JP3077268B2 - New inclusion compounds and their preparation - Google Patents

New inclusion compounds and their preparation

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JP3077268B2
JP3077268B2 JP03183027A JP18302791A JP3077268B2 JP 3077268 B2 JP3077268 B2 JP 3077268B2 JP 03183027 A JP03183027 A JP 03183027A JP 18302791 A JP18302791 A JP 18302791A JP 3077268 B2 JP3077268 B2 JP 3077268B2
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cmi
compound
water
inclusion
clathrate
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JPH054978A (en
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真 浅井
啓之 鈴木
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日本曹達株式会社
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【発明の詳細な説明】 DETAILED DESCRIPTION OF THE INVENTION

【0001】 [0001]

【産業上の利用分野】本発明は、新規包接化合物に係り、更に詳しくは、テトラキス(ヒドロキシフェニルエタン類をホスト化合物とし、5−クロロ−2−メチル− The present invention relates to relates to a novel clathrate compound, more particularly, to a tetrakis (hydroxyphenyl ethanes a host compound, 5-chloro-2-methyl -
4−イソチアゾリン−3−オンをゲスト化合物とする新規包接化合物に関する。 4-isothiazolin-3-one to novel clathrate compound to guest compound. 本発明の包接化合物は、殺菌剤として有効であるが、水溶性でかつ皮膚刺激性の強い5 Clathrate compound of the present invention is effective as a fungicide, and strong skin irritation soluble 5
−クロロ−2−メチル−4−イソチアゾリン−3−オンを包接化して固形化するものであり、皮膚刺激性が緩和されるため、取扱いの容易な殺菌剤として広範囲に使用することができる。 - chloro-2-methyl-4-isothiazolin-3-one is intended to solidify by clathration, for skin irritation is reduced, it can be widely used as easily fungicides handling.

【0002】 [0002]

【従来の技術】各種工場施設の冷却水系あるいは紙パルプ抄造系などの水循環系においては、種々の菌類、藻類、動植物類等のスライムが付着し、様々な障害の原因となっている。 BACKGROUND OF THE INVENTION Various plant facility of the cooling water system or water circulation system, such as paper pulp papermaking systems, various fungi, algae, slime, such as animals and plants such adheres, are responsible for various disorders. 例えば、冷却水系においては、ズーグレア状細菌、藻類、糸状菌等のスライムが付着し、熱効率の低下、通水の悪化、金属材料等の腐食の誘発等の原因となっている。 For example, in cooling water systems, Zooglea shaped bacteria, algae, slime, such as filamentous fungi may adhere, reduction in the thermal efficiency, deterioration of the water passing, are responsible for inducing such corrosion and metal materials. また紙パルプ抄紙系においては、細菌、 In the paper pulp papermaking systems, bacteria,
糸状菌、酵母等のスライムが主に抄紙工程で発生し、これがパルプスラリー中に混入付着して製品の品質低下や紙切れ等の生産工程での障害を引き起こす。 Filamentous fungi, the slime, such as yeast occurs mainly in the papermaking process, which causes a failure in the production process of such degradation or piece of paper products adhering mixed into the pulp slurry.

【0003】更に海水を利用する火力発電所や製鉄所等の冷却水系の取水口や冷却管内壁には、海水性の藻類やバクテリア、ムラサキガイ、ホヤ等の生物が付着し、これらの機能低下の原因となり、これら付着生物は水流等により剥離し、熱交換器のチューブやストレーナ等の部位の目詰まり等の障害も引き起こし、通水系全体の機能低下の原因となっている。 [0003] Further to the intake and cooling the inner wall of the cooling water system of the thermal power plants and steelworks like utilizing seawater, seawater of algae and bacteria, mussels, squirts organisms adhere, decrease these functions cause, these fouling organisms is removed by water or the like, failure, such as clogging of the site of the tube and a strainer or the like of the heat exchanger also causes, are responsible for hypofunction of the entire passage aqueous.

【0004】 従来、このようなスライム等による障害を防止するためには、スライムコントロール剤(抗菌剤)を使用することが、取扱上簡便であり、安価なことから一般的である。 Conventionally, in order to prevent failure due to such slime, etc., be used slime control agent (antimicrobial agent), a handling convenience, it is common because inexpensive. 汎用されている抗菌剤としては、イソチアゾリン系化合物の水溶性抗菌剤が挙げられる。 The antibacterial agent which is generally water-soluble antimicrobial agent isothiazoline based compounds. これらの中で、特に5−クロロ−2−メチル−4−イソチアゾリン−3−オン(以下、「CMI」と略記) 抗菌力に優れており、冷却水系用、紙パルプ、水泳プール用等の各種水系用スライムコントロール剤、抗菌剤、殺藻剤、殺黴剤として広く使用されている。 Among them, 5-chloro-2-methyl-4-isothiazolin-3-one (hereinafter, abbreviated as "CMI") is excellent in antibacterial activity, cooling water, pulp and paper, such as a swimming pool various water-based for slime control agents, antibacterial agents, algicides, are widely used as fungicides.

【0005】このCMIは、一般に 1) ベータチオケトアミドを酢酸エステル等の不活性有機エステル溶媒中でハロゲン化する。 [0005] CMI is generally 1) halogenating the beta-thio-keto amide in an inert organic ester solvent such as ethyl acetate. 2) ベータ置換チオシアノアクリルアミドを酸で処理してイソチアゾロンを得、更にハロゲン化する等の方法で製造されている。 2) to give the isothiazolone was treated with beta-substituted thio cyanoacrylamide acid are further produced by a method such as halides. (特公昭46−2 (JP-B-46-2
1240号公報参照) CMIの合成方法として、前記、1)及び 2)のいずれの合成方法を採用しても、CMIのみを得ることはできず、副成分として抗菌力がCMIの約1/10である2−メチル−4−イソチアゾリン−3−オン(以下、「MI」 Method for synthesizing 1240 see JP) CMI, wherein, 1) and be employed any method for the synthesis of 2), can not be obtained CMI only about antibacterial activity of CMI as a secondary component 1/10 in a 2-methyl-4-isothiazolin-3-one (hereinafter, "MI"
と略記)が混合したものしか得られない。 Abbreviated) is not only to obtain a mixture. しかも従来の技術では、反応生成混合物からCMIだけを選択的に取り出すことは困難であり、やむを得ず抗菌力が劣るMI Moreover in the conventional art, it is difficult to take out from the reaction product mixture only selectively CMI, unavoidably MI which antibacterial poor
が混合されたままの状態で使用しているのが実情である。 There are using in the state of being mixed in actuality.

【0006】一方、CMIは、優れた抗菌力を有するが、極めて皮膚刺激性が強く、その取扱いには多大な注意を払う必要があった。 [0006] On the other hand, CMI has the excellent antibacterial activity, extremely skin irritation is strong, it was necessary to pay a great deal of attention to the handling. また、水に投入して用いる際には、水中の有機物(アミン、還元性物質等)と反応して活性を失うため、長期に抗菌力を持続させることが困難であった。 Further, when used in poured into water, to lose activity by reacting with water organics (amines, reducing substances and the like), it is difficult to sustain a long-term antibacterial activity. 近年、このCMIを選択的に包接化する試みがなされ、ホスト化合物としてビスフェノール系化合物や、それに類似した化学構造を有する化合物が提案されている。 Recently, an attempt to selectively inclusion of the CMI is made, and a bisphenol-based compound, a compound having a chemical structure similar to that has been proposed as a host compound. (特開平1−190602号公報、特開昭62 (JP-A-1-190602, JP-Sho 62
−22701号公報、特開昭61−53201号公報参照)。 -22701, JP-see JP 61-53201).

【0007】 [0007]

【発明が解決使用とする問題点】前記引用文献に記載されたホスト化合物は、CMIの包接能に優れており、それらの包接化合物では皮膚刺激性が大幅に緩和され、取扱が容易となっている。 THE INVENTION Problems to solve using point host compounds described in the cited document has excellent inclusion ability of CMI, skin irritation in those inclusion compound can be greatly relaxed, and easy to handle going on. しかしながら、これらのホスト化合物を用いた包接化合物においては、使用時のCMI However, in the clathrate compound using these host compounds, when used CMI
水系中への放出速度が速すぎ 、持続性の要求される系、例えば列車等の循環式トイレの殺菌等には適用できなかった。 Release rate is too fast to the water-based, sustained required system, for example the circulation toilet sterilization or the like of a train or the like could not be applied. 本発明は、CMIを選択的に包接した、かつ水系でのCMIの放出速度の比較的遅い新規包接化合物を提供することを目的とする。 The present invention aims at providing in contact selectively wrapping the CMI, and the relatively slow novel clathrate compound of the release rate of the CMI in the water system.

【0008】 [0008]

【問題点を解決するための手段】本発明者等は、前記目的を達成すべく鋭意研究した結果、特定のテトラキス(ヒドロキシフェニル)エタン類が、CMIを選択的に包接するホスト化合物として極めて優れており、かつこれらの包接化合物からの水系におけるCMIの放出速度が、公知の包接化合物に比較して極めて速いことを見出し、本発明を完成した。 The present inventors have [Problems To achieve the], the result of intensive studies to achieve the object, the particular tetrakis (hydroxyphenyl) ethanes, very excellent as selective packaging contact host compound CMI and, and the release rate of the CMI in the water from these inclusion compounds, found that extremely fast compared to the known clathrate compounds, and completed the present invention. 本発明は、下記一般式〔1〕 The present invention has the following general formula (1)
で示されるテトラキス(ヒドロキシフェニル)エタンをホスト化合物とし、化学式〔2〕で示される5−クロロ−2−メチル−4−イソチアゾリン−3−オンをゲスト化合物とすることを特徴とする包接化合物である。 In tetrakis (hydroxyphenyl) ethane as host compounds represented, 5-chloro-2-methyl-4-isothiazolin-3-one represented by the chemical formula (2) with inclusion compounds, characterized in that the guest compound is there.

【0009】 [0009]

【化3】 [Formula 3]

【0010】 [0010]

【化4】 [Of 4] 以下、本発明を詳細に説明する。 The present invention will be described in detail.

【0011】(ホスト化合物)本発明に用いる前記一般式〔1〕で示される化合物の具体例として、1,1, [0011] Specific examples of the compound represented by (host compound) the formula used in the present invention [1], 1,1,
2,2−テトラキス(p−ヒドロキシフェニル)エタン(以下「TEP−DF」と略記) 、1,1,2,2−テトラキス(m−ヒドロキシフェニル)エタン等が挙げられる。 2,2-tetrakis (p- hydroxyphenyl) ethane (hereinafter abbreviated as "TEP-DF"), 1,1,2,2-tetrakis (m-hydroxyphenyl) ethane, and the like. 中でもTEP−DFは、得られる包接化合物が常温で固体であり、取り扱いが容易なことから特に好んで用いられる。 Among them TEP-DF is clathrate compound obtained is a solid at room temperature, is preferably used particularly because of easy handling.

【0012】 [0012]

【化5】 [Of 5] (ゲスト化合物)本発明に用いる前記化学式〔2〕で示されるCMIは、一般に市販されている合成時の副成分であるMI、安定化剤としての塩化マグネシウム、硝酸マグネシウム等を含有する水溶性殺菌剤(商品名:ケーソンWT、ローム&ハース社製)の主成分である。 CMI, which is represented by Formula for use in the (guest compound) the invention [2] is generally a sub-component in the synthesis of commercially available MI, magnesium chloride as a stabilizer, water-soluble bactericide containing magnesium nitrate and the like agent: which is the main component of the (trade name caisson WT, manufactured by Rohm & Haas Co.).

【0013】 [0013]

【化6】 [Omitted]

【0014】(包接化合物)本発明の包接化合物は、通常前記ホスト化合物を水中に懸濁したスラリー中に、前記CMIを主成分とする水溶性殺菌剤を添加、常温〜5 [0014] (clathrates) inclusion compound of the present invention, usually in a slurry suspended the host compound in water, adding a water-soluble disinfectant composed mainly of the CMI, room temperature 5
0℃で15〜180 分間攪拌して反応することにより、C By reaction was stirred 15 to 180 minutes at 0 ° C., C
MIがホスト化合物に包接される。 MI is inclusion in the host compound. CMIの包接量は、 Inclusion amount of CMI is,
ホスト化合物の種類、反応温度、反応時間により異なるがホスト化合物1モルに対し、1.2 〜2.0 モルである。 Types of host compounds, the reaction temperature varies depending on the reaction times for 1 mole of host compound is from 1.2 to 2.0 mol.
前記反応において、水溶性殺菌剤中に副成分として存在するMIも包接されるが、その包接量は、MI/CMI In the reaction, MI is also clathrate present as secondary components in a water-soluble disinfectant, the inclusion amount, MI / CMI
(モル比)は7%以下である。 (Molar ratio) is not more than 7%. 特にTEP−DFの場合はMI/CMI(モル比)は1%と小さく、ホスト化合物として好適である。 Particularly MI / CMI (molar ratio) in the case of TEP-DF 1% and less, is suitable as a host compound.

【0015】(包接化合物の使用方法)前記包接化合物は、水系中で包接したCMIを再放出し、殺菌剤としての効力を発現する。 [0015] (inclusion Using Compound) said inclusion compound is to re-emit the CMI that clathrate in the aqueous express efficacy as fungicides. 従って、従来公知の殺菌剤等の水処理剤を処理水系中に添加する各種の方法を採用することができる。 Therefore, it is possible to use various methods of adding a water treatment agent, such as known fungicides to treatment in an aqueous. 例えば、(1) 液状または粉末状の包接化合物を、処理水系に連続的または間欠的に定量添加する方法、(2) 常温で固体の包接化合物の成形体、例えば錠剤、粒剤等をカラム充填し処理水を通水する方法、(3) For example, a (1) liquid or powdered inclusion compounds, a method of continuously or intermittently quantitatively added to the process water system, (2) molding of the inclusion compound is solid at ordinary temperature, such as tablets, granules, etc. how to passed through the treated water was column packed, (3)
包接化合物を水不溶性、かつ水透過性の袋、カートリッジ等の容器に入れ、処理水に浸漬又は浮遊させる方法、 How clathrate water-insoluble and water-permeable bag, placed in a container such as a cartridge, is immersed or floating in the treated water,
(4) 直接又は塗料、樹脂等に混入し、機器、配管等の機材の処理水と接触している表面に塗布又は付着させる方法等を採用することができる。 (4) directly or coating, incorporated into the resin or the like, the device can be adopted a method in which coated or deposited on the surface in contact with the equipment treated water piping.

【0016】 [0016]

【作用】本発明は、前記詳述したようにCMIをゲスト化合物とし、ホスト化合物としてテトラキス(ヒドロキシフェニル)エタン類を選択したことを特徴とする。 DETAILED DESCRIPTION OF THE INVENTION The present invention, as a guest compound of CMI as detailed above, is characterized in that selects the tetrakis (hydroxyphenyl) ethanes as a host compound. この種のホスト化合物としての条件は、 (1)分子構造内に、 ゲスト分子を包接するためのフェ<br/>ニル基を有する。 Conditions for this type of host compound, (1) in the molecular structure, having a Fe <br/> sulfonyl group for clathrate the guest molecule. (2)水溶性のCMIを水系で徐放させるためには、ホスト化合物が水難溶性であること。 (2) a water-soluble CMI for controlled release in aqueous systems, that the host compound is a poorly water-soluble. (3)水系中でCMIの再放出速度が一定の水準であること。 (3) Re-release rate of the CMI in the aqueous system is a certain level. (4)低価格で、毒性の低いものであること (4) at a low price, it is low in toxicity.

【0017】 これらの条件を満足するホスト化合物として、前記テトラキス(ヒドロキシフェニル)エタンが選択されたが、これらの包接化合物からのCMIの再放出速度が、従来公知の類似の包接化合物に比較して遅い [0017] as a host compound satisfying these conditions, the tetrakis but (hydroxyphenyl) ethane is selected, re-release rate of CMI from these inclusion compounds, compared to the clathrate of known similar slower
理由については明らかでない。 Not clear about why. 一方、CMIは包接されることにより、その毒性、皮膚刺激性等はホスト化合物の毒性皮膚刺激性等に左右されるために低減され、また使用中に他の物質と反応して抗菌活性が低下することも防止される。 On the other hand, by CMI is inclusion, its toxicity, the toxicity of skin irritation such as a host compound, is reduced to depend on skin irritation, etc., also react with other materials during use to antibacterial activity There is also prevented to decrease.

【0018】 [0018]

【実施例】以下、本発明を実施例及び比較例により、更に詳細に説明する。 EXAMPLES Hereinafter, the present invention examples and comparative examples will be described in further detail. ただし、本発明の範囲は、これらの実施例により何等制限を受けるものではない。 However, the scope of the present invention is not subject to any limitation by these examples. (1)包接化合物の製造 (1) Preparation of inclusion compound

【0019】実施例1 水10ml中にTEP−DF(旭有機材工業製) 1.1 [0019] Example 1 TEP-DF (manufactured by Asahi Organic Chemicals Industry) in water 10 ml 1.1
355 g(2.85mmol)を加え、25℃で30分攪拌しながら分散させた後、ここへケーソンWT(ローム&ハース社製)20g(CMIとして11.4mmo 355 g of (2.85 mmol) was added and allowed to disperse with stirring for 30 minutes at 25 ° C., (Rohm & Haas) caisson WT here 20g (11.4mmo as CMI
l)を徐々に滴下し、25℃で3時間攪拌しながら反応させた。 l) was gradually added dropwise and reacted with stirring for 3 hours at 25 ° C.. 次いで、沈澱物を吸引濾過し、濾物を室温にて真空乾燥して淡黄色粉末の試料A−1を得た。 Then, the precipitate was filtered off with suction, to obtain a sample A-1 of the pale yellow powder was dried under vacuum at room temperature filtrate.

【0020】実施例2 水10ml中にTEP−DFを 1.1355gを加え、50℃で20分攪拌分散する。 [0020] Example 2 of water 10ml was added to 1.1355g of TEP-DF during the stirring dispersed 20 minutes at 50 ° C.. ここへケーソンWT20gを徐々に滴下し、50℃で30分攪拌しながら反応させた。 Slowly added dropwise caisson WT20g here was allowed to react with stirring for 30 minutes at 50 ° C.. 次いで、この液を室温まで冷却した後、沈澱物を吸引濾過し、濾物を室温にて真空乾燥して淡黄色粉末の試料A− Then, after cooling the solution to room temperature, the precipitate was filtered off with suction, the pale yellow powder was dried under vacuum filtrate at room temperature sample A-
2を得た。 2 was obtained.

【0021】実施例3 メタノール5ml中にTEP−DF 1.1355g(2.85 mmol) [0021] Example 3 Methanol 5ml during TEP-DF 1.1355g (2.85 mmol)
を加え、TEP−DFが完全に溶解するまで加温しながら攪拌する。 Was added, TEP-DF is stirred with warming until complete dissolution. この溶液を25℃まで冷却した後、ケーソンWT20gを徐々に滴下し、25℃で1時間反応させた。 The solution was cooled to 25 ° C., the caisson WT20g gradually added dropwise and reacted for 1 hour at 25 ° C.. 次いで、析出物を吸引濾過し、濾物を室温にて真空乾燥して淡黄色結晶物の試料A−3を得た。 Then, the precipitate was suction filtered, to obtain a sample A-3 as a pale yellow crystalline product was dried under vacuum at room temperature filtrate.

【0022】実施例4 メタノール5ml中にTEP−DF 1.1355g(2.85 mmol) [0022] Example 4 Methanol 5ml TEP-DF 1.1355g in (2.85 mmol)
を加え、TEP−DFが完全に溶解するまで加温しながら攪拌する。 Was added, TEP-DF is stirred with warming until complete dissolution. この溶液を40℃に保持しながら、ケーソンWT20gを徐々に滴下し、40℃で15分反応させた。 While maintaining this solution 40 ° C., the caisson WT20g gradually added dropwise and reacted for 15 minutes at 40 ° C.. 次いで、この液を室温まで冷却した後、析出物を吸引濾過し、濾物を真空乾燥して淡黄色結晶物の試料A− Then, after cooling the solution to room temperature, the precipitate is filtered off with suction, the pale yellow crystals are dried in vacuo filtrate sample A-
4を得た。 4 was obtained.

【0023】比較例1 メタノール17ml中にβ−ジナフトール 0.827g (2.85 [0023] In Comparative Example 1 methanol 17ml β- Jinafutoru 0.827g (2.85
mmol) を溶解し、ここへケーソンWT 5.04g (CMIとして 0.368g 、2.86mmol) を添加して攪拌したところ、 mmol) was dissolved, wherein the 0.368g as caisson WT 5.04g (CMI, 2.86mmol) was added and stirred,
暗黒色の析出物が析出した。 Precipitates of the dark color was precipitated. この析出物を吸引濾過し、 The precipitate is filtered off with suction,
濾物を真空乾燥して比較試料C−1を得た。 The filtrate was vacuum-dried to obtain Comparative Sample C-1. 注):実施例1〜4及び比較例1で使用した水溶性殺菌剤(ケーソンWT)の分析値は下記のとおりである。 Note): analysis of the water-soluble disinfectant used in Examples 1 to 4 and Comparative Example 1 (caisson WT) are as follows. CMI:10.1wt% MI : 3.8wt% 残部 :塩化マグネシウム+硝酸マグネシウム+水 CMI: 10.1wt% MI: 3.8wt% balance: Magnesium chloride + magnesium nitrate + water

【0024】以上のようにして得られた本発明の包接化合物試料A−1 〜試料A−4及び比較用包接化合物試料C−1おける製造条件、CMI及びMIの包接量、ゲスト再放出温度を表1に示した。 [0024] The thus-obtained inclusion compound Sample A-1 ~ Sample A-4 and comparative clathrate Sample C-1 definitive production conditions of the present invention, the inclusion amount of CMI and MI, the guest again the release temperature shown in Table 1.

【0025】 [0025]

【表1】 [Table 1] また、各包接化合物試料について、IRスペクトル、N Also, for each clathrate compound sample, IR spectrum, N
MRスペクトル、X線回折、DTA、HPLC及びTL MR spectra, X-rays diffraction, DTA, HPLC and TL
Cで解析して、包接体の形成を確認し、X線マイクロアナライザーにより、塩化マグネシウム、硝酸マグネシウムは含まれていないことが確認された。 Analyzes in C, and confirmed the formation of inclusion bodies by X-ray microanalyzer, magnesium chloride, that does not include magnesium nitrate was confirmed.

【0026】また、CMIの放出試験として、得られた試料A−3、比較試料C−1及びCMI単独のそれぞれを、CMI換算で 10 mgとなるようにセルロース透析膜に入れ、これを純水1l に浸漬し、溶出試験器を用いて攪拌速度 100rpm で攪拌しながら一定時間後のCMIの放出量を測定してその経時変化を調べた。 Further, as a release test of CMI, the obtained sample A-3, the respective comparative sample C-1 and CMI alone, placed in a cellulose dialysis membrane such that 10 mg in CMI terms, pure water which immersed in 1l, we examined the time course by measuring the release of CMI after a certain time with stirring at a stirring rate of 100rpm using a dissolution tester. その結果を表2に示し、その放出曲線を図7に示した。 The results shown in Table 2, showed that release curve in FIG.

【0027】 [0027]

【表2】 [Table 2]

【0028】更に、本発明で得られた包接化合物試料A Furthermore, inclusion compound obtained in the present invention sample A
−3、ホスト化合物TEP−DF及びゲスト水溶性殺菌剤(ケーソンWT)から単離したCMIのIRスペクトル図をそれぞれ、図1、図2及び図3に、X線回折図を図4、図5及び図6に示した。 -3, host compound TEP-DF and guest water-soluble fungicide IR spectrum of CMI isolated from (caisson WT) respectively, in FIGS. 1, 2 and 3, 4 the X-ray diffraction diagram, FIG. 5 and it is shown in FIG.

【0029】 [0029]

【発明の効果】本発明の包接化合物は、前述したように殺菌剤として有効なCMIをゲストとし、テトラキス(ヒドロキシフェニル)エタン類をホストとした新規包接化合物である。 Clathrate compound of the present invention according to the present invention is a novel clathrate compound which is a guest a valid CMI as fungicides, as described above, and a host of tetrakis (hydroxyphenyl) ethanes. 該包接化合物は、次の特徴を有する。該包 contact compound has the following features. (1)毒性および皮膚刺激性の高いCMIを、より低毒性のテトラキス(ヒドロキシフェニル)エタン類をホストとして包接したことにより、毒性および皮膚刺激性が低下させることができる。 (1) toxicity and high skin irritation CMI, by a lower toxicity of tetrakis (hydroxyphenyl) ethanes inclusion complex as a host, toxicity and skin irritation can be reduced. (2)常温で固体であるため、打錠成形も可能であり極めて取扱いが容易である。 (2) because it is a solid at room temperature, it is easy to very handling are also possible tablet compression. (3)水系中において、有効成分のCMIが、適度な速さで再放出されるため、2〜3日単位で交換する、列車用循環式トイレ用の殺菌剤として有効である。 (3) in an aqueous, CMI active ingredients, to be re-emitted at a moderate speed, exchanged 2-3 days units, are effective as fungicides for train circulation toilet. (4)ホスト化合物が、有効成分のCMIを保護するため、CMIが他の物質と反応し抗菌活性が低下するのが防止される。 (4) the host compound, to protect the CMI of the active ingredient, CMI is the reaction to the antimicrobial activity with other substances is prevented from lowering. 従って、 本発明は適度な徐放性を有する殺菌剤として有効であり、かつ取扱いの容易な新規包接化合物及びその製造方法を提供するものであり、特に水処理関連分野における利用価値は極めて大きい。 Accordingly, the present invention is effective as a disinfectant having appropriate sustained release, and there is provided an easy novel clathrate compound and a method for producing the same handling, very large utility value in particular water treatment related fields .

【0030】 [0030]

【図面の簡単な説明】 BRIEF DESCRIPTION OF THE DRAWINGS

【図1】包接化合物試料A−3のIRスペクトル図を示す。 1 shows an IR spectrum of the clathrate Sample A-3.

【図2】ホスト化合物TEP−DFのIRスペクトル図を示す。 Figure 2 shows the IR spectrum of the host compound TEP-DF.

【図3】ゲスト化合物水溶性殺菌剤(ケーソンWT)から単離したCMIのIRスペクトル図を示す。 Figure 3 shows the IR spectrum of CMI isolated from the guest compound soluble disinfectant (caisson WT).

【図4】包接化合物試料A−3のX線回折図を示す。 Figure 4 shows the X-ray diffraction diagram of inclusion complex sample A-3.

【図5】TEP−DFのX線回折図を示す。 Figure 5 shows the X-ray diffraction diagram of TEP-DF.

【図6】ゲスト化合物水溶性殺菌剤(ケーソンWT)から単離したCMIのX線回折図を示す。 6 shows the X-ray diffraction diagram of CMI isolated from the guest compound soluble disinfectant (caisson WT).

【図7】得られた試料A−3、比較試料C−1及びCM [7] obtained samples A-3, Comparative Sample C-1 and CM
I単独について、放出試験を行い、放出量を測定して得た放出曲線を示した図である。 For I alone performs release test is a diagram showing a discharge curve obtained by measuring the emission. (以下余白) (Hereinafter referred to as margin)

───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl. 7 ,DB名) C07D 275/02 - 275/03 C07C 39/15 A01N 43/80 CA(STN) REGISTRY(STN) WPI(DIALOG) ────────────────────────────────────────────────── ─── front page of the continuation (58) investigated the field (Int.Cl. 7, DB name) C07D 275/02 - 275/03 C07C 39/15 A01N 43/80 CA (STN) REGISTRY (STN) WPI (DIALOG )

Claims (2)

    (57)【特許請求の範囲】 (57) [the claims]
  1. 【請求項1】下記一般式〔1〕で示されるテトラキス(ヒドロキシフェニル)エタンをホスト化合物とし、化学式〔2〕で示される5−クロロ−2−メチル−4−イソチアゾリン−3−オンをゲスト化合物とすることを特徴とする包接化合物。 1. A tetrakis represented by the following general formula (1) to (hydroxyphenyl) ethane as a host compound, 5-chloro-2-methyl-4-isothiazolin-3-one guest compound represented by the chemical formula (2) inclusion compounds, characterized in that a. 【化1】 [Formula 1] 【化2】 ## STR2 ##
  2. 【請求項2】テトラキス(ヒドロキシフェニル)エタンと5−クロロ−2−メチル−4−イソチアゾリン−3− 2. A tetrakis (hydroxyphenyl) ethane and 5-chloro-2-methyl-4-isothiazolin-3
    オンを反応してなることを特徴とする請求項1記載の包接化合物の製造方法。 The process according to claim 1, clathrate, wherein the formed by reacting one.
JP03183027A 1991-06-27 1991-06-27 New inclusion compounds and their preparation Expired - Fee Related JP3077268B2 (en)

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US8192262B2 (en) 2004-06-28 2012-06-05 Cfph, Llc Gaming based upon intermediate points in a race event
US8246431B2 (en) 2004-06-28 2012-08-21 Cfph, Llc Bet matrix for entering bets regarding intermediate points in a race event
US8246432B2 (en) 2008-01-28 2012-08-21 Cfph, Llc Electronic gaming based on intermediate points in an event

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DE69214814T2 (en) * 1991-12-12 1997-03-20 Nippon Soda Co New inclusion compounds which contain tetrakisphenol as host
DE69421182D1 (en) * 1993-06-23 1999-11-18 Nippon Soda Co New clathrate compounds, methods for their manufacture and fäulmisverhinderndes medium
JPH08176126A (en) * 1994-12-22 1996-07-09 Nippon Soda Co Ltd New clathrate, its production and coating composition containing the same
JP2011144142A (en) * 2010-01-15 2011-07-28 Nippon Soda Co Ltd Composition and method for controlling elution of guest compound of clathrate compound

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US8192262B2 (en) 2004-06-28 2012-06-05 Cfph, Llc Gaming based upon intermediate points in a race event
US8246431B2 (en) 2004-06-28 2012-08-21 Cfph, Llc Bet matrix for entering bets regarding intermediate points in a race event
US8777709B2 (en) 2004-06-28 2014-07-15 Cfph, Llc Wagering on intermediate points of a race event
US8246432B2 (en) 2008-01-28 2012-08-21 Cfph, Llc Electronic gaming based on intermediate points in an event
US9492735B2 (en) 2008-01-28 2016-11-15 Cfph, Llc Electronic gaming based on intermediate points in an event

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