JP3744484B2 - Algae-proofing composition and algaeproofing agent for ornamental fish using this composition - Google Patents
Algae-proofing composition and algaeproofing agent for ornamental fish using this composition Download PDFInfo
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- JP3744484B2 JP3744484B2 JP2002309325A JP2002309325A JP3744484B2 JP 3744484 B2 JP3744484 B2 JP 3744484B2 JP 2002309325 A JP2002309325 A JP 2002309325A JP 2002309325 A JP2002309325 A JP 2002309325A JP 3744484 B2 JP3744484 B2 JP 3744484B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、民生用、産業用水の防藻組成物に関し、さらに詳しくは観賞魚用水槽、クーリングタワー、人工河川等に発生する藻類を防止し、除去する防藻組成物および本組成物を用いた観賞魚用防藻剤に関するものである。
【０００２】
【従来の技術】
従来これら防藻組成物としてはベンゾチアゾール系、フェニル尿素系等に代表される有機系防藻剤、銀、銅、亜鉛等に代表される防藻性を有する重金属からなる無機系防藻剤が知られていた。
【０００３】
【発明が解決しようとする課題】
しかしながらこれら防藻剤の内、有機系防藻剤は効果の持続性が不十分であり、所謂毒性が比較的強く排水時の問題や魚類に対する安全性の点から極めて限られた用途にしか用いることができず、一方無機系防藻剤は初期に藻類が完全に除去された水系では比較的長期間効果を発揮するものの、藻類の内特にアオコ（Ｍｉｃｒｏｃｙｓｔｉｓ ａｅｒｕｇｉｎｏｓａ）に代表される浮遊性藍藻類等のすでに発生した水系では効果が極めて少なく、無機系防藻剤を投入する前にあらかじめ藻類を完全に除去する必要があった。
【０００４】
本発明はかかる課題を解決するものであり、防藻効果、藻類除去効果に優れた防藻組成物および本組成物を用いた観賞魚用防藻剤を提供することを目的とする。
【０００５】
【課題を解決するための手段】
これら従来の課題を解決するために本発明者らが鋭意研究を重ねた結果、凝集剤および酸中和剤がそれぞれ無機系多孔質体に担持された時、より藻類除去効果が優れることを見いだし、本発明を完結するに至った。本発明の防藻組成物は以下の構成を具備するものである。
【０００６】
すなわち、凝集剤、酸中和剤がそれぞれ無機系多孔質体に担持され、好適には、凝集剤がポリ塩化アルミニウムであり、酸中和剤が炭酸水素ナトリウムであり、無機系多孔質体がアルミナ多孔質体である。
【００１１】
【発明の実施の形態】
本発明で用いる凝集剤とは、水中のコロイド状粒子、浮遊性の藍藻類（特にアオコ）等を凝集することによりその粒子を巨大化し、循環経路内でフィルター類により除去することを目的として用いるものであり、硫酸アルミニウム、ポリ塩化アルミニウム、硫酸第一鉄、硫酸第二鉄、塩素化コッパラス、塩化亜鉛、硫酸亜鉛等の無機系凝集剤、ポリアクリル酸ナトリウム、ポリアクリルアミド、ポリビニルピリジン塩酸塩等の有機系凝集剤が含まれる。これらの無機系および有機系凝集剤のうち、アルカリ消費量の少なさ、単位使用量当たりの凝集効果の大きさ、凝集効果に対するＰＨ範囲、温度範囲の広さの点からポリ塩化アルミニウムが好ましい。
【００１２】
本発明で用いる酸中和剤とは、凝集剤として無機系凝集剤を用いる場合、そのＰＨ低下を補償する目的で用いるものであり、炭酸ナトリウム、炭酸水素ナトリウム、水酸化カルシウム等のアルカリ性化合物である。好適には、魚類をはじめとする生体系（特に血液中）にＰＨ値緩衝剤として多く含まれ、人体に対しても胃酸の中和剤として実績が高く、安全性の高い炭酸水素ナトリウム（ＮａＨＣＯ3）が好ましい。
【００１５】
本発明で用いる無機系多孔質体とは、上記凝集剤、酸中和剤を吸着担持し、水中で徐放させることを目的とするものであり、好適には凝集剤に対する安定性、強度の点から比表面積１００〜４００ｍ2／ｇ程度のアルミナ多孔質体が好ましい。
【００１６】
本発明の構成において、初期に浮遊性藍藻類やコロイド状有機物または無機物により懸濁状態にある水系に本発明の防藻組成物を作用させることにより、本発明の防藻組成物中の凝集剤が作用し上記懸濁物を効果的に除去し、水替えをしたと同じ状態を作り出し藻類の発生を抑制する。
【００１７】
以下に本発明のいくつかの実施例について説明するが、本発明はこれら実施例に限定されるものではない。
【００１８】
試料作成方法、試験方法は以下に示す通りである。
【００１９】
（試料作成方法）
（１）銀化合物を約２重量％担持したリン酸カルシウム粒子粉体（以下Ａｇ−ＨＡＰとする）、銀化合物を約２重量％担持した炭酸カルシウム粒子粉体（以下Ａｇ−ＣＡとする）、銅化合物を約２重量％担持したリン酸カルシウム粒子粉体（以下Ｃｕ−ＨＡＰとする）、銅化合物を約２重量％担持した炭酸カルシウム粒子粉体（以下Ｃｕ−ＣＡとする）、酸化亜鉛ウイスカ、ポリ塩化アルミニウム、炭酸水素ナトリウムのうち本実施例で用いる必要な物質、およびアルギン酸ナトリウムを所定の割合に蒸留水中で混合し、濃度約２重量％の塩化カルシウム水溶液中に滴下し、直径２〜３ｍｍ程度の球状造粒物を得た。
【００２０】
得られた球状造粒物を乾燥後、濃度約１０重量％のアクリル系エマルジョン中に含浸させた後乾燥し、本発明で用いる球状造粒物（以下防藻ビードと記す）を得た。
【００２１】
（２）直径約６ｍｍ、比表面積約１５０ｍ2／ｇの球状アルミナ多孔質体に濃度約３３重量％のポリ塩化アルミニウム水溶液、および濃度約８重量％の炭酸水素ナトリウム水溶液を含浸させた後乾燥し、それぞれポリ塩化アルミニウム約２５重量％含浸アルミナ多孔質体（以下ＰＡＣ−ＡＬとする）、炭酸水素ナトリウム約９重量％含浸アルミナ多孔質体（以下ＮＡＣ−ＡＬとする）を得た。
【００２２】
（試験方法）
３５リットル水槽に循環容量１０リットル／分の上部設置型フィルターを設け、目開き約１ｍｍ角の樹脂製ネットに本発明の防藻組成物を所定量挿入し、上記フィルター内に設置した。そしてこの水槽内で熱帯魚５０匹を飼育し、１日当り６時間直射日光の当たる状態で３ヵ月間放置し、水槽ガラス面に付着した藻類の状態を評価した。
【００２３】
図２は本発明の防藻組成物を評価するために用いた上部設置型フィルターの構成を示したもので、１は樹脂製ネット６に挿入された本発明の防藻組成物、２は濾過用ガラスクロス、３は吸水口、４は排水口、５は水循環用のポンプモータであり、矢印は水の流れ方向を示す。
【００２４】
なお、試験に用いた水は浮遊性藍藻類のうち、Ｍｉｃｒｏｃｙｓｔｉｓ ａｅｒｕｇｉｎｏｓａを主成分とする藻類によって濁度約１８にまで汚染され、観賞価値の低下した水を用いた。
【００２５】
評価の基準は以下の通りである。
【００２６】
＋＋：全ガラス面積の０〜１０％を藻類が覆った状態、
＋：全ガラス面積の１０〜３０％を藻類が覆った状態、
±：全ガラス面積の３０〜５０％を藻類が覆った状態、
−：全ガラス面積の５０〜８０％を藻類が覆った状態、
−−：全ガラス面積の８０〜９０％を藻類が覆った状態、また、初期、２４時間後、３ヵ月後の水の濁度をＪＩＳ ＫＯ１０２に従い評価した。結果はすべて（表１）にまとめて示す。
【００３１】
（実施例１）
前記試料作成法によりＡｇ−ＨＡＰ１００重量部、酸化亜鉛ウイスカ１０重量部、アルギン酸ナトリウム１０重量部からなる防藻ビード１３０ｇと、ＰＡＣ−ＡＬ１０ｇと、ＮＡＣ−ＡＬ２５ｇとの混合物を作成した。得られた混合物を用いて前記試験方法に従い防藻性能を評価した。その結果、３ヵ月後のガラス面に付着した藻類の面積は全ガラス面に対して約８％であり、２４時間後には濁度１の極めて透明な水が得られ、３ヵ月経過後も濁度６を維持しており、観賞価値の高い状態が長期に渡って持続する観賞魚用防藻剤として好適な防藻組成物が得られた。
【００３２】
（実施例２）
前記試料作成法によりＰＡＣ−ＡＬ１０ｇと、ＮＡＣ−ＡＬ２５ｇとの混合物を作成した。得られた混合物を用いて前記試験方法に従い防藻性能を評価した。その結果、３ヵ月後のガラス面に付着した藻類の面積は全ガラス面に対して約３２％であり、２４時間後には濁度１の極めて透明な水が得られ、３ヵ月経過後も濁度１４を維持しており、観賞価値の高い状態が比較的長期に渡って持続する観賞魚用防藻剤として、または発生した藻類（特にアオコ）を一時的に除去する観賞魚用防藻剤として好適な防藻組成物が得られた。
【００３８】
（比較例１）
本発明の防藻組成物を用いないで前記試験方法に従い防藻性能を評価した。その結果、３ヵ月後のガラス面に付着した藻類の面積は全ガラス面に対して約９０％であり、２４時間後には濁度２１、３ヵ月後には濁度４８となり、観賞価値の全くない状態となった。
【００３９】
【表１】
なお本発明の実施例における主要成分の配合量はあくまでも本発明の内容を説明するための一例であり、配合量は各種用途の必要性能に応じて、本発明の主目的を害なわない範囲で任意になし得る。
【００４３】
【発明の効果】
以上のように本発明の防藻組成物は防藻効果、藻類除去効果に優れ、すでに藻類の発生した水系においてでも観賞価値が極めて高い状態を長期間持続することができ、特に観賞魚用防藻剤として好適である。
【図面の簡単な説明】
【図１】本発明の実施例に用いる酸化亜鉛ウイスカの電子顕微鏡写真
【図２】本発明の実施例に用いた上部設置型フィルターの構成図
【符号の説明】
１ 防藻組成物
２ 濾過用ガラスクロス
３ 吸水口
４ 排水口
５ ポンプモータ
６ 樹脂製ネット[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an algae-proof composition for consumer and industrial waters, and more specifically, an alga-proof composition for preventing and removing algae generated in an aquarium for ornamental fish, a cooling tower, an artificial river, and the like, and the present composition. It relates to an algae control agent for ornamental fish.
[0002]
[Prior art]
Conventionally, as these anti-algae compositions, there are organic anti-algae agents represented by benzothiazole, phenylurea, etc., and inorganic anti-algae agents composed of heavy metals having anti-algae properties, such as silver, copper, zinc, etc. It was known.
[0003]
[Problems to be solved by the invention]
However, among these anti-algae agents, organic-type anti-algae agents have insufficient sustainability, so-called toxicity is relatively strong, and they are used only for extremely limited purposes in terms of drainage problems and safety against fish. On the other hand, although the inorganic anti-algae agent is effective for a relatively long time in an aqueous system from which algae have been completely removed in the early stage, among the algae, in particular, planktonic cyanobacteria typified by Microcystis aeruginosa Already generated water systems such as the above have very little effect, and it is necessary to completely remove the algae before introducing the inorganic anti-algae agent.
[0004]
This invention solves this subject, and it aims at providing the algae prevention composition for an ornamental fish using this algae prevention composition excellent in the algae prevention effect and algae removal effect, and this composition.
[0005]
[Means for Solving the Problems]
As a result of intensive studies conducted by the present inventors in order to solve these conventional problems, it has been found that when the flocculant and the acid neutralizing agent are each supported on an inorganic porous body, the algae removal effect is more excellent. The present invention has been completed. The algal control composition of the present invention has the following constitution.
[0006]
That is, the flocculant and the acid neutralizer are respectively supported on the inorganic porous body, and preferably the flocculant is polyaluminum chloride, the acid neutralizer is sodium hydrogen carbonate, and the inorganic porous body is It is an alumina porous body.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The flocculant used in the present invention is used for the purpose of agglomerating colloidal particles in water, floating cyanobacteria (especially blue-green algae), etc. to enlarge the particles and removing them with a filter in the circulation path. Inorganic flocculants such as aluminum sulfate, polyaluminum chloride, ferrous sulfate, ferric sulfate, chlorinated coppers, zinc chloride, zinc sulfate, sodium polyacrylate, polyacrylamide, polyvinylpyridine hydrochloride, etc. Of organic flocculants. Of these inorganic and organic flocculants, polyaluminum chloride is preferred from the viewpoints of low alkali consumption, the magnitude of the agglomeration effect per unit usage, the PH range for the agglomeration effect, and the wide temperature range.
[0012]
The acid neutralizing agent used in the present invention is used for the purpose of compensating for the decrease in pH when an inorganic flocculant is used as the flocculant, and is an alkaline compound such as sodium carbonate, sodium hydrogen carbonate, calcium hydroxide or the like. is there. Preferably, it is contained in a large amount of PH value buffer in biological systems such as fish (especially in blood), and has a proven track record as a neutralizing agent for gastric acid for the human body, and is highly safe sodium bicarbonate (NaHCO 3). 3 ) is preferred.
[0015]
The inorganic porous material used in the present invention is intended to adsorb and support the aggregating agent and acid neutralizing agent, and to release them slowly in water, and preferably has stability and strength against the aggregating agent. From the standpoint, an alumina porous body having a specific surface area of about 100 to 400 m 2 / g is preferable.
[0016]
In the configuration of the present invention, the flocculant in the algal control composition of the present invention is caused by allowing the algal control composition of the present invention to act on an aqueous system that is initially suspended by planktonic cyanobacteria, colloidal organic substances, or inorganic substances. Acts to effectively remove the suspended matter, create the same state as water change, and suppress the generation of algae .
[0017]
Several examples of the present invention will be described below, but the present invention is not limited to these examples.
[0018]
The sample preparation method and test method are as follows.
[0019]
(Sample preparation method)
(1) Calcium phosphate particle powder (hereinafter referred to as Ag-HAP) carrying about 2% by weight of silver compound, calcium carbonate particle powder (hereinafter referred to as Ag-CA) carrying about 2% by weight of silver compound, copper compound Phosphate powder powder (hereinafter referred to as Cu-HAP) supporting about 2% by weight, calcium carbonate particle powder (hereinafter referred to as Cu-CA) supporting about 2% by weight of copper compound, zinc oxide whisker, polyaluminum chloride The necessary substances used in this embodiment of sodium bicarbonate and sodium alginate are mixed in distilled water at a predetermined ratio and dropped into an aqueous solution of calcium chloride having a concentration of about 2% by weight. A granulated product was obtained.
[0020]
The obtained spherical granulated product was dried, impregnated in an acrylic emulsion having a concentration of about 10% by weight, and then dried to obtain a spherical granulated product (hereinafter referred to as “algae-proof bead”) used in the present invention.
[0021]
(2) A spherical alumina porous body having a diameter of about 6 mm and a specific surface area of about 150 m 2 / g is impregnated with a polyaluminum chloride aqueous solution having a concentration of about 33% by weight and a sodium hydrogencarbonate aqueous solution having a concentration of about 8% by weight and then dried. Thus, about 25 wt% polyaluminum chloride impregnated alumina porous body (hereinafter referred to as PAC-AL) and about 9 wt% sodium hydrogen carbonate impregnated alumina porous body (hereinafter referred to as NAC-AL) were obtained.
[0022]
(Test method)
A 35 liter water tank was provided with an upper installation type filter having a circulation capacity of 10 liters / minute, and a predetermined amount of the algal control composition of the present invention was inserted into a resin net having an opening of about 1 mm square and installed in the filter. Then, 50 tropical fish were bred in this aquarium, and left for 3 months in direct sunlight for 6 hours per day, and the state of algae attached to the aquarium glass surface was evaluated.
[0023]
FIG. 2 shows the structure of the top-installed filter used for evaluating the algal control composition of the present invention. 1 is an algal control composition of the present invention inserted into a
[0024]
In addition, the water used for the test was contaminated to a turbidity of about 18 by algae mainly composed of Microcystis aeruginosa among the planktonic cyanobacteria, and water with a decreased ornamental value was used.
[0025]
The criteria for evaluation are as follows.
[0026]
++: 0 to 10% of the total glass area covered with algae,
+: State where algae covered 10-30% of the total glass area,
±: a state where 30 to 50% of the total glass area is covered with algae,
-: State where algae covered 50 to 80% of the total glass area,
-: The state in which algae covered 80 to 90% of the total glass area, and the turbidity of water after 24 hours and 3 months was evaluated according to JIS KO102. All results are summarized in (Table 1).
[0031]
(Example 1 )
A mixture of 100 g of Ag-HAP, 10 parts by weight of zinc oxide whisker, 10 parts by weight of sodium alginate, 130 g of an alga-proof bead, PAC-AL 10 g, and NAC-AL 25 g was prepared by the sample preparation method. The obtained mixture was used to evaluate the algal control performance according to the test method. As a result, the area of algae adhering to the glass surface after 3 months was about 8% of the total glass surface, and very clear water with a turbidity of 1 was obtained after 24 hours, and turbidity after 3 months. The algae composition suitable as an algae-proofing agent for ornamental fish which maintained the
[0032]
(Example 2 )
A mixture of PAC-AL 10 g and NAC-AL 25 g was prepared by the sample preparation method. The obtained mixture was used to evaluate the algal control performance according to the test method. As a result, the area of algae adhering to the glass surface after 3 months was about 32% of the total glass surface, and extremely clear water with a turbidity of 1 was obtained after 24 hours, and turbidity after 3 months. As an algae-proofing agent for ornamental fish that maintains a high degree of ornamental value for a relatively long period of time, or for temporarily removing algae (especially blue-green algae) that have occurred. As a result, a suitable algal control composition was obtained.
[0038]
(Comparative Example 1 )
The anti-algae performance was evaluated according to the test method without using the anti-algae composition of the present invention. As a result, the area of algae adhering to the glass surface after 3 months is about 90% of the total glass surface, turbidity is 21 after 24 hours, and turbidity is 48 after 3 months, and there is no appreciation value at all. It became a state.
[0039]
[Table 1]
Note The amount of major ingredient that put to an embodiment of the present invention is an example for merely explaining the contents of the present invention, the amount is in accordance with the required performance of the various applications, such a primary objective harm the present invention It can be done arbitrarily within a range .
[0043]
【The invention's effect】
As described above, the algal control composition of the present invention is excellent in an algal control effect and an algae removal effect, and can maintain a state of extremely high ornamental value even in an algae-generated aqueous system for a long period of time. Suitable as algae.
[Brief description of the drawings]
FIG. 1 is an electron micrograph of a zinc oxide whisker used in an embodiment of the present invention. FIG. 2 is a configuration diagram of an upper installation type filter used in an embodiment of the present invention.
DESCRIPTION OF SYMBOLS 1
Claims (5)
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| JP2002309325A JP3744484B2 (en) | 2002-10-24 | 2002-10-24 | Algae-proofing composition and algaeproofing agent for ornamental fish using this composition |
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| JP2002309325A JP3744484B2 (en) | 2002-10-24 | 2002-10-24 | Algae-proofing composition and algaeproofing agent for ornamental fish using this composition |
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| JP22482592A Division JP3381274B2 (en) | 1992-07-30 | 1992-07-30 | Algae-proofing composition and algae-proofing agent for ornamental fish using the present composition |
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| JP2003160404A JP2003160404A (en) | 2003-06-03 |
| JP3744484B2 true JP3744484B2 (en) | 2006-02-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106830253A (en) * | 2017-02-17 | 2017-06-13 | 刘畅子 | A kind of flocculant for cleaning fish jar and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4863110B2 (en) * | 2006-06-28 | 2012-01-25 | 株式会社日立プラントテクノロジー | Comprehensive immobilization carrier for breeding water purification, breeding water purification method and apparatus, and aquarium set |
| CN102649060B (en) * | 2011-02-24 | 2014-04-30 | 中国科学院合肥物质科学研究院 | Porous zinc oxide-silver composite nanorod, as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830253A (en) * | 2017-02-17 | 2017-06-13 | 刘畅子 | A kind of flocculant for cleaning fish jar and preparation method thereof |
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| JP2003160404A (en) | 2003-06-03 |
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