Lignocellulose derivative composition and method for producing same

Abstract

The present invention provides: a lignocellulose derivative which is suitable for thermoforming; and a method for producing the same.　This lignocellulose derivative composition contains at least one compound that is selected from the group consisting of a cellulose derivative, a lignin skeleton-containing compound, and a hemicellulose skeleton-containing compound. The cellulose derivative is obtained by etherifying some or all of the hydroxyl groups in cellulose with methyl groups. The lignin skeleton-containing compound is lignin and / or a lignin derivative which is obtained by etherifying some or all of the hydroxyl groups in lignin with methyl groups. The hemicellulose skeleton-containing compound is hemicellulose and / or a hemicellulose derivative which is obtained by etherifying some or all of the hydroxyl groups in hemicellulose with methyl groups. The hemicellulose skeleton-containing compound contains xylan as a constituent component. This composition includes a covalent bond or interaction between the cellulose derivative and xylan and / or a covalent bond or interaction between the lignin skeleton-containing compound and xylan.

Description

Lignocellulose derivative composition and method for producing the same

[0001] The present disclosure relates to a lignocellulose derivative composition and a method for producing the same. Further, the present disclosure relates to a molded body comprising the lignocellulose derivative composition.

[0002] Cellulose derivatives are known to exhibit a variety of physical properties depending on the introduced substituents, molecular weight, etc. These properties are utilized in various fields such as films, fibers, paints, foods, medicines, and cosmetics.

[0003] Meanwhile, growing concern about environmental issues in recent years has led to calls for the development of materials derived from biomass resources instead of petroleum-derived materials. In particular, there is a demand for the use of plant biomass, which does not compete with food and does not increase atmospheric carbon dioxide.

[0004] Cellulose is a biological resource that is abundant in plant biomass. Conventionally, methods have been proposed for producing cellulose derivatives by chemical reactions using pulp obtained from woody biomass as the raw cellulose.

[0005] For example, by reacting alkali cellulose treated under alkaline conditions with various alkylating agents, cellulose ethers in which alkyl groups have been introduced into hydroxyl groups in the cellulose can be obtained. Patent Document 1 (JP-A-2008-500426) introduces as a conventional technique a specific method for producing ethyl cellulose described in "Ullmann's Encyclopedia of Industrial Chemistry."

[0006] The chemical reaction used in the prior art disclosed in Patent Document 1 requires a cellulose raw material such as high-purity kraft pulp. However, cellulose in plant biomass typically exists as lignocellulose, a high-order structure in which lignin and hemicellulose are intricately intertwined. Specifically, cellulose, a linear polymer, forms a crystalline structure through intramolecular and intermolecular hydrogen bonds to form strong microfibrils, which are then entangled with hemicelluloses such as xylan and glucomannan. Furthermore, lignin, an irregular aromatic polymer, fills the voids in the polysaccharide matrix, forming a strong composite. Obtaining high-purity cellulose raw material from such woody biomass requires a complex pulping process. The manufacturing method disclosed in Patent Document 1 has the problem of a high environmental impact due to the raw materials. Furthermore, in the process of obtaining cellulose raw material from plant biomass, lignin and hemicellulose are removed, resulting in the problem of not utilizing the entire biomass.

[0007] Non-Patent Document 1 (Green Chem., 2020, 22, 2909-2928) discloses a method for producing methylated cellulose, lignin, and hemicellulose by methylating coniferous wood sawdust in a solvent using a methylating agent. Patent Document 2 (WO 2023-084650) discloses a lignocellulose derivative composition containing cellulose, lignin, and hemicellulose in which some or all of the hydroxyl groups have been etherified with alkyl groups having two or more carbon atoms.

[0008] JP 2008-500426 A International Publication No. 2023-084650

[0009] Green Chem. , 2020, 22, 2909-2928

[0010] The cellulose derivative etherified with a methylating agent in Non-Patent Document 1 did not have good thermoformability, limiting its application as a material. Furthermore, according to the findings of the present inventors, under the reaction conditions in Non-Patent Document 1, even when the methylating agent was replaced with another alkylating agent, a high molecular weight product could not be obtained, making it difficult to apply to molded articles. The lignocellulose composition disclosed in Patent Document 2 was thermoformable, but the mechanical properties of the resulting molded articles were insufficient.

[0011] An object of the present disclosure is to provide various lignocellulose derivatives obtainable from cellulose, hemicellulose, and lignin in plant biomass, and in particular to provide lignocellulose derivatives suitable for thermoforming. Another object of the present disclosure is to provide a method for producing lignocellulose derivatives with excellent physical properties in a single step using plant biomass as a raw material, without going through a pulping process that places a high burden on the environment.

[0012] The lignocellulose derivative composition according to the present disclosure contains at least one selected from the group consisting of (1) a cellulose derivative, (2) a lignin skeleton-containing compound, and (3) a hemicellulose skeleton-containing compound. (1) The cellulose derivative is a cellulose derivative in which some or all of the hydroxyl groups in cellulose have been etherified with methyl groups. (2) The lignin skeleton-containing compound is lignin and / or a lignin derivative in which some or all of the hydroxyl groups in lignin have been etherified with methyl groups. (3) The hemicellulose skeleton-containing compound is hemicellulose and / or a hemicellulose derivative in which some or all of the hydroxyl groups in hemicellulose have been etherified with methyl groups. (3) The hemicellulose skeleton-containing compound contains xylan as a constituent component. This lignocellulose derivative composition contains (1) a covalent bond or interaction between the cellulose derivative and xylan, and / or (2) a covalent bond or interaction between the lignin skeleton-containing compound and the xylan.

[0013] The method for producing a lignocellulose derivative composition according to the present disclosure comprises the following steps: [1] treating a raw biomass containing lignocellulose with an alkali in a solvent at a temperature of 30°C to 65°C for 1 to 40 hours; [2] adding a methylating agent to the alkali-treated raw biomass and reacting the lignocellulose at a temperature of 40°C to 70°C for 30 to 120 hours, thereby methylating the lignocellulose; and [3] fractionating the methylated lignocellulose. The raw biomass containing lignocellulose is at least one selected from the group consisting of broadleaf biomass and herbaceous plant biomass. The methylating agent is a methyl halide.

[0014] In the lignocellulose derivative composition and molded article of the present disclosure, the physical properties of the methylated cellulose derivative, the lignin skeleton-containing compound, and the hemicellulose skeleton-containing compound are each expressed depending on the composition. This lignocellulose derivative composition can be used in a variety of applications, including molding by thermoforming. By thermoforming this lignocellulose derivative composition, a molded article with excellent flexibility can be obtained.

[0015] According to the production method disclosed herein, a lignocellulose derivative composition can be obtained in a single step using broadleaf woody biomass or herbaceous plant biomass as a raw material, without going through processes that place a high burden on the environment. This production method makes it possible to effectively utilize lignin and hemicellulose, which have traditionally been discarded, as raw materials.

[0016] FIG. 1 is a flowchart illustrating a method for producing a lignocellulose derivative composition according to one embodiment of the present disclosure. FIG. 2 is an NMR chart of composition Me(ALL) when the raw biomass is beech. FIG. 3 is an NMR chart of composition Me1 when the raw biomass is beech. FIG. 4 is an NMR chart of composition Me2 when the raw biomass is beech. FIG. 5 is an NMR chart of composition Me3 when the raw biomass is beech. FIG. 6 is an NMR chart of composition Me(ALL) when the raw biomass is moso bamboo. FIG. 7 is an NMR chart of composition Me1 when the raw biomass is moso bamboo. FIG. 8 is an NMR chart of composition Me2 when the raw biomass is moso bamboo. FIG. 9 is an NMR chart of composition Me3 when the raw biomass is moso bamboo. FIG. 10 is an NMR chart of composition Me(ALL) when the raw biomass is larch. FIG. 11 is an NMR chart of composition Me1 when the raw biomass is larch. FIG. 12 is an NMR chart of composition Me2 when the raw biomass is larch. FIG. 13 is an NMR chart of composition Me3 when the raw biomass is larch. FIG. 14 is a photograph of the films obtained in Experimental Examples 3, 4, and 6 when the raw materials were beech, moso bamboo, and larch, respectively (composition Me(ALL)). FIG. 15 is an NMR chart of the chloroform- and tetrahydrofuran-insoluble portion of composition Me1 when the raw biomass is beech. FIG. 16 is an NMR chart of the chloroform- and tetrahydrofuran-soluble portion of composition Me1 when the raw biomass is beech. Figure 17 is an NMR chart of the chloroform and tetrahydrofuran insoluble portion of composition Me1 when the raw biomass is moso bamboo. Figure 18 is an NMR chart of the chloroform and tetrahydrofuran soluble portion of composition Me1 when the raw biomass is moso bamboo. Figure 19 is an NMR chart of the chloroform and tetrahydrofuran insoluble portion of composition Me1 when the raw biomass is larch.Figure 20 is an NMR chart of the chloroform- and tetrahydrofuran-soluble portion of composition Me1 when the raw biomass is larch. Figure 21 is a GPC chart of the chloroform-soluble portion of composition Me1, the chloroform- and tetrahydrofuran-insoluble portion of composition Me1, and the chloroform- and tetrahydrofuran-soluble portion of composition Me1 when the raw biomass is beech. Figure 22 is a GPC chart of the chloroform-soluble portion of composition Me1, the chloroform- and tetrahydrofuran-insoluble portion of composition Me1, and the chloroform- and tetrahydrofuran-soluble portion of composition Me1 when the raw biomass is moso bamboo. Figure 23 is a GPC chart of the chloroform-soluble portion of composition Me1, the chloroform- and tetrahydrofuran-insoluble portion of composition Me1, and the chloroform- and tetrahydrofuran-soluble portion of composition Me1 when the raw biomass is larch.

[0017] Hereinafter, an example of a preferred embodiment will be specifically described with reference to the drawings as appropriate. Each configuration and combination thereof in each embodiment is merely an example, and addition, omission, substitution, and other modifications of configurations are possible as appropriate within the scope of the gist of this disclosure. The present disclosure is not limited by the embodiments, but only by the scope of the claims. Furthermore, each aspect disclosed in this specification can be combined with any other feature disclosed in this specification.

[0018] In this specification, the range "X to Y" means "X or more and Y or less." Unless otherwise noted, all test temperatures are room temperature (20°C ± 5°C). Furthermore, "X' and / or Y'" has the same meaning as "at least one selected from the group consisting of X' and Y'," and includes all of [1] to [3] of "[1] X' only, [2] Y' only, and [3] both X' and Y'."

[0019] [Method for Producing Lignocellulose Derivative Composition] The method for producing a lignocellulose derivative composition according to the present disclosure comprises the steps of: [1] alkali-treating a raw biomass containing lignocellulose in a solvent at a temperature of 30°C to 65°C for 1 to 40 hours; [2] adding a methylating agent to the alkali-treated raw biomass and reacting at a temperature of 40°C to 70°C for 30 to 120 hours to methylate the lignocellulose; and [3] fractionating the methylated lignocellulose. The raw biomass containing lignocellulose is at least one selected from the group consisting of broadleaf biomass and herbaceous plant biomass, and the methylating agent is a methyl halide.

[0020] In this production method, the alkali treatment conditions in [1] are a temperature of 30°C to 65°C and a reaction time of 1 to 45 hours, and the alkylation reaction conditions in [2] are a temperature of 40°C to 70°C and a reaction time of 30 to 120 hours. This allows methyl groups to be efficiently introduced into lignocellulose, resulting in a lignocellulose derivative composition with an appropriate ratio of lignin skeleton-containing compounds and hemicellulose skeleton-containing compounds. Furthermore, by using broadleaf biomass and herbaceous plant biomass as raw materials, this production method allows for the production of a lignocellulose derivative composition containing cellulose derivatives and / or lignin skeleton-containing compounds covalently bonded to or interacting with xylan, a component of the hemicellulose skeleton-containing compounds. Details of the lignin skeleton-containing compounds and hemicellulose skeleton-containing compounds are provided below.

[0021] This production method allows for the production of a lignocellulose derivative composition in a single step using broadleaf biomass or herbaceous plant biomass as a raw material, without going through processes that place a high burden on the environment. Furthermore, this production method allows for the effective use of lignin and hemicellulose contained in lignocellulose, which have traditionally been discarded.

[0022] 1 is a flowchart showing a method for producing a lignocellulose derivative composition according to one embodiment of the present disclosure. The production method of the present disclosure will be described in more detail below with reference to the flowchart of FIG.

[0023] (Raw Material Biomass) As shown in FIG. 1 , in this production method, lignocellulose-containing biomass is prepared as a raw material. The lignocellulose-containing biomass is at least one selected from the group consisting of broadleaf biomass and herbaceous plant biomass. Examples of broadleaf biomass include unused wood and offcuts of broadleaf trees such as beech, eucalyptus, and birch. Examples of herbaceous plant biomass include bamboo, rice straw, and bran. By using at least one selected from the group consisting of broadleaf biomass and herbaceous plant biomass as the lignocellulose-containing biomass, the hemicellulose backbone-containing compound produced by the alkali treatment and methylation in the subsequent steps contains xylan as a constituent component, and the compound contains a covalent bond or interaction between the cellulose derivative and the xylan, and / or a covalent bond or interaction between the lignin backbone-containing compound and the xylan. Therefore, a molded article obtained by molding the resulting lignocellulose derivative composition exhibits excellent flexibility. When coniferous biomass such as larch is used as the lignocellulose-containing biomass, the resulting lignocellulose derivative composition is molded into a rigid body.

[0024] Here, lignocellulose refers to a mixture of natural polymers primarily consisting of cellulose, hemicellulose, and lignin. The contents of cellulose, hemicellulose, and lignin vary depending on the type of biomass selected, but the composition is not particularly limited in the production method of the present disclosure. One or more types of biomass containing lignocellulose with different compositions can be used as the raw material.

[0025] The size of the raw biomass is not particularly limited as long as the alkali treatment and methylation in the subsequent steps are possible. From the viewpoint of improving the reaction efficiency in the alkali treatment and methylation, it is preferable that the raw biomass is fragmented or pulverized. In other words, this production method may include a pretreatment step of fragmenting or pulverizing the prepared raw biomass. The particle size of the particles contained in the fragmented or pulverized raw biomass may be 0.10 mm to 3.0 mm, 0.15 mm to 2.0 mm, 0.20 mm to 1.0 mm, 0.25 mm to 0.75 mm, 0.30 mm to 0.55 mm, or 0.35 mm to 0.50 mm. The particle size of the fragmented or pulverized raw biomass is measured by a sieve classification method using a JIS standard sieve.

[0026] The method for fragmenting or pulverizing the raw biomass is not particularly limited. For example, the raw biomass may be fragmented (chipped) using a known cutter, chipper, or the like, or may be pulverized using a known pulverizer such as a jaw crusher, gyratory crusher, crushing roll, hammer mill, roller mill, cutter mill, hammer crusher, or Willey mill. The raw biomass may be fragmented and then pulverized, or two or more types of pulverizers may be used in combination. From the viewpoint of not inhibiting the alkali treatment and methylation, this production method may further include a step of drying the fragmented or pulverized raw biomass.

[0027] (Alkali Treatment) In this production method, a solvent and an alkali are added to the raw biomass, and the mixture is subjected to alkali treatment at a temperature of 30°C to 65°C for 1 to 40 hours. Alkali treatment under these conditions facilitates the introduction of methyl groups into lignocellulose in a subsequent step. From the viewpoint of accelerating the reaction, the alkali treatment may be performed while stirring using a known stirring means.

[0028] From the viewpoint of promoting methylation in a subsequent step, the alkali treatment temperature in this step is preferably 45°C or higher, more preferably 50°C or higher. From the viewpoint of suppressing thermal decomposition and obtaining a high molecular weight product, the alkali treatment temperature is preferably 63°C or lower, more preferably 60°C or lower. The alkali treatment temperature may be 30°C to 63°C, 30°C to 61°C, 45°C to 61°C, 45°C to 60°C, 45°C to 58°C, 50°C to 60°C, 50°C to 58°C, or 50°C to 55°C.

[0029] From the viewpoint of promoting methylation in a subsequent step, the alkali treatment time in this step is preferably 2 hours or more, more preferably 3 hours or more. From the viewpoint of suppressing thermal decomposition and obtaining a high molecular weight product, the alkali treatment time is preferably 35 hours or less, more preferably 25 hours or less. The alkali treatment time may be 1 hour to 35 hours, 1 hour to 25 hours, 2 hours to 45 hours, 2 hours to 35 hours, 2 hours to 25 hours, 3 hours to 45 hours, 3 hours to 35 hours, or 3 hours to 25 hours.

[0030] (Solvent) The solvent used for the alkali treatment is not particularly limited. Examples include aprotic solvents such as dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), and 1,4-dioxane. Alcohol-based solvents such as methanol (methyl alcohol), ethanol (ethyl alcohol), and isopropyl alcohol may be used, or a mixed solvent of these alcohol-based solvents may be used. The alkali treatment solvent may be used alone, or two or more may be used in combination. From the viewpoint of enabling uniform alkali treatment, the amount of solvent added is preferably 2,000 parts by weight or more, more preferably 2,500 parts by weight or more, even more preferably 3,000 parts by weight or more, and even more preferably 3,500 parts by weight or more, relative to 100 parts by weight of raw biomass. From the viewpoint of production efficiency, the amount of solvent added is preferably 5,000 parts by weight or less, more preferably 4,500 parts by weight or less, and even more preferably 4,000 parts by weight or less, relative to 100 parts by weight of raw biomass. The amount of solvent added may be 2000 to 5000 parts by weight, 2000 to 4500 parts by weight, 2000 to 4000 parts by weight, 2500 to 5000 parts by weight, 2500 to 4500 parts by weight, 2500 to 4000 parts by weight, 3000 to 5000 parts by weight, 3000 to 4500 parts by weight, 3000 to 4000 parts by weight, or 3500 to 4000 parts by weight.

[0031] A quaternary ammonium salt such as tetrabutylammonium fluoride may be added to the solvent. From the viewpoint of facilitating dissolution of the raw biomass, the amount of the quaternary ammonium salt added is preferably 200 parts by weight or more, more preferably 300 parts by weight or more, and even more preferably 400 parts by weight or more, per 100 parts by weight of the raw biomass. From the viewpoint of improving production efficiency, the amount of the quaternary ammonium salt added is preferably 1000 parts by weight or less, more preferably 600 parts by weight or less, even more preferably 500 parts by weight or less, and even more preferably 450 parts by weight or less, per 100 parts by weight of the raw biomass. The amount of quaternary ammonium salt added may be 200 to 1000 parts by weight, 200 to 600 parts by weight, 200 to 500 parts by weight, 300 to 1000 parts by weight, 300 to 600 parts by weight, 300 to 500 parts by weight, 400 to 1000 parts by weight, 400 to 600 parts by weight, 400 to 500 parts by weight, or 400 to 450 parts by weight, relative to 100 parts by weight of raw biomass.

[0032] (Alkali) The type of alkali is not particularly limited as long as the effects of the present disclosure can be obtained. For example, hydroxides of alkali metals such as sodium and potassium are preferably used. The alkali may be added to the raw biomass as an aqueous alkali solution. From the viewpoint of facilitating alkali treatment, the amount of alkali added is preferably 500 parts by weight or more, more preferably 600 parts by weight or more, even more preferably 630 parts by weight or more, and even more preferably 650 parts by weight or more, relative to 100 parts by weight of raw biomass, in terms of solid content. From the viewpoint of obtaining a polymer, the amount of alkali added is preferably 1000 parts by weight or less, more preferably 800 parts by weight or less, even more preferably 750 parts by weight or less, and even more preferably 700 parts by weight or less, relative to 100 parts by weight of raw biomass, in terms of solid content. The amount of alkali added may be 500 to 1000 parts by weight, 500 to 800 parts by weight, 500 to 750 parts by weight, 600 to 750 parts by weight, 630 to 730 parts by weight, 630 to 700 parts by weight, 650 to 750 parts by weight, 650 to 730 parts by weight, or 650 to 700 parts by weight, relative to 100 parts by weight of raw biomass.

[0033] (Alkylation) In this production method, a methylating agent is added to alkali-treated raw biomass and reacted at a temperature of 40°C to 70°C for 30 to 120 hours. By carrying out the reaction under these conditions, the lignocellulose in the raw biomass can be efficiently methylated. Specifically, methyl groups are introduced into hydroxyl groups in at least one component selected from the group consisting of cellulose, hemicellulose, and lignin that constitute lignocellulose. Preferably, methyl groups are introduced into hydroxyl groups in the three components of lignocellulose: cellulose, hemicellulose, and lignin. Furthermore, the alkali treatment and methylation steps are thought to disrupt the interactions between cellulose, hemicellulose, and lignin, which form a higher-order structure. To promote the reaction, the methylation reaction may be carried out while stirring using a known stirring means.

[0034] From the viewpoint of accelerating methylation, the methylation reaction temperature in this step is preferably 43°C or higher, more preferably 45°C or higher. From the viewpoint of suppressing thermal decomposition and obtaining a high molecular weight product, the methylation reaction temperature is preferably 65°C or lower, more preferably 60°C or lower. The methylation reaction temperature may be 40 to 65°C, 40 to 60°C, 43 to 65°C, 43 to 65°C, 43 to 60°C, 45 to 60°C, 45 to 60°C, or 45 to 60°C.

[0035] From the viewpoint of promoting methylation, the methylation reaction time in this step is preferably 35 hours or more, more preferably 40 hours or more. From the viewpoint of suppressing thermal decomposition and obtaining a high molecular weight product, the methylation reaction time is preferably 110 hours or less, more preferably 100 hours or less. The methylation reaction time may be 30 to 110 hours, 30 to 100 hours, 35 to 120 hours, 35 to 110 hours, 35 to 100 hours, 40 to 120 hours, 40 to 110 hours, or 40 to 100 hours.

[0036] (Methylating Agent) The methylating agent in this production method is a methyl halide having one carbon atom. Use of this methylating agent makes it possible to obtain a lignocellulose derivative composition having a glass transition temperature that allows thermoforming and a high molecular weight. Examples of this methyl halide having one carbon atom include methyl iodide, methyl bromide, methyl chloride, and methyl fluoride. Methyl iodide is more preferred from the viewpoints of obtaining a lignocellulose derivative composition that can be used in a variety of applications and ease of handling. An alkyl halide having two or more carbon atoms may be used as an alkylating agent in combination with the methylating agent, as long as the effects of the present disclosure are obtained.

[0037] From the viewpoint of promoting the methylation reaction, the amount of the methylating agent added is preferably 600 parts by weight or more, more preferably 700 parts by weight or more, and even more preferably 750 parts by weight or more, based on the solid content per 100 parts by weight of the raw biomass. From the viewpoint of production efficiency, the amount of the methylating agent added is preferably 1000 parts by weight or less, more preferably 900 parts by weight or less, and even more preferably 800 parts by weight or less, based on the solid content per 100 parts by weight of the raw biomass. The amount of the methylating agent added may be 600 to 1000 parts by weight, 700 to 1000 parts by weight, 750 to 900 parts by weight, or 750 to 800 parts by weight, based on the solid content per 100 parts by weight of the raw biomass.

[0038] (Fractionation) Lignocellulose methylated with a methyl halide having one carbon atom contains a cellulose skeleton-containing compound, a lignin skeleton-containing compound, and a hemicellulose skeleton-containing compound. In this production method, the methylated lignocellulose is fractionated to obtain a lignocellulose derivative composition containing the cellulose skeleton-containing compound, the lignin skeleton-containing compound, and the hemicellulose skeleton-containing compound in desired proportions.

[0039] In this specification, "cellulose skeleton-containing compound" means cellulose or a cellulose derivative in which some or all of the hydroxyl groups in cellulose have been etherified with alkyl groups having two or more carbon atoms. "Lignin skeleton-containing compound" means lignin or a lignin derivative in which some or all of the hydroxyl groups in lignin have been etherified with methyl groups. "Hemicellulose skeleton-containing compound" means hemicellulose or a hemicellulose derivative in which some or all of the hydroxyl groups in hemicellulose have been etherified with methyl groups.

[0040] Fractionation refers to separating a mixture into individual components by utilizing the differences in the physical properties of the constituent components. In the production method of the present disclosure, the method for fractionating methylated lignocellulose is not particularly limited. Typically, fractionation can be performed by precipitation fractionation, dialysis treatment, fractional extraction, etc., utilizing the differences in the solubilities in solvents of cellulose and cellulose derivatives, lignin and lignin derivatives, and hemicellulose and hemicellulose derivatives.

[0041] As shown in Figure 1, in this embodiment, methylated lignocellulose is added to an excess amount of water to precipitate water-insoluble or slightly soluble components as solids. Subsequently, solid-liquid separation using known means such as filtration can separate the solid fraction containing the water-insoluble or slightly soluble components from a filtrate containing the amphiphilic components. The filtrate is then subjected to dialysis to obtain the amphiphilic component (composition Me3). Composition Me3 consists of fractionated components that are soluble or readily soluble in water.

[0042] Next, alcohol (e.g., methanol) is added to and mixed with the solid fraction containing the water-insoluble or poorly soluble component, thereby precipitating the alcohol-insoluble or poorly soluble component as a solid. Thereafter, solid-liquid separation can be performed using known means such as filtration to further separate the solid fraction containing the alcohol-insoluble or poorly soluble component and a filtrate containing alcohol-soluble or readily soluble components. By appropriately drying this solid fraction, a component that is insoluble or poorly soluble in water and insoluble or poorly soluble in alcohol (composition Me1) can be obtained. Furthermore, by appropriately concentrating or drying this filtrate, a component that is insoluble or poorly soluble in water and soluble or readily soluble in alcohol (composition Me2) can be obtained.

[0043] As shown in FIG. 1, compositions Me1, Me2, and Me3 obtained by fractionating methylated lignocellulose are all lignocellulose derivative compositions of the present disclosure.

[0044] In the production method of the present disclosure, the temperature conditions for fractionating the methylated lignocellulose are not particularly limited. Typically, the temperature is room temperature (25°C ± 5°C), but can be appropriately selected depending on the type of raw biomass used, the composition of the desired lignocellulose derivative composition, etc.

[0045] [Lignocellulose Derivative Composition] The lignocellulose derivative composition of the present disclosure is a lignocellulose derivative composition, the composition comprising at least one selected from the group consisting of (1) a cellulose derivative, (2) a lignin skeleton-containing compound, and (3) a hemicellulose skeleton-containing compound, wherein the (1) cellulose derivative is a cellulose derivative in which some or all of the hydroxyl groups in cellulose have been etherified with methyl groups, the (2) lignin skeleton-containing compound is lignin and / or a lignin derivative in which some or all of the hydroxyl groups in lignin have been etherified with methyl groups, the (3) hemicellulose skeleton-containing compound is hemicellulose and / or a hemicellulose derivative in which some or all of the hydroxyl groups in hemicellulose have been etherified with methyl groups, and the (3) hemicellulose skeleton-containing compound contains xylan as a constituent component, and the (1) cellulose derivative and xylan are covalently bonded or interacting with each other, and / or the (2) lignin skeleton-containing compound and xylan are covalently bonded or interacting with each other. The lignocellulose derivative composition of the present disclosure preferably contains either or both of a lignin skeleton-containing compound and a hemicellulose skeleton-containing compound. This composition may further contain a cellulose derivative in which some or all of the hydroxyl groups in cellulose have been etherified with methyl groups. The lignin skeleton-containing compound is lignin or a lignin derivative in which some or all of the hydroxyl groups in lignin have been etherified with methyl groups. The hemicellulose skeleton-containing compound is hemicellulose or a hemicellulose derivative in which some or all of the hydroxyl groups in hemicellulose have been etherified with methyl groups. This composition may further contain cellulose.

[0046] (Methyl group) In the present disclosure, the alkyl group introduced into the cellulose derivative, lignin derivative, and hemicellulose derivative is a methyl group having one carbon atom. An alkyl group having two or more carbon atoms may be introduced into the cellulose derivative, lignin derivative, and hemicellulose derivative together with the methyl group, as long as the effects of the present disclosure are obtained. Examples of the alkyl group having two or more carbon atoms include an ethyl group and a propyl group.

[0047] (Degree of alkyl substitution (degree of methyl substitution)) As long as the effects of the present disclosure can be obtained, the degree of alkyl substitution (degree of methyl substitution) of the cellulose derivative, lignin derivative, and hemicellulose derivative is not particularly limited and can be appropriately adjusted depending on the application and physical properties. From the viewpoint of ease of thermoforming, the degree of methyl substitution of the cellulose derivative is preferably 2.0 or more, more preferably 2.5 or more, and the upper limit thereof may be 3.0. The degree of methyl substitution of the cellulose derivative may be 2.0 to 3.0, or may be 2.5 to 3.0. The degree of methyl substitution of the lignin derivative may be 1.0 or more, 1.5 or more, or 4.0 or less, or 3.5 or less. The degree of methyl substitution of the hemicellulose derivative may be 0.5 or more, 1.0 or more, or 3.0 or less, or 2.5 or less. The method for measuring the degree of methyl substitution will be described later in the examples.

[0048] (Preferred Aspect 1: Composition Me1) The lignocellulose derivative composition of the present disclosure is obtained by the production method described above. Specifically, this lignocellulose derivative composition is obtained by fractionating methylated lignocellulose by utilizing differences in the solvent solubilities of its constituent components. In a preferred embodiment, the methylated lignocellulose is fractionated into the following lignocellulose derivative compositions:

[0049] The lignocellulose derivative composition of Aspect 1 comprises a cellulose derivative in which some or all of the hydroxyl groups in the cellulose have been etherified with methyl groups. More preferably, the lignocellulose derivative composition of Aspect 1 comprises a cellulose derivative in which some or all of the hydroxyl groups in the cellulose have been etherified with methyl groups, a lignin skeleton-containing compound, and a hemicellulose skeleton-containing compound. Specifically, the lignocellulose derivative composition of Aspect 1 comprises a covalent bond or interaction between the cellulose derivative and xylan. That is, the lignocellulose derivative composition of Aspect 1 comprises a covalent bond between the cellulose derivative and xylan, or comprises an interaction between the cellulose derivative and xylan. The lignocellulose derivative composition of Aspect 1 is a composition shown as composition Me1 in Figure 1, and comprises a fraction component that is insoluble or poorly soluble in water and insoluble or poorly soluble in alcohol.

[0050] From the viewpoint of obtaining a molded body having excellent mechanical properties by thermoforming, the number-average molecular weight Mn of the lignocellulose derivative composition of Aspect 1 is preferably 30,000 or more, more preferably 40,000 or more, and even more preferably 50,000 or more. Although there are no particular limitations on the upper limit of the number-average molecular weight Mn, from the viewpoint of ease of production, a preferred number-average molecular weight Mn is 150,000 or less. The number-average molecular weight Mn of the lignocellulose derivative composition of Aspect 1 may be 30,000 to 150,000, 40,000 to 150,000, or 50,000 to 120,000.

[0051] From the viewpoint of improving the strength of the resulting molded article, the weight-average molecular weight Mw of the lignocellulose derivative composition of Aspect 1 is preferably 120,000 or more, more preferably 200,000 or more, and even more preferably 300,000 or more. While there are no particular limitations on the upper limit of the weight-average molecular weight Mw, from the viewpoint of ease of production, the weight-average molecular weight Mw is preferably 1,000,000 or less, more preferably 900,000 or less, and even more preferably 700,000 or less. The weight-average molecular weight Mw of the lignocellulose derivative composition of Aspect 1 may be 120,000 to 1,000,000, 200,000 to 900,000, or 300,000 to 700,000.

[0052] From the viewpoint of high melt fluidity, the molecular weight distribution Mw / Mn calculated from the weight average molecular weight Mw and the number average molecular weight Mn of the lignocellulose derivative composition of Aspect 1 is preferably 1.0 or more, more preferably 1.5 or more, and even more preferably 1.6 or more. From the viewpoint of improving the strength of the obtained molded article, the molecular weight distribution Mw / Mn is preferably 9.5 or less, more preferably 9.0 or less, even more preferably 8.0 or less, and particularly preferably 7.0 or less. The molecular weight distribution Mw / Mn of the lignocellulose derivative composition of aspect 1 may be 1.0 to 9.5, 1.0 to 9.0, 1.0 to 8.0, 1.0 to 7.0, 1.5 to 9.0, 1.5 to 8.0, 1.5 to 7.0, 1.5 to 6.0, 1.6 to 8.0, 1.6 to 7.0, 1.6 to 6.0, or 1.6 to 5.0.

[0053] The number-average molecular weight Mn, weight-average molecular weight Mw, and molecular weight distribution Mw / Mn of the lignocellulose derivative composition of Aspect 1 can be measured by gel permeation chromatography. Details of the measurement method and measurement conditions will be described later in the Examples.

[0054] The lignocellulose derivative composition of Aspect 1 may have a glass transition point. From the viewpoint of ease of thermoforming, the glass transition temperature Tg of the lignocellulose derivative composition of Aspect 1 is preferably 120°C or lower, more preferably 115°C or lower. The glass transition temperature Tg of the composition of Aspect 1 may be 90°C or higher, or may be 100°C or higher. The glass transition temperature Tg of the lignocellulose derivative composition of Aspect 1 may be 90 to 120°C, 90 to 115°C, 100 to 120°C, or 100 to 115°C.

[0055] The lignocellulose derivative composition of Aspect 1 may have a melting point. From the viewpoint of improving heat resistance, the melting point Tm of the lignocellulose derivative composition of Aspect 1 is preferably 200°C or higher, more preferably 220°C or higher, and even more preferably 230°C or higher. The melting point Tm of the composition of Aspect 1 may be 300°C or lower, 280°C or lower, 250°C or lower, or 240°C or lower. The melting point Tm of the lignocellulose derivative composition of Aspect 1 may be 200 to 300°C, 220 to 280°C, 230 to 250°C, or 230 to 240°C.

[0056] The glass transition temperature Tg and melting point Tm of the lignocellulose derivative composition of Aspect 1 can be measured by differential scanning calorimetry. Details of the measurement method and conditions will be described later in the Examples.

[0057] (Constituent Ratios of Aspect 1) As described above, the lignocellulose derivative composition of Aspect 1 (composition Me1) contains at least a cellulose derivative, and preferably contains a cellulose derivative, a lignin skeleton-containing compound, and a hemicellulose skeleton-containing compound. In the lignocellulose derivative composition of Aspect 1, the proportion of the lignin skeleton-containing compound relative to all constituent components may be greater than 0 wt%, may be 0.5 wt% or more, or may be 1.0 wt% or more. From the viewpoints of thermoformability and ultraviolet absorption ability, a higher proportion of the lignin skeleton-containing compound is preferable, but the proportion may be 30 wt% or less, 20 wt% or less, 15 wt% or less, or 10 wt% or less. In the lignocellulose derivative composition of aspect 1, the ratio of the lignin skeleton-containing compound to all constituent components may be greater than 0 wt% and less than 30 wt%, greater than 0 wt% and less than 20 wt%, greater than 0 wt% and less than 15 wt%, 0.5 wt% to 30 wt%, 0.5 wt% to 20 wt%, 0.5 wt% to 15 wt%, 0.5 wt% to 10 wt%, 1.0 wt% to 30 wt%, 1.0 wt% to 20 wt%, 1.0 wt% to 15 wt%, or 1.0 wt% to 10 wt%.

[0058] In the lignocellulose derivative composition of Aspect 1, the constituent ratio of the cellulose derivative may be 20 wt% or more, 30 wt% or more, or 35 wt% or more of all constituent components. The constituent ratio of the cellulose derivative may be 80 wt% or less, 70 wt% or less, or 65 wt% or less. In the lignocellulose derivative composition of Aspect 1, the constituent ratio of the cellulose derivative may be 30 to 70 wt% of all constituent components.

[0059] In the lignocellulose derivative composition of Aspect 1, the constituent ratio of the hemicellulose skeleton-containing compound may be 20.0 wt% or more, 29.0 wt% or more, 29.5 wt% or more, 30.0 wt% or more, or 35.0 wt% or more of all constituent components. Furthermore, the constituent ratio of the hemicellulose skeleton-containing compound may be 80.0 wt% or less, 70.0 wt% or less, 69.5 wt% or less, 69.0 wt% or less, or 65.0 wt% or less. In the lignocellulose derivative composition of Aspect 1, the constituent ratio of the hemicellulose skeleton-containing compound may be 29.5 to 69.5 wt% of all constituent components.

[0060] The lignocellulose derivative composition of Aspect 1 contains a covalent bond or interaction between a cellulose derivative and xylan, and / or a covalent bond or interaction between a lignin skeleton-containing compound and xylan. Specifically, the lignocellulose derivative composition of Aspect 1 contains a covalent bond or interaction between a cellulose derivative and xylan. This xylan is a xylan contained as a constituent of a hemicellulose skeleton-containing compound. More specifically, the lignocellulose derivative composition of Aspect 1 contains a component with a structure of cellulose-xylan-lignin, in which cellulose and xylan are covalently bonded or interact with each other, and xylan and lignin are covalently bonded or interact with each other. The above-mentioned "covalently bonded or interacted" means that the components are covalently bonded or interact with each other. Here, the cellulose-xylan-lignin can also be said to be a component covalently bonded between a cellulose derivative and xylan, or a component interacting between a cellulose derivative and xylan. Furthermore, this cellulose-xylan-lignin can be said to be a component formed by a covalent bond between a lignin skeleton-containing compound and xylan, or a component that interacts with a lignin skeleton-containing compound and xylan. Here, the above-mentioned interaction means a strong mutual action that cannot be separated from each other, even if it cannot be said to be a chemical covalent bond.

[0061] The weight of the component with a cellulose-xylan structure, in which cellulose and xylan are covalently bonded or interact with each other, can be determined by extracting the lignocellulose derivative composition of Aspect 1 with chloroform, drying the extracted component, and then extracting it with tetrahydrofuran and drying the extract. This component interacts with cellulose alone and xylan alone, and has been shown to have a plasticizer-like effect, promoting the thermoplasticization of cellulose and xylan.

[0062] In the lignocellulose derivative composition of Aspect 1 (composition Me1), the weight ratio (wt %) of the chloroform and tetrahydrofuran soluble portion (i.e., the THF soluble portion in the CHCl3 soluble portion of composition Me1) is preferably 5 wt % or more, more preferably 10 wt % or more, and even more preferably 15 wt % or more, relative to 100 wt % of composition Me1, from the viewpoint of further exerting the thermoplastic effect of the component having a cellulose-xylan structure in which cellulose and xylan are covalently bonded or interact with each other. Furthermore, in the lignocellulose derivative composition of the present disclosure, the weight ratio (wt %) of the chloroform and tetrahydrofuran soluble portion (i.e., the THF soluble portion in the CHCl3 soluble portion of composition Me1) is preferably 4 wt % or more, more preferably 7 wt % or more, and even more preferably 10 wt % or more, relative to 100 wt % of the total of compositions Me1, Me2, and Me3.

[0063] The ratios of the cellulose derivative, the lignin skeleton-containing compound, and the hemicellulose skeleton-containing compound in the lignocellulose derivative composition of Aspect 1 can be measured by nuclear magnetic resonance (NMR) measurement or ultraviolet-visible (UV-Vis) absorption measurement. Details will be described later in the Examples.

[0064] (Preferred Aspect 2: Composition Me2) The lignocellulose derivative composition of Aspect 2 contains a lignin skeleton-containing compound. The lignocellulose derivative composition of Aspect 2 may contain a cellulose derivative and / or a hemicellulose skeleton-containing compound in addition to the lignin skeleton-containing compound. Specifically, the lignocellulose derivative composition of Aspect 2 contains a covalent bond or interaction between the lignin skeleton-containing compound and xylan. That is, the lignocellulose derivative composition of Aspect 2 contains a covalent bond between the lignin skeleton-containing compound and xylan, or contains an interaction between the lignin skeleton-containing compound and xylan. The lignocellulose derivative composition of Aspect 2 is a composition shown as Composition Me2 in FIG. 1 and is composed of fractionated components that are insoluble or poorly soluble in water and soluble or easily soluble in alcohol. Depending on the type of raw biomass, the lignocellulose derivative composition of Aspect 2 may further contain a cellulose derivative in which some or all of the hydroxyl groups in the cellulose have been etherified with methyl groups.

[0065] From the viewpoint of obtaining a molded body having excellent mechanical properties by thermoforming, the number average molecular weight Mn of the lignocellulose derivative composition of Aspect 2 is preferably 1,000 or more, more preferably 1,100 or more. There is no particular upper limit to the number average molecular weight Mn, but from the viewpoint of ease of production, the number average molecular weight Mn is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less. The number average molecular weight Mn of the lignocellulose derivative composition of Aspect 2 may be 1,000 to 10,000, or may be 1,100 to 5,000.

[0066] From the viewpoint of improving the strength of the resulting molded article, the weight-average molecular weight Mw of the lignocellulose derivative composition of Aspect 2 is preferably 1,000 or more, more preferably 2,000 or more. While there are no particular limitations on the upper limit of the weight-average molecular weight Mw, from the viewpoint of ease of production, the weight-average molecular weight Mw is preferably 100,000 or less, more preferably 10,000 or less, and more preferably 8,000 or less. The number-average molecular weight Mw of the lignocellulose derivative composition of Aspect 2 may be 1,000 to 100,000, or may be 2,000 to 10,000.

[0067] From the viewpoint of high melt fluidity, the molecular weight distribution Mw / Mn calculated from the weight average molecular weight Mw and number average molecular weight Mn of the lignocellulose derivative composition of Aspect 2 is preferably 1.0 or more, more preferably 1.5 or more, and even more preferably 1.7 or more. From the viewpoint of improving the strength of the resulting molded article, the molecular weight distribution Mw / Mn is preferably 50.0 or less, more preferably 48.0 or less, even more preferably 10.0 or less, and even more preferably 5.0 or less. The molecular weight distribution Mw / Mn of the lignocellulose derivative composition of Aspect 2 may be 1.0 to 50.0, 1.0 to 48.0, 1.0 to 10.0, 1.0 to 5.0, 1.5 to 50.0, 1.5 to 48.0, 1.5 to 10.0, 1.5 to 5.0, or 1.7 to 5.0.

[0068] The number average molecular weight Mn, weight average molecular weight Mw and molecular weight distribution Mw / Mn of the lignocellulose derivative composition of Embodiment 2 can be measured in the same manner as for the composition of Embodiment 1.

[0069] The lignocellulose derivative composition of Aspect 2 may have a glass transition temperature. From the viewpoint of ease of thermoforming, the glass transition temperature Tg of the lignocellulose derivative composition of Aspect 2 is preferably 150°C or lower, more preferably 100°C or lower. The glass transition temperature Tg of the composition of Aspect 2 may be 30°C or higher, or may be 50°C or higher.

[0070] The glass transition temperature Tg of the lignocellulose derivative composition of the second embodiment is measured in the same manner as that of the composition of the first embodiment.

[0071] (Constituent Ratio of Aspect 2) As described above, the lignocellulose derivative composition of Aspect 2 (composition Me2) contains a lignin skeleton-containing compound. In the lignocellulose derivative composition of Aspect 2, the constituent ratio of the lignin skeleton-containing compound among all constituent components may be 55 wt % or more, 60 wt % or more, 70 wt % or more, or 80 wt % or more. From the viewpoints of thermoformability and ultraviolet absorption ability, a larger constituent ratio of the lignin skeleton-containing compound is preferable, but the constituent ratio of the lignin skeleton-containing compound may be 100 wt %, 100 wt % or less, 95 wt % or less, or 90 wt % or less. In the lignocellulose derivative composition of aspect 2, the ratio of the lignin skeleton-containing compound to all constituent components may be greater than 55 wt% and less than 100 wt%, greater than 55 wt% and less than 95 wt%, 55 wt% to 90 wt%, 60 wt% to 100 wt%, 60 wt% to 95 wt%, 60 wt% to 90 wt%, 70 wt% to 100 wt%, 70 wt% to 95 wt%, or 70 wt% to 90 wt%.

[0072] In the lignocellulose derivative composition of Aspect 2, the constituent ratio of the cellulose derivative may be 0 wt %, 0 wt % or more, more than 0 wt %, 1 wt % or more, or 5 wt % or more of all constituent components. Furthermore, the constituent ratio of the cellulose derivative may be 50 wt % or less, 45 wt % or less, 40 wt % or less, or 5 wt % or less. In the lignocellulose derivative composition of Aspect 2, the constituent ratio of the cellulose derivative may be 0 to 45 wt % of all constituent components.

[0073] In the lignocellulose derivative composition of Aspect 2, the constituent ratio of the hemicellulose skeleton-containing compound may be 0 wt %, 0 wt % or more, more than 0 wt %, or 1 wt % or more of all constituent components. Furthermore, the constituent ratio of the hemicellulose skeleton-containing compound may be 10 wt % or less, 5 wt % or less, or 2 wt % or less. In the lignocellulose derivative composition of Aspect 2, the constituent ratio of the hemicellulose skeleton-containing compound may be 0 to 5 wt % of all constituent components.

[0074] The lignocellulose derivative composition of Aspect 2 contains a covalent bond or interaction between a cellulose derivative and xylan, and / or a covalent bond or interaction between a lignin skeleton-containing compound and xylan. Specifically, the lignocellulose derivative composition of Aspect 2 contains a covalent bond or interaction between a lignin skeleton-containing compound and xylan. This xylan is a xylan contained as a constituent of a hemicellulose skeleton-containing compound. More specifically, the lignocellulose derivative composition of Aspect 2 contains a component with a cellulose-xylan-lignin structure in which cellulose and xylan are covalently bonded or interact with each other, and xylan and lignin are covalently bonded or interact with each other. The above-mentioned "covalently bonded or interacted" refers to a covalent bond or interaction. Here, the cellulose-xylan-lignin can also be said to be a component covalently bonded between a cellulose derivative and xylan, or a component interacting between a cellulose derivative and xylan. Furthermore, this cellulose-xylan-lignin can be said to be a component in which a lignin skeleton-containing compound and xylan are covalently bonded, or a component in which a lignin skeleton-containing compound and xylan interact with each other. Here, the interaction is the same as that described above.

[0075] The proportions of the cellulose derivative, the lignin skeleton-containing compound, and the hemicellulose skeleton-containing compound in the lignocellulose derivative composition of Aspect 2 can be measured in the same manner as in the composition of Aspect 1.

[0076] (Preferred Aspect 3: Composition Me3) The main component of the lignocellulose derivative composition of Aspect 3 is a hemicellulose skeleton-containing compound. Composition Me3 may contain, but does not necessarily contain, a lignin skeleton-containing compound. The lignocellulose derivative composition of Aspect 3 is the composition shown as composition Me3 in FIG. 1 and is composed of amphiphilic fractionated components. Depending on the type of raw material biomass, the lignocellulose derivative composition of Aspect 3 may further contain a cellulose derivative in which some or all of the hydroxyl groups in the cellulose have been etherified with methyl groups, a lignin skeleton-containing compound, or a hemicellulose skeleton-containing compound.

[0077] The number average molecular weight Mn of the lignocellulose derivative composition of Aspect 3 is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 40,000 or less. The number average molecular weight Mn of the composition of Aspect 3 may be 2,000 or more, 5,000 or more, or 10,000 or more. The number average molecular weight Mn of the lignocellulose derivative composition of Aspect 3 may be 2,000 to 50,000, 2,000 to 40,000, 5,000 to 40,000, or 10,000 to 40,000.

[0078] The weight average molecular weight Mw of the lignocellulose derivative composition of Aspect 3 is preferably 100,000 or less, more preferably 80,000 or less. The weight average molecular weight Mw of the composition of Aspect 3 may be 10,000 or more, 30,000 or more, or 50,000 or more. The weight average molecular weight Mw of the lignocellulose derivative composition of Aspect 3 may be 10,000 to 100,000, 10,000 to 80,000, 30,000 to 80,000, or 50,000 to 80,000.

[0079] The molecular weight distribution Mw / Mn calculated from the weight average molecular weight Mw and number average molecular weight Mn of the lignocellulose derivative composition of Aspect 3 may be 1.0 or more, 1.1 or more, or 1.5 or more. The molecular weight distribution Mw / Mn of the composition of Aspect 3 may be 7.0 or less, 5.0 or less, or 4.0 or less. The molecular weight distribution Mw / Mn of the lignocellulose derivative composition of Aspect 3 may be 1.0 to 7.0, 1.0 to 5.0, 1.0 to 4.0, 1.5 to 7.0, 1.5 to 5.0, or 1.5 to 4.0.

[0080] The number average molecular weight Mn, weight average molecular weight Mw and molecular weight distribution Mw / Mn of the lignocellulose derivative composition of Aspect 3 can be measured in the same manner as for the composition of Aspect 1.

[0081] The lignocellulose derivative composition of Aspect 3 may have a glass transition point. The glass transition temperature Tg of the lignocellulose derivative composition of Aspect 3 may be 150°C or lower, or 120°C or lower. The glass transition temperature Tg of the composition of Aspect 3 may be 50°C or higher, 70°C or higher, or 90°C or higher. The glass transition temperature Tg of the lignocellulose derivative composition of Aspect 3 may be 50 to 150°C, 50 to 120°C, 70 to 150°C, or 70 to 120°C.

[0082] The glass transition temperature Tg of the lignocellulose derivative composition of Aspect 3 is measured in the same manner as for the composition of Aspect 1.

[0083] (Constituent Ratio of Aspect 3) As described above, the main component of the lignocellulose derivative composition of Aspect 3 is a hemicellulose skeleton-containing compound. The lignocellulose derivative composition of Aspect 3 (composition Me3) preferably contains a cellulose derivative, a lignin skeleton-containing compound, and a hemicellulose skeleton-containing compound. In the lignocellulose derivative composition of Aspect 3, the constituent ratio of the lignin skeleton-containing compound may exceed 0 wt % and may be 1 wt % or more of all constituent components. From the viewpoints of thermoformability and ultraviolet absorption ability, a higher constituent ratio of the lignin skeleton-containing compound is preferable, but the constituent ratio may be 19 wt % or less, 17 wt % or less, or 15 wt % or less. In the lignocellulose derivative composition of aspect 3, the composition ratio of the lignin skeleton-containing compound among all constituent components may be greater than 0 wt% and less than 19 wt%, greater than 0 wt% and less than 17 wt%, greater than 0 wt% and less than 15 wt%, 1 wt% or more and less than 19 wt%, 1 wt% or more and less than 17 wt%, or 1 wt% or more and less than 15 wt%.

[0084] In the lignocellulose derivative composition of Aspect 3, the constituent ratio of the cellulose derivative may be 5 wt% or more, 10 wt% or more, 14 wt% or more, or 20 wt% or more of all constituent components. Furthermore, the constituent ratio of the cellulose derivative may be 55 wt% or less, 50 wt% or less, 49 wt% or less, or 40 wt% or less. In the lignocellulose derivative composition of Aspect 3, the constituent ratio of the cellulose derivative may be 14 to 49 wt% of all constituent components.

[0085] In the lignocellulose derivative composition of Aspect 3, the constituent ratio of the hemicellulose skeleton-containing compound may be 30 wt% or more, 40 wt% or more, 50 wt% or more, or 55 wt% or more of all constituent components. Furthermore, the constituent ratio of the hemicellulose skeleton-containing compound may be 95 wt% or less, 90 wt% or less, 85 wt% or less, or 80 wt% or less. In the lignocellulose derivative composition of Aspect 3, the constituent ratio of the hemicellulose skeleton-containing compound may be 50 to 85 wt% of all constituent components.

[0086] The lignocellulose derivative composition of Aspect 3 contains a covalent bond or interaction between the cellulose derivative and xylan, and / or a covalent bond or interaction between the lignin skeleton-containing compound and xylan. Specifically, the lignocellulose derivative composition of Aspect 3 contains a covalent bond or interaction between the lignin skeleton-containing compound and xylan. That is, the lignocellulose derivative composition of Aspect 3 contains a covalent bond between the lignin skeleton-containing compound and xylan, or contains an interaction between the lignin skeleton-containing compound and xylan. This xylan is a xylan contained as a constituent of the hemicellulose skeleton-containing compound. More specifically, the lignocellulose derivative composition of Aspect 3 contains a component with a xylan-lignin structure, in which xylan and lignin are covalently bonded or interacted with each other. This xylan-lignin can also be said to be a component formed by a covalent bond or interaction between the lignin skeleton-containing compound and xylan. The above-mentioned "covalent bond or interaction" means that there is a covalent bond or interaction. Here, this xylan-lignin can be said to be a component formed by a covalent bond between a lignin skeleton-containing compound and xylan, or a component that interacts with a lignin skeleton-containing compound and xylan. Here, the interaction is the same as that described above.

[0087] The proportions of the cellulose derivative, the lignin skeleton-containing compound, and the hemicellulose skeleton-containing compound in the lignocellulose derivative composition of Aspect 3 can be measured in the same manner as in the composition of Aspect 1.

[0088] (Preferred Aspect 4: Composition Me(ALL)) The lignocellulose derivative composition of Aspect 4 is a composition obtained without fractionation. A lignocellulose derivative composition obtained without fractionation also corresponds to the lignocellulose derivative composition of this embodiment. The lignocellulose derivative composition of Aspect 4 preferably comprises a cellulose derivative, a lignin skeleton-containing compound, and a hemicellulose skeleton-containing compound, wherein the hemicellulose skeleton-containing compound contains xylan as a constituent component, and comprises a covalent bond or interaction between the cellulose derivative and the xylan, and / or a covalent bond or interaction between the lignin skeleton-containing compound and xylan.

[0089] The number average molecular weight Mn of the lignocellulose derivative composition of Aspect 4 is preferably 100,000 or less, more preferably 90,000 or less. The number average molecular weight Mn of the composition of Aspect 4 may be 1,000 or more, or 1,100 or more. The number average molecular weight Mn of the lignocellulose derivative composition of Aspect 4 may be 1,000 to 100,000, 1,000 to 90,000, 1,100 to 100,000, or 1,100 to 90,000.

[0090] The weight average molecular weight Mw of the lignocellulose derivative composition of Aspect 4 is preferably 500,000 or less, more preferably 450,000 or less. The weight average molecular weight Mw of the composition of Aspect 4 may be 1,000 or more, or may be 1,500 or more. The weight average molecular weight Mw of the lignocellulose derivative composition of Aspect 4 may be 1,000 to 500,000, 1,000 to 450,000, 1,500 to 500,000, or 1,500 to 450,000.

[0091] The molecular weight distribution Mw / Mn calculated from the weight average molecular weight Mw and number average molecular weight Mn of the lignocellulose derivative composition of Aspect 4 may be 1.0 or more, 1.1 or more, or 1.3 or more. The molecular weight distribution Mw / Mn of the composition of Aspect 3 may be 7.0 or less, 6.0 or less, or 5.0 or less. The molecular weight distribution Mw / Mn of the lignocellulose derivative composition of Aspect 3 may be 1.0 to 7.0, 1.0 to 6.0, 1.0 to 5.0, 1.3 to 7.0, 1.3 to 6.0, or 1.3 to 5.0.

[0092] The number average molecular weight Mn, weight average molecular weight Mw and molecular weight distribution Mw / Mn of the lignocellulose derivative composition of Aspect 4 can be measured in the same manner as for the composition of Aspect 1.

[0093] The lignocellulose derivative composition of Aspect 4 may have a glass transition point. The glass transition temperature Tg of the lignocellulose derivative composition of Aspect 4 may be 150°C or lower, 120°C or lower, or 100°C or lower. The glass transition temperature Tg of the composition of Aspect 4 may be 50°C or higher, 70°C or higher, or 90°C or higher. The glass transition temperature Tg of the lignocellulose derivative composition of Aspect 4 may be 50 to 150°C, 70 to 120°C, 90 to 120°C, or 90 to 100°C.

[0094] The lignocellulose derivative composition of Aspect 4 may have a melting point. From the viewpoint of improving heat resistance, the melting point Tm of the lignocellulose derivative composition of Aspect 4 is preferably 200°C or higher, more preferably 210°C or higher, and even more preferably 220°C or higher. The melting point Tm of the composition of Aspect 1 may be 300°C or lower, 250°C or lower, 240°C or lower, or 230°C or lower. The melting point Tm of the lignocellulose derivative composition of Aspect 4 may be 200 to 300°C, 210 to 250°C, 220 to 240°C, or 220 to 230°C.

[0095] The glass transition temperature Tg and melting point Tm of the lignocellulose derivative composition of Aspect 4 can be measured by differential scanning calorimetry. Details of the measurement method and conditions will be described later in the Examples.

[0096] (Constituent Ratio of Aspect 4) As described above, the lignocellulose derivative composition of Aspect 4 preferably contains a cellulose derivative, a lignin skeleton-containing compound, and a hemicellulose skeleton-containing compound. In the lignocellulose derivative composition of Aspect 4, the constituent ratio of the lignin skeleton-containing compound may exceed 0 wt %, may be 1 wt % or more, or may be 3 wt % or more of all constituent components. From the viewpoints of thermoformability and ultraviolet absorption ability, a larger constituent ratio of the lignin skeleton-containing compound is preferable, but the constituent ratio may be 20 wt % or less, 15 wt % or less, or 10 wt % or less. In the lignocellulose derivative composition of aspect 4, the ratio of the lignin skeleton-containing compound to all constituent components may be greater than 0 wt% and less than 20 wt%, greater than 0 wt% and less than 15 wt%, greater than 0 wt% and less than 10 wt%, 1 wt% to 20 wt%, 1 wt% to 15 wt%, 1 wt% to 10 wt%, 3 wt% to 20 wt%, 3 wt% to 15 wt%, or 3 wt% to 10 wt%.

[0097] In the lignocellulose derivative composition of Aspect 4, the constituent ratio of the cellulose derivative may be 10 wt% or more, 20 wt% or more, or 30 wt% or more of all constituent components. The constituent ratio of the cellulose derivative may be 60 wt% or less, 50 wt% or less, 45 wt% or less, or 40 wt% or less. In the lignocellulose derivative composition of Aspect 4, the constituent ratio of the cellulose derivative may be 30 to 50 wt% of all constituent components.

[0098] In the lignocellulose derivative composition of Aspect 4, the constituent ratio of the hemicellulose skeleton-containing compound may be 30 wt% or more, 40 wt% or more, 49 wt% or more, 50 wt% or more, or 55 wt% or more of all constituent components. Furthermore, the constituent ratio of the hemicellulose skeleton-containing compound may be 80 wt% or less, 70 wt% or less, 69 wt% or less, 65 wt% or less, or 60 wt% or less. In the lignocellulose derivative composition of Aspect 4, the constituent ratio of the hemicellulose skeleton-containing compound may be 49 to 69 wt% of all constituent components.

[0099] The lignocellulose derivative composition of Aspect 4 contains a covalent bond or interaction between a cellulose derivative and a xylan, and / or a covalent bond or interaction between a lignin skeleton-containing compound and a xylan. This xylan is a xylan contained as a constituent of a hemicellulose skeleton-containing compound. More specifically, the lignocellulose derivative composition of Aspect 4 contains a component with a structure of cellulose-xylan-lignin, in which xylan and lignin are covalently bonded or interact with each other. The above-mentioned "covalently bonded or interacted" refers to a covalent bond or interaction. Here, this cellulose-xylan-lignin can also be said to be a component covalently bonded between a cellulose derivative and a xylan, or a component interacting between a cellulose derivative and a xylan. Furthermore, this cellulose-xylan-lignin can also be said to be a component covalently bonded between a lignin skeleton-containing compound and a xylan, or a component interacting between a lignin skeleton-containing compound and a xylan. Here, the interaction is the same as that described above.

[0100] The proportions of the cellulose derivative, the lignin skeleton-containing compound, and the hemicellulose skeleton-containing compound in the lignocellulose derivative composition of Aspect 4 can be measured in the same manner as in the composition of Aspect 1.

[0101] (Molded body) The molded body of the present disclosure is formed from the lignocellulose derivative composition described above. Preferably, the molded body of the present disclosure is formed from the composition of Aspect 1, Aspect 2, Aspect 3, or Aspect 4 described above. The lignin skeleton-containing compound has ultraviolet absorption ability. Among the compositions of Aspects 1 to 4, a molded body formed from a composition containing a lignin skeleton-containing compound suppresses deterioration due to ultraviolet light and exhibits excellent weather resistance without the addition of an ultraviolet absorber as an additive. This molded body may further contain known additives such as pigments, as long as the effects of the present disclosure are not impaired. The shape, etc., of the molded body of the present disclosure is not particularly limited, but typical examples of the molded body include a sheet or a film.

[0102] The method for producing the molded article of the present disclosure is not particularly limited. For example, the molded article of the present disclosure may be obtained by thermoforming the lignocellulose derivative composition by known means such as melt molding or injection molding. The molded article of the present disclosure may also be obtained by casting a solution containing the lignocellulose derivative composition onto a substrate and then drying it.

[0103] When the lignocellulose derivative composition is thermoformed, the forming temperature may be 120°C or higher, 140°C or higher, or 180°C or higher, and may be 280°C or lower, 250°C or lower, or 230°C or lower. For example, in the case of the composition of Aspect 1, the thermal decomposition temperature exceeds 300°C, so thermal degradation due to thermoforming within this temperature range is avoided. As long as the effects of the present disclosure can be obtained, a drying treatment may be performed before and / or after the forming of the lignocellulose derivative composition.

[0104] (Applications) The lignocellulose derivative compositions and molded articles according to the present disclosure can be suitably used as substrates for, for example, tableware, packaging containers, trays, agricultural materials, fishing materials, office equipment parts, home appliance parts, automotive components, daily necessities, stationery, etc. Furthermore, by selecting its physical properties and composition, the lignocellulose derivative compositions according to the present disclosure can also be used as adhesives, lacquers, binders, coating agents, and surfactants. Furthermore, lignocellulose derivative compositions containing lignin skeleton-containing compounds can be used in fields such as medicine, clothing, and housing equipment, as films, fibers, wallpaper, etc., which require functions such as antibacterial properties, UV absorption, and metal adsorption.

[0105] The effects of the present disclosure will be clarified below by examples, but the present disclosure should not be interpreted as being limited based on the description of these examples.

[0106] (Production of Lignocellulose Derivative Composition) [Experimental Example 1] Beech was prepared as raw biomass. This raw biomass was processed using a bench sliding circular saw (product name "C12RSH") manufactured by Hitachi Koki Co., Ltd., and then sieved through a 100 mesh (openings 0.149 mm). The powder that passed through this sieve was vacuum dried at 105°C for 24 hours to obtain a raw powder with a dry weight of 2.4 g.

[0107] Next, 2.4 g of the raw material powder and 10.4 g (0.0392 mmol) of tetrabutylammonium fluoride trihydrate (TBAF·3H O, manufactured by BLDpharm) were added to 80 mL of dimethyl sulfoxide (DMSO, manufactured by Nacalai Tesque) and stirred for 10 minutes. After that, 16.0 g (0.400 mol) of sodium hydroxide (NaOH, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and alkali treatment was carried out at 60°C for 24 hours. The reaction solution was then allowed to cool to room temperature, and 9.6 mL (0.1536 mol) of methyl iodide (MeI, manufactured by Nacalai Tesque) was added under ice cooling. After another hour of ice cooling, the mixture was stirred at room temperature for 18 hours. The mixture was then heated to 60°C and stirred for 48 hours to carry out methylation. During the alkali treatment and methylation steps, nitrogen gas was periodically introduced into the reaction system. As a result, the methylated composition MeX of Experimental Example 1 was obtained.

[0108] Composition MeX was collected by vacuum filtration (using an ADVANTEC H-100A047A membrane filter) and washed with distilled water to obtain a filtration residue A. The filtration residue A was freeze-dried to obtain a dried product, to which 50 ml of methanol was added, mixed, and then centrifuged (5°C, 11,000 rpm, 10 min). This operation was repeated multiple times, and then a precipitate, which was composition Me1, and a supernatant were each recovered. The solvent was removed from the supernatant under reduced pressure using a rotary evaporator to obtain composition Me2.

[0109] Furthermore, the solvent was concentrated under reduced pressure from filtrate A after vacuum filtration and washing using a rotary evaporator, and then the filtrate was dialyzed against distilled water using a dialysis membrane (MWCO 1000). After one week, the solution and precipitates in the dialysis membrane were collected and freeze-dried to obtain composition Me3. The yields (wt%) of each composition in Experimental Example 1 are shown in Table 1 below.

[0110] Furthermore, when 173 times the amount of chloroform as that of composition Me1 in Experimental Example 1 was added, the composition could be fractionated into a soluble component (Me1-chloroform soluble portion) and an insoluble component (Me1-chloroform insoluble portion). Chloroform was added to composition Me1, which had been vacuum-dried overnight at 40°C, and the mixture was mixed and centrifuged (4°C, 10,000 rpm, 20 min). This procedure was repeated three times, after which the supernatant, which was the Me1-chloroform soluble portion, and the precipitate (Me1-chloroform insoluble portion) were recovered. The entire supernatant was recovered, dried at room temperature, and then vacuum-dried. The weight ratio (wt%) of each component to the wood flour feed used in the methylation reaction was calculated from the dry weight. Furthermore, tetrahydrofuran in an amount 178 times the dry weight of the Me1-chloroform soluble portion was added, and the mixture was fractionated into a soluble component (Me1-tetrahydrofuran soluble portion) and an insoluble component (Me1-tetrahydrofuran insoluble portion). Tetrahydrofuran was added to the Me1-chloroform soluble portion of the composition, which had been dried overnight in a vacuum at 40°C, and the mixture was mixed and centrifuged (4°C, 10,000 rpm, 20 min). This operation was repeated three times, and then the supernatant, which was the Me1-tetrahydrofuran soluble portion, and the precipitate (Me1-tetrahydrofuran insoluble portion) were recovered. The entire supernatant was recovered and dried at room temperature, followed by vacuum drying. The weight ratio (wt%) of each relative to the wood flour charged for the reaction was calculated from the dry weight of each component. This is shown in Table 2 below. The Me1-chloroform soluble portion, Me1-tetrahydrofuran soluble portion, and Me1-tetrahydrofuran insoluble portion were 1 The product was subjected to H-NMR measurement (chloroform-deuterated solvent) and GPC measurement (chloroform solvent).

[0111] 1 In H-NMR measurement, a peak at 4.34 ppm indicating cellulose was mainly detected from the Me1-tetrahydrofuran insoluble fraction, and peaks indicating cellulose and xylan were observed at 4.34 ppm and 4.28 ppm from the Me1-tetrahydrofuran soluble fraction. In GPC measurement (chloroform solvent), only a peak corresponding to a broad molecular weight distribution of 1,003,000 was detected from the Me1-tetrahydrofuran insoluble fraction, and a peak corresponding to a broad molecular weight distribution of 366,900 was detected from the Me1-tetrahydrofuran soluble fraction.​1 From the H-NMR measurement, two components, cellulose and xylan, were detected in the Me1-tetrahydrofuran soluble portion. In the GPC measurement, two peaks with different molecular weights should be detected, but in this case, only one peak was detected, indicating that the cellulose and xylan are covalently bonded or interact with each other.

[0112] [Experimental Example 2] Compositions Me1, Me2, and Me3 were obtained in the same manner as in Experimental Example 1, except that moso bamboo (100 mesh pass) was used as the raw biomass and the alkali treatment time and methylation time were changed to those shown in Table 1 below. The yields (wt%) of the obtained compositions Me1, Me2, and Me3 are respectively shown in Table 1 below.

[0113] [Experimental Examples 3-4] Without fractionating MeX from Experimental Examples 1-2, a dialysis treatment was carried out with distilled water using a dialysis membrane (MWCO 1000) in order to remove reaction reagents and by-products. After one week, the solution and precipitates in the dialysis membrane were collected and freeze-dried to obtain compositions Me(ALL).

[0114] [Experimental Example 5] Compositions Me1, Me2, and Me3 were obtained in the same manner as in Experimental Example 1, except that the raw material biomass was changed to larch (100 mesh pass). The yields (wt%) of the obtained compositions Me1, Me2, and Me3 are respectively shown in Table 1 below.

[0115] [Experimental Example 6] Without fractionating MeX from Experimental Example 5, a dialysis treatment was carried out against distilled water using a dialysis membrane (MWCO 1000) in order to remove reaction reagents and by-products. After one week, the solution and precipitates in the dialysis membrane were collected and freeze-dried to obtain composition Me(ALL).

[0116] (Physical Properties of Lignocellulose Derivative Compositions) The following tests were conducted to measure the physical properties of compositions Me(ALL), Me1, Me2, and Me3 obtained in Experimental Examples 1-6. The results are shown in Table 1-5 below and Figure 2-14. In the table, the physical properties shown as Reference Example 1 are those of methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0117] [Gel Permeation Chromatography (GPC) Measurement] 5 mg of each composition was dissolved in 5 mL of tetrahydrofuran (THF, manufactured by Nacalai Tesque) to prepare a measurement sample, and the molecular weight and molecular weight distribution were measured under the following measurement conditions: Measurement apparatus: Shimadzu Corporation, product name "HPLC-Prominence" Column: Tosoh Corporation, "TSK SuperHZ 1000 (exclusion limit: 1,000)", "TSK SuperHZ 2000 (exclusion limit: 10,000)", and "TSK SuperHZ 3000 (exclusion limit: 60,000)" (column size: 4.6 mmID x 150 mm) Flow rate: 0.20 mL / min Column temperature: 40 °C Detector: RI, UV (254 nm) Sample concentration: 0.1% (w / v) Sample injection volume: 10 μL Mobile phase: THF (contains stabilizer) Standard sample: monodisperse polystyrene

[0118] [Gel Permeation Chromatography (GPC) Measurement] 4 mg of composition Me1, Me1-tetrahydrofuran soluble portion, and Me1-tetrahydrofuran insoluble portion were dissolved in 2 mL of chloroform for high performance liquid chromatography (CHCl3, manufactured by Nacalai Tesque) to prepare a measurement sample, and the molecular weight and molecular weight distribution were measured under the following measurement conditions: Measurement apparatus: "GPC-900" manufactured by JASCO Corporation Column: "KD-806M (exclusion limit: 40,000,000)" manufactured by Shodex (column size: 8 mm x 300 mm) x 2 Flow rate: 0.50 mL / min Column temperature: 40 °C Detector: RI, PDA Sample concentration: 0.2% (w / v) Sample injection volume: 100 μL Mobile phase: CHCl3 (contains stabilizer) Standard sample: monodisperse polystyrene

[0119] As shown in Table 1 below, lignocellulose derivative compositions (compositions Me1, Me2, and Me3) were obtained by selecting the type of raw material biomass, the alkali treatment time, and the methylation time.

[0120]

[0121] [Nuclear Magnetic Resonance (NMR) Measurement] Each composition was dissolved in deuterated chloroform (CDCl) or heavy water (DO) to prepare a sample solution with a concentration of 10 mg / 0.7 mL. 1 H-NMR measurement was carried out. Measurement device: "500NMR" manufactured by Varian Corporation Observation time: 5 seconds Relaxation time: 3 seconds Observation frequency: 499.8 MHz Number of accumulations: 16 times

[0122] The values ​​obtained for compositions Me(ALL), Me1, Me2 and Me3 1 The H-NMR spectra are shown in Figures 2 to 13. The chemical shift values ​​are expressed in ppm using the methyl group peak of tetramethylsilane (TMS) (0 ppm: when CDCl was used) or the hydroxy group peak of DO (4.79 ppm: when DO was used) as the internal standard.

[0123] From Figures 2-13, it was confirmed that compositions Me(ALL), Me1, Me2, and Me3 have a structure containing polysaccharides, and that methyl groups have been introduced into all of them. In Figure 3, there is a peak of an aromatic ring derived from a lignin skeleton, and there is a peak of mannan derived from hemicellulose, so it was confirmed that composition Me1 contains methylcellulose, a lignin skeleton-containing compound (hereinafter referred to as "lignin"), and a hemicellulose skeleton-containing compound (hereinafter referred to as "hemicellulose"). Next, assuming that lignin is a polymer of coniferyl alcohol, 1The composition ratio of the lignin skeleton-containing compound in composition Me1 was calculated from the H-NMR spectrum. Specifically, the integral value A of the peak at 6.5-7.2 ppm, the integral value B of the peak at 3.4-3.6 ppm, and the integral value C of the peak at 2.9-4.2 ppm were determined, and the lignin content (%) was calculated according to the following formula. The results are shown in Table 2 below: - integral value of one proton in the benzene ring A1 = A / 3 - integral value of the proton in the lignin side chain A2 = A * 7 / 3 - integral value of the methyl proton B1 = B / 3 - integral value of one proton in the pyranose ring C1 = C - A2 - B1 - lignin content (%) = A1 / (A1 + C1) × 100 Note that the components were confirmed and the composition ratio of the lignin skeleton-containing compound was calculated in the same way for Figure 7 in Experimental Example 2 and Figure 11 in Experimental Example 5.

[0124] 4, 8, and 12, the presence of peaks of aromatic rings derived from the lignin skeleton confirmed that composition Me2 contained lignin alone when the raw materials were beech in Experimental Example 1 and larch in Experimental Example 5. It was also confirmed that composition Me2 contained hemicellulose and cellulose in addition to lignin when the raw material was moso bamboo in Experimental Example 2.

[0125] 5, 9, and 13, the presence of a peak of hemicellulose-derived mannan (Man1) and a peak of an aromatic ring derived from the lignin skeleton confirmed that composition Me3 contained hemicellulose and lignin.

[0126] [Evaluation of the degree of methyl substitution] The degree of methyl substitution of each composition was evaluated by Fourier transform infrared spectroscopy (FT-IR) measurement. A Shimadzu Fourier transform infrared spectrophotometer "IR Prestage-21" was used for the measurement. The measurement conditions were as follows: Measurement method: ATR method Number of accumulations: 64 Measurement wavelength: 400-4000 cm -1 ・Resolution: 4cm -1

[0127] C-O-C bond in the pyranose ring (1050 cm -1The peak intensity of the hydroxyl group was calculated using the reference value of 1, and the results are shown in Table 2 below as "residual OH group." In Table 2, DS is the degree of methyl substitution of composition Me1, calculated using the following formula using NMR measurement. DS calculation formula: DSmethyl = (A / 3) / (B / 7) A: Peak derived from methyl protons of the methyl group (3.4 to 3.6 ppm) B: Peak derived from methyl protons of the pyranose ring (2.9 to 4.2 ppm)

[0128]

[0129] Table 2 indicates that for composition Me1, the longer the reaction time for alkali treatment and methylation, the smaller the hydroxyl group peak intensity, suggesting a larger amount of methyl groups introduced. This result correlates with the methyl substitution degree DS measured by NMR measurement, confirming that the longer the reaction time, the greater the methyl substitution degree. Similarly, for compositions Me2 and Me3, the methyl substitution degree tended to increase with increasing reaction time, but the hydroxyl group peak intensity for composition Me3 was significantly smaller than that for compositions Me1 and Me2.

[0130] [Differential Scanning Calorimetry (DSC)] DSC measurements were performed on each composition. A Hitachi High-Tech Science DSC7020 was used for the measurements. The measurement was performed by heating the sample from room temperature to 300°C at 10°C / min (first heating), then rapidly cooling to -50°C using liquid nitrogen, and again heating the sample to 300°C at 10°C / min (second heating), thereby obtaining a stable DSC thermogram. The midpoint of the baseline shift in the second heating was determined as the glass transition temperature Tg. Other measurement conditions were as follows: Sample weight: approximately 5 mg Pan: open aluminum pan Atmospheric gas: nitrogen Gas flow rate: 50 mL / min

[0131] The glass transition temperatures Tg and, if present, melting points Tm of compositions Mel, Me3 and Me(ALL) are given in Table 3 below.

[0132]

[0133] (Molded Body: Film Preparation) Films were prepared by heat pressing using the unfractionated composition Me (ALL) and compositions Me1 and Me3 from the compositions of Experimental Examples 1 to 6. Specifically, each sample was placed in a mold (100 μm thick) and molded at a temperature 15 to 20°C higher than the melting point under conditions of 3.4 MPa for 25 seconds and 10.2 MPa for 60 seconds to obtain a thermoplastic film. After heat pressing, the film was annealed in a cooling press. The film was cut into strips measuring 5 mm wide and 4 cm long, and the results of a bending test and evaluation of dynamic viscoelasticity are shown in Tables 4 and 5 below.

[0134] (Evaluation of Molded Product: Film) [Bending Test] Measurement was performed by fixing half of a strip to a desk with cellophane tape or the like at room temperature, and measuring the angle (°) at which the remaining half broke when being folded. The angle was evaluated using a protractor. The results are shown in Table 4 below.

[0135]

[0136] [Dynamic Viscoelasticity Measurement (DMA)] The width and thickness of the prepared test specimen were measured at three locations each, and the average values ​​were used as the width and thickness of the test specimen. Seiko Instruments Inc.'s DMS6100 / EXSTAR6000 was used for the measurement, and the temperature dependence of the storage modulus E' was evaluated. The value at the peak top of Tan δ was taken as the glass transition temperature (DMA). The measurement conditions are shown below. The measurement results are shown in Table 5 below. Measurement mode: tension mode, chuck distance 10 mm, measurement temperature range: -100 to 280°C, heating rate: 5°C / min, measurement frequency: 1 Hz

[0137]

[0138] As shown in Tables 4 and 5, with composition Me1, films could be produced in Experimental Examples 1, 2, and 5. With composition Me3, films could be produced in Experimental Examples 1 and 2. The films of Experimental Examples 1 and 2 made with compositions Me1 and Me3 were films imparted with flexibility, and did not break even when bent 180°.

[0139] As shown in Tables 4 and 5, using Composition Me(ALL), films could be produced in Experimental Examples 3, 4, and 6. The films in Experimental Examples 3 and 4 were films imparted with flexibility, and did not break even when bent 180°.

[0140] Experimental Example 5 was conducted in the same manner as Experimental Example 1, except that larch was used as the biomass raw material. An attempt was made to produce a film by hot pressing using the composition Me3 obtained in Experimental Example 5 in the same manner as in the film production method described above. As a result, a film could not be produced.

[0141] In Experimental Example 6, which used larch as the biomass raw material, a film was produced by hot pressing using the unfractionated composition Me(ALL) in the same manner as in the film production method described above. As a result, a film with rigidity was obtained, but the desired flexibility was not obtained.

[0142] (Summary) As shown in Tables 1-5 and Figures 2-14, the compositions of the present disclosure exhibit excellent thermal properties. These evaluation results clearly demonstrate the superiority of the present disclosure.

[0143] Disclosed Items Each of the following items discloses a preferred embodiment.

[0144] [Item 1] A lignocellulose derivative composition, the composition comprising at least one selected from the group consisting of (1) a cellulose derivative, (2) a lignin skeleton-containing compound, and (3) a hemicellulose skeleton-containing compound, wherein the (1) cellulose derivative is a cellulose derivative in which some or all of the hydroxyl groups in cellulose have been etherified with methyl groups, the (2) lignin skeleton-containing compound is lignin and / or a lignin derivative in which some or all of the hydroxyl groups in lignin have been etherified with methyl groups, the (3) hemicellulose skeleton-containing compound is hemicellulose and / or a hemicellulose derivative in which some or all of the hydroxyl groups in hemicellulose have been etherified with methyl groups, and the (3) hemicellulose skeleton-containing compound contains xylan as a constituent component, and the lignocellulose derivative composition comprises a covalent bond or interaction between the (1) cellulose derivative and the xylan and / or a covalent bond or interaction between the (2) lignin skeleton-containing compound and the xylan.

[0145] [Item 2] The lignocellulose derivative composition according to Item 1, comprising the (1) cellulose derivative, the ratio of the (1) cellulose derivative in all constituent components being 30 to 70 wt %, and the (1) cellulose derivative and the xylan containing a covalent bond or interaction.

[0146] [Item 3] The lignocellulose derivative composition according to Item 1 or 2, comprising the (1) cellulose derivative, the (2) lignin skeleton-containing compound, and the (3) hemicellulose skeleton-containing compound, wherein the ratio of the (1) cellulose derivative to all constituent components is 30 to 70 wt %, the ratio of the (2) lignin skeleton-containing compound to all constituent components is 0.5 to 20 wt %, the ratio of the (3) hemicellulose skeleton-containing compound to all constituent components is 29.5 to 69.5 wt %, and the composition contains a covalent bond or interaction between the (1) cellulose derivative and the xylan.

[0147] [Item 4] The lignocellulose derivative composition according to Item 1 or 2, comprising the (2) lignin skeleton-containing compound, wherein the ratio of the (2) lignin skeleton-containing compound to all constituent components is 55 to 100 wt %, and wherein the (2) lignin skeleton-containing compound and the xylan are covalently bonded or interact with each other.

[0148] [Item 5] The lignocellulose derivative composition according to Item 1 or 4, comprising the (2) lignin skeleton-containing compound, wherein the ratio of the (2) lignin skeleton-containing compound to all constituent components is 55 to 100 wt %, the ratio of the (1) cellulose derivative to all constituent components is 0 to 45 wt %, and the (2) lignin skeleton-containing compound and the xylan contain a covalent bond or interaction.

[0149] [Item 6] The lignocellulose derivative composition according to Item 1, comprising the (3) hemicellulose skeleton-containing compound, wherein the ratio of the (3) hemicellulose skeleton-containing compound to all constituent components is 50 to 85 wt %.

[0150] [Item 7] The lignocellulose derivative composition according to Item 1 or 6, comprising the (1) cellulose derivative, the (2) lignin skeleton-containing compound, and the (3) hemicellulose skeleton-containing compound, wherein the ratio of the (1) cellulose derivative to all constituent components is 14 to 49 wt %, the ratio of the (2) lignin skeleton-containing compound to all constituent components is 1 to 15 wt %, the ratio of the (3) hemicellulose skeleton-containing compound to all constituent components is 50 to 85 wt %, and the composition contains a covalent bond or interaction between the (2) lignin skeleton-containing compound and the xylan.

[0151] [Item 8] The lignocellulose derivative composition according to any one of Items 1 to 7, wherein, when the sum of composition Me1 consisting of a fraction component that is insoluble or poorly soluble in water and insoluble or poorly soluble in alcohol of the lignocellulose derivative composition, composition Me2 consisting of a fraction component that is insoluble or poorly soluble in water and soluble or readily soluble in alcohol of the lignocellulose derivative composition, and composition Me3 consisting of a fraction component that is soluble or readily soluble in water of the lignocellulose derivative composition is taken as 100 wt%, the weight ratio (wt%) of the chloroform-soluble portion and tetrahydrofuran-insoluble portion in composition Me1 is 4 wt% or more.

[0152] [Item 9] The lignocellulose derivative composition according to any one of Items 1 to 8, wherein, when a composition Me1 consisting of fractional components that are insoluble or poorly soluble in water and insoluble or poorly soluble in alcohol of the lignocellulose derivative composition is taken as 100 wt %, the weight ratio (wt %) of the chloroform-soluble portion and the tetrahydrofuran-soluble portion in the composition Me1 is 5 wt % or more.

[0153] [Item 10] A molded article formed from the lignocellulose derivative composition according to any one of items 1 to 9.

[0154] [Item 11] A method for producing a lignocellulose derivative composition, comprising the steps of: treating a raw material biomass containing lignocellulose with an alkali in a solvent at a temperature of 30°C to 65°C for 1 to 40 hours; adding a methylating agent to the alkali-treated raw material biomass and reacting at a temperature of 40°C to 70°C for 30 to 120 hours to methylate the lignocellulose; and fractionating the methylated lignocellulose, wherein the raw material biomass containing lignocellulose is at least one selected from the group consisting of broadleaf biomass and herbaceous plant biomass, and the methylating agent is a methyl halide.

Claims

1. A lignocellulose derivative composition, comprising at least one selected from the group consisting of (1) a cellulose derivative, (2) a lignin skeleton-containing compound, and (3) a hemicellulose skeleton-containing compound, wherein the (1) cellulose derivative is a cellulose derivative in which some or all of the hydroxyl groups in cellulose are etherified with methyl groups, the (2) lignin skeleton-containing compound is lignin and / or a lignin derivative in which some or all of the hydroxyl groups in lignin are etherified with methyl groups, the (3) hemicellulose skeleton-containing compound is hemicellulose and / or a hemicellulose derivative in which some or all of the hydroxyl groups in hemicellulose are etherified with methyl groups, and the (3) hemicellulose skeleton-containing compound contains xylan as a constituent component, and wherein the (1) cellulose derivative and xylan form a covalent bond or interaction, and / or the (2) lignin skeleton-containing compound and xylan form a covalent bond or interaction.

2. The lignocellulose derivative composition according to claim 1, comprising the (1) cellulose derivative, the (1) cellulose derivative being present in an amount of 30 to 70 wt % of all components, and comprising a covalent bond or interaction between the (1) cellulose derivative and the xylan.

3. The lignocellulose derivative composition according to claim 1 or 2, comprising the (1) cellulose derivative, the (2) lignin skeleton-containing compound, and the (3) hemicellulose skeleton-containing compound, wherein the ratio of the (1) cellulose derivative in all constituent components is 30 to 70 wt %, the ratio of the (2) lignin skeleton-containing compound in all constituent components is 0.5 to 20 wt %, the ratio of the (3) hemicellulose skeleton-containing compound in all constituent components is 29.5 to 69.5 wt %, and the composition contains a covalent bond or interaction between the (1) cellulose derivative and the xylan.

4. A lignocellulose derivative composition according to claim 1 or 2, comprising the (2) lignin skeleton-containing compound, the (2) lignin skeleton-containing compound being present in an amount of 55 to 100 wt % of all constituent components, and comprising a covalent bond or interaction between the (2) lignin skeleton-containing compound and the xylan.

5. A lignocellulose derivative composition according to claim 1 or 2, comprising the (2) lignin skeleton-containing compound, the (2) lignin skeleton-containing compound being present in a proportion of 55 to 100 wt % of all constituent components, the (1) cellulose derivative being present in a proportion of 0 to 45 wt % of all constituent components, and comprising a covalent bond or interaction between the (2) lignin skeleton-containing compound and the xylan.

6. The lignocellulose derivative composition according to claim 1, comprising the (3) hemicellulose skeleton-containing compound, and the ratio of the (3) hemicellulose skeleton-containing compound to all constituent components is 50 to 85 wt %.

7. The lignocellulose derivative composition according to claim 1 or 2, comprising the (1) cellulose derivative, the (2) lignin skeleton-containing compound, and the (3) hemicellulose skeleton-containing compound, wherein the ratio of the (1) cellulose derivative in all constituent components is 14 to 49 wt %, the ratio of the (2) lignin skeleton-containing compound in all constituent components is 1 to 15 wt %, the ratio of the (3) hemicellulose skeleton-containing compound in all constituent components is 50 to 85 wt %, and the composition contains a covalent bond or interaction between the (2) lignin skeleton-containing compound and the xylan.

8. The lignocellulose derivative composition according to claim 1 or 2, wherein, when the sum of composition Me1 consisting of a fraction component of the lignocellulose derivative composition that is insoluble or poorly soluble in water and insoluble or poorly soluble in alcohol, composition Me2 consisting of a fraction component of the lignocellulose derivative composition that is insoluble or poorly soluble in water and soluble or easily soluble in alcohol, and composition Me3 consisting of a fraction component of the lignocellulose derivative composition that is soluble or easily soluble in water, is taken as 100 wt %, the weight ratio (wt %) of chloroform-soluble and tetrahydrofuran-insoluble parts in composition Me1 is 4 wt % or more.

9. A lignocellulose derivative composition according to claim 1 or 2, wherein when a composition Me1 consisting of fractional components that are insoluble or poorly soluble in water and insoluble or poorly soluble in alcohol of the lignocellulose derivative composition is taken as 100 wt %, the weight ratio (wt %) of the chloroform-soluble portion and the tetrahydrofuran-soluble portion in the composition Me1 is 5 wt % or more.

10. A molded body formed from the lignocellulose derivative composition according to claim 1 or 2.

11. A method for producing a lignocellulose derivative composition, comprising the steps of: treating a raw biomass containing lignocellulose with an alkali in a solvent at a temperature of 30°C to 65°C for 1 to 40 hours; adding a methylating agent to the alkali-treated raw biomass and reacting it at a temperature of 40°C to 70°C for 30 to 120 hours to methylate the lignocellulose; and fractionating the methylated lignocellulose, wherein the raw biomass containing lignocellulose is at least one selected from the group consisting of broadleaf biomass and herbaceous plant biomass, and the methylating agent is a methyl halide.

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