JPH07330520A - Molecular compound of germicide - Google Patents
Molecular compound of germicideInfo
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- JPH07330520A JPH07330520A JP12007694A JP12007694A JPH07330520A JP H07330520 A JPH07330520 A JP H07330520A JP 12007694 A JP12007694 A JP 12007694A JP 12007694 A JP12007694 A JP 12007694A JP H07330520 A JPH07330520 A JP H07330520A
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は殺菌剤分子化合物に係
り、特に、水溶性殺菌剤を有機溶媒系で用いる場合の取
り扱い性や安定性などを改善した新規殺菌剤分子化合物
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fungicide molecular compound, and more particularly to a novel fungicide molecular compound having improved handleability and stability when a water-soluble fungicide is used in an organic solvent system.
【０００２】[0002]
【従来の技術】船底塗料や家庭用塗料などの、塗布後、
水まわり系で使用される塗料においては、その塗布面に
様々な菌類、動植物類のスライム、藻などが付着し、様
々な障害を引き起こしている。2. Description of the Related Art After application of ship bottom paint or household paint,
In paints used in water systems, various fungi, slimes of plants and animals, algae, etc. adhere to the application surface, causing various obstacles.
【０００３】これらの付着障害を解決するために、従
来、殺菌剤を配合した塗料が使用されている。しかし
て、塗料用殺菌剤としては、特に、下記（３）式で示さ
れる５−クロロ−２−メチル−４−イソチアゾリン−３
−オン（以下「Ｃｌ−ＭＩＴ」と称す。）が殺菌力に優
れていることから広く使用されている。In order to solve these adhesion problems, paints containing a bactericide have been conventionally used. As a bactericide for paints, 5-chloro-2-methyl-4-isothiazoline-3 represented by the following formula (3) is particularly preferable.
-ON (hereinafter referred to as "Cl-MIT") is widely used because of its excellent bactericidal activity.
【０００４】[0004]
【化３】 [Chemical 3]
【０００５】ところが、このＣｌ−ＭＩＴは優れた殺菌
力を有してはいるが、皮膚刺激性が極めて強く、取り扱
い上多大な注意が必要とされる。また、Ｃｌ−ＭＩＴは
極めて分解し易い化合物である。特に熱に対して不安定
で、例えば、４０℃程度の温度でも１〜２日で分解して
しまう。このため、保管上の注意が必要とされる。However, although this Cl-MIT has excellent bactericidal activity, it is extremely irritating to the skin and requires great care in handling. Cl-MIT is a compound that is extremely easily decomposed. In particular, it is unstable to heat and, for example, decomposes even at a temperature of about 40 ° C. in 1 to 2 days. Therefore, care must be taken in storage.
【０００６】このような問題を解決すべく、本出願人
は、Ｃｌ−ＭＩＴをアルコール系ないしフェノール系化
合物などを用いて分子化合物とすることを提案し、先に
特許出願した（特公平２−５７０４６号、特開平１−１
９０６０２号）。In order to solve such a problem, the present applicant has proposed to use Cl-MIT as a molecular compound by using an alcohol-based compound or a phenol-based compound, and previously filed a patent application (Japanese Patent Publication No. 57046, JP-A 1-1
90602).
【０００７】[0007]
【発明が解決しようとする課題】しかしながら、アルコ
ール系ないしフェノール系化合物を用いたＣｌ−ＭＩＴ
分子化合物は、塗料用の溶媒（ベンゼン、トルエン、キ
シレンなど）に比較的溶解し易いため、分子化合物とし
ての優れた特性を発揮し得ないという欠点があった。However, a Cl-MIT using an alcohol or phenol compound is used.
Since the molecular compound is relatively easy to dissolve in a solvent for paint (benzene, toluene, xylene, etc.), it has a drawback that it cannot exhibit excellent characteristics as a molecular compound.
【０００８】本発明は上記従来の問題点を解決し、Ｃｌ
−ＭＩＴの皮膚刺激性や熱安定性の問題を改善する分子
化合物であって、塗料用の溶媒に対して溶解し難く、Ｃ
ｌ−ＭＩＴ分子化合物としての特性を有効に発揮し得る
殺菌剤分子化合物を提供することを目的とする。The present invention solves the above-mentioned conventional problems, and
-A molecular compound that improves the skin irritation and heat stability problems of MIT, is difficult to dissolve in a solvent for paints, and is C
It is an object of the present invention to provide a fungicide molecular compound capable of effectively exhibiting the characteristics as an l-MIT molecular compound.
【０００９】[0009]
【課題を解決するための手段】本発明の殺菌剤分子化合
物は、水溶性殺菌剤と下記一般式（１）又は（２）で示
されるカルボン酸系化合物との分子化合物よりなること
を特徴とする。The bactericidal agent molecular compound of the present invention comprises a molecular compound of a water-soluble bactericidal agent and a carboxylic acid compound represented by the following general formula (1) or (2): To do.
【００１０】[0010]
【化４】 [Chemical 4]
【００１１】（（１）式中、Ｒは単結合、或いは、炭素
数１〜４のアルキレン基、アルケニレン基又はアルキニ
レン基を示す。）(In the formula (1), R represents a single bond, or an alkylene group having 1 to 4 carbon atoms, an alkenylene group or an alkynylene group.)
【００１２】[0012]
【化５】 [Chemical 5]
【００１３】（（２）式中、Ｒ1 ，Ｒ2 ，Ｒ3 は各々独
立して、水素、ハロゲン、カルボキシル基、水酸基、ニ
トロ基、アミノ基、アミド基、カルボン酸無水物基或い
は炭素数１〜３のアルキル基、アルケニル基、アルキニ
ル基、アルコキシ基、アルカノン基又はアルカナール基
を示す。）なお、本発明において、分子化合物とは２種
以上の安定な分子同志が直接に結合してできる化合物で
あって、比較的容易にもとの分子に分解できるものを指
し、具体的な型態としては、錯体、或いは、包接化合物
等が挙げられる。(In the formula (2), R 1 , R 2 and R 3 are each independently hydrogen, halogen, carboxyl group, hydroxyl group, nitro group, amino group, amide group, carboxylic anhydride group or carbon number. 1 to 3 represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkanone group, or an alkanal group.) In the present invention, the molecular compound is two or more kinds of stable molecular groups directly bonded to each other. It refers to a compound that can be decomposed into the original molecule relatively easily, and its specific form includes a complex or an inclusion compound.
【００１４】以下に本発明を詳細に説明する。The present invention will be described in detail below.
【００１５】本発明において、水溶性殺菌剤と分子化合
物を形成する相手化合物は、前記一般式（１）又は
（２）で示されるカルボン酸系化合物であるが、このう
ち、一般式（１）で示されるカルボン酸系化合物として
は、例えば、シュウ酸、マロン酸、コハク酸、グルタル
酸、フマル酸、マレイン酸、アセチレンジカルボン酸等
が挙げられる。In the present invention, the partner compound forming a molecular compound with the water-soluble bactericide is a carboxylic acid compound represented by the above general formula (1) or (2). Examples of the carboxylic acid compound represented by are oxalic acid, malonic acid, succinic acid, glutaric acid, fumaric acid, maleic acid, acetylenedicarboxylic acid, and the like.
【００１６】また、前記一般式（２）で示されるカルボ
ン酸系化合物としては、例えば安息香酸、４−クロロ安
息香酸、２，４−ジクロロ安息香酸、２，４，６−トリ
クロロ安息香酸、４−ブロモ安息香酸、２，４−ジブロ
モ安息香酸、２，４，６−トリブロモ安息香酸、４−ヨ
ード安息香酸、２，４−ジヨード安息香酸、２，４，６
−トリヨード安息香酸、３，５−ジヨードサリチル酸、
４−クロロ−３−ニトロ安息香酸、２−クロロ−４−ニ
トロ安息香酸、４−クロロ−２−ニトロ安息香酸、フタ
ル酸、イソフタル酸、テレフタル酸、トリメリット酸、
ピロメリット酸、４−ニトロ安息香酸、２，４−ジニト
ロ安息香酸、４−ニトロフタル酸、３，５−ジニトロサ
リチル酸、２−アミノ安息香酸、無水トリメリット酸、
ゲンチシン酸（２，５−ジヒドロキシ安息香酸）、プロ
トカテキュ酸（３，４−ジヒドロキシ安息香酸）、サリ
チル酸、２，４，６−トリヒドロキシ安息香酸、４−メ
チル安息香酸、４−メトキシ安息香酸、４−カルボキシ
ベンズアミド、４−ビニル安息香酸、４−エチニル安息
香酸、４−アセチル安息香酸、４−カルボキシベンズア
ルデヒド等が挙げられる。Examples of the carboxylic acid compound represented by the general formula (2) include benzoic acid, 4-chlorobenzoic acid, 2,4-dichlorobenzoic acid, 2,4,6-trichlorobenzoic acid, 4 -Bromobenzoic acid, 2,4-dibromobenzoic acid, 2,4,6-tribromobenzoic acid, 4-iodobenzoic acid, 2,4-diiodobenzoic acid, 2,4,6
-Triiodobenzoic acid, 3,5-diiodosalicylic acid,
4-chloro-3-nitrobenzoic acid, 2-chloro-4-nitrobenzoic acid, 4-chloro-2-nitrobenzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid,
Pyromellitic acid, 4-nitrobenzoic acid, 2,4-dinitrobenzoic acid, 4-nitrophthalic acid, 3,5-dinitrosalicylic acid, 2-aminobenzoic acid, trimellitic anhydride,
Genticic acid (2,5-dihydroxybenzoic acid), protocatechuic acid (3,4-dihydroxybenzoic acid), salicylic acid, 2,4,6-trihydroxybenzoic acid, 4-methylbenzoic acid, 4-methoxybenzoic acid, 4 -Carboxybenzamide, 4-vinylbenzoic acid, 4-ethynylbenzoic acid, 4-acetylbenzoic acid, 4-carboxybenzaldehyde and the like can be mentioned.
【００１７】一方、水溶性殺菌剤としてはこれらのカル
ボン酸系化合物と分子化合物を形成し得るものであれば
良く、一般に有効な殺菌剤として広く用いられているＣ
ｌ−ＭＩＴが挙げられるが、これに限定されるものでは
ない。On the other hand, the water-soluble bactericidal agent may be any one as long as it can form a molecular compound with these carboxylic acid compounds, and it is widely used as a generally effective bactericidal agent.
1-MIT, but not limited thereto.
【００１８】このような水溶性殺菌剤とカルボン酸系化
合物とからなる本発明の殺菌剤分子化合物は、有機溶媒
中もしくは水中での反応にて容易に製造することができ
る。The bactericide molecular compound of the present invention comprising such a water-soluble bactericide and a carboxylic acid compound can be easily produced by a reaction in an organic solvent or in water.
【００１９】有機溶媒を用いる場合には、メタノール、
エタノール、アセトン等の通常の有機溶媒に前記カルボ
ン酸系化合物を溶解させた溶液と、Ｃｌ−ＭＩＴ等の水
溶性殺菌剤或いはこれに更に不純物等を含む混合物とを
混合して反応させる。これにより、分子化合物が固形物
として析出するので、これを常法により濾過分離して目
的とする分子化合物を得る。When an organic solvent is used, methanol,
A solution prepared by dissolving the carboxylic acid compound in an ordinary organic solvent such as ethanol or acetone is mixed with a water-soluble bactericidal agent such as Cl-MIT or a mixture containing impurities, and the mixture is reacted. As a result, the molecular compound precipitates as a solid, and this is filtered and separated by a conventional method to obtain the target molecular compound.
【００２０】水中で反応させる場合には、前記カルボン
酸系化合物を直接水溶性殺菌剤を溶解した水溶液中に添
加して混合、攪拌する。用いる水溶液は、必ずしも水溶
性殺菌剤のみを含むものである必要はなく、上記有機溶
媒反応の場合と同様、水溶性殺菌剤と不純物等を含むも
のであっても良い。即ち、本発明において、水溶性殺菌
剤と前記カルボン酸系化合物とは極めて選択的に反応す
るため、本発明の分子化合物の製造にあたって、原料の
水溶性殺菌剤として、副生成物等の不純物を含有するも
のをそのまま用いても良く、この場合においても、目的
とする水溶性殺菌剤のみと選択的に分子化合物が形成さ
れる。When the reaction is carried out in water, the carboxylic acid compound is directly added to an aqueous solution in which a water-soluble bactericide is dissolved, mixed and stirred. The aqueous solution to be used does not necessarily need to contain only the water-soluble bactericidal agent, and may contain the water-soluble bactericidal agent and impurities as in the case of the above organic solvent reaction. That is, in the present invention, since the water-soluble bactericidal agent and the carboxylic acid-based compound react extremely selectively, in the production of the molecular compound of the present invention, as a water-soluble bactericidal agent of the raw material, impurities such as by-products What is contained may be used as it is, and even in this case, the molecular compound is selectively formed only with the desired water-soluble bactericide.
【００２１】なお、反応温度は０〜１００℃の範囲にお
いて任意で良いが、通常の場合１０〜３０℃程度とす
る。反応時間は０．５〜２４時間程度で十分である。The reaction temperature may be arbitrary in the range of 0 to 100 ° C, but is usually about 10 to 30 ° C. A reaction time of about 0.5 to 24 hours is sufficient.
【００２２】反応終了後、分子化合物は通常固形物とし
て得られるので、これを水層と分離し、水洗、乾燥し
て、目的とする分子化合物を得ることができる。After completion of the reaction, the molecular compound is usually obtained as a solid, and this can be separated from the aqueous layer, washed with water and dried to obtain the desired molecular compound.
【００２３】なお、水溶性殺菌剤とカルボン酸系化合物
との反応モル比は、通常の場合、１：０．１〜１０であ
る。The reaction molar ratio between the water-soluble bactericide and the carboxylic acid compound is usually 1: 0.1-10.
【００２４】このようにして得られる本発明の分子化合
物は、通常は粉末状の固体であり、打錠等の成型も容易
である。また有機溶媒中あるいは水中で微粉化させた流
動化剤としての製剤化も可能である。The thus obtained molecular compound of the present invention is usually a powdery solid and can be easily molded into tablets. It is also possible to formulate it as a fluidizing agent pulverized in an organic solvent or in water.
【００２５】[0025]
【作用】本発明の殺菌剤分子化合物では、分子化合物を
形成することにより水溶性殺菌剤が安定化されるため、
保管性も良く、しかも、皮膚刺激性が低く、取り扱いが
容易となる。その上、使用中に水溶性殺菌剤が他の物質
と反応して、殺菌力が低下することも防止される。In the bactericide molecular compound of the present invention, the water-soluble bactericide is stabilized by forming the molecular compound,
Good storability, low skin irritation, and easy handling. In addition, it is prevented that the water-soluble bactericide reacts with other substances during use to reduce the bactericidal power.
【００２６】また、本発明に係る殺菌剤分子化合物は、
塗料用溶媒に溶解し難いため、塗料に混合して塗布した
後の殺菌効果が長く維持される。Further, the fungicide molecular compound according to the present invention is
Since it is difficult to dissolve in a paint solvent, the bactericidal effect after being mixed and applied to the paint is maintained for a long time.
【００２７】[0027]
【実施例】以下に実施例を挙げて本発明をより具体的に
説明する。EXAMPLES The present invention will be described in more detail with reference to the following examples.
【００２８】実施例１ Ｃｌ−ＭＩＴとアセチレンジカルボン酸との分子化
合物の合成 Ｃｌ−ＭＩＴを主成分として含む水溶性殺菌剤５００ｇ
（Ｃｌ−ＭＩＴ濃度１０．４重量％）をクロロホルム２
００ｇで抽出し、クロロホルム層の溶媒を留去して、Ｃ
ｌ−ＭＩＴを分取した（収量５０ｇ，２〜３重量％のＭ
ＩＴを含む）。Example 1 Synthesis of molecular compound of Cl-MIT and acetylenedicarboxylic acid 500 g of water-soluble fungicide containing Cl-MIT as a main component
(Cl-MIT concentration 10.4% by weight) with chloroform 2
It is extracted with 00 g, the solvent of the chloroform layer is distilled off, and C
l-MIT was fractionated (yield 50 g, 2-3% by weight M
(Including IT).
【００２９】アセチレンジカルボン酸１０ｇ（８７．６
ｍｍｏｌ）を、サンプル瓶にとり、２０ｍｌのメタノー
ルで溶解した後、分取したＣｌ−ＭＩＴ１３．１１ｇ
（８７．６ｍｍｏｌ）を加えて混合した。混合後放置し
て溶媒を揮散させ、結晶を析出させた。析出した結晶を
分離して１０ｍｌの水で洗浄した後、乾燥した。生成物
についてＩＲスペクトル、ＮＭＲスペクトル分析及びＨ
ＰＬＣによるＣｌ−ＭＩＴの含有率の測定を行った結
果、表１に示す如く、生成物はアセチレンジカルボン酸
／Ｃｌ−ＭＩＴ≒１／２（モル比）（Ｃｌ−ＭＩＴ含有
率７３．４重量％）の分子化合物（包接化合物）である
ことが確認された。10 g of acetylenedicarboxylic acid (87.6
(mmol) was taken in a sample bottle, dissolved with 20 ml of methanol, and then 13.11 g of separated Cl-MIT.
(87.6 mmol) was added and mixed. After mixing, the mixture was allowed to stand and the solvent was volatilized to precipitate crystals. The precipitated crystals were separated, washed with 10 ml of water and then dried. IR spectrum, NMR spectrum analysis and H
As a result of measuring the Cl-MIT content by PLC, as shown in Table 1, the product was acetylenedicarboxylic acid / Cl-MIT≈1 / 2 (molar ratio) (Cl-MIT content 73.4% by weight). ) Was confirmed to be a molecular compound (inclusion compound).
【００３０】 他の分子化合物の合成 表１に示す相手化合物それぞれ１０ｇと、これと等モル
のＣｌ−ＭＩＴとを用い、上記と同様にして合成及び
分析を行った結果、表１に示す如く、各々、分子化合物
（包接化合物）が得られたことが確認された。Synthesis of Other Molecular Compounds Using 10 g of each of the partner compounds shown in Table 1 and an equimolar amount of Cl-MIT, synthesis and analysis were carried out in the same manner as above, and as a result, as shown in Table 1. It was confirmed that each molecular compound (inclusion compound) was obtained.
【００３１】[0031]
【表１】 [Table 1]
【００３２】 分子化合物中のＣｌ−ＭＩＴの熱安定
性試験（４０℃） 前記，で得られた表１のＮｏ．１〜１５の分子化合
物を、各々、１０ｇねじ口瓶に入れ、栓をして４０℃の
恒温槽中に放置した。経時時間ごとにサンプルの１部を
取り出し、ＨＰＬＣ分析により分子化合物中のＣｌ−Ｍ
ＩＴ含有率を測定し、その結果と初期含有率とから包接
化合物中のＣｌ−ＭＩＴ残留率を求め、結果を表２に示
した。Thermal stability test of Cl-MIT in molecular compound (40 ° C.) No. 1 in Table 1 obtained in the above. Each of the molecular compounds 1 to 15 was placed in a screw cap bottle of 10 g, stoppered, and allowed to stand in a constant temperature bath at 40 ° C. A part of the sample was taken out at each lapse of time, and Cl-M in the molecular compound was analyzed by HPLC analysis.
The IT content was measured, and the Cl-MIT residual rate in the clathrate compound was determined from the result and the initial content, and the results are shown in Table 2.
【００３３】比較のため、Ｃｌ−ＭＩＴ単独についても
同様に試験し、結果を表２に示した。For comparison, Cl-MIT alone was tested in the same manner, and the results are shown in Table 2.
【００３４】表２より、Ｃｌ−ＭＩＴのみの場合は１週
間後には黒色に変化して分解してしまうが、Ｃｌ−ＭＩ
Ｔを分子化合物としたものでは分子化合物内のＣｌ−Ｍ
ＩＴ残留率が高く、この分解が防止されることが認めら
れる。From Table 2, in the case of Cl-MIT alone, it turns black and decomposes after 1 week, but Cl-MI
If T is a molecular compound, Cl-M in the molecular compound
It is recognized that the IT residual rate is high and this decomposition is prevented.
【００３５】[0035]
【表２】 [Table 2]
【００３６】 分子化合物のトルエンに対する溶解性
試験（２０℃） 前記，で得られた表１のＮｏ．１〜１５の分子化合
物を各々０．１ｇづつ２００ｍｌ容の三角フラスコに入
れ、これに１００ｇのトルエンをそれぞれ加え、スパー
テルで１分間攪拌した後、栓をして２０℃の恒温槽に２
４時間放置した。２４時間後、分子化合物の溶解性を外
観観察により調べ、結果を表３に示した。Solubility test of molecular compounds in toluene (20 ° C.) No. 1 in Table 1 obtained in the above. 0.1 g of each of the molecular compounds 1 to 15 were placed in a 200 ml Erlenmeyer flask, 100 g of toluene was added to each, and the mixture was stirred with a spatula for 1 minute, and then capped and placed in a 20 ° C. constant temperature bath.
It was left for 4 hours. After 24 hours, the solubility of the molecular compound was examined by visual observation, and the results are shown in Table 3.
【００３７】また、比較のため１，１−ジ（４−ヒドロ
キシフェニル）シクロヘキサンとＣｌ−ＭＩＴとの分子
化合物（特公平２−５７０４６号に記載されている化合
物）とについても同様に試験し、結果を表３に示した。For comparison, a molecular compound of 1,1-di (4-hydroxyphenyl) cyclohexane and Cl-MIT (compound described in JP-B-2-57046) was also tested in the same manner. The results are shown in Table 3.
【００３８】表３より、本発明による分子化合物は、比
較例のものと比べてトルエンに対する溶解性が低く、塗
料に対して有効に使用できることが認められる。From Table 3, it can be seen that the molecular compound according to the present invention has a lower solubility in toluene than that of the comparative example, and can be effectively used for paints.
【００３９】[0039]
【表３】 [Table 3]
【００４０】[0040]
【発明の効果】以上詳述した通り、本発明の殺菌剤分子
化合物によれば、 i) Ｃｌ−ＭＩＴ等の水溶性殺菌剤の安定性が改善さ
れ、熱等に対しても分解し難くなる。 ii) Ｃｌ−ＭＩＴ等の水溶性殺菌剤の皮膚刺激性等の
問題が改善され、取り扱いが容易になる。 iii) 塗料用溶媒に対して溶解し難いために、塗料に対
して用いた場合においても、分子化合物としての特性を
有効に発揮し得る。 iv) 塗料に配合して塗布した後の殺菌効果を長期間持
続させることができる。 といった優れた効果を奏する殺菌剤分子化合物が提供さ
れる。As described in detail above, according to the fungicide molecular compound of the present invention, i) the stability of a water-soluble fungicide such as Cl-MIT is improved, and it becomes difficult to decompose it against heat or the like. . ii) Problems such as skin irritation of water-soluble bactericides such as Cl-MIT are improved and handling becomes easier. iii) Since it is difficult to dissolve in a paint solvent, it can effectively exhibit its properties as a molecular compound even when used in a paint. iv) It is possible to maintain the bactericidal effect for a long period of time after being mixed and applied in a paint. There is provided a bactericidal molecule compound having an excellent effect.
Claims (1)
（２）で示されるカルボン酸系化合物との分子化合物よ
りなる殺菌剤分子化合物。 【化１】 （（１）式中、Ｒは単結合、或いは、炭素数１〜４のア
ルキレン基、アルケニレン基又はアルキニレン基を示
す。） 【化２】 （（２）式中、Ｒ1 ，Ｒ2 ，Ｒ3 は各々独立して、水
素、ハロゲン、カルボキシル基、水酸基、ニトロ基、ア
ミノ基、アミド基、カルボン酸無水物基或いは炭素数１
〜３のアルキル基、アルケニル基、アルキニル基、アル
コキシ基、アルカノン基又はアルカナール基を示す。）1. A bactericidal molecular compound comprising a molecular compound of a water-soluble bactericidal agent and a carboxylic acid compound represented by the following general formula (1) or (2). [Chemical 1] (In the formula (1), R represents a single bond, or an alkylene group having 1 to 4 carbon atoms, an alkenylene group or an alkynylene group.) (In the formula (2), R 1 , R 2 and R 3 are each independently hydrogen, halogen, carboxyl group, hydroxyl group, nitro group, amino group, amide group, carboxylic acid anhydride group or carbon number 1
To 3 alkyl, alkenyl, alkynyl, alkoxy, alkanone or alkanal groups. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12007694A JP3463349B2 (en) | 1994-06-01 | 1994-06-01 | Fungicide molecular compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12007694A JP3463349B2 (en) | 1994-06-01 | 1994-06-01 | Fungicide molecular compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07330520A true JPH07330520A (en) | 1995-12-19 |
| JP3463349B2 JP3463349B2 (en) | 2003-11-05 |
Family
ID=14777313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12007694A Expired - Lifetime JP3463349B2 (en) | 1994-06-01 | 1994-06-01 | Fungicide molecular compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3463349B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0923867A1 (en) * | 1997-12-22 | 1999-06-23 | Kurita Water Industries Ltd. | Antimicrobial composition and their use |
| JPH11189565A (en) * | 1997-09-02 | 1999-07-13 | Nippon Soda Co Ltd | Molecular compound containing phenol derivative as component compound |
-
1994
- 1994-06-01 JP JP12007694A patent/JP3463349B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11189565A (en) * | 1997-09-02 | 1999-07-13 | Nippon Soda Co Ltd | Molecular compound containing phenol derivative as component compound |
| EP0923867A1 (en) * | 1997-12-22 | 1999-06-23 | Kurita Water Industries Ltd. | Antimicrobial composition and their use |
| US6159999A (en) * | 1997-12-22 | 2000-12-12 | Kurita Water Industries Ltd. | Antimicrobial and antiseptic methods using antimicrobial composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3463349B2 (en) | 2003-11-05 |
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