JP2004339081A - Powder for bordeaux mixture and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a Bordeaux mixture composition which comes to a homogeneous Bordeaux mixture having a fine particle diameter and stabilized quality when only diluted with water, does not cause the deterioration of a product even at low temperatures and exhibits good suspendibility when diluted with water. <P>SOLUTION: The Bordeaux mixture composition is composed of a powder which can be obtained by drying a reaction product of a slaked lime suspension with a copper sulfate aqueous solution containing a surfactant and has a water content of ≤4.5 wt.%. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

（ただし、Ｒ^１、Ｒ^２およびＲ^３はそれぞれ独立に水素原子またはメチル基を表し、Ｒ^４は炭素数１〜４のアルキレン基を表し、Ｒ^５は水素原子または炭素数１〜２２の炭化水素基、ＡＯは炭素数２〜４のオキシアルキレン基の１種または２種以上で、２種以上の場合はブロック状でもランダム状でも良く、ｐは炭素数２〜４のオキシアルキレン基の平均付加モル数でｐ＝１〜１５０である。）
【化６】

（ただし、Ｘは−ＯＭ^２または−Ｙ−（ＡＯ）_ｒＲ^６〔式（３）〕を表し、Ｍ^１およびＭ^２はそれぞれ独立に水素原子、アルカリ金属、アルカリ土類金属、アンモニウムまたは有機アンモニウムを表し、Ｙはエーテル基またはイミノ基を表し、Ｒ^６は水素原子または炭素数１〜２２の炭化水素基、ＡＯは炭素数２〜４のオキシアルキレン基の１種または２種以上で、２種以上の場合はブロック状でもランダム状でも良く、ｒは炭素数２〜４のオキシアルキレン基の平均付加モル数でｒ＝１〜１５０である。）
また、好適な実施形態においては、前記ポリカルボン酸系化合物が、式（４）で示されるポリアルキレングリコールエステルに基づく構成単位（エ）５０〜９９重量％、式（５）で示されるモノカルボン酸に基づく構成単位（オ）１〜５０重量％および共重合可能な他の単量体に基づく構成単位（ウ）０〜３０重量％を有する共重合体である。
【化７】

（ただし、Ｒ^７は水素原子またはメチル基を表し、Ｒ^８は水素原子または炭素数１〜２２の炭化水素基を表し、ＡＯは炭素数２〜４のオキシアルキレン基の１種または２種以上で、２種以上の場合はブロック状でもランダム状でも良く、ｓは炭素数２〜４のオキシアルキレン基の平均付加モル数でｓ＝１〜１５０である。）
【化８】

（ただし、Ｒ^９は水素原子またはメチル基を表し、Ｍ^３は水素原子、アルカリ金属、アルカリ土類金属、アンモニウムまたは有機アンモニウムを表す。）
【００１２】
【発明の実施の形態】
本発明においては、消石灰懸濁液と硫酸銅水溶液との反応生成物を得、この反応生成物を乾燥することによってボルドー液用粉体を得る。
消石灰懸濁液は、消石灰粉末を水に混合して得られた懸濁液であってよく、あるいは、生石灰を消化して得られた消石灰懸濁液であってよい。
【００１３】
界面活性剤の添加時期は特に限定されず、少なくとも乾燥直前の反応生成物中に含有されていればよい。具体的には、消石灰懸濁液中に界面活性剤を添加することができ、硫酸銅水溶液中に界面活性剤を添加することができる。あるいは、消石灰懸濁液と硫酸銅水溶液とを混合するときに界面活性剤を添加することができる。あるいは、消石灰懸濁液と硫酸銅水溶液とを混合して混合物を得た後に、混合物中に界面活性剤を添加することができる。
【００１４】
この際、界面活性剤の有効成分添加量を、Ｃａ（ＯＨ）_２とＣｕＳＯ_４・５Ｈ_２Ｏとしての固形分の合計濃度に対して１重量％以上とすることによって、本発明の効果が一層顕著となる。また、これが２０重量％を越えても添加量の増加に見合うだけの効果は期待できないので、コストの面からは２０重量％以下とすることが好ましい。
【００１５】
本発明に用いる界面活性剤は、特に制限されることはなく、単独で用いることもできるし、２種以上を併用して用いることも可能である。
界面活性剤としては、例えば、ナフタレンスルホン酸及びその塩、アルキルナフタレンスルホン酸及びその塩、メラミンスルホン酸及びその塩、アミノスルホン酸及びその塩などの芳香族スルホン酸塩、あるいは、ナフタレンスルホン酸とホルムアルデヒドの縮合物及びその塩、アルキルナフタレンスルホン酸とホルムアルデヒドの縮合物及びその塩、メラミンスルホン酸とホルムアルデヒドの縮合物及びその塩、アミノスルホン酸とホルムアルデヒドの縮合物及びその塩などの芳香族化合物とホルムアルデヒドの縮合物のスルホン酸およびその塩が挙げられる。それぞれの塩としては、リチウム、ナトリウム、カリウム等のアルカリ金属、カルシウム等のアルカリ土類金属、アンモニウム、有機アミン由来の有機アンモニウムが挙げられる。有機アミンとしては、エタノールアミン、ジエタノールアミン、トリエタノールアミン、メチルアミン、ジメチルアミン、トリエチルアミンなどが挙げられる。芳香族化合物とホルムアルデヒドの縮合物のスルホン酸およびその塩の平均分子量は１，０００〜１０，０００である。
【００１６】
また、本発明に用いる界面活性剤として、リグニンスルホン酸、変性リグニンスルホン酸及びそれらの塩を用いることができる。塩としては、リチウム、ナトリウム、カリウム等のアルカリ金属、カルシウム等のアルカリ土類金属、アンモニウム、有機アミン由来の有機アンモニウムが挙げられる。有機アミンとしては、エタノールアミン、ジエタノールアミン、トリエタノールアミン、メチルアミン、ジメチルアミン、トリエチルアミンなどが挙げられる。
このようなリグニンスルホン酸、変性リグニンスルホン酸及びそれらの塩は、例えば特開昭５６−１６４０５１号公報、特開昭５９−９２９５４号公報に例示されている。
【００１７】
本発明に用いる界面活性剤としては、ポリアミンのアルキレンオキシド付加物も用いることができ、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン、ジエチレントリアミン、１，２，３−トリアミノプロパン、トリエチレンテトラミン、分子量５００〜１００，０００のポリエチレンイミンのアルキレンオキシド付加物であり、アルキレンオキシドとしては、エチレンオキシド、プロピレンオキシド、ブチレンオキシド等のアルキレンオキシドを、ポリアミンの活性水素に対して単独または２種以上のブロックまたはランダム状付加物として付加重合させてなるものであり、アルキレンオキシドとしては、その３０モル％以上がエチレンオキシドであり、活性水素１モルに対して、１〜１００モル付加させた物が好ましい。
本発明で用いられるスチリルフェニルエーテル系界面活性剤は、モノスチリルフェノール、ジスチリルフェノール、トリスチリルフェノールに炭素数２〜４のアルキレンオキシドを付加させたものや、それらの硫酸エステルおよびその塩、リン酸エステルおよびその塩があり、アルキレンオキシド付加物としては、ポリオキシエチレンモノスチリルフェニルエーテル、ポリオキシエチレンジスチリルフェニルエーテル、ポリオキシエチレントリスチリルフェニルエーテル、ポリ（オキシエチレンオキシプロピレン）モノスチリルフェニルエーテル、ポリ（オキシエチレンオキシプロピレン）ジスチリルフェニルエーテル、ポリ（オキシエチレンオキシプロピレン）トリスチリルフェニルエーテルなどがあり、硫酸エステル及びその塩としては、ポリオキシエチレンモノスチリルフェニルエーテル硫酸エステルおよびその塩、ポリオキシエチレンジスチリルフェニルエーテル硫酸エステルおよびその塩、ポリオキシエチレントリスチリルフェニルエーテル硫酸エステルおよびその塩、ポリ（オキシエチレンオキシプロピレン）モノスチリルフェニルエーテル硫酸エステルおよびその塩、ポリ（オキシエチレンオキシプロピレン）ジスチリルフェニルエーテル硫酸エステルおよびその塩、ポリ（オキシエチレンオキシプロピレン）トリスチリルフェニルエーテル硫酸エステルおよびその塩などがあり、リン酸エステルとしては、ポリオキシエチレンモノスチリルフェニルエーテルリン酸エステルおよびその塩、ポリオキシエチレンジスチリルフェニルエーテルリン酸エステルおよびその塩、ポリオキシエチレントリスチリルフェニルエーテルリン酸エステルおよびその塩、ポリ（オキシエチレンオキシプロピレン）モノスチリルフェニルエーテルリン酸エステルおよびその塩、ポリ（オキシエチレンオキシプロピレン）ジスチリルフェニルエーテルリン酸エステルおよびその塩、ポリ（オキシエチレンオキシプロピレン）トリスチリルフェニルエーテルリン酸エステルおよびその塩があり、硫酸エステルの塩やリン酸エステルの塩の塩としては、ナトリウム塩、カリウム塩、アンモニウム塩、エタノールアミン塩などがあげられ、これらは単独で用いても、２種類以上を混合して用いても良い。
【００１８】
本発明に用いる界面活性剤としてより好ましいのは、ポリカルボン酸系化合物であり、ポリアクリル酸およびその塩、ポリメタクリル酸およびその塩、ポリマレイン酸及びその塩、マレイン酸−スチレンスルホン酸塩の共重合物またはその塩、無水マレイン酸−スチレン共重合物、その加水分解物またはその塩、無水マレイン酸−オレフイン共重合物、その加水分解物またはその塩、ポリオキシアルキレンモノアルキルエーテル（メタ）アクリレート−（メタ）アクリル酸共重合物またはその塩、ポリオキシアルキレンモノ（メタ）アリルエーテル−マレイン酸共重合物またはその塩、ポリオキシアルキレンモノアルキルモノ（メタ）アリルエーテル−無水マレイン酸共重合物、その加水分解物またはその塩等が挙げられる。
【００１９】
この中でも、さらに好ましくは、以下の共重合体が挙げられる。
１）式（１）で示されるポリアルキレングリコールエーテルに基づく構成単位（ア）５０〜９９重量％と、式（２）で示されるジカルボン酸または無水マレイン酸に基づく構成単位（イ）１〜５０重量％および共重合可能な他の単量体に基づく構成単位（ウ）０〜３０重量％を有する共重合体
２）式（４）で示されるポリアルキレングリコールエステルに基づく構成単位（エ）５０〜９９重量％と式（５）で示されるモノカルボン酸に基づく構成単位（オ）１〜５０重量％および共重合可能な他の単量体に基づく構成単位（ウ）０〜３０重量％を有する共重合体
【００２０】
式（１）において、Ｒ^１、Ｒ^２およびＲ^３は水素原子またはメチル基である。
式（１）、式（３）および式（４）において、ＡＯは炭素数２〜４のオキシアルキレン基であり、オキシエチレン基、オキシプロピレン基、オキシブチレン基が挙げられ、好ましくはオキシエチレン基とオキシプロピレン基であり、より好ましくはオキシエチレン基である。
Ｒ^４は炭素数１〜４のアルキレン基であり、メチレン基、エチレン基、プロピレン基、ブチレン基があり、プロピレン基としては、１，２−プロピレン基が好適であり、ブチレン基としては、１，２−ブチレン基、２，３−ブチレン基が好適である。Ｒ^４の炭素数が４を超えると製造が困難なため好ましくない。
ｐは炭素数２〜４のオキシアルキレン基の付加モル数であり、１〜１５０であり、好ましくは１０〜１００である。
式（３）および式（５）のＭ^１、Ｍ^２およびＭ^３は水素原子、アルカリ金属、アルカリ土類金属、アンモニウムまたは有機アンモニウムである。アルカリ金属としてはリチウム、ナトリウム、カリウム、ルビジウム等が挙げられる。アルカリ土類金属としては、マグネシウム、カルシウムが挙げられる。有機アンモニウムとしては、有機アミン由来のアンモニウムであり、有機アミンとしては、例えばモノエタノールアミン、ジエタノールアミン、トリエタノールアミンなどのアルカノールアミン、メチルアミン、ジメチルアミン、トリエチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン等が挙げられ、好ましくはモノエタノールアミン、メチルアミン、エチルアミン、ジエチルアミンである。
Ｘは−ＯＭ^２または−Ｙ−（ＡＯ）_ｒＲ^６〔式（３）〕である。Ｙはエーテル基またはイミノ基であり、エーテル基は−Ｏ−を表し、イミノ基は−ＮＨ−を表す。
Ｒ^５、Ｒ^６およびＲ^８は水素原子または炭素数１〜２２の炭化水素基であり、炭素数１〜２２の炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、第三ブチル基、アミル基、イソアミル基、ヘキシル基、ヘプチル基、２−エチルヘキシル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、イソトリデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、オレイル基、ドコシル基、フェニル基、ベンジル基、クレジル基、ブチルフェニル基、オクチルフェニル基、ノニルフェニル基、ナフチル基等がある。Ｒ^５、Ｒ^６およびＲ^８で示される炭化水素基の炭素数が２２を超えると、式（１）、式（３）および式（４）で示される化合物の親水性が十分でなくなるので好ましくない。
好ましくは、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、第三ブチル基、アミル基、イソアミル基、ヘキシル基、シクロヘキシル基、フェニル基など炭素数１〜６の炭化水素基である。
式（５）において、Ｒ^９は水素原子またはメチル基である。
式（３）において、ｒは１〜１５０であり、好ましくは１〜１００である。
式（４）において、ｓは１〜１５０であり、好ましくは１〜１００である。
本発明に用いるポリカルボン酸系化合物の重量平均分子量は、５００〜１００，０００であり、好ましくは５，０００〜３０，０００である。重量平均分子量が１００，０００を超える化合物は分散性が低下してしまい、また高粘度のため製造が困難になるので好ましくない。
【００２１】
また、本発明に用いるポリカルボン酸系化合物は、公知の方法により、重合開始剤を用いて重合することにより得ることができる。重合の方法については、塊状重合でも溶液重合でも良い。溶液重合で水を溶剤として用いる場合は、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウムなどの過硫酸塩や、過酸化水素、水溶性のアゾ系開始剤を用いることができ、その際に亜硫酸水素ナトリウム、ヒドロキシルアミン塩酸塩、チオ尿素、次亜リン酸ナトリウムなどの促進剤を併用することもできる。また、溶液重合でメタノール、エタノール、イソプロパノールなどの低級アルコール、ｎ−ヘキサン、２−エチルヘキサン、シクロヘキサンなどの脂肪族炭化水素、トルエン、キシレン等の芳香族炭化水素、アセトン、メチルエチルケトン、酢酸エチル等の有機溶剤を用いた重合の場合や塊状重合の際には、ベンゾイルペルオキシド、ジ−ｔ−ブチルペルオキシド、ｔ−ブチルペルオキシイソブチレートなどの有機過酸化物やアゾイソブチロニトリルなどのアゾ系化合物を用いることができる。また、その際にはチオグリコール酸、メルカプトエタノールなどの連鎖移動剤を用いることもできる。
【００２２】
構成単位（ウ）として共重合可能な他の単量体としては、例えばエチレン、プロピレン、ブタジエン、イソプレン、２−メチル−１−ブテン、１−ヘキセン、イソブチレン、ジイソブチレン、１−ドデセン、スチレン、ｐ−メチルスチレン、イソプロピルビニルエーテル、ブチルビニルエーテル、イソプロペニルメチルエーテル、酢酸ビニル、アクリルアミド等が挙げられ、好ましくはイソブチレン、スチレンである。
【００２３】
消石灰懸濁液と硫酸銅水溶液との反応条件は特に限定されない。
例えば、以下の方法で行なうことができる。
消石灰懸濁液に、硫酸銅を水に溶解させた硫酸銅水溶液を加えても良く、消石灰懸濁液に、硫酸銅粉末を加えて混合することもできる。また、硫酸銅を水に溶解させた硫酸銅水溶液に、生石灰または消石灰の粉体を直接混合しても良く、硫酸銅水溶液に消石灰懸濁液を加えても良い。なかでも、消石灰懸濁液に硫酸銅水溶液を加えて調整する方法が好ましい。
上記の反応は、１０〜４０℃で行なうことが特に好ましい。
【００２４】
上記のようにして調製したボルドー液用反応生成物は、そのまま乾燥処理し、あるいは湿式粉砕後に乾燥処理し、粒子径の小さい粉体とすることができる。また、得られた乾燥品を更に乾式粉砕処理することによって、粒子径の小さいボルドー液用粉体として使用できる。
【００２５】
反応生成物を湿式粉砕処理するための処理機としては、ボールミル、チューブミル、タワーミル、ビーズミル、パールミル、アトライター等や、凝集したものをほぐす作用のあるホモジナイザーや超音波乳化機等を用いることができる。
【００２６】
乾燥機としてはスプレードライヤー、フラッシュドライヤー、真空凍結乾燥機、媒体乾燥機等を用いることができる。これらの乾燥機を用いることによって、反応生成物の乾燥を行いながら更に整粒することが好ましい。
乾式粉砕機としては、ジェットミル、堅型ミル（ローラミル）、高速回転ミル、容器駆動媒体ミル、媒体攪拌ミル等を用いることができる。
【００２７】
乾燥機における入り口温度は、１５０〜２８０℃とすることが好ましく、１８０〜２５０℃とすることが更に好ましい。乾燥機における出口温度は、６０〜１００℃とすることが好ましく、７０〜９０℃とすることが更に好ましい。また、アトマイザーディスクの回転速度を９０００〜１１０００ｒｐｍとすることが好ましい。
【００２８】
本発明においては、生石灰粉末及び消石灰粉末を各々水で懸濁液としたものと硫酸銅５水塩との混合割合は一般的に広く使用されている６−６式、４−８式、４−１２式ボルドー液等に適用可能で種々の式数提供が可能である。
本発明のボルドー液用粉体は、粉体の粒子径は必要に応じて適宜選択して用いられる。
【００２９】
【実施例】
以下に実施例により本発明を更に詳細に説明する。
（実施例１）
消石灰微粉末３８４ｇと表１に示す共重合体Ａ６０ｇを水道水４６６ｇにスリーワンモーターで良く分散させた溶液に、硫酸銅５水塩（ＣｕＳＯ_４・５Ｈ_２Ｏ）２９０ｇを水８００ｇに溶解させた溶液を加え、スリーワンモーターで混合反応させ、反応終了後２４時間熟成した。次いで、得られた反応物スラリーを湿式粉砕機アトライタ型式ＭＡ１Ｓ（三井鉱山（株）製）で５ｍｍのアルミナボールを使用して回転数２００ｒｐｍで１回湿式粉砕した。得られた粉砕組成物をマイクロミストドライヤー型式ＭＤＬ−０５０（藤崎電機（株）製）を用いて入口温度１８０℃、排出温度７０℃で３０ｍＬ／ｍｉｎの供給で乾燥して、６−６式ボルドー液相当の粉末品を製造した。得られた粉体の銅濃度は１１．２％で平均粒子径は４．０μであった。この粉体の水分含有量は１．３重量％であった。
【００３０】
【表１】

【００３１】
（実施例２）
消石灰微粉末５１８ｇと表１に示す共重合体Ａ６０ｇを水道水６２６ｇにスリーワンモーターで良く分散させた溶液に、硫酸銅５水塩（ＣｕＳＯ_４・５Ｈ_２Ｏ）１９６ｇを水６００ｇに溶解させた溶液を加え、スリーワンモーターで混合反応させ、反応終了後２４時間熟成した。次いで、得られた反応物スラリーを湿式粉砕機アトライタ型式ＭＡ１Ｓ（三井鉱山（株）製）で５ｍｍのアルミナボールを使用して回転数２００ｒｐｍで１回湿式粉砕した。次いで、得られた反応物スラリーをマイクロミストドライヤー型式ＭＤＬ−０５０（藤崎電機（株）製）を用いて入口温度１８０℃、排出温度７０℃で３０ｍＬ／ｍｉｎの供給で乾燥して、４−８式ボルドー液相当の粉末品を製造した。得られた粉体の銅濃度は６．９％で平均粒子径は４．４μであった。この粉体の水分含有量は１．５重量％であった。
【００３２】
（実施例３）
消石灰微粉末６２６ｇと表１に示す共重合体Ａ６０ｇを水道水７５６ｇにスリーワンモーターで良く分散させた溶液に、硫酸銅５水塩（ＣｕＳＯ_４・５Ｈ_２Ｏ）１５８ｇを水４００ｇに溶解させた溶液を加え、スリーワンモーターで混合反応させ、反応終了後２４時間熟成した。次いで、得られた反応物スラリーを湿式粉砕機アトライタ型式ＭＡ１Ｓ（三井鉱山（株）製）で５ｍｍのアルミナボールを使用して回転数２００ｒｐｍで１回湿式粉砕した。次いで、得られた反応物スラリーをマイクロミストドライヤー型式ＭＤＬ−０５０（藤崎電機（株）製）を用いて入口温度１８０℃、排出温度７０℃で３０ｍＬ／ｍｉｎの供給で乾燥して、４−１２式ボルドー液相当の粉末品を製造した。得られた粉体の銅濃度は４．８％で平均粒子径は４．５μであった。この粉体の水分含有量は１．５重量％であった。
【００３３】
（実施例４）
消石灰微粉末１９２ｇを水道水２３３ｇに良く分散させた溶液に、硫酸銅５水塩（ＣｕＳｏ_４・５Ｈ_２Ｏ）１４５ｇを水４００ｇに溶解させた溶液を加え、真空練合機型式ＰＶＫ−３（みづほ工業（株））で混合反応させ、２４時間熟成した。次いで、得られた反応物に表１に示す共重合体Ａ ３０ｇ加えて真空練合機型式ＰＶＫ−３ （みづほ工業（（株））で混合して、得られた反応物スラリーをスプレードライヤー型式ＳＤ−１２（三井鉱山（株）製）を用いて、入口温度２５０℃、出口温度８０℃、アトマイザーディスク回転数１０，０００ｒｐｍの条件で乾燥した。得られた粉体をジェットミル型式ＣＯ−ＪＥＴ ＳＹＳＴＥＭα ＭａｒｋＩＩ（（株）セイシン企業製）で粉砕して、６−６式ボルドー液相当の粉末品を製造した。得られた粉体の銅濃度は１１．３％で平均粒子径は５．３μであった。この粉体の水分含有量は１．７重量％であった。
【００３４】
（実施例５）
消石灰微粉末１９２ｇと表１に示す共重合体Ｂ１６ｇを水道水２４７ｇにスリーワンモーターで良く分散させた溶液に、硫酸銅５水塩（ＣｕＳＯ_４・５Ｈ_２Ｏ）１４５ｇを水４００ｇに溶解させた溶液を加え、スリーワンモーターで混合反応させ、反応終了後２４時間熟成した。次いで、得られた反応物スラリーをスプレードライヤー型式ＳＤ−１２（三井鉱山（株）製）を用いて、入口温度２５０℃、出口温度８０℃、アトマイザーディスク回転数１０，０００ｒｐｍの条件で乾燥して、６−６式ボルドー液相当の粗粉末品を製造した。次いで、本品をジェットミル型式ＣＯ−ＪＥＴ ＳＹＳＴＥＭα ＭａｒｋＩＩ（（株）セイシン企業製）で粉砕して、６−６式ボルドー液相当の粉末品を製造した。得られた粉体の銅濃度は１１．４％で平均粒子径は５．０μであった。
得られた粉体の水分含有量は１．７重量％であった。
【００３５】
（実施例６）
消石灰微粉末３８４ｇと変成リグニンスルホン酸とポリカルボン酸系化合物を主成分とする界面活性剤（チューポールＥＸ６０Ｒ 竹本油脂（株）製）１００ｇを水道水４２６ｇに良く分散させた溶液に、硫酸銅５水塩（ＣｕＳＯ_４・５Ｈ_２Ｏ）２９０ｇを水８００ｇに５０℃で溶解させた溶液を加え、スリーワンモーターで混合反応させ、反応終了後２４時間熟成した。次いで、得られた反応物スラリーを湿式粉砕機アトライタ型式ＭＡ１Ｓ（三井鉱山（株）製）で５ｍｍのアルミナボールを使用して回転数２００ｒｐｍで１回湿式粉砕した。得られた反応物スラリーをマイクロミストドライヤー型式ＭＤＬ−０５０（藤崎電機（株）製）を用いて入口温度２００℃、排出温度８０℃で３０ｍＬ／ｍｉｎの供給で乾燥して、６−６式ボルドー液相当の粉末品を製造した。得られた粉体の銅濃度は１１．０％で平均粒子径は４．９μであった。粉体の水分含有量は１．５重量％であった。
【００３６】
（実施例７）
消石灰微粉末５７６ｇと表１に示す共重合体Ｂ６０ｇを水道水７２９ｇにスリーワンモーターで良く分散させた溶液に、硫酸銅５水塩（ＣｕＳＯ_４・５Ｈ_２Ｏ）４３５ｇを水１，２００ｇに溶解させた溶液を加え、スリーワンモーターで混合反応させ、反応終了後１時間熟成した。次いで、得られた反応物スラリーをスプレードライヤー型式ＳＤ−１２（三井鉱山（株）製）を用いて乾燥して、６−６式ボルドー液相当の粗粉末品を製造した。次いで、本品を乾式アトライタ型式ＭＡ１−Ｄ（三井鉱山（株）製）で５ｍｍアルミナボールを用いて粉砕して、６−６式ボルドー液相当の粉末品を製造した。得られた粉体の銅濃度は１１．１％で平均粒子径は４．３μであった。粉体の水分含有量は１．７重量％であった。
【００３７】
（比較例１）
生石灰微粉末０．６ｋｇを水２．４ｋｇで湿式消化し、放冷後、２００リットルポリ容器に移し、水を加えて２０ｋｇとして消石灰乳液を作成した。この消石灰乳液を攪拌しながら、硫酸銅５水塩０．６ｋｇを水８０ｋｇに溶解した硫酸銅水溶液を徐々に加えてよく混合し、反応終了後２４時間熟成した。次いで、得られた反応物を湿式粉砕機アトライタ型式ＭＡ１Ｓ（三井鉱山（株）製）で５ｍｍのアルミナボールを使用して回転数２００ｒｐｍで１回湿式粉砕後、スプレードライヤー型式ＳＤ−１２（三井鉱山（株）製）を用いて乾燥して、６−６式ボルドー液相当の粉末品を製造した。次いで、本品を乾式アトライタ型式 ＭＡ１−Ｄ（三井鉱山（株）製）で５ｍｍアルミナボールを用いて粉砕して、６−６式ボルドー液相当の粉末品を製造した。得られた粉体の銅濃度は１１．９％で平均粒子径は５．２μであった。粉体の水分含有量は１．６重量％であった。
【００３８】
（比較例２）
消石灰微粉末０．７９ｋｇに水を加えて２０ｋｇとして消石灰乳液を作成した。この消石灰乳液を攪拌しながら、硫酸銅５水塩０．６ｋｇを水８０ｋｇに溶解した硫酸銅水溶液を徐々に加えてよく混合し、反応終了後２４時間熟成した。次いで、得られた反応物スラリーを湿式粉砕機アトライタ型式ＭＡ１Ｓ（三井鉱山（株）製）で５ｍｍのアルミナボールを使用して回転数２００ｒｐｍで１回湿式粉砕した。得られた反応物スラリーをマイクロミストドライヤー型式ＭＤＬ−０５０（藤崎電機（株）製）を用いて入口温度２００℃、排出温度８０℃で３０ｍＬ／ｍｉｎの供給で乾燥して、６−６式ボルドー液相当の粉末品を製造した。得られた粉体の銅濃度は１２．０％で平均粒子径は５．３μであった。
粉体の水分含有量は１．５重量％であった。
【００３９】
（比較例３）
特開２０００−２６２２２号公報に開示された実施例７によりウエットパウダー状ボルドー液用組成物を試作した。７５Ｌのヘンシェルミキサーに平均粒子径６．５μｍ、比表面積３０．８ｍ^２／ｇ、水分０．９％の微消石灰１３．６ｋｇを入れ、攪拌しながらマレイン酸とスチレンのモル比１：２の共重合物のアンモニウム塩１６０ｇを溶解した常温の水１．２ｋｇを加え、５分間攪拌後、硫酸銅（ＣｕＳＯ_４・５Ｈ_２Ｏ）２．０ｋｇを水３．２ｋｇに溶解した５０℃の硫酸銅水溶液を加え、更に、５分間攪拌して固形分濃度（Ｃａ（ＯＨ）_２とＣｕＳＯ_４・５Ｈ_２Ｏ）約７８重量％の２−１０式ボルドー液相当のウエットパウダー状ボルドー液用組成物約２０ｋｇを製造した。得られた組成物の銅濃度は３．１％で平均粒子径は６．８μであった。粉体の水分含有量は２２．４重量％であった。
【００４０】
（比較例４）
特開２００２−１２５１０号公報に開示された実施例１に準じてペースト状ボルドー液用組成物を試作した。硫酸銅（ＣｕＳＯ_４・５Ｈ_２Ｏ）１５０ｇを３４０ｍＬの水に溶解し、硫酸銅溶液を調整した。また、生石灰（酸化カルシウム）１５０ｇを３５０ｍＬの水に攪拌しながら溶解分散させ石灰乳母液を調整した。石灰乳母液に表１に示す共重合体Ｂ１３．５ｇ（固形分濃度４０％）を添加した後、硫酸銅溶液を少しずつ滴下しながら加えてボルドー液の濃度が約３０％のボルドー原液を調整した。このボルドー原液を湿式粉砕機磁性ボールミル（浅田鉄工（株）製：容量３Ｌ、磁性ボール径２５ｍｍを３０個充填）を用い、３０ｒｐｍ、１時間粉砕処理することにより６−６式ボルドー液相当のペースト状ボルドー液用組成物約１ｋｇを製造した。得られた組成物の銅濃度は３．７％で平均粒子径は３．９μであった。このペーストの水分含有量は６５．４重量％であった。
【００４１】
以上の通りに得られた実施例及び比較例の粉体のボルドー液と各々の試料をポリエチレン袋に５００ｇ入れてヒートシールして、−１８℃の冷凍庫に６時間暴露して解凍した試料を用いて、以下の評価試験を行った。
実施例及び比較例で製造した、各ボルドー液の分散液の懸垂性を見る為に、有栓付１００ｍＬメスシリンダーに各試料がボルドー液の相当式数になるように所定の量採取希釈して、１分間振とう後、水平な机上に静置して、１０分後、３０分後、６０分後の沈降容積をメスシリンダーの目盛にて読んだ。
測定結果を表２、表３に示す。
【００４２】
【表２】

【００４３】
【表３】

【００４４】
以上の結果からわかるように、本発明の粉体のボルドー液用粉体は、製造直後と低温暴露後の解凍後においても、良好な懸垂性を有するボルドー液を提供することができる。
【００４５】
【発明の効果】
本発明のボルドー液用粉体は、水で希釈するだけで粒子経が細かく、均質で品質の安定したボルドー液となり、また低温時においても製品の劣化が見られないことから、非常に優れたものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention provides a powder having a fine particle diameter, a uniform and stable Bordeaux solution, and a long-term storage, which is excellent in storability at low temperatures such as in cold regions, simply by dilution with water. Bordeaux liquid composition in the form of
[Prior art]
[0002]
Bordeaux liquid has been used for a long time as a pesticide for disinfecting various agricultural crops, including fruit trees such as apples, grapes and citrus fruits, vegetables such as konjac and tomatoes.
Bordeaux solution is not only inexpensive, but also has a long-lasting effect in order to avoid organic pesticides containing chemicals (environmental hormones) suspected of having an endocrine disrupting effect, which has recently become a problem. It is widely used without waste for the purpose of pesticide reduction to reduce the number of applications using its properties.
The preparation of the Bordeaux solution is usually performed by making quicklime powder into a slaked lime suspension by wet digestion in which water is reacted in water, then cooling the slaked lime suspension, which has been heated by the heat of reaction, and further adding water appropriately. In addition, a diluted aqueous solution of copper sulfate prepared by dissolving copper sulfate pentahydrate separately in water is gradually added to the diluted slaked lime emulsion while stirring at room temperature.
[0003]
However, the work of preparing the Bordeaux solution as described above requires a great deal of labor and labor for digesting quicklime, dissolving and mixing the cooling time, copper sulfate pentahydrate, and the method for digesting quicklime and slaked lime. Depending on the reaction conditions, such as the concentration of the slurry and the aqueous solution of copper sulfate, temperature, etc., the quality of the Bordeaux solution produced varies, and the fine particles have good suspension properties in water. It takes time.
Furthermore, the bordeaux solution thus obtained cannot be prepared and must be used as soon as possible. This is due to the fact that the particles grow or aggregate with the passage of time, the particle radius increases, the suspension in water deteriorates, the adhesion to crops during spraying deteriorates, or the concentration changes due to sedimentation in the container. This can cause spraying and clogging of the nozzles of the sprayer, making uniform and effective spraying impossible.
The bordeaux solution having a predetermined concentration obtained by preparing a high-concentration bordeaux solution in advance and diluting it with water later has a large particle size, poor suspension in water, and the same results as described above.
[0004]
Further, as the slaked lime slurry, it is necessary to use a slaked lime powder obtained by wet-digesting quick lime using water three times or more by weight and appropriately adding water to further dilute the slaked lime. Even if a slurry suspended in water is used, the particle size of the resulting Bordeaux solution will be large, and thus will produce the same results as described above.
In order to solve these problems, for example, Patent Documents 1 and 2 disclose, as a dispersant for a concentrated Bordeaux liquid, a copolymer of a carboxyl group-containing vinyl compound and another vinyl compound, or a salt of these polymers. Is described. Patent Document 3 describes a concentrated Bordeaux solution to which naphthalenesulfonic acid, alkylnaphthalene acid, or a salt of any of these formalin condensates is added. Further, Patent Document 4 describes a method of adding a styrylphenyl ether-based surfactant and, after completion of the reaction, producing a concentrated bordeaux liquid dispersant to which an anionic surfactant is added.
[Patent Document 1]
JP-A-2-279610
[Patent Document 2]
JP-A-2002-12510
[Patent Document 3]
JP-A-2-279612
[Patent Document 4]
JP-A-2002-293707
[0005]
[Problems to be solved by the invention]
However, the concentrated bordeaux solution prepared by these methods is in the form of a paste, and the copper content of the active ingredient is at most about 3.7% by weight at most. The concentrated Bordeaux solution is transported and stored under various environments. In particular, the concentrated Bordeaux liquid may freeze in cold regions or during logistics and storage at low temperatures in winter. Once the concentrated bordeaux solution is frozen, the particles aggregate and the effect of the surfactant is lost, and even when thawed, when dispersed in water at the time of use, there is a problem that the suspension is extremely poor and cannot be used.
[0006]
The object of the present invention is to obtain a Bordeaux liquid having a fine particle size, uniform quality and stable quality only by dilution with water, and no deterioration of the product even at low temperatures, and good suspension properties when diluted with water. The object of the present invention is to provide a composition for bordeaux solution,
[0007]
[Means for Solving the Problems]
The present invention is a reaction product of a slaked lime suspension and an aqueous solution of copper sulfate, which is obtained by drying a reaction product containing a surfactant, and has a water content of 4.5% by weight or less. The present invention relates to a powder for a Bordeaux liquid.
[0008]
The present invention also provides a reaction product of a slaked lime suspension and an aqueous solution of copper sulfate, wherein the water content is 4.5% by weight or less by drying a reaction product containing a surfactant. The present invention relates to a production method characterized by obtaining a powder for bordeaux liquid.
[0009]
The inventor of the present invention disclosed a Bordeaux solution having a water content of 4.5% by weight or less by drying a reaction product of a slaked lime suspension and an aqueous copper sulfate solution, the reaction product containing a surfactant. Powder was obtained. When the powder was diluted with water after storage, the powder component was easily dispersed in water, and a homogeneous Bordeaux solution could be regenerated. When this Bordeaux solution was sprayed, the wetness (spreadability) of the crop surface could be improved. Then, after the present powder for bordeaux liquid was stored at a low temperature and then diluted with water, the suspension of bordeaux liquid particles in water could be improved.
As a result, it was possible to stably produce a homogeneous Bordeaux liquid having good spreadability under a wide range of distribution and storage environments including cold regions, and succeeded in providing a lightweight and easy-to-handle Bordeaux liquid composition.
On the viewpoint, the water content of the powder for bordeaux liquid of the present invention is more preferably 3.5% by weight or less.
[0010]
In a preferred embodiment, the powder for bordeaux liquid contains Ca (OH) ₂ And CuSO ₄ ・ 5H ₂ It is contained within the range of 1 to 20% by weight of the total concentration of solids as O.
In a preferred embodiment, the surfactant contains a polycarboxylic acid compound as an active ingredient.
In a preferred embodiment, the surfactant is naphthalenesulfonic acid and its salt, alkylnaphthalenesulfonic acid and its salt, melaminesulfonic acid and its salt, aminosulfonic acid and its salt, formaldehyde condensate of naphthalenesulfonic acid And a salt thereof, a formaldehyde condensate of alkylnaphthalenesulfonic acid and its salt, a formaldehyde condensate of melaminesulfonic acid and its salt, and a formaldehyde condensate of aminosulfonic acid and its salt.
In a preferred embodiment, the surfactant comprises lignin sulfonic acid, modified lignin sulfonic acid and a salt thereof as an active ingredient.
In a preferred embodiment, the surfactant contains an alkylene oxide adduct of a polyalkylene polyamine as an active ingredient.
In a preferred embodiment, the surfactant is a styrylphenyl ether-based surfactant.
[0011]
In a preferred embodiment, the polycarboxylic acid-based compound is represented by the formula (2): 50 to 99% by weight of a structural unit (A) based on the polyalkylene glycol ether represented by the formula (1). A copolymer having 1 to 50% by weight of a structural unit (a) based on dicarboxylic acid or maleic anhydride and 0 to 30% by weight of a structural unit (c) based on another copolymerizable monomer.
Embedded image

(However, R ¹ , R ² And R ³ Each independently represents a hydrogen atom or a methyl group; ⁴ Represents an alkylene group having 1 to 4 carbon atoms; ⁵ Is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and AO is one or more of oxyalkylene groups having 2 to 4 carbon atoms. The average number of moles of the added oxyalkylene group having 2 to 4 carbon atoms is p = 1 to 150. )
Embedded image

(However, X is -OM ² Or -Y- (AO) _r R ⁶ [Expression (3)] ¹ And M ² Each independently represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or organic ammonium; Y represents an ether group or an imino group; ⁶ Is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and AO is one or more of oxyalkylene groups having 2 to 4 carbon atoms. R = 1 to 150 in the average number of moles of the oxyalkylene group having 2 to 4 carbon atoms. )
In a preferred embodiment, the polycarboxylic acid compound is a polyalkylene glycol ester represented by the formula (4): 50 to 99% by weight of a structural unit (d), and a monocarboxylic acid represented by the formula (5). A copolymer having 1 to 50% by weight of a structural unit (E) based on an acid and 0 to 30% by weight of a structural unit (C) based on another copolymerizable monomer.
Embedded image

(However, R ⁷ Represents a hydrogen atom or a methyl group; ⁸ Represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, AO is one or more of oxyalkylene groups having 2 to 4 carbon atoms, and in the case of two or more, it may be block-shaped or random; s is the average number of moles of the oxyalkylene group having 2 to 4 carbon atoms, and s = 1 to 150. )
Embedded image

(However, R ⁹ Represents a hydrogen atom or a methyl group; ³ Represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or organic ammonium. )
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
In the present invention, a reaction product of a slaked lime suspension and an aqueous solution of copper sulfate is obtained, and the reaction product is dried to obtain a powder for a Bordeaux liquid.
The slaked lime suspension may be a suspension obtained by mixing slaked lime powder with water, or a slaked lime suspension obtained by digesting quicklime.
[0013]
The timing of adding the surfactant is not particularly limited as long as it is contained at least in the reaction product immediately before drying. Specifically, a surfactant can be added to the slaked lime suspension, and a surfactant can be added to the aqueous copper sulfate solution. Alternatively, a surfactant can be added when mixing the slaked lime suspension and the aqueous copper sulfate solution. Alternatively, a surfactant can be added to the mixture after mixing the slaked lime suspension and the aqueous copper sulfate solution to obtain a mixture.
[0014]
At this time, the amount of the active ingredient added to the surfactant was adjusted to Ca (OH) ₂ And CuSO ₄ ・ 5H ₂ The effect of the present invention is further remarkable by setting the content of O to 1% by weight or more based on the total concentration of the solid content. Further, even if this exceeds 20% by weight, the effect corresponding to the increase in the added amount cannot be expected, so that it is preferably 20% by weight or less from the viewpoint of cost.
[0015]
The surfactant used in the present invention is not particularly limited and can be used alone or in combination of two or more.
As the surfactant, for example, naphthalene sulfonic acid and its salt, alkyl naphthalene sulfonic acid and its salt, melamine sulfonic acid and its salt, aminosulfonic acid and its aromatic sulfonic acid salt such as, or naphthalene sulfonic acid Formaldehyde condensates and salts thereof, alkylnaphthalenesulfonic acid and formaldehyde condensates and salts thereof, melaminesulfonic acid and formaldehyde condensates and salts thereof, aminosulfonic acid and formaldehyde condensates and aromatic compounds such as salts thereof Sulfonic acid of a condensate of formaldehyde and a salt thereof are included. Examples of the respective salts include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as calcium, ammonium, and organic ammonium derived from organic amines. Examples of the organic amine include ethanolamine, diethanolamine, triethanolamine, methylamine, dimethylamine, and triethylamine. The average molecular weight of the sulfonic acid of a condensate of an aromatic compound and formaldehyde and a salt thereof is 1,000 to 10,000.
[0016]
Lignin sulfonic acid, modified lignin sulfonic acid and salts thereof can be used as the surfactant used in the present invention. Examples of the salt include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as calcium, ammonium, and organic ammonium derived from organic amines. Examples of the organic amine include ethanolamine, diethanolamine, triethanolamine, methylamine, dimethylamine, and triethylamine.
Such ligninsulfonic acid, modified ligninsulfonic acid and salts thereof are exemplified in, for example, JP-A-56-164051 and JP-A-59-92954.
[0017]
As the surfactant used in the present invention, an alkylene oxide adduct of a polyamine can also be used, and ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, 1,2,3-triaminopropane, triethylenetetramine, and a molecular weight of 500 to 500 are used. An alkylene oxide adduct of 100,000 polyethyleneimine, wherein the alkylene oxide is an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide, alone or two or more blocks or random additions to the active hydrogen of the polyamine; As the alkylene oxide, 30 mol% or more of ethylene oxide is ethylene oxide, and 1 to 100 mol of the alkylene oxide is preferably added to 1 mol of active hydrogen.
The styrylphenyl ether-based surfactant used in the present invention includes monostyrylphenol, distyrylphenol, and tristyrylphenol obtained by adding an alkylene oxide having 2 to 4 carbon atoms, and sulfates thereof, salts thereof, and phosphorus. Acid esters and salts thereof; and alkylene oxide adducts include polyoxyethylene monostyryl phenyl ether, polyoxyethylene distyryl phenyl ether, polyoxyethylene tristyryl phenyl ether, and poly (oxyethylene oxypropylene) monostyryl phenyl ether , Poly (oxyethyleneoxypropylene) distyrylphenyl ether, poly (oxyethyleneoxypropylene) tristyrylphenyl ether, and the like. Polyoxyethylene monostyryl phenyl ether sulfate and its salt, polyoxyethylene distyryl phenyl ether sulfate and its salt, polyoxyethylene tristyryl phenyl ether sulfate and its salt, poly (oxyethyleneoxypropylene) monostyryl phenyl ether Sulfuric acid esters and salts thereof, poly (oxyethyleneoxypropylene) distyryl phenyl ether sulfate and its salts, poly (oxyethyleneoxypropylene) tristyryl phenyl ether sulfate and its salts, and the like. Oxyethylene monostyryl phenyl ether phosphate and its salt, polyoxyethylene distyryl phenyl ether phosphate and its salt , Polyoxyethylene tristyryl phenyl ether phosphate and salts thereof, poly (oxyethylene oxypropylene) monostyryl phenyl ether phosphate and salts thereof, poly (oxyethylene oxypropylene) distyryl phenyl ether phosphate and salts thereof , Poly (oxyethyleneoxypropylene) tristyryl phenyl ether phosphate and its salts. Examples of sulfate and phosphate salts include sodium, potassium, ammonium and ethanolamine salts. These may be used alone or as a mixture of two or more.
[0018]
More preferred as the surfactant used in the present invention are polycarboxylic acid compounds, and polyacrylic acid and its salts, polymethacrylic acid and its salts, polymaleic acid and its salts, and maleic acid-styrene sulfonate. Polymer or salt thereof, maleic anhydride-styrene copolymer, hydrolyzate or salt thereof, maleic anhydride-olefin copolymer, hydrolyzate or salt thereof, polyoxyalkylene monoalkyl ether (meth) acrylate -(Meth) acrylic acid copolymer or salt thereof, polyoxyalkylene mono (meth) allyl ether-maleic acid copolymer or salt thereof, polyoxyalkylene monoalkyl mono (meth) allyl ether-maleic anhydride copolymer , A hydrolyzate thereof or a salt thereof.
[0019]
Among them, the following copolymers are more preferable.
1) 50 to 99% by weight of a structural unit (a) based on a polyalkylene glycol ether represented by the formula (1), and (a) 1 to 50 based on a dicarboxylic acid or maleic anhydride represented by the formula (2) Copolymer having 0 to 30% by weight and a structural unit (C) based on another copolymerizable monomer
2) 50 to 99% by weight of a structural unit (d) based on a polyalkylene glycol ester represented by the formula (4) and 1 to 50% by weight of a structural unit (e) based on a monocarboxylic acid represented by the formula (5) Copolymer having structural unit (C) based on another polymerizable monomer (0) to 30% by weight
[0020]
In the formula (1), R ¹ , R ² And R ³ Is a hydrogen atom or a methyl group.
In the formulas (1), (3) and (4), AO is an oxyalkylene group having 2 to 4 carbon atoms, such as an oxyethylene group, an oxypropylene group and an oxybutylene group, and preferably an oxyethylene group. And an oxypropylene group, and more preferably an oxyethylene group.
R ⁴ Is an alkylene group having 1 to 4 carbon atoms, and includes a methylene group, an ethylene group, a propylene group, and a butylene group. As the propylene group, a 1,2-propylene group is preferable, and as a butylene group, 1,2 -Butylene group and 2,3-butylene group are preferred. R ⁴ If the number of carbon atoms exceeds 4, it is not preferable because the production is difficult.
p is the number of moles of the added oxyalkylene group having 2 to 4 carbon atoms, and is 1 to 150, preferably 10 to 100.
M in equations (3) and (5) ¹ , M ² And M ³ Is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or organic ammonium. Examples of the alkali metal include lithium, sodium, potassium, rubidium and the like. Examples of the alkaline earth metal include magnesium and calcium. The organic ammonium is ammonium derived from an organic amine.Examples of the organic amine include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, methylamine, dimethylamine, triethylamine, ethylamine, diethylamine, and triethylamine. Preferred are monoethanolamine, methylamine, ethylamine and diethylamine.
X is -OM ² Or -Y- (AO) _r R ⁶ [Equation (3)]. Y is an ether group or an imino group, the ether group represents -O-, and the imino group represents -NH-.
R ⁵ , R ⁶ And R ⁸ Is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. Examples of the hydrocarbon group having 1 to 22 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tert-butyl group. , Amyl, isoamyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, oleyl, docosyl Phenyl, benzyl, cresyl, butylphenyl, octylphenyl, nonylphenyl, naphthyl and the like. R ⁵ , R ⁶ And R ⁸ When the number of carbon atoms of the hydrocarbon group represented by is more than 22, the compounds represented by the formulas (1), (3) and (4) are not sufficiently hydrophilic, which is not preferable.
Preferably, a hydrocarbon group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, an amyl group, an isoamyl group, a hexyl group, a cyclohexyl group, and a phenyl group. It is.
In the formula (5), R ⁹ Is a hydrogen atom or a methyl group.
In the formula (3), r is 1 to 150, preferably 1 to 100.
In the formula (4), s is 1 to 150, preferably 1 to 100.
The weight average molecular weight of the polycarboxylic acid compound used in the present invention is from 500 to 100,000, preferably from 5,000 to 30,000. A compound having a weight-average molecular weight of more than 100,000 is not preferred because the dispersibility decreases and the production becomes difficult due to high viscosity.
[0021]
The polycarboxylic acid compound used in the present invention can be obtained by polymerization using a polymerization initiator by a known method. Regarding the polymerization method, bulk polymerization or solution polymerization may be used. When water is used as a solvent in the solution polymerization, persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate, hydrogen peroxide, and a water-soluble azo initiator can be used. Accelerators such as sodium, hydroxylamine hydrochloride, thiourea and sodium hypophosphite can be used in combination. In solution polymerization, methanol, ethanol, lower alcohols such as isopropanol, n-hexane, 2-ethylhexane, aliphatic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene, acetone, methyl ethyl ketone, ethyl acetate and the like In the case of polymerization using an organic solvent or in the case of bulk polymerization, azo compounds such as benzoyl peroxide, di-t-butyl peroxide, organic peroxides such as t-butyl peroxyisobutyrate and azoisobutyronitrile are used. Can be used. In that case, a chain transfer agent such as thioglycolic acid or mercaptoethanol can also be used.
[0022]
Other monomers copolymerizable as the structural unit (C) include, for example, ethylene, propylene, butadiene, isoprene, 2-methyl-1-butene, 1-hexene, isobutylene, diisobutylene, 1-dodecene, styrene, Examples include p-methylstyrene, isopropyl vinyl ether, butyl vinyl ether, isopropenyl methyl ether, vinyl acetate, acrylamide, and the like, with isobutylene and styrene being preferred.
[0023]
The reaction conditions of the slaked lime suspension and the aqueous copper sulfate solution are not particularly limited.
For example, it can be performed by the following method.
An aqueous copper sulfate solution in which copper sulfate is dissolved in water may be added to the slaked lime suspension, or copper sulfate powder may be added to the slaked lime suspension and mixed. In addition, powder of quicklime or slaked lime may be directly mixed into a copper sulfate aqueous solution in which copper sulfate is dissolved in water, or a slaked lime suspension may be added to the copper sulfate aqueous solution. Above all, a method of adjusting by adding an aqueous solution of copper sulfate to the slaked lime suspension is preferable.
The above reaction is particularly preferably performed at 10 to 40 ° C.
[0024]
The reaction product for bordeaux solution prepared as described above can be dried as it is, or dried after wet pulverization to obtain a powder having a small particle diameter. Further, the obtained dried product can be used as a powder for a Bordeaux liquid having a small particle diameter by further performing a dry pulverization treatment.
[0025]
As a processing machine for wet-milling the reaction product, a ball mill, a tube mill, a tower mill, a bead mill, a pearl mill, an attritor, or the like, or a homogenizer or an ultrasonic emulsifier having an action of loosening agglomerated materials may be used. it can.
[0026]
As the dryer, a spray dryer, a flash dryer, a vacuum freeze dryer, a medium dryer, or the like can be used. By using these dryers, it is preferable to further size the particles while drying the reaction product.
As the dry pulverizer, a jet mill, a hard mill (roller mill), a high-speed rotation mill, a container driving medium mill, a medium stirring mill, or the like can be used.
[0027]
The entrance temperature in the dryer is preferably from 150 to 280C, more preferably from 180 to 250C. The outlet temperature in the dryer is preferably 60 to 100 ° C, more preferably 70 to 90 ° C. Further, it is preferable that the rotation speed of the atomizer disk be 9000 to 11000 rpm.
[0028]
In the present invention, the mixing ratio of the powdered lime powder and the slaked lime powder each in suspension with water and the copper sulfate pentahydrate are generally widely used in the formulas 6-6, 4-8 and 4 It is applicable to -12 formula Bordeaux solution and the like, and various formula numbers can be provided.
In the powder for bordeaux liquid of the present invention, the particle diameter of the powder is appropriately selected and used as needed.
[0029]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
(Example 1)
Copper sulfate pentahydrate (CuSO5) was added to a solution in which 384 g of slaked lime fine powder and 60 g of the copolymer A shown in Table 1 were well dispersed in 466 g of tap water using a three-one motor. ₄ ・ 5H ₂ O) A solution prepared by dissolving 290 g in 800 g of water was added, mixed and reacted by a three-one motor, and aged for 24 hours after completion of the reaction. Next, the obtained reaction product slurry was wet-milled once at a rotation speed of 200 rpm using a 5 mm alumina ball with a wet mill pulverizer Attritor Model MA1S (manufactured by Mitsui Mining Co., Ltd.). The obtained pulverized composition was dried using a micro mist dryer model MDL-050 (manufactured by Fujisaki Electric Co., Ltd.) at an inlet temperature of 180 ° C. and an outlet temperature of 70 ° C. at a supply of 30 mL / min to obtain a 6-6 type Bordeaux liquid A considerable powder product was produced. The obtained powder had a copper concentration of 11.2% and an average particle diameter of 4.0 μm. The water content of this powder was 1.3% by weight.
[0030]
[Table 1]

[0031]
(Example 2)
In a solution in which 518 g of slaked lime fine powder and 60 g of the copolymer A shown in Table 1 were well dispersed in 626 g of tap water with a three-one motor, copper sulfate pentahydrate (CuSO ₄ ・ 5H ₂ O) A solution obtained by dissolving 196 g in 600 g of water was added, and mixed and reacted by a three-one motor. After completion of the reaction, the mixture was aged for 24 hours. Next, the obtained reaction product slurry was wet-milled once at a rotation speed of 200 rpm using a 5 mm alumina ball with a wet mill pulverizer Attritor Model MA1S (manufactured by Mitsui Mining Co., Ltd.). Next, the obtained reaction product slurry was dried using a micro mist dryer model MDL-050 (manufactured by Fujisaki Electric Co., Ltd.) at an inlet temperature of 180 ° C. and an outlet temperature of 70 ° C. at a supply of 30 mL / min to obtain 4-8. A powder product equivalent to the formula Bordeaux liquid was produced. The obtained powder had a copper concentration of 6.9% and an average particle size of 4.4 μm. The water content of this powder was 1.5% by weight.
[0032]
(Example 3)
A solution of 626 g of slaked lime fine powder and 60 g of the copolymer A shown in Table 1 in 756 g of tap water well dispersed by a three-one motor was added to copper sulfate pentahydrate (CuSO4). ₄ ・ 5H ₂ O) A solution prepared by dissolving 158 g in 400 g of water was added, mixed and reacted with a three-one motor, and aged for 24 hours after completion of the reaction. Next, the obtained reaction product slurry was wet-milled once at a rotation speed of 200 rpm using a 5 mm alumina ball with a wet mill pulverizer Attritor Model MA1S (manufactured by Mitsui Mining Co., Ltd.). Next, the obtained reaction product slurry was dried using a micro mist dryer model MDL-050 (manufactured by Fujisaki Electric Co., Ltd.) at an inlet temperature of 180 ° C. and an outlet temperature of 70 ° C. at a supply of 30 mL / min, and dried. A powder product equivalent to the formula Bordeaux liquid was produced. The obtained powder had a copper concentration of 4.8% and an average particle size of 4.5 μm. The water content of this powder was 1.5% by weight.
[0033]
(Example 4)
In a solution in which 192 g of slaked lime fine powder was well dispersed in 233 g of tap water, copper sulfate pentahydrate (CuSo ₄ ・ 5H ₂ O) A solution prepared by dissolving 145 g in 400 g of water was added, and mixed and reacted using a vacuum kneader model PVK-3 (Mizuho Industry Co., Ltd.), followed by aging for 24 hours. Next, 30 g of the copolymer A shown in Table 1 was added to the obtained reaction product and mixed with a vacuum kneader model PVK-3 (Mizuho Kogyo Co., Ltd.), and the obtained reaction product slurry was spray-dried. The powder was dried using SD-12 (manufactured by Mitsui Mining Co., Ltd.) under the conditions of an inlet temperature of 250 ° C., an outlet temperature of 80 ° C., and an atomizer disk rotation speed of 10,000 rpm. The powder was pulverized with a SYSTEMα Mark II (manufactured by Seishin Enterprise Co., Ltd.) to produce a powdery product equivalent to the formula 6-6 Bordeaux solution, with a copper concentration of 11.3% and an average particle size of 5.3 μm. The water content of the powder was 1.7% by weight.
[0034]
(Example 5)
Copper sulfate pentahydrate (CuSO5) was added to a solution in which 192 g of slaked lime fine powder and 16 g of the copolymer B shown in Table 1 were well dispersed in 247 g of tap water with a three-one motor. ₄ ・ 5H ₂ O) A solution obtained by dissolving 145 g in 400 g of water was added, and mixed and reacted with a three-one motor, followed by aging for 24 hours after completion of the reaction. Next, the obtained reaction product slurry was dried using a spray dryer model SD-12 (manufactured by Mitsui Mining Co., Ltd.) under the conditions of an inlet temperature of 250 ° C., an outlet temperature of 80 ° C., and an atomizer disk rotation speed of 10,000 rpm. , A crude powder product corresponding to the formula 6-6 Bordeaux solution was produced. Next, this product was pulverized with a jet mill model CO-JET SYSTEMα MarkII (manufactured by Seishin Enterprise Co., Ltd.) to produce a powder product equivalent to a 6-6 type Bordeaux solution. The obtained powder had a copper concentration of 11.4% and an average particle size of 5.0 μm.
The water content of the obtained powder was 1.7% by weight.
[0035]
(Example 6)
Copper sulfate 5 was added to a solution obtained by well dispersing 384 g of slaked lime fine powder and 100 g of a surfactant mainly composed of modified lignin sulfonic acid and a polycarboxylic acid compound (TUPOL EX60R manufactured by Takemoto Yushi Co., Ltd.) in 426 g of tap water. Water salt (CuSO ₄ ・ 5H ₂ O) A solution prepared by dissolving 290 g of water in 800 g of water at 50 ° C. was added, and mixed and reacted with a three-one motor. Next, the obtained reaction product slurry was wet-milled once at a rotation speed of 200 rpm using a 5 mm alumina ball with a wet mill pulverizer Attritor Model MA1S (manufactured by Mitsui Mining Co., Ltd.). The obtained reaction product slurry was dried using a micro mist dryer model MDL-050 (manufactured by Fujisaki Electric Co., Ltd.) at an inlet temperature of 200 ° C. and an outlet temperature of 80 ° C. at a supply of 30 mL / min to obtain a 6-6 type Bordeaux solution A considerable powder product was produced. The obtained powder had a copper concentration of 11.0% and an average particle diameter of 4.9 μm. The water content of the powder was 1.5% by weight.
[0036]
(Example 7)
A solution of 576 g of slaked lime fine powder and 60 g of the copolymer B shown in Table 1 in 729 g of tap water well dispersed by a three-one motor was added to copper sulfate pentahydrate (CuSO4). ₄ ・ 5H ₂ O) A solution prepared by dissolving 435 g in 1,200 g of water was added, and mixed and reacted by a three-one motor. After completion of the reaction, the mixture was aged for 1 hour. Next, the obtained reaction product slurry was dried using a spray dryer model SD-12 (manufactured by Mitsui Mining Co., Ltd.) to produce a crude powder product equivalent to a 6-6 type Bordeaux solution. Next, this product was pulverized with a dry attritor model MA1-D (manufactured by Mitsui Mining Co., Ltd.) using 5 mm alumina balls to produce a powder product equivalent to a 6-6 type Bordeaux solution. The obtained powder had a copper concentration of 11.1% and an average particle size of 4.3 μm. The water content of the powder was 1.7% by weight.
[0037]
(Comparative Example 1)
0.6 kg of quicklime powder was wet digested with 2.4 kg of water, allowed to cool, transferred to a 200-liter plastic container, and water was added to make 20 kg of slaked lime emulsion. While stirring this slaked lime emulsion, an aqueous solution of copper sulfate in which 0.6 kg of copper sulfate pentahydrate was dissolved in 80 kg of water was gradually added and mixed well, followed by aging for 24 hours after the reaction was completed. Next, the obtained reaction product was wet-milled once using a 5 mm alumina ball at a rotation speed of 200 rpm with a wet mill attritor model MA1S (manufactured by Mitsui Mining Co., Ltd.), and then spray dryer model SD-12 (Mitsui Mining Co., Ltd.) (Manufactured by Co., Ltd.) to produce a powdery product equivalent to the 6-6 type Bordeaux solution. Next, this product was pulverized with a dry attritor type MA1-D (manufactured by Mitsui Mining Co., Ltd.) using 5 mm alumina balls to produce a powder product equivalent to a 6-6 type Bordeaux solution. The obtained powder had a copper concentration of 11.9% and an average particle size of 5.2 μm. The water content of the powder was 1.6% by weight.
[0038]
(Comparative Example 2)
Water was added to 0.79 kg of the slaked lime fine powder to make up to 20 kg to prepare a slaked lime emulsion. While stirring the slaked lime emulsion, an aqueous solution of copper sulfate in which 0.6 kg of copper sulfate pentahydrate was dissolved in 80 kg of water was gradually added and mixed well, followed by aging for 24 hours after the completion of the reaction. Next, the obtained reaction product slurry was wet-pulverized once with a wet pulverizer Attritor Model MA1S (manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 200 rpm using 5 mm alumina balls. The obtained reaction product slurry was dried using a micro mist dryer model MDL-050 (manufactured by Fujisaki Electric Co., Ltd.) at an inlet temperature of 200 ° C. and an outlet temperature of 80 ° C. at a supply of 30 mL / min to obtain a 6-6 type Bordeaux solution. A considerable powder product was produced. The obtained powder had a copper concentration of 12.0% and an average particle size of 5.3 μm.
The water content of the powder was 1.5% by weight.
[0039]
(Comparative Example 3)
According to Example 7 disclosed in Japanese Patent Application Laid-Open No. 2000-26222, a wet powder-like composition for a Bordeaux liquid was experimentally produced. Average particle size 6.5 μm, specific surface area 30.8 m in a 75 L Henschel mixer ² / G, 13.6 kg of slaked lime having a water content of 0.9% was added, and 1.2 kg of room temperature water in which 160 g of an ammonium salt of a copolymer of maleic acid and styrene having a molar ratio of 1: 2 was dissolved was added with stirring. After stirring for 5 minutes, copper sulfate (CuSO ₄ ・ 5H ₂ O) An aqueous solution of copper sulfate at 50 ° C. in which 2.0 kg was dissolved in 3.2 kg of water was added, and the mixture was further stirred for 5 minutes to obtain a solid content concentration (Ca (OH) ₂ And CuSO ₄ ・ 5H ₂ O) Approximately 20 kg of a wet powder-like bordeaux liquid composition corresponding to about 2 wt. The obtained composition had a copper concentration of 3.1% and an average particle diameter of 6.8 μm. The water content of the powder was 22.4% by weight.
[0040]
(Comparative Example 4)
According to Example 1 disclosed in JP-A-2002-12510, a paste-like composition for a bordeaux liquid was trial-produced. Copper sulfate (CuSO ₄ ・ 5H ₂ O) 150 g was dissolved in 340 mL of water to prepare a copper sulfate solution. In addition, 150 g of quicklime (calcium oxide) was dissolved and dispersed in 350 mL of water while stirring to prepare a lime mother liquor. After adding 13.5 g (solids concentration: 40%) of the copolymer B shown in Table 1 to the lime mother liquor, a copper sulfate solution was added dropwise little by little to prepare a Bordeaux stock solution having a Bordeaux solution concentration of about 30%. . This Bordeaux undiluted solution was pulverized at 30 rpm for 1 hour using a wet-type crusher magnetic ball mill (manufactured by Asada Tekko Co., Ltd .: capacity 3 L, filled with 30 magnetic balls having a diameter of 25 mm) to obtain a paste equivalent to a 6-6 type bordeaux solution. About 1 kg of a composition for Bordeaux liquid was produced. The obtained composition had a copper concentration of 3.7% and an average particle diameter of 3.9 μm. The water content of this paste was 65.4% by weight.
[0041]
500 g of each of the bordeaux solutions of the powders of the examples and the comparative examples obtained as described above and each sample were put in a polyethylene bag, heat-sealed, and exposed to a freezer at −18 ° C. for 6 hours to be thawed. The following evaluation tests were performed.
In order to check the suspension of the bordeaux liquid dispersions produced in the examples and comparative examples, a predetermined amount was collected and diluted in a stoppered 100 mL graduated cylinder so that each sample had the equivalent number of bordeaux liquids. After shaking for a minute, the sample was allowed to stand on a horizontal desk, and the sedimentation volume after 10, 30, and 60 minutes was read on a graduated cylinder scale.
Tables 2 and 3 show the measurement results.
[0042]
[Table 2]

[0043]
[Table 3]

[0044]
As can be seen from the above results, the powder for bordeaux liquid of the powder of the present invention can provide a bordeaux liquid having good suspension properties immediately after production and after thawing after low-temperature exposure.
[0045]
【The invention's effect】
The powder for bordeaux liquid of the present invention has a fine particle diameter only by dilution with water, and becomes a uniform and stable bordeaux liquid with a stable quality. is there.

Claims (12)

A reaction product of slaked lime suspension and an aqueous solution of copper sulfate, which is obtained by drying a reaction product containing a surfactant, and having a water content of 4.5% by weight or less. , Powder for Bordeaux liquid. The powder for bordeaux liquid according to claim 1, wherein the reaction product is obtained by wet pulverization and drying. The powder for bordeaux liquid according to claim 1 or 2, wherein the surfactant is contained within a range of 1 to 20% by weight of a total concentration of solid content in terms of an active ingredient. The powder for bordeaux liquid according to any one of claims 1 to 3, wherein the surfactant is a polycarboxylic acid compound. The surfactant is naphthalene sulfonic acid and its salt, alkyl naphthalene sulfonic acid and its salt, melamine sulfonic acid and its salt, aminosulfonic acid and its salt, formaldehyde condensate of naphthalene sulfonic acid and its salt, alkyl naphthalene sulfonic acid The formaldehyde condensates and salts thereof, melamine sulfonic acid formaldehyde condensates and salts thereof, and aminosulfonic acid formaldehyde condensates and salts thereof, are selected from the group consisting of, characterized in that: The powder for a Bordeaux liquid according to claim 1. The surfactant according to any one of claims 1 to 3, wherein the surfactant is selected from the group consisting of ligninsulfonic acid, a salt of ligninsulfonic acid, modified ligninsulfonic acid, and a salt of modified ligninsulfonic acid. A powder for a bordeaux liquid according to one of the claims. The powder for bordeaux liquid according to any one of claims 1 to 3, wherein the surfactant is an alkylene oxide adduct of a polyalkylene polyamine. The powder for bordeaux liquid according to any one of claims 1 to 3, wherein the surfactant is a styrylphenyl ether-based surfactant. Wherein the polycarboxylic acid-based compound is composed of 50 to 99% by weight of a structural unit (A) based on a polyalkylene glycol ether represented by the formula (1), and based on a dicarboxylic acid or maleic anhydride represented by the formula (2) The bordeaux solution according to claim 4, characterized in that it is a copolymer having 1 to 50% by weight of the unit (A) and 0 to 30% by weight of the structural unit (C) based on another copolymerizable monomer. For powder.

(However, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group, R ⁴ represents an alkylene group having 1 to ⁴ carbon atoms, and R ⁵ represents a hydrogen atom or a carbon atom having 1 to 22 carbon atoms. The hydrogen group and AO are one or more of oxyalkylene groups having 2 to 4 carbon atoms, and in the case of two or more, they may be block-shaped or random, and p is an average of oxyalkylene groups having 2 to 4 carbon atoms. P = 1 to 150 in terms of the number of moles added.)

(Wherein, X represents a -OM ² or -Y- _(AO) r ^{R 6} [wherein (3)], respectively ^{M 1} and ^{M 2} are independently a hydrogen atom, an alkali metal, alkaline earth metal, ammonium or organic Represents ammonium, Y represents an ether group or an imino group, R ⁶ is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and AO is one or more of an oxyalkylene group having 2 to 4 carbon atoms; In the case of two or more kinds, it may be block-shaped or random, and r is the average number of moles of the oxyalkylene group having 2 to 4 carbon atoms, and r is 1 to 150.) The polycarboxylic acid-based compound is composed of 50 to 99% by weight of a structural unit (d) based on a polyalkylene glycol ester represented by the formula (4), and a structural unit (e) 1 based on a monocarboxylic acid represented by the formula (5) The powder for bordeaux liquid according to claim 4, which is a copolymer having a structural unit (C) of from 0 to 30% by weight based on another copolymerizable monomer.

(However, R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and AO represents one or more of oxyalkylene groups having 2 to 4 carbon atoms.) In the case of two or more, s is an average addition mole number of an oxyalkylene group having 2 to 4 carbon atoms, and s is 1 to 150.)

(However, R ⁹ represents a hydrogen atom or a methyl group, and M ³ represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or organic ammonium.) A reaction product of a slaked lime suspension and an aqueous solution of copper sulfate, which is a reaction product containing a surfactant, is dried to obtain a powder for a Bordeaux liquid having a water content of 4.5% by weight or less. A method for producing a powder for a Bordeaux liquid, comprising: The method according to claim 11, wherein the reaction product is dried after wet grinding.