JP3822288B2 - Acaricide and acaricide-containing dispersion containing the same - Google Patents

Description

【００７３】
【比較製造例１】
製造例１で油相液を調製する際に、水不溶性のポリオールであるヒマシ油、および触媒であるジブチルチンジラウレートを用いなかった。それ以外は製造例１と同様の操作を行った。得られた乳化液を遠心分離したところ、マイクロカプセルは得られなかった。さらに、この乳化液を、２５℃で８時間攪拌して反応を完結させることにより、ピレトリンを内包したマイクロカプセルを得た。このマイクロカプセルの粒子を遠心分離により取り出し、製造例１と同様にして電子顕微鏡で観察したところ、粒子径４μｍの粒子が観察された。そして、このマイクロカプセルを割ったものを電子顕微鏡で観察したところ、芯部にピレトリンのみが存在しており、単に、ピレトリンが内包された芯−殻構造をとるマイクロカプセルであることがわかる。
【００７４】
また、上記油相液を、２５℃で１０時間そのまま放置したが、ゲル化状態とはならず液状のままであった。
【００７５】
これらのことから、比較製造例１で得られたマイクロカプセルは、芯部がピレトリンのみからなる従来のマイクロカプセルであることが明らかである。
【００７６】
【実施例１〜６、比較例１】
〔ダニ忌避効果判定試験〕
前記製造例１〜６および比較製造例１で得られたピレトリン内包マイクロカプセル分散液を各々試験布処理薬剤とし、下記に示す試験方法に従って防ダニ試験、耐洗濯性評価を行った。その結果を後記の表２に示す。
【００７７】
〔試験布処理条件〕
前記各試験布処理薬剤を１％に希釈した処理液に、試験布（綿１００％ブロード）を浸漬した後、マングルにより、試験布への処理薬剤の有効成分量が０．１％となるよう絞った。その後、予備乾燥（１２０℃×２分）を行った。これを用いて下記に示す防ダニ試験を行い、さらに下記に示すようにして耐洗濯性の評価を行った。
【００７８】
〔防ダニ試験〕
供試ダニ：ヤケヒョウヒダニ
試験項目：忌避効果判定試験（侵入阻止法）
試験方法：直径３５ｍｍ×高さ１０ｍｍのプラスチックシャーレを直径９０ｍｍ×高さ２０ｍｍのガラスシャーレの中央部に設置し、これを粘着シート上に載置した。上記直径３５ｍｍのプラスチックシャーレと直径９０ｍｍのガラスシャーレの間によく繁殖したと認められるダニ培地を生存ダニ数として約１００００個体均一に投入した。上記中央部の直径３５ｍｍのプラスチックシャーレには、シャーレの底面と密着するようにくり抜いた処理試料（薬剤処理済み試験布）を敷き込み、中央部に誘引物質として粉末飼料０．０５ｇを置いた。上記同様の操作を対照（未処理）試料についても行った。このようにしてセットしたシャーレを粘着シートごと２７ｃｍ×１３ｃｍ×９ｃｍのプラスチック製食品保存用密閉容器に入れ、飽和食塩水を用いて湿度７５±５％に保ち、温度２５±１℃の恒温器中で保存した。そして、２４時間後、各試料およびシャーレ内面のダニを水洗法、誘引物質とした粉末飼料中のダニを飽和食塩水浮遊法により、生存ダニ数を観察した。そして、ダニ忌避効果を下記の算定方法によりダニ忌避率として算定し判定した。
【００７９】
〔算定方法〕
【数１】

【００８０】
〔耐洗濯性試験〕
上記処理薬剤処理布を、洗剤（ザブコーソＹＫ、花王社製）２ｇ／リットルを含む水中で、温度４０℃、浴比１：３０（試験布：処理液）により、家庭洗濯機を用いて５分間洗濯した。ついで、２分間のすすぎ、２分間の脱水、さらに２分間のすすぎ、２分間の脱水を行った。これを１サイクルとして、１サイクル、１０サイクル、２０サイクル、３０サイクル時において、前記防ダニ試験を行った。
【００８１】
【表２】

【００８２】
つぎに、前記製造例１〜６で得られたピレトリン内包マイクロカプセル分散液に水溶性ポリウレタン樹脂が配合された例について述べる。
【００８３】
【製造例７】
〔水溶性ポリウレタン樹脂の製造〕
グリセリンに、エチレンオキシドおよびプロピレンオキシドを付加重合させたもの、および、プロピレンオキシドとエチレンオキシドのランダム付加重合体の混合物（重量比２０：８０）を、ＨＭＤＩと反応させて（９０〜１００℃）ポリウレタン化し、末端イソシアネート基を、メチルエチルケトオキシム（ＭＥＫＯ）でブロックし、さらに冷却して水を添加して熱反応水溶性ポリウレタン樹脂（重量平均分子量１万５千）が分散した分散体（Ｂ１）を作製した。
【００８４】
〔防ダニ剤含有分散液の製造〕
つぎに、前記製造例１で得られたピレトリン内包マイクロカプセルを含有した分散液（マイクロカプセル固形分２０％）１００部に対して、上記熱反応水溶性ポリウレタン樹脂が分散した分散体（Ｂ１）を４０部添加し、さらにジブチルチンジラウレートを０．８％添加し、攪拌することによって目的とする防ダニ剤含有分散液を得た。この分散液の固形分濃度は２５％であった。
【００８５】
【製造例８〜１２】
まず、下記に示す製法に従って、水溶性ポリウレタン樹脂α〜εを作製した。
【００８６】
〔水溶性ポリウレタン樹脂α〕
グリセリンにプロピレンオキシドを付加重合させたもの、および、プロピレンオキシドとエチレンオキシドのランダム付加重合体の混合物（重量比２０：８０）を、ＨＭＤＩと反応させて（９０〜１００℃）ポリウレタン化し、末端イソシアネート基を、無水重亜硫酸ソーダでブロックし、さらに冷却して水を添加して水溶性ポリウレタン樹脂αが分散した分散体α（Ｂ１）を作製した。
【００８７】
〔水溶性ポリウレタン樹脂β〕
無水マレイン酸と１，６−ヘキサンジオールとのポリエステルポリオールと、ポリエチレングリコールの混合物（重量比５：１）を、ＨＭＤＩと反応させて（９０〜１００℃）ポリウレタン化し、末端イソシアネート基を、無水重亜硫酸ソーダでブロックし、さらに冷却して水を添加して水溶性ポリウレタン樹脂βが分散した分散体β（Ｂ１）を作製した。
【００８８】
〔水溶性ポリウレタン樹脂γ〕
グリセリンにプロピレンオキシドを付加重合させたもの、および、グリセリンにエチレンオキシドおよびプロピレンオキシドをランダム付加重合させたもの（エチレンオキシドとプロピレンオキシドの重量比１３：８７）の混合物（重量比５０：５０）を、ＨＭＤＩと反応させて（９０〜１００℃）ポリウレタン化し、末端イソシアネート基を、無水重亜硫酸ソーダでブロックし、さらに冷却して水を添加して水溶性ポリウレタン樹脂γが分散した分散体γ（Ｂ１）を作製した。
【００８９】
〔水溶性ポリウレタン樹脂δ〕
ブチレンアジペートと、プロピレンオキシドとエチレンオキシドのランダム付加重合体と、ポリカプロラクトンの混合物（重量比１２：４：１）を、ＨＭＤＩと反応させて（９０〜１００℃）ポリウレタン化し、水を添加して、末端イソシアネート基の一部をアミノエチルスルホン酸ソーダと反応させ、さらに冷却して水溶性ポリウレタン樹脂δが分散した分散体δ（Ｂ２）を作製した。
【００９０】
〔水溶性ポリウレタン樹脂ε〕
ポリテトラメチレングリコールと、プロピレンオキシドとエチレンオキシドのランダム付加重合体と、ポリエチレングリコールと、１，４−ブタンジオールと、トリメチロールプロパンの混合物（重量比５０：４：４：４：１．５）を、水添ＭＤＩと反応させて（９０〜１００℃）ポリウレタン化し、さらに活性剤（ジスチレン化フェノールのエチレンオキシド付加物）を固形分１００部に対して５部添加して、ついで、大量の水を添加し乳化させ、末端イソシアネート基をエチレンジアミンで架橋させて水溶性ポリウレタン樹脂εが分散した分散体ε（Ｂ２）を作製した。
【００９１】
そして、前記製造例２〜６で作製した各ピレトリン内包マイクロカプセル分散液（マイクロカプセル固形分２０％）１００部に対して、上記各水溶性ポリウレタン樹脂α〜εが分散した分散体α〜εを固形分が１０部となるよう４０部添加した。各製造例８〜１２に対して用いた水溶性ポリウレタン樹脂α〜ε（分散体α〜ε）の組み合わせを、各水溶性ポリウレタン樹脂α〜εの重量平均分子量とともに下記の表３に示す。なお、製造例８〜１０に関しては、上記分散体を添加した後、さらにジブチルチンジラウレートを０．８％添加し、攪拌することによって目的とする防ダニ剤含有分散液を得た。上記分散液の固形分濃度は２５％であった。
【００９２】
【表３】

【００９３】
つぎに、前記ピレトリン内包マイクロカプセル分散液に、合成樹脂の水性エマルジョンが配合された例について述べる。
【００９４】
【製造例１３】
前記製造例１のピレトリン内包マイクロカプセルが分散した液（マイクロカプセル固形分２０％）１００部に対して、酢酸ビニル−エチレン共重合樹脂の水性エマルジョン（濃度５０％、ヘキスト合成社製「モビニール１８０Ｅ」）を固形分が１０部となるように２０．０部添加した。この分散液の固形分濃度は２５％であった。
【００９５】
【実施例７〜１３】
上記製造例７〜１３で得られた各分散液を実施例１〜６と同様にして防ダニにおける耐洗濯性の試験を前記の方法に従って実施した。ただし、製造例７〜１０を使用した試験布は予備乾燥（１２０℃×２分）の後、キュアー（１６０℃×２分）行った。これらの結果を下記の表４に示した。
【００９６】
【表４】

【００９７】
上記表４の結果から、ピレトリン内包マイクロカプセル分散液に、バインダー成分として上記各水溶性ポリウレタン樹脂α〜εおよび合成樹脂の水性エマルジョン（酢酸ビニル−エチレン共重合樹脂）が配合されたものは、先の実施例１〜６（バインダー成分なし）と比較して、より一層耐洗濯性に優れていることが明らかである。
【００９８】
【発明の効果】
以上のように、本発明は、ピレスロイド系殺虫剤を含有するゲル状ポリウレタン樹脂からなる芯部が、ポリウレア樹脂からなる殻部で被覆された特殊な芯部構造を有するピレスロイド系殺虫剤内包マイクロカプセルを含有する防ダニ剤であり、ピレスロイド系殺虫剤あるいはピレスロイド系殺虫剤を含む疎水性媒体に、多官能性イソシアネート、水不溶性のポリオールおよび触媒を溶解して油相とし、これを乳化剤を添加した水中に乳化分散した後、油滴界面およびその内部で反応させることにより得られるものである。このように、上記マイクロカプセルが特殊な芯部構造をとることから、ゲル状ポリウレタン樹脂に含有されたピレスロイド系殺虫剤はポリウレタン樹脂から経時的に徐々にしか放出されず、長期にわたってその薬効を発揮させることが可能となる。また、上記ピレスロイド系殺虫剤内包マイクロカプセルが分散された分散液は、紙や繊維等の各種材料に対して、塗布、噴霧あるいは含浸させる等、様々な形態をとって使用可能となり、上記優れた残効性を有効に発揮することができる。
【００９９】
さらに、本発明のピレスロイド系殺虫剤内包マイクロカプセルが分散された分散液に、バインダー成分としての、水溶性ポリウレタン樹脂、および、合成樹脂の水性エマルジョンの少なくとも一方を配合することにより、この分散液を用いた処理対象となる各種材料の耐洗濯性が一層向上する。
【図面の簡単な説明】
【図１】本発明のピレトリン内包マイクロカプセルの一例を模式的に示す断面図である。
【符号の説明】
１ ゲル状ポリウレタン樹脂
２ ポリウレア樹脂製の殻部[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an acaricide containing a microcapsule containing a pyrethroid insecticide and an anti-acaricide-containing dispersion containing the same.
[0002]
[Prior art]
Conventionally, pyrethroid insecticides are emulsified in water with an active agent and processed into paper, clothing, etc., and have a medicinal effect as an acaricide.
[0003]
[Problems to be solved by the invention]
However, when it is used as an acaricide as described above, for example, the washing resistance is poor and the effect cannot be sustained sufficiently over a long period of time.
[0004]
The object of the present invention is to provide an acaricide capable of exerting the medicinal effects of a pyrethroid insecticide encapsulated over a long period of time, and an anti-acaricide-containing dispersion containing the same.
[0005]
[Means for Solving the Problems]
In order to achieve the above object, the present invention includes a microcapsule having a core formed of a gel-like polyurethane resin containing a pyrethroid insecticide and a shell covering the core formed of a polyurea resin. The acaricide is an oil phase obtained by dissolving a polyfunctional isocyanate, a water-insoluble polyol and a catalyst in a hydrophobic medium containing a pyrethroid insecticide or a pyrethroid insecticide. The acaricide is obtained by emulsifying and dispersing in water containing an emulsifier and then reacting at the oil droplet interface and inside thereof. The acaricide is dispersed in an aqueous medium. The anti-tick agent-containing dispersion is the second gist.
[0006]
The inventors of the present invention have made a series of studies in order to obtain microcapsules that can exhibit the medicinal effects of pyrethroid insecticides encapsulated over a long period of time. In the process, as a result of further research centering on the structure of the core part containing the pyrethroid insecticide, not the shell part, in the microcapsule having a core-shell structure, the core part contains the pyrethroid insecticide as it is. However, when a pyrethroid insecticide is contained in the gel-like polyurethane resin, the pyrethroid insecticide is strongly retained in the gel-like polyurethane resin, and as a result, it has been found that the medicinal effect can be exhibited over a long period of time. Reached.
[0007]
Furthermore, a dispersion liquid in which microcapsules containing pyrethroid insecticides having a special core structure dispersed in an aqueous medium are used in various forms such as coating, spraying or impregnation on paper or fiber. be able to.
[0008]
And in the said dispersion liquid, it contains at least one of water-soluble polyurethane resin and the aqueous emulsion of a synthetic resin as a binder component with a special pyrethroid type insecticide inclusion microcapsule, The pyrethroid type insecticide inclusion microcapsule dispersion liquid Is used for processing paper or clothing, the washing resistance is improved and the tick-proof performance can be further exhibited over a long period of time.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in detail.
[0010]
The acaricide of the present invention comprises a microcapsule containing a pyrethroid insecticide as an active ingredient, and the microcapsule has a core-shell structure in which a core part is covered with a shell part. The part is formed of a gel-like polyurethane resin containing a pyrethroid insecticide, and the shell is formed of a polyurea resin.
[0011]
Examples of pyrethroid insecticides contained and retained in the gel-like polyurethane resin in the core include, for example, aresulin, resmethrin, permethrin, cyhalothrin, cyfluthrin, fenpropatoline, tralomethrin, cycloprotorin, fenvalerate, fluntrinate, fullvalid. Examples include synthetic pyrethroid insecticides such as nate and etofenprox, and natural pyrethroid insecticides such as pyrethrin.
[0012]
And in the acaricide of the present invention, the microcapsule encapsulating the pyrethroid insecticide, which is an active ingredient, is contained in the core of the pyrethroid insecticide or the hydrophobic medium containing the pyrethroid insecticide, It is obtained by dissolving polyfunctional isocyanate, water-insoluble polyol and catalyst into an oil phase, emulsifying and dispersing this in water (aqueous phase) to which an emulsifier has been added, and then reacting at the oil droplet interface and inside thereof. .
[0013]
In the above reaction, the reaction is completed in 20 to 40 ° C. in about 0.5 to 2 hours, and a microcapsule dispersion containing a pyrethroid insecticide is produced in an extremely short time and at a low temperature as compared with the conventional method. Can do.
[0014]
First, each component constituting the oil phase will be described.
[0015]
The oil phase is composed of a pyrethroid insecticide or a hydrophobic medium containing a pyrethroid insecticide, a polyfunctional isocyanate, a water-insoluble polyol, and a catalyst.
[0016]
The pyrethroid insecticide may be used as it is, but may be contained in a hydrophobic medium as described above. Preferably, a pyrethroid insecticide is used as it is from the viewpoint of the strength of the microcapsule.
[0017]
The hydrophobic medium is used as a volatility inhibitor for pyrethroid insecticides, and examples thereof include esters such as benzyl benzoate and dioctyl phthalate, and vegetable oils such as mineral oils and cottonseed oils.
[0018]
The polyfunctional isocyanate used to form the shell and the gel core is phenylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, polymeric diphenylmethane diisocyanate, isophorone diisocyanate. , Triphenylmethane triisocyanate and the like, and isocyanurate-modified and burette-modified products of the above polyfunctional isocyanates, and isocyanate prepolymers that are adducts with polyols such as trimethylolpropane and hexanetriol. . These may be used alone or in combination of two or more.
[0019]
Examples of polyols other than trimethylolpropane and hexanetriol include aliphatic polyols such as ethylene glycol, propylene glycol, and hexanediol, aromatic polyols such as xylylene glycol, polyhydric phenols such as hydroquinone and catechol, or these polyhydric phenols. And a polyol prepolymer such as a polyester polyol and a polyether polyol. These may be used alone or in combination of two or more. Of these polyols, it is preferable to use trimethylolpropane from the viewpoint that pyrethroid insecticide-encapsulating microcapsules having excellent residual effects can be obtained.
[0020]
Among the polyfunctional isocyanates, hexamethylene diisocyanate and isophorone diisocyanate are preferably used from the viewpoint of obtaining a non-yellowing pyrethroid insecticide-encapsulating microcapsule and economical.
[0021]
Specific examples of the water-insoluble polyol used together with the polyfunctional isocyanate include polyether polyols such as castor oil, polyoxyalkylene polyol, polytetramethylene ether glycol, condensed polyester polyol, lactone polyester diol, and polycarbonate. Examples thereof include polyester polyols such as diols. These may be used alone or in combination of two or more. Of these water-insoluble polyols, castor oil is preferably used from the viewpoint of reactivity and residual effect. The blending amount of the water-insoluble polyol is preferably set to 10 to 300 parts, particularly preferably 50 to 200 parts, with respect to 100 parts by weight (hereinafter abbreviated as “parts”) of the polyfunctional isocyanate. When the blending amount of the water-insoluble polyol is less than 10 parts or more than 300 parts, that is, outside the above blending amount range, it is possible to obtain a pyrethroid-based insecticide-containing microcapsule having a gel-like core. There is a tendency to become difficult. Of these water-insoluble polyols, those having at least two hydroxyl groups must be used. That is, when one hydroxyl group is used, the core portion is not crosslinked and the core portion is not gelled. In addition, if a polyol that dissolves in water is used, it is difficult to produce microcapsules, which is not suitable for use. From this point, the above water-insoluble polyol is used.
[0022]
Furthermore, as a catalyst used with the said polyfunctional isocyanate and water-insoluble polyol, an organotin compound is used, for example, tri-n-butyltin acetate, n-butyltin trichloride, dimethyltin dichloride, dibutyltin dilaurate. And trimethyltin hydroxide. These catalysts may be used as they are, or dissolved in a solvent such as ethyl acetate so as to have a concentration of 0.1 to 20% by weight (hereinafter abbreviated as “%”), which is an isocyanate component in the oil phase. You may add so that it may become 0.01-1 part as solid content with respect to 100 parts of polyfunctional isocyanate. Thus, the blending amount of the catalyst is set so as to be 0.01 to 1 part with respect to 100 parts of the polyfunctional isocyanate as a solid content in any case as it is or dissolved in a solvent. The amount is preferably 0.05 to 0.5 part. That is, if the amount of the catalyst is too small, such as less than 0.01 part, the polyfunctional isocyanate is used for the shell formation reaction before the gel polyurethane resin in the core part is formed. This is because when the shell part is formed and, on the other hand, more than 1 part, the core part is extremely rapidly formed, and the target pyrethroid insecticide-containing microcapsules tend to be hardly obtained.
[0023]
By adding the catalyst, the reaction between the polyfunctional isocyanate in the oil phase and the water-insoluble polyol reacts more rapidly than the reaction between the polyfunctional isocyanate and water in the water phase. Therefore, in the formation of the core-shell microcapsules, the core is formed in a gel-like polyurethane resin containing a pyrethroid insecticide, and the outer periphery (shell) of the core is formed in a polyurea resin. Thus, pyrethroid insecticide-containing microcapsules having a special structure of the present invention can be obtained.
[0024]
In addition, it is preferable not to contain a solvent in the oil phase comprised from said each component. That is, if the solvent is contained, the following problems occur. (1) Due to the odor of the solvent itself, a preferable product cannot be obtained. (2) In the case of water-soluble solvents, the water-soluble solvent shifts to the aqueous phase when microcapsules are formed, and the pyrethroid insecticide also shifts from the oil phase to the water phase along with this transition, and the desired pyrethroid insecticide inclusion This is because it becomes difficult to obtain microcapsules.
[0025]
Next, an aqueous phase in which the oil phase is emulsified and dispersed will be described.
[0026]
As the emulsifier added to the aqueous phase, anionic, cationic, nonionic, amphoteric water-soluble polymer substances and various surfactants can be used.
[0027]
Examples of the anionic polymer substance include natural polymers such as gum arabic and alginic acid, semi-synthetic polymers such as carboxymethylcellulose, sulfated cellulose, and phthalated gelatin, carboxy-modified polyvinyl alcohol, styrenesulfonic acid polymers, Examples thereof include synthetic polymers such as polymers and maleic anhydride copolymers.
[0028]
Examples of the cationic polymer substance include cationized starch.
[0029]
Examples of the nonionic polymer substance include polyvinyl alcohol, methyl cellulose, hydroxyethyl cellulose, xanthan gum, and the amphoteric polymer substance includes gelatin.
[0030]
Further, as the above various surfactants, anionic surfactants such as sodium lauryl sulfate, sodium lauryl benzene sulfonate, sodium polyoxyethylene alkylphenyl ether sulfate, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, etc. Nonionic surfactants, cationic surfactants such as alkyltrimethylammonium salts, and amphoteric surfactants such as alkylbetaine type and alkylimidazoline type are exemplified.
[0031]
These emulsifiers are generally prepared by adding an aqueous solution concentration of 1 to 20% with respect to water to obtain an aqueous phase.
[0032]
In the present invention, the pyrethroid insecticide-encapsulating microcapsule dispersion is produced, for example, as follows. That is, an oil phase liquid and an aqueous phase are prepared using the above-described components. Then, the prepared oil phase liquid is added to the aqueous phase, and stirred and reacted under predetermined conditions, whereby the core part is a core-shell structure covered with the shell part, and the core part is a pyrethroid type. A pyrethroid insecticide-encapsulated microcapsule dispersion is produced in which a special pyrethroid insecticide-encapsulated microcapsule formed of a gel-like polyurethane resin containing an insecticide and having a shell formed of a polyurea resin is dispersed. Subsequently, the microcapsules containing pyrethroid insecticides can be obtained by separating water from this dispersion by a predetermined method.
[0033]
In the pyrethroid insecticide-encapsulated microcapsule dispersion obtained as described above, the content of the pyrethroid insecticide-encapsulated microcapsule in the dispersion is, for example, coated, sprayed, and impregnated on paper or fiber. Considering the expected medicinal properties and retention when used, it is preferable to set the content in the range of 2 to 70% in the dispersion.
[0034]
The mixing ratio of the oil phase liquid and the water phase is preferably set so that the water phase is 0.5 to 50 with respect to the oil phase 1 in weight ratio. Particularly preferably, the water phase is 0.8 to 1.5 with respect to the oil phase 1. That is, if the water phase is less than 0.5 relative to the oil phase 1, it is difficult to make water a continuous phase. Further, when the aqueous phase exceeds 50, there is a tendency that only products having a microcapsule concentration too low can be obtained.
[0035]
As said stirring conditions, generally it is set to 500-5000 rpm, Most preferably, it is 1000-3000 rpm. Further, the reaction conditions are set at 20 to 40 ° C. for a short time of about 0.5 to 2 hours as described above.
[0036]
It is also possible to obtain only pyrethroid insecticide-encapsulated microcapsules by separating water from the dispersion of pyrethroid insecticide-encapsulated microcapsules. The separation method is not particularly limited, and conventionally known methods such as a centrifugal separation method, a pressure filtration method, a vacuum suction filtration method and the like can be mentioned. Furthermore, the pyrethroid insecticide-encapsulating microcapsules obtained by the separation may be appropriately dried by a conventionally known method such as heat drying, spray drying, vacuum drying, freeze drying and the like.
[0037]
Thus, about the production | generation mechanism in which the special pyrethroid type insecticide inclusion microcapsule is obtained, the present inventors guess as follows from the knowledge obtained by the research of a series of microcapsules. That is, due to the presence of a catalyst which is one of the components constituting the oil phase, when the oil phase liquid containing this catalyst is added to the aqueous phase and stirred, the polyfunctional isocyanate and the water-insoluble polyol in the oil phase This reaction is faster than the reaction between the polyfunctional isocyanate and water. For this reason, in the formation of core-shell microcapsules, first, a gel-like polyurethane resin containing a pyrethroid insecticide as a core is produced by reaction, and then, on its surface, polyfunctional isocyanate and water It is considered that the polyurea resin reacts and reacts to form a shell.
[0038]
As another method for producing a microcapsule dispersion containing pyrethroid insecticides for use in the present invention, the following method may also be mentioned. That is, the oily liquid containing an organic tin compound is added to an aqueous liquid containing a polyvalent amine compound having at least two amino groups and an emulsifier, and emulsified and dispersed. According to this method, the polyhydric amine is contained in the aqueous liquid, so that the polyfunctional isocyanate in the oil phase and the polyhydric amine in the aqueous liquid react very quickly at the interface of the oil droplets. After the formation of the shell part, the catalysis of the organotin compound causes the polyfunctional isocyanate to react with the water-insoluble polyol, and the gelling of the inside of the shell part begins, and the gel contains a pyrethroid insecticide A core of polyurethane resin is formed, and a dispersion of pyrethroid insecticide-encapsulating microcapsules in which a core made of a gel polyurethane resin containing a pyrethroid insecticide used in the present invention is formed as a shell is obtained.
[0039]
A schematic diagram of the microcapsules containing pyrethroid insecticides thus obtained is shown in FIG. As shown in the drawing, a core-shell structure is formed in which the outer periphery of a gel-like polyurethane resin 1 containing a pyrethroid insecticide as a core is encapsulated by a shell 2 made of polyurea resin. The particle size of the pyrethroid insecticide-encapsulating microcapsules of the present invention is not particularly limited, but is generally set in the range of 0.5 to 500 μm.
[0040]
In the present invention, it can be confirmed by observing the cross section of the obtained pyrethroid insecticide-encapsulating microcapsule with an electron microscope that the core of the microcapsule encapsulating pyrethroid insecticide is in a gelled state. In addition, as a result of the extraction operation of the residual water-insoluble polyol with a solvent using the obtained pyrethroid insecticide-encapsulated microcapsules, an extract cannot be obtained, so that the water-insoluble polyol is completely mixed with the polyfunctional isocyanate. It reacts and it is judged that the inside is a gelled state. Furthermore, when a pyrethroid insecticide, a polyfunctional isocyanate, a water-insoluble polyol, and a catalyst are mixed at 20 to 40 ° C. and left for 0.5 to 2 hours, the fluidity is lost and the gelled state is obtained. Is also inferred.
[0041]
Next, after manufacturing a liquid in which the special pyrethroid insecticide-containing microcapsules are dispersed in an aqueous medium, at least one of a water-soluble polyurethane resin and an aqueous emulsion of a synthetic resin is used as a binder component in the dispersion. By blending, it is possible to obtain the effect of improving the durability of the mite-proofing effect and the washing resistance, which are the problems of the present invention.
[0042]
Among the binder components, it is preferable to use at least one of the following (B1) and (B2) as the water-soluble polyurethane resin.
[0043]
(B1) A heat-reacting water-soluble polyurethane resin in which a terminal isocyanate group is blocked with a blocking agent in a reaction product obtained by reacting the following (a1) and (b1).
(A1) At least one of polyether polyol and polyester polyol.
(B1) Diisocyanate component.
(B2) A water-soluble polyurethane resin obtained by crosslinking a terminal isocyanate group of at least one of water and an amine of a reaction product obtained by reacting the following (a2) and (b2).
(A2) At least one of polyether polyol and polyester polyol.
(B2) Diisocyanate component.
[0044]
First, the heat reaction water-soluble polyurethane resin (B1) will be described.
[0045]
Examples of the polyether polyol (a1) include block polymers of ethylene oxide and propylene oxide, or random addition polymers thereof, propylene oxide of glycerin, ethylene oxide or random addition polymers thereof, and addition polymers of propylene oxide. It is done.
[0046]
Examples of the polyester polyol (a1) include polyester polyols of maleic anhydride and 1,4-butanediol, polyester polyols of maleic anhydride and 1,6-hexanediol, and the like.
[0047]
As the isocyanate component (b1), aliphatic diisocyanate is preferably used from the viewpoint of preventing yellowing. Specifically, hexamethylene diisocyanate (HMDI), trimethylxylene diisocyanate (TMXDI), isophorone diisocyanate (IPDI), and the like. Is given.
[0048]
Furthermore, examples of the blocking agent for blocking the terminal isocyanate group of the reaction product obtained by reacting (a1) and (b1) in (B1) include anhydrous sodium bisulfite and methyl ethyl ketoxime. .
[0049]
The heat-reactive water-soluble polyurethane resin (B1) is obtained, for example, as follows. That is, the above (a1) and (b1) are reacted at 90 to 100 ° C. (until the terminal isocyanate group becomes about 3 to 4%), and the unreacted terminal isocyanate group is blocked with the blocking agent, After cooling, activator is added as needed. Next, water is added to this to make an emulsion.
[0050]
The heat-reactive water-soluble polyurethane resin (B1) thus obtained preferably has a weight average molecular weight of 5,000 to 20,000 from the viewpoint of heat reactivity.
[0051]
Next, the water-soluble polyurethane resin (B2) will be described.
[0052]
The polyether polyol of (a2) includes polytetramethylene glycol, a random addition polymer of ethylene oxide propylene oxide, or a random addition polymer thereof, an addition polymer of propylene oxide, an addition polymer of ethylene oxide of bisphenol A, bisphenol. A propylene oxide addition polymer of A, 1,4-butanediol, trimethylolpropane and the like.
[0053]
Examples of the polyester polyol (a2) include butylene adipate, hexylene carbonate, and ethylene terephthalate.
[0054]
Examples of the isocyanate component (b2) include tolylene diisocyanate-80 (TDI-80), HMDI, diphenylmethane diisocyanate (MDI), IPDI and the like.
[0055]
Furthermore, ethylenediamine, hydrazine, diethylenetriamine, etc. are mention | raise | lifted as an amine which bridge | crosslinks a terminal isocyanate group of the reaction product formed by making said (a2) and (b2) react in said (B2).
[0056]
The water-soluble polyurethane resin (B2) is obtained as follows, for example. That is, the above (a2) is reacted with (b2) in a solvent (70 to 75 ° C.) until the desired amount of terminal isocyanate groups. Next, it is cooled, an activator is added as required, and a large amount of water is further added to hydrocrosslink the terminal isocyanate groups. At this time, diamine can also be added for efficient crosslinking.
[0057]
The water-soluble polyurethane resin (B2) thus obtained preferably has a weight average molecular weight of 30,000 or more from the viewpoint of washing resistance. More preferably, the weight average molecular weight is 100,000 or more.
[0058]
And as a water-soluble polyurethane resin mix | blended with the pyrethroid type insecticide inclusion microcapsule dispersion liquid in this invention, it is especially (B1) to use (B1) from the point of washing resistance among the said (B1) and (B2). preferable. About the said (B1) component, in order to improve a binder force, it is preferable to add the said organotin compound 0.5 to 1.0% with respect to a microcapsule dispersion liquid.
[0059]
The addition amount of at least one of the above (B1) and (B2) is 30 to 100%, more preferably 50 to 80% in terms of solid content with respect to the solid content of the special pyrethroid insecticide-containing microcapsule dispersion. Set to a percentage.
[0060]
Among the binder components, the synthetic resin aqueous emulsion includes, for example, vinyl acetate resin, vinyl acetate-acrylic copolymer resin, vinyl acetate-ethylene copolymer resin, acrylic resin, acrylic-styrene copolymer resin, vinyl acetate-ethylene. -Aqueous emulsions such as vinyl chloride copolymer resin, vinyl acetate-maleate copolymer resin, acrylic-ethylene-vinyl acetate copolymer resin, vinylidene chloride resin. These synthetic resins may be used alone or in combination of two or more. Especially, it is preferable to use the aqueous emulsion of a vinyl acetate-ethylene copolymer resin from the point of washing resistance.
[0061]
The synthetic resin aqueous emulsion is used in a concentration of 30 to 60%, and the addition amount thereof is 30 to 100 in terms of solid content ratio relative to the solid content of the liquid in which the pyrethroid insecticide-containing microcapsules are dispersed. % Is preferably set, and more preferably 50 to 80%.
[0062]
An acaricide containing these binder components is prepared by adding the above-mentioned special pyrethroid insecticide-containing microcapsule dispersion to at least one of the above (B1) and (B2) or an aqueous emulsion of the above synthetic resin. Can be obtained by adding
[0063]
Such an anti-mite agent of the present invention containing a microcapsule containing a pyrethroid insecticide as an active ingredient may be used as it is, or the microcapsule containing a pyrethroid insecticide may be used as an active ingredient. And a dispersion containing at least one of the water-soluble polyurethane resin and the synthetic resin aqueous emulsion described above, for example, paper or fiber. It can be applied to various articles using an appropriate method such as coating or spraying on the surface, or dipping and impregnating the dispersion.
[0064]
Next, examples will be described together with comparative examples.
[0065]
First, prior to Examples, a microcapsule dispersion containing a pyrethroid insecticide (pyretrin) was produced.
[0066]
[Production Example 1]
110 parts of pyrethrin, 120 parts of an adduct of hexamethylene diisocyanate and trimethylolpropane (manufactured by Nippon Polyurethane, Coronate HL) (isocyanate component), 1 part of a 10% ethyl acetate solution of dibutyltin dilaurate (catalyst), 120 parts of castor oil ( A water-insoluble polyol) was mixed and dissolved to prepare an oil phase liquid. Subsequently, this oil phase liquid was added to 350 parts of a 10% aqueous solution of partially saponified polyvinyl alcohol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Gohsenol KM-11, saponification degree 80%) at 25 ° C. Emulsified solution was obtained by stirring at 1000 rpm for 5 minutes. Subsequently, the emulsion was stirred at 100 to 500 rpm for 1.5 hours at 25 ° C. to complete the reaction, thereby obtaining a microcapsule dispersion containing pyrethrin (pyrethroid insecticide). The microcapsule particles were taken out by centrifugation and observed with an electron microscope (JSM-T300, manufactured by JEOL Ltd.). As a result, particles with a particle size of 5 μm were observed. Furthermore, when the microcapsules were observed with an electron microscope, it was confirmed that the core was in a gelled state. This shows that the gel-like polyurethane resin (core part) containing pyrethrin is a special microcapsule having a core-shell structure encapsulated by a shell part made of polyurea resin (see FIG. 1).
[0067]
Further, using the obtained pyrethrin-encapsulated microcapsules, extraction operation of residual castor oil (water-insoluble polyol) with tetrahydrofuran was carried out, and no castor oil was detected. Also from this result, it is understood that castor oil is not present in the core part and is completely reacted with the isocyanate component, and the core part is a gel-like polyurethane resin.
[0068]
Furthermore, when the prepared oil phase liquid was allowed to stand at 25 ° C. for 1.5 hours, the fluidity was lost and a gelled state was obtained.
[0069]
From these facts, it is clear that the core part of the pyrethrin-encapsulated microcapsules obtained in Production Example 1 is gelled.
[0070]
[Production Examples 2-6]
As the pyrethrin, isocyanate component, catalyst, and water-insoluble polyol, the materials shown in Table 1 below were used in the proportions shown in the same table, and the intended pyrethrin-encapsulated microcapsule dispersion was produced in the same manner as in Production Example 1. The obtained pyrethrin-encapsulated microcapsules were taken out by centrifugation, and the particle diameter was measured by observation with an electron microscope in the same manner as in Production Example 1 and is shown in Table 1 below.
[0071]
Moreover, when the microcapsule was divided and the electron micrograph was taken similarly to manufacture example 1, it was confirmed that the core part has gelatinized in all. Further, in the same manner as described above, the extraction operation of the water-insoluble polyol and the reaction with only the oil phase liquid were carried out, and the same result as in Production Example 1 was obtained. From these, it is clear that the core part of the pyrethrin-encapsulating microcapsules of Production Examples 2 to 6 is gelled.
[0072]
[Table 1]

[0073]
[Comparative Production Example 1]
In preparing the oil phase liquid in Production Example 1, castor oil, which is a water-insoluble polyol, and dibutyltin dilaurate, which is a catalyst, were not used. Otherwise, the same operation as in Production Example 1 was performed. When the obtained emulsion was centrifuged, microcapsules were not obtained. Further, the emulsion was stirred at 25 ° C. for 8 hours to complete the reaction, thereby obtaining microcapsules enclosing pyrethrin. The microcapsule particles were taken out by centrifugation and observed with an electron microscope in the same manner as in Production Example 1. As a result, particles with a particle size of 4 μm were observed. When the microcapsules are observed with an electron microscope, it is found that only the pyrethrin is present in the core, and the microcapsules have a core-shell structure in which pyrethrin is included.
[0074]
The oil phase liquid was left as it was at 25 ° C. for 10 hours, but it did not become a gelled state but remained liquid.
[0075]
From these facts, it is clear that the microcapsule obtained in Comparative Production Example 1 is a conventional microcapsule whose core portion is composed only of pyrethrin.
[0076]
Examples 1-6, Comparative Example 1
[Tick repellent effect test]
Each of the pyrethrin-encapsulated microcapsule dispersions obtained in Production Examples 1 to 6 and Comparative Production Example 1 was used as a test cloth treatment agent, and an anti-mite test and washing resistance evaluation were performed according to the test methods described below. The results are shown in Table 2 below.
[0077]
[Test cloth treatment conditions]
After immersing the test cloth (cotton 100% broad) in a treatment solution in which each test cloth treatment chemical is diluted to 1%, the active ingredient amount of the treatment chemical on the test cloth is 0.1% by mangle. Squeezed. Thereafter, preliminary drying (120 ° C. × 2 minutes) was performed. Using this, the mite prevention test shown below was performed, and the washing resistance was evaluated as shown below.
[0078]
[Tick prevention test]
Test ticks: Leopard mite test item: repellent effect test (intrusion prevention method)
Test method: A plastic petri dish having a diameter of 35 mm and a height of 10 mm was placed in the center of a glass petri dish having a diameter of 90 mm and a height of 20 mm, and this was placed on an adhesive sheet. About 10,000 individual mite cultures, which were found to have proliferated well between the plastic petri dish with a diameter of 35 mm and a glass petri dish with a diameter of 90 mm, were uniformly added as the number of surviving mites. A treatment sample (medicine-treated test cloth) cut out so as to be in close contact with the bottom surface of the petri dish was laid on the plastic petri dish having a diameter of 35 mm at the center, and 0.05 g of powdered feed was placed as an attractant in the center. The same operation as described above was performed for the control (untreated) sample. The petri dish set in this way is put into a sealed plastic food storage container of 27 cm × 13 cm × 9 cm together with the pressure-sensitive adhesive sheet, kept in a humidity of 75 ± 5% using saturated saline, and kept in a thermostat at a temperature of 25 ± 1 ° C. Saved with. After 24 hours, the number of surviving ticks was observed by the water washing method for each sample and the mite on the inner surface of the petri dish, and the mite in the powder feed using the attractant by the saturated saline floating method. And the tick repellent effect was calculated and judged as a tick repellent rate by the following calculation method.
[0079]
[Calculation method]
[Expression 1]

[0080]
[Washing resistance test]
The above treatment chemical-treated cloth is washed in water containing 2 g / liter of detergent (Zabkoso YK, manufactured by Kao Corporation) at a temperature of 40 ° C. and a bath ratio of 1:30 (test cloth: treatment liquid) using a home washing machine for 5 minutes. Washed. Then, a 2-minute rinse, a 2-minute dehydration, a further 2-minute rinse, and a 2-minute dehydration were performed. With this as one cycle, the mite prevention test was conducted at 1 cycle, 10 cycles, 20 cycles, and 30 cycles.
[0081]
[Table 2]

[0082]
Next, an example in which a water-soluble polyurethane resin is blended in the pyrethrin-encapsulated microcapsule dispersion obtained in Production Examples 1 to 6 will be described.
[0083]
[Production Example 7]
[Production of water-soluble polyurethane resin]
Glycerin obtained by addition polymerization of ethylene oxide and propylene oxide and a mixture of a random addition polymer of propylene oxide and ethylene oxide (weight ratio 20:80) are reacted with HMDI (90 to 100 ° C.) to form a polyurethane, The terminal isocyanate group was blocked with methyl ethyl ketoxime (MEKO), further cooled and added with water to prepare a dispersion (B1) in which a heat-reactive water-soluble polyurethane resin (weight average molecular weight 15,000) was dispersed.
[0084]
[Manufacture of anti-tick agent-containing dispersion]
Next, with respect to 100 parts of the dispersion (microcapsule solid content 20%) containing the pyrethrin-encapsulated microcapsules obtained in Production Example 1, the dispersion (B1) in which the heat-reactive water-soluble polyurethane resin is dispersed is used. 40 parts were added, and 0.8% of dibutyltin dilaurate was further added, followed by stirring to obtain a target anti-acaricide-containing dispersion. The solid content concentration of this dispersion was 25%.
[0085]
[Production Examples 8 to 12]
First, according to the manufacturing method shown below, water-soluble polyurethane resin (alpha)-(epsilon) was produced.
[0086]
[Water-soluble polyurethane resin α]
A glycerin-added polymer of propylene oxide and a mixture of a random addition polymer of propylene oxide and ethylene oxide (weight ratio 20:80) are reacted with HMDI (90 to 100 ° C.) to form a polyurethane, and a terminal isocyanate group Was blocked with anhydrous sodium bisulfite, further cooled and added with water to prepare dispersion α (B1) in which water-soluble polyurethane resin α was dispersed.
[0087]
[Water-soluble polyurethane resin β]
A mixture of a polyester polyol of maleic anhydride and 1,6-hexanediol and polyethylene glycol (weight ratio 5: 1) is reacted with HMDI (90 to 100 ° C.) to form a polyurethane, and the terminal isocyanate group is converted to anhydrous weight. Blocked with sodium sulfite, further cooled and added with water to prepare dispersion β (B1) in which water-soluble polyurethane resin β was dispersed.
[0088]
[Water-soluble polyurethane resin γ]
A mixture (weight ratio 50:50) of glycerin obtained by addition polymerization of propylene oxide and glycerin obtained by random addition polymerization of ethylene oxide and propylene oxide (weight ratio of ethylene oxide and propylene oxide 13:87) was added to HMDI. (90 to 100 ° C.) to make a polyurethane, block the terminal isocyanate group with anhydrous sodium bisulfite, further cool and add water to disperse dispersion γ (B1) in which water-soluble polyurethane resin γ is dispersed Produced.
[0089]
[Water-soluble polyurethane resin δ]
Butylene adipate, a random addition polymer of propylene oxide and ethylene oxide, and a mixture of polycaprolactone (weight ratio 12: 4: 1) is reacted with HMDI (90-100 ° C.) to make a polyurethane, and water is added. A part of the terminal isocyanate group was reacted with sodium aminoethyl sulfonate and further cooled to prepare dispersion δ (B2) in which water-soluble polyurethane resin δ was dispersed.
[0090]
[Water-soluble polyurethane resin ε]
A mixture of polytetramethylene glycol, a random addition polymer of propylene oxide and ethylene oxide, polyethylene glycol, 1,4-butanediol, and trimethylolpropane (weight ratio 50: 4: 4: 4: 1.5) Then, it is reacted with hydrogenated MDI (90-100 ° C) to form polyurethane, and 5 parts of activator (ethylene oxide adduct of distyrenated phenol) is added to 100 parts of solid content, and then a large amount of water is added. This was emulsified and the terminal isocyanate group was cross-linked with ethylenediamine to prepare a dispersion ε (B2) in which the water-soluble polyurethane resin ε was dispersed.
[0091]
Then, with respect to 100 parts of each pyrethrin-encapsulated microcapsule dispersion (microcapsule solid content 20%) prepared in Production Examples 2 to 6, dispersions α to ε in which the water-soluble polyurethane resins α to ε are dispersed are used. 40 parts were added so that solid content might be 10 parts. The combinations of water-soluble polyurethane resins α to ε (dispersions α to ε) used for each of Production Examples 8 to 12 are shown in Table 3 below together with the weight average molecular weights of the water-soluble polyurethane resins α to ε. In addition, about manufacture examples 8-10, after adding the said dispersion, 0.8% of dibutyltin dilaurate was further added, and the target anti-acaricide containing dispersion liquid was obtained by stirring. The solid content concentration of the dispersion was 25%.
[0092]
[Table 3]

[0093]
Next, an example in which an aqueous emulsion of a synthetic resin is blended in the pyrethrin-encapsulated microcapsule dispersion will be described.
[0094]
[Production Example 13]
An aqueous emulsion of vinyl acetate-ethylene copolymer resin (concentration 50%, “Hovinyl 180E” manufactured by Hoechst Chemical Co., Ltd.) with respect to 100 parts of the liquid (microcapsule solid content 20%) in which the pyrethrin-encapsulated microcapsules of Production Example 1 are dispersed. 20.0 parts was added so that solid content might be 10 parts. The solid content concentration of this dispersion was 25%.
[0095]
Examples 7 to 13
Each of the dispersions obtained in Production Examples 7 to 13 was subjected to the washing resistance test for mite prevention according to the method described above in the same manner as in Examples 1 to 6. However, the test cloths using Production Examples 7 to 10 were pre-dried (120 ° C. × 2 minutes) and then cured (160 ° C. × 2 minutes). These results are shown in Table 4 below.
[0096]
[Table 4]

[0097]
From the results of Table 4 above, the above-mentioned water-soluble polyurethane resins α to ε and an aqueous emulsion of a synthetic resin (vinyl acetate-ethylene copolymer resin) were blended as a binder component in the pyrethrin-encapsulated microcapsule dispersion. Compared with Examples 1 to 6 (no binder component), it is clear that the washing resistance is further improved.
[0098]
【The invention's effect】
As described above, the present invention is a microcapsule containing pyrethroid insecticide having a special core structure in which a core made of a gel-like polyurethane resin containing a pyrethroid insecticide is coated with a shell made of a polyurea resin. tick repellent der containing is, the hydrophobic medium containing a pyrethroid insecticide or a pyrethroid insecticide, polyfunctional isocyanates, by dissolving the polyol in water insoluble and catalyst to an oil phase, which adding an emulsifier after the emulsified and dispersed in water, Ru der those obtained by reacting the oil droplet interface and therein. In this way, since the microcapsule has a special core structure, the pyrethroid insecticide contained in the gel polyurethane resin is only gradually released from the polyurethane resin over time, and exhibits its medicinal effect over a long period of time. It becomes possible to make it. In addition, the dispersion in which the microcapsules containing pyrethroid insecticides are dispersed can be used in various forms such as coating, spraying or impregnation on various materials such as paper and fibers, and the above-described excellent The residual effect can be exhibited effectively.
[0099]
Further, by blending at least one of a water-soluble polyurethane resin and an aqueous emulsion of a synthetic resin as a binder component into the dispersion in which the microcapsules containing pyrethroid insecticides of the present invention are dispersed, The washing resistance of various materials to be used for treatment is further improved.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view schematically showing an example of a pyrethrin-encapsulating microcapsule of the present invention.
[Explanation of symbols]
1 Gel-like polyurethane resin 2 Polyurea resin shell

Claims (5)

  An anti-mite agent comprising a microcapsule having a core part formed of a gel-like polyurethane resin containing a pyrethroid insecticide and a shell part covering the core part formed of a polyurea resin, However, after a polyfunctional isocyanate, a water-insoluble polyol and a catalyst are dissolved in a hydrophobic medium containing a pyrethroid insecticide or a pyrethroid insecticide to form an oil phase, this is emulsified and dispersed in water to which an emulsifier is added. An acaricidal agent obtained by reacting at an oil droplet interface and inside thereof. An acaricide-containing dispersion, wherein the acaricide according to claim 1 is dispersed in an aqueous medium.   The anti-mite agent-containing dispersion according to claim 2, further comprising at least one of a water-soluble polyurethane resin and an aqueous emulsion of a synthetic resin in the anti-mite agent-containing dispersion. 4. The acaricide-containing dispersion according to claim 3, wherein the water-soluble polyurethane resin is at least one of the following (B1) and (B2).
(B1) A heat-reacting water-soluble polyurethane resin in which a terminal isocyanate group is blocked with a blocking agent in a reaction product obtained by reacting the following (a1) and (b1).
(A1) At least one of polyether polyol and polyester polyol.
(B1) Diisocyanate component.
(B2) A water-soluble polyurethane resin obtained by crosslinking a terminal isocyanate group of at least one of water and an amine of a reaction product obtained by reacting the following (a2) and (b2).
(A2) At least one of polyether polyol and polyester polyol.
(B2) Diisocyanate component.   The acaricide-containing dispersion according to claim 3 or 4, wherein the aqueous emulsion of the synthetic resin is an aqueous emulsion of vinyl acetate-ethylene copolymer resin.

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