JP2010024197A - Aqueous solution of saponin originating from strained lees of camellia seeds, and method of preparing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous solution that contains highly pure saponin of good quality in a high concentration extracted from strained lees of camellia seeds, as a means of more effectively making use of strained lees of camellia seeds. <P>SOLUTION: The aqueous solution of saponin originating from strained lees of camellia seeds is characterized by comprising saponin extracted from strained lees of camellia seeds by subcritical water under the conditions of a treatment temperature of 100 to 347°C, a treatment pressure of 3.0 to 22.1 MPa, and a treatment time of 1 to 30 minutes. A process of preparing the same is disclosed. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a technical field of recycling that effectively uses squeezed cocoons of cocoon seeds discharged in the process of producing cocoon oil.

  Camellia oil is produced by squeezing cocoon seeds, which are the seeds of vines, and has been widely applied since ancient times, including edible, medicinal, cosmetic and industrial uses. When cocoon seeds are squeezed in order to extract the cocoon oil, squeezed cocoons consisting of seed coats and seed nuclei from which the oil has been removed remain. For example, according to the experiments conducted by the present inventors, 70% of the squeezed koji is equivalent to 30% of the koji oil by weight. Remain. An effective reusable method as a natural resource is desired for squeezed residue remaining by this oil extraction.

  As an example of the reuse method, a means for utilizing saponin, which is a glycoside having a surface-active action, which is known to be contained in squeezed rice bran oil, can be considered. Saponin can be used for emulsification and washing because of its surface-active effect, and also has an effect of stimulating the mucous membrane (Non-patent Document 1).

  Focusing on the action of this saponin, and the saponin saponin derived from cocoon seeds and the saponins derived from them are derived from natural products and do not adversely affect the human body, crops and the environment. Research into the above uses is underway. For example, since saponin destroys the cell membrane of some organisms due to surface activity and irritation to the mucous membrane, it has an insect repellent effect, and also inhibits respiration and exhibits toxicity to aquatic organisms. The technique regarding the control agent and the pest control method (for example, patent document 1, 2, 3) which spread the composition containing this saponin in a household or agriculture is disclosed.

  The saponins derived from these vines are not only when the seeds and skins of the moths are ground and sprayed as they are (Patent Documents 1 and 2), but also when the seeds and skins are ground (Patent Documents 1 and 3) It is based on the method of processing by an organic solvent (patent document 1) and extracting and using saponin.

  On the other hand, the boundary between liquid and gas disappears at the critical point of high temperature and high pressure, and the water in the subcritical state where the temperature and pressure are close to the critical point is in a state that combines high molecular density and energy and is very reactive. Becomes higher. Since the water in this subcritical state has a very high decomposition ability, means for applying the treatment with these waters as a waste treatment method and a reusable material production method has been studied. As an example, treatment with water in a subcritical state is considered to be widely applicable to decomposition treatment of plants, fish bones and mollusk residues, raw garbage, plastics, etc. and reusable resource recovery. For example, Patent Document 4 discloses a method for producing a plant-derived raw material containing a tar-like oil component by treating plant-derived waste such as woody waste with subcritical water.

"Science and chemistry dictionary fifth edition" (1998) Iwanami Shoten JP-A-9-30916 JP2002-212020 JP 2003-342110 A Japanese Patent No. 40615544

  However, in the methods as described in Patent Documents 1 to 3, it is difficult to effectively use the saponin contained in the cocoon seeds. For example, in the method of using and squeezing squeezed rice cake as described in Patent Documents 1 and 2, it is difficult to say that the action of saponin in an unextracted state in the squeezed rice cake works effectively. Squeeze is generally squeezed from high-pressure cocoon seeds, and is pressed and densely condensed. It is estimated that it is difficult.

  Further, in the method of extracting saponin by immersing the squeezed pods of pod seeds in the water, it is difficult to extract the components from the squeezed pestle in a highly condensed state as described above. In Patent Documents 1 and 2, the content of saponin after extraction is not described, but according to the study by the inventors, a concentration of about 0.9 W / V% is obtained even when hot water is used for extraction with water. Only an aqueous solution of saponin can be obtained. If the amount of saponin extracted is small, a sufficient effect as a surfactant cannot be obtained.

  Furthermore, the method of extracting with water or hot water has a problem that it takes time for extraction. In Patent Document 2, it is described that several hours are required in the process of leaching from water. However, according to the research by the inventors, at least two hours are required for extraction with water, and time elapses in the extraction process. If this is longer, it may affect the quality of the saponin active ingredient.

  Moreover, in the method of performing extraction with an organic solvent as described in Patent Document 1, for example, the components to be extracted are limited. In addition, since a large amount of impurities are extracted, a purification step such as a column is further required for separation, which requires complexity and time, and the yield also decreases. In addition, if the organic solvent used in the extraction process remains, there is a possibility of adversely affecting the human body, crops, and environment when saponin or an aqueous solution thereof is used as a cleaning agent or an insect repellent.

  In other words, there are still problems in the use of these squeezed seeds, and the amount of use is limited. It is in a state that cannot be said as a means.

  On the other hand, supercritical water and subcritical water have a high decomposing ability, so that the squeezed rice cake condensed at high density can be decomposed. The better, the smaller the cracker can handle the material intensively, taking advantage of the high energy state. However, high-temperature and high-pressure supercritical water is very reactive and has a high oxidation ability, and thus may extract or degrade the extracted saponin. Supercritical water may decompose many organic substances into carbon dioxide in a short time. In addition, carbon dioxide is required for the treatment with water in a supercritical state, and high temperature and pressure are required. Therefore, the energy cost is very high.

  The inventors of the present invention have made researches on components that can be extracted from pomace and more effective extraction methods as means for more effectively using pomace of cocoon seeds. Then, the idea of applying the extraction method with subcritical water, which has a lower pressure and temperature than supercritical water, to the processing method of squeezed squeezed oil was further pursued. As a result, it has been found that an aqueous solution containing high-quality saponin in high purity and high concentration can be obtained by extracting the squeezed cocoon oil with subcritical water, and the present invention has been completed.

  In order to achieve the above object, the present invention provides the following saponin aqueous solution derived from squeezed potato seeds.

  The saponin-derived saponin aqueous solution of cocoon seeds according to the present invention is obtained by extracting cocoon seeds from cocoon seeds with subcritical water at a treatment temperature of 100 ° C. to 347 ° C. and a treatment pressure of 3.0 to 22.1 MPa for 1 to 30 minutes. And saponin.

  And, the saponin aqueous solution derived from squeezed cocoon seeds uses squeezed cocoons that are squeezed and condensed at high density as a raw material, so compared to the case where the seeds are used as they are or just crushed, In the saponin aqueous solution, the content of oil as an impurity and its reaction product can be kept constant. In addition, since the components are condensed at a high density, the reaction efficiency of the raw material is high in highly reactive extraction such as extraction with subcritical water.

  And since the seeds are squeezed, crushed and separated, the cross-section is exposed rather than the seeds as they are, and the subcritical water is easy to touch the pressed gap, and the reaction It is easy to happen. Therefore, various components are extracted from squeezed potato seeds at high concentrations, and various saponins are extracted at high concentrations.

  And it is extracted in a state in which decomposition and reaction of saponin are suppressed by using water in a subcritical state whose processing pressure and temperature are lower than those in the supercritical state. In the state where the pressure and temperature are above the critical point, that is, in the supercritical state, the interface between the liquid and the gas disappears, and the water has a density comparable to the liquid and a high energy comparable to the gas. Water in this state has a strong reactivity and completely reacts and decomposes organic matter into inorganic matter. In contrast, subcritical water does not lose the boundary between liquid and gas, it is water in which evaporation and condensation are repeated, and it has lower decomposition power than supercritical water, so that organic matter is completely removed. It can be dissolved, separated and taken out without being decomposed.

  And the saponin-derived saponin aqueous solution of cocoon seeds contains cocoon seed squeezed cocoon as a raw material, and therefore contains a certain amount of cocoon oil as an oil component. Furthermore, an emulsion in which this oil is dispersed in water is formed by the surface-active action of saponin. Therefore, in this saponin-derived saponin aqueous solution, the oil component acts as a spreading agent due to the surface-active action of saponin, and the adsorption efficiency is enhanced even on a surface portion having low hydrophilicity.

  And since the saponin aqueous solution derived from squeezed cocoon seeds is extracted with subcritical water, it does not contain an organic solvent or the like.

  Moreover, the saponin-derived saponin aqueous solution of cocoon seeds according to the present invention is characterized in that it contains a seed nucleus and a seed coat in a state where each cross section is exposed.

  And since it is a squeezed rice cake that contains both the seed coat and seed nucleus of the seeds that make up the cocoon seeds, and the cross-sections that are crushed by the squeezing at the time of oil extraction are exposed, both are separated. Unlike the case where the seed nucleus is used as it is covered with the seed coat as it is, the extraction with the water in the subcritical state is performed not only from the surface of the seed coat but also from the back and cross sections, from the surface of the seed nucleus, and from the cross section.

  The saponin-derived saponin aqueous solution of cocoon seeds according to the present invention is characterized by containing 0.1 to 20 W / V% of oil.

  And the saponin aqueous solution derived from squeezed cocoon seeds contains a moderate amount of oil derived from squeezed squeezed oil after oil extraction and recovery of oil, and various components are extracted from the oil by subcritical water. Has been. Moreover, since the oil component is appropriately contained, the appropriate oil component is dispersed in the aqueous solution by the surface-active action of saponin.

  Moreover, the manufacturing method of the saponin aqueous solution derived from the cocoon seed of the cocoon seed of this invention is the subcritical state water of the processing temperature of 100 to 347 degreeC, and the processing pressure of 3.0 to 22.1 MPa, the squeezing seed of the cocoon seed, It includes a step of extracting a processing time of 1 to 30 minutes.

  And the manufacturing method of this saponin saponin aqueous solution of a cocoon seed has a sufficient quality and high density | concentration saponin aqueous solution with few processes compared with the leaching by water and extraction by an organic solvent. In addition, an aqueous solution containing saponin can be obtained in a particularly high yield without saponin reacting or decomposing. In addition, a sufficient amount of saponin is extracted in a short time compared to leaching with water or extraction with an organic solvent, and there is little mixing of other substances that are decomposed by long-time treatment.

  According to the saponin-derived saponin aqueous solution according to the present invention, the saponin is extracted from the squeezed cocoon seeds that have been squeezed and condensed to a high density, and the cross section of the seeds is exposed, by highly reactive subcritical water. By using subcritical water that is efficiently extracted and less reactive than the supercritical state, an aqueous solution containing a large amount of glycoside saponins with various surface-active effects can be obtained. The action of saponin as an agent can be used effectively, and it can be suitably used for insect repellents and cleaning agents.

  Furthermore, since no organic solvent is used in the manufacturing process, it contains only natural products derived from squeezed cocoon oil, so when used as a cleaning agent or pesticide, the human body, crops, environment Does not adversely affect

  Furthermore, the squeezed cocoon oil, which is a waste product, can be effectively used as a raw material. In addition, the pomace after the saponin and other components are removed by extraction with water in a subcritical state is reduced in molecular weight and oil is removed, and can be effectively used as a fertilizer.

  Furthermore, the oil component derived from the cocoon seed is dispersed in the aqueous solution by the surface-active action of saponin, and acts as a spreading agent for the surface having low hydrophilicity. For example, in agriculture, when sprayed on an oak tree and used as an insect repellent, the sprayed aqueous solution tends to be adsorbed on the surface of the leaf where it is easy to play water.

  In addition, according to the present invention, the saponin aqueous solution derived from squeezed cocoon seeds is used to extract various and large amounts of ingredients without waste from seed coats and seed nuclei, and contains abundant ingredients including various saponins that can be used as surfactants. A saponin aqueous solution derived from the squeezed cocoon oil is obtained.

  Moreover, according to the saponin-derived saponin aqueous solution of cocoon seeds according to the present invention, oil is contained, and the oil contains various components and is close to a natural product state. In addition, when an appropriate amount of oil is contained, the function as a spreading agent for a surface having low hydrophilicity is effectively performed.

  Moreover, according to the method for producing a saponin aqueous solution derived from squeezed cocoon seeds according to the present invention, an aqueous solution containing high-concentration saponin at a high concentration is obtained, and in the process than leaching with water or extraction of saponin with an organic solvent. It is few and simple. Therefore, quality degradation is minimized even in the manufacturing process.

  Furthermore, an aqueous solution having a particularly high quality and yield of the saponin contained therein can be obtained, and the squeezed pods of cocoon seeds can be used particularly effectively as resources. In addition, the extraction is short. In addition, an aqueous solution containing various and large amounts of saponin can be obtained.

  Hereinafter, the present invention will be described in detail.

  First, the embodiment (1) will be described as an example. The camellia seeds are seeds of leguminous plants, and varieties that are mainly used as raw materials for camellia oil, and seeds of other legumes can also be used. Examples of vines from which seeds are used as raw materials for camellia oil include japonica, sasanqua, and chanoki. In this Embodiment (1), the seed of a camellia is used as it is.

  The cocoon seed squeezed is produced as a residue obtained by squeezing the cocoon oil from the cocoon seeds. As described in Patent Documents 1 and 2, etc., oil extraction can be carried out by crushing and pressurizing seeds of leguminous plants with a roller, a press, etc., and obtaining a cocoon oil and a solid squeezed potato. . The squeeze crushed the seeds into seed seed coats and seed nuclei that were separated and crushed and pressed and flattened. It is easy to penetrate and the reaction is likely to occur.

  The saponin-derived saponin aqueous solution of the cocoon seed according to Embodiment (1) is obtained by extracting the cocoon seed from the cocoon seed with subcritical water. Here, the subcritical state is water in a state where the critical pressure of water is 22.1 MPa and the critical temperature is around 347 ° C., which is lower than the critical temperature and the critical pressure. In the present embodiment (1), as a guideline, the pressure is 3.0 MPa or more and the critical pressure is 22.1 MPa or less, and the temperature is from 100 ° C. to the critical temperature of 347 ° C. or less.

  The aqueous solution extracted from submerged cocoon seeds with subcritical water preferably contains saponin and contains 2.0 to 3.0 W / V% in view of its usefulness as a cleaning agent and insect repellent. . The saponin-derived saponin aqueous solution of camellia seed according to Embodiment (1) contains 2.5 to 2.8 W / V% saponin.

  Next, the suitable manufacturing method of the saponin aqueous solution derived from the persimmon seed of Embodiment (1) is demonstrated based on FIG.

  First, squeezed cocoon oil is obtained by squeezing cocoon seed 1. The oil extraction method can be either manual or mechanical as long as it is a means for crushing by applying pressure. In Embodiment (1), the pressure is applied as it is to the cocoon seed 1 by the screw press 2 to separate the coconut oil 3 of the oil and the squeezed potato 4 of the solid cocoon seed. At this time, heat may be generated slightly by the operation of the screw press 2, but it is desirable to minimize the heating so that the saponin does not chemically react and in order to maintain the quality. If it is in the range of heat generation when operating a normal screw press, there is almost no problem.

  Next, the cocoon seed squeezed cocoon 4 is mixed with water so that subcritical extraction is possible. Water can be used without problems as long as the mixture is as small as tap water in extraction, but purified water, deionized water, etc. are used if importance is placed on the purity of the aqueous solution after extraction. You can also. In the embodiment (1), purified water is used, and the squeezed cocoon seeds: water is mixed so as to have a volume of 1: 2 to obtain a squeezed sachet mixture 5.

  Subsequently, this squeezed lees mixture 5 is extracted with subcritical water using a subcritical extraction device 6. As the subcritical extraction device 6, a device capable of bringing water into a subcritical pressure and temperature can be appropriately used. For example, a device equipped with a reactor as described in Patent Document 4 can be used.

  The water in the subcritical state in the present invention is water having a critical point of water of 22.1 MPa, 347 ° C. or lower, and as a guide, water in a state of 3.0 MPa, 100 ° C. or higher. It is in a state that combines.

  In particular, in order to prevent decomposition of saponin and decomposition of impurities, 3.5 to 6.5 MPa is desirable for use in extraction. The temperature is preferably from 100 to 160 ° C. from the viewpoint of preventing saponin decomposition and alteration, and the range from 115 to 125 ° C. is particularly desirable because the saponin that can be extracted is the largest. The treatment time is 1 to 30 minutes, and 5 to 10 minutes is particularly desirable because it is preferable to perform the treatment for a short time.

  By this subcritical extraction, the solid extraction residue 7 and the saponin aqueous solution 8 derived from the cocoon seeds are obtained.

  This saponin aqueous solution contains an oil component derived from the cocoon oil remaining in the squeezed potato seeds. Depending on the state at the time of oil extraction, the amount contained in the saponin aqueous solution takes a value of around 0.1 to 20 W / V%, but in the case of oil extraction by the screw press in this embodiment (1), it becomes less than 12 W / V%. .

  Next, the embodiment (2) will be described. Embodiment (2) is an insect repellent using a saponin-derived saponin aqueous solution of cocoon seeds. The saponin-derived saponin aqueous solution obtained by the production method of Embodiment (1) can be used as it is, diluted with water, or mixed with other household and agricultural spraying agents.

  The saponin aqueous solution derived from the squeezed cocoon seed damages the insect cell tissue by the action of the saponin as a surfactant, and has an insecticidal and insecticidal action. Here, reptiles include insects, invertebrates such as molluscs and arthropods, and a wide range of small organisms that can be repelled mainly in agriculture and home. For the purpose of repelling insects, it can be used for various purposes such as spraying and spraying in the process and agriculture, for example spraying on the leaves of agricultural crops, mixing with water such as water storage and repelling aquatic organisms.

  When spraying outdoors, in the case of an aqueous solution containing about 2.8% saponin of the present embodiment, a sufficient insecticidal effect can be obtained at a dilution factor of about 8 to 12 times. What is necessary is just to spray and spread these to the area | region which wants to remove insects outdoors. Moreover, when mixing with water for use, it can be diluted 10-1000 times and used.

  Since this insect repellent does not contain other solid components derived from squeezed rice cake, it can be widely used regardless of the place or situation of application at home or agriculture. Since saponin damages cell membranes as a surfactant, it can be widely used to control insects, small organisms that can be repelled in agriculture and households, and sterilization. In particular, it is also effective as a means of using waste in the industry of camellia oil because it exerts an effect also on Chadokuga, which is a pest that sticks to the wood of vines.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

[Test Example 1]
[Production test of saponin aqueous solution derived from cocoon seeds]
Squeeze seed 1 collected from a camellia is squeezed and squeezed with a screw press 2 at a speed of 40 kg / 1 hour, and the resulting plate-shaped pod seed pomace 4 is crushed. It mixed so that it might become. Subsequently, this squeezed lees mixture 5 was extracted with subcritical water using a subcritical device 6.

Extraction with subcritical water was performed for 5 minutes each using purified water at a pressure of 5 MPa and at the temperatures shown in Table 1 to obtain an aqueous saponin solution 8 derived from squeezed potato seeds. As a comparative example, extraction at normal pressure and 100 ° C. was also performed. The saponin content in the aqueous solution extracted under each condition is shown.

  In the subcritical water extraction temperature range of 110 ° C. to 140 ° C., the saponin content was effectively extracted as 2.5 to 2.8 W / V% in all cases. Moreover, all were remarkably larger than 0.9 W / V% of extraction by 100 degreeC hot water of normal pressure. In addition, none of the theanine can be detected as a free amino acid, indicating that there are few impurities. Among these, the aqueous solution on 120 degreeC conditions with most saponin content was set as Example 1. FIG.

[Test Example 2]
[Repellent effect test 1 of insect repellent]
In the center of a transparent plastic cylinder having a length of 30 cm and a radius of 3.5 cm, the insect repellent cotton impregnated with the saponin aqueous solution derived from the cocoon seeds of Example 1 was placed. Three larvae of white-spotted starfish, which are pests on the cherry blossoms, were placed in the tube and allowed to stand.

  Three days later, all the larvae died while escaping to both ends of the tube. From this result, it is shown that the insect repellent containing the saponin aqueous solution derived from cocoon seeds according to the present invention can control some insect larvae.

[Test Example 3]
[Repellent effect test 2 of insect repellent]
At the time of occurrence of Chadokuga that occurs as an insect pest on the oak tree, an insect repellent obtained by diluting the saponin aqueous solution derived from the oak seeds of Example 1 10 times was sprayed before the oak tree. Even if it observed after that, generation | occurrence | production of Chadokuga was not seen in front of the sprayed tree. The repellant repellent of the present invention has a repellent effect on Chadokuga, and it shows that the repellant repellent reusing squeezed cocoon oil can be used effectively in the cocoon industry.

It is a figure which shows the manufacturing method of the saponin aqueous solution derived from the persimmon seed of a persimmon seed.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 椿 Seed 2 Screw press 3 椿 Oil 4 椿 Seed squeezed ５ 5 Squeezed sachet mixture 6 Subcritical extraction device 7 Extraction residue 8 椿 Seed squeezed saponin aqueous solution

Claims (4)

  An extract of cocoon seeds is extracted with subcritical water at a treatment temperature of 100 ° C. to 347 ° C. and a treatment pressure of 3.0 to 22.1 MPa for 1 to 30 minutes, and contains saponins. Squeeze-derived saponin aqueous solution.   The saponin-derived saponin aqueous solution of strawberry seeds according to claim 1, wherein the squeezed cocoon seeds contain seed nuclei and seed coats in a state where their cross-sections are exposed.   The saponin-derived saponin aqueous solution of strawberry seeds according to claim 1 or 2, comprising 0.1 to 20 W / V% of oil.   The process includes extracting the squeezed pods of cocoon seeds with a subcritical water having a processing temperature of 100 ° C. to 347 ° C. and a processing pressure of 3.0 to 22.1 MPa for a processing time of 1 to 30 minutes. Method for producing saponin aqueous solution derived from squeezed koji.

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