JP6997440B2 - Drugs, their usage and manufacturing methods - Google Patents

Description

The present invention relates to a drug, a method of using the same, and a method of producing the same.

Wood is usually subjected to antiseptic treatment as necessary to protect it from decay caused by wood-rotting fungi and the like. Various preservatives used for wood and the like, such as creosote oil, copper naphthenate and zinc naphthenate, are used, but some of them are highly toxic and their use is restricted. .. In addition, there are many preservatives with low durability, and there is a problem that preservative treatment must be repeated.

On the other hand, lignin, which is a main constituent of wood and the like, is used in a wide range of fields due to heightened environmental awareness. Lignin is decomposed by the above-mentioned wood-rotting fungi, but it is known that some types of wood-rotting fungi have a low action on lignin, and preservatives using lignin are being developed.
For example, in Patent Document 1, it is effective that the toxicity is low, the possibility of adversely affecting the environment and the human body due to volatilization and elution is low, the workability of the antiseptic treatment is easy, and lignin acetate is contained as an active ingredient. The characteristic preservatives are disclosed.

Japanese Unexamined Patent Publication No. 2006-11599

Since the lignin-based compound used in Patent Document 1 has a large number average molecular weight of about 1000 to about 4000, the viscosity of the preservative is high, and the workability when applying / impregnating to wood or the like is deteriorated. It is expected that it will be negative in terms of cost and environment, such as using a large amount of solvent to suppress the viscosity.

Therefore, it is an object of the present invention to provide a drug having extremely low toxicity, excellent antiseptic properties, less volatilization and elution, and good workability, a method for using the same, and a method for producing the same.

As a result of diligent studies to solve the above problem, the present inventors have found that the problem can be solved by light lignin.
That is, the present invention is as follows.

[1] A drug containing polyphenols having a number average molecular weight of 100 or more and 800 or less as a main component.
[2] The agent according to the above [1], which has a softening point of 30 ° C. or higher and 100 ° C. or lower.
[3] The agent according to the above [1] or [2], wherein the polyphenols are lignin.
[4] The agent according to any one of the above [1] to [3], wherein the agent is a preservative.
[5] The method for using the drug according to any one of the above [1] to [4], which comprises applying.
[6] The method for using the drug according to the above [5], which comprises diluting and applying the drug.
[7] A method for producing a base material, which comprises applying the agent according to any one of the above [1] to [4] to the base material.
[8] The method for producing a substrate according to the above [7], wherein the drug is diluted and applied.
[9] A method for producing a drug, which comprises a step (I) of fractionating a solution containing lignin having a number average molecular weight of 100 or more and 800 or less as a main component from a raw material lignin solution.
[10] The raw material lignin solution is obtained by dissolving the lignin contained in the plant biomass in a lignin solution (i) obtained by solubilizing the lignin in a solvent containing an organic solvent, or by dissolving the solid lignin in a solvent containing an organic solvent. The method for producing a drug according to the above [9], which is a lignin solution (ii) to be obtained.
[11] In the step (I), the raw material lignin solution and at least one solvent (a) selected from water and a hydrocarbon having a dipole moment of 0.25 d or less are applied to the raw material lignin solution. The method for producing a drug according to the above [9] or [10], which is a step (I') of mixing the solvent (a) in a volume of 1 to 50 times or less.

According to the present invention, it is possible to provide a drug which is extremely low in toxicity because it is a component derived from a natural product, has excellent antiseptic properties, and has little volatilization and elution, and a method for using the same and a method for producing the same. Further, since the number average molecular weight of the obtained drug is relatively low, it has high thermal meltability and solvent solubility, and has good workability.

It is a figure which shows the antiseptic property evaluation result in an Example and a comparative example of this invention.

<Drug>
The agent of the present invention contains polyphenols having a number average molecular weight of 100 or more and 800 or less (sometimes simply referred to as "polyphenols") as a main component.
Examples of polyphenols include tannin, lignite, and lignin, and the agent of the present invention preferably has lignite, lignin, and the like from the viewpoint of usefulness as a preservative or an antibacterial agent, and lignin is particularly preferable.

The drug of the present invention is mainly composed of polyphenols having a number average molecular weight of 100 or more and 800 or less, but the "main component" is usually 5% by mass from the viewpoint of exhibiting antiseptic or antibacterial properties against the drug. The above is preferably 25% by mass or more, more preferably 45% by mass or more, further preferably 60% by mass or more, particularly preferably 80% by mass or more, and the upper limit is usually 100% by mass. It is important for the agent of the present invention that the polyphenols are in the range of the above number average molecular weight in order to exhibit antiseptic and antibacterial properties, and usually, if the polyphenols are 5% by mass or more, the antiseptic or antibacterial properties are exhibited. ..
In addition, examples of the components other than the polyphenols that can be contained in the drug include phenols such as vanillin and sugar peroxides such as furfural, but are not particularly limited.

The number average molecular weight of polyphenols is 100 or more and 800 or less. If the number average molecular weight exceeds 800, excellent antiseptic and antibacterial properties cannot be exhibited, and workability also deteriorates. The number average molecular weight is preferably 200 or more and 700 or less, more preferably 200 or more and 500 or less, and further preferably 250 or more and 450 or less, from the viewpoint of having high thermal meltability and solvent solubility and exhibiting better antiseptic and antibacterial properties. , More preferably 300 or more and 400 or less.
The number average molecular weight is determined by measurement by gel permeation chromatography (GPC) using polystyrene as a conversion standard.

The softening point of the agent of the present invention is preferably 30 ° C. or higher and 100 ° C. or lower, more preferably 30 ° C. or higher and 80 ° C. or lower, still more preferably 30 ° C. or higher and 70 ° C. or lower, and further preferably 40 ° C. or higher and 70 ° C. or lower. .. When the softening point is within the above range, the antiseptic property and antibacterial property of the drug are excellent.

As described above, the agent of the present invention is useful as an antiseptic and an antibacterial agent because it is excellent in antiseptic and antibacterial properties, and is particularly suitable as an antiseptic because of its excellent antiseptic properties. The agent of the present invention exhibits antiseptic and antibacterial properties against fungi, but shows better effects against fungi. Among fungi, it is more preferable as a preservative and an antibacterial agent against wood-rotting fungi and yeast, further preferable as a preservative and an antibacterial agent against white-rot fungus and brown-rot fungus, and particularly preferable as a preservative and antibacterial agent against white-rot fungus. As the white-rot fungus, it is preferable to Shiitake, Nameko, Enokitake, Hiratake, Sugihiratake, Maitake, Pleurotus cornucopiae, Schizophyllum communis, Kawaratake, Stake, Hoshigetake, and Hiirotake, and more preferably to Kawaratake. The brown rot fungus is preferable to Gloeophyllum, Polyporaceae, Namidatake, Matsuoji, Chalkanatake, Gloeophyllum, Ginkgotake, and Wet Rot.

The method of using the drug of the present invention is not particularly limited, and examples thereof include a method of applying or immersing the drug in the drug, but it is preferable to apply the drug from the viewpoint of workability. In addition, the drug may be diluted with an appropriate solvent and used at the time of application. The suitable solvent is not particularly limited as long as it can dissolve or disperse the drug, but a mixed solvent of water and an organic solvent such as acetone can be used.
When the agent of the present invention is diluted and applied, if the content of the polyphenols is about 5% by mass or more, it can be diluted to a viscosity sufficient for application.

Further, the present invention can provide a base material obtained by applying the above-mentioned drug to the base material. The drug can also be diluted and applied as described above.
For example, when the agent of the present invention is used as a preservative, the preservative treatment using the preservative can be carried out according to a method known per se. Specifically, it can be carried out by applying the preservative of the present invention to the surface of the base material or by immersing the base material in a solution of the preservative of the present invention, whereby the preservative effect can be obtained on the surface of the base material. It can form an excellent protective film. When the base material is a material such as wood that allows liquid to easily permeate, it is more effective to permeate the preservative liquid not only on the surface but also on the inside. When the preservative is infiltrated into the base material, a method such as pressurization or depressurization can be used in combination, if necessary.

Examples of the base material that can be used for the antiseptic treatment include wood, fiber, concrete, brick, resin foam, and the like, and among these, wood is particularly suitable.
The protective film formed can be dried at room temperature or, if necessary, heat-cured. In this case, it is desirable to appropriately select the optimum heating temperature and heating time in consideration of the heat resistance of the base material.

<Manufacturing method of drug>
The method for producing the drug of the present invention in the case where the drug of the present invention contains lignin suitable as the polyphenols as a main component will be described.
[Step (I)]
The method for producing a drug of the present invention is a step (I) of fractionating a solution containing lignin having a number average molecular weight of 100 or more and 800 or less (hereinafter, may be referred to as "light lignin") as a main component from a raw material lignin solution. Has.
The above "main component" has the same meaning as described above. Further, as the component other than the light lignin that can be contained in the mixture containing the light lignin as the main component, the same components as the above-mentioned "component other than the above polyphenol that can be contained in the drug" can be exemplified.

(Raw material lignin solution)
The raw material lignin solution used in the step (I) is preferably the following lignin solution (i) or lignin solution (ii).
<Lignin solution (i)>
The lignin solution (i) is obtained by solubilizing the lignin contained in the plant biomass in a solvent containing an organic solvent.
As a method for solubilizing lignin contained in plant biomass in a solvent containing an organic solvent, an existing method can be used. For example, a method for treating plant biomass in a mixed solvent of water and an aliphatic alcohol having 4 to 10 carbon atoms described in International Publication No. 2014/142289, and water described in Japanese Patent No. 52566679. A method for treating plant-based biomass according to the above can be mentioned.
As a specific example of the method for obtaining the lignin solution (i), the plant-based biomass is treated with a solvent containing an organic solvent under the conditions of a specific charging concentration of the plant-based biomass and the solvent, a specific reaction temperature and time. By doing so, lignin can be separated.

Examples of plant-based biomass include wood-based biomass and herbaceous biomass. Examples of woody biomass include conifers such as Sugi, Hinoki, Hiba, Sakura, Eucalyptus, Beech, and Bamboo, and broad-leaved trees.
Herbaceous biomass includes palm palm tree trunks and bunches, palm palm fruit fibers and seeds, bagasse (corn and high biomass squeezed shavings), cane tops (corn tops and leaves), energy canes, rice straw, and straw. Corn cobs, foliage, residues (corn stover, corn cob, corn hull), sorghum (including sweet sorghum) residues, yatrofa skins and shells, cashew husks, switchgrass, eranthus, high biomass yield crops, energy crops, etc. Can be mentioned.
Among these, herbaceous biomass is preferable from the viewpoint of availability and compatibility with the production method applied in the present invention, such as palm palm air chamber, straw, corn foliage, bagasse, cane top, and energy cane. , The residue after extraction of these useful components is more preferable, and bagasse, cane top, energy cane, and the residue after extraction of these useful components are further preferable. Useful ingredients include, for example, hemicellulose, sugars, minerals, water and the like.

Bagasse contains about 5 to 30% by mass of lignin. In addition, lignin in bagasse contains all of H nucleus, G nucleus and S nucleus as a basic skeleton. The G nucleus has one methoxy group (-OCH ₃ ) at the ortho position of the phenol skeleton portion, the S nucleus has two methoxy groups at the ortho position, and the H nucleus is It does not have a methoxy group at the ortho position. The lignin derived from Kimoto-based biomass does not contain H nuclei.
As the plant-based biomass, crushed biomass can also be used. Further, it may be in the form of a block, a chip, a powder, or a water-containing substance containing water.

Examples of the solvent containing an organic solvent include a mixed solvent of water and an organic solvent.
Examples of water include tap water, industrial water, ion-exchanged water, distilled water and the like.
The organic solvent is not particularly limited, but may be either saturated or unsaturated, selected from linear alcohols and branched alcohols. In addition, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, ethylene glycol and polyethylene glycol may be used. Further, the organic solvent may be used alone or in combination of two or more.
Among them, at least one selected from methanol, ethanol, propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, pentanol, hexanol, heptanol, octanol, acetone and tetrahydrofuran. The species is preferred, and more preferably one or more selected from 1-butanol, 2-methyl-1-propanol, 2-butanol, ethanol, pentanol, hexanol and acetone, 1-butanol and 2-methyl-1. -It is more preferably at least one selected from propanol, 2-butanol, ethanol and acetone, further preferably 1-butanol, 2-methyl-1-propanol and 2-butanol, and 1-butanol. Is particularly preferred.

As for the mixing ratio of water and the organic solvent, the molar ratio (water / alcohol) of water and the organic solvent is preferably 1/1 to 40/1, more preferably 1.5 / 1 to 30/1. More preferably, it is 2/1 to 24/1. When the molar ratio of water to the organic solvent is within the above range, the solution containing lignin can be separated into two phases under predetermined conditions.

The concentration of the plant biomass charged to the solvent containing the organic solvent is preferably 1% by mass or more and 50% by mass or less, more preferably 3% by mass or more and 20% by mass or less, and further preferably 5% by mass or more and 18% by mass or less. .. When the concentration of the plant-based biomass is 1% by mass or more, the energy efficiency of the process of solubilizing lignin is kept good. On the other hand, if the concentration of the plant-based biomass exceeds 50% by mass, the amount of the solvent is not sufficient and the separation efficiency of lignin decreases.

The treatment reaction temperature is preferably 100 ° C. or higher and 350 ° C. or lower, more preferably 150 ° C. or higher and 300 ° C. or lower, and further preferably 170 ° C. or higher and 270 ° C. or lower. When the temperature is 100 ° C. or higher, the separation of lignin is promoted, and when the temperature exceeds 350 ° C., the decomposition of cellulose and the formation of cork due to the repolymerization of lignin can be suppressed.
The treatment reaction time is 0.1 hours or more and 10 hours or less, preferably 0.2 hours or more and 8 hours or less, more preferably 1 hour or more and 6 hours or less, and further preferably 1 hour or more. It is less than 3 hours. If it is 0.1 hours or more, the separation of lignin proceeds sufficiently, and if it is within 10 hours, the decomposition of cellulose and the production of cork due to the repolymerization of lignin can be suppressed.

<Lignin solution (ii)>
The lignin solution (ii) is obtained by dissolving solid lignin in a solvent containing an organic solvent.
Any solid lignin can be used, and there is no particular limitation. For example, solid lignin obtained by solubilizing lignin from the above-mentioned plant-based biomass and then concentrating it, and solid lignin obtained from black liquor (sulfite lignin, kraft lignin, soda lignin, etc.) produced in the pulp production process. Etc. can be used.

The organic solvent is not particularly limited, but may be selected from saturated or unsaturated linear alcohols and branched alcohols. In addition, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, ethylene glycol and polyethylene glycol may be used. Further, the organic solvent may be used alone or in combination of two or more.

Among them, at least one selected from methanol, ethanol, propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, pentanol, hexanol, heptanol, octanol, acetone and tetrahydrofuran. Species are preferred, and more preferably one or more selected from 1-butanol, 2-methyl-1-propanol, 2-butanol, ethanol, pentanol, hexanol and acetone, 1-butanol and 2-methyl-1. -It is more preferably at least one selected from propanol, 2-butanol, ethanol and acetone, further preferably at least one selected from ethanol and acetone, and particularly preferably acetone.
Examples of the solvent containing the organic solvent include a mixed solvent of these organic solvents and, for example, water. The mixing ratio of water and the organic solvent is not particularly limited, but the molar ratio of water to the organic solvent (water: organic solvent) is usually about 5:95 to 95: 5, preferably 10:90 to 80. : 20, more preferably 10:90 to 70:30, and even more preferably 10:90 to 60:40.

<Lignin concentration>
The raw material lignin solution preferably has a lignin concentration of 1% by mass or more and 90% by mass or less at 25 ° C. in an organic solvent. When the concentration of lignin at 25 ° C. is 1% by mass or more, there is no possibility that the energy efficiency of the production process of the mixture containing light lignin as a main component is deteriorated. Further, when the concentration of lignin at 25 ° C. is 90% by mass or less, the degree of separation in the step (I) described later is good.

The concentration of lignin at 25 ° C. is preferably 1% by mass or more and 70% by mass or less, more preferably 1% by mass or more and 50% by mass or less, still more preferably 2% by mass or more and 40% by mass or less, and particularly preferably 4% by mass or more. It is 30% by mass or less. When a plurality of kinds of organic solvents are used, the concentration of the lignin means the concentration in the total amount of the organic solvents.

[Step (I')]
In the step (I) of fractionating a solution containing lignin having a number average molecular weight of 100 or more and 800 or less as a main component from the raw material lignin solution, the above-mentioned raw material lignin solution and water and hydrocarbons having a dipole moment of 0.25 d or less are carried out. It is preferable to carry out the step (I') in which at least one solvent (a) selected from the above is mixed with the raw material lignin solution in a volume of 1 to 50 times or less.
By going through the step (I'), a mixture containing light lignin having excellent antiseptic properties, antibacterial properties and workability as a main component can be obtained.

(water)
As the water, for example, tap water, industrial water, ion-exchanged water, distilled water and the like can be used.
(Hydrocarbon with dipole moment of 0.25d or less)
As the hydrocarbon having a bipolar moment of 0.25d or less, a saturated chain hydrocarbon, an unsaturated chain hydrocarbon, a saturated ring hydrocarbon or an unsaturated ring hydrocarbon having 5 to 8 carbon atoms is preferable. .. When the dipole moment of the hydrocarbon is 0.25d or less, the purification efficiency can be improved. Here, the "dipole moment" is a value calculated by Winmostar MOPAC AMI (MOP6W70). An example of a compound that can be used as such a hydrocarbon is shown below together with its dipole moment value.

The dipole moment of the hydrocarbon is preferably 0.20 d or less, more preferably 0.10 d or less, still more preferably 0.05 or less. The lower limit of the dipole moment of the hydrocarbon is not particularly limited, but is, for example, 0.00d.

(Volume of solvent (a))
The amount of at least one solvent (a) selected from water and a hydrocarbon having a dipole moment of 0.25 d or less when mixed with the raw material lignin solution is 1 times or more in volume with respect to the raw material lignin solution. If so, the mixture containing the light lignin contained in the raw material lignin solution as a main component can be sufficiently separated.
On the other hand, if the amount of the solvent (a) is 50 times or less in volume, the mixture containing the above-mentioned number average molecular weight of lignin as a main component can be efficiently recovered without excessively increasing the amount of wastewater and hydrocarbons used. can.
When a plurality of types of hydrocarbon solvents are used, the amount of the solvent (a) means the total amount of water and the plurality of types of hydrocarbon solvents.

The amount of the solvent (a) to be mixed with the raw material lignin solution is preferably 1 to 40 times or less, more preferably 1 to 30 times or less, still more preferably 2 to 20 times or more in terms of volume with respect to the raw material lignin solution. It is twice or less, particularly preferably 2 times or more and 15 times or less.
The mixing method is not particularly limited as long as the raw material lignin solution and the solvent (a) can be uniformly mixed. The equipment used for mixing includes, for example, an edge runner, a stirring mixer, a roll mill, a cone mill, a flat stone mill, a speed line mill, a ball mill, a bead mill, a sand grind mill, a pearl mill, an attritor, a vertical mixer, a kneader, and a high-speed stirring. Machines (dissolvers) and the like can be mentioned.

The solution temperature in the above step (I') of mixing the raw material lignin solution with water and at least one solvent (a) selected from hydrocarbons having a dipole moment of 0.25 d or less is the stability of the solution and lignin. The temperature is preferably 0 ° C. or higher and 100 ° C. or lower, more preferably 10 ° C. or higher and 90 ° C. or lower, further preferably 20 ° C. or higher and 80 ° C. or lower, and particularly preferably 25 ° C. or higher and 70 ° C. It is as follows.

Further, when mixing the raw material lignin solution and at least one solvent (a) selected from water and a hydrocarbon having a dipole moment of 0.25 d or less in the step (I'), stirring is necessary. May be done. When stirring is performed, static separation may be further performed if necessary. The standing time is usually 1 minute or more and 120 minutes or less. If the standing time is 1 minute or more, the mixture containing light lignin as a main component can be sufficiently separated. Further, the upper limit of the standing time is 120 minutes, which is sufficient. The standing time is preferably 5 minutes or more and 100 minutes or less, more preferably 10 minutes or more and 60 minutes or less, and further preferably 15 minutes or more and 30 minutes or less.

[Step (II-1) or (II-2)]
It is preferable to carry out either of the following steps (II-1) or (II-2) depending on whether the solution obtained in the above step (I) is two-phase or one-phase.
If the solution obtained in step (I) is two-phase, light lignin can be separated from the raw material lignin solution by separating the solution in the following step (II-1). When the solution obtained in step (I) is one phase, light lignin can be obtained from the raw material lignin solution by solid-liquid separation of the solid precipitated due to the difference in solubility in the following step (II-2). Can be separated in solution.

(Step (II-1))
When the solution obtained in the step (I) is two-phase, it is preferable to carry out the step (II-1) in succession after the step (I). In the step (II-1), the phase containing the light lignin as the main component obtained in the step (I) is separated from the above two phases, the separated phases are concentrated, and then the obtained solid content is dried. The drug is obtained.

For example, the solution obtained in step (I) is a two-phase of an aqueous phase and an organic phase (an organic phase other than a hydrocarbon having a bipolar moment of 0.25 d or less, hereinafter synonymous), or an aqueous phase and an organic phase and When the dipole moment is divided into two phases with a hydrocarbon phase of 0.25d or less, the mixture containing light lignin as a main component is dissolved on the aqueous phase side, so that the aqueous phase is in step (II-1). The side is separated, the aqueous phase side is concentrated, and then the obtained solid content is dried.
When the solution obtained in step (I) is divided into two phases, a hydrocarbon phase having a dipole moment of 0.25d or less and an organic phase, a mixture containing a light lignin as a main component in the hydrocarbon phase. In step (II-1), the hydrocarbon phase is separated, the hydrocarbon phase is concentrated, and then the obtained solid content is dried.
When the solid content is generated in the two-phase state, the aqueous phase side or the hydrocarbon phase side is separated after the solid-liquid separation.

(Step (II-2))
When the solution obtained in the step (I) is one phase, that is, when the solid content precipitates, it is preferable to continue the step (II-2). In step (II-2), the solution is solid-liquid separated, the obtained solution is concentrated, and then dried to obtain a drug.

Since the drug obtained by the above-mentioned production method of the present invention has a relatively low number average molecular weight, it is possible to produce a drug having high thermal meltability and solvent solubility and excellent workability.
In addition, the agent of the present invention has extremely low toxicity because it is a component derived from a natural product, has antiseptic and antibacterial properties, and has particularly excellent antiseptic properties, and is volatile even though it is a relatively small molecule. Since it is small and basically insoluble in water, there is very little concern about loss of antiseptic effect due to volatilization and elution once it is treated.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[Example 1]
(Preparation of raw material lignin solution)
As a raw material, bagasse (sample size 3 mm square or less) and a mixed solvent of water and 1-butanol, which is an organic solvent (prepared so that water / 1-butanol = 8/1 in molar ratio), have an internal volume of 0. Placed in a .92 L SUS batch device. The mass of the mixed solvent composed of water and 1-butanol was 300 g. The bagasse charging concentration was 10% by mass in terms of mass ratio with respect to the above mixed solvent.
After purging the inside of the SUS batch type apparatus with nitrogen, the temperature was raised to 200 ° C., and the decomposition reaction was carried out at a reaction temperature of 200 ° C. for 2 hours. The reaction time was defined as the elapsed time after reaching 200 ° C. In addition, the temperature was measured with a thermocouple. The internal pressure during the reaction was 1.9 MPa.
After the treatment was completed, the SUS batch type apparatus was cooled to near room temperature, and then all the contents were taken out and filtered to separate the biomass residue and the liquid phase. Further, the aqueous phase of the filtrate and the 1-butanol phase were liquid / liquid separated by a separating funnel. The separated 1-butanol phase was used as the raw material lignin solution. The solid content (lignin) concentration was 50 g / L-butanol phase when the butanol phase was separately concentrated and determined.
(Step I)
178 mL of ion-exchanged water was added to 14 mL of the obtained raw material lignin solution (water + butanol phase) (lignin concentration was 6% by mass, 0.7 g of lignin was dissolved in 14 mL of butanol + water mixed solvent). The amount of water was 12.7 times that of the raw material lignin solution. The resulting mixed solution was stirred at 25 ° C. for 15 minutes. The liquid phase after stirring was one phase.
(Step II-2)
The solid content was filtered off by filtration, the obtained filtrate was concentrated, and vacuum dried at 100 ° C. to obtain a viscous solid 1 containing lignin as a main component (61% by mass).
The number average molecular weight of the viscous solid 1 measured by the method described later was 344, and the softening point was 45 ° C. The results of the antiseptic property evaluation by the method described later are shown in Table 2 and FIG.

[Example 2]
(Preparation of raw material lignin solution)
As a raw material, a mixed solvent of cedar (sample size 1 mm square or less) and water and 1-butanol, which is an organic solvent (prepared so that water / 1-butanol = 4/1 in molar ratio), has an internal volume of 0. It was placed in a 0.7 L SUS batch type device. The mass of the mixed solvent composed of water and 1-butanol was 300 g. The concentration of Sugi was set to 1/30 by mass ratio with respect to the mixed solvent.
After purging the inside of the SUS batch type apparatus with nitrogen, the temperature was raised to 200 ° C., and the decomposition reaction was carried out at a reaction temperature of 200 ° C. for 2 hours. The reaction time was defined as the elapsed time after reaching 200 ° C. In addition, the temperature was measured with a thermocouple. The internal pressure during the reaction was 1.8 MPa.
After the treatment was completed, the SUS batch type apparatus was cooled to near room temperature, and then all the contents were taken out and filtered to separate the biomass residue and the liquid phase. Further, the aqueous phase of the filtrate and the 1-butanol phase were liquid / liquid separated by a pipette. The separated 1-butanol phase was vacuum dried at 125 ° C. for 30 minutes after removing the solvent with an evaporator (80 ° C., water bath) to obtain a solubilized lignin concentrate.
(Step I)
70 mL of ethyl acetate was added to 1 g of the obtained solubilized lignin concentrate. The solid matter was removed by filtration, and the filtrate was vacuum-dried at 130 ° C. for 30 minutes after removing the solvent with an evaporator (70 ° C., water bath) to obtain an ethyl acetate-soluble component. A mixed solvent of hexane and ethyl acetate (hexane / ethyl acetate = 4/1 volume ratio) was added to 1 g of the ethyl acetate-soluble component.
(Step II-2)
The solid matter was removed by filtration, and the filtrate was vacuum-dried at 130 ° C. for 30 minutes after removing the solvent with an evaporator (80 ° C., water bath) to obtain a viscous solid matter 2 containing lignin as a main component. rice field.
The number average molecular weight of the viscous solid 2 measured by the method described later was 378, and the softening point was 50 ° C. In addition, Table 2 and FIG. 1 show the results of the antiseptic property evaluation by the method described later.

[Comparative Example 1]
The solid content filtered off in (Step II-2) of Example 1 was vacuum dried at 125 ° C. to obtain solid substance 1 containing lignin as a main component (95% by mass).
The number average molecular weight of the solid substance 1 measured by the method described later was 1158, and the softening point was 160 ° C. The results of the antiseptic property evaluation by the method described later are shown in Table 2 and FIG.

[Measurement and evaluation method]
1. 1. Content of lignin in viscous solids or solids [pretreatment]
As a pretreatment, a raw material (viscous solid or solid) as a sample was pulverized using a Willey mill and dried at 105 ° C.
An appropriate amount of the viscous solid or solid sample was weighed, 72% sulfuric acid was added, and the mixture was left at 30 ° C. for 1 hour with occasional stirring. This reaction solution was completely transferred to a pressure-resistant bottle while being mixed with pure water, treated in an autoclave at 120 ° C. for 1 hour, and then the filtrate and the residue were filtered off.
[Lignin]
The residue obtained by filtration in the pretreatment process was dried at 105 ° C., weighed, and the decomposition residue rate was calculated. Furthermore, the lignin content was calculated by correcting the ash content.

2. 2. Molecular Weight: Number Average Molecular Weight (Mn)
The number average molecular weight (Mn) was measured under the following conditions by a gel permeation chromatograph (GPC) method using a tetrahydrofuran solvent.
[Measurement condition]
SEC equipment: HLC-8220 GPC (manufactured by Tosoh Corporation)
Column: TSKgel guardcolumn HXL-H + TSKgel GMH-XL 2 + G2000H-XL 1 (manufactured by Tosoh Corporation)
Solvent: THF (Stabilizer-free special grade manufactured by Wako Pure Chemical Industries, Ltd.)
Detector: Differential refractive index (RI) detector, UV detector Concentration: 0.1w / v%
Injection volume: 100 μl
Flow velocity: 1.0 ml / min
Column temperature: 40 ° C
Standard sample for calibration curve: Tosoh Corporation, TSK standard polystyrene Analysis software: GPC-8020model II

3. 3. Softening point (℃)
The viscous solid content or solid content (solid sample) obtained in Examples and Comparative Examples was crushed in a mortar, sieved through a sieve (40 mesh) to remove large particles, and the crushed sample was placed in an aluminum cup (circular upper φ60, lower φ53). × Depth 15 mm) was placed in 10 to 20 mg. The aluminum cup containing the sample was placed on a hot plate (ASONEND-2A) and covered with a glass plate (thickness 0.5 mm). After heating to 80 ° C., the temperature was raised in increments of 5 ° C., visual observation was performed through the glass, and the temperature at which melting was completed by visual inspection was adopted as the softening point.

4. Antiseptic property evaluation The antiseptic test was performed by the paper disc method. C. versicolor was used as a test bacterium, and a mixture previously cultured on an agar medium containing a malt extract was collected, dispersed in sterile water, and diluted so that the absorbance was 0.02. The cells were inoculated by dropping 500 μL of the diluted test bacterial dispersion onto an agar medium prepared in a sterile petri dish having a diameter of 9 cm. The viscous solid 1 of Production Example 1 was diluted to 10% by mass by adding a mixed solvent of water and acetone (water / acetone = 1/9 weight ratio), and the diameter was placed in the center of the agar medium after inoculation. 15 μl was dropped on a 6 mm filter paper (paper disc). The inoculum was cultured in a constant temperature bath set at 26 ° C., and the state around the filter paper was observed after 3 weeks.
Evaluation was made based on the following evaluation criteria. The photograph of the petri dish after the antiseptic evaluation test is shown in the figure.
⊚: No bacterial growth was observed.
◯: Bacteria propagated and white mold was observed on a part of the filter paper.
X: Bacteria propagated and white mold covered the entire filter paper.

The present invention is a method for producing a drug and a drug having extremely low toxicity, excellent antiseptic property, less volatilization and elution, and good workability, and the drug has not only antiseptic property but also antibacterial property. Since it can have, it can be used as an antiseptic and an antibacterial agent.

Claims (10)

A drug containing polyphenols having a number average molecular weight of 100 or more and 800 or less as a main component, and the polyphenols being lignin . The drug according to claim 1, wherein the softening point of the drug is 30 ° C. or higher and 100 ° C. or lower. The agent according to claim 1 or 2 , wherein the agent is a preservative. The method for using a drug according to any one of claims 1 to 3 , wherein the drug is applied. The method for using a drug according to claim 4 , wherein the drug is diluted and applied. A method for producing a base material, which comprises applying the agent according to any one of claims 1 to 3 to the base material. The method for producing a base material according to claim 6 , wherein the drug is diluted and applied. A method for producing a drug, which comprises a step (I) of fractionating a solution containing lignin having a number average molecular weight of 100 or more and 800 or less as a main component from a raw material lignin solution. The raw material lignin solution is a lignin solution (i) obtained by solubilizing lignin contained in plant biomass in a solvent containing an organic solvent, or a lignin solution obtained by dissolving solid lignin in a solvent containing an organic solvent. (Ii) The method for producing a drug according to claim 8 . In the step (I), the raw material lignin solution and at least one solvent (a) selected from water and a hydrocarbon having a dipole moment of 0.25 d or less are added to the raw material lignin solution. The method for producing a drug according to claim 8 or 9 , which is a step (I') of mixing a) in a volume of 1 to 50 times.

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