JP2019089732A - Agent, method for use thereof and production method - Google Patents

Abstract

To provide an agent having extremely low toxicity, excellent antisepticity, less volatilization and elution, and excellent workability, and used for preservative treatment of wood, a method for use thereof and a production method.SOLUTION: The present invention provides an agent mainly composed of a polyphenol, with a number average molecular weight of 100-800 and a softening point of 30-100°C, such as lignin obtained by extraction from bagasse, cedar or the like with water-butanol or the like, a method for use thereof and production method.SELECTED DRAWING: None

Description

  The present invention relates to medicaments, methods of their use and methods of manufacture.

  Wood is usually subjected to preservative treatment as necessary to protect it from decay caused by wood decay fungi and the like. Although various preservatives such as creosote oil, copper naphthenate and zinc naphthenate are used as preservatives for wood etc., some of them are highly toxic, and their use was limited. . In addition, there are many low-preservative preservatives, and there is also a problem that repeated antiseptic treatment is required.

On the other hand, lignin, which is a main component of wood and the like, is used in a wide range of fields due to rising environmental awareness. Lignin is degraded by the above-mentioned wood rot fungus, but it is known that some kinds of wood rot fungus have a low effect on lignin, and development of preservatives utilizing lignin has also been carried out.
For example, Patent Document 1 has low toxicity, is less likely to adversely affect the environment or human body by volatilization or elution, and has an effect of easy workability of preservative treatment, and contains acetic acid lignin as an active ingredient. The disclosed preservative is disclosed.

JP, 2006-111599, A

  The lignin-based compound used in Patent Document 1 has a high number average molecular weight of about 1000 to about 4000, so the viscosity of the preservative is high, and the workability at the time of coating and impregnating on wood etc. becomes worse, The use of a large amount of solvent or the like to suppress viscosity is expected to be negative in terms of cost and environment.

  Then, this invention makes it a subject to provide the chemical | medical agent which has very low toxicity, has the outstanding antiseptic property, there are few volatilization and elution, and favorable workability, its use method, and a manufacturing method.

As a result of intensive studies to solve the above problems, the present inventors have found that light lignin can solve the problems.
That is, the present invention is as follows.

[1] A drug whose main component is a polyphenol having a number average molecular weight of 100 or more and 800 or less.
[2] The agent according to the above [1], which has a softening point of 30 ° C. or more and 100 ° C. or less.
[3] The agent according to the above [1] or [2], wherein the polyphenols are lignin.
[4] The drug according to any one of the above [1] to [3], wherein the drug is a preservative.
[5] A method of using the drug according to any one of the above [1] to [4], which is characterized by applying.
[6] A method of using the drug according to the above [5], which comprises diluting and applying the drug.
[7] A method for producing a substrate comprising applying the drug according to any one of the above [1] to [4] to a substrate.
[8] The method for producing a substrate according to the above [7], which comprises diluting and applying the drug.
[9] A method for producing a medicament, which comprises the step (I) of fractionating a solution mainly composed of lignin having a number average molecular weight of 100 or more and 800 or less from a raw material lignin solution.
[10] The raw material lignin solution is obtained by dissolving lignin solution (i) obtained by solubilizing lignin contained in plant biomass in a solvent containing an organic solvent, or solid lignin in a solvent containing an organic solvent The manufacturing method of the chemical | medical agent as described in said [9] which is lignin solution (ii).
[11] The above step (I) is carried out by using the above 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 with respect to the above raw material lignin solution The method for producing a medicament according to the above [9] or [10], which is the step (I ') of mixing the solvent (a) in a volume of 1 to 50 times.

  According to the present invention, it is possible to provide a drug which is extremely low in toxicity due to a component derived from a natural product, has excellent antiseptic properties, and is low in volatilization and elution, and a method of using and manufacturing the same. In addition, since the number average molecular weight of the obtained drug is relatively low, the heat melting property and the solvent solubility are high, and the workability is good.

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

<Medication>
The agent of the present invention contains, as a main component, polyphenols having a number average molecular weight of 100 or more and 800 or less (sometimes referred to simply as "polyphenols").
The polyphenols are tannin, lignite, lignin and the like, and the agent of the present invention is preferably lignite and lignin 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, and the "main component" is usually 5% by mass from the viewpoint of exhibiting antiseptic or antibacterial properties to the drug. It is the above, Preferably it is 25 mass% or more, More preferably, it is 45 mass% or more, More preferably, it is 60 mass% or more, Especially preferably, it is 80 mass% or more, Upper limit is 100 mass% normally. The drug of the present invention is important for polyphenols to exhibit the above-mentioned number average molecular weight in the range of the above-mentioned number average molecular weight in order to exert antiseptic property and antibacterial property, and when it is usually 5% by mass or more, antiseptic property or antibacterial property is exhibited .
Moreover, as components other than the said polyphenol which may be contained in a chemical | medical agent, although phenols, such as vanillin, saccharide | sugar perhydrolysis products, such as furfural, etc. are mentioned, It does not specifically limit.

The number average molecular weight of polyphenols is 100 or more and 800 or less. When the number average molecular weight exceeds 800, excellent antiseptic and antibacterial properties can not be exhibited, and the workability also decreases. The number average molecular weight is preferably 200 or more and 700 or less, more preferably 200 or more and 500 or less, and still more preferably 250 or more and 450 or less, from the viewpoint of exhibiting high heat melting property and solvent solubility and expressing more excellent preservative and antibacterial properties. More preferably, it is 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. to 100 ° C., more preferably 30 ° C. to 80 ° C., still more preferably 30 ° C. to 70 ° C., still more preferably 40 ° C. to 70 ° C. . When the softening point is in the above range, the antiseptic and antibacterial properties of the drug are excellent.

  As described above, the agent of the present invention is useful as a preservative and an antibacterial agent since it is excellent in preservative resistance and antibacterial properties etc., and is particularly suitable as a preservative because of its excellent preservative resistance. The agents of the present invention are antiseptic and antifungal against fungi but show better effects against fungi. Among fungi, it is more preferable as a preservative and an antibacterial agent for wood sterile bacteria and yeast, more preferable as a preservative and an antibacterial agent for white rot fungus and brown rot fungus, and particularly preferable as a preservative and an antibacterial agent for white rot fungus. As the white-rot fungus, it is preferable to shiitake, nameko, enokitake, oyster mushroom, sugitake mushroom, shiitake mushroom, shiitake mushroom, suehirotake, kawaratake, shitake, hosigetake, hiirotake, and more preferable for kawatake. As brown-rot fungi, it is preferable to Pleurotus edulis, Sarnophysalis, Namitake, Matsuouji, Chokinanatake, Kikaigaratake, Gingotake, Idobe.

The method of using the drug of the present invention is not particularly limited, and examples thereof include a method of coating or immersing the drug, and the like, but the coating is preferable from the viewpoint of workability. In addition, at the time of coating, the drug may be used after being diluted in an appropriate solvent. A suitable solvent is not particularly limited as long as it can dissolve or disperse a 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 above-mentioned polyphenols is about 5% by mass or more, it can be diluted to a viscosity sufficient for application.

Moreover, this invention can provide the base material which apply | coated the said chemical | medical agent 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, preservative treatment using the preservative can be performed 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 a substrate, or immersing the substrate in a solution of the preservative of the present invention, whereby a preservative effect is obtained on the surface of the substrate. An excellent protective film can be formed. In the case where the substrate is a material which is easy to permeate liquid, such as wood, it is more effective to permeate the preservative solution not only to the surface but also to the inside. When the preservative is allowed to penetrate to the inside of the substrate, methods such as pressurization and depressurization can be used in combination, as necessary.

As a base material which can be used for the said preservative processing, wood, fiber, concrete, a brick, a resin foam etc. are mentioned, Among these, wood is especially suitable.
The formed protective film can be dried at normal temperature, or can be heat-cured as needed. In this case, it is desirable to appropriately select the optimum heating temperature and heating time in consideration of the heat resistance of the substrate.

<Manufacturing method of medicine>
The method for producing the agent of the present invention in the case of using lignin suitable as the polyphenols in the agent of the present invention as a main component will be described.
[Step (I)]
The method for producing a drug of the present invention comprises the step of fractionating a solution mainly composed of lignin having a number average molecular weight of 100 or more and 800 or less (hereinafter sometimes referred to as "light lignin") from a raw material lignin solution (I) Have.
In addition, the above-mentioned "main component" is synonymous with the above-mentioned. Moreover, as components other than light lignin which may be contained in the mixture which has light lignin as a main component, the component similar to "components other than the said polyphenol which may be contained in a chemical | medical agent" mentioned above can be illustrated.

(Raw material lignin solution)
The raw material lignin solution used in step (I) is preferably the following lignin solution (i) or lignin solution (ii).
<Lignin solution (i)>
The lignin solution (i) is obtained by solubilizing lignin contained in plant biomass in a solvent containing an organic solvent.
As a method of solubilizing lignin contained in plant biomass in a solvent containing an organic solvent, it is possible to carry out by the existing method. For example, a method of treating plant biomass in a mixed solvent of water and aliphatic alcohol having 4 to 10 carbon atoms described in WO 2014/142289, and water described in Japanese Patent No. 5256679 Methods of treating plant biomass by
As a specific example of the method of obtaining the lignin solution (i), the plant biomass is treated with a solvent containing an organic solvent under the conditions of a specific preparation concentration of the plant biomass and the solvent, a specific reaction temperature and time By doing this, lignin can be separated and carried out.

Examples of plant biomass include woody biomass and herbaceous biomass. Examples of woody biomass include conifers such as cedar, cypress, hiba, cherry, eucalyptus, beech and bamboo, and hardwoods.
As herbaceous biomass, there are palm palm trunk / empty, palm palm fiber and seeds, bagasse (sugarcane and high biomass amount sugarcane squeezed), cane top (sugarcane top and leaf), energy cane, rice straw, straw, Corn cobs / stalks / leaves (corn stover, corn cob, corn hull), sorghum (including sweet sorghum) residue, hides and shells of Jatropha seeds, cashew shells, switchgrass, erianthus, high biomass yield crops, energy crops, etc. Can be mentioned.
Among them, herbaceous biomass is preferable from the viewpoint of easy availability and compatibility with the production method applied in the present invention, and it is preferable that the biomass is herbaceous biomass, palm palm empty straw, straw, corn foliage, bagasse, cane top, energy cane The residue after extracting the useful components is more preferable, and bagasse, cane top, energy cane, and the residue after extracting the useful components are more preferable. Useful ingredients include, for example, hemicellulose, carbohydrates, minerals, water and the like.

The 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 is one having one methoxy group (-OCH ₃ ) at the ortho position of the phenol skeleton, the S nucleus is one having 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 woody biomass does not contain H nuclei.
Plant-based biomass can also be used after being crushed. Also, it may be in the form of a block, a chip, a powder, or a water-containing hydrate.

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 any 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. 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 is preferable, and one or more selected from 1-butanol, 2-methyl-1-propanol, 2-butanol, ethanol, pentanol, hexanol and acetone, more preferably 1-butanol, 2-methyl-1 It is more preferably at least one selected from propanol, 2-butanol, ethanol and acetone, more preferably 1-butanol, 2-methyl-1-propanol, 2-butanol, 1-butanol Rukoto is particularly preferred.

  The mixing ratio of water to the organic solvent is preferably such that the molar ratio of water to the organic solvent (water / alcohol) is 1/1 to 40/1, more preferably 1.5 / 1 to 30/1, More preferably, it is 2/1 to 24/1. If 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 plant biomass to the solvent containing the organic solvent is preferably 1% by mass to 50% by mass, more preferably 3% by mass to 20% by mass, and still more preferably 5% by mass to 18% by mass . When the concentration of plant biomass is 1% by mass or more, the energy efficiency of the process of solubilizing lignin is well maintained. On the other hand, when the concentration of plant biomass exceeds 50% by mass, the amount of solvent is not sufficient, and the separation efficiency of lignin decreases.

The treatment reaction temperature is preferably 100 ° C. or more and 350 ° C. or less, more preferably 150 ° C. or more and 300 ° C. or less, and still more preferably 170 ° C. or more and 270 ° C. or less. When the temperature is 100 ° C. or higher, the separation of lignin is promoted, and when the temperature exceeds 350 ° C., the generation of coke due to the decomposition of cellulose and the repolymerization of lignin can be suppressed.
The treatment reaction time is 0.1 hour 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, still more 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 formation of coke due to the decomposition of cellulose and 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.
As solid lignin, arbitrary things can be used and there is no restriction | limiting in particular. For example, solid lignin obtained by solubilizing lignin from the above-mentioned plant biomass and then concentrated, 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 any 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. 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 is preferable, and one or more selected from 1-butanol, 2-methyl-1-propanol, 2-butanol, ethanol, pentanol, hexanol and acetone, more preferably 1-butanol, 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, particularly preferably acetone There.
As a solvent containing the said organic solvent, the mixed solvent of these organic solvents and water, for example can be mentioned. The mixing ratio of water to 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. It is preferably 20:90 to 70:30, and more preferably 10:90 to 60:40.

<Lignin concentration>
In the raw material lignin solution, the concentration of lignin at 25 ° C. in an organic solvent is preferably 1% by mass or more and 90% by mass or less. If the concentration of lignin at 25 ° C. is 1% by mass or more, there is no possibility that the energy efficiency of the process of producing a mixture mainly composed of light lignin is deteriorated. Moreover, if the density | concentration of lignin in 25 degreeC is 90 mass% or less, the isolation | separation degree in below-mentioned process (I) will become favorable.

  The concentration of lignin at 25 ° C. is preferably 1% by mass to 70% by mass, more preferably 1% by mass to 50% by mass, still more preferably 2% by mass to 40% by mass, particularly preferably 4% by mass or more It is 30 mass% or less. In addition, when using multiple types of organic solvents, the density | concentration of the said lignin means the density | concentration in the total amount of an organic solvent.

[Step (I ')]
The step (I) of fractionating a solution mainly composed of lignin having a number average molecular weight of 100 or more and 800 or less from a raw material lignin solution comprises the above-mentioned raw material lignin solution, water and a hydrocarbon having a dipole moment of 0.25 d or less It is preferable to carry out by the process (I ') of mixing the solvent (a) with the volume of the raw material lignin solution at a volume of 1 to 50 times with at least one solvent (a) selected from
By passing through the said process (I '), the mixture which has as a main component the light lignin which is excellent in preservative property, antibacterial property, and workability can be obtained.

(water)
As water, for example, tap water, industrial water, ion exchanged water, distilled water or the like can be used.
(Hydrocarbons with a dipole moment of 0.25 d or less)
As a hydrocarbon having a dipole moment of 0.25 d or less, a saturated chain hydrocarbon, unsaturated chain hydrocarbon, saturated cyclic hydrocarbon or unsaturated cyclic hydrocarbon having 5 to 8 carbon atoms is preferable. . If the dipole moment of the hydrocarbon is 0.25 d or less, the purification efficiency can be improved. Here, "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 along with its dipole moment value.

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

(Volume of solvent (a))
The amount of at least one solvent (a) selected from water and hydrocarbon having a dipole moment of 0.25 d or less when mixed with the raw material lignin solution is at least 1 time by volume relative to the raw lignin solution If it exists, the mixture mainly composed of light lignin contained in the raw material lignin solution can be sufficiently separated.
On the other hand, if the amount of the solvent (a) is 50 times or less by volume, waste water and hydrocarbon usage will not increase excessively, and a mixture mainly composed of lignin of the above-mentioned number average molecular weight can be efficiently recovered. it can.
In addition, when using multiple types of hydrocarbon solvents, the quantity of the said solvent (a) means the total amount of water and several 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, more preferably 1 to 30 times, further preferably 2 to 20 times the volume of the raw material lignin solution. It is preferably not more than twice, particularly preferably not less than 2 times and not more than 15 times.
The mixing method is not particularly limited as long as the raw material lignin solution and the solvent (a) can be uniformly mixed. The apparatus used for mixing includes, for example, edge runners, stirring mixers, roll mills, cone mills, flat stone mills, speed line mills, ball mills, bead mills, bead mills, sand mills, pearl mills, attritors, vertical mixers, kneaders, high speed agitation Machine (dissolver) etc. can be mentioned.

  The solution temperature in the above step (I ') of mixing the raw material lignin solution with at least one solvent (a) selected from water and hydrocarbon having a dipole moment of 0.25 d or less is the solution stability, lignin In view of the solubility in the solution, etc., it is preferably 0 ° C. to 100 ° C., more preferably 10 ° C. to 90 ° C., still more preferably 20 ° C. to 80 ° C., particularly preferably 25 ° C. to 70 ° C. It is below.

  When mixing the raw material lignin solution with at least one solvent (a) selected from water and a hydrocarbon having a dipole moment of 0.25 d or less in step (I ′), stirring is performed as necessary. You may When stirring is performed, stationary separation may be further performed as necessary. The standing time is usually from 1 minute to 120 minutes. If the standing time is one minute or more, the mixture mainly composed of light lignin can be sufficiently separated. Moreover, the upper limit of stationary time is enough for 120 minutes. The standing time is preferably 5 minutes to 100 minutes, more preferably 10 minutes to 60 minutes, and still more preferably 15 minutes to 30 minutes.

[Step (II-1) or (II-2)]
It is preferable to perform either of the following steps (II-1) or (II-2) depending on whether the solution obtained by the above step (I) is biphasic or monophasic.
If the solution obtained in step (I) has two phases, light lignin can be separated from the raw material lignin solution by phase separation in the following step (II-1). Moreover, when the solution obtained by process (I) is one phase, solid lignin-separated from the raw material lignin solution is carried out by solid-liquid separation of the solid which precipitated by the solubility difference at the following process (II-2). It can be separated into solutions.

(Step (II-1))
When the solution obtained in step (I) is biphasic, it is preferable to carry out step (II-1) continuously after step (I). In the step (II-1), the light lignin-based phase obtained by the step (I) is separated from the above two phases, the separated phase is concentrated, and then the obtained solid content is dried, The drug is obtained.

For example, the solution obtained by the step (I) may be a two phase comprising an aqueous phase and an organic phase (an organic phase other than a hydrocarbon having a dipole moment of 0.25 d or less, as defined below), or an aqueous phase and an organic phase When the dipole moment is divided into two phases with a hydrocarbon phase of 0.25 d or less, the mixture mainly composed of light lignin is dissolved in the water phase side, so in step (II-1) the water phase After separating the sides and concentrating the aqueous phase, the resulting solid is dried.
In addition, when the solution obtained in step (I) is divided into two phases of a hydrocarbon phase having a dipole moment of 0.25 d or less and an organic phase, a mixture mainly containing light lignin in the hydrocarbon phase Is dissolved, in step (II-1), the hydrocarbon phase is separated, the hydrocarbon phase is concentrated, and the resulting solid is dried.
In addition, when solid content is producing | generating in the state of two phases, the water phase side or the hydrocarbon phase side is isolate | separated after solid-liquid separation.

(Step (II-2))
When the solution obtained by step (I) is single phase, ie, when solid content precipitates, it is preferable to carry out step (II-2) continuously. In the step (II-2), the solution is subjected to solid-liquid separation, and 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 molecular number average molecular weight, it can produce a drug having high heat melting property and solvent solubility, and excellent in workability.
In addition, the agent of the present invention is extremely low in toxicity due to a naturally occurring component, has antiseptic and antibacterial properties, particularly excellent antiseptic properties, and is volatile although it has a relatively low molecular weight. As it is small and basically insoluble in water, there is very little concern of loss of preservative effect due to volatilization or elution if treated once.

  Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1
(Preparation of raw material lignin solution)
A mixed solvent of bagasse (sample size: 3 mm square or less), water and 1-butanol which is an organic solvent (prepared so that water / 1-butanol = 8/1 in molar ratio) as raw materials, internal volume 0 It was placed in a .92 L SUS batch-type apparatus. The mass of the mixed solvent consisting of water and 1-butanol was 300 g. The feed concentration of the bagasse was 10% by mass 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 performed at a reaction temperature of 200 ° C. for 2 hours. The reaction time was an elapsed time after reaching 200 ° C. In addition, the temperature was measured by a thermocouple. The internal pressure at the time of reaction was 1.9 MPa.
After the treatment was completed, the SUS batch-type apparatus was cooled to around room temperature, and then all the contents were taken out and filtered to separate into biomass residue and liquid phase. Further, the aqueous phase of the filtrate and the 1-butanol phase were liquid / liquid separated by a separatory funnel. The separated 1-butanol phase was used as a raw material lignin solution. The solid content (lignin) concentration was determined by separately concentrating the butanol phase, and it was 50 g / L-butanol phase.
(Step I)
To 14 mL of the obtained raw material lignin solution (water + butanol phase) (concentration of lignin: 6% by mass, 0.7 g of lignin dissolved in 14 mL of butanol + water mixed solvent) was added 178 mL of ion exchanged water. 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 separated by filtration, and 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 below-mentioned method was 344 and the softening point was 45 ° C. Moreover, the result of antiseptic evaluation by the below-mentioned method is shown in Table 2 and FIG.

Example 2
(Preparation of raw material lignin solution)
A mixed solvent (prepared so that water / 1-butanol = 4/1 in molar ratio) of cedar (sample size 1 mm square or less), water and 1-butanol which is an organic solvent as a raw material, internal volume 0 It was placed in a .7 L SUS batch-type apparatus. The mass of the mixed solvent consisting of water and 1-butanol was 300 g. The feed concentration of cedar was 1/30 in 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 performed at a reaction temperature of 200 ° C. for 2 hours. The reaction time was an elapsed time after reaching 200 ° C. In addition, the temperature was measured by a thermocouple. The internal pressure at the time of reaction was 1.8 MPa.
After the treatment was completed, the SUS batch-type apparatus was cooled to around room temperature, and then all the contents were taken out and filtered to separate into biomass residue and liquid phase. Further, the aqueous phase of the filtrate and the 1-butanol phase were liquid / liquid separated by a pipette. The solvent was removed from the separated 1-butanol phase with an evaporator (80 ° C., water bath) and then vacuum dried at 125 ° C. for 30 minutes to obtain a solubilized lignin concentrate.
(Step I)
70 mL of ethyl acetate was added to 1 g of the obtained concentrate of solubilized lignin. 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 ethyl acetate soluble matter. A mixed solvent of hexane and ethyl acetate (hexane / ethyl acetate = 4/1 volume ratio) was added to 1 g of ethyl acetate soluble matter.
(Step II-2)
The solid is removed by filtration, and the filtrate is evaporated in vacuo (80 ° C., water bath) and vacuum dried under conditions of 130 ° C. for 30 minutes to obtain lignin-based viscous solid 2 The
The number average molecular weight of the viscous solid 2 measured by the method described later was 378, and the softening point was 50.degree. Moreover, the result of antiseptic evaluation by the below-mentioned method is shown in Table 2 and FIG.

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

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

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

3. Softening point (° C)
The viscous solid or solid content (solid sample) obtained in Examples and Comparative Examples is ground in a mortar, sieved (40 mesh) to remove large particles, and the crushed sample is made of an aluminum cup (circular upper portion 60, lower portion 53) × 10 to 20 mg in a depth of 15 mm). The aluminum cup containing the sample was placed on a hot plate (ASONEND-2A) and covered with a glass plate (0.5 mm thick). After heating to 80 ° C., the temperature was raised in steps of 5 ° C., and visual observation was carried out through the glass, and the temperature at which melting was completed visually was adopted as the softening point.

4. Antiseptic Evaluation The antiseptic test was conducted by the paper disc method. Using C. versicolor as a test fungus, those cultured in advance on an agar medium containing malt extract were fractionated, dispersed in sterile water, and diluted to an absorbance of 0.02. Inoculation was carried out by dropping 500 μL of the diluted test fungus dispersion on an agar medium prepared in a sterile petri dish having a diameter of 9 cm. A diameter obtained by adding viscous water 1 of Production Example 1 to a mixed solvent of water and acetone (water / acetone = 1/9 weight ratio) and diluting it to 10% by mass was placed at the center of the agar medium after inoculation. 15 μl was dropped onto a 6 mm filter paper (paper disk). The inoculum was cultured in a constant temperature bath set at 26 ° C., and the condition around the filter paper after 3 weeks was observed.
It evaluated based on the following evaluation criteria. Moreover, the photograph in the petri dish after the said preservative evaluation test is shown to a figure.
◎: The breeding of the fungus could not be observed.
○: A fungus was propagated and white mold was observed on part of the filter paper.
X: A fungus was propagated and a white mold covered the entire filter paper.

  The present invention is a drug and a method for producing a drug which has extremely low toxicity, excellent antiseptic properties, low volatilization and elution, and good workability, and the drug has antiseptic as well as antibacterial properties. Since it can be used, it can be used as a preservative and an antibacterial agent.

Claims (11)

  A drug whose main component is polyphenols having a number average molecular weight of 100 or more and 800 or less.   The agent according to claim 1, wherein the softening point is 30 ° C or more and 100 ° C or less.   The agent according to claim 1 or 2, wherein the polyphenols are lignin.   The agent according to any one of claims 1 to 3, wherein the agent is a preservative.   A method of using the agent according to any one of claims 1 to 4, which is applied.   The method of using a drug according to claim 5, wherein the drug is diluted and applied.   A method for producing a substrate comprising applying the drug according to any one of claims 1 to 4 to a substrate.   The method for producing a substrate according to claim 7, wherein the drug is diluted and applied.   The manufacturing method of the chemical | medical agent which has process (I) which fractionates the solution which has lignin whose number average molecular weight is 100-800 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 The method for producing a medicament according to claim 9, which is (ii).   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 with respect to the raw material lignin solution are The method for producing a medicament according to claim 9 or 10, which is the step (I ') of mixing a) by a volume of 1 to 50 times.