JPH0873435A - 8-hydroxyquinoline-copper composition and its production - Google Patents
8-hydroxyquinoline-copper composition and its productionInfo
- Publication number
- JPH0873435A JPH0873435A JP6214045A JP21404594A JPH0873435A JP H0873435 A JPH0873435 A JP H0873435A JP 6214045 A JP6214045 A JP 6214045A JP 21404594 A JP21404594 A JP 21404594A JP H0873435 A JPH0873435 A JP H0873435A
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- water
- acid
- aqueous solution
- copper
- salt
- Prior art date
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- Other In-Based Heterocyclic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Quinoline Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、水又は水を主とする水
性溶媒に８−オキシキノリン銅を溶解した８−オキシキ
ノリン銅水溶液からなる組成物及びその製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition comprising an aqueous 8-oxyquinoline copper solution in which copper 8-oxyquinoline is dissolved in water or an aqueous solvent mainly containing water, and a method for producing the same.
【０００２】[0002]
【従来の技術】８−オキシキノリン銅（以下、８ＨＱ−
Ｃｕと略称する）は果樹、蔬菜用の殺菌剤として重要な
物質であり、黒点病、そうか病、黄斑病、潰瘍病、べと
病、炭疽病、斑点細菌病、軟腐病、腐敗病、黒腐病その
他の病害防除に活用されている。このように８ＨＱ−Ｃ
ｕは有用な殺菌剤でありながら水や汎用有機溶媒への溶
解性が低く、特に水への溶解度は0.02ppm と極めて小さ
い値を示す。このため、従来から水和剤として水に分散
させた形で実用に供されており、分散状態の安定化を図
るための種々の工夫がなされている。2. Description of the Related Art Copper 8-oxyquinoline (hereinafter referred to as 8HQ-
(Abbreviated as Cu) is an important substance as a fungicide for fruit trees and vegetables, and it has black spot, scab, yellow spot, ulcer, downy mildew, anthrax, spot bacterial disease, soft rot, rot, It is used to control black rot and other diseases. 8HQ-C
Although u is a useful germicide, its solubility in water and general-purpose organic solvents is low, and its solubility in water is 0.02 ppm, which is an extremely small value. Therefore, it has been conventionally put to practical use in the form of being dispersed in water as a wettable powder, and various measures have been taken to stabilize the dispersed state.
【０００３】８ＨＱ−Ｃｕを水溶液として利用すること
が可能になればその利用分野が拡大され、また、従来の
農薬分野においてもその重要性がさらに増すものと考え
られる。８ＨＱ−Ｃｕを溶液として利用するための研究
は、これまでにも多くの研究機関で研究されたものと考
えられるが、公知の方法としては下記の方法が知られて
いるに過ぎない。すなわち、殺菌剤カルベンダジムをN-
メチルピロリドン、シクロヘキサノンその他の極性有機
溶媒に溶解させるに際して、ドデシルベンゼンスルホン
酸等の芳香族スルホン酸、ノニオン系界面活性剤および
アルキルジメチルアミンを共存させ、さらに、第２殺菌
成分としてナフテン酸亜鉛を加えることを特徴とする木
材防腐剤である（Eur.Pat.0351195 A2,公報）。この公
報の中で殺菌成分として８ＨＱ−Ｃｕも例示されている
が、各種共存成分を添加する過程で８ＨＱ−Ｃｕが析出
し、均一溶液として調製することができない。また、上
記手順で８ＨＱ−Ｃｕが微量溶解した溶液が得られて
も、この溶液は水溶液ではないので、取扱が不便という
問題がある。さらに、この溶液を例えば木材防腐剤とし
て利用する場合、溶液が酸性であるため、木材を使用す
る過程で接触する釘、止め金具その他の金属材料を腐食
させる原因となる。If 8HQ-Cu can be used as an aqueous solution, its field of use will be expanded, and its importance will be further increased in the field of conventional agricultural chemicals. The research for utilizing 8HQ-Cu as a solution is considered to have been carried out by many research institutions so far, but only the following methods are known as known methods. That is, the fungicide carbendazim N-
When dissolved in a polar organic solvent such as methylpyrrolidone, cyclohexanone or the like, coexist with an aromatic sulfonic acid such as dodecylbenzene sulfonic acid, a nonionic surfactant and alkyldimethylamine, and further add zinc naphthenate as a second bactericidal component. A wood preservative characterized by the above (Eur. Pat. 0351195 A2, gazette). Although 8HQ-Cu is also exemplified as a bactericidal component in this publication, 8HQ-Cu precipitates during the process of adding various coexisting components and cannot be prepared as a uniform solution. Further, even if a solution in which a small amount of 8HQ-Cu is dissolved is obtained by the above-mentioned procedure, this solution is not an aqueous solution, so that there is a problem that handling is inconvenient. Further, when this solution is used as a wood preservative, for example, the solution is acidic, which causes corrosion of nails, fasteners, and other metal materials that come into contact during the process of using wood.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、殺菌剤とし
て有用な８ＨＱ−Ｃｕと、防食剤として有用なアルキル
キノリニウム塩及び／又はアルキルイソキノリニウム塩
（これらを総称して、アルキル（イソ）キノリニウム塩
という）とを含む８ＨＱ−Ｃｕの水溶液からなる組成物
及びそれを容易に製造し得る技術を提供するものであ
る。DISCLOSURE OF THE INVENTION The present invention provides 8HQ-Cu, which is useful as a bactericide, and alkylquinolinium salts and / or alkylisoquinolinium salts, which are useful as anticorrosive agents (collectively, alkyl The present invention provides a composition comprising an aqueous solution of 8HQ-Cu containing (iso) quinolinium salt) and a technique capable of easily producing the composition.
【０００５】[0005]
【課題を解決するための手段】本発明は、８−オキシキ
ノリン銅の水溶液を製造するに際し、水性溶媒中に無機
酸及び有機酸から選ばれる１種以上の水溶性の酸と、ア
ルキルキノリニウム塩及びアルキルイソキノリニウム塩
から選ばれる１種以上のアルキル（イソ）キノリニウム
塩を共存させることを特徴とする８−オキシキノリン銅
水溶液の製造方法、並びに水溶液中に、水溶性の酸２〜
３０重量％、８−オキシキノリン銅１〜２０重量％及び
アルキル（イソ）キノリニウム塩０．１〜１０重量％
を、水溶性の酸／８−オキシキノリン銅（モル比）４〜
４０となる割合で溶解させてなる８−オキシキノリン銅
組成物である。The present invention provides a method for producing an aqueous solution of copper 8-oxyquinoline, wherein one or more water-soluble acids selected from inorganic acids and organic acids in an aqueous solvent and an alkylquinolin are used. And at least one alkyl (iso) quinolinium salt selected from alkylisoquinolinium salts are allowed to coexist, and a method for producing an aqueous 8-oxyquinoline copper solution, and a water-soluble acid 2 ~
30% by weight, 8-oxyquinoline copper 1-20% by weight and alkyl (iso) quinolinium salt 0.1-10% by weight
A water-soluble acid / 8-oxyquinoline copper (molar ratio) 4 to
It is an 8-oxyquinoline copper composition dissolved in a ratio of 40.
【０００６】アルキル（イソ）キノリニウム塩として
は、アルキルキノリニウム塩及びアルキルイソキノリニ
ウム塩のいずれか一方又は両方であり、アルキル基とし
ては、炭素数１〜１８のアルキル基、ベンジル基やアル
キル置換ベンジル基が挙げられ、好ましくは非置換のア
ルキル基及びアラルキル基である。また、アニオンはＣ
ｌ-、Ｂｒ-、Ｉ-、ＳＯ4 2-、ＨＳＯ4 -やＣｌＯ4 -等の酸
残基である。アルキル（イソ）キノリニウム塩は防食作
用に加えて、抗菌作用や界面活性剤としての作用も併せ
持つため、用途に合わせてアルキル基を選択することが
できる。例えば、防食作用に加えて抗菌作用をも期待す
るときには、炭素数８〜１４のアルキル基を持つアルキ
ル（イソ）キノリニウム塩が好ましい。これらのアルキ
ル（イソ）キノリニウム塩の使用量は、水液中に２０重
量％以下、好ましくは、０．１〜１０重量％の範囲内で
ある。０．１重量％以下では、防食効果がない。The alkyl (iso) quinolinium salt is either or both of an alkylquinolinium salt and an alkylisoquinolinium salt, and the alkyl group is an alkyl group having 1 to 18 carbon atoms, a benzyl group or Examples thereof include an alkyl-substituted benzyl group, preferably an unsubstituted alkyl group and an aralkyl group. The anion is C
Acid residues such as l − , Br − , I − , SO 4 2− , HSO 4 −, and ClO 4 − . The alkyl (iso) quinolinium salt has an antibacterial action, an antibacterial action and a surfactant action, so that the alkyl group can be selected according to the intended use. For example, when antibacterial action as well as antibacterial action is expected, an alkyl (iso) quinolinium salt having an alkyl group having 8 to 14 carbon atoms is preferable. The amount of these alkyl (iso) quinolinium salts used is 20% by weight or less, preferably 0.1 to 10% by weight in the water solution. If it is less than 0.1% by weight, there is no anticorrosion effect.
【０００７】水性溶媒中に共存させる水溶性の酸のう
ち、無機酸としては塩酸、硫酸や燐酸等の鉱酸を、また
有機酸としてはp-トルエンスルホン酸、アルキルベンゼ
ンスルホン酸やナフタレンスルホン酸及びこれらの縮合
物等の水溶性スルホン酸を挙げることができる。これら
の酸は、単独でも混合してでも使用できるが、使用量は
８ＨＱ−Ｃｕに対してモル比で４〜４０倍の範囲であ
り、水溶液中に２〜３０重量％の範囲である。酸の使用
量を増すと８ＨＱ−Ｃｕの溶解量を増すことができる
が、実用濃度、溶解作業時の安全性や運搬時の経済性等
を考慮すれば、水溶液中に５〜２５重量％の範囲が好適
である。また、水溶性の酸／８ＨＱ−Ｃｕのモル比は酸
濃度に応じて選択できるが、４〜１５の範囲で選択する
のが経済的である。Of the water-soluble acids that are allowed to coexist in the aqueous solvent, inorganic acids include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and organic acids include p-toluenesulfonic acid, alkylbenzenesulfonic acid and naphthalenesulfonic acid. Water-soluble sulfonic acids such as these condensates can be mentioned. These acids can be used either alone or as a mixture, but the amount used is in the range of 4 to 40 times the molar ratio of 8HQ-Cu, and in the range of 2 to 30% by weight in the aqueous solution. If the amount of acid used is increased, the amount of 8HQ-Cu dissolved can be increased, but considering the practical concentration, the safety during dissolution work, the economic efficiency during transportation, etc. Ranges are preferred. The molar ratio of water-soluble acid / 8HQ-Cu can be selected according to the acid concentration, but it is economical to select it in the range of 4 to 15.
【０００８】水性溶媒としては、水がもっとも入手容易
で有利といえるが、必要により水溶性の有機溶媒を加え
ることが出来る。このような有機溶媒としては、アルコ
−ル、ジメチルホルムアミド、Ｎ−メチルピロリドン等
が挙げられ、これらは水に対して等量以下加えることが
よい。As the aqueous solvent, water can be said to be most easily available and advantageous, but a water-soluble organic solvent can be added if necessary. Examples of such an organic solvent include alcohol, dimethylformamide, N-methylpyrrolidone and the like, and these may be added in equal amounts or less to water.
【０００９】酸水溶液に８ＨＱ−Ｃｕ及びアルキル（イ
ソ）キノリニウム塩を溶解させるに際しては、室温下で
攪拌するだけでよく、加熱や特殊な攪拌は必要としな
い。また、ドデシルベンゼンスルホン酸共存下に８ＨＱ
−ＣｕをＮ−メチルピロリドンに溶解させる場合のよう
に、急激な発熱を伴うこともない。酸水溶液に８ＨＱ−
Ｃｕ及びアルキル（イソ）キノリニウム塩を溶解させる
際の手順も、特に制限することはない。When the 8HQ-Cu and the alkyl (iso) quinolinium salt are dissolved in the aqueous acid solution, they need only be stirred at room temperature, and heating and special stirring are not required. 8HQ in the presence of dodecylbenzene sulfonic acid
There is no sudden heat generation as in the case of dissolving -Cu in N-methylpyrrolidone. 8HQ- for acid aqueous solution
The procedure for dissolving Cu and the alkyl (iso) quinolinium salt is also not particularly limited.
【００１０】このようにして製造される８ＨＱ−Ｃｕ水
溶液は、防腐剤、殺菌剤等として使用することができ
る。このような目的で使用されるとき、それぞれの配合
割合は水溶液、すなわち組成物中に、８ＨＱ−Ｃｕ１〜
２０重量％、好ましくは２〜１４重量％、アルキル（イ
ソ）キノリニウム塩０．１〜１０重量％、水溶性の酸２
〜３０重量％を、水溶性の酸／８ＨＱ−Ｃｕ（ＥＵ比）
４〜４０となる割合で溶解させることがよい。The thus-prepared 8HQ-Cu aqueous solution can be used as an antiseptic and a bactericide. When used for such purposes, the respective compounding ratios are 8HQ-Cu1 to
20% by weight, preferably 2-14% by weight, alkyl (iso) quinolinium salt 0.1-10% by weight, water-soluble acid 2
~ 30% by weight of water-soluble acid / 8HQ-Cu (EU ratio)
It is preferable to dissolve it in a ratio of 4 to 40.
【００１１】[0011]
【作用】８ＨＱ−Ｃｕは酸水溶液中ではスルホン酸塩等
の塩の形で溶解しているものと考えられるが、その形態
について正確には分かっていない。また、アルキル（イ
ソ）キノリニウム塩は金属表面に吸着し金属表面と腐食
性成分との接触を防止することで、防食効果を発揮する
ものと考えられる。金属の溶出を抑制することで、金属
表面への銅の析出量が減少するものと考えられる。Function 8HQ-Cu is considered to be dissolved in the form of a salt such as a sulfonate in an aqueous acid solution, but its form is not known exactly. Further, it is considered that the alkyl (iso) quinolinium salt exerts an anticorrosion effect by adsorbing on the metal surface and preventing contact between the metal surface and corrosive components. It is considered that the amount of copper deposited on the metal surface is reduced by suppressing the elution of the metal.
【００１２】[0012]
【実施例】以下、本発明を実施例により詳細に説明する
が、本発明はこれらに限定されるものではない。実施例
において部は重量部を、％は重量％を示す。EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. In the examples, “part” means “part by weight” and “%” means “% by weight”.
【００１３】参考例１ 無機酸として塩酸、硫酸および燐酸を用い、５、１０、
２０％水溶液をマグネティックスタ−ラ−で攪拌しなが
ら、室温下で８ＨＱ−Ｃｕを溶解させた。８ＨＱ−Ｃｕ
は数分間で溶解し、溶液は暗緑褐色の透明液体であっ
た。酸濃度と８ＨＱ−Ｃｕ溶解度とを表１に示した。Reference Example 1 Using hydrochloric acid, sulfuric acid and phosphoric acid as the inorganic acid,
8HQ-Cu was dissolved at room temperature while stirring the 20% aqueous solution with a magnetic stirrer. 8HQ-Cu
Dissolved in a few minutes and the solution was a dark green-brown clear liquid. Table 1 shows the acid concentration and 8HQ-Cu solubility.
【００１４】[0014]
【表１】 [Table 1]
【００１５】実施例１ 参考例１と同様に１０％塩酸水溶液１００ｇに８ＨＱ−
Ｃｕ１１ｇを溶かし、次いでイソプロパノ−ル３０ｇ及
びミリスチルイソキノリニウムクロリド（MIQC）１２ｇ
を溶解させた。この溶液に炭素鋼（SS-400）又はステン
レス鋼（SUS-304 ）試験片を浸漬し、２時間後に試験片
を取り出して、重量変化を測定した。結果を表２に示し
た。また、SS-400を用いた場合の溶出した鉄イオンの濃
度を測定したところ、ＭＩＱＣを溶解させたときは、
０．１１％であり、比較のためＭＩＱＣを溶解させない
ときは０．２８％であった。Example 1 Similar to Reference Example 1, 8HQ- was added to 100 g of a 10% hydrochloric acid aqueous solution.
Dissolve 11 g of Cu, then 30 g of isopropanol and 12 g of myristylisoquinolinium chloride (MIQC)
Was dissolved. A carbon steel (SS-400) or stainless steel (SUS-304) test piece was immersed in this solution, and after 2 hours, the test piece was taken out and the weight change was measured. The results are shown in Table 2. In addition, when the concentration of eluted iron ions was measured when SS-400 was used, when MIQC was dissolved,
It was 0.11% and 0.28% when MIQC was not dissolved for comparison.
【００１６】[0016]
【表２】 [Table 2]
【００１７】実施例２ p-トルエンスルホン酸水溶液に８ＨＱ−Ｃｕを溶解させ
た溶液に、ラウリルイソキノリニウムクロリド（LIQC）
を０．４％又は１．０％溶解させ、この溶液に炭素鋼試
験片（SS-400）を１時間浸漬して、浸漬前後での試験片
の外観変化を観察した。イソキノリニウム塩を加えた溶
液では、炭素鋼表面の約１／１０に金属銅が薄く析出し
たが、同塩を加えなかった溶液では炭素鋼全面に厚く金
属銅が析出した。Example 2 Laurylisoquinolinium chloride (LIQC) was added to a solution prepared by dissolving 8HQ-Cu in a p-toluenesulfonic acid aqueous solution.
Was dissolved in 0.4% or 1.0%, and a carbon steel test piece (SS-400) was immersed in this solution for 1 hour, and the appearance change of the test piece before and after the immersion was observed. In the solution containing the isoquinolinium salt, metallic copper was thinly deposited on about 1/10 of the surface of the carbon steel, whereas in the solution containing no salt, thick metallic copper was deposited on the entire surface of the carbon steel.
【００１８】参考例２ 参考例１で使用した塩酸、硫酸および実施例２で使用し
たp-トルエンスルホン酸の水溶液に対するキノリニウム
塩類の防食効果を確認するため、ポテンシオスタットを
つかって電気化学的に腐食速度を測定した。測定結果を
表３に示した。Reference Example 2 In order to confirm the anticorrosion effect of quinolinium salts on the aqueous solution of hydrochloric acid, sulfuric acid used in Reference Example 1 and p-toluenesulfonic acid used in Example 2, electrochemical analysis was carried out using a potentiostat. The corrosion rate was measured. The measurement results are shown in Table 3.
【００１９】[0019]
【表３】 [Table 3]
【００２０】[0020]
【発明の効果】本発明の方法によれば、水に対して溶解
度が極めて小さい８ＨＱ−Ｃｕを２〜１４％という高濃
度で水溶液として調製できるうえ、酸性水溶液に起因す
る金属の腐食も抑制することができる。その結果、木材
防腐剤や新たな殺菌剤として、農業用のみならず広く８
ＨＱ−Ｃｕの殺菌作用を活用することができる。EFFECTS OF THE INVENTION According to the method of the present invention, 8HQ-Cu, which has extremely low solubility in water, can be prepared as an aqueous solution at a high concentration of 2 to 14%, and corrosion of metals caused by an acidic aqueous solution is suppressed. be able to. As a result, it is widely used not only for agriculture but also as a wood preservative and a new fungicide.
The bactericidal action of HQ-Cu can be utilized.
Claims (3)
るに際し、水性溶媒中に無機酸及び有機酸から選ばれる
１種以上の水溶性の酸と、アルキルキノリニウム塩及び
アルキルイソキノリニウム塩から選ばれる１種以上のア
ルキル（イソ）キノリニウム塩を共存させることを特徴
とする８−オキシキノリン銅水溶液の製造方法。1. When producing an aqueous solution of 8-oxyquinoline copper, at least one water-soluble acid selected from an inorganic acid and an organic acid in an aqueous solvent, an alkylquinolinium salt and an alkylisoquinolinium. A method for producing an 8-oxyquinoline copper aqueous solution, which comprises allowing one or more alkyl (iso) quinolinium salts selected from salts to coexist.
キル基が炭素数１から１８の非置換アルキル基又はアラ
ルキル基であり、水性溶媒が水又は水と水溶性有機溶媒
との混合溶媒である請求項１記載の８−オキシキノリン
銅水溶液の製造方法。2. The alkyl group of the alkyl (iso) quinolinium salt is an unsubstituted alkyl group having 1 to 18 carbon atoms or an aralkyl group, and the aqueous solvent is water or a mixed solvent of water and a water-soluble organic solvent. 1. A method for producing an 8-oxyquinoline copper aqueous solution according to 1.
％、８−オキシキノリン銅１〜２０重量％及びアルキル
（イソ）キノリニウム塩０．１〜１０重量％を、水溶性
の酸／８−オキシキノリン銅（モル比）４〜４０となる
割合で溶解させてなる８−オキシキノリン銅組成物。3. An aqueous solution containing 2 to 30% by weight of a water-soluble acid, 1 to 20% by weight of copper 8-oxyquinoline and 0.1 to 10% by weight of an alkyl (iso) quinolinium salt, An 8-oxyquinoline copper composition obtained by dissolving 8-oxyquinoline copper (molar ratio) at a ratio of 4 to 40.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6214045A JPH0873435A (en) | 1994-09-07 | 1994-09-07 | 8-hydroxyquinoline-copper composition and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6214045A JPH0873435A (en) | 1994-09-07 | 1994-09-07 | 8-hydroxyquinoline-copper composition and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0873435A true JPH0873435A (en) | 1996-03-19 |
Family
ID=16649363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6214045A Withdrawn JPH0873435A (en) | 1994-09-07 | 1994-09-07 | 8-hydroxyquinoline-copper composition and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0873435A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001240505A (en) * | 2000-02-29 | 2001-09-04 | Dainippon Wood-Preserving Co Ltd | Wood preservative of non-chlorin |
-
1994
- 1994-09-07 JP JP6214045A patent/JPH0873435A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001240505A (en) * | 2000-02-29 | 2001-09-04 | Dainippon Wood-Preserving Co Ltd | Wood preservative of non-chlorin |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20011120 |