JP2007291097A - Clay mineral-based composite material and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a clay mineral-based composite material, and to provide a method for producing the composite material. <P>SOLUTION: The clay mineral-based composite material is composed mainly of a clay mineral having anion-exchange ability between layers and is introduced, in the case where an alkali or alkaline-earth metal is combined with an organic compound having bioactive function, the organic compound between the layers on the stable or metastable state by exchanging with interlayer water between the layers. The method for producing the clay mineral-based composite material comprises introducing the organic compound between the layers of the clay mineral by removing the interlayer water by previously heat-treating the clay mineral and, before condensing between the layers of the clay mineral, immediately mixing the clay mineral with the organic compound or a solution thereof to introduce the organic compound between the layers of the clay mineral. The organic compound having bioactive functions is easily introduced between the layers within a short time to produce inorganic or organic composite materials with unnecessarily requiring complexing of interlayer anion with the organic compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a clay mineral-based composite material having a physiologically active function, and more specifically, an organic compound having a physiologically active function such as an insect repellent / insect repellent function, an antimicrobial function, a freshness maintaining function, an aroma function, The present invention relates to a clay mineral composite material having a physiologically active function, which is composite-integrated with an inorganic clay mineral, and a method for producing the same. The present invention is a functional substance that is friendly to ecosystems including humans in business, industrial, and human life, and that is excellent in stability and sustainability of functions and effects. A manufacturing method is provided.

  Conventionally, antimicrobial agents such as insect repellents / insect repellents, antibacterial / antifungal agents, freshness maintaining agents and fragrances for fresh foods such as vegetables and fruits are practical for both liquids and solids. Processed and used in a suitable form. In such products, inorganic substances are often used as a carrier in order to retain the active ingredients, maintain the effects, and provide convenience in handling. For example, talc, clay, wax stone Inorganic powders such as limestone, diatomaceous earth, perlite, and pumice are often used.

  For example, as an insect repellent / insect repellent, there are examples in which natural essential oils and synthetic pesticides, which are active ingredients, are used as a carrier of natural / synthetic fibers and glass fibers, zeolite, talc, diatomaceous earth, lime, silica gel, activated carbon, etc. (Patent Document 1). Examples of the purpose of maintaining the freshness of fresh food products include a mixture of cinnamic acid and its derivatives and titanium oxide (Patent Document 2), garlic, chili ingredients, wasabi ingredients, perilla ingredients using talc as a carrier. There is an example (Patent Document 3) in which these are combined. As antimicrobial agents such as antibacterial and antifungal agents, functional materials in which catechins, saponins, and tannin (acid) are supported on vermiculite and bentonite have been proposed (Patent Document 4).

  As described above, the role of carriers such as talc, kaolin, and wax used as a carrier is effective when adhering and adsorbing active ingredients on the surface and used for business, industrial and household purposes. The purpose is to limit the range, to give the residual effect by the affinity of the active ingredient to the carrier, or to ensure the convenience in processing into various forms including handling properties. However, since the affinity of the active ingredient to such an inorganic carrier is based on the adhesion and adsorption phenomenon to the material, the active ingredient moves relatively easily from the carrier when subjected to some washing operation during use. However, its residual effect is generally inferior to that of emulsions. In addition, since the retention of the active ingredient is not strong, the sustained release of the active ingredient has not been achieved.

  In order to solve these problems, in recent years, a composition in which a specific compound is introduced between layers using an inorganic layered compound having ion exchange ability between layers such as smectite and vermiculite has been proposed (Patent Document 5). Such). As a guest compound introduced between the layers, a metal ion having antibacterial activity such as silver, copper, zinc, etc. and an organic compound having a function such as mold prevention are combined to introduce both functions of antibacterial action and mold prevention. Inorganic / organic composite materials can be made.

  Further, it has been found that when a metal hydroxide cation such as aluminum or zirconium is introduced between layers together with the metal ion-organic compound complex, the heat resistance is significantly improved (Patent Document 6). Furthermore, as a substance having a physiologically active function, a method has been proposed in which an organic compound having a plant growth regulating function, a pest control function, an antimicrobial function, etc. is introduced between layers of an inorganic layered compound in combination with an appropriate metal ion. (Patent Document 7).

  Introduction of a physiologically active substance into such an inorganic layered compound having ion exchange ability is achieved by combining a non-dissociated organic compound with a metal ion to form a metal complex ion. In order for an organic compound and a cation to form a complex, it is necessary to have conditions for both to form a complex, i.e., stability as a complex. In combination, it is usually considered difficult to introduce them between layers of inorganic layered compounds.

  In addition to the above-mentioned silver, copper, and zinc, transition metal ions such as iron, nickel, and cobalt are often selected as the metal ion. However, depending on the metal ion species, its use can be considered for safety and hygiene reasons. It may be restricted. Among alkali metals and alkaline earth metals, there are ionic species with few restrictions, but it is not expected that such metal ionic species will form a stable organometallic complex with a central metal. Thus, when a cation exchange type inorganic layered compound is used as the host compound, the combination of metal ions and organic compounds has the problem of safety and hygiene constraints of metal ion species in addition to the stability of the complex. Exists.

Japanese Patent Laid-Open No. 2002-173407 JP 11-332460 A Japanese Patent Laid-Open No. 10-210958 JP 2000-271201 A JP 2002-327090 A JP 2002-20158 A JP 2005-281263 A

  For this reason, the use of repellents has recently been attracting attention. If it has a certain level of repellent activity against major species such as whiteflies and aphids and can maintain its efficacy for a long period of time, safe and effective control is possible by combining with the above control method. . However, the present situation is that the development of pest repellents in the agricultural field is not progressing compared to the environmental health field. One reason is that there are few known ingredients that have repellent activity against the main species of pests, and that the repellent activity of known ingredients is not strong, so it is not possible to obtain a control effect alone, Furthermore, many of the repellent components are not effective in the field because of their volatility and instability.

  Under such circumstances, the present inventors have conducted intensive research with the goal of developing a new clay mineral-based composite material capable of solving the above-described problems and a method for producing the same, in view of the above-described conventional technology. As a result of stacking the layers, using clay minerals with cation exchange capacity between layers as the main raw material, exchangeable cations and interlayer water in the layers are exchanged with alkali / alkaline earth metals and organic compounds of different types of cations. In order to complete the present invention, it has been found that by introducing an organic compound between layers in combination with an alkali or alkaline earth metal, it is possible to introduce these between layers in a stable or metastable state. It came.

The present invention for solving the above problems is composed of the following technical problems.
(1) A clay mineral having a cation exchange capacity between layers is used as a main raw material, is exchanged with interlayer water between layers, and in a combination of an alkali or alkaline earth metal and an organic compound having a physiologically active function, A clay mineral composite material in which an organic compound is introduced in a stable or metastable state.
(2) The clay mineral composite material according to (1), wherein the alkali or alkaline earth metal is sodium, potassium, calcium and / or magnesium.
(3) The clay mineral composite material according to (3), wherein the physiologically active function is an insect repellent, antimicrobial, freshness maintenance, or aroma function.
(4) The clay mineral composite material according to (1), which is provided with functions of insect repellent, antimicrobial, freshness maintenance, or aroma as functionality.
(5) Clay minerals with cation exchange capacity between layers are used as the main raw materials, and exchangeable cations and interlayer water between layers are exchanged with different types of cations and organic compounds, respectively. In the manufacturing method, after intercalation water is excluded by pre-heat treatment of the clay mineral, and before the interlayer of the clay mineral is condensed, the clay mineral is immediately mixed with an organic compound or a solution thereof. A method for producing a clay mineral-based composite material, wherein an organic compound is introduced between layers of clay mineral.
(6) The method for producing a clay mineral composite material according to (5), wherein the heat treatment for removing the interlayer water of the clay mineral is performed by heating, microwave irradiation, or infrared irradiation.
(7) As a device or container for immediately mixing clay minerals with an organic compound or a solution thereof, use a tron mill, ball mill, planetary ball mill, centrifugal mill, vibration mill, and mortar with a structure capable of eliminating contact with outside air. The method for producing a clay mineral composite material according to (5) above.
(8) The method for producing a clay mineral composite material according to (5), wherein smectite, vermiculite, or kaolin clay mineral is used as the clay mineral.
(9) Production of a clay mineral composite material according to (5) above, wherein an organic compound having an insect repellent function, an antimicrobial function, a freshness maintaining function, and an aromatic function is used as the organic compound to be introduced into the clay mineral after the heat treatment Method.
(10) Organic compounds having any of insect repellent function, antimicrobial function, freshness maintaining function and fragrance function are cinnamon oil, thyme white oil, clove bud oil, cinnamon leaf oil, lavender french oil, lemon Glass oil, peppermint oil, bergamot oil, tea tree oil, geranium oil, citronella oil, rose oil, lemon oil, eucalyptus oil, origanum oil, cinnamaldehyde, eugenol, methyl salicylate, citral, allyl isothiocyanate, benzyl isothiocyanate, phenyl At least ethyl isothiocyanate, linalool, menthol, geraniol, thymol, terpineol, hinokitiol, diethyl toluamide, cyazofamide, metalaxyl, epigallocatechin gallate, myricitrin, caffeine At least one method for producing a clay mineral composite material according to claim 9.
(11) The method for producing a clay mineral composite material according to (5), wherein the interlayer cation of the clay mineral is sodium, potassium, calcium, or magnesium.
(12) A functional product using the clay mineral composite material according to any one of (1) to (4) as a functional material.

Next, the present invention will be described in more detail.
The present invention uses a clay mineral having a cation exchange capacity between layers as a main raw material, exchanges it with interlayer water between layers, and in a combination of an alkali or alkaline earth metal and an organic compound having a physiological activity function, It is characterized by a clay mineral composite material characterized in that the organic compound is introduced in a stable or metastable state. The present invention also uses a clay mineral having a cation exchange capacity between layers as a main raw material, and exchanges exchangeable cations and interlayer water between layers with different types of cations and organic compounds, respectively. In the method for producing a composite material, after the intercalation water is eliminated by preheating the clay mineral, the clay mineral is immediately mixed with the organic compound or a solution thereof before the interlayer of the clay mineral is condensed. Thus, an organic compound is introduced between the layers of the clay mineral.

  Furthermore, the present invention is characterized in that it is a functional product characterized by using the above clay mineral composite material as a functional material. In the present invention, the interlayer cation of the clay mineral is preferably sodium, potassium, calcium and magnesium, but metal ions such as iron, cobalt, titanium, manganese, nickel, zinc, gold, silver and copper are interposed between the layers. Even in such a case, since the organic compound can be easily introduced between the layers, the present invention does not exclude the combination of the metal ion and the organic compound.

Hereinafter, in order to avoid complications, the present invention will be described by taking smectite as a clay mineral as a host compound, and particularly montmorillonite among them, but the present invention is not limited thereto. In the present invention, montmorillonite, which is a main raw clay mineral, is a clay having a crystal structure called a so-called 2: 1 type in which an SiO ₄ tetrahedral sheet sandwiches AlO ₄ (OH) ₂ octahedral sheets in a sandwich shape. It is a mineral. A part of Al in the octahedron sheet of montmorillonite crystal is replaced with divalent Mg or Fe, so that the clay layer is negatively charged. In order to electrically neutralize this negative charge, a cation called an interlayer cation is contained between the layers.

  In the case of montmorillonite, the interlayer cation is usually a sodium ion in many cases, so the following description will be made with the original interlayer cation fixed to the sodium ion. Since this sodium ion can be exchanged with an organic or inorganic cation outside the system relatively easily, by contacting a suitable metal complex cation with montmorillonite, a metal complex cation can be substituted for the sodium ion originally present between the layers. Can be introduced. Since the introduced metal complex cation is kept in a relatively stable state between the layers even if the montmorillonite particles are in the dispersion medium, the elution of the metal complex cation into the dispersion medium gradually occurs. That is, it has sustained release properties.

  In the above ion exchange reaction, when metal complex ions are exchanged with sodium ions, water molecules existing between layers are also exchanged in the same manner as sodium ions and excluded from the clay layer. On the other hand, the removal of water molecules from the clay layer is not necessarily only accompanied by the exchange of interlayer cations. The exchange reaction between interlayer water and glycerin or ethylene glycol is a well-known phenomenon. However, in this case, no change occurs in the sodium ions between the clay layers. Therefore, the prior document (Japanese Patent Laid-Open No. 2005-281263) also shows that the exchange reaction between interlayer cations and water molecules can be performed independently.

  Montmorillonite is called 15Å clay mineral, but it is known that up to three water molecule layers enter the layer in the air. Depending on the number of water molecule layers included between the layers, the corresponding bottom surface spacing is 10 mm (0 sheets), 12 to 13 mm (1 sheet), 14 to 16 mm (2 sheets), and 18 to 19 mm (3 sheets). . Again, as mentioned above, the water molecule layer is taken in between the layers by hydrating (coordinating) the metal ions between the layers. Need to be replaced. Even if the intermolecular compound is placed in the interlayer instead of the water molecule, the exchange of the water molecule and the complexing molecule requires a certain amount of time, and the temperature during the exchange reaction is increased. It is possible to take measures such as raising the reaction. In addition, in the case of complex-forming molecules that are less stable between layers than water molecules, it has been thought that the exchange reaction has hardly occurred so far.

  The present invention was made to facilitate the exchange of such water molecules and organic compounds that are complex-forming molecules, and organic compounds that would normally lack stability between layers, It was possible to introduce it into the interlayer. That is, in the present invention, for example, montmorillonite is heated to 220 ° C. or more to quickly remove water molecules between clay layers, and before condensate between clay layers (re-entry of water molecules between layers) occurs, It is characterized in that the complex-forming molecule is introduced between the clay layers by immediately contacting an organic compound to be introduced into the clay.

  Polar organic compounds such as alcohols, aldehydes, and ketones that have already been found to be stable by exchanging with intercalated water of montmorillonite can be dissolved in water and an appropriate organic solvent and added to the montmorillonite suspension. Although it can be exchanged with intercalation water of montmorillonite, even if it is an organic compound that is stable between montmorillonite layers, the exchange of interlaminar water and organic compound usually takes about one day. Even in such a case, by applying the method of the present invention, the time required for the introduction can be greatly shortened. That is, the intercalation of the montmorillonite is removed in advance by heat treatment, and the organic compound is readily added to the organic compound or its solution before the interlayer is condensed, whereby the introduction of the organic compound into the interlayer is easily achieved.

  Further, in the case of a polar organic compound having a very low intramolecular polarity, exchange with interlayer water hardly occurs, but by applying the method of the present invention, metastable introduction between layers can be achieved. That is, by immediately adding montmorillonite from which interlayer water has been removed to the organic compound or the solution thereof, introduction into the montmorillonite layer is performed in the same manner as the polar organic compound that is stable between the layers. However, when the organic compound introduced between the layers in this way continues to be stirred or mixed for a long time, the exchange of water molecules (condensation) gradually proceeds and moves away from the layers and is removed. Therefore, when introducing such a polar organic compound, which is not sufficiently stable between the layers, between the montmorillonite layers, it is desirable to stop the contact via the liquid medium in a necessary and sufficient time.

  In the present invention, a method is adopted in which an organic compound having a high vapor pressure at room temperature is introduced into montmorillonite in which an alkali or alkaline earth metal is placed between the layers. The organic compound introduced by such a method is montmorillonite. Not stable enough between layers. Thus, even when the particles are in the air rather than in the liquid, the organic compound vapor is gradually released into the air. That is, it has a gas sustained release property. The present inventors have found many organic compounds that bring such properties to montmorillonite in natural product essential oils having physiologically active functions. Specific examples will be described in the examples. In addition, although an Example demonstrates the example using a natural-product essential oil, if it is an organic compound which is introduce | transduced between the layers of a clay mineral and shows the same property, it will not be limited to the kind.

  As described above, in the present invention, when an organic compound having a physiologically active function is introduced between layers of clay mineral having a cation exchange capacity between layers, interlayer water is previously removed by heat treatment, and the above-mentioned Immediate contact with an organic compound (1) An inorganic / organic composite material can be easily introduced in a short period of time without necessarily requiring the stability of a complex between an interlayer cation and an organic compound. (2) Further, the method of the present invention is applied even to an organic compound that has so far been insufficiently stable between the layers of the clay mineral and has been difficult to introduce between the layers. (3) Depending on the application, complex formation with metal ion species such as transition metals and heavy metals, which are undesirable to be included in the material, is possible. It becomes unnecessary Can meet the demands of safety and hygiene, and (4) in exchange between the interlayer water between the layers, in the combination of alkali or alkaline earth metal and organic compound having bioactive function, There is an advantage that an inorganic / organic composite material into which the organic compound is introduced in a stable or metastable state can be produced and provided.

  The present invention is a combination of a metal ion and an organic compound that is unlikely to form a stable complex by eliminating inter-layer water in advance when sodium, potassium, calcium, and magnesium are present between the layers. However, it can be introduced between the layers while being metastable. In other words, a stable organometallic complex is generally formed by coordinating bonds with an organic compound having an unshared electron pair by hybridizing the inner shell or outer shell orbitals that are the electron arrangement of the central metal. In general, an inorganic / organic composite material is prepared by previously forming a stable organometallic complex cation using these materials and then introducing it between montmorillonite layers.

  On the other hand, in the case of sodium ions and calcium ions, water molecules as interlayer water are coordinated around them, but their bonds are weak and easily lost by heating. Further, when polar molecules such as glycerin and ethylene glycol approach, water molecules are easily exchanged and excluded from the interlayer. However, in this case, there is no change in the sodium ions between layers. In the present invention, an organic compound having a physiologically active function that has a very small polarity and that does not easily exchange with water molecules under normal contact is removed by intercalation of the interlayer water in advance by heat treatment. In combination with other metals, we succeeded in introducing it in a metastable manner. Here, metastable means that even if water molecules are once removed from the clay mineral layer, when they come into contact with water again, exchange with water molecules occurs gradually. .

  The clay mineral-based composite material according to the present invention is characterized in that an organic compound having a physiologically active function such as essential oil is introduced between the layers according to the principle as described above, and the organic compound is gradually released from the layers. A further feature is that these organic compounds are combined with alkali, alkaline earth metals, such as sodium, potassium, calcium and magnesium, which usually have little known toxicity or toxicity by themselves (formation of complexes). ) Can be introduced. If the stability between clay mineral layers is to be retained by a complex of organic ligands with heavy metal ions as the central atom, heavy metal ions are expected to bring about one end of physiological activity such as antibacterial activity. For example, in recent years, it is inevitable that there will be a considerable impact on the safety of various consumer goods that have become a global trend. According to the present invention, it is possible to provide a clay-mineral composite material composed of the above metal ions, which is a stable typical element that hardly meets such concerns. Further, as described above, as described above, the natural product essential oil that has a high vapor pressure at normal temperature and easily volatilizes as it is as it is or a main component thereof is a complex with the above-mentioned alkali metal or the like. Since it can be introduced between layers of clay minerals, the natural product essential oil and its main components can be stored relatively stably over a long period of time. According to the investigation by the present inventors, the sustained release period extends for several months in a state of being released into the airflow.

  The present invention uses the above clay mineral composite material as an insect repellent using, for example, a natural product essential oil, and by installing it in a field where crops are cultivated, fine pests such as whiteflies and aphids are removed. Insect repellent material that has an insect repellent effect to prevent flying, invasion and parasitic on crops, and it is gentle on ecosystems including humans due to its slow release, and it has excellent function and stability and sustainability. It provides a method for controlling pests.

  Among agricultural pests, the fine pests such as whiteflies and aphids are vegetables (cucumbers, tomatoes, eggplants, peppers, strawberries, etc.), flowers (roses, chrysanthemum, gerberas, etc.), fruits (mandarin oranges, peaches, pears, etc.) This is an important pest of this species, and causes damage caused by sucking of this species infesting crops and damage of soot disease, in which miscellaneous bacteria propagate in excreta and inhibit crop photosynthesis. The micro pests are not only direct damages, but also cause great damage as mediators of phytopathogenic viruses.

  As a conventional control technique for micro pests, a method using an insecticide is mainly used, and as an active ingredient of the insecticide, for example, an organic phosphorus agent, a synthetic pyrethroid agent, an IGR agent (insect growth regulator), Neonicochi Drugs such as noid agents have been used. However, the main species of micro pests such as whiteflies and aphids develop resistance to many insecticides, and it is difficult to obtain a control effect even if they are sprayed. The fact is that it cannot be controlled without spraying at intervals. On the other hand, however, there has been an ever-increasing interest in environmental and food safety, and the heavy use of pesticides that pose a risk of residual pesticides goes against the needs of farmers and consumers. .

  For this reason, other control techniques include, for example, a method of applying an insect net to the opening to prevent intrusion into the facility, a method of suppressing the invasion of pests by covering with a near ultraviolet cut film, and attracting micro pests. Blue and yellow adhesive tapes and adhesive plates are installed and captured to reduce the pest density. Recently, the development of a method for introducing and controlling pest natural enemies in a facility has been promoted. However, micro pests have a small body size of about 1 to 2 mm and extremely high breeding ability, so that in fact, any of the above-described control methods has not been sufficiently effective.

  For this reason, there is the use of repellents as a control technique that has recently attracted attention, and it has a repellent activity of a certain level or more against major species such as whiteflies and aphids, and if its efficacy can be sustained for a long period of time, Combining with the control method enables safe and effective control. However, the present situation is that the development of pest repellents in the agricultural field is not progressing compared to the environmental health field. One reason is that there are few known ingredients that have repellent activity against the main species of pests, and that the repellent activity of known ingredients is not strong, so it is not possible to obtain a control effect alone, Furthermore, many of the repellent components are not effective in the field because of their volatility and instability.

  The present invention provides, for example, a sustained release property and stability of a repellent component so that it has a certain repellent function and can maintain its efficacy for a long period of time against major pest species such as whiteflies and aphids. It provides an excellent insect repellent.

  Therefore, in the present invention, plant mineral oil such as cinnamon leaf, geranium, citronella and rose oil having an insect repellent function, and citral, benzylisothiocyanate, geraniol, thymol, citronellal, hinokitiol, diethyltoluene, and the like, with clay mineral as the main raw material. The insect repellent effect containing one or more selected from organic compounds such as amides as an active ingredient was examined, and an insect repellent excellent in slowness and stability was constructed.

  The present invention also provides an antimicrobial agent that suppresses mold contamination of strawberries and the like, particularly by steam treatment, using the clay mineral-based composite material as, for example, a natural product-derived gray mold inhibitor. Currently, food safety and security are demanded, and degradation of agricultural products includes aging by ethylene, browning, and decay by microorganisms. Until now, various antimicrobial agents have been studied, and these have been required to contact directly or in a liquid phase or a solid phase with a substance intended for antimicrobial. Recently, substances having antimicrobial activity due to vapor contact have attracted attention. In addition, antimicrobial agents have so far been centered on chemically synthesized substances, but natural product-derived component substances are required for safety and the like.

  In addition, cut vegetables meet the diversifying consumer needs such as convenience, and in recent years, the demand has been increasing not only for business use but also for home use. However, since it is cut, the quality deterioration is faster than that of normal vegetables, and the occurrence of browning on the appearance most reduces the consumer's willingness to purchase. In particular, cut lettuce has a limited consumption period in a very short time because browning occurs earlier than the growth of microorganisms among cut vegetables.

  Some natural substances have problems with heat resistance and stability. Although the safety of natural substances is not necessarily guaranteed, there are several natural ingredients and many plant extracts registered as food additives in the food field, and these are guaranteed to have a certain level of safety. ing. The risk of mold contamination of food depends on the storage conditions, but the risk increases as the storage period increases. Molds are generated during transportation due to the cultivation management status of agricultural products and the temperature management during distribution, which is a factor in lowering the commercialization rate.

  As a conventional antimicrobial technique, an antimicrobial technique in which allyl isothiocyanate contained in horseradish, cabbage or the like is brought into direct contact with it has been reported. However, the volatility of this substance is extremely high and long-term antibacterial effects cannot be expected. Also, due to this volatility, when trying to process as a packaging material, most of it is lost in the process, and even if it remains in the material, the lifetime of antimicrobial activity is short.

  For this reason, in the present invention, an antimicrobial control technology for agricultural products that can suppress mold, bacteria, etc., can extend the expiration date, and is environmentally friendly with low cost and a slow-release of agricultural products has been constructed. . The present invention provides, for example, a technique for suppressing the browning of cut vegetables such as lettuce, particularly a technique for suppressing the browning of cut vegetables caused by steam.

The following effects are exhibited by the present invention.
(1) In the present invention, when introducing an organic compound having a physiologically active function between layers of clay mineral having a cation exchange capacity between layers, the interlayer water is previously removed by heat treatment, and the above organic compound Is immediately brought into contact with each other, so that the stability of the complex between the interlayer cation and the organic compound is not necessarily required, and it can be easily introduced between the layers in a short time to produce an inorganic / organic composite material.
(2) Further, even in the case of an organic compound that has so far been insufficiently stable between the layers of the clay mineral and has been difficult to introduce between the layers, it is metastable by applying the method of the present invention. However, it can be introduced between the layers.
(3) Depending on the use, complex formation with metal ion species such as transition metals and heavy metals, which are undesirable to be included in the material, is not necessary, so that it is possible to meet safety and hygiene demands.
(4) Organic compounds having a high vapor pressure at room temperature, which have been considered difficult to complex with clay minerals such as natural product essential oils, can be easily complexed with clay minerals in a short time.

  EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by the following Example. In the following, an example will be described in which a physiologically active organic substance or a solution thereof was immediately brought into contact with heat-treated clay. For convenience of explanation, the method of the present invention is hereinafter referred to as “heat treatment / contact method”.

4 g of montmorillonite (Kunipia F, manufactured by Kunimine Kogyo) was heated in an electric furnace at 230 ° C. for 3 h, and this heat-treated montmorillonite sample was epigallocatechin gallate (C ₂₂₎ equivalent to 1 mol per 1 mol equivalent of intercalated CEC of montmorillonite. The solution was taken out from an electric furnace and immediately charged into 100 ml of an aqueous solution containing H ₁₈ O ₁₁ ) or myricitrin (extract of bayberry, C ₂₁ H ₂₀ O ₁₂ ). In any sample, after the sample was dispersed in an aqueous solution in an ultrasonic bath, pure water was added to make the total volume 200 ml, and stirring was continued with a magnetic stirrer. Samples were collected 24 h and 48 h after the start of stirring, and after solid-liquid separation, the carbon and nitrogen contents in the sample were determined by CHN analysis.

  The production conditions and analysis values of the obtained samples are shown in Table 1. According to this, epigallocatechin gallate contains 12.3 mass% of carbon after 24 hours of contact, but it decreases to 5.9 mass% after 48 hours. In the preliminary experiment, the carbon content of the sample obtained by normal stirring and contact in the suspension was 5.3 mass% (after 20 days) and 4.0 mass% (40 ° C.-24 h). The carbon content after 24 hours is much higher than that value. On the other hand, the value is reduced by half after 48 hours of contact, and it is considered that epigallocatechin gallate once taken in between the layers of montmorillonite eluted into the dispersion medium when the contact time was increased.

  As with epigallocatechin gallate, in the sample contacted with myristitrin, the carbon content was 23.4 mass% (24 h) and 32.7 mass% (48 h), and the value decreased even when the contact time was increased. I never did.

  All of the natural product eucalyptus oil, origanum oil, rose oil, lemon oil and cinnamon oil were dissolved in 50 ml of ethanol, and pure water was added to make the total amount 200 ml. These were emulsified in an ultrasonic bath and stirred at 40 ° C. with a magnetic stirrer. Separately, 4 g of montmorillonite (Kunipia F, manufactured by Kunimine Kogyo Co., Ltd.) was heated at 230 ° C. for 3 hours, and this was taken out from the furnace and immediately charged, and stirring was continued. A part of the sample was collected after 24 h and 48 h, and the amounts of carbon and nitrogen were measured with a CHN coder.

  Table 2 shows the carbon and nitrogen contents of samples in which the natural product essential oil was introduced by the heat treatment / contact method. According to this, the carbon content of the cinnamon oil composite sample was 42.1 mass%, the carbon content of the origanum oil composite sample was as high as 11.0 mass%, and the carbon content of other samples was 3 to 6 mass%. % Value is shown. From the bottom surface reflection of each sample by thin film X-ray diffraction, the interlayer distance of each sample is as follows: Eucalyptus oil composite sample: 2.45 nm, Origanum oil composite sample: 1.44 nm, Rose oil composite sample: 1.77 nm, Lemon oil composite sample 1.76 nm, cinnamon oil composite sample: 2.70 nm. It can be seen that the interlayer distance of any sample is uniformly extended, and each essential oil component is introduced between the layers of montmorillonite (FIG. 1).

Synthetic pesticide cyazofamide wettable powder (C ₁₃ H ₁₃ ClN ₄ O ₂ S, trade name: Lanman Flowable) 4 g, metalaxyl wettable powder (C ₁₅ H ₂₁ NO ₄ , trade name: Ridomil wettable powder) 2 g, respectively In addition to 200 ml of pure water suspension containing 4 g of montmorillonite, the mixture was stirred and brought into contact with a magnetic stirrer at 40 ° C. A part of the sample was collected 24 hours and 48 hours after the start of contact, freeze-dried, and then the carbon and nitrogen contents were measured with a CHN coder.
Table 3 shows the preparation conditions and analysis values of the sample obtained as described above.

  According to this, the cyazofamid wettable powder composite sample contained 9.3 mass% carbon and 2.8 mass% nitrogen. The N / C ratio calculated from the chemical formula of siazofamide is 0.36, but the N / C value obtained from the analytical value is 0.3, which is close to this, confirming the presence of siazofamide between montmorillonite layers. Further, a sample obtained from metalaxyl hydrate (Lidomil) contained 2.7 mass% carbon and 0.3 mass% nitrogen. The interplanar spacing has expanded to 1.54 nm (FIG. 2). It can be seen that 2 g of Lidomil similarly contained 0.5 g (25 mass%) of metalaxyl, and 33.5% of the added metalaxyl wettable powder was complexed with montmorillonite.

A predetermined amount of caffeine (C ₈ H ₁₀ N ₄ O ₂ ) was added to pure water to 200 ml, stirred for 1 hour, and then 4 g of montmorillonite was heated at 230 ° C. for 3 hours, and this was added to the above-mentioned caffeine aqueous solution. The battery was taken out of the furnace and immediately charged. The sample suspension was stirred with a magnetic stirrer, and samples were collected after 4h and 24h and freeze-dried. The carbon / nitrogen content of the sample was determined by CHN analysis, and the change in the layer spacing due to the introduction of the layer was examined by thin film X-ray diffraction. The results are shown in Table 4.

  When caffeine was added at a ratio of 1 mole to 1 mole equivalent of intercalation CEC of montmorillonite, the carbon content of the resulting sample was 5.9 mass% after lyophilization. Moreover, when 4 mol caffeine was added with respect to 1 mol equivalent of interlayer CEC, carbon content was 6.8 mass%. Furthermore, when added in the same amount ratio and then contacted in an ultrasonic bath, the carbon content slightly increased to 7.5 mass%. In all samples, the ratio of carbon to nitrogen was almost similar to that of caffeine, and the layer spacing value increased from 0.95 nm in the dehydrated state to 1.47 to 1.61 nm (FIG. 3). It is thought that the caffeine molecule entered. Thus, by introducing the montmorillonite before heat treatment and before the condensate into the caffeine aqueous solution, caffeine can be easily introduced between the montmorillonite layers.

All 4 ml of citral (C ₁₀ H ₁₆ O), thymol (C ₁₀ H ₁₄ O), and carvacrol (C ₁₀ H ₁₄ O) were dissolved in 50 ml of ethanol, and further made up to 200 ml with pure water. Separately, 4 g of montmorillonite (Kunipia F, manufactured by Kunimine Kogyo Co., Ltd.) was heated at 230 ° C. for 3 hours, and this heat-treated montmorillonite sample was taken out from the furnace and immediately charged. Each sample was then irradiated with ultrasonic waves for 30 min, stirred with a magnetic stirrer, sampled after 24 hours, solid-liquid separation, and air-dried at 40 ° C. The carbon / nitrogen component of the sample was determined by CHN analysis, and the change in the layer spacing due to interlayer introduction was examined by thin film X-ray diffraction.

  Table 5 shows the preparation conditions and analytical values of the samples in which carvacrol, thymol and citral were introduced by the heat treatment / contact method. In the carvacrol composite sample, the bottom surface spacing value increased to 1.86 nm and contained 2.5 mass% of carbon after sample cleaning. In the thymol composite sample, the carbon content was as low as 0.2 mass%, and the bottom spacing value of montmorillonite was 1.11 nm, which was expanded by about 0.16 nm from 0.95 nm during dehydration. Further, in the citral composite sample, the interplanar spacing value is 1.69 nm, suggesting that an intercalation compound was formed (FIG. 4), but the carbon content value is as small as 0.2 mass%.

  As described above, even when water was used as the main dispersion medium of montmorillonite and carvacrol, thymol, or citral were brought into contact with each other by a heat treatment / contact method, the introduction into the montmorillonite layer did not seem to proceed much. Although only methanol was used instead of water and contact was attempted by a heat treatment / contact method, no effect was seen as in the case of using water. Thus, even if contact is made with a large amount of dispersion medium on the heat-treated montmorillonite, the expected result may not always be obtained depending on the type of organic compound. The clear cause is awaiting future research, but the present inventors have found that the heat-treated montmorillonite and the organic compound can be brought into contact with each other by using almost no dispersion medium. This will be described in Example 6.

  As described in Example 4, when water was used as a main dispersion medium of montmorillonite and an attempt was made to introduce an interlayer between citral, carvacrol and thymol by a heat treatment / contact method, the introduction was not so advanced. As described above, a dry heat treatment / contact method was tried as a method not using a dispersion medium. Predetermined amounts of citral, carvacrol, and thymol (amount calculated by associating 1 mol of organic matter with 1 mol equivalent of interlayer CEC of test montmorillonite) in an agate vessel of planetary ball mill, A montmorillonite sample heated at 3 ° C. for 3 hours was added, agate balls were added, and mixed at 500 rpm for 10 minutes. The obtained sample was taken out from the ball mill container, and then air-dried in a draft chamber at room temperature for 3 h, and then the surface spacing and the organic content were measured by thin film X-ray diffraction using a CHN coder.

  Table 6 shows the carbon and nitrogen contents of the obtained sample. According to this, the carbon content of each sample is approximately 17 mass% or more, which is significantly increased as compared with Example 4. In addition to the vicinity of 1.0 nm when water molecules do not enter between the layers, the sample layer spacing value is 1.70 nm and 3.33 nm for the citral composite sample, and 2.20 nm for the carvacrol composite sample. It is shown (FIG. 5), and this is considered to be a result of the above-mentioned organic substance brought into contact with montmorillonite being introduced between the layers. Thus, in the planetary ball mill, the method of bringing the heat-treated montmorillonite into contact with the organic compound is compared with the heat treatment / contact method using a large amount of dispersion medium tried so far, and the carbon in the obtained sample is obtained. High content. This is also because the process is performed in a closed mill vessel, so that the disappearance of raw materials can be suppressed during mixing.

Take 2 moles of methyl salicylate (C ₈ H ₈ O ₃ ) for 1 mole equivalent of intercalation CEC of montmorillonite into a planetary ball mill container, add montmorillonite heat-treated at 230 ° C. for ₃ h from the furnace, add the balls immediately After that, the contents were stirred and contacted at 500 rpm for 15 minutes. Further, methyl salicylate prepared in the same manner as described above was added to montmorillonite that had been heat-treated in the same manner and then allowed to cool in a desiccator, and stirred and contacted under the same conditions. After removing the sample from the container and air-drying at room temperature for 3 hours, the carbon content was determined. The sample added with montmorillonite immediately after the heat treatment was 11.0 mass%, and the sample added with montmorillonite after being cooled in a desiccator was 12.6 mass. %Met.

  The layer spacing value of the obtained montmorillonite sample was 1.84 nm for the sample mixed immediately after the heat treatment and 1.68 nm for the sample contacted after the heat treatment / cooling, both from 0.75 from 0.95 nm in the dehydrated state. An increase of 0.9 nm was shown (FIG. 6). In a preliminary experiment, after the methyl salicylate was dissolved in 50 ml of ethanol, the total volume was made up to 200 ml with pure water, and the sample containing carbon contained in montmorillonite that had been heat-treated at 230 ° C. was immediately put into contact with the furnace. The amount was less than 0.5 mass%. Even if it is an organic compound that is not easy to be introduced between montmorillonite layers even if it is brought into contact in a suspension state as described above, it can be easily introduced between the layers when brought into contact with a mixing device having a closed structure such as a planetary ball mill. I understand. Further, it can be seen that the heat-treated montmorillonite is not immediately brought into contact with the organic compound from the furnace, and if it is not condensed, there is no influence on intercalation.

  Cinnamon oil, citronella oil, peppermint oil, rose oil, lemon oil and origanum oil were dissolved as they were or in a small amount of ethanol, respectively, and the total amount was made up to 200 ml with pure water. 4 g of montmorillonite was heated at 230 ° C. for 3 hours, taken out of the furnace into the solution and immediately charged. All samples were then dispersed by irradiating with ultrasonic waves for 30 minutes, and then stirred with a magnetic stirrer. Samples were collected after 24 and 48 hours, separated into solid and liquid, and air-dried at 40 ° C. The carbon / nitrogen component of the sample was determined by CHN analysis, and the change in the layer spacing due to interlayer introduction was examined by thin film X-ray diffraction.

  Table 7 shows the carbon and nitrogen contents of the obtained samples. After contact with montmorillonite, the carbon content increased in any sample. When it shows with respect to the natural product essential oil which added the layer surface interval value of each sample, cinnamon oil: 1.53 nm, citronella oil: 1.43 nm, peppermint oil: 1.30 nm, rose oil: 1.77 nm, lemon oil: 1 .76 nm, origanum oil: 1.41 nm, both of which indicate that the layer spacing is wider than when montmorillonite is used alone (FIGS. 7-8). Along with the increase in the carbon content, it is considered that the components of the natural product essential oil have entered the layers and have been combined. As described above, the intrusion of the organic substance between the montmorillonite layers is promoted by performing ultrasonic treatment together when both are in contact.

Components of natural product essential oil, geraniol (C ₁₀ H ₁₈ O), terpineol (C ₁₀ H ₁₈ O), linalool (C ₁₀ H ₁₈ O), eugenol (C ₁₀ H ₁₂ O ₂ ), cinnamaldehyde (C ₉₎ H ₈ O) as it is, or in the case of hinokitiol (C ₁₀ H ₁₂ O ₂ ), add 2 ml of ethanol, put them in a planetary ball mill container, and remove montmorillonite that has been heat-treated at 230 ° C. from the furnace. Immediately added, capped and mixed at 500 rpm for 15 minutes. The sample taken out from the planetary ball mill was air-dried at 25 ° C. for 3 hours, and then the carbon / nitrogen components were determined by CHN analysis, and the change in the interlaminar spacing due to interlayer introduction was examined by thin film X-ray diffraction. Table 8 shows the carbon content of each sample.

  In all the samples, the carbon content increased uniformly (no nitrogen content was quantified in any sample). When it shows corresponding to the natural product component to which the layer spacing is added, geraniol: 2.4 nm, eugenol: 2.86 nm, hinokitiol: 1.89 nm, cinnamaldehyde: 1.71 nm, terpineol: 1.32 nm, linalool: 1. It was 31 nm. In both cases, the width was larger than 0.95 nm, which is the value of the layer spacing before contact, indicating that the natural product essential oil component was complexed with montmorillonite (FIGS. 9-10).

Take a predetermined amount of allyl isothiocyanate (C ₄ H ₅ NS), phenylethyl isothiocyanate (C ₉ H ₉ NS) and benzyl isothiocyanate (C ₈ H ₇ NS) extracted from natural products such as spices, To these, montmorillonite, which had been heat-treated at 230 ° C., was taken out of the furnace and immediately added, covered, and mixed at 500 rpm for 15 minutes. The sample taken out from the planetary ball mill was air-dried at 25 ° C. for 3 hours, and then the carbon / nitrogen components were determined by CHN analysis, and the change in the interlaminar spacing due to interlayer introduction was examined by thin film X-ray diffraction. The results are shown in Table 9.

  In any sample, not only the carbon content but also the nitrogen content increased, indicating that a complex of an isothiocyanate compound and montmorillonite was formed. In the allyl isothiocyanate composite sample, the carbon content decreased to 1 mass% after several hours, and the stability of the composite was not high. In X-ray diffraction, allyl isothiocyanate: 1.16 nm, phenylethyl isothiocyanate: 1.30 nm, and benzyl isothiocyanate: 1.13 nm were observed, indicating that an intercalation compound was formed while being unstable (see FIG. 11).

(Combining natural product essential oils)
Cinnamon oil, citronella oil, clove bad oil, thyme white oil, geranium oil, tea tree oil, lavender french oil, bergamot oil, peppermint oil, lemongrass oil (all commercially available essential oils), or 2 ml After dissolving in ethanol, pure water was added to make 200 ml. Separately, 4 g of montmorillonite (Kunipia F, manufactured by Kunimine Kogyo Co., Ltd.) was heated in an electric furnace at 230 ° C. for 3 hours, and then taken out from the electric furnace into the various organic compound solutions and immediately charged.

  Each sample was stirred with a magnetic stirrer, and after 24 hours, the sample was solid-liquid separated and then air-dried or freeze-dried, and the carbon and nitrogen components of the sample were determined by CHN analysis. Moreover, the change of the layer surface interval accompanying the penetration | invasion of the organic compound between montmorillonite layers was investigated by the thin film X-ray diffraction. Table 10 shows the carbon content and layer spacing of the sample obtained by the above method.

  According to the table, it can be seen that any natural product essential oil composite sample contains carbon. As shown below, many of the main components of such natural product essential oils are composed of the organic compounds already exemplified, and the carbon component in the natural product essential oil composite sample is considered to be due to such main components.

<Natural product essential oil name>: <Main component name>
Cinnamon oil: cinnamaldehyde citronella oil: citronellal, geraniol clove bad oil: eugenol thyme white oil: thymol geranium oil: citronellol, geraniol tea tree oil: terpenene-4-ol lavender French oil: linalyl bergamot acetate: linalyl acetate Lemongrass oil: citral cinnamon leaf oil: eugenol

  Next, the Example performed about the physiological activity evaluation by the clay mineral type composite material of this invention is shown.

(Example of clay mineral composite material with insect repellent function)
In the experiment, ten silver leaf whitefly adults were confined in a glass tube (diameter 2.5 cm, length 15 cm) closed with a cork stopper on one end and a goose cloth on the other, and the cork stopper was placed upright. went. On the lower surface of the cork stopper, 20 μl of a test sample prepared by diluting the drug substance to 10,000 ppm with ethanol was contained, and 1.5 cm square filter paper which was air-dried for about 15 minutes was attached. A light source (100w incandescent lamp) is installed above the glass tube at a position of about 20cm, and the position where the whitefly stops is divided into three parts: 0cm, 0-2cm, 2cm or more from the top (position on the bottom of the cork stopper). The number of individuals was investigated. The survey was conducted 4 times every 15 minutes until 60 minutes later. The result is shown in FIG.

  Whitefly is phototaxis, and many individuals gather around 0 cm as seen in the Cont ward. On the other hand, in the diethyltoluamide section, the number of individuals near 0 cm decreased and the number of individuals above 2 cm increased, so that it can be considered that the filter paper holding the sample was avoided. The hinokitiol group is inferior to the diethyltoluamide group, but the number of individuals near 0 cm decreased and increased in other sections, indicating that it has repellent activity against whiteflies.

One side of a glass tube having an inner diameter of 25 mm and a height of 25 mm was sealed with a wrap, and about 3 ml of 1% agar solution was added. A kidney leaf leaf disk having a diameter of 25 mm was pasted and held on the surface of the hardened agar. For plant essential oils, etc., the sample base is adjusted to a predetermined concentration with ethanol, impregnated in a qualitative filter paper (10 mm × 60 mm) affixed to the inner wall of the glass tube, and air-dried for 20 minutes. Fifteen were placed in the mouths of the flasks released. For the sample (hereinafter referred to as “composite sample” after the name of the active ingredient) brought into contact with montmorillonite by contacting each organic compound described above, a sticking agent is applied to the lower edge of the glass tube. Attached. Three hours after the start of the test, the parasitic rate on the leaf surface of whitefly was investigated, and the corrected repellent rate was calculated by the following formula. The results are shown in Tables 11 and 12.
Corrected repellent rate = (Repellent rate of treated area−Cont repellent rate) / (100−Cont repellent rate) × 100

  In the sample raw material, diethyltoluamide had the highest repellent activity, followed by geranium, cinnamon leaf, citronella, hinokitiol, and rose oil in this order. Among organic compound-montmorillonite composite samples, diethyl toluamide composite sample and geraniol composite sample have the highest activity, and the next most active group is cinnamon leaf, citronellal, citronella oil, hinokitiol, and geranium organic compound composite samples. Met. For the benzyl isothiocyanate composite sample, all of the test insects died after agonizing. Such a phenomenon is considered to have repellent activity including an insecticidal effect.

  0.5 g of a diethyl toluamide-montmorillonite composite sample was suspended in 5 ml of a 0.2% aqueous solution of polyvinyl alcohol (PVA), impregnated into a filter paper with a pipette as much as possible, and air-dried. A filter paper (length 60 cm, width 1 cm) with an organic compound composite sample attached around a rectangular frame with a height of 40 cm and a side of 15 cm is attached so that one or three or five papers are evenly spaced. It was. In this frame, green seedlings (only the primary leaves settled) were placed and allowed to stand in an insect breeding box, and then about 300 silver leaf whitefly were released. After the start of the test, the number of parasites on the kidney seedling was examined over time. The results are shown in Table 13. From this result, it is determined that the diethyltoluamide composite sample has a repellent effect by the treatment with five filter papers.

  As described above, organic compound composite samples prepared by contacting organic compounds with insect repellent activity with clay minerals have the property of gradually releasing organic compounds to the outside of the sample, and their functions over a long period of time. It can be seen that it is possible to maintain

  Next, the Example regarding tick avoidance is shown.

(Mite prevention test by the durability confirmation test method of nanosheets mite prevention material containing essential oil)
An organic compound-montmorillonite composite sample containing hinokitiol, benzylisothiocyanate, eugenol, and cinnamaldehyde was used as a sample for the mite prevention test. In addition, females of Dermatophagoides farinae were used as test ticks for the mite prevention test. The medium used was a mixture of MF powder and dry yeast shrimp at a ratio of 5: 1, and was cultured at 25 ° C. and a relative humidity of 75-80% in a constant temperature and humidity chamber.

  Each test sample was weighed 100 mg in a plastic container (φ: about 13 mm, height: about 9 mm) and exposed to the indoor environment for 1 day. A test sample was put in a φ45 mm glass petri dish together with the container, and in order to keep the humidity in the petri dish at 80%, a plastic container (φ about 13 mm, height about 9 mm) containing 500 μl of KBr saturated aqueous solution was put. Ten ticks were placed in a mesh bag containing cotton as a cushioning material using a cotton needle, sealed with a policyler, and placed in a petri dish. After sealing with parafilm and rearing in an incubator at 25 ° C. for 24 hours, the life and death of ticks were observed using a stereomicroscope to determine the mortality rate. After the test, the petri dish lid was opened and exposed to the indoor environment, and at the time of the test, 500 μl of a saturated aqueous KBr solution was put in again. The results are shown in Table 14.

  From Table 14, the montmorillonite composite samples of eugenol, hinokitiol, and cinnamaldehyde were all found to have an anti-mite effect 19 days after exposure to the indoor environment. The benzyl isothiocyanate-containing nanosheet sample was found to have an antifungal effect until after 13 days.

(Examples concerning selection test of antibacterial activity of organic compound-montmorillonite composite sample)
An antibacterial activity selection test was performed on samples obtained by bringing various essential oils into contact with montmorillonite. Each sample was weighed 100.0 mg and dispersed in 10 ml of sterilized distilled water to prepare a test stock solution. 1 ml of the test stock solution is inserted into an L-shaped test tube containing 9 ml of cation-adjusted Mueller Hinton Broth (CSMHB: Cation-Supplemented Mueller Broth) in advance to make a test solution with a final concentration of 1000 mg / l. A solution containing 1 ml of sterilized distilled water was used as a control. CSMHB is obtained by adding calcium chloride and magnesium chloride (final concentrations of 50 mg / l and 25 mg / l, respectively) to Mueller-Hinton bouillon medium (DIFCO).

Staphylococcus aureus NBRC12732 (Staphylococcus aureus) and Escherichia coli NBRC3982 (Escherichia coli) subcultured twice were used for the test. It adjusted to about 10 < ^-4 > CFU / ml with Mueller Hinton bouillon (MHB), and 0.1 ml of it was inoculated into the above-mentioned test solution for every microbial species. After shaking culture at 100 ° C. for 18-24 hours at 35 ° C., 10 μl of each test solution was transplanted to a normal agar medium (Eiken Chemical), dried, cultured at 35 ° C. for 18-24 hours, and then compared with the control Thus, those that clearly inhibited or suppressed the growth of bacteria were regarded as positive for antibacterial activity selection test. The results are shown in Table 15. As is clear from the table, antibacterial activity was observed in samples obtained by contacting hinokitiol, cinnamaldehyde, and benzylisothiocyanate with montmorillonite.

(Examples related to the evaluation of antibacterial activity value of materials compounded with organic compounds)
The minimum growth inhibitory concentration test of the organic compound composite sample that showed positive in the antibacterial activity test in Example 16 was performed. As a test method, an antibacterial product evaluation council method (1998 version) was applied. That is, 160.0 mg of each sample was weighed and dispersed in 10 ml of sterilized distilled water to obtain a test stock solution. Using the test stock solution, a 6-stage 2-fold dilution series (up to 15 stages as required) was prepared, and 1 ml of each was inserted in advance into an L-shaped test tube containing 9 ml CSMMHB and stirred sufficiently. A solution containing sterilized distilled water instead of the test stock solution was used as a control.

Staphylococcus aureus NBRC12732 (Staphylococcus aureus) and Escherichia coli NBRC3982 (Escherichia coli) subcultured twice were used for the test. Each was adjusted to about 10 ⁻⁴ CFU / ml using MHB, and 0.1 ml thereof was inoculated into the aforementioned L-shaped test tube dilution series for each bacterial species. After shaking culture at 35 ° C. for 18-24 hours and 100 rpm, visually, compared to the control, the one that clearly inhibited or suppressed the growth of bacteria was determined as growth inhibition, and the minimum concentration at which growth was inhibited was determined. The minimum growth inhibitory concentration was used. The results are shown in Table 16.

  As is clear from the table, the hinokitiol complex sample showed growth inhibitory action at a concentration of 200 mg / l against E. coli and 100 mg / l against Staphylococcus aureus, and the benzylisothiocinate complex sample against Staphylococcus aureus. On the other hand, all showed growth inhibitory action at 400 mg / l. The growth inhibitory effect of the cinnamaldehyde composite sample on the test bacteria was 1600 mg / l in MIC.

  Next, an antifungal activity test for the strawberry gray mold of the clay mineral composite material will be shown as an example relating to the mold prevention characteristics of the clay mineral composite material.

(Antimicrobial effect of essential oil components: gray mold)
In this example, commercially available benzyl isothiocyanate was used as the physiologically active substance. Apply 50 μl of gray mold with a spore concentration of 10 ⁵ cells / ml to a 90 mm petri dish (PDA medium), place a paper disk (8 mm) at the center of the petri dish, and drop 50 μl of benzylisothiocyanate diluted with DMSO. And sealed with parafilm and cultured at 25 ° C. for 7 days. After the incubation period, the inhibitory effect of the components was evaluated according to the growth inhibition status of the paper disk. That is, the growth may be completely suppressed when growing completely in the petri dish or when forming a blocking circle. In addition, when the inhibition circle was formed, the suppression situation differed depending on the degree. The components of this example completely inhibited the growth of gray mold up to a concentration of 0.155 μl / 50 μl.

On the other hand, the test using the benzyl isothiocyanate composite sample produced by the method described in Example 10 was performed as follows. 50 μl of gray mold with a spore concentration of 10 ⁵ cells / ml was applied to a 90 mm petri dish (PDA medium), and a straw filled with 0.5 g of a benzylisothiocyanate composite sample was attached to the center of the petri dish lid, from the opening of the straw The vaporized component was able to move into the petri dish. The petri dish was sealed with parafilm and cultured at 25 ° C. for 7 days. As a result, a gray mold inhibitory effect was clearly observed.

(Minimum growth inhibition test of hypha in culture medium for various natural substances against strawberry anthracnose)
Seven types of plant extracts and essential oils were used. A fungus of strawberry anthracnose fungus (Glomerella singulata, 96C-1) cultured at 28 ° C. for 5 to 10 days in a PDA medium supplemented with various substances at concentrations of 20, 50, 100, 200, 400 and 1000 ppm. Punched with a cork borer with a diameter of 5 mm, using a petri dish with 1 concentration, placed sections of 3 bacteria each. Then, it culture | cultivated at 28 degreeC for 5 days, and calculated | required minimum growth inhibitory concentration (MIC) by the presence or absence of the growth and extension of a mycelium. The results are shown in Table 17. As shown in the table, all the samples suppressed the growth of anthrax. That is, the MIC value of hinokitiol was the lowest at 50 ppm, followed by allyl isothiocyanate, benzyl isothiocyanate, phenylethyl isothiocyanate at 100 ppm, carvacrol and thymol at 200 ppm, and origanum oil at 400 ppm.

(Inhibition test of strawberry anthracnose mycelium growth in nanosheet medium containing various natural substances)
Since all the samples in Example 19 showed the effect of suppressing the growth of strawberry anthracnose fungi, 9 types of samples prepared by bringing these organic compounds into contact with montmorillonite were used. A fungus of strawberry anthracnose fungus (Glomerella singulata, 96C-1) cultured at 28 ° C. for 5 to 10 days was punched into a PDA medium added with each sample to a concentration of 100 and 1000 ppm with a cork borer having a diameter of 5 mm. Using a petri dish with 1 concentration, sections were placed one by one. Then, it culture | cultivated at 28 degreeC for 3 to 4 days, the presence or absence of the growth of a mycelium and the elongation of a mycelium were measured, and the hyphal elongation suppression rate was calculated | required. The results are shown in Table 18.

  As shown in the table, the hyphal elongation / montmorillonite NS and the phenylethylisothiocyanate / montmorillonite NS were 100%, and the following exceeded 90%. 92.8% of copper / hinokitiol / montmorillonite NS. Moreover, hinokitiol / montmorillonite NS had an extremely high hyphal elongation suppression rate of 89.7% even when added at 100 ppm.

(Minimum growth inhibition test of mycelia in medium for various natural substances against strawberry plague)
In contrast to 16 types of extracts such as plant extracts and essential oils, a chemically synthesized pesticide metalaxyl wettable powder was used as a control. Strawberry plague (Phytophthora nicotianae var. Parasitica) cultured for 5-10 days at 23 ° C. in V-8 juice agar medium with various substances added to concentrations of 20, 50, 100, 200, 400, 800 and 1000 ppm. , PY2102) was punched out with a cork borer having a diameter of 5 mm, and sections were placed on each of the three strains using a 1 dish of 1 concentration. Then, it culture | cultivated at 23 degreeC for 4 to 5 days, and calculated | required minimum growth inhibitory concentration (MIC) by the presence or absence of the growth and extension of a mycelium. The results are shown in Table 19.

  As shown in the table, the lowest MIC value was 50 ppm for allyl isothiocyanate and benzyl isothiocyanate, followed by 100 ppm for phenylethyl isothiocyanate, hinokitiol, carvacrol, and then 200 ppm for thymol and origanum oil. It was. Cinnamon oil (cinnamon oil), trans-cinnamaldehyde, citronellol, clove oil (clove-bad oil), eugenol and geraniol were 400 ppm, and citral and rose oil were 800 ppm. The MIC value of the metalloxil wettable powder of the control chemically synthesized pesticide was 50 ppm.

(Test for inhibiting the growth of strawberry plague mycelium in various medium / montmorillonite composite samples)
Extracts from plants, essential oils, and the like, and 34 composite samples obtained by contacting a chemically synthesized pesticide metalaxyl wettable powder with montmorillonite as a control were used. A fungus of Phytophthora nicotiana var. Parasitica (PY2102) cultured at 23 ° C. for 5 to 10 days on a V-8 juice agar medium to which various substances are added at a concentration of 100 and 1000 ppm has a diameter of 5 mm. Punched with a cork borer, using a petri dish with 1 concentration, and placed the sections one by one. Then, it culture | cultivated at 23 degreeC for 5 days, the presence or absence of the growth of a mycelium and the growth of a mycelium were measured, and the hyphal elongation suppression rate was calculated | required. The results are shown in Table 20.

  As shown in the table, 100% of the hinokitiol / montmorillonite composite sample and the phenylethylisothiocyanate / montmorillonite composite sample had the highest mycelial elongation inhibition rate when 1000 ppm was added to the medium. Was 95.3% of the cinnamon oil / montmorillonite composite sample and 92.0% of the thymol / montmorillonite composite sample. In addition, the metalaxyl composite sample in which the control chemically synthesized pesticide was made into a nanosheet was 91.4%.

(Effect of organic compound composite sample on strawberry)
In tupperware (capable of sealing, volume 5.2 liters), 15 strawberries (variety: Sachinoka) and benzyl isothiocyanate (BITC) composite sample were spread on a petri dish (diameter 90 mm), placed and sealed. This tupperware was treated at 10 ° C. for 1 week. One week later, the hardness and the appearance (mold) of the strawberry were investigated. The results are shown in Table 21. As shown in the table, good results were obtained even when 0.01 g was added.

  Agricultural products to which the present invention is applied and which can achieve the same effects include loquat and mandarin oranges that are frequently prone to mold, in addition to strawberries.

(Anti-fungal test of clay mineral composite material containing essential oil)
Samples obtained by bringing hinokitiol, benzylisothiocyanate, eugenol, and cinnamaldehyde into contact with each other were used as samples for the mold prevention test. As test bacteria, Aspergillus niger (NBRC6341, black mold), Penicillium citrinum (NBRC6352, blue mold), Aureobasidium pullulans (NBRC6353, blackberry), Rhizopus oryzae medium B , RPMI1640 was dissolved in distilled water, MOPS was added at a rate of 34.5 g / l, adjusted to pH 7.0 with 1M NaOH, and then sterilized by filtration with a membrane filter (pore size 0.2 μm). It was.

The sample was prepared to 20,000 to 313 μg / ml or 2,000 to 31.3 μg / ml using sterile distilled water, diluted 10-fold using a medium, and then 2,000 to 31.3 μg / ml or It adjusted to 200-3.13 microgram / ml, and was set as the test liquid. 0.1 ml of each of these test solutions was dispensed into 96-well microplates to prepare test solutions. The test bacterium was prepared using a physiological saline supplemented with 0.005% Aerosol OT to a spore concentration of 10 ⁵ cells / ml, centrifuged at 3000 rpm for 10 minutes, the supernatant was removed, and the medium was replaced with the same amount of medium. After sufficiently suspending, 0.1 ml each was inoculated into the well of the microplate in which the sample was placed (the final concentration of the sample was 1,000 to 15.6 μg / ml or 100 to 1.56 μg / ml) ). After culturing at 25 ° C. for 4 days in a thermostat, the presence or absence of mycelial growth was confirmed macroscopically, and the MIC (minimum growth inhibitory concentration) was determined. The results are shown in Table 22.

  From the table, the antifungal effect of the hinokitiol-containing nanosheet sample was clearly recognized against 4 bacterial species. Benzyl isothiocyanate, eugenol, and cinnamaldehyde complex samples are available from R.I. Antifungal effect was observed in 3 bacterial species except for oryzae.

(Effects of essential oil ingredients on browning suppression effect of cut lettuce)
2.4 ml of an essential oil base diluted with 20 ml of dimethyl sulfoxide was placed in a glass petri dish in a plastic container capable of sealing the essential oil. 20 g of cut lettuce in another glass petri dish was sealed together with 3-4 pieces and stored at 10 ° C. for 2 days. In order to clearly determine the change in color tone of the lettuce edible portion, the cut lettuce was removed from the outer leaf, particularly the dark green part. After the test storage period, the color tone of the cut lettuce was measured with a spectrocolorimeter (CM-2500d, manufactured by Konica Minolta). The change of the color tone was displayed by Hunter Lab used for the browning evaluation measurement already reported. Furthermore, in order to evaluate browning among Lab of measured value, the case where a value with the most remarkable color tone change was high was made into the parameter | index of browning.

  In the case of lettuce, since the a value varies depending on the individual quality, a control plot was set up, and individual comparisons were made using the relative values. If the a value alone is used for discoloration other than browning due to the essential oil component, the determination becomes impossible. The results are shown in Table 23. Among these, the possibility of the browning inhibitory effect was examined in order of a value, relative value, and objective. That is, the a value was 1.00 or less, the relative value was 60 or less, and in the objective, the browning situation and the thing without discoloration were determined to have a browning inhibiting effect. As is apparent from the results, it was found that the 6 components of the raw material in the sample showed a good browning inhibitory effect when lettuce was stored for 2 days.

(Effect of browning of cut lettuce of essential oil / montmorillonite composite sample)
The essential oil / montmorillonite composite material produced by the method of Example 9 was put in a 0.5 g glass petri dish, and 3-4 pieces of cut lettuce 20 g put in another glass petri dish were prepared, and these were sealed together at 10 ° C. for 2 days. saved. Evaluation of the browning inhibition effect of lettuce by the essential oil / montmorillonite composite material was performed by the method of Example 25. The results are shown in Table 24. With the exception of the eugenol / clay composite sample, all other essential oil / clay composite samples were found to exhibit browning-inhibiting effects on lettuce.

(Inhibiting effect on browning enzyme in cut lettuce of essential oil)
Typical enzymes related to vegetable browning include polyphenol oxidase (PPO) and phenylalanine ammonia lyase (PAL), and substances effective in inhibiting browning affect the activity of this enzyme. Therefore, since the essential oil evaluated in Examples 25 and 26 was considered to have an inhibitory effect on these enzyme activities, the activity was suppressed when PPO and PAL enzyme activities were measured after the treatment in the above Examples. I understood that. Thus, it became clear that the essential oil in which browning suppression was recognized in Example 26 has suppressed the function of the enzyme which acts at the time of browning of lettuce.

(Essential oil release from essential oil / clay composite sample)
0.5 mg of a geraniol / clay composite sample (20 ml) was added to a vial, and the gas phase geraniol concentration was measured with a gas chromatograph mass spectrometer (GC / MS) under the following conditions.

(GC / MS conditions)
SPME: DVD / carboxen / PDMS (Fibre film thickness: 50/30 μm, Bonding type: Viaduct type)
Extraction: 20 min headspace sampling 95 ° C
Desorption: 3.0 min 250 ° C
Column: Stabil-WAX, 60 m × 0.25 mm, 0.25 μm
Carrier gas: He (120 kPa)
Even: 70 ° C. (3 min) to 250 ° C. at 10 ° C./min, hold 10 min
Inj: 250 ° C

  As a result of the measurement, it was found that geraniol vapor corresponding to 1500 ppm was present in the gas phase of the vial, and the gas released from the geraniol / clay composite sample was the original geraniol. . That is, it is considered that the essential oil complexed with clay exists as the same essential oil vapor as before complexing when released.

  Examples of brown-denatured cut vegetables that are expected to have the same browning-suppressing effect by the essential oil / clay composite sample include lotus root, potato, sweet potato, burdock, cabbage and the like in addition to lettuce.

  Citral composite sample prepared in Example 6, rose oil composite sample prepared in Example 8, cinnamaldehyde, eugenol, linalool, geraniol, terpineol, hinokitiol composite samples prepared in Example 9, and prepared in Example 10 Each of the benzyl isothiocyanate contact samples taken was placed in a glass petri dish and placed on a silicon rubber heater whose temperature was adjusted to 25 ° C. in a draft chamber and brought into contact with the air flow flowing into the draft chamber. A small amount of a sample was collected every predetermined time from the start of contact between each sample and the air flow, and the carbon content was analyzed by a CHN coder to examine the amount of organic compounds volatilized from each sample. Changes in the carbon content of each sample are shown in FIGS. 13-14.

  Since a considerable amount of time is required for the organic compounds in each sample to be completely lost by sustained release and volatilization, the time until the initial carbon content is approximately halved is determined from the figure as the carbon half-life. The sustained release properties of the samples were evaluated. In the case of a sample that does not reach the half-life during the measurement period, a regression equation was obtained from the measurement result, and the carbon half-life was obtained by calculation. The carbon half-life of each composite sample is shown together with its corresponding organic compound name: citral: 1600 h, cinnamaldehyde: 650 h, eugenol: 750 h, linalool: 350 h, geraniol: 340 h, terpineol: 130 h, hinokitiol: 3400 h , Benzyl isothiocyanate: 150 h. Thus, when the sustained release property of the organic compound / montmorillonite composite sample prepared according to the present invention is expressed in terms of carbon half-life, it can be seen that both have a sustained release property, regardless of the difference in length.

  The organic compound / montmorillonite composite material having a physiologically active function, prepared by the method described above, was contacted with an air stream at 25 ° C. in the same manner as in Example 29, and the sustained release property was examined. The initial carbon content and carbon half-life of each sample are listed in Table 25 including those described in Example 29. Similar to the results of Example 29, it can be seen that the sustained release properties of the organic compound / montmorillonite composite sample produced according to the present invention have sustained release properties, although there are differences in length.

  As described above in detail, the present invention relates to a clay mineral composite material and a method for producing the same, and according to the present invention, an organic compound having an insect repellent function, an antimicrobial function, a freshness maintaining function, and the like is obtained by heat treatment. Immediate contact with the clay mineral from which interlaminar water has been removed enables efficient complexation with the clay mineral in an extremely short time. The organic compound-clay mineral complex obtained in this way can handle organic compounds that are unstable due to oxidation or volatilization in the air as solids. It can be processed into various forms like the body. Furthermore, organic compounds constrained by clay minerals by complexing with clay minerals have a so-called sustained release property that is gradually released to the outside of the sample, and can maintain their functions over a long period of time. Become. The clay mineral composite material provided by the present invention has various functions such as insect repellent, antibacterial and antifungal, maintenance of freshness of plants and fruits, and mite prevention in various industrial fields and daily life. It can be suitably used as a material.

It is a thin film X-ray diffraction pattern of the sample obtained by making natural product essential oil contact immediately after heat processing of a montmorillonite. It is a thin-film X-ray-diffraction pattern of the sample obtained by making a siazofamide wettable powder and a metalaxyl wettable powder contact immediately after the heat processing of a montmorillonite. It is an example of the thin film X-ray diffraction pattern of the sample obtained by making caffeine contact immediately after heat processing of a montmorillonite. It is the thin film X-ray diffraction pattern of the sample obtained by making carvacrol, thymol, and citral contact immediately from a liquid phase after heat processing of montmorillonite. It is the thin film X-ray diffraction pattern of the sample obtained by making carvacrol, thymol, and citral contact immediately in a planetary ball mill after heat processing of montmorillonite. It is the thin film X-ray diffraction pattern of the sample obtained by contacting methyl salicylate in the planetary ball mill immediately after the heat treatment of montmorillonite (top) and after cooling after heat treatment. It is the thin film X-ray diffraction pattern of the sample obtained by making cinnamon oil, citronella oil, and peppermint oil contact in a planetary ball mill immediately after heat processing of montmorillonite. It is the thin film X-ray diffraction pattern of the sample obtained by making rose oil, lemon oil, origanum oil contact in a planetary ball mill immediately after heat processing of montmorillonite. It is a thin film X-ray diffraction pattern of a sample obtained by bringing geraniol, eugenol, and hinokitiol into contact with each other in a planetary ball mill immediately after heat treatment of montmorillonite. It is a thin film X-ray diffraction pattern of a sample obtained by bringing terpineol, linalool and cinnamaldehyde into contact in a planetary ball mill immediately after heat treatment of montmorillonite. It is a thin film X-ray diffraction pattern of a sample obtained by contacting allyl isothiocyanate, benzyl isothiocyanate and phenylethyl isothiocyanate in a planetary ball mill immediately after heat treatment of montmorillonite. It is a figure which shows the insect repellent effect by the clay mineral type composite material produced by the contact of diethyl toluamide and hinokitiol. The cinnamaldehyde, eugenol, citral, and benzyl isothiocyanate composite samples are each taken in a glass petri dish, and the carbon content change of each sample when the air flow is forcibly contacted at 25 ° C. The half-life in the figure indicates the half-life of the carbon content. This is a change in the carbon content of each sample when a linalool, geraniol, terpineol, and hinokitiol composite sample are each placed in a glass petri dish and forcedly contacted with an air stream at 25 ° C. The half-life in the figure indicates the half-life of the carbon content.

Claims (12)

  Using a clay mineral having a cation exchange capacity between layers as a main raw material, it is exchanged with interlayer water between layers, and in a combination of an alkali or alkaline earth metal and an organic compound having a physiologically active function, A clay mineral composite material characterized by being introduced in a stable or metastable state.   The clay mineral composite material according to claim 1, wherein the alkali or alkaline earth metal is sodium, potassium, calcium and / or magnesium.   The clay mineral composite material according to claim 1, wherein the physiologically active function is an insect repellent function, an antimicrobial function, a freshness maintenance function, or an aroma function.   The clay mineral composite material according to claim 1, which is provided with functions of insect repellent, antimicrobial, freshness maintenance, or aroma as functionality.   A method of producing clay mineral composites by using clay minerals with cation exchange capacity between layers as the main raw material, and exchanging exchangeable cations and interlayer water between layers with different types of cations and organic compounds. In this method, after removing the interlayer water by heat-treating the clay mineral in advance, and before condensing the interlayer of the clay mineral, the clay mineral is immediately mixed with an organic compound or a solution thereof to thereby remove the clay mineral. A method for producing a clay mineral composite material, wherein an organic compound is introduced between layers.   The method for producing a clay mineral-based composite material according to claim 5, wherein the heat treatment for removing interlayer water of the clay mineral is performed by heating, microwave irradiation, or infrared irradiation.   A device or container for immediately mixing clay minerals with an organic compound or a solution thereof is a tron mill, a ball mill, a planetary ball mill, a centrifugal mill, a vibration mill, or a mortar having a structure capable of breaking contact with outside air. 5. A method for producing a clay mineral composite material according to 5.   The method for producing a clay mineral composite material according to claim 5, wherein smectite, vermiculite, or kaolin group clay mineral is used as the clay mineral.   The method for producing a clay mineral composite material according to claim 5, wherein an organic compound having an insect repellent function, an antimicrobial function, a freshness maintaining function, and an aroma function is used as the organic compound to be introduced into the clay mineral after the heat treatment.   Organic compounds having any one of insect repellent function, antimicrobial function, freshness maintenance function and fragrance function are cinnamon oil, thyme white oil, clove bud oil, cinnamon leaf oil, lavender french oil, lemongrass oil, Peppermint oil, bergamot oil, tea tree oil, geranium oil, citronella oil, rose oil, lemon oil, eucalyptus oil, origanum oil, cinnamaldehyde, eugenol, methyl salicylate, citral, allyl isothiocyanate, benzyl isothiocyanate, phenyl ethyl isothiocyanate , Linalool, menthol, geraniol, thymol, terpineol, hinokitiol, diethyl toluamide, cyazofamide, metalaxyl, epigallocatechin gallate, myricitrin, caffeine In a method for producing a clay mineral composite material according to claim 9.   The method for producing a clay mineral composite material according to claim 5, wherein the interlayer cation of the clay mineral is sodium, potassium, calcium, or magnesium.   A functional product, wherein the clay mineral composite material according to any one of claims 1 to 4 is used as a functional material.