JPH03279373A - Clathrate compound - Google Patents
Clathrate compoundInfo
- Publication number
- JPH03279373A JPH03279373A JP2081506A JP8150690A JPH03279373A JP H03279373 A JPH03279373 A JP H03279373A JP 2081506 A JP2081506 A JP 2081506A JP 8150690 A JP8150690 A JP 8150690A JP H03279373 A JPH03279373 A JP H03279373A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- clathrate
- group
- formula
- guest
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 68
- -1 bisphenol compound Chemical class 0.000 claims abstract description 23
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 14
- KXGVEGMKQFWNSR-LLQZFEROSA-N deoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 KXGVEGMKQFWNSR-LLQZFEROSA-N 0.000 claims abstract description 10
- 229960003964 deoxycholic acid Drugs 0.000 claims abstract description 10
- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract 3
- 125000003342 alkenyl group Chemical group 0.000 claims abstract 2
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 125000002015 acyclic group Chemical group 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 125000006165 cyclic alkyl group Chemical group 0.000 claims 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 125000004434 sulfur atom Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000003242 anti bacterial agent Substances 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003247 decreasing effect Effects 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 238000002844 melting Methods 0.000 description 16
- 230000008018 melting Effects 0.000 description 16
- 230000000844 anti-bacterial effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000009472 formulation Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000000645 desinfectant Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- JPMIIZHYYWMHDT-UHFFFAOYSA-N octhilinone Chemical compound CCCCCCCCN1SC=CC1=O JPMIIZHYYWMHDT-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000006561 solvent free reaction Methods 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical class O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000016709 nutrition Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- PHXZQPLQBTYCFV-UHFFFAOYSA-N 4-chloro-2-octyl-1,2-thiazol-3-one Chemical compound CCCCCCCCN1SC=C(Cl)C1=O PHXZQPLQBTYCFV-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003619 algicide Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Thiazole And Isothizaole Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は包接化合物に係り、特に水系に適用しにくい油
溶性殺菌剤であるイソチアゾロン系化合物を、水系に適
用可能とする新規包接化合物に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to clathrate compounds, and in particular, a novel clathrate compound that makes it possible to apply isothiazolone compounds, which are oil-soluble disinfectants that are difficult to apply to aqueous systems, to aqueous systems. It is related to.
［従来の技術］
各種工場プラントの冷却水系では、細菌、糸状菌、藻類
等から構成されるスライムが系内に発生、付着し、熱効
率の低下、通水配管の閉塞、配管金属材質の腐食等のス
ライム障害を引き起こしている。[Prior art] In the cooling water systems of various industrial plants, slime consisting of bacteria, filamentous fungi, algae, etc. occurs and adheres to the system, resulting in decreased thermal efficiency, blockage of water pipes, corrosion of metal pipe materials, etc. causing a slime disorder.
また、紙バルブ抄紙系では、セルロースやデンプン等の
各種添加物を栄養源として、細菌、糸状菌等を主構成微
生物としたスライムが系内壁面に形成される。そして、
このようなスライムが壁面から剥離することにより、製
品中に異物として混入し、製品品質を低下させたり、紙
抄造工程において紙切れを誘発して連続操業を阻害し、
生産効率を大幅に低下させるなどの障害の原因となる。In addition, in the paper valve paper making system, slime mainly composed of microorganisms such as bacteria and filamentous fungi is formed on the inner wall surface of the system using various additives such as cellulose and starch as nutritional sources. and,
When such slime peels off from the wall surface, it can become mixed into the product as foreign matter, reducing product quality, or causing paper breakage in the papermaking process, impeding continuous operation.
This can cause problems such as significantly reducing production efficiency.
特に、紙パルブ工業では、添加物としてデンプン、ラテ
ックス、カゼイン等が大量に使用されているが、これら
の添加物質はいずれも微生物繁殖のための栄養源となる
ことから、微生物により腐敗し、製品劣化の大きな原因
となる。In particular, in the pulp and paper industry, large amounts of additives such as starch, latex, and casein are used, but since all of these additives serve as nutritional sources for the growth of microorganisms, they spoil and spoil the product. This is a major cause of deterioration.
その他、有機物買を豊富に含む水性塗料、エマルジョン
塗料、エマルジョン接着剤、金属加工油、ラテックス、
デンプン糊液、紙塗工液等の関連分野においても、微生
□物による製品品質の低下、生産性の低下などの様々な
障害が発生する。In addition, water-based paints, emulsion paints, emulsion adhesives, metal processing oils, latex, etc., which are rich in organic materials,
In related fields such as starch paste liquids and paper coating liquids, various problems occur such as deterioration of product quality and productivity due to microorganisms.
従来、このような各種工業分野における細菌、糸状菌、
酵母、藻類等の微生物障害に対しては、その実施が比較
的簡便で、安価であることから、抗菌剤（スライムコン
トロール剤）による処理がなされている。そして、抗菌
剤としては、特に下記［ｒＶ］式で示される４、５−ジ
クロロ−２＝オクチル−３（２Ｈ）−イソチアゾロン（
以下ｒＤｃＩＪと略称する。）が、抗菌力に優れている
ことから、冷却水系用、紙パルプ用など各種水系用スラ
イムコントロール剤、殺菌剤、殺藻剤、殺かび剤として
の適用が期待されている。Conventionally, bacteria, filamentous fungi,
Microbial disorders such as yeast and algae are treated with antibacterial agents (slime control agents) because they are relatively simple and inexpensive to implement. As an antibacterial agent, in particular, 4,5-dichloro-2=octyl-3(2H)-isothiazolone (
Hereinafter, it will be abbreviated as rDcIJ. ) has excellent antibacterial activity, and is expected to be used as a slime control agent, bactericide, algaecide, and fungicide for various water systems such as cooling water systems and pulp and paper systems.
［発明が解決しようとする課題］
しかし、このＤＣＩは優れた抗菌力を有する抗菌剤であ
りながら、皮膚刺激性があり、取り扱い上多大な注意が
必要であった。また、有機溶媒系には溶は易いが、極め
て水に溶は難いため、水系へ適用する場合には、効率良
く水系に分散させるための何らかの製剤的な改善技術が
必要である。[Problems to be Solved by the Invention] However, although this DCI is an antibacterial agent having excellent antibacterial activity, it is irritating to the skin and requires great care in handling. In addition, although it is easy to dissolve in organic solvent systems, it is extremely difficult to dissolve in water, so when it is applied to an aqueous system, some kind of formulation improvement technique is required to efficiently disperse it in an aqueous system.
しかしながら、このＤＣＩは融点が４０℃と極めて低く
、製剤化時に発生するわずかの熱で溶けて油状物となる
ため、製剤化し難いという欠点があった。However, this DCI has an extremely low melting point of 40° C. and melts into an oily substance with a small amount of heat generated during formulation, making it difficult to formulate into formulations.
このように油溶性殺菌剤ＤＣＩは、毒性があること、水
への溶解性が悪いこと、融点が低いことなどから、取り
扱い、抗菌効果、製剤化の面で不都合を有するものであ
った。As described above, the oil-soluble disinfectant DCI has disadvantages in terms of handling, antibacterial effect, and formulation due to its toxicity, poor solubility in water, and low melting point.
本発明は上記従来の問題点を解決し、ＤＣＩ等の水系へ
の通用を可能にする優れた抗菌剤を提供することがで°
きる包接化合物を提供することを目的とする。The present invention solves the above conventional problems and provides an excellent antibacterial agent that can be used in aqueous systems such as DCI.
The purpose is to provide clathrate compounds that can
［課題を解決するための手段］
本発明の包接化合物は、下記一般式［Ｉ］で表わされる
難水溶性イソチアゾロン系化合物をゲスト化合物とし、
下記一般式［ＩＩ ］で表わされるビスフェノール系化
合物又は下記構造式［ＩＩＩ ］で表わされるデオキシ
コール酸をホスト化合物とすることを特徴とする特
ＨＵ
以下に本発明の詳細な説明する。[Means for Solving the Problems] The clathrate compound of the present invention uses a poorly water-soluble isothiazolone compound represented by the following general formula [I] as a guest compound,
A special HU characterized by using a bisphenol compound represented by the following general formula [II] or deoxycholic acid represented by the following structural formula [III] as a host compound.The present invention will be described in detail below.
本発明の包接化合物において、ゲスト化合物となる前記
一般式［Ｉ］で示される難水溶性イソチアゾロン系化合
物としては、前記一般式［ＩＩ ］で表わされるビスフ
ェノール系化合物又は前記構造式［ｍｌで表わされるデ
オキシコール酸と包接化合物を形成し得るものであれば
良く、特に限定はされないが、具体的には次の■〜■等
が挙げられる。In the clathrate compound of the present invention, the poorly water-soluble isothiazolone compound represented by the general formula [I] that serves as a guest compound is a bisphenol compound represented by the general formula [II] or the structural formula [ml]. Any compound may be used as long as it can form a clathrate compound with deoxycholic acid, and is not particularly limited, but specific examples include the following (1) to (2).
■ 前記［ｒＶ］式で示される４、５−ジクロロ−２−
オクチル−３（２Ｈ）−イソチアゾロン（ＤＣり■ ４
−クロロ−２−オクチル−３（２Ｈ）−イソチアゾロン
■ ４．５−ジクロロ−２−ベンチルー３ （２Ｎ）−
イソチアゾロン
■ ４．５−ジクロロ−２−デシル−３（２Ｈ）−イソ
チアゾロン
■ ４．５−ジクロロ−２−オクテニル−３（２１（）
−イソチアゾロン
■ ４−クロロ−２−ペンテニル−３（２）１）−イソ
チアゾロン
本発明においては、これらのうち、特にＤＣＩが好適で
あるが、これに何ら限定されるものではない。■ 4,5-dichloro-2- represented by the above [rV] formula
Octyl-3(2H)-isothiazolone (DC) 4
-Chloro-2-octyl-3(2H)-isothiazolone ■ 4.5-dichloro-2-benthyl-3 (2N)-
Isothiazolone■ 4.5-dichloro-2-decyl-3(2H)-isothiazolone■ 4.5-dichloro-2-octenyl-3(21()
-Isothiazolone ■ 4-chloro-2-pentenyl-3(2)1)-isothiazolone Among these, DCI is particularly preferred in the present invention, but is not limited thereto.
一方ホスト化合物のうち、前記一般式［ＩＩ ］で表わ
させるビスフェノール系化合物としては、例えば、４．
４°−シクロへキシリデンビスフェノール、４．４°−
スルホニルビスフェノール、４．４゜ブチリデンビス（
３−メチル−６−ｔｅｒｔ−ブチルフェノール）等が挙
げられる。On the other hand, among the host compounds, examples of bisphenol compounds represented by the general formula [II] include 4.
4°-cyclohexylidene bisphenol, 4.4°-
Sulfonylbisphenol, 4.4゜butylidene bis(
3-methyl-6-tert-butylphenol) and the like.
前記イソチアゾロン系化合物をゲスト化合物とし、前記
ビスフェノール系化合物又はデオキシコール酸をホスト
化合物とする本発明の包接化合物は、溶媒中若しくは無
溶媒反応にて容易に製造することができる。The clathrate compound of the present invention, which uses the isothiazolone compound as a guest compound and the bisphenol compound or deoxycholic acid as a host compound, can be easily produced in a solvent or by a solvent-free reaction.
溶媒中反応の場合には、例えばエーテル、塩化メチレン
、メタノール、ベンゼン、酢酸エチルなどの通常使用さ
れる溶媒にＤＣＩ等のイソチアゾロン系化合物を溶解し
、これにホスト化合物を添加して反応させる。これによ
り、包接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包接化合物を得る。こ
のような溶媒中での反応によって、本発明の包接化合物
は容易に得ることができるが、本発明においては、無溶
媒反応にて行なうのが有利である。In the case of reaction in a solvent, an isothiazolone compound such as DCI is dissolved in a commonly used solvent such as ether, methylene chloride, methanol, benzene, ethyl acetate, etc., and a host compound is added thereto for reaction. As a result, the clathrate compound is precipitated as a solid, which is separated by filtration by a conventional method to obtain the desired clathrate compound. Although the clathrate compound of the present invention can be easily obtained by such a reaction in a solvent, in the present invention, it is advantageous to conduct the reaction without a solvent.
即ち、溶媒中反応の場合には、 ■ 溶媒を選定する必要がある。That is, in the case of reaction in a solvent, ■ It is necessary to select a solvent.
■ 条件設定が比較的離しい。■ Condition settings are relatively far apart.
■ □固液分離後の反応濾液の処理が必要となる。■ □It is necessary to treat the reaction filtrate after solid-liquid separation.
■ 特に有機溶媒使用時には人体及び作業環境を保護す
るための設備が必要となる。■ Especially when using organic solvents, equipment is required to protect the human body and the working environment.
■ ホスト化合物ベースでの収率が比較的低い。■ Relatively low yield based on host compound.
などの問題があるが、無溶媒反応の場合には、このよう
な問題が解消される。However, in the case of a solvent-free reaction, these problems are solved.
無溶媒反応の場合には、まず、ゲスト化合物であるイソ
チアゾロン系化合物を溶融させて液体とする。即ち、ゲ
スト化合物のイソチアゾロン系化合物を、その融点より
高い温度に加温、加熱して溶融させる０例えば、ＤＣＩ
は融点が４０℃であるので、温水浴上にて６０±１０℃
程度に加熱して溶融させる。次いで、ゲスト化合物の溶
融液中に、ホスト化合物の粉末を直接添加して混合、攪
拌する。この場合、反応温度はゲスト化合物が溶融状態
である温度以上であって、１００℃以下の範囲において
任意で良く、反応時間は１〜６０分程度、通常５分程度
で十分である。反応により、包接化合物が生成し、反応
混合物が固化したら、これを室温に戻し、反応を終了す
る。包接化合物の生成はＩＲスペクトルにより確認する
ことができる。In the case of a solvent-free reaction, first, the isothiazolone compound as a guest compound is melted into a liquid. That is, an isothiazolone compound as a guest compound is heated to a temperature higher than its melting point to melt it. For example, DCI
has a melting point of 40℃, so heat it at 60±10℃ on a hot water bath.
Heat to a moderate temperature to melt. Next, the host compound powder is directly added to the guest compound melt and mixed and stirred. In this case, the reaction temperature may be any value within the range of not less than the temperature at which the guest compound is in a molten state and not more than 100°C, and the reaction time may be about 1 to 60 minutes, usually about 5 minutes is sufficient. After the reaction produces an clathrate and solidifies the reaction mixture, the temperature is returned to room temperature to complete the reaction. The formation of clathrate compounds can be confirmed by IR spectroscopy.
なお、本発明において、ゲスト化合物であるイソチアゾ
ロン系化合物とホスト化合物であるビスフェノール系化
合物又はデオキシコール酸との包接比には特に制限はな
いが、一般には包接化合物のイソチアゾロン系化合物含
有量は２０〜５０重量％、ホスト化合物含有量は５０〜
８０重量％である。In the present invention, there is no particular restriction on the inclusion ratio between the isothiazolone compound as the guest compound and the bisphenol compound or deoxycholic acid as the host compound, but generally the isothiazolone compound content of the clathrate compound is 20-50% by weight, host compound content 50-50%
It is 80% by weight.
［作用コ
本発明の包接化合物は、通常は固体であって、ホスト化
合物の融点がゲスト化合物の融点よりも高いので、包接
化合物の融点もゲスト化合物の融点より高くなっている
。即ち、イソチアゾロン系化合物は、ビスフェノール系
化合物又はデオキシコール酸のホスト化合物により包接
化合物とされることによりイソチアゾロン系化合物より
融点の高い固形物となる。従って、粉砕時に発生する熱
によりて溶融することなく、所望の粒子径に粉砕するこ
とができる。このようにして得られた粉砕物は適宜、分
散剤等を用いて製剤化することができ、水系へも任意に
通用することができる。また殺菌剤は包接されることに
よりその危険性が低減されるため、安全に取り扱うこと
ができる。[Function] The clathrate compound of the present invention is usually solid, and since the melting point of the host compound is higher than the melting point of the guest compound, the melting point of the clathrate compound is also higher than the melting point of the guest compound. That is, the isothiazolone compound becomes a solid substance having a higher melting point than the isothiazolone compound by being made into an clathrate compound by a bisphenol compound or a host compound of deoxycholic acid. Therefore, the particles can be pulverized to a desired particle size without being melted by the heat generated during pulverization. The pulverized product thus obtained can be formulated into a formulation using a dispersant or the like as appropriate, and can also be used in an aqueous system as desired. Moreover, since the danger of disinfectants is reduced by inclusion, they can be handled safely.
本発明の包接化合物は、水中に投入した場合、ゲスト化
合物自体よりも水に溶は易くなっており、ゲスト化合物
だけの場合にくらべて、抗菌活性を発現する濃度により
短時間で達することができる。When the clathrate compound of the present invention is added to water, it is more easily soluble in water than the guest compound itself, and can reach a concentration that exhibits antibacterial activity in a shorter time than when the guest compound alone is used. can.
本発明の包接化合物を抗菌剤（以下、「末剤」という。The clathrate compound of the present invention is an antibacterial agent (hereinafter referred to as "powder").
）として用いる場合、その使用方法としては、以下に示
すような方法が挙げられる。), examples of how to use it include the following methods.
■ 末剤を水浸透性で、水に溶解しない袋やカートリッ
ジに入れ、水系に浸漬若しくは浮遊させて使用する。■ Place the powder in a water-permeable, water-insoluble bag or cartridge, and use it by immersing or suspending it in a water system.
■ 製剤化した粉末状の末剤を水系に分散させて流す。■ Disperse the formulated powder into an aqueous system and pour it away.
■ 末剤を塗料、その他の樹脂等と混合して水系等の機
器表面に塗る。■ Mix the powder with paint, other resins, etc. and apply it to the surface of water-based equipment.
■ 末剤を保護物体の表面に適当な方法により付着させ
る。■ Apply the powder to the surface of the protected object using an appropriate method.
［実施例］
以下に本発明を実施例を挙げて更に具体的に説明するが
、本発明はその要旨を超えない限り以下の実施例に限定
されるものではない。[Examples] The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
実施例１：ＤＣＩと４，４°−シクロへキシリデンビス
フェノールとの包接化合物の製造ＤＣＩ ７．０５ｇ
を温水浴上で約６５℃に加温して溶かした。これに同温
度で４．４°−シクロへキシリデンビスフェノール １
０．５ｇを加えよく攪拌した。反応は直ちに進行し、固
形物が得られた。得られた固形物のＩＲスペクトル（第
１図）より、このものはＤＣＩを包接した包接化合物（
ＤＣｒ含量４０重量％）であることが確認された。本物
質の融点は８８〜９５℃（包接化合物の融点）と１８０
℃（未反応の４．４′−シクロへキシリデンビスフェノ
ールの融点）の２点であった。Example 1: Preparation of clathrate compound of DCI and 4,4°-cyclohexylidene bisphenol DCI 7.05g
was heated to about 65°C on a hot water bath to dissolve it. At the same temperature, 4.4°-cyclohexylidene bisphenol 1
0.5 g was added and stirred well. The reaction proceeded immediately and a solid was obtained. The IR spectrum (Figure 1) of the obtained solid shows that it is a clathrate compound containing DCI (
It was confirmed that the DCr content was 40% by weight. The melting point of this substance is 88-95℃ (melting point of the clathrate compound) and 180℃
℃ (melting point of unreacted 4.4'-cyclohexylidene bisphenol).
実施例２：ＤＣｒとデオキシコール酸との包接化金物の
製造
ＤＣＩ ２．８２ｇを温水浴上で約６５℃に加温して
溶かした。これに同温度でデオキシコール酸３．９２ｇ
を加え、よく攪拌した。反応は直ちに進行し、固形物が
得られた。得られた固形物のＩＲスペクトル（第２図）
より、このものはＤＣＩを包接した包接化合物（ＤＣＩ
含量４１．８重量％）であることがＦｔ１認された。本
物質の融点は１６０〜１７０ｔ：であった。Example 2: Production of clathrated metal product of DCr and deoxycholic acid 2.82 g of DCI was heated to about 65° C. on a hot water bath and dissolved. Add to this 3.92g of deoxycholic acid at the same temperature.
was added and stirred well. The reaction proceeded immediately and a solid was obtained. IR spectrum of the obtained solid (Fig. 2)
Therefore, this compound is a clathrate compound containing DCI (DCI
Ft1 was found to have a content of 41.8% by weight). The melting point of this substance was 160-170t:.
実施例１．２の結果から、ＤＣＩを包接した包接化合物
は、ＤＣＩの融点よりもはるかに高い融点を有し、取り
扱い性が向上することが明らかである。From the results of Example 1.2, it is clear that the clathrate containing DCI has a melting point much higher than the melting point of DCI and has improved handleability.
実施例３＋ＤＣＩと４，４°−シクロへキシリデンビス
フェノールとの包接化合物の水中ゲスト溶解性試験
実施例１で製造したＤＣＩと４．４°−シクロへキシリ
デンビスフェノールとの包接化合物７５ｍｇ（Ｄｃｔと
して３０ ｍ ｇ ）を純水１１中に分散させ、２５℃
で攪拌した。経時的にサンプリングし、ＤＣＩの水中へ
の溶出濃度を調べた。結果を第１表に示す。Example 3 + Guest solubility test in water of the clathrate compound of DCI and 4,4°-cyclohexylidene bisphenol 75 mg of the clathrate compound of DCI and 4,4°-cyclohexylidene bisphenol produced in Example 1 ( Dct (30 mg) was dispersed in pure water 11 and heated at 25°C.
It was stirred with Samples were taken over time to examine the elution concentration of DCI into water. The results are shown in Table 1.
また、比較のため、ＤＣ１単独の水中溶解性を調べた。For comparison, the solubility of DC1 alone in water was also investigated.
即ち、ＤＣＩ ３０ｍｇを純水１１中に分散させ、２５
℃で攪拌した。経時的にサンプリングし、ＤＣＩの水中
への溶出濃度を調べた。結果を第１表に併記した。That is, 30 mg of DCI was dispersed in 11 of pure water,
Stir at ℃. Samples were taken over time to examine the elution concentration of DCI into water. The results are also listed in Table 1.
第 １ 表 （濃度：ｐｐｍ）
この結果から、本発明の包接化合物は、抗菌剤として用
いた場合、有効成分の溶出が、ゲスト化合物（ＤＣＩ）
のみの場合に比べて速くなる効果により、抗菌活性を発
現するための濃度に短時間で達することが明らかである
。Table 1 (Concentration: ppm) From these results, when the clathrate compound of the present invention is used as an antibacterial agent, the elution of the active ingredient is lower than that of the guest compound (DCI).
It is clear that the concentration required to exhibit antibacterial activity can be reached in a short time due to the faster effect than in the case of only the antibacterial activity.
［発明の効果］
以上詳述した通り、本発明の包接化合物によれば、油溶
性抗菌剤等として有用なイソチアゾロン系化合物をゲス
ト化合物として包接することにより、
■ ゲスト化合物のイソチアゾロン系化合物自体よりも
融点が高くなり、熱安定性が増すため、粉砕、成形など
の製剤化が可能になり、水系にも容易に適用できるよう
になる。[Effects of the Invention] As detailed above, according to the clathrate compound of the present invention, by including an isothiazolone compound useful as an oil-soluble antibacterial agent etc. as a guest compound, ■ The melting point of the compound also becomes higher and the thermal stability increases, making it possible to formulate formulations by pulverization and molding, and it also becomes easier to apply to aqueous systems.
■ ゲスト化合物のみの場合よりも水に溶解し易くなり
、効果を発現できる濃度に達するまでの時間が短縮され
る。■ It becomes more soluble in water than the guest compound alone, and the time required to reach a concentration that produces an effect is shortened.
■ 危険性が低減し、取り扱い性が向上する。■ Reduced danger and improved handling.
等の効果が奏され、イソチアゾロン系化合物の通用分野
を大幅に拡大することが可能とされる。These effects are expected to be achieved, making it possible to significantly expand the field of application of isothiazolone compounds.
第１図は実施例１で得られた包接化合物のＩＲスペクト
ル線図、第２図は実施例２で得られた包接化合物のＩＲ
スペクトル線図である。Figure 1 is an IR spectrum diagram of the clathrate compound obtained in Example 1, and Figure 2 is an IR spectrum diagram of the clathrate compound obtained in Example 2.
It is a spectrum diagram.
Claims (1)
アゾロン系化合物をゲスト化合物とし、下記一般式［I
I］で表わされるビスフェノール系化合物又は下記構造
式［III］で表わされるデオキシコール酸をホスト化合
物とする包接化合物。 ▲数式、化学式、表等があります▼［ I ］ ［式中、Ｒ＾１はフェニル基又は炭素数４〜１０の非環
式もしくは環式アルキル基、アルケニル基を表わし、Ｒ
＾２、Ｒ＾３は水素原子又はハロゲン原子、或いはＲ＾
２とＲ＾３とが縮合して形成されたベンゼン環を表わす
。］ ▲数式、化学式、表等があります▼……［II］ ［式中、Ｘは水素原子、炭素数１〜４の低級アルキル基
又はハロゲン原子を表わし、Ｒ＾４はメチレン基、ブチ
リデン基、シクロヘキシリデン基、イオウ原子又はスル
ホニル基を表わし、ｎは１、２又は３を示す。］ ▲数式、化学式、表等があります▼(1) A poorly water-soluble isothiazolone compound represented by the following general formula [I] is used as a guest compound, and the following general formula [I] is used as a guest compound.
A clathrate compound whose host compound is a bisphenol compound represented by [I] or deoxycholic acid represented by the following structural formula [III]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R^1 represents a phenyl group or an acyclic or cyclic alkyl group or alkenyl group having 4 to 10 carbon atoms, and R
^2, R^3 are hydrogen atoms or halogen atoms, or R^
Represents a benzene ring formed by condensation of 2 and R^3. ] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[II] [In the formula, X represents a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a halogen atom, and R^4 represents a methylene group, a butylidene group, It represents a cyclohexylidene group, a sulfur atom or a sulfonyl group, and n represents 1, 2 or 3. ] ▲Contains mathematical formulas, chemical formulas, tables, etc.▼
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2081506A JP2973455B2 (en) | 1990-03-29 | 1990-03-29 | Clathrate compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2081506A JP2973455B2 (en) | 1990-03-29 | 1990-03-29 | Clathrate compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03279373A true JPH03279373A (en) | 1991-12-10 |
| JP2973455B2 JP2973455B2 (en) | 1999-11-08 |
Family
ID=13748247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2081506A Expired - Lifetime JP2973455B2 (en) | 1990-03-29 | 1990-03-29 | Clathrate compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2973455B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995000465A1 (en) * | 1993-06-23 | 1995-01-05 | Nippon Soda Co., Ltd. | Novel clathrate compound, process for producing the same, and antifouling agent |
| EP0648415A2 (en) * | 1993-10-01 | 1995-04-19 | Kurita Water Industries Ltd. | Clathrate compound including water-soluble microbicide |
| EP0923867A1 (en) * | 1997-12-22 | 1999-06-23 | Kurita Water Industries Ltd. | Antimicrobial composition and their use |
| US6566548B1 (en) | 1998-10-08 | 2003-05-20 | Nippon Soda Co., Ltd. | Molecular compounds containing novel carboxylic acid derivatives as the constituent compound |
-
1990
- 1990-03-29 JP JP2081506A patent/JP2973455B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995000465A1 (en) * | 1993-06-23 | 1995-01-05 | Nippon Soda Co., Ltd. | Novel clathrate compound, process for producing the same, and antifouling agent |
| EP0648415A2 (en) * | 1993-10-01 | 1995-04-19 | Kurita Water Industries Ltd. | Clathrate compound including water-soluble microbicide |
| EP0648415A3 (en) * | 1993-10-01 | 1995-10-25 | Kurita Water Ind Ltd | Clathrate compound including water-soluble microbicide. |
| US5523020A (en) * | 1993-10-01 | 1996-06-04 | Kurita Water Industries Ltd. | Clathrate compound including water-soluble microbicide |
| 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 |
| US6566548B1 (en) | 1998-10-08 | 2003-05-20 | Nippon Soda Co., Ltd. | Molecular compounds containing novel carboxylic acid derivatives as the constituent compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2973455B2 (en) | 1999-11-08 |
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