JP2003137702A - Colloidal solution of metal complex - Google Patents
Colloidal solution of metal complexInfo
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- JP2003137702A JP2003137702A JP2001339858A JP2001339858A JP2003137702A JP 2003137702 A JP2003137702 A JP 2003137702A JP 2001339858 A JP2001339858 A JP 2001339858A JP 2001339858 A JP2001339858 A JP 2001339858A JP 2003137702 A JP2003137702 A JP 2003137702A
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- Prior art keywords
- ligand
- metal complex
- aqueous solution
- complex
- water
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】有機化合物を配位子とする水
難溶性金属錯体のコロイド溶液に関する。さらに詳しく
は、有機化合物を配位子とする水難溶性の金属錯体を、
その溶解度をはるかに上回る濃度で水中に安定に分散さ
せることが可能であり、水主体の製品への配合等におい
て有用なコロイド溶液に関する。TECHNICAL FIELD The present invention relates to a colloidal solution of a poorly water-soluble metal complex having an organic compound as a ligand. More specifically, a poorly water-soluble metal complex having an organic compound as a ligand,
The present invention relates to a colloidal solution that can be stably dispersed in water at a concentration far exceeding its solubility and is useful in blending with water-based products.
【０００２】[0002]
【従来の技術】有機化合物を配位子とする金属錯体の多
くは水難溶性であるが、該金属錯体の効果・機能を発現
するためには水への溶解度を上回る濃度が必要となる場
合が多い。そのため、有機化合物を配位子とする水難溶
性金属錯体を水への溶解度を上回る濃度で水中に分散さ
せる技術は既に検討されており、例えば、水難溶性であ
るトロポロン化合物金属錯体を分岐シクロデキストリン
に包接する技術が特開平１１−２２２４５５号公報に開
示されている。しかしながら、分岐シクロデキストリン
は高価で汎用品ではない上に、分子量が大きいため、包
接化に必要な分岐シクロデキストリン重量がホスト化合
物であるトロポロン化合物重量よりはるかに大きくな
り、トロポロン化合物金属錯体の本来の機能が損なわれ
るという問題点があった。2. Description of the Related Art Most of metal complexes having an organic compound as a ligand are poorly soluble in water, but in order to exert the effects and functions of the metal complex, a concentration higher than the solubility in water may be required. Many. Therefore, a technique of dispersing a poorly water-soluble metal complex having an organic compound as a ligand in water at a concentration exceeding the solubility in water has already been studied. A technique for inclusion is disclosed in Japanese Patent Laid-Open No. 11-222455. However, since branched cyclodextrin is expensive and not a general-purpose product, and has a large molecular weight, the weight of branched cyclodextrin required for inclusion is much larger than the weight of the tropolone compound that is the host compound, and the original nature of the tropolone compound metal complex is large. There was a problem that the function of was impaired.
【０００３】一方、ヨウ化銀や水酸化鉄などの難溶性無
機塩においては、安定なコロイド水溶液が形成されるこ
とは公知である。しかしながら、有機化合物を配位子と
する金属錯体において安定なコロイドが形成された例、
およびそれによって該金属錯体を水中に安定に分散し得
た例は未だ報告されていない。以上述べたように、有機
化合物を配位子とする金属錯体を安価かつ簡便に溶解度
を大きく上回る濃度で水中に安定に分散させる技術は未
だ開示されていない。On the other hand, it is known that a stable colloidal aqueous solution is formed in a poorly soluble inorganic salt such as silver iodide or iron hydroxide. However, an example in which a stable colloid was formed in a metal complex with an organic compound as a ligand,
And, there has not yet been reported any example in which the metal complex can be stably dispersed in water. As described above, a technique for stably and inexpensively dispersing a metal complex having an organic compound as a ligand in water at a concentration greatly exceeding the solubility has not been disclosed yet.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、有機化合物
を配位子とする水難溶性金属錯体を安価かつ簡便に溶解
度を大きく上回る濃度で水中に安定に分散させる技術を
提供することを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a technique for stably and inexpensively dispersing a poorly water-soluble metal complex having an organic compound as a ligand in water at a concentration greatly exceeding the solubility. To do.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意検討した結果、有機化合物を配位
子とする水難溶性金属錯体をコロイド化することが可能
であることを見出したとともに、それによって該金属錯
体の溶解度を大きく上回る濃度で水中に安定に分散させ
ることが可能となることを見出し、本発明を完成した。
すなわち、本発明は下記の通りである。Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that it is possible to colloid a poorly water-soluble metal complex having an organic compound as a ligand. The present invention has been completed and the present invention has been completed, and the present invention was completed, and it was found that it becomes possible to stably disperse it in water at a concentration that greatly exceeds the solubility of the metal complex.
That is, the present invention is as follows.
【０００６】１．有機化合物を配位子とする水難溶性金
属錯体のコロイド溶液。
２．配位子がトロポロン化合物である１．に記載のコロ
イド溶液。
３．配位子が４−イソプロピルトロポロンである１．ま
たは２．のいずれかに記載のコロイド溶液。
４．金属イオンの希薄水溶液と、電気的中性の金属錯体
を形成するに必要なモル数未満の有機化合物の配位子を
含む希薄水溶液を、攪拌条件下で混和する水難溶性金属
錯体のコロイド溶液の製造方法。1. A colloidal solution of a poorly water-soluble metal complex having an organic compound as a ligand. 2. 1. The ligand is a tropolone compound The colloidal solution according to 1. 3. 1. The ligand is 4-isopropyltropolone Or 2. The colloidal solution according to any one of 1. 4. A colloidal solution of a sparingly water-soluble metal complex is prepared by mixing a dilute aqueous solution of a metal ion and a dilute aqueous solution containing a ligand of an organic compound in an amount less than the number of moles required to form an electrically neutral metal complex under stirring conditions. Production method.
【０００７】５．有機化合物の配位子の希薄水溶液と、
電気的中性の金属錯体を形成するに必要なモル数未満の
金属イオンを含む希薄水溶液を、攪拌条件下で混和する
水難溶性金属錯体のコロイド溶液の製造方法。
６．金属イオンおよび配位子の希薄水溶液におけるそれ
らの濃度が、それぞれ０．２ｍｏｌ／Ｌ以下であること
を特徴とする水難溶性金属錯体のコロイド溶液。5. A dilute aqueous solution of an organic compound ligand,
A method for producing a colloidal solution of a sparingly water-soluble metal complex, in which a dilute aqueous solution containing less than the number of moles of metal ions required to form an electrically neutral metal complex is mixed under stirring conditions. 6. A colloidal solution of a poorly water-soluble metal complex, wherein the concentrations of the metal ion and the ligand in a dilute aqueous solution are each 0.2 mol / L or less.
【０００８】[0008]
【発明の実施の形態】以下、本発明の好ましい態様につ
いて具体的に説明する。本発明においては、有機化合物
を配位子とする水難溶性金属錯体が、コロイドを形成し
ており、コロイドを形成することにより、該金属錯体の
溶解度を大きく上回る濃度で水中に安定に分散すること
が可能となる。コロイドとは、粒子径が１０-5〜１０-7
ｃｍの分散系を意味し、チンダル現象によってその形成
を確認することができる。BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be specifically described below. In the present invention, a poorly water-soluble metal complex having an organic compound as a ligand forms a colloid, and by forming the colloid, the metal complex is stably dispersed in water at a concentration far exceeding the solubility of the metal complex. Is possible. A colloid has a particle size of 10 -5 to 10 -7.
cm disperse system, the formation of which can be confirmed by the Tyndall phenomenon.
【０００９】本発明でいうところの有機化合物を配位子
とする水難溶性金属錯体とは、下記一般式で表される。
ＭmＡn
（ただし、Ｍは、Ｍｇ、Ｃａ、Ｚｎ、Ｎｉ、Ｃｕ、Ａ
ｌ、Ａｇ、Ｆｅ、Ｐｔなどの金属元素を表し、mおよび
ｎはＭの価数に応じた整数を表す。また、Ａは有機化合
物の配位子を表し、中性でも陰イオン性でもかまわな
い。）The poorly water-soluble metal complex having an organic compound as a ligand in the present invention is represented by the following general formula. M m A n (where M is Mg, Ca, Zn, Ni, Cu, A
1, represents a metal element such as Ag, Fe, and Pt, and m and n represent integers corresponding to the valence of M. A represents a ligand of an organic compound, which may be neutral or anionic. )
【００１０】本発明における配位子としては、金属イオ
ンに配位して錯体を形成するものであれば特に制限はな
い。例えば、トロポロン化合物、２−メルカプトピリジ
ンＮ−オキサイド、２−（４−チアゾリル）ベンズイミ
ダゾール、２−メルカプトベンゾチアゾール、ジメチル
ジチオカルバメート、８−ヒドロキシキノリン、８−キ
ノリンチオール、クロラニル酸、アリザリン、ジフェニ
ルカルバゾン、ジフェニルグアニジン、ジフェニルチオ
カルバゾン、１，１０−フェナントロリン、４，７−ジ
フェニルフェナントロリン、２，２−ジピリジル、２，
２−ビキノリンなどがあげられる。これらの中で、本発
明の金属錯体としてトロポロン化合物や２−メルカプト
ピリジンＮ−オキサイドを配位子とする金属錯体が好ま
しく、トロポロン化合物を配位子とする金属錯体がさら
に好ましい。もっとも好ましくは４−イソプロピルトロ
ポロン（ヒノキチオール）を配位子とする金属錯体であ
る。The ligand in the present invention is not particularly limited as long as it coordinates with a metal ion to form a complex. For example, tropolone compound, 2-mercaptopyridine N-oxide, 2- (4-thiazolyl) benzimidazole, 2-mercaptobenzothiazole, dimethyldithiocarbamate, 8-hydroxyquinoline, 8-quinolinethiol, chloranilic acid, alizarin, diphenylcarbamate. Zon, diphenylguanidine, diphenylthiocarbazone, 1,10-phenanthroline, 4,7-diphenylphenanthroline, 2,2-dipyridyl, 2,
2-biquinoline and the like can be mentioned. Among these, the metal complex of the present invention is preferably a tropolone compound or a metal complex having 2-mercaptopyridine N-oxide as a ligand, and more preferably a metal complex having a tropolone compound as a ligand. Most preferably, it is a metal complex having 4-isopropyltropolone (hinokitiol) as a ligand.
【００１１】本発明でいうところのトロポロン化合物を
配位子とする金属錯体とは一般式（１）で表される置換
もしくは非置換のトロポロン化合物の金属錯体である。The metal complex having a tropolone compound as a ligand in the present invention is a metal complex of a substituted or unsubstituted tropolone compound represented by the general formula (1).
【００１２】[0012]
【化１】 [Chemical 1]
【００１３】式（１）中、Ｒ1、Ｒ2、Ｒ3は、水素、ま
たは直鎖または分岐のアルキル基、アルケニル基、アル
キニル基、シクロアルキル基を表し、直鎖状または分岐
状を問わない。また、不飽和結合が含まれていてもかま
わない。また、酸素、ケイ素、ハロゲンなどのヘテロ原
子が含まれていてもかまわない。Ｒ1，Ｒ2，Ｒ3は、そ
れぞれ同一でもよく、異なっていてもかまわない。式
（１）中、Ｍは金属元素を表し、例えばＭｇ、Ｃａ，Ｚ
ｎ，Ｎｉ，Ｃｕ，Ａｌ，Ａｇ、Ｆｅ、Ｐｔなどがあげら
れる。式中ｎは金属の価数を表す。In the formula (1), R 1 , R 2 and R 3 represent hydrogen or a linear or branched alkyl group, an alkenyl group, an alkynyl group or a cycloalkyl group, which may be linear or branched. Absent. Further, it may contain an unsaturated bond. Further, a hetero atom such as oxygen, silicon or halogen may be contained. R 1 , R 2 and R 3 may be the same or different. In the formula (1), M represents a metal element, for example, Mg, Ca, Z
Examples thereof include n, Ni, Cu, Al, Ag, Fe and Pt. In the formula, n represents the valence of the metal.
【００１４】本発明のコロイド溶液の調製法としては、
コロイド領域１０-5〜１０-7ｃｍの微細粒子分散系が得
られる方法であれば特に制限はないが、本発明者らの実
験によれば、以下の方法が好ましい。（１）金属イオン
の希薄水溶液と、電気的中性の金属錯体を形成するに必
要なモル数未満の配位子を含む希薄水溶液を、攪拌条件
下で混和する、（２）配位子の希薄水溶液と、電気的中
性の金属錯体を形成するに必要なモル数未満の金属イオ
ンを含む希薄水溶液を、攪拌条件下で混和する。金属イ
オンの希薄水溶液を得る方法も特に制限はなく、例えば
Ｍｇ、Ｃａ，Ｚｎ，Ｎｉ，Ｃｕ，Ａｌ，Ａｇ、Ｆｅ、Ｐ
ｔなどのハロゲン化塩、酢酸塩、硫酸塩、硝酸塩などの
金属塩を水に溶解することによって得ることが出来る。
金属イオンおよび配位子の希薄水溶液の濃度も特に制限
はないが、より安定なコロイドが得られるという意味
で、それぞれ０．２ｍｏｌ／Ｌ以下が好ましい。さらに
好ましくは０．１ｍｏｌ／Ｌ以下である。必要に応じて
保護コロイドを添加してもかまわない。保護コロイドは
特に制限はなく、ゼラチン、アルブミン、アラビアゴ
ム、デキストリン、ポリビニルアルコール、ポリアクリ
ル酸ナトリウム、アルギン酸ナトリウム、メチルセルロ
ース、カルボキシメチルセルロース、アルキル硫酸塩、
臭化アルキルトリメチルアンモニウム、ソルビタンモノ
脂肪酸エステルなどがあげられる。これらから選ばれる
２以上の混合物であってもよい。The method for preparing the colloidal solution of the present invention is as follows:
The method is not particularly limited as long as it is a method capable of obtaining a fine particle dispersion system having a colloidal region of 10 −5 to 10 −7 cm, but the following method is preferred according to the experiments of the present inventors. (1) A dilute aqueous solution of a metal ion is mixed with a dilute aqueous solution containing a ligand in an amount less than the number of moles required to form an electrically neutral metal complex under stirring conditions. A dilute aqueous solution and a dilute aqueous solution containing less than the required number of moles of metal ions for forming an electrically neutral metal complex are mixed under stirring conditions. The method for obtaining a dilute aqueous solution of metal ions is not particularly limited, and examples thereof include Mg, Ca, Zn, Ni, Cu, Al, Ag, Fe and P.
It can be obtained by dissolving a halogenated salt such as t, a metal salt such as an acetate, a sulfate or a nitrate in water.
The concentration of the dilute aqueous solution of the metal ion and the ligand is not particularly limited, but it is preferably 0.2 mol / L or less for the purpose of obtaining a more stable colloid. More preferably, it is 0.1 mol / L or less. A protective colloid may be added if necessary. The protective colloid is not particularly limited, gelatin, albumin, gum arabic, dextrin, polyvinyl alcohol, sodium polyacrylate, sodium alginate, methyl cellulose, carboxymethyl cellulose, alkyl sulfate,
Examples thereof include alkyl trimethyl ammonium bromide and sorbitan monofatty acid ester. It may be a mixture of two or more selected from these.
【００１５】次に実施例を挙げて更に詳細に説明する
が、本発明はこれらの例に制限されるものではない。な
お、実施例において、得られた溶液がコロイド溶液であ
ることは、レーザー光線を照射するとチンダル現象が見
られたことにより確認した。また、４−イソプロピルト
ロポロン銅錯体濃度の測定は高速液体クロマトグラフィ
ー（株式会社島津製作所製、カラム：ｉｎｅｒｔｃｉｌ
Ｃ４（４．６×１５０ｍｍ）、展開溶媒：１０ｍＭ‐
ＫＨ2ＰＯ4、１ｍＭ‐ＥＤＴＡ・２Ｎａ、水／ＣＨ3Ｃ
Ｎ=６０／４０、流速：１．０ｍｌ／ｍｉｎ）にて４−
イソプロピルトロポロンとして検出測定し、その後４−
イソプロピルトロポロン銅錯体濃度に換算した。Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, it was confirmed that the obtained solution was a colloidal solution by observing the Tyndall phenomenon when irradiated with a laser beam. The concentration of 4-isopropyltropolone copper complex was measured by high performance liquid chromatography (manufactured by Shimadzu Corporation, column: inertcil).
C4 (4.6 x 150 mm), developing solvent: 10 mM-
KH 2 PO 4 , 1 mM-EDTA / 2Na, water / CH 3 C
N = 60/40, flow rate: 1.0 ml / min) 4-
Detected and measured as isopropyl tropolone, then 4-
It was converted to the isopropyltropolone copper complex concentration.
【００１６】[0016]
【実施例１】室温にてＣｕＣｌ2（和光純薬工業株式会
社製）０．０８ｍｏｌ／L水溶液１００ｍｌに４−イソ
プロピルトロポロン（ヒノキチオール）０．０４ｍｏｌ
／L水溶液１００ｍｌを攪拌しながら５分間かけて滴下
した。滴下終了後、さらに１０分間攪拌し、安定な４−
イソプロピルトロポロン銅錯体水溶液（４−イソプロピ
ルトロポロン銅錯体として３９０ｐｐｍ含有）を得た。
該水溶液にレーザー光線を照射したところ、明瞭なチン
ダル現象が観測され、コロイド溶液であることが確認で
きた。Example 1 At room temperature, CuCl 2 (Wako Pure Chemical Industries, Ltd.) 0.08 mol / L 4-isopropyltropolone (hinokitiol) 0.04 mol in 100 ml of aqueous solution
100 ml of the / L aqueous solution was added dropwise with stirring over 5 minutes. After completion of dropping, the mixture was stirred for 10 minutes to give stable 4-
An isopropyl tropolone copper complex aqueous solution (containing 390 ppm of 4-isopropyl tropolone copper complex) was obtained.
When the aqueous solution was irradiated with a laser beam, a clear Tyndall phenomenon was observed, and it was confirmed that the solution was a colloidal solution.
【００１７】本実施例では、４−イソプロピルトロポロ
ン銅錯体として３９０ｐｐｍ含有しているコロイド溶液
を得ることができた。この濃度は４−イソプロピルトロ
ポロン銅錯体の水への溶解度（室温、６ｐｐｍ）をはる
かに上回っている。In this example, a colloidal solution containing 390 ppm of 4-isopropyltropolone copper complex could be obtained. This concentration is far above the solubility of 4-isopropyltropolone copper complex in water (room temperature, 6 ppm).
【００１８】[0018]
【実施例２】室温にてＣｕ（ＯＡｃ）2（和光純薬工業
株式会社製）０．０８ｍｏｌ／Ｌ水溶液１００ｍｌに４
−イソプロピルトロポロン（ヒノキチオール）０．０４
ｍｏｌ／L水溶液１００ｍｌを攪拌しながら５分間かけ
て滴下した。滴下終了後、１％ゼラチン水溶液０．２ｇ
を添加し１０分間攪拌すると、安定な４−イソプロピル
トロポロン銅錯体水溶液（４−イソプロピルトロポロン
銅錯体として３９０ｐｐｍ含有）が得られた。該水溶液
にレーザー光線を照射したところ、明瞭なチンダル現象
が観測され、コロイド溶液であることが確認できた。Example 2 At room temperature, Cu (OAc) 2 (manufactured by Wako Pure Chemical Industries, Ltd.) 4 was added to 100 ml of 0.08 mol / L aqueous solution
-Isopropyltropolone (hinokitiol) 0.04
100 ml of mol / L aqueous solution was added dropwise over 5 minutes while stirring. After completion of dropping, 0.2 g of 1% gelatin aqueous solution
Was added and stirred for 10 minutes to obtain a stable 4-isopropyltropolone copper complex aqueous solution (containing 390 ppm of 4-isopropyltropolone copper complex). When the aqueous solution was irradiated with a laser beam, a clear Tyndall phenomenon was observed, and it was confirmed that the solution was a colloidal solution.
【００１９】本実施例では、４−イソプロピルトロポロ
ン銅錯体として３９０ｐｐｍ含有しているコロイド溶液
を得ることができた。この濃度は４−イソプロピルトロ
ポロン銅錯体の水への溶解度（室温、６ｐｐｍ）をはる
かに上回っている。In this example, a colloidal solution containing 390 ppm of 4-isopropyltropolone copper complex could be obtained. This concentration is far above the solubility of 4-isopropyltropolone copper complex in water (room temperature, 6 ppm).
【００２０】[0020]
【実施例３】室温にてＺｎＣｌ2（和光純薬工業株式会
社製）０．００２ｍｏｌ／Ｌ水溶液１００ｍｌに２−メ
ルカプトピリジンN−オキサイド（東京化成工業株式会
社製）０．００２ｍｏｌ／Ｌ水溶液１００ｍｌを攪拌し
ながら５分間かけて滴下した。滴下終了後、さらに１０
分間攪拌し、安定な２−メルカプトピリジンN−オキサ
イド亜鉛錯体水溶液（２−メルカプトピリジンN−オキ
サイド亜鉛錯体として１６０ｐｐｍ含有）を得た。該水
溶液にレーザー光線を照射したところ、明瞭なチンダル
現象が観測され、コロイド溶液であることが確認でき
た。Example 3 At room temperature, 100 ml of 0.002 mol / L aqueous solution of ZnCl 2 (manufactured by Wako Pure Chemical Industries, Ltd.) was added with 100 ml of 0.002 mol / L aqueous solution of 2-mercaptopyridine N-oxide (manufactured by Tokyo Chemical Industry Co., Ltd.). The mixture was added dropwise with stirring for 5 minutes. 10 more after dropping
After stirring for a minute, a stable 2-mercaptopyridine N-oxide zinc complex aqueous solution (containing 160 ppm as a 2-mercaptopyridine N-oxide zinc complex) was obtained. When the aqueous solution was irradiated with a laser beam, a clear Tyndall phenomenon was observed, and it was confirmed that the solution was a colloidal solution.
【００２１】本実施例では、２−メルカプトピリジンN
−オキサイド亜鉛錯体として１６０ｐｐｍ含有している
コロイド溶液を得ることができた。この濃度は２−メル
カプトピリジンN−オキサイド亜鉛錯体の水への溶解度
（室温、１５ｐｐｍ）をはるかに上回っている。In this example, 2-mercaptopyridine N
A colloidal solution containing 160 ppm as an oxide zinc complex could be obtained. This concentration is far above the solubility of the 2-mercaptopyridine N-oxide zinc complex in water (room temperature, 15 ppm).
【００２２】[0022]
【比較例１】室温にて４−イソプロピルトロポロン銅錯
体０．１ｇ（０．２６ｍｍｏｌ）を水１００ｍｌに加え
１時間攪拌後、静置し上澄みをろ過した。ろ液に溶解し
ている４−イソプロピルトロポロン銅錯体濃度を測定し
たところ６ｐｐｍであった。本比較例では４−イソプロ
ピルトロポロン銅錯体はコロイドを形成していないため
水に対する溶解度分しか溶けていない。[Comparative Example 1] At room temperature, 0.1 g (0.26 mmol) of 4-isopropyltropolone copper complex was added to 100 ml of water, stirred for 1 hour, allowed to stand, and the supernatant was filtered. When the concentration of 4-isopropyltropolone copper complex dissolved in the filtrate was measured, it was 6 ppm. In this comparative example, the 4-isopropyltropolone copper complex does not form a colloid, and therefore only dissolves in water.
【００２３】なお、４−イソプロピルトロポロン銅錯体
濃度の測定は高速液体クロマトグラフィー（株式会社島
津製作所製、カラム：ｉｎｅｒｔｃｉｌ Ｃ４（４．６
×１５０ｍｍ）、展開溶媒：１０ｍＭ‐ＫＨ2ＰＯ4、１
ｍＭ‐ＥＤＴＡ・２Ｎａ、水／ＣＨ3ＣＮ=６０／４０、
流速：１．０ｍｌ／ｍｉｎ）にて４−イソプロピルトロ
ポロンとして検出測定し、その後４−イソプロピルトロ
ポロン銅錯体濃度に換算したThe concentration of 4-isopropyltropolone copper complex was measured by high performance liquid chromatography (Shimadzu Corporation, column: inertcil C4 (4.6).
× 150 mm), developing solvent: 10 mM-KH 2 PO 4 , 1
mM-EDTA · 2Na, water / CH 3 CN = 60/40,
Flow rate: 1.0 ml / min) was detected and measured as 4-isopropyltropolone, and then converted to 4-isopropyltropolone copper complex concentration.
【００２４】[0024]
【比較例２】分岐シクロデキストリンであるグルコシル
−βシクロデキストリン（塩水港精糖株式会社製）０．
０１２ｍｏｌ／Ｌ水溶液１００ｍｌに４−イソプロピル
トロポロン銅錯体を０．２３ｇ（０．００６ｍｍｏｌ）
を加え室温にて攪拌した。溶け残った４−イソプロピル
トロポロン銅錯体をろ過後、溶液の一部を採取し、４−
イソプロピルトロポロン銅錯体を９５％エタノール（片
山化学工業株式会社製）にてグルコシル−βシクロデキ
ストリンから抽出し濃度測定を行った。４−イソプロピ
ルトロポロン銅錯体としての濃度は３２０ｐｐｍであっ
た。[Comparative Example 2] Glucosyl-β cyclodextrin which is a branched cyclodextrin (manufactured by Shimizu Minato Sugar Co., Ltd.)
0.23 g (0.006 mmol) of 4-isopropyltropolone copper complex in 100 ml of 012 mol / L aqueous solution
Was added and stirred at room temperature. After filtering the undissolved 4-isopropyltropolone copper complex, a part of the solution was collected,
The isopropyltropolone copper complex was extracted from glucosyl-β cyclodextrin with 95% ethanol (Katayama Chemical Co., Ltd.), and the concentration was measured. The concentration of 4-isopropyltropolone copper complex was 320 ppm.
【００２５】本比較例で得られた水溶液中のグルコシル
−βシクロデキストリン濃度は１．５％で、４−イソプ
ロピルトロポロン銅錯体（３２０ｐｐｍ）の４６倍もの
重量が溶解していることになり、４−イソプロピルトロ
ポロン銅錯体本来の機能が発揮されない。The concentration of glucosyl-β cyclodextrin in the aqueous solution obtained in this Comparative Example was 1.5%, which means that 46 times as much weight as 4-isopropyltropolone copper complex (320 ppm) was dissolved. -Isopropyltropolone copper complex The original function is not exhibited.
【００２６】[0026]
【発明の効果】本発明により、有機化合物を配位子とす
る水難溶性金属錯体を安価かつ簡便に溶解度を大きく上
回る濃度で水中に安定に分散させる技術を提供すること
が可能となる。その結果、化粧品、塗料、入浴剤、洗
剤、害虫防除剤等へ水難溶性金属錯体を容易に配合する
ことが可能となった。Industrial Applicability According to the present invention, it is possible to provide a technique for stably and inexpensively dispersing a poorly water-soluble metal complex having an organic compound as a ligand in water at a concentration greatly exceeding the solubility. As a result, it has become possible to easily mix poorly water-soluble metal complexes into cosmetics, paints, bath agents, detergents, pest control agents and the like.
Claims (6)
錯体のコロイド溶液。1. A colloidal solution of a poorly water-soluble metal complex having an organic compound as a ligand.
１に記載のコロイド溶液。2. The colloidal solution according to claim 1, wherein the ligand is a tropolone compound.
ある請求項１または２のいずれかに記載のコロイド溶
液。3. The colloidal solution according to claim 1, wherein the ligand is 4-isopropyltropolone.
の金属錯体を形成するに必要なモル数未満の有機化合物
の配位子を含む希薄水溶液を、攪拌条件下で混和する水
難溶性金属錯体のコロイド溶液の製造方法。4. A sparingly water-soluble metal in which a dilute aqueous solution of a metal ion is mixed with a dilute aqueous solution containing a ligand of an organic compound in an amount less than the required number of moles to form an electrically neutral metal complex under stirring conditions. Method for producing colloidal solution of complex.
気的中性の金属錯体を形成するに必要なモル数未満の金
属イオンを含む希薄水溶液を、攪拌条件下で混和する水
難溶性金属錯体のコロイド溶液の製造方法。5. A sparingly water-soluble metal in which a dilute aqueous solution of a ligand of an organic compound and a dilute aqueous solution containing less than the number of moles of metal ions necessary to form an electrically neutral metal complex are mixed under stirring conditions. Method for producing colloidal solution of complex.
におけるそれらの濃度が、それぞれ０．２ｍｏｌ／Ｌ以
下であることを特徴とする水難溶性金属錯体のコロイド
溶液。6. A colloidal solution of a sparingly water-soluble metal complex, wherein the concentration of the metal ion and the ligand in a dilute aqueous solution is 0.2 mol / L or less, respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001339858A JP2003137702A (en) | 2001-11-05 | 2001-11-05 | Colloidal solution of metal complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001339858A JP2003137702A (en) | 2001-11-05 | 2001-11-05 | Colloidal solution of metal complex |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003137702A true JP2003137702A (en) | 2003-05-14 |
Family
ID=19154149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001339858A Pending JP2003137702A (en) | 2001-11-05 | 2001-11-05 | Colloidal solution of metal complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003137702A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006036733A (en) * | 2004-07-30 | 2006-02-09 | Asahi Kagaku Kogyo Kk | Method for vaporizing hinokithiol |
| WO2007079212A2 (en) * | 2005-12-30 | 2007-07-12 | E. I. Du Pont De Nemours And Company | Tropolone complexes as wood preservatives |
| US7462227B2 (en) | 2005-12-30 | 2008-12-09 | E.I. Du Pont De Nemours And Company | Ibuprofen complexes as wood preservatives |
| US7497901B2 (en) | 2005-12-30 | 2009-03-03 | E. I. Dupont De Nemours And Company | Tungstate and molybate wood preservatives |
| US7540906B2 (en) | 2005-12-30 | 2009-06-02 | E.I. Du Pont De Nemours & Company | Metal salts of hydrolyzed olefin/maleic anhydride copolymers and their use as wood preservatives |
| JP2012206965A (en) * | 2011-03-29 | 2012-10-25 | Nara Prefecture | Metal complexing method of tropolones and/or phenols in plant essential oil, and plant essential oil containing tropolones and/or phenols metal-complexed by using the method |
-
2001
- 2001-11-05 JP JP2001339858A patent/JP2003137702A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006036733A (en) * | 2004-07-30 | 2006-02-09 | Asahi Kagaku Kogyo Kk | Method for vaporizing hinokithiol |
| WO2007079212A2 (en) * | 2005-12-30 | 2007-07-12 | E. I. Du Pont De Nemours And Company | Tropolone complexes as wood preservatives |
| WO2007079212A3 (en) * | 2005-12-30 | 2007-08-23 | Du Pont | Tropolone complexes as wood preservatives |
| US7427316B2 (en) | 2005-12-30 | 2008-09-23 | E.I. Du Pont De Nemours And Company | Tropolone complexes as wood preservatives |
| US7462227B2 (en) | 2005-12-30 | 2008-12-09 | E.I. Du Pont De Nemours And Company | Ibuprofen complexes as wood preservatives |
| US7497901B2 (en) | 2005-12-30 | 2009-03-03 | E. I. Dupont De Nemours And Company | Tungstate and molybate wood preservatives |
| US7540906B2 (en) | 2005-12-30 | 2009-06-02 | E.I. Du Pont De Nemours & Company | Metal salts of hydrolyzed olefin/maleic anhydride copolymers and their use as wood preservatives |
| JP2012206965A (en) * | 2011-03-29 | 2012-10-25 | Nara Prefecture | Metal complexing method of tropolones and/or phenols in plant essential oil, and plant essential oil containing tropolones and/or phenols metal-complexed by using the method |
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