JP2007112779A - Antimicrobial agent consisting of oil of condensate obtained from drying process of japanese cedar lumber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antimicrobial agent comprising an oil obtained by separation/recovery using a cheap separation method from a condensate obtained by cooling the exhaust discharged when drying a Japanese cedar lumber. <P>SOLUTION: This antimicrobial agent uses an oil obtained by either one of a method in which the condensate obtained by drying a Japanese cedar lumber, favorably "obisugi" Japanese cedar lumber, Cryptomeria japonica, is left at rest and the supernatant oil is decanted, a method in which solvent extraction is used, or a method in which the condensate is adsorbed in an adsorber column made of a synthetic resin and is desorbed later. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antibacterial agent comprising an oil separated from a condensate obtained by cooling exhaust gas discharged from a discharge port in a step of drying cedar wood.

  Sugi is produced and used in large quantities for construction lumber. In recent years, wood dryers that use water vapor as a heating source have been widely used for artificial drying of cedar wood. Moisture in the cedar wood is exhausted from the exhaust port of the wood dryer by heating. Although there are not many examples in which useful components in the exhaust gas are collected, Non-Patent Document 1 and Patent Document 1 can be cited. In Non-Patent Document 1, domestically produced cedar wood is dried using steam as a heating source under the conditions of high temperature drying at a maximum temperature of 120 ° C and medium temperature drying at a maximum temperature of 80 ° C. ing. For the purpose of examining the suitability of exhaust waste liquid (condensate) to the drainage standards, we are investigating water pollution items of the obtained condensate. The condensate obtained by drying cedar has pointed out problems that the biochemical oxygen demand (BOD) and the amount of normal hexane extract exceed the drainage standard. The amount of normal hexane extract is reported to be 15 mg for high temperature drying at a maximum temperature of 120 ° C. in 1 liter of condensate and 14 mg for medium temperature drying at a maximum temperature of 80 ° C. In Non-Patent Document 1, in addition to domestically produced cedar wood, water pollution items of condensate of bay pine wood, pine wood wood, and asiata pine wood are measured. Condensed liquid of Asiatapine material is analyzed by constituent sugar analysis, component analysis by gas chromatography mass spectrometry (GCMS) of ethyl acetate extract, and has ammonia deodorization effect, plant growth promotion effect and cement setting adjustment effect States that. However, it does not mention the use of condensate from other materials including cedar, and hardly mentions the components contained therein. Patent document 1 is a patent of the content which uses a lower water layer which obtained condensate by cooling of the discharge | emission steam of a cedar material drying process, and removed the oil component (wood essential oil) as a deodorizer. It has been clarified that acetic acid and propionic acid contained in the condensate cause a neutralization reaction with amines and reduce amine gas concentration to deodorize. However, Patent Document 1 does not touch on the content or use of the removed oil.

On the other hand, essential oils obtained from various trees have various physiological activities and have unique fragrances, so they are used in various applications such as fragrances, essential oils for aromatherapy, bathing agents, antibacterial agents, etc. . When the essential purpose is to extract essential oil obtained from cedar wood, cedar wood essential oil is generally produced by steam distillation or solvent extraction of the wood. It is known that cedar wood essential oil already has antibacterial activity, acaricidal activity, anti-ant activity, and the like (see Non-Patent Documents 2 to 9). Patents listed in Patent Documents 2 to 4 include descriptions of antibacterial agents, acaricides, and preservatives for ophthalmic preparations containing essential oils from cedar leaves and materials. However, the essential oils and extracts used in these documents are either obtained by steam distillation of cedar wood or leaves, or obtained by extraction with a solvent such as hexane and then concentration. For this reason, there is a problem that the production price of cedar essential oil is high due to the cost of equipment and operation of the steam distillation apparatus and a large amount of extraction solvent. In commercialization of cedar essential oil, there is a problem that usage and method are limited due to cost. Moreover, about the dry condensate of domestic cedar wood in the nonpatent literature 1 relevant to this invention, normal hexane extract amount is reported to be 14-15 mg in 1 liter, and it can be said that the obtained oil content is quite low. . For this reason, it is thought that there are still many difficulties in using the obtained oil for industrial use as it is in the method of Non-Patent Document 1.
JP 2005-87614 A JP 2004-238316 A JP-A-6-239714 JP 2002-37747 A Japanese Patent No. 2681808 Japan Housing and Wood Technology Center, “Fiscal 2004 Innovative Technology Development Promotion Project for Wood Utilization” (FY 2004 Subsidy Project of Ministry of Agriculture, Forestry and Fisheries), March 2005, p. 5-29 Tree Extraction Component Utilization Technology Research Association, "Tree Extraction Component Utilization Technology Research Results Collection", Tree Extraction Component Utilization Technology Research Association (1995) S. -S. Cheng et al., “Bioactivity of selected plant essential oils against the yellow fever mosquito Aedes aegypti larvae”, Bioresource Technology 89, 200 years. 99-102 J. et al. Morizawa et al., "Repellents in the Japan cedar, Cryptomeria japonica, against the pill-bug, Armadillium vulgare, Bioscience, Biotechnology, 66. 2424-2428 X. H. Chen et al., “Antified against Aske despair from the Japan cedar, Cryptomeria Japan II,” Bioscience, Biotechnology, and Biochemistry 65, 1 1434-1437 Akiyoshi Sogabe et al., “Anticide component of Cryptomeria japonica D. Don”, Journal of the Wood Society, 2000, 46, 2, p. 124-131 Shinichi Morita et al., “Anti-mite active ingredient in hexane extract of Yakusugi soil buried wood”, Journal of the Wood Society, 1994, Vol. 40, No. 9, p. 996-1002 Yatsugai Mitsukatsu et al., “Extracted Yakusugi-Embedded Wood and Its Acaricide / Plant Growth Control Activity”, Journal of the Wood Society, 1991, 37, 4, p. 345-351 Shinichi Morita et al., “Acaricidal and antibacterial activity of hexane extract of Yakusugi soil buried wood”, Journal of the Wood Society, 1991, Vol. 37, No. 4, p. 352-357

  The problem to be solved by the present invention is that the condensate obtained by cooling the exhaust exhausted from the drying process of cedar is used as a raw material, and oil is separated by a method that can be produced in a large amount and at low cost. The object is to provide an antibacterial agent comprising a liquid oil.

  The inventors have found that the oil separated from the condensate obtained by cooling the exhaust gas discharged from the drying process of cedar (Cryptomeria japonica) material has antibacterial activity against bacteria, and solved the problem. That is, many cedar varieties are known, and any oil separated from the condensate obtained by cooling the exhaust discharged from the drying process of any cedar wood has antibacterial activity.

  For the problem of inexpensively producing a large amount of oil from cedar dry condensate, it is advantageous to use a condensate collected when drying cedar varieties with a high oil content. Examples of cedar varieties having a high oil content in the lumber include Obisugi and Yakusugi. Obisugi materials are already widely used in the production of dried cedar materials using steam as a heating source mainly in Miyazaki Prefecture, so that a large amount of dried condensate can be collected and is particularly preferable as a raw material of the present invention. There are about 15 varieties of obis, arakawa, haara, edanaga, garin, hinoki maki, mizorogi, hiki, tosaaka, tosagro, chirimendosa, black, tsukitsuki, tanaka, ganbei, etc., but these varieties It can be preferably selected from among the above. In the description of the present invention, when simply referred to as Obisugi material, it refers to any material of these varieties or a mixture of varieties. In addition to Obisugi, cedar varieties containing many essential oil components such as Yakusugi can be used as well, and are included in the Obisugi variety group of the present invention.

  In the present invention, the oil recovery method of the cedar dry condensate may include liquid separation recovery, extraction recovery, and adsorption recovery. First, a method of leaving the condensate and separating and recovering the oil floating in the upper layer can be mentioned as one of simple methods. In the case of this separation recovery, some oil remains as fine oil droplets in the water layer from which the oil has been separated. Therefore, when the purpose is to separate a larger amount of the condensate oil, a method of extracting the condensate with an organic solvent such as hexane or ethyl acetate and concentrating as necessary can be performed. Further, the oil can be adsorbed through an aqueous layer through an adsorbent column manufactured from a synthetic resin, and then desorbed using an organic solvent or the like, and concentrated as necessary to obtain the oil of the present invention. . This adsorption recovery method is advantageous in that the amount of solvent used can be reduced as compared with the extraction method using only the solvent. Specifically, the amount of oil that can be recovered from the dried coniferous condensate varies depending on the separation method, but is approximately 0.9 to 1.3 g per liter. Although the varieties of domestically produced cedar wood in Non-Patent Document 1 are not specified, the hexane extract of the dried condensate was about 0.015 g per liter. Compared with this, if the dried condensate of the material of the Obisugi variety group is used, at least tens of times as much oil can be collected, which can be used particularly preferably in the present invention. It was confirmed that the oil from the dried coniferous condensate produced had antibacterial activity against bacteria and could be used as an antibacterial agent composed of the condensate dried condensate oil, and completed the present invention. It was.

  That is, one of the preferred embodiments of the present invention is an antibacterial agent comprising an oil component separated from a condensate obtained by cooling exhaust discharged from a discharge port in the step of drying cedar wood.

  As described above, cedars of the Obisugi variety group can be particularly preferably used in the present invention because a large amount of dry condensate can be collected. One of the particularly preferred embodiments of the present invention is an antibacterial agent comprising an oil separated from a condensate obtained by cooling the exhaust gas discharged from a discharge port in a drying process of a material comprising cedar varieties, and a method for producing the same. is there.

  A suitable drying temperature for cedar wood, particularly preferably wood made of cedar varieties, is in the range of 60-140 ° C. Therefore, one of the preferred embodiments of the present invention is an antibacterial agent comprising an oil separated from a condensate and a method for producing the same, wherein the drying temperature is in the range of 60 to 140 ° C.

  Moreover, one of the preferable embodiments of the present invention is an antibacterial agent comprising an oil component separated from the upper layer by standing the above-mentioned cedar wood and the condensate obtained at the drying temperature, and a method for producing the same.

  One of the preferred embodiments of the present invention is an antibacterial agent comprising the above-mentioned cedar wood, an oil component obtained by extracting the condensate obtained at the drying temperature with a solvent, and a method for producing the same. Among them, more preferred are an antibacterial agent comprising an oil obtained by using an organic solvent as a solvent and a method for producing the same. Particularly preferred is an antibacterial agent comprising an oil obtained by extraction with an organic solvent, followed by concentration and separation, and a method for producing the same.

  Also, one of the preferred embodiments of the present invention is an antibacterial agent comprising the above-mentioned cedar wood, an oil component separated and separated by treating the condensate obtained from the drying temperature with an adsorbent to adsorb the oil component, It is a manufacturing method. In the case of this adsorption method, one of the more preferred embodiments is an antibacterial agent comprising an oil obtained by using a synthetic resin-based adsorbent and a method for producing the same, and particularly preferably a crosslink having no ionic group. An antibacterial agent comprising an oil obtained using a polymerized porous resin and a method for producing the same. Furthermore, a method using a solvent can be employed in the present invention as a desorption method. As a preferable solvent, water vapor or warm water can be used in addition to the organic solvent. Particularly preferred are organic solvents. Accordingly, one of the preferred embodiments of the present invention is an antibacterial agent comprising an oil component that has been adsorbed using the above-mentioned adsorbent and then separated by desorption and concentration using an organic solvent or the like.

  The oil separated from the condensate discharged from the cedar wood drying process obtained by the above-described method of the present invention is extremely safe and exhibits an excellent antibacterial effect against various microorganisms. Therefore, the oil of the present invention obtained by the various processes described above may be used alone as an antibacterial agent. Further, as long as the effects of the present invention are not impaired, other known antibacterial agents and preservative components such as hinokitiol and benzoic acid are used in combination as antibacterial agents, such as pharmaceuticals, cosmetics, foods, industrial products, and household products. It can be used in a wide range of fields.

  Furthermore, when actually used as an antibacterial agent, the dosage form of the antibacterial agent is not particularly limited, and it can be appropriately prepared in any form such as a solution, paste, powder, or block. When a surfactant is added to the cedar dry condensate oil component of the present invention, a uniformly dissolved aqueous solution or emulsified aqueous solution can be obtained by adjusting the type and addition amount of the surfactant and can be used as a water-soluble antibacterial agent. it can. As the type of the surfactant, any of anionic, cationic, amphoteric or nonionic types can be used. In addition, since the antibacterial active ingredient of the present invention stably exhibits an antibacterial effect both in a water-soluble state and dissolved in an organic solvent, it is not limited to the selection of the dosage form, and is supported on a carrier. It can also be prepared in a dosage form for sustained release using the vapor pressure. In addition, by applying a method of encapsulating an oily liquid in a microcapsule, a microcapsule of the cedar material dried condensed liquid oil of the present invention can be prepared and used. As is obvious from the above, one of the preferred embodiments of the present invention is that the oil separated from the condensate obtained from the above step by the above-mentioned method is formed into a dosage form such as a solution, paste, powder, or block. An antibacterial agent form prepared.

  Thus, the antibacterial agent comprising the oil of the present invention is, for example, in the form of a mixture with dry ice, a sterilization / antibacterial spray, or an air shower device, in the form of a spray, such as food, pharmaceuticals, cosmetics, industrial products, and household products. It can be used in a wide range of fields. That is, one of the preferred embodiments of the present invention is an antibacterial propellant in which the oil separated from the condensate obtained from the above step by the method described above is used in a spray form.

  It can be used as anti-corrosion agent for food waste from households and pets in the food industry and households, and as an antibacterial agent for spraying livestock and pets. One of the preferred embodiments of the present invention is an antibacterial spraying agent that sprays oil separated from the condensate obtained from the above-described process by the above-described method to an anti-corruption agent for raw garbage, livestock or a pet building. is there.

  Moreover, it can utilize as an antimicrobial paint which mix | blends the oil of this invention in the coating-material field | area. Accordingly, one of the preferred embodiments of the present invention is an antibacterial paint that contains oil separated from the condensate obtained from the above process by the method described above.

  ADVANTAGE OF THE INVENTION According to this invention, the oil component isolate | separated and collect | recovered by the method of this invention from the condensate obtained by cooling and collecting the exhaust gas of a cedar material drying process can be utilized now as an oil component which has antibacterial activity. As cedar varieties, the use of cedar timber from the Obisugi cultivar group, which is a cultivar with a high essential oil content, is advantageous in that the amount of oil separated from cedar timber can be increased. By using the condensate of by-products (waste materials) from the cedar wood drying process, compared to the solvent extraction method and steam distillation method, which are existing techniques for collecting essential oils of trees such as cedar wood, raw material costs and oil separation / There is a merit that the recovery cost is extremely low. Thus, the antibacterial agent composed of the oil separated from the cedar dry condensate that can be practically and mass-produced can be provided in various usage forms. In addition, it is possible to provide effective and effective water pollution countermeasures for by-products (waste materials) from the cedar wood drying process. The effect of the present invention is particularly remarkable when applied to Obisugi materials.

  The antibacterial agent consisting of the oil component of the condensate obtained in the drying process of the biscuits of the present invention was manufactured by the manufacturing method described in the following item 1. The efficacy of the antibacterial agent of the present invention was evaluated by the following two methods.

1. Separation of oil from condensate obtained in the drying process

(1) Recovery of coniferous condensate The condensate can be recovered from the cedar drying process from a steam drying type wood dryer generally used for drying wood. The outlet of the dryer usually has a structure that releases the exhaust as it is to the outside air. For this reason, it may be improved so that the exhaust duct can be extended and cooled by air cooling, or a water-cooled condenser can be connected to the exhaust port so that the exhaust can be cooled and recovered as condensate. The drying temperature of the cedar wood is not particularly specified in the present invention. In general, a temperature of 60 to 140 ° C. is used as a drying condition, and the drying temperature is often changed according to the elapsed time of drying, but the condensate may be collected throughout the entire drying period. However, since the water vapor is introduced into the dryer at the start of drying to increase the temperature in the dryer, the condensate collected at this time contains almost no organic compound. Therefore, it is possible to preferably increase the oil content by stopping cooling and collecting the exhaust gas at the start of drying and starting collecting the condensate after the temperature inside the dryer rises to near the drying temperature. The condensate obtained by cooling exhibits a state in which an oil layer floats in the upper layer, minute oil droplets are dispersed in the aqueous layer, and turbidity is observed. Although the condensate can be recovered by drying any kind of cedar wood, it is preferable to collect the condensate from the drying process of yakusugi or obisgi, which is known to contain a large amount of essential oil components. Varieties in which dry cedar wood is widely produced in large quantities, such as Obisugi, are preferable because the condensate as a raw material can be obtained in large quantities at low cost. The amount of oil that can be recovered from the dried coniferous condensate varies depending on the separation method as shown below, but was about 0.9 to 1.3 g per liter.

(2) Separation of oil by separation of condensate supernatant When the condensate is allowed to stand for several days, separation of the oil layer and the water layer proceeds. The condensate oil can be separated by separating the upper oil layer. This oil can be used without any special treatment. In the remaining water layer, fine oil droplets are dispersed and turbidity is observed, and there is an oil component that cannot be recovered by separating the oil layer. The oil obtained by this method is called the condensate oil.

(3) Separation of oil by organic solvent extraction of condensate or water layer below condensate. Condensate or water layer remaining after the operation described in (2) is mixed with 0.05 to 5.0 parts of hexane or ethyl acetate. After stirring and extracting with such an organic solvent for 0.2 to 10 hours, preferably 1 to 3 hours, the organic solvent layer is separated after standing. If this operation is repeated 1 to 5 times, preferably 1 to 2 times, the oil can be extracted with an organic solvent. The extracted organic solvent layer is dried with a desiccant such as anhydrous sodium sulfate, anhydrous magnesium sulfate, and anhydrous calcium chloride and then concentrated to obtain a condensate extract. Extraction with low-polarity hexane cannot extract highly polar organic substances in the condensate, so extraction with a highly polar solvent such as dichloromethane, chloroform, or ethyl acetate after extraction with hexane makes it possible to recover most oils. Become. The amount of oil that can be recovered is affected by the varieties of cedar wood used as a raw material, but the hexane extract from the Obisugi wood steam-dried condensate of the present invention is 1.0 g or more per liter. The amount of hexane extract of the domestically produced cedar steam dried condensate performed in Non-Patent Document 1 is 0.014 to 0.015 g per liter, which is different from the present invention. Of course, a method of extracting from the beginning with dichloromethane, chloroform, ethyl acetate or the like without performing hexane extraction may be used. The oil obtained by extracting the condensate by this method is called a condensate solvent extract.

(4) Separation of oil by adsorption / desorption of condensate or water layer below condensate into a condensate or a column packed with hydrophobic adsorbent resin particles in the water layer remaining after the operation described in (2) Adsorb through a column and drain the column water, then elute with an organic solvent such as methanol, acetone, or ethyl acetate, and dry the eluate with a desiccant such as anhydrous sodium sulfate, anhydrous magnesium sulfate, or anhydrous calcium chloride. After concentrating, a condensate adsorbed separation is obtained. A wide variety of resins can be used as the hydrophobic adsorptive resin particles as long as they are crosslinked polymerized porous resin particles having no ionic group. For example, cross-linked polystyrene resin, resin obtained by halogenating cross-linked polystyrene, cross-linked polyethylene resin, cross-linked polypropylene resin, cross-linked poly (methacrylic ester) resin, cross-linked poly (acrylic ester) resin can be used, or cross-linked copolymers thereof. Resin particles can also be used. The oil can be adsorbed through 50 to 1000 parts of the condensate on the column of 1 part of the adsorbent resin particles, but preferably 50 to 200 parts with respect to 1 part of the adsorbent. The adsorption resin column in which the oil is adsorbed through the condensate removes the water of the adsorption resin particles sufficiently filled by flowing air or nitrogen for a while. Thereafter, an organic solvent such as methanol, ethanol, acetone or ethyl acetate is flowed to desorb the adsorbed oil. Alternatively, it is also effective for desorption to sequentially change a plurality of types of solvents to flow or to flow as a mixed solvent. The amount of the organic solvent to flow is set to the time when organic substances can no longer be confirmed from the distillate. Compared with the extraction method using an organic solvent, the method using an adsorption separation using a hydrophobic adsorption resin can reduce the amount of the organic solvent used. The oil obtained from the condensate by this method is called a condensate adsorbed separation.

2. Antibacterial action on bacteria of oil obtained from condensate The antibacterial effect of oil obtained from condensate can be confirmed by either a method using an agar medium or a method using a liquid medium. Also good. In the present invention, from the condensate according to “Minimum Growth Inhibitory Concentration (MIC) Measurement Method (revised in 1981)” (Chemotherapie, 1981, 29, No. 1, p. 76-79) determined by the Japanese Society of Chemotherapy. Using a test medium in which the obtained oil was added to the medium by a 2-fold dilution method, precultured bacteria were inoculated, and after 48 hours at 30 ° C., the presence or absence of colony formation was determined to determine the MIC value. The antibacterial test was carried out as Bacillus subtilis subsp. subtilis NBRC 13719, Micrococcus luteus NBRC 3333, Mycobacterium vaccae NBRC 14118, Staphylococcus epidermidis NBRC 12993, and also gram Escherichia coliK-12NBRC 3301 as negative bacteria, Proteus mirabilis NBRC 13300, Pseudomonas fluorescens NBRC 3757, Ralstonia solanearum No. 8224 was used. R. Solanearum is a phytopathogenic bacterium that causes bacterial wilt in solanaceous plants such as tomatoes. In addition, some other bacteria have been pointed out as possible opportunistic infections. The above oil separation method 1. The oil content of any of the condensates obtained in (2) to (4) showed antibacterial action against gram-positive bacteria at 1024 μg / mL or less. In the case of gram-negative bacteria, P. mirabilis and R.M. Solanearum exhibits an antibacterial action at 1024 μg / mL or less, and is considered to be usable for various purposes as an antibacterial agent.

  The following examples illustrate the present invention in more detail.

  56 Obisugi cored squares (130 × 130 × 3000 mm) from Miyazaki Prefecture were placed in a wood dryer (model MHB-5MR, manufactured by Kyushu Olympia Co., Ltd.), and high temperature drying was performed according to the following schedule. First stage: dry bulb temperature 90 ° C. (7 hours), then dry bulb temperature 85 ° C. (17 hours), second stage: dry bulb temperature 120 ° C., wet bulb temperature 95 ° C. (27 hours), third stage: dry bulb Temperature 110 ° C., wet bulb temperature 90 ° C. (49 hours), fourth stage: dry bulb temperature 100 ° C., wet bulb temperature 80 ° C. (49 hours). The exhaust gas discharged from the second stage through the fourth stage from the dryer outlet was cooled to about 50 ° C. or less through a water-cooled condenser, and the liquefied solution was collected and used as a cedar dry condensate. The pH of the condensate was 3.3.

  After 10 L of cedar condensate was allowed to stand for 1 week, the upper oil layer was separated to obtain a condensate oil as about 9.5 g of a light brown oil. The obtained condensate oil component was analyzed for components by gas chromatograph mass spectrum (GCMS) measurement. GCMS measurement was performed using a gas chromatogram mass spectrometer GCMS-QP2010 (Shimadzu Corporation). GCMS measurement conditions are: sample concentration 10 mg / mL (solvent is ethyl acetate), capillary column DB-WAX (0.25 mm inner diameter, length 30 m, coating thickness 0.25 μm, J & W Scientific), carrier gas He, column gas flow rate 1.0 mL / min, split ratio 30/1, injection temperature 250 ° C., constant temperature bath temperature change [40 ° C. (1 minute hold), temperature rise to 40-245 ° C. (temperature increase rate 10 ° C./min, 1.0- 21.5 minutes), 245 ° C. hold (21.5-50 minutes)], interface temperature 250 ° C., nuclear quadrupole mass meter detector, ion source temperature 200 ° C. The measurement results are shown in FIG.

  1000 mL of cedar dry condensate was placed in an Erlenmeyer flask, and 200 mL of hexane was added. A stir bar was placed therein, and the mixture was stirred for 1 hour at room temperature on a magnetic stirrer. Thereafter, the solution was separated into an organic layer and an aqueous layer with a separatory funnel. For the aqueous layer, the same hexane extraction operation was repeated twice more. To the combined hexane extracts, anhydrous sodium sulfate was added and dried, and then sodium sulfate was removed by filtration. The solvent was distilled off from the filtrate under reduced pressure to obtain 1.10 g of a light brown oily hexane extract.

  200 mL of ethyl acetate was added to the aqueous layer remaining after hexane extraction. A stir bar was added and the mixture was stirred on a magnetic stirrer at room temperature for 1 hour. For the aqueous layer, the same ethyl acetate extraction operation was repeated two more times. To the combined ethyl acetate extract, anhydrous sodium sulfate was added and dried, and then sodium sulfate was removed by filtration. The solvent was distilled off from the filtrate under reduced pressure to obtain 0.187 g of a light brown oily ethyl acetate extract.

  GCMS measurement of the obtained hexane extract and the ethyl acetate extract of the residual aqueous solution after hexane extraction was carried out in the same manner as in Example 1. The measurement results are shown in FIGS.

The cedar wood dry condensate 2000mL was put into the Erlenmeyer flask, and ethyl acetate 400mL was added. A stir bar was placed therein, and the mixture was stirred for 1 hour at room temperature on a magnetic stirrer. Thereafter, the solution was separated into an organic layer and an aqueous layer with a separatory funnel. For the aqueous layer, the same ethyl acetate extraction operation was repeated two more times. To the combined ethyl acetate extract, anhydrous sodium sulfate was added and dried, and then sodium sulfate was removed by filtration. The solvent was distilled off from the filtrate under reduced pressure to obtain 1.23 g of ethyl acetate extract as a light brown oil. The results of GCMS measurement of the obtained ethyl acetate extract in the same manner as in Example 1 showed almost the same spectrum as the GCMS chromatogram of the condensate oil in Example 1, and no difference was found in the components contained. .

HP20 (specific surface area 600 m ² / g, pore radius 20-30 nm, manufactured by Mitsubishi Chemical Corporation) was used as a crosslinked polystyrene-based synthetic adsorption resin. 20 g of HP20 vacuum-dried overnight was taken, and methanol was added to make a suspension. This was poured into a glass column tube (2.0 cm ID × 30 cm) with a glass wool stopper, and washed with 100 mL of methanol from above. Further, 150 mL of a mixed solvent of methanol: distilled water = 1: 1 and 500 mL of distilled water were sequentially flowed to replace with distilled water. The water surface in the column was lowered to the upper surface of the adsorbent, and 1000 mL of the condensate was allowed to flow at a flow rate of about 40 mL / min to adsorb the oil. The aqueous solution distilled from the column was used as the adsorption residue. After all the condensate had flowed, a rubber stopper having a gas inlet was provided at the top of the column, and nitrogen gas was flowed to remove as much water as possible in the column. 150 mL of methanol was passed through the column to desorb and elute the adsorbate. Next, 150 mL of ethyl acetate was flowed to elute the adsorbate completely. The combined eluate was concentrated under reduced pressure. Since a small amount of water remained in the concentrate, the concentrate was dissolved in ethyl acetate and dried over anhydrous sodium sulfate. Sodium sulfate was removed by filtration, and the filtrate was concentrated again under reduced pressure to obtain 1.17 g of an HP20 adsorbed product as a pale brown oil-buddha. FIG. 4 shows the GCMS measurement results of the obtained HP20 adsorption / separation product. The GCMS chromatogram of the condensate oil component of Example 1 was almost the same as that of the GCMS chromatogram, and no difference was found in the contained components.

The adsorption resin is HP20 to crosslinked polystyrene resin SP700 (specific surface area 1200 m ² / g, pore radius 9 nm, manufactured by Mitsubishi Chemical Corporation), brominated crosslinked polystyrene resin SP207 (specific surface area 600 m ² / g, pore radius 8 − 12 nm, manufactured by Mitsubishi Chemical Co., Ltd.) and crosslinked polymethyl methacrylate resin HP2MG (specific surface area 500 m ² / g, pore radius 20-30 nm, manufactured by Mitsubishi Chemical Co., Ltd.). An adsorption separation product was obtained in the same manner. The light brown oily adsorption separation obtained from 1000 mL of the condensate was 1.10 g for SP700, 0.81 g for SP207, and 1.20 g for HP2MG.

  100 mg of the oil (test sample) of the condensate prepared in Examples 1 to 4 was taken into a sample tube, and 2.5 mL of ethanol was added to dissolve well, and sterile filtered through a 0.22 μm membrane filter to obtain 40 mg / mL. A test sample ethanol solution having a sample concentration of was prepared. A predetermined amount of a test sample ethanol solution was added to and mixed with 20 mL of autoclaved Mueller Hinton agar medium, poured into a petri dish, cooled to room temperature, and an agar plate test medium was prepared. The test sample concentration of the test medium was prepared as a 2-fold dilution series from 4096 μm to 128 μm. Similarly, three petri dish test media were prepared for one concentration series.

The test bacteria were introduced with a platinum loop from a sloped medium for storage into a test tube containing 10 mL of sterilized Mueller Hinton liquid medium. Static culture was performed at 30 ° C. for 48 hours to prepare a preculture solution. A calibration curve in which the relationship between turbidity (660 nm) and the number of bacteria (CFU) was plotted was prepared for each bacterium. The number of bacteria was determined from the turbidity of the preculture and diluted with sterile saline to a bacterial concentration of about 10 ⁶ CFU / mL. This bacterial solution was smeared on the test medium and then statically cultured at 30 ° C. for 48 hours. After 48 hours, the presence or absence of bacterial colonies was determined and the minimum inhibitory concentration (MIC) was determined. In addition, it confirmed using the blank culture medium which added only ethanol that there was no influence on bacterial growth by ethanol used for melt | dissolution of a test sample. Moreover, MIC was calculated | required by the same method using ampicillin sodium salt and chloramphenicol which are commercially available antibiotics as a positive control. The antibacterial test results are summarized in a table.

The oil content of the cedar dry condensate having antibacterial activity of the present invention is mainly composed of essential oil components contained in the cedar wood, and since it can be expected to be highly natural and safe, it can be sterilized by mixing or applying it. It is useful for producing products that require antiseptic effects. For example, it can be used as an anti-corrosion agent for garbage from the food industry and households, and as an antibacterial agent to be sprayed on livestock or pet buildings. Moreover, it can utilize as an antimicrobial paint which mix | blends the oil of this invention in the coating-material field | area. In addition, it is possible to provide effective and effective water pollution countermeasures for by-products (waste materials) from the cedar wood drying process. Since the effect of the present invention is particularly remarkable when applied to Obisugi materials, the industrial applicability increases.

2 is a GCMS chromatogram of the condensate oil obtained in Example 1. FIG. The vertical axis represents total ion chromatography (TIC), and the horizontal axis represents retention time (minutes). 2 is a GCMS chromatogram of the condensate hexane extract obtained in Example 2. FIG. It is a GCMS chromatogram of the ethyl acetate extract obtained by extracting the condensate obtained in Example 2 with hexane and then extracting with ethyl acetate. 4 is a GCMS chromatogram of the HP20 adsorption separated product obtained in Example 4.

Claims (12)

  An antibacterial agent consisting of oil separated from the condensate obtained by cooling the exhaust gas from the cedar drying process.   The antibacterial agent comprising an oil according to claim 1, wherein the cedar material is a material made of cedar from the Obisugi variety group.   The antibacterial agent comprising an oil according to any one of claims 1 to 2, wherein the drying temperature is in the range of 60 to 140 ° C.   The antibacterial agent comprising an oil according to any one of claims 1 to 3, wherein the condensate is allowed to stand to separate the oil layer.   The antibacterial agent comprising an oil according to any one of claims 1 to 3, wherein the condensate is extracted with an organic solvent and separated.   The antibacterial agent comprising an oil according to any one of claims 1 to 3, wherein the condensate is treated with an adsorbent to adsorb an oil, and then desorbed and separated from the adsorbent.   A method for producing an antibacterial agent comprising an oil separated from a condensate obtained by cooling exhaust gas discharged in a cedar wood drying process.   The method for producing an antibacterial agent comprising an oil according to claim 7, wherein the cedar material is a material made of cedar from the Obisugi variety group.   The method for producing an antibacterial agent comprising an oil according to any one of claims 7 to 8, wherein the drying temperature is in the range of 60 to 140 ° C.   The method for producing an antibacterial agent comprising an oil according to any one of claims 7 to 9, wherein the condensate is allowed to stand to separate the oil layer.   The method for producing an antibacterial agent comprising an oil according to any one of claims 7 to 9, wherein the condensate is extracted with an organic solvent and separated.   The method for producing an antibacterial agent comprising an oil according to any one of claims 7 to 9, wherein the condensate is treated with an adsorbent to adsorb the oil, and then desorbed and separated from the adsorbent.

Images