JP2008050267A - Sparingly water-soluble quality-improving agent for plant - Google Patents
Sparingly water-soluble quality-improving agent for plant Download PDFInfo
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本発明は植物品質向上剤に関し、更に詳しくは、植物の生理障害、特に柑橘の浮き皮防止、水腐れ防止、ぶどう、オウトウ等の裂果防止を目的とした、葉面、果実散布剤として用いる水難溶性植物品質向上剤に関する。 The present invention relates to a plant quality improver, and more particularly, water damage used as a foliar and fruit spraying agent for the purpose of preventing physiological disorders of plants, particularly prevention of citrus floats, water rot, ripening of grapes, sweet potatoes, etc. It relates to a soluble plant quality improver.
果樹類、果菜類、葉菜類、根菜類等では気象条件等により、様々な障害が発生することが知られている。このような障害としては、例えば、柑橘類では浮き皮や水腐れ、ぶどうやオウトウの裂果等が挙げられる。
これら問題点を解決する方法として、水難溶性の薬剤として炭酸カルシウムやゼオライト等を水に分散懸濁させ、これを散布して果面を保護する事により、果実の品質向上が図られている。
例えば、結合剤と炭酸カルシウム粉末と分散剤を主成分とする果実品質向上用果面保護剤が提案されている（特許文献１）。この製剤は、使用している炭酸カルシウムの平均粒子径が０．５〜３．０μm であり、炭酸カルシウムは比重が２．７と大きい上、この製剤は、分散状態が必ずしも良いとは言えず、水懸濁物が容器底部に沈降し易い問題がある。また、該製剤を用いた場合、散布し水分が蒸散した後、散布した炭酸カルシウムの粗大粒子・二次凝集物等が主要因で果実の表面が白く汚れるという問題点があり、この汚れをふき取るためには大きな労力、時間が必要であるという問題点を抱えている。
It is known that various troubles occur in fruit trees, fruit vegetables, leaf vegetables, root vegetables and the like depending on weather conditions. Examples of such obstacles include floating skin, water rot, grapes and sweet berries in citrus fruits.
As a method for solving these problems, the quality of fruits is improved by dispersing and suspending calcium carbonate, zeolite or the like as a poorly water-soluble drug in water and spraying it to protect the fruit surface.
For example, a fruit quality improving fruit surface protective agent mainly composed of a binder, calcium carbonate powder, and a dispersant has been proposed (Patent Document 1). In this preparation, the average particle diameter of calcium carbonate used is 0.5 to 3.0 μm, the specific gravity of calcium carbonate is as large as 2.7, and this preparation is not necessarily in a good dispersion state. There is a problem that the water suspension easily settles at the bottom of the container. In addition, when the preparation is used, after the sprayed water is evaporated, there is a problem that the surface of the fruit is stained white mainly due to the sprayed coarse particles and secondary aggregates of calcium carbonate. In order to do so, it has the problem of requiring a lot of labor and time.
また、ゼオライト、モンモリロナイト、珪藻土、及びシリカゲル等の固形剤を水で希釈した薬剤を果実及び／又は葉面に散布する事により、果面及び／又は葉面を保護し、日焼け・サビ果・薬害等予防し、軽減する方法が提案されている（特許文献２）。この方法は、固形剤として粉末の比表面積の高い多孔質粉体を用いる事で作物に有害な物質を迅速に吸収させる。また、気孔率の高い皮膜が形成されるため、保温性が向上し日焼けが抑制される。更に、吸水性・乾燥力が高く薬液が速やかに乾くため、薬害を予防・軽減できると考えられる。しかし、ここで用いられる多孔質粉体も粒子径が２．０μm （実施例１）と大きく、水懸濁物が容器底部に沈降し易いという問題がある。更に該製剤を用いた場合、水分が蒸散した後、散布した多孔質粉体の粗大粒子・二次凝集物等が主要因で果実の表面が白く汚れるという問題点がある。該特許文献２では、この汚れは散水で取り除けるとしているが、散水によってせっかく散布した薬剤が洗い流され、効果が発現しにくくなり、また収穫直前に果実に散水を行う事は、浮き皮等の生理障害を助長する結果となり好ましくない。 In addition, by spraying the fruit and / or leaf surface with a solution obtained by diluting solid agents such as zeolite, montmorillonite, diatomaceous earth, and silica gel with water, the fruit surface and / or leaf surface is protected, and sunburn, rust fruit, and chemical damage are caused. A method for preventing and mitigating the same has been proposed (Patent Document 2). This method uses a porous powder having a high specific surface area of the powder as a solid agent to quickly absorb substances harmful to crops. In addition, since a film having a high porosity is formed, heat retention is improved and sunburn is suppressed. Furthermore, it is thought that chemical damage can be prevented / reduced because water absorption and drying power are high and the chemical solution dries quickly. However, the porous powder used here also has a problem that the particle diameter is as large as 2.0 μm (Example 1) and the water suspension easily settles at the bottom of the container. Further, when the preparation is used, there is a problem that the surface of the fruit is stained white mainly due to the coarse particles, secondary aggregates, etc. of the dispersed porous powder after the water has evaporated. In Patent Document 2, this dirt can be removed by watering. However, the sprayed chemical is washed away by watering, and the effect becomes difficult to be expressed. This is not preferable because it promotes disability.
また、可溶性アルミニウム又は鉄化合物と珪酸系微粉末またはアルミナ系微粉末（但し、塩基性塩化アルミニウムと珪酸微粉末からなる成分資材を除く。）からなる植物保護剤が提案されている（特許文献３）。該製剤は、植物体に噴霧・塗布等することにより、植物体への病原菌等の侵入或いは接触を防止し、以て植物体の病害感染予防や品質保持を行うことを目的とする資材である。この製剤は、可溶性アルミニウム又は鉄化合物が必須であり、対イオンである塩素イオンや硝酸イオンが薬害を引き起こす問題がある。 Further, a plant protective agent comprising a soluble aluminum or iron compound and a silicate fine powder or an alumina fine powder (however, excluding component materials consisting of basic aluminum chloride and silicate fine powder) has been proposed (Patent Document 3). ). The preparation is a material intended to prevent invasion or contact of pathogenic bacteria into the plant body by spraying / coating, etc. on the plant body, thereby preventing disease infection and maintaining the quality of the plant body. . In this preparation, soluble aluminum or iron compounds are essential, and there is a problem that counter ions such as chloride ions and nitrate ions cause phytotoxicity.
更に、上記生理障害を軽減する方法として、水溶性カルシウム剤を散布する方法がある。
該目的で使用されている水溶性カルシウム剤としては、従来から塩化カルシウムや硝酸カルシウム等の水溶性カルシウムが用いられているが、これらのカルシウム剤は、対イオンである塩素イオンや硝酸イオンが薬害を引き起こすという問題点を有している。この薬害問題を回避するために、水溶性のカルシウム剤として、例えば、蟻酸カルシウムを有効成分とするものが提案されている（特許文献４）。この製剤を用いた場合、対イオン起因の薬害問題は解消されるものの、例えば、りんごのビタービット等の生理障害や柑橘類の浮き皮問題等に対しては、必ずしも十分な効果があるとは言えない。
Furthermore, as a method of reducing the physiological disorder, there is a method of spraying a water-soluble calcium agent.
As water-soluble calcium agents used for this purpose, water-soluble calcium such as calcium chloride and calcium nitrate has been conventionally used. Have the problem of causing. In order to avoid this problem of phytotoxicity, as a water-soluble calcium agent, for example, one having calcium formate as an active ingredient has been proposed (Patent Document 4). When this preparation is used, the problem of phytotoxicity caused by counterions is solved, but it is not always effective for physiological disorders such as apple bitterbits and citrus floating skin problems. Absent.
更にまた、高溶解性のカルシウム塩１０〜５０％、低溶解性のカルシウム塩９０〜５０％の割合で混合する事を特徴とする葉面散布用カルシウム肥料が提案されている（特許文献５）。該肥料によれば、高溶解性カルシウム塩と低溶解性カルシウム塩を所定の割合で混合する事で薬害の軽減は可能としているが、薬害の原因となる対イオンが一定量存在しているため、薬害の問題が完全に解消されているとは言い難い。また、該肥料は、特許文献４の製剤と同様、単に薬害が発生する可能性の低いカルシウム剤を散布しているに過ぎないため、ビタービット等の生理障害や柑橘類の浮き皮問題を解消するに至る程充分な効果があるとは言い難い。更に、リン酸肥料と反応してしまうため混用が出来ないという欠点も含んでいる。
本発明は、かかる実状に鑑み、上記課題を解決した植物の品質向上剤を提供するものであり、更に詳しくは、柑橘類果実の浮き皮抑制、水腐れ抑制、ぶどうやオウトウの裂果防止等に優れるとともに、従来の水難溶性薬剤散布時に見られた果面の白斑等の汚れを解決した水難溶性植物品質向上剤を提供することを目的とする。 In view of the actual situation, the present invention provides a plant quality improver that solves the above-mentioned problems, and more specifically, is excellent in suppressing citrus fruit floating skin, water rot, and preventing grapes and sweet berries. Another object of the present invention is to provide a poorly water-soluble plant quality improver that resolves stains such as white spots on the face that were observed when spraying conventional poorly water-soluble drugs.
本発明の請求項１は、酸化アルミニウム、酸化ビスマス、酸化セレニウム、酸化コバルト、酸化銅、酸化鉄、酸化ホルミウム、酸化インジウムスズ、酸化マンガン、酸化スズ、酸化イットリウム、酸化亜鉛、酸化ニッケル、酸化チタン、コロイダルシリカ、硫酸バリウムから選ばれる少なくとも１種の無機粒子からなり、５０％重量平均径ｄ５０が０．００２μm ≦ｄ５０≦０．２μm である事を特徴とする、浮き皮防止、水腐れ防止、裂果防止用の水難溶性植物品質向上剤を内容とする。
ｄ５０：ナノトラックＵＰＡ１５０により測定した粒子の５０％重量平均径。
Claim 1 of the present invention is aluminum oxide, bismuth oxide, selenium oxide, cobalt oxide, copper oxide, iron oxide, holmium oxide, indium tin oxide, manganese oxide, tin oxide, yttrium oxide, zinc oxide, nickel oxide, titanium oxide , Colloidal silica, at least one kind of inorganic particles selected from barium sulfate, 50% weight average diameter d50 is 0.002 μm ≦ d50 ≦ 0.2 μm, preventing floating skin, preventing water rot, Contains a poorly water-soluble plant quality improver for preventing fruit cracking.
d50: 50% weight average particle diameter measured by Nanotrac UPA150.
本発明の請求項２は、無機粒子が酸化アルミニウム、酸化スズ、酸化亜鉛、酸化ニッケル、酸化チタン、コロイダルシリカ、硫酸バリウムから選ばれる少なくとも１種からなる事を特徴とする請求項１記載の水難溶性植物品質向上剤を内容とする。 Claim 2 of the present invention is that the inorganic particles comprise at least one selected from aluminum oxide, tin oxide, zinc oxide, nickel oxide, titanium oxide, colloidal silica, and barium sulfate. Contains soluble plant quality improver.
本発明の請求項３は、無機粒子が酸化スズ、コロイダルシリカから選ばれる少なくとも１種からなる事を特徴とする請求項１又は２記載の水難溶性植物品質向上剤を内容とする。 A third aspect of the present invention includes the poorly water-soluble plant quality improver according to the first or second aspect, wherein the inorganic particles comprise at least one selected from tin oxide and colloidal silica.
本発明の請求項４は、下記ａ）の式を満たすことを特徴とする請求項１〜４のいずれか１項に記載の水難溶性植物品質向上剤を内容とする。
ａ）２０≦α≦１００
α：分光光度計にて測定した水難溶性植物品質向上剤を固形分として１重量％に調製した時の波長660nm 透過光の強度（％）。
A fourth aspect of the present invention includes the poorly water-soluble plant quality improver according to any one of the first to fourth aspects, which satisfies the following formula a).
a) 20 ≦ α ≦ 100
α: Intensity (%) of transmitted light having a wavelength of 660 nm when a poorly water-soluble plant quality improver measured with a spectrophotometer is prepared as 1% by weight as a solid content.
本発明の請求項５は、下記ｂ）の式を満たすことを特徴とする請求項１〜３のいずれか１項に記載の水難溶性植物品質向上剤を内容とする。
ｂ）０．０１≦α×（β／１０15）≦５０００
β：水難溶性植物品質向上剤を固形分として１重量％に調製した時の１ｍｌ中に含有する粒子の数（ｄ５０より計算した粒子の数）。
The fifth aspect of the present invention includes the poorly water-soluble plant quality improver according to any one of the first to third aspects, which satisfies the following formula b).
b) 0.01 ≦ α × (β / 10 15 ) ≦ 5000
β: Number of particles (number of particles calculated from d50) contained in 1 ml when the poorly water-soluble plant quality improver is adjusted to 1% by weight as a solid content.
本発明の水難溶性植物品質向上剤は、植物の生理障害、特に柑橘の浮き皮防止、水腐れ防止、ぶどう、オウトウ等の裂果防止に優れるとともに、粒子サイズが細かく且つ均一であるため、植物に散布した際に果実表面を汚すことなく、各種生理障害を防止する事が出来る。また、本発明の水難溶性植物品質向上剤は、水溶性の薬品と比較して薬害が起こりにくく、また、天候の影響を受けにくい。更に、水中における再分散性が極めて良好であり、特殊な分散機、撹拌機等を用いずとも容易に水中に分散し、品質向上効果が一定であるのは勿論、散布機中で沈殿を起こさないため、通常用いられている水難溶性薬品に見られるような装置の故障、噴霧器の目詰まり、錆等が起こりにくい。 The poorly water-soluble plant quality improver of the present invention is excellent in preventing physiologic disorders of plants, in particular, prevention of citrus floats, water rot, ripening of grapes, sweet potatoes, etc., and has a fine and uniform particle size. Various physiological disorders can be prevented without soiling the fruit surface when sprayed. In addition, the poorly water-soluble plant quality improver of the present invention is less susceptible to phytotoxicity than the water-soluble chemicals and is less susceptible to the weather. Furthermore, redispersibility in water is extremely good, and it can be easily dispersed in water without using a special disperser or stirrer, and the quality improvement effect is constant. Therefore, the failure of the apparatus, the clogging of the sprayer, the rust, etc. which are found in the commonly used poorly water-soluble chemicals hardly occur.
本発明の水難溶性植物品質向上剤は、無機粒子からなり、このような無機粒子としては、酸化アルミニウム、酸化ビスマス、酸化セレニウム、酸化コバルト、酸化銅、酸化鉄、酸化ホルミウム、酸化インジウムスズ、酸化マンガン、酸化スズ、酸化イットリウム、酸化亜鉛、酸化ニッケル、酸化チタン、コロイダルシリカ等の金属酸化物及び硫酸バリウムが挙げられる。これらの中で、より好ましくは安全性やコストの点で、酸化アルミニウム、酸化スズ、酸化亜鉛、酸化ニッケル、酸化チタン、コロイダルシリカ、硫酸バリウムであり、更に好ましくは、酸化スズ、コロイダルシリカである。これらは単独で又は２種以上組み合わせて用いられる。 The poorly water-soluble plant quality improver of the present invention is composed of inorganic particles. Examples of such inorganic particles include aluminum oxide, bismuth oxide, selenium oxide, cobalt oxide, copper oxide, iron oxide, holmium oxide, indium tin oxide, and oxide. Examples thereof include metal oxides such as manganese, tin oxide, yttrium oxide, zinc oxide, nickel oxide, titanium oxide, colloidal silica, and barium sulfate. Among these, aluminum oxide, tin oxide, zinc oxide, nickel oxide, titanium oxide, colloidal silica, and barium sulfate are more preferable in terms of safety and cost, and tin oxide and colloidal silica are more preferable. . These may be used alone or in combination of two or more.
本発明で用いられる金属酸化物の製造方法には特に制限はなく、アークプラズマ法等の気相法、ゾルゲル法、水熱合成法、金属アルコキシド法等の液相法、物理蒸着法等各種製造方法等が用いられ、市販されている金属酸化物としては、例えば、NanoTek （登録商標、シーアイ化成製）やスノーテックス（商品名、日産化学工業株式会社製）、セラメース（商品名、多木化学株式会社製）が挙げられる。
本発明で用いられる硫酸バリウムに特に制限はないが硫酸基を含む硫酸塩とバリウム塩を反応させた沈降性硫酸バリウムが好ましく、例えば、BARIFINE（登録商標、堺化学工業株式会社製）が挙げられる。
The production method of the metal oxide used in the present invention is not particularly limited, and various production methods such as a gas phase method such as an arc plasma method, a sol-gel method, a hydrothermal synthesis method, a liquid phase method such as a metal alkoxide method, and a physical vapor deposition method Examples of commercially available metal oxides include NanoTek (registered trademark, manufactured by CI Kasei), Snowtex (trade name, manufactured by Nissan Chemical Industries, Ltd.), and Cerames (trade name, Taki Chemical). Manufactured by the same company).
The barium sulfate used in the present invention is not particularly limited, but precipitated barium sulfate obtained by reacting a sulfate containing a sulfate group with a barium salt is preferable, and examples thereof include BARIFINE (registered trademark, manufactured by Sakai Chemical Industry Co., Ltd.). .
本発明の金属酸化物や硫酸バリウムは反応物をそのまま用いてもよいし、粉砕機及び／または分散機を用いて粉砕及び／又は分散させても差し支えない。粉砕機及び／又は分散機については、特に制限はないが、ダイノーミル、サンドミル、コボールミル等の湿式粉砕機、超音波分散機、ナノマイザ−、マイクロフルイタイザ−、アルティマイザー、ホモジナイザ−等の乳化・分散機等が好ましく使用できる。 The reaction product of the metal oxide or barium sulfate of the present invention may be used as it is, or may be pulverized and / or dispersed using a pulverizer and / or a disperser. The pulverizer and / or disperser is not particularly limited, but emulsification / wet pulverizer such as dyno mill, sand mill, coball mill, ultrasonic disperser, nanomizer, microfluidizer, optimizer, homogenizer, etc. A disperser or the like can be preferably used.
本発明の水難溶性植物品質向上剤は、ナノトラックＵＰＡ１５０により測定した粒子の５０％重量平均径ｄ５０が０．００２μm ≦ｄ５０≦０．２μm の範囲内であることが必要で、好ましくは０．００２μm ≦ｄ５０≦０．１５μm 、より好ましくは０．００２μm ≦ｄ５０≦０．１μm である。このｄ５０が０．２μm より大きい場合は、製品が沈降しやすく、散布機中で沈殿し、効果が不安定となる傾向がある。更に、果実表面が粗大粒子等の凝集物で汚れが残りやすく、製品の外観上を損なう。一方、ｄ５０が０．００２μm より小さくなると、物性的には問題はないが、多大な分散エネルギーコストが必要となるため、経済的でない。 The poorly water-soluble plant quality improver of the present invention requires that the 50% weight average diameter d50 of the particles measured by Nanotrac UPA150 is in the range of 0.002 μm ≦ d50 ≦ 0.2 μm, preferably 0.002 μm. ≦ d50 ≦ 0.15 μm, more preferably 0.002 μm ≦ d50 ≦ 0.1 μm. When this d50 is larger than 0.2 μm, the product tends to settle, tends to settle in the spreader, and the effect tends to become unstable. Further, the fruit surface is likely to remain dirty with aggregates such as coarse particles, which impairs the appearance of the product. On the other hand, if d50 is smaller than 0.002 μm, there is no problem in physical properties, but it is not economical because a great amount of dispersion energy cost is required.
本発明における水難溶性植物品質向上剤中のｄ５０は、下記の要領で測定計算されたものである。
測定機種 ：日機装（株） ナノトラック UPA150
試料の調製：水難溶性植物品質向上剤を固形分として１重量％となるように下記２０℃の溶媒中に滴下し、粒度分布測定試料とする。
溶媒 ：蒸留水
予備分散 ：Ｕｌｔｒａｓｏｎｉｃ Ｈｏｍｏｇｅｎｉｚｅｒ（（株）日本精機製）を用い、超音波分散２０ＫＨｚ、６０秒
測定温度 ：２０．０℃±２．５℃
D50 in the poorly water-soluble plant quality improver in the present invention is measured and calculated in the following manner.
Measurement model: Nikkiso Co., Ltd. Nanotrack UPA150
Preparation of sample: A poorly water-soluble plant quality improver is dropped into a solvent at 20 ° C. below so as to be 1% by weight as a solid content to prepare a particle size distribution measurement sample.
Solvent: distilled water Preliminary dispersion: Ultrasonic Homogenizer (manufactured by Nippon Seiki Co., Ltd.), ultrasonic dispersion 20 KHz, 60 seconds Measurement temperature: 20.0 ° C. ± 2.5 ° C.
本発明における水難溶性植物品質向上剤は、下記ａ）の要件を具備することが好ましく、下記ｃ）の要件を具備する事がより好ましく、下記ｄ）の要件を具備することが更に好ましい。
ａ）２０≦α≦１００
ｃ）３０≦α≦１００
ｄ）４０≦α≦１００
α：分光光度計にて測定した水難溶性植物品質向上剤を固形１重量％に調製した時の波長660nm 透過光の強度（％）。
The poorly water-soluble plant quality improver in the present invention preferably has the following requirement a), more preferably has the following requirement c), and more preferably has the following requirement d).
a) 20 ≦ α ≦ 100
c) 30 ≦ α ≦ 100
d) 40 ≦ α ≦ 100
α: Intensity (%) of transmitted light at a wavelength of 660 nm when a poorly water-soluble plant quality improver measured with a spectrophotometer was prepared to 1 wt% solids.
透過光の強度αが２０％未満の場合は、水難溶性植物品質向上剤の分散が悪く、果実に散布した際に果面の汚れが目立ちやすくなる傾向があり、一方、１００％を越える場合、水溶性の割合が高くなる傾向にあり、薬害を助長する場合がある。 When the intensity α of the transmitted light is less than 20%, the poorly water-soluble plant quality improver is poorly dispersed, and there is a tendency for the stains on the surface to be noticeable when sprayed on the fruit, whereas when it exceeds 100%, The water-soluble ratio tends to be high, which may promote phytotoxicity.
本発明における透過光の強度αは、下記の要領で測定計算されたものである。
測定機種 ：分光光度計UV-200（（株）島津製）
対照 ： 蒸留水
試料の調製：水難溶性植物品質向上剤を固形分として１重量％となるように下記２０℃の溶媒中に滴下し、測定試料とする。
溶媒 ：蒸留水
予備分散 ：Ｕｌｔｒａｓｏｎｉｃ Ｈｏｍｏｇｅｎｉｚｅｒ（（株）日本精機製）を用い、超音波分散２０ＫＨｚ、６０秒
測定温度 ：２０．０℃±２．５℃
The transmitted light intensity α in the present invention is measured and calculated in the following manner.
Measurement model: Spectrophotometer UV-200 (manufactured by Shimadzu Corporation)
Control: Distilled water Sample preparation: A poorly water-soluble plant quality improver is dropped into a solvent at 20 ° C. as follows to give a solid content of 1% by weight, and used as a measurement sample.
Solvent: distilled water Preliminary dispersion: Ultrasonic Homogenizer (manufactured by Nippon Seiki Co., Ltd.), ultrasonic dispersion 20 KHz, 60 seconds Measurement temperature: 20.0 ° C. ± 2.5 ° C.
透過光の強度αの調整は、水難溶性植物品質向上剤の粒子の均一度（粗大粒子の頻度）の調整によって行う事が出来る。具体的にはαを大きくするには、水難溶性品質向上剤の粒子を均一に分散させ、粗大粒子を少なくすれば良い。一方、水難溶性植物品質向上剤の粒子が均一に分散されず、粗大粒子が多く存在する場合にはαは小さくなる。 The intensity α of the transmitted light can be adjusted by adjusting the uniformity of particles of the poorly water-soluble plant quality improver (frequency of coarse particles). Specifically, in order to increase α, particles of poorly water-soluble quality improver may be uniformly dispersed and coarse particles may be reduced. On the other hand, when the poorly water-soluble plant quality improver particles are not uniformly dispersed and there are many coarse particles, α is small.
本発明における水難溶性植物品質向上剤は、下記ｂ）の要件を具備することが好ましく、下記ｅ）の要件を具備する事がより好ましく、下記ｆ）の要件を具備することが更に好ましい。
ｂ）０．０１≦α×（β／１０15）≦５０００
ｅ）０．０５≦α×（β／１０15）≦３０００
ｆ）０．１≦α×（β／１０15）≦１０００
β：水難溶性植物品質向上剤を固形分として１重量％に調製した時の１ｍｌ中に含有する粒子の数（ｄ５０より計算した粒子の数）。
ｄ５０：ナノトラックＵＰＡ１５０により測定した粒子の５０％重量平均径。
The poorly water-soluble plant quality improver in the present invention preferably has the following requirement b), more preferably has the following requirement e), and still more preferably has the following requirement f).
b) 0.01 ≦ α × (β / 10 15 ) ≦ 5000
e) 0.05 ≦ α × (β / 10 15 ) ≦ 3000
f) 0.1 ≦ α × (β / 10 15 ) ≦ 1000
β: Number of particles (number of particles calculated from d50) contained in 1 ml when the poorly water-soluble plant quality improver is adjusted to 1% by weight as a solid content.
d50: 50% weight average particle diameter measured by Nanotrac UPA150.
尚、βは１０11〜１０17オーダーの値であるが、便宜上１０15で除した値とする。
α×（β／１０15）が０．０１未満の場合、液中に存在する水難溶性植物品質向上剤の粒子数が少なくなり、気象条件の変化、例えば長雨等の場合、安定した効果を得る事ができにくくなる傾向がある。一方、５０００を越えても効果には差が無いが、散布機等への付着が激しく洗浄性が悪くなる傾向がある。
本発明におけるβは、水難溶性植物品質向上剤を固形分として１重量％に調製した時の１ｍｌ中に含有する粒子の数（ｄ５０より計算した粒子の数）であり、計算方法は以下の通りである。
βは１重量％の溶液１ｍｌの粒子数、即ち0.01g の水難溶性植物品質向上剤の粒子数であり、ナノトラックＵＰＡ１５０により測定した粒子の５０％重量平均径ｄ５０を粒子の１辺とし、密度を用いて粒子数を計算した。
例えば、ｄ５０＝０．１μm 、密度２．２のコロイダルシリカの場合、0.01ｇの粒子数は１ｇ＝（１００００／０．１）3 ÷２．２＝４．５５×１０14
０．０１ｇ＝４．５５×１０14÷１００＝４．５５×１０12となる。
（α×β／１０15）の調整は、水難溶性植物品質向上剤粒子の均一度（粗大粒子の頻度）及び同重量あたりの粒子数の調整によって行う事が出来る。この値を大きくするには、水難溶性植物品質向上剤の重量あたりの粒子数を多くするか、あるいは水難溶性植物品質向上剤の粒子を均一に分散させ、粗大粒子を少なくすれば良い。一方、小さくなる場合は、水難溶性植物品質向上剤の重量あたりの粒子数が少ない場合、あるいは水難溶性植物品質向上剤の粒子を均一に分散されず、粗大粒子が多く存在する場合である。
上記α×（β／１０15）の技術的意義について説明すると、本発明の水難溶性植物品質向上剤の生理障害防止効果のメカニズムは、果面をコーティングし表面が濡れることを防ぐこと、並びに、果実の気孔を詰めることで気孔が塞がるのを制御し、水分の蒸散を物理的に促進させることである。このメカニズムで効果を強めるには、重量あたりの水難溶性品質向上剤の粒子数を多くすればよい。水難溶性植物品質向上剤の場合、雨によって散布した粒子が流されることが考えられるが、粒子数を多くすることにより、例え一部の粒子が流されても、残りの多数の粒子で効果を維持することが可能となる。
一方で粒子の数を増やす方法として、散布濃度を高くするという方法も考えられるが、この場合、果面の汚れが助長される傾向にある。この果面の汚れは、分光光度計での透過度で判断することができる。
透過度が高いほど、より高濃度に散布可能であり、例え重量あたりの粒子数が少なくても高濃度に散布する事で生理障害防止効果を向上させる事が可能となる。
これらの事から、粒子数と透過度の積を特定の範囲にすることにより、生理障害防止効果と散布時の汚れが無いという効果を併せ持つ水難溶性品質向上剤を得ることが可能となる。
Β is a value on the order of 10 11 to 10 17 , but is a value divided by 10 15 for convenience.
When α × (β / 10 15 ) is less than 0.01, the number of particles of poorly water-soluble plant quality improver present in the liquid is reduced, and a stable effect is obtained in the case of changes in weather conditions such as long rain. It tends to be difficult to do things. On the other hand, even if it exceeds 5000, there is no difference in effect, but there is a tendency that the adhesion to the spreader or the like is intense and the cleaning property is deteriorated.
Β in the present invention is the number of particles (the number of particles calculated from d50) contained in 1 ml when the poorly water-soluble plant quality improver is prepared as 1% by weight as a solid content, and the calculation method is as follows. It is.
β is the number of particles in 1 ml of a 1% by weight solution, that is, the number of particles of 0.01 g of poorly water-soluble plant quality improver, and the 50% weight average diameter d50 of the particles measured by Nanotrac UPA150 is one side of the particle. Was used to calculate the number of particles.
For example, in the case of colloidal silica with d50 = 0.1 μm and density 2.2, the number of particles of 0.01 g is 1 g = (10000 / 0.1) 3 ÷ 2.2 = 4.55 × 10 14
0.01g = 4.55 × 10 14 ÷ 100 = 4.55 × 10 12
(Α × β / 10 15 ) can be adjusted by adjusting the uniformity of the poorly water-soluble plant quality improver particles (frequency of coarse particles) and the number of particles per weight. In order to increase this value, the number of particles per weight of the poorly water-soluble plant quality improver may be increased, or the particles of the poorly water-soluble plant quality improver may be uniformly dispersed to reduce coarse particles. On the other hand, when it becomes small, the number of particles per weight of the poorly water-soluble plant quality improver is small, or the particles of the poorly water-soluble plant quality improver are not uniformly dispersed and there are many coarse particles.
Explaining the technical significance of the above α × (β / 10 15 ), the mechanism of the physiological disorder preventing effect of the poorly water-soluble plant quality improver of the present invention is to coat the fruit surface and prevent the surface from getting wet; By filling the pores of the fruit, it is possible to control the clogging of the pores and physically promote the transpiration of moisture. In order to strengthen the effect by this mechanism, the number of particles of poorly water-soluble quality improver per weight may be increased. In the case of poorly water-soluble plant quality improvers, it is conceivable that particles dispersed by rain will be washed away, but by increasing the number of particles, even if some of the particles are washed away, the remaining many particles will be effective. Can be maintained.
On the other hand, as a method of increasing the number of particles, a method of increasing the spraying concentration is also conceivable. This stain on the surface can be judged by the transmittance with a spectrophotometer.
The higher the permeability, the higher the concentration, and even if the number of particles per weight is small, the effect of preventing physiological disorders can be improved by applying the high concentration.
From these facts, it is possible to obtain a poorly water-soluble quality improver having both the effect of preventing physiological disorders and the absence of dirt during spraying by setting the product of the number of particles and the permeability within a specific range.
本発明の水難溶性植物品質向上剤の使用時期は、植物の種類、施用目的及び地帯によって異なる。例えば果樹の場合、一般に落花直後から収穫期までとされる。特にみかんの品質向上及び浮き皮軽減を目的に使用する場合には７月〜１１月にかけて果面に１〜６回、３〜６週間おきに散布することが望ましい。また、柑橘の水腐れ防止を目的に使用する場合には、７月〜１月にかけて果面に１〜１０回、３〜６週間おきに散布することが望ましい。また、ぶどうやオウトウの裂果の軽減を目的にする場合はそれぞれの果樹で適期より１〜６回、１〜６週間おきに散布することが望ましい。例えばオウトウの場合、満開２週間後頃から１〜６回、１〜６週間おきに散布するのがよい。ぶどうの場合、ジベレリン処理時あるいはジベレリン処理後１〜６回、１〜６週間おきに散布するのがよい。 The time of use of the poorly water-soluble plant quality improver of the present invention varies depending on the kind of plant, the purpose of application, and the zone. For example, in the case of fruit trees, the period is generally from the time immediately after flowering to the harvest period. In particular, when used for the purpose of improving the quality of mandarin oranges and reducing floating skin, it is desirable to spray the fruit surface 1 to 6 times every 3 to 6 weeks from July to November. Moreover, when using it for the purpose of water rot prevention of citrus, it is desirable to spray on the fruit surface 1 to 10 times and every 3 to 6 weeks from July to January. Moreover, when aiming at the reduction | decrease of the ripening of a grape or sweet cherry, it is desirable to spray with each fruit tree 1-6 times from a suitable time, and every 1-6 weeks. For example, in the case of sweet cherry, it should be sprayed 1 to 6 times every 1 to 6 weeks from about 2 weeks after full bloom. In the case of grapes, it is preferable to spray every 1 to 6 weeks 1 to 6 times after gibberellin treatment or after gibberellin treatment.
散布濃度としては、施用する作物の種類、作柄、目的、気候及び天候により一概には規定できないが、一般的には金属酸化物及び／又は硫酸バリウムとして１ppm 〜２重量％の範囲が好ましく、より好ましくは10ppm 〜0.5 重量％の範囲である。１ppm 未満の場合、目的とする効果が得られにくい場合があり、２重量％を越えても効果に差はほとんどなくコスト的に有利でない。
また、散布量も作物の種類、作柄、目的、気候及び天候により一概には規定できないが、上記散布濃度で５０L 〜２０００L ／１０００ｍ2 散布すれば良く、好ましくは１００L 〜１０００L ／１０００ｍ2 散布すれば良い。５０L ／１０００ｍ2 未満の場合、薬剤が作物に充分にかからない場合があり、効果が得られにくい場合がある。一方、２０００L ／１０００ｍ2 を超えても効果にほとんど差はなく、コスト的に有利でない。
The spraying concentration cannot be generally specified depending on the type, crop, purpose, climate, and weather of the crop to be applied, but generally it is preferably in the range of 1 ppm to 2% by weight as metal oxide and / or barium sulfate. Preferably, it is in the range of 10 ppm to 0.5% by weight. If it is less than 1 ppm, the desired effect may not be obtained, and even if it exceeds 2% by weight, there is almost no difference in the effect and the cost is not advantageous.
Also, the amount of application cannot be generally defined depending on the type, crop, purpose, climate and weather of the crop, but it is sufficient to apply 50 L to 2000 L / 1000 m 2 at the application concentration, preferably 100 L to 1000 L / 1000 m 2. good. If it is less than 50 L / 1000 m 2 , the drug may not be sufficiently applied to the crop, and the effect may be difficult to obtain. On the other hand, even if it exceeds 2000 L / 1000 m 2 , there is almost no difference in effect, which is not advantageous in terms of cost.
また、本発明の水難溶性植物品質向上剤には、本発明の効果を損なわない範囲で、乳酸カルシウム、塩化カルシウム、硝酸カルシウム、蟻酸カルシウム、プロピオン酸カルシウム、イタコン酸カルシウム、グルタミン酸カルシウム、リンゴ酸・クエン酸カルシウム、マレイン酸・クエン酸カルシウム、乳酸マグネシウム、硫酸マグネシウム、塩化マグネシウム、第一リン酸マグネシウム、第二リン酸マグネシウム、クエン酸鉄ナトリウム、クエン酸鉄アンモニウム等の水溶性ミネラル塩、炭酸カルシウム、炭酸マグネシウム、水酸化カルシウム、水酸化マグネシウム、第一リン酸カルシウム、第二リン酸カルシウム、リン酸三カルシウム、ヒドロキシアパタイト、第三リン酸マグネシウム、リン酸鉄等の水難溶性ミネラル剤、珪酸塩等の１種又は２種以上と併用しても何ら差し支えない。 Further, in the poorly water-soluble plant quality improver of the present invention, calcium lactate, calcium chloride, calcium nitrate, calcium formate, calcium propionate, calcium itaconate, calcium glutamate, malic acid, as long as the effects of the present invention are not impaired. Water-soluble mineral salts such as calcium citrate, maleic acid / calcium citrate, magnesium lactate, magnesium sulfate, magnesium chloride, primary magnesium phosphate, secondary magnesium phosphate, sodium iron citrate, ammonium iron citrate, calcium carbonate , Magnesium carbonate, calcium hydroxide, magnesium hydroxide, monocalcium phosphate, dicalcium phosphate, tricalcium phosphate, hydroxyapatite, tribasic magnesium phosphate, iron phosphate and other poorly water-soluble mineral agents, silicates, etc. No problem even when used in conjunction with two or more.
また、本発明の水難溶性植物品質向上剤には、効果の更なる向上を目的として、一般に農業用に使用される展着剤、乳化剤、補助剤、ｐＨ調整剤、キレート剤その他の添加物を適宜添加してもよい。また、殺菌剤や殺虫剤等の農薬や他の肥料も添加可能である。 In addition, the poorly water-soluble plant quality improver of the present invention contains spreading agents, emulsifiers, adjuvants, pH adjusters, chelating agents and other additives generally used for agriculture for the purpose of further improving the effect. You may add suitably. Also, agricultural chemicals such as bactericides and insecticides and other fertilizers can be added.
展着剤や乳化剤として好適な代表例としては、非イオン系界面活性剤ではポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレンアルキルエステル、ポリエチレンソルビタンアルキルエステル及びソルビタンアルキルエステル等、陰イオン界面活性剤ではアルキルベンゼンスルホネート、アルキルスルホサクシネート、アルキルサルフェート、ポリオキシエチレンアルキルサルフェート及びアリルスルホネート等、陽イオン界面活性剤ではラウリルアミン、アルキルメチルジヒドロキシエチルアンモニウム塩、ステアリルトリメチルアンモニウムクロライド、アルキルジメチルベンジルアンモニウムクロリド及びポリオキシエチレンアルキルアミン等、両性界面活性剤ではラウリルベタイン、ステアリルベタイン及びイミダゾリニウムベタイン等を挙げることができる。これらの界面活性剤は単独で又は２種以上混合して使用できる。補助剤の好適な代表例としては、ポリビニルアルコール、カルボキシメチルセルロース、アラビアガム、ポリビニルアセテート、ゼラチン、カゼイン、アルギン酸ソーダ、アルギンサンプロピレングリコールエステル、キサンタンガム、パラフィン及びトラガントガム等を挙げることができ、これらは単独で又は２種以上混合して使用できる。 Representative examples suitable as spreading agents and emulsifiers include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene alkyl ester, polyethylene sorbitan alkyl ester, and sorbitan alkyl ester. For ionic surfactants, alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl sulfate and allyl sulfonate, etc., for cationic surfactant, laurylamine, alkylmethyldihydroxyethylammonium salt, stearyltrimethylammonium chloride, alkyldimethylbenzyl Lauryl betaine for amphoteric surfactants such as ammonium chloride and polyoxyethylene alkylamines It can be mentioned stearyl betaine and betaine and the like. These surfactants can be used alone or in admixture of two or more. Preferable representative examples of the adjuvant include polyvinyl alcohol, carboxymethyl cellulose, gum arabic, polyvinyl acetate, gelatin, casein, sodium alginate, algin sun propylene glycol ester, xanthan gum, paraffin and gum tragacanth. Or a mixture of two or more.
上記の如く調製された水難溶性植物品質向上剤は、粒子サイズが細かく且つ均一であるため、植物に散布した際に果面を汚すことなく効果を発現する事が出来る。また、水難溶性粒子が果実気孔を塞ぎ、水分の蒸散をコントロールするので、水溶性植物品質向上剤と比較して効果が高い。更に、本発明の水難溶性植物品質向上剤は、水溶性の薬品と比較して薬害が起こりにくく、また、天候の影響を受けにくく、更には水溶性リン酸肥料との混用も可能である。更に、水中における再分散性が極めて良好であり、特殊な分散機、撹拌機等を用いずとも容易に水中に分散するため、品質向上効果が一定であるのは勿論であるが、散布機中で沈殿を起こさないため、通常用いられている水難溶性薬品に見られるような装置の故障、噴霧器の目詰まり、錆等が起こりにくい。 Since the poorly water-soluble plant quality improver prepared as described above has a fine and uniform particle size, it can exhibit an effect without polluting the fruit surface when sprayed on plants. In addition, since the poorly water-soluble particles block the pores of the fruit and control the transpiration of water, the effect is higher than that of the water-soluble plant quality improver. Furthermore, the poorly water-soluble plant quality improver of the present invention is less susceptible to phytotoxicity than water-soluble chemicals, is not easily affected by the weather, and can be mixed with water-soluble phosphate fertilizers. Furthermore, the redispersibility in water is very good, and it is easily dispersed in water without using a special disperser, stirrer, etc., so the quality improvement effect is of course constant. Therefore, it is difficult to cause breakdown of equipment, clogging of sprayer, rust, etc. as seen in commonly used poorly water-soluble chemicals.
以下、実施例及び比較例を挙げて本発明を更に詳細に説明するが、本発明はこれらにより何ら限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited at all by these.
実施例１
水２７７３ｇと５％ＮａＯＨ２６．５ｇを攪拌し、８０℃に加温後、２１４ｇの市販のテトラエチルシリケートを３時間かけて滴下した。その後、液温を約１２０℃まで上昇させ、１時間水熱処理を行った。次いで上記反応液をロータリーエバポレーターにて濃縮し、ＳｉＯ2 濃度２０重量％のコロイダルシリカ水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のナノトラックＵＰＡによる重量平均径ｄ５０は0.005 μm であった。分光光度計により測定した、水難溶性植物品質向上剤を固形分として１重量％に調製した時の透過光の強度αは９８％であった。また、水難溶性植物品質向上剤を固形分として１重量％に調製した時の１ｍｌ中に含有する粒子の数（ｄ５０より計算した粒子の数）βは36.36 ×1015であった。α×（β／１０15）は３５７０であった。
Example 1
2773 g of water and 26.5 g of 5% NaOH were stirred and heated to 80 ° C., and 214 g of commercially available tetraethyl silicate was added dropwise over 3 hours. Thereafter, the liquid temperature was raised to about 120 ° C. and hydrothermal treatment was performed for 1 hour. Then concentrated the reaction solution by a rotary evaporator to give a SiO 2 concentration of 20% by weight of colloidal silica poorly water-soluble plant quality improver.
The weight-average diameter d50 by Nanotrac UPA of the poorly water-soluble plant quality improver obtained was 0.005 μm. The intensity α of the transmitted light was 98% when the poorly water-soluble plant quality improver was adjusted to 1% by weight as a solid content, measured with a spectrophotometer. The number of particles contained in 1 ml (number of particles calculated from d50) β was 36.36 × 10 15 when the poorly water-soluble plant quality improver was adjusted to 1% by weight as a solid content. α × (β / 10 15 ) was 3570.
実施例２
実施例１で得た２０重量％のコロイダルシリカ５０ｇと水１５５０ｇと１０％ＮａＯＨ１３．７ｇを攪拌し、８０℃に加温後、３５０ｇの市販のテトラエチルシリケートを６時間かけて滴下した。その後、液温を約９０℃まで上昇させ、１時間環流を行った。次いで上記反応液をロータリーエバポレーターにて濃縮し、ＳｉＯ2 濃度２０重量％のコロイダルシリカ水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 2
50 g of 20% by weight colloidal silica obtained in Example 1, 1550 g of water and 13.7 g of 10% NaOH were stirred, heated to 80 ° C., and 350 g of commercially available tetraethyl silicate was added dropwise over 6 hours. Thereafter, the liquid temperature was raised to about 90 ° C. and refluxing was performed for 1 hour. Then concentrated the reaction solution by a rotary evaporator to give a SiO 2 concentration of 20% by weight of colloidal silica poorly water-soluble plant quality improver.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例３
水１７７３ｇと１０％ＮａＯＨ１３．３ｇを攪拌し、８０℃に加温後、２１４ｇの市販のテトラエチルシリケートを３時間かけて滴下した。その後、液温を約９０℃まで上昇させ、１時間環流を行った。次いで上記反応液をロータリーエバポレーターにて濃縮し、ＳｉＯ2 濃度２０重量％のコロイダルシリカを得た。上記２０重量％のコロイダルシリカ５０ｇと水１５５０ｇと１０％ＮａＯＨ１３．７ｇを攪拌し、８０℃に加温後、３５０ｇの市販のテトラエチルシリケートを６時間かけて滴下した。その後、液温を約９０℃まで上昇させ、１時間環流を行った。次いで上記反応液をロータリーエバポレーターにて濃縮し、ＳｉＯ2 濃度２０重量％のコロイダルシリカを得た。更に該コロイダルシリカ５０ｇを用い同様の反応を行いＳｉＯ2 濃度２０重量％のコロイダルシリカ水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 3
1773 g of water and 13.3 g of 10% NaOH were stirred and heated to 80 ° C., and 214 g of commercially available tetraethyl silicate was added dropwise over 3 hours. Thereafter, the liquid temperature was raised to about 90 ° C. and refluxing was performed for 1 hour. Subsequently, the reaction solution was concentrated with a rotary evaporator to obtain colloidal silica having a SiO 2 concentration of 20% by weight. 50 g of the 20 wt% colloidal silica, 1550 g of water, and 13.7 g of 10% NaOH were stirred, heated to 80 ° C., and 350 g of commercially available tetraethyl silicate was added dropwise over 6 hours. Thereafter, the liquid temperature was raised to about 90 ° C. and refluxing was performed for 1 hour. Subsequently, the reaction solution was concentrated with a rotary evaporator to obtain colloidal silica having a SiO 2 concentration of 20% by weight. Furthermore, the same reaction was carried out using 50 g of the colloidal silica to obtain a poorly colloidal silica water-soluble plant quality improver having a SiO 2 concentration of 20 wt%.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例４
実施例３で得た２０重量％のコロイダルシリカ５０ｇと水１５５０ｇと１０％ＮａＯＨ１３．７ｇを攪拌し、８０℃に加温後、３５０ｇの市販のテトラエチルシリケートを６時間かけて滴下した。その後、液温を約９０℃まで上昇させ、１時間環流を行った。次いで上記反応液をロータリーエバポレーターにて濃縮し、ＳｉＯ2 濃度２０重量％のコロイダルシリカを得た。更に該コロイダルシリカ５０ｇを用い同様の反応を行いＳｉＯ2 濃度２０重量％のコロイダルシリカ水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 4
50 g of 20% by weight colloidal silica obtained in Example 3, 1550 g of water and 13.7 g of 10% NaOH were stirred and heated to 80 ° C., and 350 g of commercially available tetraethyl silicate was added dropwise over 6 hours. Thereafter, the liquid temperature was raised to about 90 ° C. and refluxing was performed for 1 hour. Subsequently, the reaction solution was concentrated with a rotary evaporator to obtain colloidal silica having a SiO 2 concentration of 20% by weight. Furthermore, the same reaction was carried out using 50 g of the colloidal silica to obtain a poorly colloidal silica water-soluble plant quality improver having a SiO 2 concentration of 20% by weight.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例５
市販のコロイダルシリカ スノーテックスＣ（日産化学社製）を用い水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 5
Using a commercially available colloidal silica Snowtex C (manufactured by Nissan Chemical Co., Ltd.), a poorly water-soluble plant quality improver was obtained.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例６
水９００ｇに水酸化バリウム２０６ｇを加え攪拌しＡ液とした。また、水９７７ｇに硫酸６２．３ｇと６０％メタン−１−ヒドロキシ−１，１−ジホスホン酸３．３ｇを溶解しＢ液とした。これらＡ液とＢ液を５０℃に加温した後、１．５Ｌ／ｍｉｎの流速でスタティックミキサーにＡ液、Ｂ液を同時供給し、反応させた。該反応液をダイノミルＫＤ１．４（株式会社シンマルエンタープライゼス社製）で流量２００ｇ／分で８回粉砕を行った。上記反応液をエバポレーターにて濃縮し、２０重量％の沈降性硫酸バリウム水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 6
The solution A was stirred by adding 206 g of barium hydroxide to 900 g of water. Further, 62.3 g of sulfuric acid and 3.3 g of 60% methane-1-hydroxy-1,1-diphosphonic acid were dissolved in 977 g of water to prepare a solution B. After heating these A liquid and B liquid to 50 degreeC, A liquid and B liquid were simultaneously supplied to the static mixer with the flow rate of 1.5 L / min, and it was made to react. The reaction solution was pulverized 8 times with a Dynomill KD1.4 (manufactured by Shinmaru Enterprises Co., Ltd.) at a flow rate of 200 g / min. The reaction solution was concentrated with an evaporator to obtain 20% by weight of a precipitated barium sulfate water poorly soluble plant quality improver.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例７
ダイノミルＫＤ１．４で流量２００ｇ／分で２回粉砕を行う以外は実施例５と同様な方法で沈降性硫酸バリウム水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 7
A precipitated barium sulfate poorly water-soluble plant quality improver was obtained in the same manner as in Example 5 except that pulverization was performed twice with Dynomill KD1.4 at a flow rate of 200 g / min.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例８
市販の沈降性硫酸バリウム ＢＡＲＩＦＩＮＥ ＢＦ−１０（堺化学工業（株）製）を用い水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 8
Commercially available precipitated barium sulfate BARIFINE BF-10 (manufactured by Sakai Chemical Industry Co., Ltd.) was used to obtain a poorly water-soluble plant quality improver.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例９
重炭酸アンモニウム水溶液（ＮＨ3 ２．９％）１０００ｇに塩化第二スズ水溶液（ＳｎＯ2 濃度１６．５％）３００ｇを攪拌下徐々に添加してゲルを得た。このゲルを塩素イオンが認められなくなるまでろ過洗浄を行った。
この洗浄ゲル（ＳｎＯ2 濃度３５％）１００ｇに１．０％アンモニア水１１２ｇ及び水１５３ｇを添加した後、９５℃で２時間水熱処理を行い、ＳｎＯ2 濃度１０重量％の酸化スズ水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 9
To 1000 g of an aqueous ammonium bicarbonate solution (NH 3 2.9%), 300 g of an aqueous stannic chloride solution (SnO 2 concentration 16.5%) was gradually added with stirring to obtain a gel. The gel was washed by filtration until no chlorine ions were observed.
After adding 112 g of 1.0% aqueous ammonia and 153 g of water to 100 g of this washing gel (SnO 2 concentration 35%), hydrothermal treatment was performed at 95 ° C. for 2 hours, and tin oxide water poorly soluble plant quality with SnO 2 concentration of 10% by weight An improver was obtained.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例１０
市販の酸化スズ セラメースＳ−８（多木化学（株）製）を用い水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 10
A commercially available tin oxide Cerames S-8 (manufactured by Taki Chemical Co., Ltd.) was used to obtain a poorly water-soluble plant quality improver.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例１１
炭酸アンモニウム水溶液（0.2mol／L ）に硫酸亜鉛水溶液（0.2mol／L ）を滴下して塩基性炭酸亜鉛を生成させ、水洗によって塩類を除去し粉末化した後、３００℃で１時間加熱分解させて酸化亜鉛水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 11
A zinc sulfate aqueous solution (0.2 mol / L) is dropped into an aqueous ammonium carbonate solution (0.2 mol / L) to form basic zinc carbonate. After removing the salt by washing with water and pulverizing, it is thermally decomposed at 300 ° C. for 1 hour. Thus, a poorly soluble plant quality improver was obtained.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例１２
四塩化チタン水溶液（TiO2 ３．０％）１０００ｇに塩化第二スズ水溶液（ＳｎＯ2 １０．０％）１４１．５ｇを加えて均一化した。この溶液に、アンモニア水２．０％アンモニア水１６９０ｇを約１．５時間かけて攪拌下滴下し、ゲルを得た。このゲルを塩素イオンが認められなくなるまでろ過洗浄を行った。
この洗浄ゲル（ＴｉＯ2 7.1%、ＳｎＯ2 3.3%）３００ｇに２．０％アンモニア水１６ｇ及び水を１１０ｇ添加した後、２００℃で７時間水熱処理を酸化チタン−酸化スズ水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 12
141.5 g of a stannic chloride aqueous solution (SnO 2 10.0%) was added to 1000 g of a titanium tetrachloride aqueous solution (TiO 2 3.0%) to make it uniform. To this solution, 1690 g of 2.0% ammonia water was added dropwise with stirring over about 1.5 hours to obtain a gel. The gel was washed by filtration until no chlorine ions were observed.
After adding 16 g of 2.0% ammonia water and 110 g of water to 300 g of this washing gel (TiO 2 7.1%, SnO 2 3.3%), hydrothermal treatment at 200 ° C. for 7 hours is a titanium oxide-tin oxide water poorly soluble plant quality improver. Got.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例１３
直流アークプラズマ装置でアルミニウム原料を消費アノート電極とし、カソード電極からアルゴンガス等のプラズマフレームを発生させ、消費アノートのアルミニウム原料を加熱、蒸発させ、そのプラズマ状態のアルミニウムを酸化、冷却する事で酸化アルミニウムを得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 13
In a DC arc plasma device, aluminum material is used as a consumption electrode, a plasma flame such as argon gas is generated from the cathode electrode, the aluminum material in consumption air is heated and evaporated, and the aluminum in the plasma state is oxidized and cooled to oxidize Aluminum was obtained.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例１４
市販の酸化ビスマス NanoTek （登録商標、シーアイ化成製）を用い水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 14
Using a commercially available bismuth oxide NanoTek (registered trademark, manufactured by CI Kasei), a poorly water-soluble plant quality improver was obtained.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例１５
市販の酸化セレニウム NanoTek （登録商標、シーアイ化成製）を用い水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 15
A poorly water-soluble plant quality improver was obtained using a commercially available selenium oxide NanoTek (registered trademark, manufactured by CI Kasei).
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例１６
市販の酸化コバルト NanoTek （登録商標、シーアイ化成製）を用い水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 16
A commercially available cobalt oxide NanoTek (registered trademark, manufactured by Cii Kasei) was used to obtain a poorly water-soluble plant quality improver.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例１７
市販の酸化銅 NanoTek （登録商標、シーアイ化成製）を用い水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 17
Using a commercially available copper oxide NanoTek (registered trademark, manufactured by Cii Kasei), a poorly water-soluble plant quality improver was obtained.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例１８
市販の酸化鉄 NanoTek （登録商標、シーアイ化成製）を用い水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 18
A poorly water-soluble plant quality improver was obtained using commercially available iron oxide NanoTek (registered trademark, manufactured by Cii Kasei).
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例１９
市販の酸化ホルミウム NanoTek （登録商標、シーアイ化成製）を用い水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 19
Using a commercially available holmium oxide NanoTek (registered trademark, manufactured by CI Kasei), a poorly water-soluble plant quality improver was obtained.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例２０
市販の酸化インジウムスズ NanoTek （登録商標、シーアイ化成製）を用い水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 20
Using a commercially available indium tin oxide NanoTek (registered trademark, manufactured by CI Kasei), a poorly water-soluble plant quality improver was obtained.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例２１
市販の酸化マンガン NanoTek （登録商標、シーアイ化成製）を用い水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 21
Using a commercially available manganese oxide NanoTek (registered trademark, manufactured by Cii Kasei), a poorly water-soluble plant quality improver was obtained.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例２２
市販の酸化イットリウム NanoTek （登録商標、シーアイ化成製）を用い水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 22
Using a commercially available yttrium oxide NanoTek (registered trademark, manufactured by CI Kasei), a poorly water-soluble plant quality improver was obtained.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例２３
市販の酸化ニッケル NanoTek （登録商標、シーアイ化成製）を用い水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 23
A commercially available nickel oxide NanoTek (registered trademark, manufactured by Cii Kasei) was used to obtain a poorly water-soluble plant quality improver.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
実施例２４
市販の酸化チタン NanoTek （登録商標、シーアイ化成製）を用い水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Example 24
Using a commercially available titanium oxide NanoTek (registered trademark, manufactured by Cii Kasei), a poorly water-soluble plant quality improver was obtained.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
比較例１
水９ｋｇ及びゲルシリカ（NIPGEL AZ-200 東ソー・シリカ株式会社製）１ｋｇを攪拌した混合液をダイノミルＫＤ１．４で流速２００ｇ／分で５回粉砕しゲルシリカ水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Comparative Example 1
A mixed solution obtained by stirring 9 kg of water and 1 kg of gel silica (NIPGEL AZ-200 manufactured by Tosoh Silica Co., Ltd.) was pulverized 5 times with a Dynomill KD1.4 at a flow rate of 200 g / min to obtain a gel silica water poorly soluble plant quality improver.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
比較例２
ダイノミルＫＤ１．４で粉砕を行わない以外は実施例５と同様な方法で硫酸バリウム水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する。
Comparative Example 2
A barium sulfate water poorly soluble plant quality improver was obtained in the same manner as in Example 5 except that pulverization was not carried out with Dinomill KD1.4.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
比較例３
特公平７−８４３６９号公報の実施例１に記載の炭酸カルシウムを用い水難溶性植物品質向上剤を得た。
得られた水難溶性植物品質向上剤のｄ５０、α、β／１０15及びα×（β／１０15）を表１に記載する
Comparative Example 3
A poorly water-soluble plant quality improver was obtained using calcium carbonate described in Example 1 of JP-B-7-84369.
Table 1 shows d50, α, β / 10 15 and α × (β / 10 15 ) of the poorly water-soluble plant quality improver obtained.
応用例１
柑橘（温州みかん：青島）の木を用い、浮き皮軽減及び果実品質の確認を行った。
即ち、前記のみかんの木を用い、９月上旬より、３回（１ヶ月間隔）に渡って、実施例１記載の水難溶性植物品質向上剤を表２に示す濃度で散布した。また、処理は樹別処理とし、背負い式噴霧器により散布した。散布量は１０Ｌ／１樹とした。
評価は、ランダムに選択した５０果を用いて行った。浮き皮度は果実の切断面を浮き皮度０（無し）、１（軽）、２（中）、３（甚）の４段階で評価し、浮き皮指数：｛（１×浮き皮度合い軽の数）＋（２×中の数）＋（３×甚の数）｝×１００÷（３×調査果数）で示した。糖度は屈折糖度計にて測定し、酸度は滴定クエン酸を測定した。果面の汚れは果実表面の水難溶性植物品質向上剤による汚れの割合から、汚れ無し：１、極微量の汚れ：２、少量の汚れ：３、中程度の汚れ：４、多量の汚れ：５とした。薬害は正常：１、極少害：２、少害：３、中害：４、大害：５とした。結果は表２に示す。
Application example 1
Using a citrus tree (Unshu mandarin orange: Qingdao), the floating skin was reduced and the fruit quality was confirmed.
That is, using the tangerine tree, the poorly water-soluble plant quality improver described in Example 1 was sprayed at a concentration shown in Table 2 three times (at an interval of one month) from the beginning of September. Moreover, the process was a tree-separation process and it sprayed with the back-type sprayer. The application amount was 10 L / 1 tree.
Evaluation was performed using 50 fruits selected at random. Floating skin degree is evaluated on 4 levels of floating skin degree 0 (none), 1 (light), 2 (medium), 3 (甚), and floating skin index: {(1 × light skin degree is light Number) + (number of 2 × number) + (number of 3 × 甚)} × 100 ÷ (3 × number of results). The sugar content was measured with a refractometer, and the acidity was measured with titrated citric acid. The stain on the fruit surface is based on the ratio of stains due to poorly water-soluble plant quality improver on the fruit surface. No stain: 1, very small amount of stain: 2, small amount of stain: 3, moderate stain: 4, large amount of stain: 5 It was. The phytotoxicity was normal: 1, minimal harm: 2, minor harm: 3, moderate harm: 4, major harm: 5. The results are shown in Table 2.
応用例２〜２４、比較応用例１〜３
実施例１の水難溶性植物品質向上剤の代わりに表２記載の水難溶性植物品質向上剤を用いる他は、応用例１と同様の方法で試験を行った。結果は、表２、表３に示す。
Application Examples 2-24, Comparative Application Examples 1-3
A test was conducted in the same manner as in Application Example 1 except that the poorly water-soluble plant quality improver described in Table 2 was used instead of the poorly water-soluble plant quality improver of Example 1. The results are shown in Tables 2 and 3.
比較応用例４
実施例１の水難溶性植物品質向上剤の代わりに蟻酸カルシウムを用いることを除き、他は応用例１と同様の方法で試験を行った。結果は表３に示す。
Comparative application example 4
The test was conducted in the same manner as in Application Example 1 except that calcium formate was used instead of the poorly water-soluble plant quality improver of Example 1. The results are shown in Table 3.
比較応用例５
実施例１の水難溶性植物品質向上剤の代わりに硫酸カルシウム・２水塩５７％、塩化カルシウム２７％、分散剤等１６％の製剤を用いることを除き、他は応用例１と同様の方法で試験を行った。結果は表３に示す。
Comparative application example 5
In the same manner as in Application Example 1 except that instead of the poorly water-soluble plant quality improver of Example 1, a preparation of 57% calcium sulfate dihydrate, 27% calcium chloride, 16%, etc. is used. A test was conducted. The results are shown in Table 3.
比較応用例６
実施例１の水難溶性植物品質向上剤の代わりに塩化カルシウムを用いることを除き、他は応用例１と同様の方法で試験を行った。結果は表３に示す。
Comparative application example 6
The tests were conducted in the same manner as in Application Example 1 except that calcium chloride was used instead of the poorly water-soluble plant quality improver of Example 1. The results are shown in Table 3.
比較応用例７
実施例１の水難溶性植物品質向上剤の代わりに水（コントロール）を用いることを除き、他は応用例１と同様の方法で試験を行った。結果は表３に示す。
Comparative application example 7
The test was conducted in the same manner as in Application Example 1 except that water (control) was used instead of the poorly water-soluble plant quality improver of Example 1. The results are shown in Table 3.
応用例２５
ぶどう（ナガノパープル）の木を用い、裂果軽減及び果実品質の確認を行った。即ち、前記のぶどうの木を用い、６月中旬より３回（２週間間隔）に渡って、実施例１の水難溶性植物品質向上剤を表４に示す濃度で散布した。また、処理は樹別処理とし、背負い式噴霧器により散布した。散布量は１０Ｌ／１樹とした。評価は、ランダムに選択した２０房を用いて行った。裂果度は全果数に対する裂果粒数の割合（％）とした。糖度は屈折糖度計にて測定し、酸度は滴定酒石酸を測定した。果面の汚れは果実表面の水難溶性植物品質向上剤による汚れの割合から、汚れ無し：１、極微量の汚れ：２、少量の汚れ：３、中程度の汚れ：４、多量の汚れ：５とした。薬害は正常：１、極少害：２、少害：３、中害：４、大害：５とした。結果は表４に示す。
Application Example 25
Using vine (Nagano purple) trees, fruit reduction and fruit quality were confirmed. That is, using the vine, the poorly water-soluble plant quality improver of Example 1 was sprayed at the concentration shown in Table 4 three times (2 weeks interval) from the middle of June. Moreover, the process was a tree-separation process and it sprayed with the back-type sprayer. The application amount was 10 L / 1 tree. Evaluation was carried out using 20 randomly selected tresses. The degree of ripening was defined as the ratio (%) of the number of berries to the total number of fruits. The sugar content was measured with a refractometer, and the acidity was measured with titrated tartaric acid. The stain on the fruit surface is based on the ratio of stains due to poorly water-soluble plant quality improver on the fruit surface. No stain: 1, very small amount of stain: 2, small amount of stain: 3, moderate stain: 4, large amount of stain: 5 It was. The phytotoxicity was normal: 1, minimal harm: 2, minor harm: 3, moderate harm: 4, major harm: 5. The results are shown in Table 4.
応用例２６〜４８、比較応用例８〜１０
実施例１の水難溶性植物品質向上剤の代わりに表４記載の水難溶性植物品質向上剤を用いる他は、応用例２５と同様の方法で試験を行った。結果は、表４、表５に示す
Application examples 26-48, comparative application examples 8-10
A test was conducted in the same manner as in Application Example 25 except that the poorly water-soluble plant quality improver described in Table 4 was used instead of the poorly water-soluble plant quality improver of Example 1. The results are shown in Tables 4 and 5.
比較応用例１１
実施例１の水難溶性植物品質向上剤の代わりに蟻酸カルシウムを用いることを除き、他は応用例２５と同様の方法で試験を行った。結果は表５に示す。
Comparative application example 11
A test was conducted in the same manner as in Application Example 25 except that calcium formate was used in place of the poorly water-soluble plant quality improver of Example 1. The results are shown in Table 5.
比較応用例１２
実施例１の水難溶性植物品質向上剤の代わりに硫酸カルシウム・２水塩５７％、塩化カルシウム２７％、分散剤等１６％の製剤を用いることを除き、他は応用例２５と同様の方法で試験を行った。結果は表５に示す。
Comparative application example 12
In the same manner as in Application Example 25 except that instead of the poorly water-soluble plant quality improver of Example 1, a preparation of 57% calcium sulfate dihydrate, 27% calcium chloride, 16%, etc. is used. A test was conducted. The results are shown in Table 5.
比較応用例１３
実施例１の水難溶性植物品質向上剤の代わりに塩化カルシウムを用いることを除き、他は応用例２５と同様の方法で試験を行った。結果は表５に示す。
Comparative application example 13
The test was conducted in the same manner as in Application Example 25 except that calcium chloride was used instead of the poorly water-soluble plant quality improver of Example 1. The results are shown in Table 5.
比較応用例１４
実施例１の水難溶性植物品質向上剤の代わりに水（コントロール）を用いることを除き、他は応用例２５と同様の方法で試験を行った。結果は表５に示す。
Comparative application example 14
The test was performed in the same manner as in Application Example 25 except that water (control) was used instead of the poorly water-soluble plant quality improver of Example 1. The results are shown in Table 5.
応用例４９
オウトウ（佐藤錦）の木を用い、裂果軽減及び果実品質の確認を行った。即ち、前記のオウトウの木を用い、５月初旬より３回（２週間間隔）に渡って、実施例１の水難溶性植物品質向上剤を表６に示す濃度で散布した。また、処理は樹別処理とし、背負い式噴霧器により散布した。散布量は１０Ｌ／１樹とした。評価は、ランダムに選択した５０果を用いて行った。裂果率は全果数に対する裂果発生果数の割合（％）とした。糖度は屈折糖度計にて測定し、酸度は滴定リンゴ酸を測定した。果面の汚れは果実表面の水難溶性植物品質向上剤による汚れの割合から、汚れ無し：１、極微量の汚れ：２、少量の汚れ：３、中程度の汚れ：４、多量の汚れ：５とした。薬害は正常：１、極少害：２、少害：３、中害：４、大害：５とした。結果は表６に示す。
Application Example 49
Using cherry (Sato Nishiki) trees, reduction of fruit ripening and fruit quality were confirmed. That is, using the above-mentioned cherry tree, the poorly water-soluble plant quality improver of Example 1 was sprayed at a concentration shown in Table 6 three times (at an interval of 2 weeks) from the beginning of May. Moreover, the process was a tree-separation process and it sprayed with the back-type sprayer. The application amount was 10 L / 1 tree. Evaluation was performed using 50 fruits selected at random. The rate of fruit splitting was defined as the ratio (%) of the number of fruit cracks generated to the total number of fruits. The sugar content was measured with a refractometer, and the acidity was measured with titrated malic acid. The stain on the fruit surface is based on the ratio of stains due to poorly water-soluble plant quality improver on the fruit surface. No stain: 1, very small amount of stain: 2, small amount of stain: 3, moderate stain: 4, large amount of stain: 5 It was. The phytotoxicity was normal: 1, minimal harm: 2, minor harm: 3, moderate harm: 4, major harm: 5. The results are shown in Table 6.
応用例５０〜７２、比較応用例１５〜１７
実施例１の水難溶性植物品質向上剤の代わりに表６記載の水難溶性植物品質向上剤を用いる他は、応用例４９と同様の方法で試験を行った。結果は、表６、表７に示す
Application examples 50-72, comparative application examples 15-17
A test was conducted in the same manner as in Application Example 49, except that the poorly water-soluble plant quality improver described in Table 6 was used instead of the poorly water-soluble plant quality improver of Example 1. The results are shown in Tables 6 and 7.
比較応用例１８
実施例１の水難溶性植物品質向上剤の代わりに蟻酸カルシウムを用いることを除き、他は応用例４９と同様の方法で試験を行った。結果は表７に示す。
Comparative application example 18
A test was conducted in the same manner as in Application Example 49 except that calcium formate was used in place of the poorly water-soluble plant quality improver of Example 1. The results are shown in Table 7.
比較応用例１９
実施例１の水難溶性植物品質向上剤の代わりに硫酸カルシウム・２水塩５７％、塩化カルシウム２７％、分散剤等１６％の製剤を用いることを除き、他は応用例４９と同様の方法で試験を行った。結果は表７に示す。
Comparative application example 19
In the same manner as in Application Example 49 except that a preparation of calcium sulfate dihydrate 57%, calcium chloride 27%, dispersant 16%, etc. is used instead of the poorly water-soluble plant quality improver of Example 1. A test was conducted. The results are shown in Table 7.
比較応用例２０
実施例１の水難溶性植物品質向上剤の代わりに塩化カルシウムを用いることを除き、他は応用例４９と同様の方法で試験を行った。結果は表７に示す。
Comparative application example 20
A test was conducted in the same manner as in Application Example 49 except that calcium chloride was used in place of the poorly water-soluble plant quality improver of Example 1. The results are shown in Table 7.
比較応用例２１
実施例１の水難溶性植物品質向上剤の代わりに水（コントロール）を用いることを除き、他は応用例４９と同様の方法で試験を行った。結果は表７に示す。
Comparative application example 21
The test was performed in the same manner as in Application Example 49 except that water (control) was used instead of the poorly water-soluble plant quality improver of Example 1. The results are shown in Table 7.
応用例７３
柑橘（不知火）の木を用い、みつ症軽減及び果実品質の確認を行った。即ち、前記の不知火の木を用い、９月中旬より３回（３０日間隔）に渡って、実施例１の水難溶性植物品質向上剤を表８に示す濃度で散布した。また、処理は樹別処理とし、背負い式噴霧器により散布した。散布量は１０Ｌ／１樹とした。
評価は、ランダムに選択した１００果を用いて行った。水腐れ発生度は指数０（障害無し）、１（軽）、２（中）、３（甚）の４段階で評価し、発生度：｛（１×指数１の数）＋（２×指数２の数）＋（３×指数３の数）｝×１００÷（調査果数×３）で示した。また、発生率は全果数に対する水腐れ指数１以上の果実の割合とした。糖度は屈折糖度計にて測定した。果面の汚れは、果実表面の水難溶性植物品質向上剤による汚れの割合から、汚れ無し：１、極微量の汚れ：２、少量の汚れ：３、中程度の汚れ：４、多量の汚れ：５とした。薬害は正常：１、極少害：２、少害：３、中害：４、大害：５とした。結果は表８に示す。
Application example 73
Using citrus (shiranui) trees, mitigation was reduced and fruit quality was confirmed. That is, using the above-mentioned Shiranui tree, the poorly water-soluble plant quality improver of Example 1 was sprayed at a concentration shown in Table 8 three times (30-day intervals) from mid-September. Moreover, the process was a tree-separation process and it sprayed with the back-type sprayer. The application amount was 10 L / 1 tree.
Evaluation was performed using 100 fruits selected at random. The degree of water rot is evaluated on an index 0 (no obstacle), 1 (light), 2 (medium), and 3 (甚) scale, and the degree of occurrence: {(1 × number of index 1) + (2 × index) 2 number) + (3 × number of index 3)} × 100 ÷ (number of investigation results × 3). In addition, the occurrence rate was the ratio of fruits with water rot index of 1 or more to the total number of fruits. The sugar content was measured with a refractometer. As for the stain on the fruit surface, from the ratio of stain due to the poorly water-soluble plant quality improver on the fruit surface, there is no stain: 1, very small amount of stain: 2, small amount of stain: 3, moderate stain: 4, large amount of stain: It was set to 5. The phytotoxicity was normal: 1, minimal harm: 2, minor harm: 3, moderate harm: 4, major harm: 5. The results are shown in Table 8.
応用例７４〜９６、比較応用例２２〜２４
実施例１の水難溶性植物品質向上剤の代わりに表１記載の水難溶性植物品質向上剤を用いる他は、応用例７３と同様の方法で試験を行った。結果は、表８、表９に示す
Application examples 74-96, comparative application examples 22-24
A test was conducted in the same manner as in Application Example 73 except that the poorly water-soluble plant quality improver described in Table 1 was used instead of the poorly water-soluble plant quality improver of Example 1. The results are shown in Table 8 and Table 9.
比較応用例２５
実施例１の水難溶性植物品質向上剤の代わりに蟻酸カルシウムを用いることを除き、他は応用例７３と同様の方法で試験を行った。結果は表９に示す。
Comparative application example 25
A test was conducted in the same manner as in Application Example 73 except that calcium formate was used in place of the poorly water-soluble plant quality improver of Example 1. The results are shown in Table 9.
比較応用例２６
実施例１の水難溶性植物品質向上剤の代わりに硫酸カルシウム・２水塩５７％、塩化カルシウム２７％、分散剤等１６％の製剤を用いることを除き、他は応用例７３と同様の方法で試験を行った。結果は表９に示す。
Comparative Application Example 26
In the same manner as in Application Example 73 except that instead of the poorly water-soluble plant quality improver of Example 1, a preparation of 57% calcium sulfate dihydrate, 27% calcium chloride, 16%, etc. is used. A test was conducted. The results are shown in Table 9.
比較応用例２７
実施例１の水難溶性植物品質向上剤の代わりに塩化カルシウムを用いることを除き、他は応用例７３と同様の方法で試験を行った。結果は表９に示す。
Comparative application example 27
The test was performed in the same manner as in Application Example 73 except that calcium chloride was used instead of the poorly water-soluble plant quality improver of Example 1. The results are shown in Table 9.
比較応用例２８
実施例１の水難溶性植物品質向上剤の代わりに水（コントロール）を用いることを除き、他は応用例７３と同様の方法で試験を行った。結果は表９に示す。
Comparative application example 28
A test was conducted in the same manner as in Application Example 73 except that water (control) was used instead of the poorly water-soluble plant quality improver of Example 1. The results are shown in Table 9.
以上のように、水溶性の薬剤を用いた場合、各種生理障害の軽減効果が弱く、また、薬害が発生する結果となった。それに対して、本発明の水難溶性植物品質向上剤は、各種植物で発生する生理障害を抑制・軽減するとともに、植物の糖度や酸味等の品質を向上させる作用も併せ持つ。また、果面の汚れも少なく商品価値を高めることができる。更に、薬害も少なく安全性が高い。 As described above, when a water-soluble drug was used, the effect of reducing various physiological disorders was weak, and phytotoxicity was generated. In contrast, the poorly water-soluble plant quality improver of the present invention suppresses / reduces physiological disorders that occur in various plants, and also has the effect of improving the quality of plants such as sugar content and acidity. In addition, the product value can be increased with less fouling. Furthermore, there is little phytotoxicity and high safety.
叙上のとおり、本発明の水難溶性植物品質向上剤は、各種生理障害の軽減効果、特に、柑橘類果実の浮き皮抑制、水腐れ抑制、ぶどうやオウトウの裂果防止に優れるとともに、従来の水難溶性薬剤散布時に見られた果面の白斑等の汚れを解決したもので、その有用性は頗る大である。
As described above, the poorly water-soluble plant quality improver of the present invention is effective in alleviating various physiological disorders, in particular, citrus fruit floating skin suppression, water rot suppression, and prevention of grape and sweet cherry ripening, as well as conventional poor water solubility. It is a solution that solves the stains such as vitiligo on the face seen during the spraying of the drug, and its usefulness is enormous.
Claims (5)
ｄ５０：ナノトラックＵＰＡ１５０により測定した粒子の５０％重量平均径。 Choose from aluminum oxide, bismuth oxide, selenium oxide, cobalt oxide, copper oxide, iron oxide, holmium oxide, indium tin oxide, manganese oxide, tin oxide, yttrium oxide, zinc oxide, nickel oxide, titanium oxide, colloidal silica, barium sulfate Water-insoluble plant quality for prevention of floating skin, prevention of water rot, and prevention of ripening, characterized by comprising 50% weight average diameter d50 of 0.002 μm ≦ d50 ≦ 0.2 μm. Improver.
d50: 50% weight average particle diameter measured by Nanotrac UPA150.
ａ）２０≦α≦１００
α：分光光度計にて測定した水難溶性植物品質向上剤を固形分として１重量％に調製した時の波長660nm 透過光の強度（％）。 The poorly water-soluble plant quality improver according to any one of claims 1 to 3, wherein the following formula a) is satisfied.
a) 20 ≦ α ≦ 100
α: Intensity (%) of transmitted light having a wavelength of 660 nm when a poorly water-soluble plant quality improver measured with a spectrophotometer is prepared as 1% by weight as a solid content.
ｂ）０．０１≦α×（β／１０15）≦５０００
β：水難溶性植物品質向上剤を固形分として１重量％に調製した時の１ｍｌ中に含有する粒子の数（ｄ５０より計算した粒子の数）。
The poorly water-soluble plant quality improver according to any one of claims 1 to 4, wherein the following formula b) is satisfied.
b) 0.01 ≦ α × (β / 10 15 ) ≦ 5000
β: Number of particles (number of particles calculated from d50) contained in 1 ml when the poorly water-soluble plant quality improver is adjusted to 1% by weight as a solid content.
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| JP2006224913A JP4795167B2 (en) | 2006-08-22 | 2006-08-22 | Poorly water-soluble plant quality improver |
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| JP2006224913A JP4795167B2 (en) | 2006-08-22 | 2006-08-22 | Poorly water-soluble plant quality improver |
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| JP4795167B2 JP4795167B2 (en) | 2011-10-19 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019031432A (en) * | 2017-08-09 | 2019-02-28 | 三洋化成工業株式会社 | Spray type fertilizer |
| KR102060690B1 (en) * | 2018-02-19 | 2019-12-30 | 농업회사법인 주식회사 엘바이오텍 | Composition for increasing the sugar contents and the storage stability of citrus fruits and uses thereof |
| CN116376556A (en) * | 2023-04-04 | 2023-07-04 | 中国科学院南京土壤研究所 | Nanometer micro-alkali irrigation water for controlling acid and reducing cadmium and method for irrigating rice |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0881317A (en) * | 1994-09-08 | 1996-03-26 | Catalysts & Chem Ind Co Ltd | Growth promoter for plant |
| JP2004298046A (en) * | 2003-03-31 | 2004-10-28 | Royal Industries Kk | Method for preventing flotation of exocarp of citrus and agent for preventing the same |
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- 2006-08-22 JP JP2006224913A patent/JP4795167B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0881317A (en) * | 1994-09-08 | 1996-03-26 | Catalysts & Chem Ind Co Ltd | Growth promoter for plant |
| JP2004298046A (en) * | 2003-03-31 | 2004-10-28 | Royal Industries Kk | Method for preventing flotation of exocarp of citrus and agent for preventing the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019031432A (en) * | 2017-08-09 | 2019-02-28 | 三洋化成工業株式会社 | Spray type fertilizer |
| JP7079172B2 (en) | 2017-08-09 | 2022-06-01 | 三洋化成工業株式会社 | Spray fertilizer |
| KR102060690B1 (en) * | 2018-02-19 | 2019-12-30 | 농업회사법인 주식회사 엘바이오텍 | Composition for increasing the sugar contents and the storage stability of citrus fruits and uses thereof |
| CN116376556A (en) * | 2023-04-04 | 2023-07-04 | 中国科学院南京土壤研究所 | Nanometer micro-alkali irrigation water for controlling acid and reducing cadmium and method for irrigating rice |
| CN116376556B (en) * | 2023-04-04 | 2023-11-28 | 中国科学院南京土壤研究所 | Nanometer micro-alkali irrigation water for controlling acid and reducing cadmium and method for irrigating rice |
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| JP4795167B2 (en) | 2011-10-19 |
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