JP2008195600A - Organic-inorganic composite material supporting metal-tropolone complex between layers and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic-inorganic composite material having excellent persistence of physiologically active function and sustained release properties of a physiologically active substance and also water retentivity and environmental affinity, and to provide its manufacturing method and a processed product containing the material. <P>SOLUTION: In the manufacturing method of the organic inorganic composite material wherein a metal-tropolone complex having the physiologically active function is supported between the layers, an inorganic laminar compound is used as a main raw material and one or more kinds of selected metal ions and tropolones having the physiologically active function are inserted as an interlayer ion between layers of the inorganic laminar compound by cation exchange reaction in form of the metal-tropolone complex. The organic inorganic composite material prepared by the manufacturing method and the processed product using the material are provided. In the organic inorganic composite material obtained by supporting the metal-tropolone complex having the physiologically active function between the layers capable of controlling a sustained-release speed of an organic compound having the active function, a metal ion and an organic metal complex, the sustained release property of the physiologically active function is greately improved. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an organic-inorganic composite material in which a metal-tropolone complex having a physiological activity function is supported between layers and a method for producing the same, and more specifically, an inorganic layered compound as a main raw material, and a plant growth regulating function between the layers, Organic-inorganic composite material having a novel physiologically active function in which a metal-tropolone complex having a physiologically active action such as a pest control function, a weed control function, an antimicrobial function or the like is inserted and supported between layers, a method for producing the same, and the method The present invention relates to a processed product containing the organic-inorganic composite material produced in (1).

  The present invention provides a novel organic-inorganic composite material in which a metal-tropolone complex having a bioactive function is supported between layers and a method for producing the same, and in particular, has excellent bioactivity function sustainability, water retention, weather resistance, and the like. An organic-inorganic composite material having a bioactive function that has environmental affinity and can be applied to living environment, medical welfare environment, plant tissue culture, agriculture, general forestry including afforestation, plant cultivation, etc., the organic-inorganic composite A processed product containing the material is provided.

  Tropolones such as hinokitiol are crystalline substances contained in Taiwan coconut oil, Aomori coconut oil, Western red cedar oil, and the like. This naturally-derived compound is now available as a synthetic product, and is widely used in various fields such as antibacterial and antifungal agents, hair restorers, aromatherapy fragrances, toothpaste and food additives. Has been.

  However, since this tropolone compound has a low melting point of 52-53 ° C. and high sublimation and photodegradability, it has been difficult to maintain the above effects for a long time. Therefore, internal or external preparations in which they are gradually released so that such physiologically active substances or drugs are gradually supplied are referred to as sustained-release drugs, sustained-release tablets, sustained-release preparations, sustained-release preparations, etc. It has been actively used.

  So far, several means relating to pharmaceuticals have been reported to improve sustained release, heat resistance or dispersibility by combining a drug with an inorganic layered substance. As a product containing hinokitiol which is a tropolone compound, the prior art documents include, for example, a molded article containing hinokitiol-clay complex, a clay compound containing hinokitiol, a fungicide composition containing hinokitiol, and a quality preservation mixed with hinokitiol. Agents (see Patent Literatures 1 to 4), ceramic compositions obtained by coordinating hinokitiol to metal ions in ceramics (see Patent Literatures 5 to 6), and the like have been reported.

  Therefore, when these means are examined in detail, for example, means for introducing hinokitiol as a guest into the interlayer void of the layered clay component has been proposed (see Patent Document 1). However, this is merely a product obtained by combining hinokitiol, which has been difficult to be molded into a thermoplastic resin, with clay.

  In addition, for example, a clay composite containing hinokitiol as an oil-soluble antibacterial / antifungal agent (see Patent Document 2), a bactericidal composition containing hinokitiol (see Patent Document 3), a quality preservative containing hinokitiol and garlic components and chili components (See Patent Document 4). However, these are only mixed with the above-mentioned physiologically active substances, are not considered for sustained release, and do not introduce these components between the layers of the inorganic layered compound.

  A ceramic composition obtained by coordinating hinokitiol to calcium ions or magnesium ions contained in ceramics (see Patent Document 5) has been proposed. However, the obtained hinokitiol inclusion ceramics have not been shown to have a mutual relationship that hinokitiol is incorporated between layers of ceramics such as tobermorite and zonotolite, and the hinokitiol content of the composition is as high as several percent. Low.

  Furthermore, hinokitiol inclusion ceramics obtained by exchanging calcium ions or magnesium ions in ceramics with other metal ions and coordinating hinokitiol to the introduced metal ions (see Patent Document 6) have been proposed. However, there is no clear demonstration that hinokitiol has been inserted between the layers of ceramic clay mineral, and the content of metal ions and hinokitiol that have been introduced is about several percent. Yes, it does not actively insert physiologically active substances between clay mineral layers.

JP 2004-18661 A JP 2003-104719 A Japanese Patent Laid-Open No. 10-265408 Japanese Patent Laid-Open No. 10-210958 Japanese Patent Laid-Open No. 11-21201 Japanese Patent Laid-Open No. 11-71215

  Under such circumstances, the present inventors have aimed at developing a functional material that combines the long-term sustainability, sustained release, heat resistance and weather resistance of the active ingredient in view of the above-described conventional technology. As a result of intensive research, an organometallic complex consisting of a tropolone compound having a bioactive function and a metal ion having an antibacterial and antifungal function is inserted and supported between layers of a clay mineral that is an inorganic layered compound. The inventors have found that the intended purpose can be achieved by controlling the release amount of the organometallic complex from the interlayer, and the present invention has been completed.

  That is, the present invention is an organic-inorganic composite material having a new physiologically active function and a novel production method thereof, which is capable of imparting a function according to the purpose at low cost and safely, and is produced by the method. To provide a novel organic-inorganic composite material having heat resistance, weather resistance, water retention, environmental compatibility, and a processed product using the same, as well as sustained sustainability of bioactive functions or sustained release of bioactive substances It is the purpose.

The present invention for solving the above-described problems comprises the following technical means.
(1) An organic-inorganic composite material in which a metal-tropolone complex is supported on an interlayer to improve the sustained release of the physiologically active function, using an inorganic layered compound as a main raw material, and the physiological activity between the layers of the inorganic layered compound An organic-inorganic composite material carrying a metal-tropolone complex as an interlayer, wherein a metal-tropolone complex having a function is inserted and supported.
(2) In the above (1), the metal cation forming the metal-tropolone complex having a physiologically active function is at least one or more metal ions selected from Cu, Zn, Ni and Al or a transition metal group. An organic-inorganic composite material in which the metal-tropolone complex described above is supported between layers.
(3) The organic ligand that forms the metal-tropolone complex having a physiologically active function is at least one organic compound selected from hinokitiol, β-drabrin, α-tyaprisin, γ-tyaprisin, and 4-acetyltropolone. An organic-inorganic composite material comprising a metal-tropolone complex according to (1) above, which is a ligand.
(4) An organic-inorganic composite material having an interlayer-supported metal-tropolone complex according to (1) above, wherein the inorganic layered compound as a main raw material is a natural or synthetic layered clay mineral, or a natural or synthetic swelling mica .
(5) The layered clay mineral is montmorillonite, beidellite, nontronite, saponite, hectorite, smectite group clay mineral of stevensite, vermiculite, or mica clay mineral or fluorinated mica which is a swellable mica (4) An organic-inorganic composite material in which the metal-tropolone complex described in 1) is supported between layers.
(6) A method for producing the organic-inorganic composite material according to any one of (1) to (5) above, wherein an inorganic layered compound is used as a main raw material and a metal having a physiologically active function between the layers of the inorganic layered compound -An organic-inorganic composite material in which a metal-tropolone complex is supported between layers by inserting a tropolone complex and exchanging exchangeable cations existing between layers of the inorganic layered compound with a metal-tropolone complex having a physiologically active function A method for producing an organic-inorganic composite material carrying a metal-tropolone complex as an interlayer, characterized in that
(7) In the above (6), the metal cation forming the metal-tropolone complex having a physiologically active function is at least one metal ion selected from the group consisting of Cu, Zn, Ni and Al or transition metals. The manufacturing method of the organic inorganic composite material which carry | supported the metal-tropolone complex of description to an interlayer.
(8) The organic ligand that forms the metal-tropolone complex having a physiologically active function is at least one organic compound selected from hinokitiol, β-drabrin, α-tyaprisin, γ-tyaprisin, and 4-acetyltropolone. A method for producing an organic-inorganic composite material having a metal-tropolone complex according to (6) above, which is a ligand.
(9) An organic-inorganic composite material having an interlayer-supported metal-tropolone complex according to (6), wherein the inorganic layered compound as a main raw material is natural or synthetic layered clay mineral, or natural or synthetic swellable mica Manufacturing method.
(10) A processed product comprising an organic-inorganic composite material in which the metal-tropolone complex according to any one of (1) to (5) above is supported, and being processed into a desired form.

Next, the present invention will be described in more detail.
The organic-inorganic composite material having a physiologically active function of the present invention is, in particular, an inorganic layered compound such as a layered clay mineral, montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, etc. Mineral, vermiculite, or mica clay mineral or fluorinated mica that is a natural or synthetic swelling mica is used. In the present invention, a metal-tropolone complex formed of at least one metal ion selected from Cu, Zn, Ni, Al, etc. or a transition metal group and a tropolone compound is interposed between the inorganic layered compounds. It is characterized by being inserted and carried.

  The present invention makes it possible to control the release amount of a metal-tropolone complex from an interlayer of an inorganic layered compound by inserting a metal-tropolone complex having a bioactive function between the layers of the inorganic layered compound. Due to the electrostatic interaction between the compound layer and the metal-tropolone complex, it has excellent bioactivity and sustained release of the bioactive substance, as well as heat resistance, weather resistance, water retention and environmental compatibility. It is possible to manufacture and provide a novel organic-inorganic composite material having a processed product and a processed product using the same.

  Next, the inorganic layered compound of the present invention will be described in detail. Clay minerals are inorganic crystal substances, and there are various types depending on the composition and structure, but the basic structures are all similar. Here, the structure of these clay minerals will be described. All clay minerals have a layered structure with some exceptions. The layered structure is a laminated structure in which a large number of inorganic crystal layers are stacked.

  For example, montmorillonite, which is the main component of bentonite, will be described as a representative example. Montmorillonite is a clay mineral classified into the smectite group, which is a kind of layered silicate mineral. The crystal structure of the layered silicate mineral is determined by the number and arrangement of oxygen atoms having a large ionic radius. The basic structure of a silicate mineral is a regular tetrahedron having an oxygen atom at each vertex of a tetrahedron centered on one silicate atom. Most silicate minerals share the three tetrahedron atoms with each adjacent tetrahedron to form a one-dimensional hexagonal network layer.

In addition to this tetrahedral layer, one anion such as O ²⁻ and OH ⁻ is located at each vertex of the octahedron, and cations such as Al ³⁺ and Mg ²⁺ are present at the center. There is an octahedral layer that connects two adjacent octahedrons to form a two-dimensional network. This is because the octahedron is centered on atoms such as Mg and Al, and the oxygen atoms are six-coordinated, and the octahedron shares the edge (the side that connects the oxygen atom and the oxygen atom). It is an octahedral layer forming a two-dimensional network.

  The connection between these tetrahedral layers and octahedral layers is a two-layer structure (1: 1 type) in which each layer is one, and a structure in which an octahedral layer is sandwiched between two tetrahedral layers (2: 1 Type), a structure in which an octahedral layer is located in an interlayer region of 2: 1 type (2: 1: 1 type), etc., and a combination of tetrahedral layer and octahedral layer, a set of unit layers Is forming.

The montmorillonite crystal structure is composed of three layers of silicate tetrahedral layer-alumina octahedral layer-silicate tetrahedral layer (2: 1 type), and the unit layer is about 10 mm (1 nm) thick and spreads. It has a very thin plate shape of 0.1 to 1 μm. A portion of Al ³⁺ that is the central atom of the alumina octahedral layer is replaced with Mg ²⁺ , resulting in insufficient positive charge, and each crystal layer itself is negatively charged, but Na ⁺ , K ⁺ , By sandwiching cations such as Ca ²⁺ and Mg ²⁺ , neutralization of charge shortage is achieved, and montmorillonite becomes stable.

  Therefore, montmorillonite exists in a state where a number of crystal layers overlap each other, and cations and voids exist between the layers. The specific properties of montmorillonite are exhibited by the negative charge on the surface of the layer and interlayer cations causing various actions. Since the binding force between the negative charge on the surface of the montmorillonite unit layer and the interlayer cation is weak, when it comes into contact with a solution containing other ions, the interlayer cation and the cation in the liquid instantaneously undergo an exchange reaction, resulting in cation exchange. A reaction occurs.

  By measuring the amount of cations released into water, the amount of charge involved in the reaction (cation exchange capacity: CEC) of montmorillonite can be known. It is known that the cation exchange capacity varies depending on the pH and concentration of the solution, and montmorillonite is known to increase the cation exchange capacity when the pH is 6 or more. Since montmorillonite has a layered structure, it has a very large surface area. On the surface, hydrogen bonds with oxygen atoms and hydroxyl groups on the surface of the layer, and electrostatic bonds with interlayer negative charges and interlayer cations occur between layers, exhibiting adsorptive capacity, especially for polar molecules It is easy to act.

  In the present invention, the inorganic layered compound means a layered silicate mineral having an exchangeable cation between layers. The layered silicate is not particularly limited, and preferably, for example, mica clay that is a smectite group clay mineral such as montmorillonite, beidellite, nontronite, saponite, hectorite, stevensite, vermiculite, or swelling mica. Mineral or fluorinated mica is used. The layered silicate and the swellable mica may be natural products or synthetic products, and one or more of these may be used in combination as appropriate.

  Among the layered silicates, smectite montmorillonite and swellable mica are preferable. When the layered silicate and the swellable mica are in contact with water, the layered silicate and the swellable mica have an action of adsorbing and swelling (swell) the water, and this is caused by the interaction between interlayer cations and water molecules. Since the binding force between the negative charge on the unit layer surface of the layered silicate and the swellable mica and the interlayer cation is weaker than the interaction energy between the interlayer cation and water molecule, the force of the interlayer cation attracting the water molecule The layers are spread out. The intercalation reaction easily proceeds due to the interaction between the interlayer cations and water molecules.

  Smectite clay minerals such as montmorillonite, which has a negative three-dimensional crystal layer, and swellable mica have remarkable chemical activities such as ion exchange, swelling, and organic or inorganic complex formation ability. These exchange reactions play a major role in natural material circulation, and ion exchange capacity is also used directly and indirectly in the industrial application of clay minerals and swellable mica. The formation of complexes between clay minerals and swellable mica and various substances is an adsorption phenomenon by the surface of the clay layer including the adsorption of polar molecules and ion exchange ability. A typical composite is a composite of clay and various organic compounds, and is widely used for interpretation of natural phenomena, including the use of smectite group clay minerals and swellable mica. That is, in the case where a smectite group clay mineral having ion exchange ability or a swellable mica having ion exchange ability other than montmorillonite is used in the present invention, the organic-inorganic composite having the metal-tropolone complex according to the present invention supported between layers. Can be formed using ion exchange reactions, which can be carried out as well.

  The exchangeable cation existing between the layers of the layered silicate is an ion such as sodium or calcium on the crystal surface, and these ions have an ion exchange property with respect to the cationic substance. Various materials can be inserted between the layered silicate layers. The cation exchange capacity (CEC) of the layered silicate is not particularly limited, but is preferably CEC = 30 to 400 milliequivalent / 100 g. If the amount is less than 30 milliequivalents / 100 g, the amount of the physiologically active substance that can be inserted between the crystal layers by cation exchange decreases, so that the expression and sustainability of the physiologically active function may not be sufficiently exhibited. On the other hand, when it exceeds 400 milliequivalents / 100 g, the bonding strength between the layers of the layered silicate becomes strong, and the intercalation of the physiologically active substance may be difficult.

  Commercially available inorganic layered compounds can be used. Examples of commercially available smectite layered silicates include “Kunipia Series”, “Smecton Series” (Kunimine Industries Co., Ltd.) and Examples of commercially available swellable mica and smectite layered silicates include “TN series”, “TS series”, “NHT series” (Topy Industries, Ltd.), “Lucentite series” and “Micro mica series”. "Somasif series" (Coop Chemical Co., Ltd.). Each commercial product has various grades depending on the properties such as crystal structure, cation exchange capacity, specific surface area, etc., but any of them can be used in the present invention.

  In the present invention, the metal-tropolone complex having a physiologically active function is preferably, for example, hinokitiol, β-drabrin, α-tyaprisin, γ-tyaprisin as a tropolone compound that is an organic ligand forming the complex. And 4-acetyltropolone and the like. Examples of the central metal forming the complex include Cu, Zn, Ni, Al, and the like, or at least one metal ion selected from the group of transition metals. In the present invention, the metal-tropolone complex having a physiologically active function is physically or electrostatically held between the layers of the inorganic layered compound. That is, in general, a cation is electrostatically held between layers of an inorganic layered compound, but in the present invention, a metal-tropolone complex having a physiologically active function is held between layers.

  In order to produce an organic-inorganic composite material in which the metal-tropolone complex having a physiologically active function of the present invention is incorporated between layers, for example, the following method can be used. First, the inorganic layered compound is weighed arbitrarily. An appropriate amount of deionized water is added to this and sufficiently stirred to prepare an inorganic layered compound suspension in which the inorganic layered compound has a weight concentration of about 0.1 to 10 wt%. Next, 0.1 to 3 times the amount of deionized water or an organic solvent metal salt solution is prepared with respect to the cation exchange capacity equivalent of the inorganic layered compound to be used. On the other hand, 0.3 to 9 times the amount of tropolone compound is weighed with respect to this cation exchange capacity equivalent and dissolved in deionized water or an organic solvent to obtain a tropolone compound solution.

  At this time, the organic solvent to be used is only required to dissolve the metal salt or the tropolone compound. For example, methanol, ethanol, 1-propanol, 2-propanol, acetone and the like can be used. Next, the metal salt solution and the tropolone compound solution are sufficiently mixed and stirred to obtain a metal-tropolone complex. If necessary, the complex formation reaction may be accelerated by heating. The synthesized metal-tropolone complex can be obtained in a solution state or a suspension state depending on the type of metal solution or solvent used.

  This metal-tropolone complex is put into an inorganic layered compound suspension that has been dispersed in advance, and a cation exchange reaction is performed while stirring, so that the metal-tropolone complex is inserted and supported between layers of the inorganic layered compound. To do. The exchange reaction rate can be accelerated by heating the mixed suspension. Although the reaction proceeds even when the suspension temperature is around 5 ° C., it is desirable to heat the suspension up to about 5 to 90 ° C. to smoothly advance the exchange reaction. The reaction time varies depending on the set temperature condition, but about 0.5 to 72 hours is appropriate.

  Of course, the optimum reaction temperature and reaction time vary depending on the type of central metal ion and organic ligand used. It is preferable to equip the upper part of the reaction vessel with a water-cooled cooling tube so that the water in the reaction system does not evaporate during the heating reaction. After completion of the reaction, an organic-inorganic composite material in which the solid-liquid is separated and washed to incorporate the metal-tropolone complex between the layers can be obtained. The drying method is not particularly limited, and examples thereof include freeze drying, spray drying, and heat drying. Furthermore, the organic-inorganic composite material suspension incorporating the metal-tropolone complex between the layers can be spread and dried on a plane to obtain a cast film.

  The organic-inorganic composite material carrying the metal-tropolone complex having a physiologically active function of the present invention between layers can of course be used as it is, but it can be applied or applied to ointments, creams, emulsions, pellets, etc. The product can be arbitrarily processed into a form suitable for a processed product. The method for producing the processed product is not particularly limited, and it is produced by a method in which an organic-inorganic composite material carrying a metal-tropolone complex having a bioactive function between layers is mixed and dissolved in an oily base or a commonly used method. be able to.

  In the organic-inorganic composite material having a physiologically active function of the present invention, a metal-tropolone complex having a physiologically active function is ionized and present between inorganic layers. The sustained release rate can be controlled, and the physiologically active effect is extremely high. Depending on the purpose and use environment, it is also possible to mix and use organic-inorganic composite materials carrying a metal-tropolone complex having a bioactive function between layers and other organic or inorganic materials to form molded products. is there.

  The organic-inorganic composite material in which the metal-tropolone complex having a physiologically active function of the present invention is supported between layers has the metal-tropolone complex electrostatically immobilized between the inorganic layers. Therefore, by appropriately selecting the inorganic layered compound used for the synthesis of the organic-inorganic composite material of the present invention from the cation exchange capacity, crystal structure, specific surface area, etc., and considering the charge amount and charge distribution ratio of the layer, It is possible to control the amount of the metal-tropolone complex having a physiologically active function in the interlayer and the holding power of the metal-tropolone complex having a physiologically active function in the interlayer.

  That is, by selectively controlling the above factors, it is possible to control the sustained release rate at which the metal-tropolone complex having a physiological activity is gradually released. The weather resistance can be controlled, and the durability can be very long. Depending on the purpose and use environment, it is also possible to mix and use organic-inorganic composite materials carrying a metal-tropolone complex having a physiological activity function with other organic or inorganic materials to form a molded body. .

  Conventionally, an antibacterial antifungal agent and a basic substance are contained in a layered clay component having interlayer struts, a hinokitiol-clay complex in which hinokitiol is introduced as a guest in the interlayer gap, and a swellable clay having base exchange ability. Clay composites, composites of fungicides such as hinokitiol and water-swellable clay minerals, ceramic compositions in which hinokitiol is coordinated and included in calcium ions or magnesium ions in ceramics, etc. have been proposed. . However, they are those in which hinokitiol alone is mixed or coordinated with clay or ceramics, and its sustained release effect is limited, and it has been difficult to impart high sustained release properties.

  On the other hand, the present invention uses an inorganic layered compound having an exchangeable cation between layers and having a predetermined cation exchange capacity (CEC) as a main raw material, and a physiologically active function between layers of the inorganic layered compound. A metal-tropolone complex having a bioactive function by exchanging the exchangeable cation existing between layers of this inorganic layered compound by utilizing its cation exchange property, thereby It is important to support the tropolone compound between the layers in the form of a metal-tropolone complex, thereby stably supporting the metal-tropolone complex between the layers of the inorganic layered compound and significantly improving the sustained release property. It is feasible to synthesize organic-inorganic composite materials.

The present invention has the following effects.
(1) According to the present invention, it is possible to provide a novel organic-inorganic composite material in which a metal-tropolone complex having a physiologically active function is supported between layers, a production method thereof, and a processed product using the same.
(2) The organic-inorganic composite material of the present invention has excellent physiological activity functions, such as pest control function, weed control function, antimicrobial function, etc., sustainability, water retention, weather resistance and environmental compatibility, It can be applied to environment, medical welfare environment, plant tissue culture, agriculture, general forestry including plantation, and plant cultivation.
(3) Between the layers of the organic-inorganic composite material of the present invention, the metal-tropolone complex having a physiologically active function is uniformly dispersed on the nanometer order, so the organic-inorganic composite material is used on the surface of the medium or in the field. Even in this case, since it can be uniformly sprayed or applied and mixed uniformly with a medium or soil, physiologically active effects such as a plant growth control function, a pest control function, a weed control function, and an antimicrobial function can be effectively exerted.
(4) The organic-inorganic composite material with the intercalated metal-tropolone complex having a physiologically active function of the present invention can of course be used as it is. However, the organic substance, metal ion, or organometallic complex having the active function can be used gradually. Since the release rate can be controlled, the sustainability of the physiologically active effect is extremely high, and for example, a processed product having an arbitrary preparation form can be obtained.
(5) A processed product imparted with a function according to the purpose can be manufactured at low cost and safely.
(6) The method for producing the processed product is not particularly limited, and can be produced by a method in which an organic-inorganic composite material having a physiologically active function is mixed and dissolved in an oily base, or a generally used method.
(7) The processed product can be designed in a suitable manner according to the usage environment, so that it can be used in a wide range of industrial fields.

  EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by the following Examples.

(1) Manufacture of an organic-inorganic composite in which a copper-hinokitiol complex is supported between layers of an inorganic layered compound montmorillonite A predetermined amount of montmorillonite powder (Kunimine Industries, Ltd., Kunipia F) is weighed in a round bottom flask and deionized. After adding an appropriate amount of water, the mixture was sufficiently stirred to prepare a montmorillonite sol of 1 to 2 wt%. On the other hand, a copper chloride dihydrate aqueous solution equivalent to a cation exchange capacity (CEC) and a hinokitiol (C ₁₀ H ₁₂ O ₂ ) ethanol solution _twice as much as CEC were mixed and stirred, and a yellow-green copper- A hinokitiol complex was obtained.

  This copper-hinokitiol complex was added to a montmorillonite sol prepared in advance, and the exchange reaction was carried out while maintaining at 40 ° C. for 48 hours. After completion of the reaction, the resulting product was washed with deionized water and then dried in an electric dryer at 40 ° C., and a copper-hinokitiol complex in powder form was supported between layers of montmorillonite, and had a physiologically active function. An organic-inorganic composite carrying hinokitiol as an interlayer was obtained.

(2) Confirmation test of organic-inorganic complex carrying copper-hinokitiol complex between montmorillonite layers The obtained copper-hinokitiol / clay complex is more hydrophobic than raw material montmorillonite, and intercalation of organometallic complexes is performed. It was suggested that FIG. 1 shows the results of powder X-ray diffraction of an organic-inorganic composite in which a copper-hinokitiol complex is supported between layers. From the result of the powder X-ray diffraction of the organic-inorganic composite shown in FIG. 1, a (001) diffraction line of 2.28 nm was confirmed on the low angle side. The inter-layer spacing at this time is about 1.32 nm, and this inter-layer distance is such that the seven-membered ring of two molecules of hinokitiol, which is a ligand surrounding the copper-hinokitiol complex around copper, is a layer. It corresponds approximately to the distance that stands vertically with respect to the plane.

  Furthermore, a diffraction line of 1.31 nm is confirmed on the low angle side, which is almost equal to the distance at which the copper-hinokitiol complexes are arranged in parallel between the layers. In this system, it can be seen that the copper-hinokitiol complex exists between montmorillonite layers in two different configurations. Moreover, as a result of measuring the carbon content of this organic-inorganic composite, it was found that the copper-hinokitiol complex was present in the interlayer at a content of 80% or more with respect to the cation exchange capacity. . From these results, it was found that the copper-hinokitiol complex was reliably supported between montmorillonite layers.

For comparison, an X-ray diffraction profile of a raw material montmorillonite supporting only Na ⁺ between inorganic layers is shown in FIG. 1 as a control sample. From the results of powder X-ray diffraction, many diffraction peaks peculiar to clay minerals were confirmed from the diffraction pattern of montmorillonite. The basal plane spacing, the (00 l) diffraction line and the (0 kl) diffraction line resulting therefrom were confirmed, and the basal plane spacing value calculated from the (001) diffraction line was 1.24 nm including the water monomolecular layer. Considering the size of water molecules in the interlayer, it was found that the thickness of one clay layer was about 0.96 nm.

(Production of an organic-inorganic composite in which an aluminum-hinokitiol complex is supported between montmorillonite layers)
A predetermined amount of montmorillonite powder (Kunipia F, manufactured by Kunimine Kogyo Co., Ltd.) was weighed into a round bottom flask, and after adding an appropriate amount of deionized water, the mixture was sufficiently stirred to prepare a 1-2 wt% montmorillonite sol. On the other hand, an aluminum chloride hexahydrate aqueous solution having an equivalent cation exchange capacity (CEC) and a hinokitiol (C ₁₀ H ₁₂ O ₂ ) ethanol solution three times as much as CEC were mixed and stirred to produce white aluminum-hinokitiol. A complex was obtained.

  This complex was added to a montmorillonite sol prepared in advance, and the exchange reaction was carried out with stirring at 40 ° C. for 48 hours. After completion of the reaction, the obtained product is washed with deionized water and then dried in an electric dryer at 40 ° C., and an organic-inorganic composite having a physiologically active function in which a powdery aluminum-hinokitiol complex is supported between layers of montmorillonite. Got the body. FIG. 2 shows the result of powder X-ray diffraction of the obtained organic-inorganic composite carrying the aluminum-hinokitiol complex as an interlayer.

(Production of an organic-inorganic composite in which a zinc-hinokitiol complex is supported between montmorillonite layers)
Montmorillonite powder (Kunimine Kogyo Co., Ltd., Kunipia F) is weighed into a round-bottomed flask, and a suitable amount of deionized water is added, followed by thorough stirring to prepare a 1-2 wt% montmorillonite sol. did. On the other hand, an aqueous solution of zinc nitrate hexahydrate having an equivalent cation exchange capacity (CEC) and a hinokitiol (C ₁₀ H ₁₂ O ₂ ) ethanol solution twice the amount of CEC are mixed and stirred to obtain a zinc-hinokitiol complex. Obtained.

  This complex was added to a montmorillonite sol prepared in advance, and the exchange reaction was carried out with stirring at 40 ° C. for 48 hours. After completion of the reaction, the obtained product is washed with deionized water, and then dried in an electric dryer at 40 ° C., and an organic-inorganic composite having a physiologically active function in which a powdery zinc-hinokitiol complex is supported between montmorillonite layers. Got the body. FIG. 2 shows the result of powder X-ray diffraction of the obtained organic-inorganic composite carrying the zinc-hinokitiol complex as an interlayer.

(1) Manufacture of an organic-inorganic composite in which a nickel-hinokitiol complex is supported between montmorillonite layers A predetermined amount of montmorillonite powder (Kunimine Kogyo Co., Ltd., Kunipia F) is weighed into a round bottom flask, and an appropriate amount of deionized water is added. Then, the mixture was sufficiently stirred to prepare a montmorillonite sol of 1 to 2 wt%. On the other hand, a nickel nitrate hexahydrate aqueous solution having a cation exchange capacity (CEC) equivalent and a quinolthiol (C ₁₀ H ₁₂ O ₂ ) ethanol solution three times as much as CEC were mixed and stirred to produce a yellow nickel-hinokitiol. A complex was obtained.

  This complex was added to a montmorillonite sol prepared in advance, and the exchange reaction was carried out with stirring at 40 ° C. for 48 hours. After completion of the reaction, the resulting product is washed with deionized water and then dried in an electric dryer at 40 ° C., and an organic-inorganic composite having a physiologically active function in which a powdered nickel-hinokitiol complex is supported between montmorillonite layers. Got. FIG. 2 shows the result of powder X-ray diffraction of the obtained organic-inorganic composite carrying the nickel-hinokitiol complex as an interlayer.

(2) Confirmation test of organic-inorganic composite in which aluminum, zinc and nickel-hinokitiol complexes of Examples 2, 3 and 4 are supported between montmorillonite layers From the result of powder X-ray diffraction shown in FIG. 2, the basal plane of montmorillonite The interval value is 1.24 nm, which corresponds to one layer of water molecules in which water molecules are coordinated to sodium ions between layers, and (00l) and (hk0) diffraction lines were confirmed. When the metal-hinokitiol complex was added to the montmorillonite suspension, it was suggested that an intercalation reaction occurred due to the observed phase separation due to the aggregated salt effect.

  The sample in which the aluminum-hinokitiol complex was inserted expanded the interlayer distance to 1.59 nm. The distance between layers at this time is 0.63 nm, which is substantially equal to the distance in which two layers of 7-membered rings of hinokitiol are arranged in parallel to the inside of the layer. Moreover, the (003) diffraction line resulting from a long-period structure and the (hk0) diffraction line of raw material montmorillonite were also confirmed.

  The same behavior was confirmed for the sample in which the zinc-hinokitiol complex was inserted, and the basal plane spacing value was 1.52 nm. In the system in which the nickel-hinokitiol complex was reacted, the basal plane spacing value was 1.51 nm, and (003) and (005) diffraction lines due to the layer structure were also confirmed.

  Considering that the basal plane spacing values of the synthesized composites are all about 1.5 nm, and the hydration radius of the transition metal ions used is approximately equivalent to two molecules of water, the ligand is between the layers. On the other hand, it is almost equal to the distance arranged in parallel (while bending). Since this basal plane spacing value is clearly larger than 0.96 nm, which is the basal plane spacing value of montmorillonite before the reaction with the metal complex, these metal complexes are inserted between montmorillonite layers. Turned out to be.

(3) Thermal behavior of organic-inorganic composites carrying the copper, aluminum, zinc and nickel-hinokitiol complexes of Examples 1, 2, 3 and 4 between montmorillonite layers Composites obtained by a method according to the examples In order to investigate the thermal behavior, a differential thermogravimetric analyzer was used for analysis. Each sample was heat-treated at a heating rate of 5 ° C./min up to 1050 ° C., thermogravimetric change (TG) in the thermal process, and differential heat change in the thermal process, ie endothermic and exothermic behavior (DTA). Was monitored. FIG. 3 shows a differential thermogravimetric analysis curve of the raw material montmorillonite. FIG. 4 shows a differential thermogravimetric analysis curve of hinokitiol. 5 and 6 show differential thermogravimetric analysis curves of an organic-inorganic composite in which copper and an aluminum-hinokitiol complex are supported between layers.

  From the raw material montmorillonite shown in FIG. 3, a rapid thermogravimetric decrease and an endothermic peak at around 100 ° C. were confirmed. This is due to the separation of water adsorbed on the surface and water molecules coordinated with sodium ions present in the interlayer. Further, the heat loss and endothermic peak around 600 to 700 ° C. are attributed to the elimination of hydroxyl groups in the crystal structure. From the TG curve of only hinokitiol shown in FIG. 4, heat loss starts from around 150 ° C. and ends at around 300 ° C. An endothermic peak due to melting and molecular desorption at around 50 ° C and around 200 ° C, and an exothermic peak of residual carbonaceous combustion were observed at 250 to 300 ° C.

  The copper and aluminum-hinokitiol-supported montmorillonite shown in FIGS. 5 and 6 showed similar thermal analysis curves. An exothermic peak due to combustion of carbonaceous carbon in the interlayer near 300 to 400 ° C. and a decrease in thermogravimetry from around 300 ° C. were observed. When the respective theoretical organic matter contents were calculated, they were 26.6 wt% and 36.1 wt%, which almost coincided with the values calculated from the final thermogravimetric weight loss rate and the adsorbed water rate.

  7 and 8 show thermal analysis curves of montmorillonite supported with zinc and nickel-hinokitiol. Considering both samples of the montmorillonite complex carrying zinc and nickel-hinokitiol complex, the height of the exothermic peak around 400 ° C. (calorific value) from the respective DTA curves is copper and aluminum-hinokitiol carrying montmorillonite. It can be seen that it is extremely low compared to that.

  Furthermore, rapid heat loss of 10 wt% or more was confirmed in a low temperature region up to around 200 ° C., and the final weight loss rate was about 25 wt% in both cases. Considering that the respective theoretical organic substance contents are 26.6 wt% and 35.4 wt%, the hinokitiol complex of zinc and nickel is present between the clay layers, but the stability of forming a complex with hinokitiol. Since the constant is lower than that of copper or aluminum, it is considered that the constant is separated on the low temperature side.

  Hinokitiol itself is an organic substance that has sublimation, low melting point, and extremely low heat resistance. However, when intercalation into an inorganic layered compound is performed as a metal-hinokitiol complex, the combustion start temperature of the internal organic substance reaches around 400 ° C. To rise. From the above results, the heat resistance of the organic ligand electrostatically fixed inside the layer is greatly improved by inserting the tropolone compound into the layer of the inorganic layered compound in the form of a metal-tropolone complex. Thus, it has been clarified that the sustained release of the physiologically active function can be improved.

(4) Behavior after heat treatment of an organic-inorganic composite in which the copper-hinokitiol complex of Example 1 is supported between montmorillonite layers To examine the heat resistance of the antibacterial and antifungal material in which the copper-hinokitiol complex is supported between montmorillonite layers Various measurements were performed on the samples after the heat treatment. The copper-hinokitiol clay composite obtained in Example 1 was subjected to heat treatment using an electric furnace (in air, heating rate 10 ° C./min, holding 1 hour). The processing temperatures were 200, 250, 300, 400 and 500 ° C., respectively.

  Samples obtained at each heat treatment temperature were analyzed by powder X-ray diffraction. FIG. 9 shows the result. From the result of the powder X-ray diffraction, a diffraction line showing a basal plane spacing value of 2.28 nm and a diffraction line that is considered to be adjacent to the layer structure were confirmed from the untreated sample. The hinokitiol, a ligand, is known to form a 2: 1 type planar complex with copper ions, and assuming that it is placed upright with respect to the interlayer, the basal plane spacing value is 2.45 nm. It becomes. The (001) diffraction line showed a value of about 2.2 nm until the treatment at 250 ° C., but decreased to 1.46 nm after the treatment at 300 ° C. Along with this, the diffraction line considered to be (002) also shifted to the high angle side. In the treatment at 400 to 500 ° C., it decreased to 1.3 nm with the separation of organic substances in the layer, but the redox state of copper as the central chemical species was not confirmed by X-ray.

  In order to investigate the structural change of the sample in each heat treatment stage, the carbon content measurement results using a CHN coder and the change in the basal plane spacing value obtained by powder X-ray diffraction are shown for each sample at each heat treatment temperature. 10 shows. According to this, the change in the carbon content is kept constant until after treatment at 250 ° C., and it is confirmed that the thermal influence on the copper-hinokitiol complex which is an organic substance in the interlayer is slight. This also shows the same tendency with respect to the basal plane spacing value, and the change in the layer spacing up to this temperature region is very small. However, when the processing temperature is 300 ° C. or higher, both the carbon content and the basal plane spacing value start to rapidly decrease. After the treatment at 500 ° C., the organic substances in the interlayer are almost eliminated and the layer spacing is also shrunk accordingly. From these, it can be seen that the internal organic matter has heat resistance up to about 250 ° C.

(5) Infrared absorption spectrum of the organic-inorganic composite in which the copper-hinokitiol complex of Example 1 is supported between montmorillonite layers. FIG. 11 shows the obtained organic-inorganic composite in which the copper-hinokitiol complex is supported in an interlayer. The result of the infrared absorption spectrum of hinokitiol which is a ligand is shown. Absorption due to octahedral Al—OH stretching was observed at 3624 cm ^−1, and absorption due to OH stretching vibration of interlayer water molecules was observed at 3434 cm ^{−1, which} was absorption specific to the clay mineral that was the raw material montmorillonite used. The absorption at 1639 cm ⁻¹ is also due to the OH stretching vibration of the adsorbed water. Furthermore, tetrahedral Si-O-Si stretching vibration is to 1038cm ^-1 is octahedral Al-OH bending vibration in 914 cm ^-1, and the 847cm ^-1 (Al, Mg) -OH attributed to deformation vibration A strong absorption was confirmed.

Furthermore, Si-O-Al deformation vibration and Si-O-Mg deformation vibration were respectively confirmed at 520 and 467 cm- ¹ . From the results of the infrared absorption spectrum of the copper-hinokitiol-supported montmorillonite, 2965, 2873 cm ⁻¹ CH ₃ group and seven-membered CH stretching vibration, 1593, 1513 cm ⁻¹ belonging to the seven-membered ring molecular skeleton C stretching vibration is present, and absorption due to CH ₃ radicals and seven-membered C—H bending vibrations are observed at 1434 and 1356 cm ⁻¹ , and aromatic ring C—H bending vibrations are observed at 812 and 741 cm ^−1. It was. For the above complex system, absorption specific to the inserted organic matter and slight shift accompanying their interlayer loading were confirmed, and from these, it was confirmed that the target organic-inorganic complex was synthesized. .

  As described above in detail, the present invention relates to an organic-inorganic composite material in which a metal-tropolone complex having a physiological activity function is supported between layers and a method for producing the same, and according to the present invention, an excellent physiological activity function, for example, Pest control function, weed control function, antimicrobial function, etc., sustainability, water retention, environmental compatibility, living environment, medical welfare environment, plant tissue culture, agriculture, forestry including plantation, plant cultivation It is possible to provide an organic-inorganic composite material in which a metal-tropolone complex is supported between layers, which can be applied to, for example. This organic-inorganic composite material is excellent in dispersibility even when used on the surface of a medium or in fields because organometallic complexes having physiologically active functions are uniformly dispersed in the order of nanometers between layers of inorganic layered compounds. Has the advantage of being.

  In addition, the organic-inorganic composite material in which the metal-tropolone complex having a physiologically active function of the present invention is supported on an interlayer can be used as it is, but the sustained release of the metal-tropolone complex having an active function to the outside of the system is possible. Since the speed can be controlled, the physiologically active effect is extremely high, and a processed product having any formulation form can be obtained. The method for producing the processed product is not particularly limited, and can be appropriately produced by a method of mixing and dissolving an organic-inorganic composite material having a physiologically active function in an oily base or a generally used method. Since such a processed product can be designed and manufactured according to the usage environment, the processed product containing the organic-inorganic composite material of the present invention can be used in a wide range of industrial fields.

It is a powder X-ray diffraction pattern of the organic-inorganic composite which carry | supported the copper- hinokitiol complex which has a bioactive function based on Example 1 of this invention between the layers of montmorillonite, and the raw material montmorillonite which is a control sample. Powder X-ray diffraction of an organic-inorganic composite in which aluminum, zinc, and nickel-hinokitiol complexes having bioactive functions are supported between montmorillonite layers and a reference montmorillonite as a control sample according to Examples 2, 3 and 4 of the present invention It is a figure. It is a differential thermogravimetric analysis curve of the raw material montmorillonite which is an inorganic layered compound based on Example 1 of this invention. It is a differential thermogravimetric analysis curve of hinokitiol which is an organic ligand based on Example 1 of this invention. It is a differential thermogravimetric analysis curve of the organic inorganic composite which carry | supported the copper- hinokitiol complex which has a bioactivity function based on Example 1 of this invention between layers. It is a differential thermogravimetric analysis curve of the organic inorganic composite which carried | supported the aluminum- hinokitiol complex which has a bioactivity function based on Example 2 of this invention between layers. It is a differential thermogravimetric analysis curve of the organic inorganic composite which carry | supported the zinc- hinokitiol complex which has a bioactivity function based on Example 3 of this invention between layers. It is a differential thermogravimetric analysis curve of the organic-inorganic composite which carry | supported the nickel- hinokitiol complex which has a bioactivity function based on Example 4 of this invention. It is a powder X-ray-diffraction figure before and behind heat processing of the organic inorganic composite which carry | supported the copper- hinokitiol complex which has a bioactive function based on Example 1 of this invention between the layers of montmorillonite. It is the carbon content rate before and behind heat processing of the organic-inorganic composite which carry | supported the copper- hinokitiol complex which has a bioactive function based on Example 1 of this invention between the layers of a montmorillonite, and a basal plane space | interval value. It is an infrared absorption spectrum of the organic-inorganic composite which carry | supported the copper- hinokitiol complex which has a bioactivity function based on Example 1 of this invention between the layers of montmorillonite.

Claims (10)

  An organic-inorganic composite material in which a metal-tropolone complex is supported on an interlayer to improve the sustained release of the physiologically active function, using an inorganic layered compound as a main raw material and having a physiologically active function between the layers of the inorganic layered compound An organic-inorganic composite material in which a metal-tropolone complex is supported between layers, wherein a metal-tropolone complex is inserted and supported.   2. The metal of claim 1, wherein the metal cation forming the metal-tropolone complex having a physiologically active function is at least one metal ion selected from Cu, Zn, Ni, Al, or a transition metal group. An organic-inorganic composite material with a tropolone complex supported between layers.   The organic ligand forming the metal-tropolone complex having a physiologically active function is at least one organic ligand selected from hinokitiol, β-drabrin, α-tyaprisin, γ-tyaprisin and 4-acetyltropolone. An organic-inorganic composite material comprising an interlayer-supported metal-tropolone complex according to claim 1.   The organic-inorganic composite material carrying an interlayer-supported metal-tropolone complex according to claim 1, wherein the inorganic layered compound as a main raw material is a natural or synthetic layered clay mineral or a natural or synthetic swellable mica.   The layered clay mineral is montmorillonite, beidellite, nontronite, saponite, hectorite, a smectite group clay mineral of stevensite, vermiculite, or a mica clay mineral or fluorinated mica that is a swellable mica. An organic-inorganic composite material in which a metal-tropolone complex is supported between layers.   A method for producing an organic-inorganic composite material according to any one of claims 1 to 5, wherein an inorganic layered compound is used as a main raw material, and a metal-tropolone complex having a physiologically active function is inserted between the layers of the inorganic layered compound. By exchanging exchangeable cations existing between the layers of the inorganic layered compound and metal-tropolone complex having a bioactive function, an organic-inorganic composite material carrying the metal-tropolone complex is synthesized. A method for producing an organic-inorganic composite material in which a metal-tropolone complex is supported between layers.   The metal- according to claim 6, wherein the metal cation forming the metal-tropolone complex having a physiologically active function is at least one metal ion selected from Cu, Zn, Ni and Al or a transition metal group. A method for producing an organic-inorganic composite material in which a tropolone complex is supported between layers.   The organic ligand forming the metal-tropolone complex having a physiologically active function is at least one organic ligand selected from hinokitiol, β-drabrin, α-tyaprisin, γ-tyaprisin and 4-acetyltropolone. The manufacturing method of the organic inorganic composite material which carry | supported the metal-tropolone complex of Claim 6 with an interlayer.   The method for producing an organic-inorganic composite material having an interlayer-supported metal-tropolone complex according to claim 6, wherein the inorganic layered compound as a main raw material is a natural or synthetic layered clay mineral or a natural or synthetic swellable mica.   A processed product comprising an organic-inorganic composite material in which the metal-tropolone complex according to any one of claims 1 to 5 is supported between layers, and being processed into a desired form.

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