非イオン性界面活性剤（Ｘ）を含む水面浮遊型農薬製剤用拡展剤であって、
前記水面浮遊型農薬製剤用拡展剤が含有する全ての（Ｘ）におけるＲ１中のメチル基の１分子あたりの数平均個数が３．０以上であり、
前記水面浮遊型農薬製剤用拡展剤が含有する全ての（Ｘ）におけるｐの１分子あたりの数平均ｐＡが１～５であり、
前記水面浮遊型農薬製剤用拡展剤が含有する全ての（Ｘ）におけるｑの１分子あたりの数平均ｑＡが１～８である水面浮遊型農薬製剤用拡展剤。
Ｒ１Ｏ－［（Ｃ３Ｈ６Ｏ）ｐ／（Ｃ２Ｈ４Ｏ）ｑ］Ｈ （１）
［一般式（１）中、Ｒ１は炭素数８～１１のアルキル基を表し；ｐは０～１００の整数であり；ｑは０～１００の整数であり；［（Ｃ３Ｈ６Ｏ）ｐ／（Ｃ２Ｈ４Ｏ）ｑ］は、ｐ個あるプロピレンオキシ基と、ｑ個あるエチレンオキシ基の結合順序が任意であることを表す。］
The present inventors have reached the present invention as a result of diligent studies to solve these problems. That is, the present invention is a spreading agent for a water-floating pesticide formulation containing a nonionic surfactant (X) represented by the following general formula (1).
The number average number of methyl groups in R1 in all (X) contained in the spreading agent for water-suspended pesticide formulations is 3.0 or more per molecule.
The number average pA per molecule of p in all (X) contained in the spreading agent for water - floating pesticide formulations is 1 to 5.
A spreading agent for a water-floating pesticide formulation, wherein the number average q A per molecule of q in all (X) contained in the spreading agent for a water-floating pesticide formulation is 1 to 8.
R 1 O- [(C 3 H 6 O) p / (C 2 H 4 O) q ] H (1)
[In general formula (1), R 1 represents an alkyl group having 8 to 11 carbon atoms; p is an integer of 0 to 100; q is an integer of 0 to 100; [(C 3 H 6 O). p / (C 2 H 4 O) q ] indicates that the bonding order of the p propyleneoxy groups and the q ethyleneoxy groups is arbitrary. ]
本発明の水面浮遊型農薬製剤用拡展剤は、農薬製剤と併用することで優れた拡展性を付与することができるという効果を奏する。 The spreading agent for a water-floating pesticide formulation of the present invention has an effect that excellent spreadability can be imparted when used in combination with a pesticide formulation.
本発明の水面浮遊型農薬製剤用拡展剤は、下記一般式（１）で表される非イオン性界面活性剤（Ｘ）を含む。
なお、非イオン性界面活性剤（Ｘ）は、１種を単独で使用しても、２種以上を併用しても良い。
Ｒ１Ｏ－［（Ｃ３Ｈ６Ｏ）ｐ／（Ｃ２Ｈ４Ｏ）ｑ］Ｈ （１）
The spreading agent for a water-floating pesticide formulation of the present invention contains a nonionic surfactant (X) represented by the following general formula (1).
The nonionic surfactant (X) may be used alone or in combination of two or more.
R 1 O- [(C 3 H 6 O) p / (C 2 H 4 O) q ] H (1)
一般式（１）中、Ｒ１は炭素数８～１１のアルキル基を表し、前記の水面浮遊型農薬製剤用拡展剤が含有する全ての（Ｘ）におけるＲ１中のメチル基の１分子あたりの数平均個数が３．０以上である。 In the general formula (1), R 1 represents an alkyl group having 8 to 11 carbon atoms, and one molecule of the methyl group in R 1 in all (X) contained in the above-mentioned spreading agent for water-suspended pesticide formulations. The number average number per unit is 3.0 or more.
炭素数８～１１のアルキル基としては、メチル基を１個有する（ｒ１）、メチル基を２個有するアルキル基（ｒ２）、メチル基を３個有するアルキル基（ｒ３）、メチル基を４個有するアルキル基（ｒ４）及びメチル基を５個以上有するアルキル基（ｒ５）等が挙げられる。 Alkyl groups having 8 to 11 carbon atoms include an alkyl group having one methyl group (r1), an alkyl group having two methyl groups (r2), an alkyl group having three methyl groups (r3), and four methyl groups. Examples thereof include an alkyl group (r4) having an alkyl group and an alkyl group (r5) having 5 or more methyl groups.
前記のメチル基を１個有するアルキル基（ｒ１）としては、オクタン－１－イル基、ノナン－１－イル基、デカン－１－イル基及びウンデカン－１－イル基等が挙げられる。 Examples of the alkyl group (r1) having one methyl group include an octane-1-yl group, a nonane-1-yl group, a decane-1-yl group and an undecane-1-yl group.
前記のメチル基を２個有するアルキル基（ｒ２）としては、オクタン－２－イル基、２－エチルヘキサン－１－イル基、６－メチルヘプタン－１－イル基、ノナン－２－イル基、７－メチルオクタン－１－イル基、８－メチルノナン－１－イル基及び９－メチルデカン－１－イル基等が挙げられる。 Examples of the alkyl group (r2) having two methyl groups include an octane-2-yl group, a 2-ethylhexane-1-yl group, a 6-methylheptane-1-yl group, and a nonan-2-yl group. Examples thereof include a 7-methyloctane-1-yl group, an 8-methylnonan-1-yl group and a 9-methyldecane-1-yl group.
前記のメチル基を３個有するアルキル基（ｒ３）としては、３－メチルヘプタン－３－イル基、３，５－ジメチルヘキサン－１－イル基、２－メチルノナン－３－イル基及び２－メチルデカン－２－イル基等が挙げられる。 Examples of the alkyl group (r3) having three methyl groups include 3-methylheptane-3-yl group, 3,5-dimethylhexane-1-yl group, 2-methylnonan-3-yl group and 2-methyldecane. -2-Il group and the like can be mentioned.
前記のメチル基を４個有するアルキル基（ｒ４）としては、３，５，５－トリメチルヘキサン－１－イル基及び２，６－ジメチルヘプタン－４－イル基、２，３，５－トリメチルヘキサン－１－イル基、３，５，５－トリメチルヘプタン－１－イル基及び３，５，５－トリメチルオクタン－１－イル基等が挙げられる。 Examples of the alkyl group (r4) having four methyl groups include 3,5,5-trimethylhexane-1-yl group, 2,6-dimethylheptane-4-yl group, and 2,3,5-trimethylhexane. Examples thereof include a -1-yl group, a 3,5,5-trimethylheptane-1-yl group and a 3,5,5-trimethyloctane-1-yl group.
前記のメチル基を５個以上有するアルキル基（ｒ５）としては、２，２－ジメチル－５－メチルヘキサン－４－イル基等が挙げられる。 Examples of the alkyl group (r5) having 5 or more of the methyl groups include 2,2-dimethyl-5-methylhexane-4-yl group and the like.
これらのＲ１の内、拡展性の観点から好ましいのは、前記のメチル基を３個有するアルキル基（ｒ３）、メチル基を４個有するアルキル基（ｒ４）及びメチル基を５個以上有するアルキル基（ｒ５）であり、更に好ましいのは、メチル基を４個有するアルキル基（ｒ４）及びメチル基を５個以上有するアルキル基（ｒ５）であり、特に好ましいのは３，５，５－トリメチルヘキサン－１－イル基である。 Among these R1 , from the viewpoint of expandability, the alkyl group (r3) having three methyl groups, the alkyl group (r4) having four methyl groups, and five or more methyl groups are preferable. The alkyl group (r5) is more preferable, an alkyl group having four methyl groups (r4) and an alkyl group having five or more methyl groups (r5), and particularly preferable are 3,5,5-. It is a trimethylhexane-1-yl group.
前述の通り、前記水面浮遊型農薬製剤用拡展剤が含有する全ての（Ｘ）におけるＲ１が有するメチル基の数平均個数は３．０以上である。
メチル基の数平均個数が３．０未満であると、拡展性が悪化する。
また、メチル基の数平均個数は、例えば、（Ｘ）を合成する際（合成方法については後に詳述）に用いた原料のＲ１に水酸基が結合したアルコールについて、１Ｈ－ＮＭＲ測定及びガスクロマトグラフィー測定することにより、算出することができる。
As described above, the average number of methyl groups of R 1 in all (X) contained in the spreading agent for water-suspended pesticide formulations is 3.0 or more.
If the number average number of methyl groups is less than 3.0, the spreadability deteriorates.
The number average number of methyl groups is, for example, 1 H-NMR measurement and gas for the alcohol in which the hydroxyl group is bonded to R1 of the raw material used when synthesizing (X) (the synthesis method will be described in detail later). It can be calculated by chromatographic measurement.
一般式（１）中、ｐは０～１００の整数であり、前記の水面浮遊型農薬製剤用拡展剤が含有する全ての（Ｘ）におけるｐの１分子あたりの数平均ｐＡは１～５である。
ｐＡが１未満であると拡展性が悪化する。特に水面浮遊型農薬製剤中に一般式（１）で表される非イオン性界面活性剤（Ｘ）を１％未満しか含有しない時に著しく悪化する。ｐＡが５を超えると拡展性が悪化する。
また、ｐＡは、拡展性の観点から１～３であることが好ましい。
In the general formula (1), p is an integer of 0 to 100, and the number average p A per molecule of p in all (X) contained in the above-mentioned spreading agent for water-floating pesticide formulation is 1 to 1. It is 5.
If p A is less than 1, the malleability deteriorates. In particular, it is remarkably deteriorated when the nonionic surfactant (X) represented by the general formula (1) is contained in less than 1% in the water-floating pesticide preparation. When p A exceeds 5, the malleability deteriorates.
Further, pA is preferably 1 to 3 from the viewpoint of malleability.
一般式（１）中、ｑは０～１００の整数であり、前記の水面浮遊型農薬製剤用拡展剤が含有する全ての（Ｘ）におけるｑの１分子あたりの数平均ｑＡは１～８である。
ｑＡが１未満であると拡展性が悪化する。ｑＡが８を超えると拡展性が悪化する。
また、ｑＡは、拡展性の観点から２～８であることが好ましく、３～６であることが更に好ましい。
In the general formula (1), q is an integer of 0 to 100, and the number average q A per molecule of q in all (X) contained in the above-mentioned spreading agent for water-floating pesticide preparation is 1 to 1. It is 8.
If q A is less than 1, the malleability deteriorates. q When A exceeds 8, the malleability deteriorates.
Further, q A is preferably 2 to 8 from the viewpoint of malleability, and more preferably 3 to 6.
ｐＡとｑＡの関係としては、拡展性の観点からｐＡ＋ｑＡが２～１０であることが好ましく、ｐＡ＋ｑＡが３～１０であることが更に好ましく、ｐＡ＋ｑＡが４～８であることが特に好ましい。
また、ｐＡとｑＡの関係としては、拡展性の観点からｑＡ≧ｐＡであることが好ましい。
Regarding the relationship between p A and q A , from the viewpoint of malleability, p A + q A is preferably 2 to 10, p A + q A is more preferably 3 to 10, and p A + q A is. It is particularly preferably 4 to 8.
Further, as for the relationship between p A and q A , it is preferable that q A ≧ p A from the viewpoint of malleability.
また、更に拡展性を高める観点からは、本発明の水面浮遊型農薬製剤用拡展剤は、一般式（１）において、ｐが１～５であり、かつｑが１～８である分子を含有していることが好ましく、一般式（１）において、ｐが１～３であり、かつｑが２～８である分子を含有していることが更に好ましい。 Further, from the viewpoint of further enhancing the spreadability, the spread agent for water-floating pesticide preparation of the present invention is a molecule having p of 1 to 5 and q of 1 to 8 in the general formula (1). Is preferable, and in the general formula (1), it is more preferable to contain a molecule having p of 1 to 3 and q of 2 to 8.
一般式（１）中、（Ｃ３Ｈ６Ｏ）はプロピレンオキシ基を表し、（Ｃ２Ｈ４Ｏ）はエチレンオキシ基を表す。
［（Ｃ３Ｈ６Ｏ）ｐ／（Ｃ２Ｈ４Ｏ）ｑ］は、ｐ個のプロピレンオキシ基と、ｑ個のエチレンオキシ基の結合順序が任意であることを表す。
ここで、［（Ｃ３Ｈ６Ｏ）ｐ／（Ｃ２Ｈ４Ｏ）ｑ］におけるプロピレンオキシ基とエチレンオキシ基の結合順序は、拡展性の観点から［（Ｃ３Ｈ６Ｏ）ｐ－（Ｃ２Ｈ４Ｏ）ｑ］［即ち、「Ｒ１Ｏ」にｐ個の（Ｃ３Ｈ６Ｏ）が結合し、続いてｑ個の（Ｃ２Ｈ４Ｏ）が結合する付加形式］又は［（Ｃ２Ｈ４Ｏ）ｑ－（Ｃ３Ｈ６Ｏ）ｐ］［即ち、「Ｒ１Ｏ」にｑ個の（Ｃ２Ｈ４Ｏ）ｑが結合し、続いてｐ個の（Ｃ３Ｈ６Ｏ）が結合する付加形式］であることが好ましく、［（Ｃ３Ｈ６Ｏ）ｐ－（Ｃ２Ｈ４Ｏ）ｑ］であることが更に好ましい。
In the general formula (1), (C 3 H 6 O) represents a propyleneoxy group, and (C 2 H 4 O) represents an ethylene oxy group.
[(C 3 H 6 O) p / (C 2 H 4 O) q ] indicates that the bonding order of p propyleneoxy groups and q ethyleneoxy groups is arbitrary.
Here, the bonding order of the propyleneoxy group and the ethyleneoxy group in [(C 3 H 6 O) p / (C 2 H 4 O) q ] is [(C 3 H 6 O) p ] from the viewpoint of expandability. -(C 2 H 4 O) q ] [that is, an additional form in which p (C 3 H 6 O) are bound to "R 1 O", followed by q (C 2 H 4 O). ] Or [(C 2 H 4 O) q- (C 3 H 6 O) p ] [that is, q (C 2 H 4 O) q are bound to "R 1 O", followed by p. (Additional form to which (C 3 H 6 O) is bound] is preferable, and [(C 3 H 6 O) p − (C 2 H 4 O) q ] is more preferable.
前記の非イオン性界面活性剤（Ｘ）は、公知の方法により製造することができる。例えば、前記のＲ１に水酸基が結合したアルコールに、アルカリ触媒（水酸化カリウム等）又は酸触媒（三フッ化ホウ素等）を加え窒素雰囲気下にてエチレンオキサイド及びプロピレンオキサイドを付加反応させて製造することができる。
なお、前記のＲ１に水酸基が結合したアルコールとしては、エクソンモービル社製「エクサール９Ｓ」、「エクサール１０」及び「エクサール１１」、並びに、ＫＨネオケム（株）製「オキソコール９００」、「ノナノール」及び「デカノール」等として市場から入手することができる。
The nonionic surfactant (X) can be produced by a known method. For example, it is produced by adding an alkali catalyst (potassium hydroxide or the like) or an acid catalyst (boron trifluoride or the like) to the alcohol in which a hydroxyl group is bonded to R 1 and subjecting it to an addition reaction of ethylene oxide and propylene oxide under a nitrogen atmosphere. can do.
The alcohols having a hydroxyl group bonded to R 1 include ExxonMobil's "Exxon9S", "Exxon10" and "Exxon11", and KH Neochem's "Oxocol 900" and "Nonanol". And can be obtained from the market as "decanol" and the like.
本発明の水面浮遊型農薬製剤用拡展剤は、非イオン性界面活性剤（Ｘ）以外にも、（Ｘ）以外の非イオン性界面活性剤及びアニオン性界面活性剤等を含有していても良い。また、本発明の水面浮遊型農薬製剤用拡展剤は、後述の水面浮遊型農薬製剤に用いる成分（崩壊分散剤及び結合剤等）を含有していても良い。
前記の（Ｘ）以外の非イオン性界面活性剤としては、炭素数１２～１８のアルコール（ドデカノール及びオクタデカノール等）への炭素数２～４のアルキレンオキサイド１～４０モル付加物、アルキルフェノール（オクチルフェノール及びノニルフェノール等）への炭素数２～４のアルキレンオキサイド１～４０モル付加物及び脂肪酸（オレイン酸及びステアリン酸等）への炭素数２～４のアルキレンオキサイド１～４０モル付加物等が挙げられる。
前記のアニオン性界面活性剤としては、スルホン酸塩（ドデシルベンゼンスルホン酸ナトリウム及びテトラデシルベンゼンスルホン酸ナトリウム等）、硫酸塩（ラウリル硫酸ナトリウム及びポリオキシエチレンラウリルエーテル硫酸ナトリウム等）及びアルキル脂肪酸塩（ラウリン酸モノエタノールアミン塩及びラウリン酸ジエタノールアミン塩等）等が挙げられる。
The spreading agent for a water-floating pesticide formulation of the present invention contains a nonionic surfactant other than the nonionic surfactant (X), an anionic surfactant and the like in addition to the nonionic surfactant (X). Is also good. Further, the spreading agent for a water-floating pesticide formulation of the present invention may contain components (disintegrant dispersant, binder, etc.) used in the water-floating pesticide formulation described later.
Examples of the nonionic surfactant other than the above (X) include an alkylene oxide 1 to 40 mol additive having 2 to 4 carbon atoms to an alcohol (dodecanol, octadecanol, etc.) having 12 to 18 carbon atoms, and an alkylphenol (alkylphenol). Examples include 1 to 40 mol of alkylene oxide having 2 to 4 carbon atoms to octylphenol and nonionic phenol, and 1 to 40 mol of alkylene oxide having 2 to 4 carbon atoms to fatty acids (oleic acid, stearic acid, etc.). Be done.
Examples of the anionic surfactant include sulfonates (sodium dodecylbenzene sulfonate, sodium tetradecylbenzene sulfonate, etc.), sulfates (sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, etc.), and alkyl fatty acid salts (such as sodium lauryl lauryl ether sulfate). Lauric acid monoethanolamine salt, laurate diethanolamine salt, etc.) and the like can be mentioned.
本発明の水面浮遊型農薬製剤用拡展剤が含有する非イオン性界面活性剤（Ｘ）の重量割合は、拡展性の観点から、水面浮遊型農薬製剤用拡展剤の重量を基準として、５０～１００重量％であることが好ましい。 The weight ratio of the nonionic surfactant (X) contained in the spreading agent for water-floating pesticide formulation of the present invention is based on the weight of the spreading agent for water-floating pesticide formulation from the viewpoint of spreadability. , 50 to 100% by weight is preferable.
水面浮遊型農薬製剤は、本発明の水面浮遊型農薬製剤用拡展剤及び農薬原体（有効成分）を必須成分として含有し、これら以外に浮遊助剤、崩壊分散剤、結合剤及び増量剤等を含有してもよい。 The water-floating pesticide formulation contains the spreading agent for the water-floating pesticide formulation of the present invention and the pesticide drug substance (active ingredient) as essential ingredients, and in addition to these, a floating aid, a disintegrant dispersant, a binder and a bulking agent. Etc. may be contained.
農薬原体は水面施用が可能であれば液体でも固体でも良く、殺虫剤、殺菌剤、除草剤及び植物調節剤等が挙げられる。 The pesticide drug substance may be liquid or solid as long as it can be applied to the water surface, and examples thereof include insecticides, fungicides, herbicides and plant growth regulators.
殺虫剤としては、イソキサチオン、ダイアジノン、ダイスルフォトン、プロパホス、トリクロルフォン、ホルモチオン、ジメトエート、モノクロトフォス、アセフェート、カルボフラン、カルボスルファン、チオシクラム、カルタップ、ベンスルタップ、ベンフラカルブ、フラチオカルブ、ブプロフェジン、フェノブカルブ、メトールカルブ、プロポクシュア、イミダクロプリド、ニッテンピラム、アセタミプリド、シクロプロトリン、エトフェンプロックス及びシラフルオフェン等が挙げられる。 Insecticides include isoxathion, diazinon, disulphoton, propaphos, trichlorfon, formothion, dimethoate, monochromotophos, acetamiprid, carbofuran, carbosulfan, nereistoxin, cartap, bensultap, benfracarb, furathiocarb, buprofezin, phenocarb, metolcarb, Examples thereof include propoxure, imidacloprid, nittenpyram, acetamiprid, cycloprothrin, etofenprox and silafluofen.
殺菌剤としては、プロベナゾール、イソプロチオラン、イプロベンフォス、トリシクラゾール、ピロキロン、カルプロパミド、オリブライト、アゾキシストロビン、フルトラニル、メプロニル、チフルザミド、フラメトピル及びテクロフタラム等が挙げられる。 Examples of the bactericide include probenazole, isoprothiolan, iprobenphos, tricyclazole, pyroquilone, carpropamide, oliverite, azoxystrobin, flutranil, mepronil, tifluzamide, flametopil, tecrophthalam and the like.
除草剤としては、ピラゾレール、ベンゾフェナップ、ピラゾキシフェン、ピリブチカルブ、ブロモプチド、ブタミホス、メフェナセット、アニロホス、ブタクロール、チオベンカルブ、クロルニトロフェン、ダイムロン、ビフェノックス、ナプロアニリド、オキサジアゾン、オキサジアルギル、ベンタゾン、モリネート、ピペロホス、ジメピペレート、エスプロカルブ、ジチオピル、カフェンストロール、プレチラクロール、シメトリン、ベンスルフロンメチル、キンクロラック、ペントキサゾン、テニルクロール、エトベンザニド、ジメタメトリン及びインダノファン等が挙げられる。 Herbicides include pyrazol, benzophenap, pyrazoxifene, pyribuchicarb, bromopetite, butamiphos, mephenacet, anilophos, butachlor, thiobencarb, chlornitrofen, dimuron, bifenox, naproanilide, oxadiazone, oxadiargyl, ventazone, molinate, piperophos, dipelophos. , Cafentrol, Pretilachlor, Simetrin, Bensulfuronmethyl, Kinchlorac, Pentoxazone, Tenilchlor, Etobenzanide, Dimetamethrin, Indanophan and the like.
植物調節剤としては、イナベンフィド、パクロブトラゾール、ウニコナゾール及びトリアペンテノール等が挙げられる。 Examples of the plant growth regulator include inabenfide, paclobutrazol, uniconazole, triapentenol and the like.
前記の浮遊助剤としては、農薬製剤を水面に浮かせるものであればよく、中空性ガラス（発泡シラス及び発泡パーライト等）、発泡軽石、焼成バーミキュライト、コルク、木粉、発泡スチロール、合成樹脂粉末及びプラスチック中空体等が挙げられる。 The floating aid may be any one that floats the pesticide product on the surface of the water, such as hollow glass (foamed silas and foamed pearlite), foamed pumice, calcined vermiculite, cork, wood powder, foamed styrol, synthetic resin powder and plastic. Examples include hollow bodies.
崩壊分散剤としては、農薬製剤を水面又は水中で崩壊させ、農薬原体を水中に懸濁、分散させるものであればよく、リグニンスルホン酸塩、ナフタレンスルホン酸塩、ナフタレンスルホン酸塩とホルマリンとの縮合物、フェノールスルホン酸塩、フェノールスルホン酸塩とホルマリンとの縮合物、スチレンスルホン酸塩及びその重合物、ポリアクリル酸塩、アクリル酸とマレイン酸の共重合物の塩、アルキルベンゼンスルホン酸塩、ジアルキルスルホコハク酸塩及びポリオキシアルキレンアルキルエーテル硫酸塩等が挙げられる。 The disintegrant dispersant may be any one that disintegrates the pesticide preparation on the water surface or in water and suspends and disperses the pesticide substance in water, and includes lignin sulfonate, naphthalene sulfonate, naphthalene sulfonate and formarin. Condensate of, phenol sulfonate, condensate of phenol sulfonate and formalin, styrene sulfonate and its polymer, polyacrylic acid salt, salt of copolymer of acrylic acid and maleic acid, alkylbenzene sulfonate , Dialkyl sulfosuccinate, polyoxyalkylene alkyl ether sulfate and the like.
結合剤としては、造粒して得られた粒状の農薬製剤に硬度を付与するものであればよく、でんぷん及びその誘導体、ポリビニルピロリドン、ポリアクリル酸塩、カルボキシメチルセルロースの塩、ポリビニルアルコール、リグニンスルホン酸塩、アラビアゴム及びモンモリロナイト等が挙げられる。
なお、結合剤には、崩壊分散剤として機能する化合物（ポリアクリル酸塩、カルボキシメチルセルロースの塩及びリグニンスルホン酸塩等）も含まれる。
The binder may be any as long as it imparts hardness to the granular pesticide preparation obtained by granulation, and is starch and its derivatives, polyvinylpyrrolidone, polyacrylic acid salt, carboxymethyl cellulose salt, polyvinyl alcohol, and lignin sulfone. Examples thereof include acid salts, gum arabic and montmorillonite.
The binder also includes a compound (polyacrylic acid salt, a salt of carboxymethyl cellulose, a lignin sulfonate, etc.) that functions as a disintegrant dispersant.
増量剤としては、液状の農薬原体を吸収させたり、固状の農薬原体を希釈できれば良く、タルク、クレー（ベントナイト等）、珪藻土、非晶質シリカ、炭酸カルシウム及び炭酸マグネシウム等が挙げられる。 Examples of the bulking agent include talc, clay (bentonite, etc.), diatomaceous earth, amorphous silica, calcium carbonate, magnesium carbonate, etc., as long as they can absorb the liquid pesticide substance or dilute the solid pesticide substance. ..
水面浮遊型農薬製剤は、水面浮遊型農薬製剤用拡展剤を、拡展性の観点から、水面浮遊型農薬製剤の重量を基準として非イオン性界面活性剤（Ｘ）の重量割合が０．０１～１０重量％となるように含有していることが好ましく、更に好ましくは０．１～８重量％である。
水面浮遊型農薬製剤が含有する農薬原体の重量割合は、防除効果の観点から、水面浮遊型農薬製剤の重量を基準として０．１～８０重量％であることが好ましく、更に好ましくは１～５０重量％である。
水面浮遊型農薬製剤が含有する浮遊助剤の重量割合は、拡展性の観点から、水面浮遊型農薬製剤の重量を基準として１～８０重量％であることが好ましく、更に好ましくは１０～５０重量％である。
水面浮遊型農薬製剤が含有する崩壊分散剤及び結合剤の合計重量の割合は、崩壊性及び製剤強度等の観点から、水面浮遊型農薬製剤の重量を基準として０．０１～３０重量％であることが好ましく、更に好ましくは０．０５～２０重量％である。
水面浮遊型農薬製剤が含有する増量剤の重量割合は、ハンドリング性の観点から、水面浮遊型農薬製剤の重量を基準として１～８０重量％であることが好ましく、更に好ましくは２～５０重量％である。
The water-floating pesticide formulation is a spreading agent for the water-floating pesticide formulation, and the weight ratio of the nonionic surfactant (X) is 0. It is preferably contained in an amount of 01 to 10% by weight, more preferably 0.1 to 8% by weight.
From the viewpoint of the control effect, the weight ratio of the pesticide substance contained in the water-floating pesticide preparation is preferably 0.1 to 80% by weight, more preferably 1 to 80% based on the weight of the water-floating pesticide preparation. It is 50% by weight.
From the viewpoint of malleability, the weight ratio of the floating aid contained in the water-floating pesticide preparation is preferably 1 to 80% by weight, more preferably 10 to 50% based on the weight of the water-floating pesticide preparation. It is% by weight.
The ratio of the total weight of the disintegrant dispersant and the binder contained in the water-floating pesticide product is 0.01 to 30% by weight based on the weight of the water-floating pesticide product from the viewpoint of disintegration, formulation strength and the like. It is preferable, and more preferably 0.05 to 20% by weight.
From the viewpoint of handleability, the weight ratio of the bulking agent contained in the water-floating pesticide preparation is preferably 1 to 80% by weight, more preferably 2 to 50% by weight, based on the weight of the water-floating pesticide preparation. Is.
水面浮遊型農薬製剤は公知の方法で調製できる。例えば、
１）本発明の水面浮遊型農薬製剤用拡展剤、農薬原体、浮遊助剤、崩壊分散剤、結合剤、増量剤及び水を混合機で混練した後、造粒機を用いて造粒し、乾燥する方法、
２）本発明の水面浮遊型農薬製剤用拡展剤、浮遊助剤、崩壊分散剤、結合剤、増量剤及び水を混合機で混練した後、造粒機を用いて造粒し、その造粒物に農薬原体を含浸、吸着させ、乾燥する方法等が挙げられる。
なお、前記の混合機としては、ナウターミキサー、リボンミキサー、ロータリーブレンダー及びＶ型混合機等を適用できる。
また、前記の造粒機としては、押し出し造粒機、混合造粒機及び転動造粒機等が適用できる。
The water-floating pesticide preparation can be prepared by a known method. for example,
1) After kneading the spreading agent for water-floating pesticide formulation, pesticide drug substance, floating aid, disintegrant dispersant, binder, bulking agent and water of the present invention with a mixer, granulation using a granulator. And how to dry,
2) The spreading agent, floating aid, disintegrant dispersant, binder, bulking agent and water of the present invention for floating pesticides are kneaded with a mixer, and then granulated using a granulator to produce the same. Examples thereof include a method of impregnating the granules with the pesticide substance, adsorbing the granules, and drying the granules.
As the above-mentioned mixer, a Nauter mixer, a ribbon mixer, a rotary blender, a V-type mixer and the like can be applied.
Further, as the above-mentioned granulator, an extrusion granulator, a mixing granulator, a rolling granulator and the like can be applied.
前記の水面浮遊型農薬製剤は、一般的な農薬粒剤と同様、手撒き散布、機械散布、振込散布及び額縁散布等の方法で散布できる。
また、前記の水面浮遊型農薬製剤は、水溶紙に分包して畦から投げ込むこともできる。投げ込み施用に用いる水溶紙は、水中での溶解性又は分散性を有するフィルム又はシートであり、ポリビニルアルコール又はその誘導体、プルラン、カルボキシメチルセルロース塩及びセルロース等が挙げられる。
The above-mentioned water-floating pesticide preparation can be sprayed by a method such as hand-spraying, mechanical spraying, transfer spraying, or frame spraying, as in the case of general pesticide granules.
In addition, the above-mentioned water-floating pesticide preparation can be packaged in water-soluble paper and thrown from the ridge. The water-soluble paper used for throwing application is a film or sheet having solubility or dispersibility in water, and examples thereof include polyvinyl alcohol or a derivative thereof, pullulan, carboxymethyl cellulose salt and cellulose.
以下、実施例により本発明を更に説明するが、本発明はこれに限定されるものではない。なお、実施例３、５、８および１３は参考例１、２、３および４である。 Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto. In addition, Examples 3, 5, 8 and 13 are Reference Examples 1, 2, 3 and 4.
製造例１
撹拌機、温度計、圧力計、耐圧滴下ボンベ、減圧及び窒素導入ラインの付いた２Ｌオートクレーブ中に３，５，５－トリメチル－１－ヘキサノール１４４重量部（１モル部）、水酸化カリウム０．５重量部を加え撹拌を開始し窒素封入し１００℃に昇温した後、圧力－０．１ＭＰａＧで１時間脱水した。次いで１３０℃に昇温し、圧力０．３ＭＰａＧ以下でプロピレンオキサイド５８重量部（１モル部）を５時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した（１段階目）。次いでエチレンオキサイド１７６重量部（４モル部）を３時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した（２段階目）。その後６０℃に冷却し、酢酸０．５重量部で中和し、非イオン性界面活性剤（Ｘ－１）を得た。
Production Example 1
144 parts by weight (1 mol) of 3,5,5-trimethyl-1-hexanol, 0. After adding 5 parts by weight, stirring was started, the mixture was filled with nitrogen, the temperature was raised to 100 ° C., and the mixture was dehydrated at a pressure of −0.1 MPaG for 1 hour. Then, the temperature was raised to 130 ° C., 58 parts by weight (1 mol part) of propylene oxide was sequentially added dropwise over 5 hours at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached (first step). .. Next, 176 parts by weight (4 mol parts) of ethylene oxide was sequentially added dropwise over 3 hours, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached (second step). Then, the mixture was cooled to 60 ° C. and neutralized with 0.5 parts by weight of acetic acid to obtain a nonionic surfactant (X-1).
製造例２
製造例１において、プロピレンオキサイド５８重量部（１モル部）を１１６重量部（２モル部）に、エチレンオキサイド１７６重量部（４モル部）を１３２重量部（３モル部）に変更した以外は製造例１と同様に製造し、非イオン性界面活性剤（Ｘ－２）を得た。
Manufacturing example 2
Except for changing propylene oxide 58 parts by weight (1 mol part) to 116 parts by weight (2 mol parts) and ethylene oxide 176 parts by weight (4 mol parts) to 132 parts by weight (3 mol parts) in Production Example 1. It was produced in the same manner as in Production Example 1 to obtain a nonionic surfactant (X-2).
製造例３
製造例１において、プロピレンオキサイド５８重量部（１モル部）を２３２重量部（４モル部）に、エチレンオキサイド１７６重量部（４モル部）を８８重量部（２モル部）に変更した以外は製造例１と同様に製造し、非イオン性界面活性剤（Ｘ－３）を得た。
Production example 3
Except for changing propylene oxide 58 parts by weight (1 mol part) to 232 parts by weight (4 mol parts) and ethylene oxide 176 parts by weight (4 mol parts) to 88 parts by weight (2 mol parts) in Production Example 1. It was produced in the same manner as in Production Example 1 to obtain a nonionic surfactant (X-3).
製造例４
製造例１において、プロピレンオキサイド５８重量部（１モル部）を２３２重量部（４モル部）に、エチレンオキサイド１７６重量部（４モル部）を２６４重量部（６モル部）に変更した以外は製造例１と同様に製造し、非イオン性界面活性剤（Ｘ－４）を得た。
Production example 4
Except for changing propylene oxide 58 parts by weight (1 mol part) to 232 parts by weight (4 mol parts) and ethylene oxide 176 parts by weight (4 mol parts) to 264 parts by weight (6 mol parts) in Production Example 1. It was produced in the same manner as in Production Example 1 to obtain a nonionic surfactant (X-4).
製造例５
製造例１において、エチレンオキサイド１７６重量部（４モル部）を４４重量部（１モル部）に変更した以外は製造例１と同様に製造し、非イオン性界面活性剤（Ｘ－５）を得た。
Production Example 5
The nonionic surfactant (X-5) was produced in the same manner as in Production Example 1 except that 176 parts by weight (4 mol parts) of ethylene oxide was changed to 44 parts by weight (1 mol part) of ethylene oxide in Production Example 1. Obtained.
製造例６
製造例１において、プロピレンオキサイド５８重量部（１モル部）を１１６重量部（２モル部）に、エチレンオキサイド１７６重量部（４モル部）を３５２重量部（８モル部）に変更した以外は製造例１と同様に製造し、非イオン性界面活性剤（Ｘ－６）を得た。
Production Example 6
Except for changing propylene oxide 58 parts by weight (1 mol part) to 116 parts by weight (2 mol parts) and ethylene oxide 176 parts by weight (4 mol parts) to 352 parts by weight (8 mol parts) in Production Example 1. It was produced in the same manner as in Production Example 1 to obtain a nonionic surfactant (X-6).
製造例７
製造例１において、３，５，５－トリメチルヘキサノール１４４部をエクサール９Ｓ（エクソンモービル社製）１４４部に変更した以外は製造例１と同様に製造し、非イオン性界面活性剤（Ｘ－７）を得た。
なお、エクサール９Ｓは、１Ｈ－ＮＭＲ及びガスクロマトグラフィーによる分析の結果、前記のＲ１に水酸基が結合したアルコールであった。また、Ｒ１の炭素数は９．０であり、Ｒ１中のメチル基の１分子あたりの数平均個数は３．０であった。
Production example 7
In Production Example 1, 144 parts of 3,5,5-trimethylhexanol were produced in the same manner as in Production Example 1 except that 144 parts of Exal 9S (manufactured by ExxonMobil) were changed, and a nonionic surfactant (X-7) was produced. ) Was obtained.
As a result of analysis by 1 H-NMR and gas chromatography, Exar 9S was an alcohol in which a hydroxyl group was bonded to R1 . The number of carbon atoms in R 1 was 9.0, and the average number of methyl groups in R 1 per molecule was 3.0.
製造例８
製造例１において、３，５，５－トリメチルヘキサノール１４４部をエクサール９Ｓ（エクソンモービル社製）１４４部に変更し、プロピレンオキサイド５８重量部（１モル部）を２９０重量部（５モル部）に、エチレンオキサイド１７６重量部（４モル部）を２２０重量部（５モル部）に変更した以外は製造例１と同様に製造し、非イオン性界面活性剤（Ｘ－８）を得た。
Production Example 8
In Production Example 1, 144 parts of 3,5,5-trimethylhexanol was changed to 144 parts of Exar 9S (manufactured by Exxon Mobile Co., Ltd.), and 58 parts by weight (1 mol part) of propylene oxide was changed to 290 parts by weight (5 mol parts). , Ethylene oxide was produced in the same manner as in Production Example 1 except that 176 parts by weight (4 mol parts) was changed to 220 parts by weight (5 mol parts) to obtain a nonionic surfactant (X-8).
製造例９
製造例１において、３，５，５－トリメチルヘキサノール１４４部をデカノール［ＫＨネオケム（株）製］１５８部に変更し、プロピレンオキサイド５８重量部（１モル部）を１１６重量部（２モル部）に、エチレンオキサイド１７６重量部（４モル部）を１３２重量部（３モル部）に変更した以外は製造例１と同様に製造し、非イオン性界面活性剤（Ｘ－９）を得た。
なお、デカノールは、１Ｈ－ＮＭＲ及びガスクロマトグラフィーによる分析の結果、前記のＲ１に水酸基が結合したアルコールであった。また、Ｒ１の炭素数は１０．０であり、Ｒ１中のメチル基の１分子あたりの数平均個数は３．５であった。
Production Example 9
In Production Example 1, 144 parts of 3,5,5-trimethylhexanol was changed to 158 parts of decanol [manufactured by KH Neochem Co., Ltd.], and 58 parts by weight (1 mol part) of propylene oxide was changed to 116 parts by weight (2 mol parts). A nonionic surfactant (X-9) was obtained in the same manner as in Production Example 1 except that 176 parts by weight (4 mol parts) of ethylene oxide was changed to 132 parts by weight (3 mol parts).
As a result of analysis by 1 H-NMR and gas chromatography, decanol was an alcohol in which a hydroxyl group was bonded to R1 . The number of carbon atoms in R 1 was 10.0, and the average number of methyl groups in R 1 per molecule was 3.5.
製造例１０
製造例１において、３，５，５－トリメチルヘキサノール１４４部をエクサール１１（エクソンモービル製）１７２部に変更し、プロピレンオキサイド５８重量部（１モル部）を１１６重量部（２モル部）に、エチレンオキサイド１７６重量部（４モル部）を１３２重量部（３モル部）に変更した以外は製造例１と同様に製造し、非イオン性界面活性剤（Ｘ－１０）を得た。
なお、エクサール１１は、１Ｈ－ＮＭＲ及びガスクロマトグラフィーによる分析の結果、前記のＲ１に水酸基が結合したアルコールであった。また、Ｒ１の炭素数は１１．０であり、Ｒ１中のメチル基の１分子あたりの数平均個数は３．７であった。
Production Example 10
In Production Example 1, 144 parts of 3,5,5-trimethylhexanol was changed to 172 parts of Exar 11 (manufactured by Exxon Mobile), and 58 parts by weight (1 mol part) of propylene oxide was changed to 116 parts by weight (2 mol parts). The same production as in Production Example 1 was carried out except that 176 parts by weight (4 mol parts) of ethylene oxide was changed to 132 parts by weight (3 mol parts) to obtain a nonionic surfactant (X-10).
As a result of analysis by 1 H-NMR and gas chromatography, Exar 11 was an alcohol in which a hydroxyl group was bonded to R1 . The number of carbon atoms in R 1 was 11.0, and the average number of methyl groups in R 1 per molecule was 3.7.
製造例１１
撹拌機、温度計、圧力計、耐圧滴下ボンベ、減圧及び窒素導入ラインの付いた２Ｌオートクレーブ中に３，５，５－トリメチル－１－ヘキサノール１４４重量部（１モル部）、水酸化カリウム０．５重量部を加え撹拌を開始し窒素封入し１００℃に昇温した後、圧力－０．１ＭＰａＧで１時間脱水した。次いで１３０℃に昇温し、圧力０．３ＭＰａＧ以下でエチレンオキサイド１３２重量部（３モル部）を３時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した（１段階目）。次いでプロピレンオキサイド１１６重量部（２モル部）を５時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した（２段階目）。その後６０℃に冷却し、酢酸０．５重量部で中和し、非イオン性界面活性剤（Ｘ－１１）を得た。
Production Example 11
144 parts by weight (1 mol) of 3,5,5-trimethyl-1-hexanol, 0. After adding 5 parts by weight, stirring was started, the mixture was filled with nitrogen, the temperature was raised to 100 ° C., and the mixture was dehydrated at a pressure of −0.1 MPaG for 1 hour. Next, the temperature was raised to 130 ° C., 132 parts by weight (3 mol parts) of ethylene oxide was sequentially added dropwise over 3 hours at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached (first step). .. Next, 116 parts by weight (2 mol parts) of propylene oxide was sequentially added dropwise over 5 hours, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached (second step). Then, the mixture was cooled to 60 ° C. and neutralized with 0.5 parts by weight of acetic acid to obtain a nonionic surfactant (X-11).
製造例１２
撹拌機、温度計、圧力計、耐圧滴下ボンベ、減圧及び窒素導入ラインの付いた２Ｌオートクレーブ中に３，５，５－トリメチル－１－ヘキサノール１４４重量部（１モル部）、水酸化カリウム０．５重量部を加え撹拌を開始し窒素封入し１００℃に昇温した後、圧力－０．１ＭＰａＧで１時間脱水した。次いで１３０℃に昇温し、圧力０．３ＭＰａＧ以下でエチレンオキサイド１３２重量部（３モル部）及びプロピレンオキサイド１１６重量部（２モル部）の混合物を５時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した。その後６０℃に冷却し、酢酸０．５重量部で中和し、非イオン性界面活性剤（Ｘ－１２）を得た。
Production Example 12
144 parts by weight (1 mol) of 3,5,5-trimethyl-1-hexanol, 0. After adding 5 parts by weight, stirring was started, the mixture was filled with nitrogen, the temperature was raised to 100 ° C., and the mixture was dehydrated at a pressure of −0.1 MPaG for 1 hour. Then, the temperature was raised to 130 ° C., and a mixture of 132 parts by weight (3 mol parts) of ethylene oxide and 116 parts by weight (2 mol parts) of propylene oxide was sequentially added dropwise over 5 hours at a pressure of 0.3 MPaG or less, and the pressure was increased at the same temperature. The mixture was stirred for 1 hour until equilibrium was reached. Then, the mixture was cooled to 60 ° C. and neutralized with 0.5 parts by weight of acetic acid to obtain a nonionic surfactant (X-12).
製造例１３
製造例１において、プロピレンオキサイド５８重量部（１モル部）を２９０重量部（５モル部）に、エチレンオキサイド１７６重量部（４モル部）を３５２重量部（８モル部）に変更した以外は製造例１と同様に製造し、非イオン性界面活性剤（Ｘ－１３）を得た。
Production Example 13
Except for changing propylene oxide 58 parts by weight (1 mol part) to 290 parts by weight (5 mol parts) and ethylene oxide 176 parts by weight (4 mol parts) to 352 parts by weight (8 mol parts) in Production Example 1. It was produced in the same manner as in Production Example 1 to obtain a nonionic surfactant (X-13).
比較製造例１
撹拌機、温度計、圧力計、耐圧滴下ボンベ、減圧及び窒素導入ラインの付いた２Ｌオートクレーブ中に１－オクタノール１３０重量部（１モル部）、水酸化カリウム０．５重量部を加え撹拌を開始し窒素封入し１００℃に昇温した後、圧力－０．１ＭＰａＧで１時間脱水した。次いで１３０℃に昇温し、圧力０．３ＭＰａＧ以下でプロピレンオキサイド１１６重量部（２モル部）を５時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した（１段階目）。次いでエチレンオキサイド１３２重量部（３モル部）を３時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した（２段階目）。その後６０℃に冷却し、酢酸０．５重量部で中和し、非イオン性界面活性剤（Ｘ’－１）を得た。
Comparative manufacturing example 1
Add 130 parts by weight (1 mol) of 1-octanol and 0.5 part by weight of potassium hydroxide into a 2 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping cylinder, decompression and nitrogen introduction line, and start stirring. After filling with nitrogen and raising the temperature to 100 ° C., the mixture was dehydrated at a pressure of −0.1 MPaG for 1 hour. Next, the temperature was raised to 130 ° C., 116 parts by weight (2 mol parts) of propylene oxide was sequentially added dropwise over 5 hours at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached (first step). .. Next, 132 parts by weight (3 mol parts) of ethylene oxide was sequentially added dropwise over 3 hours, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached (second step). Then, the mixture was cooled to 60 ° C. and neutralized with 0.5 parts by weight of acetic acid to obtain a nonionic surfactant (X'-1).
比較製造例２
撹拌機、温度計、圧力計、耐圧滴下ボンベ、減圧及び窒素導入ラインの付いた２Ｌオートクレーブ中に１－デカノール１５８重量部（１モル部）、水酸化カリウム０．５重量部を加え撹拌を開始し窒素封入し１００℃に昇温した後、圧力－０．１ＭＰａＧで１時間脱水した。次いで１３０℃に昇温し、圧力０．３ＭＰａＧ以下でプロピレンオキサイド２３２重量部（４モル部）を５時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した（１段階目）。次いでエチレンオキサイド２６４重量部（６モル部）を３時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した（２段階目）。その後６０℃に冷却し、酢酸０．５重量部で中和し、非イオン性界面活性剤（Ｘ’－２）を得た。
Comparative manufacturing example 2
Add 158 parts by weight (1 mol) of 1-decanol and 0.5 part by weight of potassium hydroxide into a 2 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping cylinder, decompression and nitrogen introduction line, and start stirring. After filling with nitrogen and raising the temperature to 100 ° C., the mixture was dehydrated at a pressure of −0.1 MPaG for 1 hour. Next, the temperature was raised to 130 ° C., 232 parts by weight (4 mol parts) of propylene oxide was sequentially added dropwise over 5 hours at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached (first step). .. Next, 264 parts by weight (6 mol parts) of ethylene oxide was sequentially added dropwise over 3 hours, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached (second step). Then, the mixture was cooled to 60 ° C. and neutralized with 0.5 parts by weight of acetic acid to obtain a nonionic surfactant (X'-2).
比較製造例３
撹拌機、温度計、圧力計、耐圧滴下ボンベ、減圧及び窒素導入ラインの付いた２Ｌオートクレーブ中に２－エチルヘキサノール１３０重量部（１モル部）、水酸化カリウム０．５重量部を加え撹拌を開始し窒素封入し１００℃に昇温した後、圧力－０．１ＭＰａＧで１時間脱水した。次いで１３０℃に昇温し、圧力０．３ＭＰａＧ以下でエチレンオキサイド１３２重量部（３モル部）を３時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した。その後６０℃に冷却し、酢酸０．５重量部で中和し、非イオン性界面活性剤（Ｘ’－３）を得た。
Comparative manufacturing example 3
Add 130 parts by weight (1 mol part) of 2-ethylhexanol and 0.5 part by weight of potassium hydroxide into a 2L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping cylinder, decompression and nitrogen introduction line, and stir. After starting, the mixture was filled with nitrogen and heated to 100 ° C., and then dehydrated at a pressure of −0.1 MPaG for 1 hour. Then, the temperature was raised to 130 ° C., 132 parts by weight (3 mol parts) of ethylene oxide was sequentially added dropwise over 3 hours at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached. Then, the mixture was cooled to 60 ° C. and neutralized with 0.5 parts by weight of acetic acid to obtain a nonionic surfactant (X'-3).
比較製造例４
撹拌機、温度計、圧力計、耐圧滴下ボンベ、減圧及び窒素導入ラインの付いた２Ｌオートクレーブ中に３，５，５－トリメチルヘキサノール１４４重量部（１モル部）、水酸化カリウム０．５重量部を加え撹拌を開始し窒素封入し１００℃に昇温した後、圧力－０．１ＭＰａＧで１時間脱水した。次いで１３０℃に昇温し、圧力０．３ＭＰａＧ以下でエチレンオキサイド１３２重量部（３モル部）を３時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した。その後６０℃に冷却し、酢酸０．５重量部で中和し、非イオン性界面活性剤（Ｘ’－４）を得た。
Comparative manufacturing example 4
144 parts by weight (1 mol) of 3,5,5-trimethylhexanol, 0.5 parts by weight of potassium hydroxide in a 2 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping cylinder, decompression and nitrogen introduction line. Was added, stirring was started, the mixture was filled with nitrogen, the temperature was raised to 100 ° C., and the mixture was dehydrated at a pressure of −0.1 MPaG for 1 hour. Then, the temperature was raised to 130 ° C., 132 parts by weight (3 mol parts) of ethylene oxide was sequentially added dropwise over 3 hours at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached. Then, the mixture was cooled to 60 ° C. and neutralized with 0.5 parts by weight of acetic acid to obtain a nonionic surfactant (X'-4).
比較製造例５
撹拌機、温度計、圧力計、耐圧滴下ボンベ、減圧及び窒素導入ラインの付いた２Ｌオートクレーブ中にトリデカノール［ＫＨネオケム（株）製］２００重量部（１モル部）、水酸化カリウム０．５重量部を加え撹拌を開始し窒素封入し１００℃に昇温した後、圧力－０．１ＭＰａＧで１時間脱水した。次いで１３０℃に昇温し、圧力０．３ＭＰａＧ以下でプロピレンオキサイド１１６重量部（２モル部）を５時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した（１段階目）。次いでエチレンオキサイド１３２重量部（３モル部）を３時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した（２段階目）。その後６０℃に冷却し、酢酸０．５重量部で中和し、非イオン性界面活性剤（Ｘ’－５）を得た。
なお、トリデカノールは、１Ｈ－ＮＭＲ及びガスクロマトグラフィーによる分析の結果、前記のＲ１に水酸基が結合したアルコールであった。また、Ｒ１の炭素数は１３．０であり、Ｒ１中のメチル基の１分子あたりの数平均個数は４．０であった。
Comparative manufacturing example 5
200 parts by weight (1 mol part) of tridecanol [manufactured by KH Neochem Co., Ltd.], 0.5 weight by weight of potassium hydroxide in a 2 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping cylinder, decompression and nitrogen introduction line. The mixture was added, stirring was started, the mixture was filled with nitrogen, the temperature was raised to 100 ° C., and the pressure was reduced to −0.1 MPaG for 1 hour. Next, the temperature was raised to 130 ° C., 116 parts by weight (2 mol parts) of propylene oxide was sequentially added dropwise over 5 hours at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached (first step). .. Next, 132 parts by weight (3 mol parts) of ethylene oxide was sequentially added dropwise over 3 hours, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached (second step). Then, the mixture was cooled to 60 ° C. and neutralized with 0.5 parts by weight of acetic acid to obtain a nonionic surfactant (X'-5).
As a result of analysis by 1 H-NMR and gas chromatography, tridecanol was an alcohol in which a hydroxyl group was bonded to R1 . The number of carbon atoms in R 1 was 13.0, and the average number of methyl groups in R 1 per molecule was 4.0.
比較製造例６
製造例１において、プロピレンオキサイド５８重量部（１モル部）を３４８重量部（６モル部）に、エチレンオキサイド１７６重量部（４モル部）を２６４重量部（６モル部）に変更した以外は製造例１と同様に製造し、非イオン性界面活性剤（Ｘ’－６）を得た。
Comparative manufacturing example 6
Except for changing propylene oxide 58 parts by weight (1 mol part) to 348 parts by weight (6 mol parts) and ethylene oxide 176 parts by weight (4 mol parts) to 264 parts by weight (6 mol parts) in Production Example 1. It was produced in the same manner as in Production Example 1 to obtain a nonionic surfactant (X'-6).
比較製造例７
撹拌機、温度計、圧力計、耐圧滴下ボンベ、減圧及び窒素導入ラインの付いた２Ｌオートクレーブ中に３，５，５－トリメチルヘキサノール１４４重量部（１モル部）、水酸化カリウム０．５重量部を加え撹拌を開始し窒素封入し１００℃に昇温した後、圧力－０．１ＭＰａＧで１時間脱水した。次いで１３０℃に昇温し、圧力０．３ＭＰａＧ以下でプロピレンオキサイド１７４重量部（３モル部）を３時間かけて逐次滴下し、同温度で圧平衡になるまで１時間撹拌した。その後６０℃に冷却し、酢酸０．５重量部で中和し、非イオン性界面活性剤（Ｘ’－７）を得た。
Comparative manufacturing example 7
144 parts by weight (1 mol) of 3,5,5-trimethylhexanol, 0.5 parts by weight of potassium hydroxide in a 2 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure-resistant dropping cylinder, decompression and nitrogen introduction line. Was added, stirring was started, the mixture was filled with nitrogen, the temperature was raised to 100 ° C., and the mixture was dehydrated at a pressure of −0.1 MPaG for 1 hour. Then, the temperature was raised to 130 ° C., 174 parts by weight (3 mol parts) of propylene oxide was sequentially added dropwise over 3 hours at a pressure of 0.3 MPaG or less, and the mixture was stirred at the same temperature for 1 hour until pressure equilibrium was reached. Then, the mixture was cooled to 60 ° C. and neutralized with 0.5 parts by weight of acetic acid to obtain a nonionic surfactant (X'-7).
比較製造例８
製造例１において、プロピレンオキサイド５８重量部（１モル部）を１７４重量部（３モル部）に、エチレンオキサイド１７６重量部（４モル部）を３９６重量部（９モル部）に変更した以外は製造例１と同様に製造し、非イオン性界面活性剤（Ｘ’－８）を得た。
Comparative manufacturing example 8
Except for changing propylene oxide 58 parts by weight (1 mol part) to 174 parts by weight (3 mol parts) and ethylene oxide 176 parts by weight (4 mol parts) to 396 parts by weight (9 mol parts) in Production Example 1. It was produced in the same manner as in Production Example 1 to obtain a nonionic surfactant (X'-8).
＜実施例１～１６及び比較例１～１０＞
水面浮遊型農薬製剤用拡展剤として表１記載の本発明の非イオン性界面活性剤（Ｘ－１）～（Ｘ－１３）又は比較用の非イオン性界面活性剤（Ｘ’－１）～（Ｘ’－８）、農薬原体としてカフェンストロール、浮遊助剤として中空性ガラス［東海工業（株）製、「ＣＥＬ－ＳＴＡＲ Ｚ－２７」］及び増量剤としてベントナイト［クニミネ工業（株）製、「クニゲルＶ１」］を表２の配合量で混合し、その混合物に水４０部を加えて充分混練した。得られた混練物を目開き１．０ｍｍのスクリーンを装着したバスケット型造粒機に供して成型し、切断した後、５０℃の循風乾燥機で乾燥した。得られた乾燥物を長さ約３ｍｍに整粒して、本発明の水面浮遊型農薬製剤（Ｐ－１）～（Ｐ－１６）及び比較用の水面浮遊型農薬製剤（Ｐ’－１）～（Ｐ’－１０）を得た。
なお、表１において、ＰＯはプロピレンオキシ基を意味し、ＥＯはエチレンオキシ基を意味する。
<Examples 1 to 16 and Comparative Examples 1 to 10>
The nonionic surfactants (X-1) to (X-13) of the present invention shown in Table 1 as spreading agents for water-floating pesticide formulations or the nonionic surfactants (X'-1) for comparison. ~ (X'-8), Caffenttrol as the pesticide drug substance, hollow glass [manufactured by Tokai Kogyo Co., Ltd., "CEL-STAR Z-27"] as the floating aid, and bentonite [manufactured by Kunimine Kogyo Co., Ltd.] as the bulking agent. , "Kunigel V1"] was mixed in the blending amounts shown in Table 2, and 40 parts of water was added to the mixture and sufficiently kneaded. The obtained kneaded product was subjected to a basket-type granulator equipped with a screen having an opening of 1.0 mm, molded, cut, and then dried in a circulation dryer at 50 ° C. The obtained dried product is sized to a length of about 3 mm, and the water-floating pesticide preparations (P-1) to (P-16) of the present invention and the water-floating pesticide preparation (P'-1) for comparison are prepared. -(P'-10) was obtained.
In Table 1, PO means a propyleneoxy group and EO means an ethyleneoxy group.
＜拡展性試験＞
縦２００ｃｍ、横１０ｃｍ、深さ４ｃｍのステンレス製直方容器の横方向に３．３ｃｍ間隔、縦方向に１０ｃｍ間隔で、直径２ｃｍ、高さ５ｃｍの円筒形障害物を合計３８本設置した。容器内に深さ２ｃｍまで水を入れ、容器の縦方向一端中央部から水面浮遊型農薬製剤０．２ｇを投入し、２分後の縦方向の拡展距離を測定した。結果を表２に記載した。
<Ductile test>
A total of 38 cylindrical obstacles with a diameter of 2 cm and a height of 5 cm were installed at intervals of 3.3 cm in the horizontal direction and at intervals of 10 cm in the vertical direction of a stainless steel rectangular container having a length of 200 cm, a width of 10 cm, and a depth of 4 cm. Water was poured into the container to a depth of 2 cm, 0.2 g of the water-floating pesticide preparation was added from the center of one end in the vertical direction of the container, and the spread distance in the vertical direction after 2 minutes was measured. The results are shown in Table 2.
表２に示されるように、本発明の非イオン界面活性剤（Ｘ－１）～（Ｘ－１３）を用いた実施例１～１３の水面浮遊型農薬製剤は、比較用の非イオン性界面活性剤（Ｘ’－１）～（Ｘ’－８）を用いた比較例１～８の水面浮遊型農薬製剤と比べ拡展距離が長く、拡展性に優れていた。
また、実施例１４～１６と比較例９～１０との比較から、本発明の非イオン性界面活性剤（Ｘ）を面浮遊型農薬製剤用拡展剤として用いた場合は、水面浮遊型農薬製剤用拡展剤の配合量が少ない場合でも拡展性に優れていることが分かる。
As shown in Table 2, the water-floating pesticide formulations of Examples 1 to 13 using the nonionic surfactants (X-1) to (X-13) of the present invention have a nonionic surfactant for comparison. Compared with the water-floating pesticide formulations of Comparative Examples 1 to 8 using the activators (X'-1) to (X'-8), the spread distance was long and the spreadability was excellent.
Further, from the comparison between Examples 14 to 16 and Comparative Examples 9 to 10, when the nonionic surfactant (X) of the present invention is used as a spreading agent for a surface-floating pesticide formulation, a water-floating pesticide is used. It can be seen that the expandability is excellent even when the blending amount of the spreading agent for the formulation is small.
本発明の水面浮遊型農薬製剤用拡展剤は、障害物が存在する水面での拡展性に優れ、１度の施用で広範囲に農薬原体を広げることができるため、防除作業の省力に貢献する。 The spreading agent for water-floating pesticide formulations of the present invention has excellent spreadability on the water surface where obstacles are present, and can spread the pesticide drug substance over a wide range with one application, thus saving labor in pest control work. To contribute.
Claims (6)
前記水面浮遊型農薬製剤用拡展剤が含有する全ての（Ｘ）におけるＲ１中のメチル基の１分子あたりの数平均個数が３．０以上であり、
前記水面浮遊型農薬製剤用拡展剤が含有する全ての（Ｘ）におけるｐの１分子あたりの数平均ｐＡが１～５であり、
前記水面浮遊型農薬製剤用拡展剤が含有する全ての（Ｘ）におけるｑの１分子あたりの数平均ｑＡが１～８であり、
一般式（１）において、ｐＡ＋ｑＡが５～１０であり、ｐＡ＜ｑＡである水面浮遊型農薬製剤用拡展剤。
Ｒ１Ｏ－［（Ｃ３Ｈ６Ｏ）ｐ／（Ｃ２Ｈ４Ｏ）ｑ］Ｈ （１）
［一般式（１）中、Ｒ１は炭素数８～１１のアルキル基を表し；ｐは０～１００の整数であり；ｑは０～１００の整数であり；［（Ｃ３Ｈ６Ｏ）ｐ／（Ｃ２Ｈ４Ｏ）ｑ］は、ｐ個あるプロピレンオキシ基と、ｑ個あるエチレンオキシ基の結合順序が任意であることを表す。］ A spreading agent for a water-floating pesticide formulation containing a nonionic surfactant (X) represented by the following general formula (1).
The number average number of methyl groups in R1 in all (X) contained in the spreading agent for water-suspended pesticide formulations is 3.0 or more per molecule.
The number average pA per molecule of p in all (X) contained in the spreading agent for water - floating pesticide formulations is 1 to 5.
The number average q A per molecule of q in all (X) contained in the spreading agent for water-floating pesticide formulations is 1 to 8.
In the general formula (1), p A + q A is 5 to 10, and p A <q A , which is a spreading agent for a water-floating pesticide formulation.
R 1 O- [(C 3 H 6 O) p / (C 2 H 4 O) q ] H (1)
[In general formula (1), R 1 represents an alkyl group having 8 to 11 carbon atoms; p is an integer of 0 to 100; q is an integer of 0 to 100; [(C 3 H 6 O). p / (C 2 H 4 O) q ] indicates that the bonding order of the p propyleneoxy groups and the q ethyleneoxy groups is arbitrary. ]
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