Method for producing cellulose derivative and method for producing chemical product

Abstract

To provide a new method for utilizing a waste mushroom bed or a method for producing a useful cellulose derivative while reducing an environmental load.SOLUTION: The method for producing a cellulose derivative of the present disclosure is a method for obtaining a cellulose derivative having a repeating unit represented by the following formula (1) by using, as a cellulose raw material, lignin-degraded biomass in which at least a part of lignin is degraded by a white-rot fungus, and subjecting the cellulose raw material to a derivatization step. In the following formulae, R1 to R3 are hydrogen atoms, R groups, COR groups, or COOR groups, and R is a hydrocarbyl group, or a group in which two or more hydrocarbyl groups are bonded via a linking group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a novel method for producing cellulose derivatives and a novel method for producing chemical products. [Background technology]

[0002] The cell walls of trees and herbs are mainly composed of polysaccharides, including cellulose, and lignin, and cellulose is the most abundant natural polymer on earth.

[0003] Derivatization of cellulose improves its solubility in solvents and makes it easier to handle, and cellulose derivatives are used in a wide range of applications, including cosmetics that are applied to the skin, coating agents, paints, and film-forming agents.

[0004] However, the cellulose contained in biomass such as trees and herbs is extremely difficult to extract because it forms a complex with lignin. To extract cellulose from biomass, it is first necessary to decompose and remove the lignin.

[0005] Decomposing and removing the lignin contained in biomass requires complicated processes such as defibration and bleaching, as well as large amounts of chemicals, which results in high energy consumption and a large environmental impact.

[0006] For example, Patent Document 1 discloses that lignin is removed by subjecting eucalyptus chips to hydrolysis and alkaline cooking, followed by bleaching, and then depolymerizing the chips by adding hydrogen peroxide under sulfuric acid acidity, thereby producing pulp containing high-purity cellulose. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-227705 Summary of the Invention [Problem to be solved by the invention]

[0008] Meanwhile, in the artificial cultivation of mushrooms such as Maitake, a medium made by mixing sawdust, which is made by powdering wood, with the nutrients necessary for mushroom cultivation is used as a mushroom bed, and mushroom mycelium is planted and cultivated there. After mushrooms are harvested, the mushroom bed (i.e., waste mushroom bed) is disposed of as industrial waste, but since the amount of waste mushroom bed generated is two to three times the weight of the harvested mushrooms, disposal of the waste mushroom bed is extremely expensive. Therefore, there is a need to find an effective way to utilize waste mushroom bed.

[0009] Therefore, an object of the present disclosure is to provide a new method for utilizing waste mushroom beds. Another object of the present disclosure is to provide a method for producing cellulose derivatives that are useful in a wide range of fields while reducing the environmental impact. Another object of the present disclosure is to provide a method for producing chemical products used in a wide range of fields while reducing the environmental burden. [Means for solving the problem]

[0010] As a result of intensive research by the inventors to solve the above-mentioned problems, they found that edible mushrooms such as Maitake belong to the white-rot fungi that have the ability to decompose the lignin contained in wood, and that in the waste mushroom beds left after cultivating edible mushrooms, some or all of the lignin contained in the sawdust has been decomposed, making it easier to extract cellulose.They also found that using waste mushroom beds as a raw material for cellulose derivatives eliminates the need for complicated processes such as defibration and bleaching, and also obviates the need to use large amounts of chemicals, making it possible to produce cellulose derivatives that are highly soluble, have high molecular weights, and have excellent film-forming properties, while reducing the environmental burden. The present disclosure has been completed based on these findings.

[0011] That is, the present disclosure provides a method for producing cellulose using lignin-decomposed biomass in which at least a portion of lignin has been decomposed by white-rot fungi as a cellulose raw material, The present invention provides a method for producing a cellulose derivative, which comprises subjecting the cellulose raw material to a derivatization step to obtain a cellulose derivative having a repeating unit represented by the following formula (1): [ka] (In the formula, R 1 ~R 3 are the same or different and are a hydrogen atom, an R group, a COR group, or a COOR group, and R 1 ~R 3 At least one of the groups is an R group, a COR group, or a COOR group. The R group is a hydrocarbon group or a group in which two or more hydrocarbon groups are linked via a linking group.

[0012] The present disclosure also provides a method for producing the cellulose derivative, wherein the cellulose raw material is first subjected to an impurity removal step and then subjected to the derivatization step.

[0013] The present disclosure also provides the method for producing the cellulose derivative, wherein the impurity removing step includes a step of removing impurities using an alcohol.

[0014] The present disclosure also provides the method for producing the cellulose derivative, wherein the impurity removal step includes a step of removing impurities using sodium hypochlorite.

[0015] The present disclosure also provides the method for producing the cellulose derivative, wherein the lignin-decomposing biomass is a waste mushroom bed.

[0016] The present disclosure also provides the method for producing the cellulose derivative, wherein the impurity is residual lignin.

[0017] The present disclosure also provides a method for producing the cellulose derivative, which does not include a step of subjecting the cellulose raw material to mechanical or chemical defibration treatment.

[0018] The present disclosure also provides a method for producing a chemical product, which comprises producing a cellulose derivative having a repeating unit represented by the following formula (1) by the method for producing a cellulose derivative, and using the produced cellulose derivative to produce a chemical product containing the cellulose derivative. [ka] (In the formula, R 1 ~R 3 are the same or different and are a hydrogen atom, an R group, a COR group, or a COOR group, and R 1 ~R 3 At least one of the groups is an R group, a COR group, or a COOR group, wherein R represents a hydrocarbon group.

[0019] The present disclosure also provides a method for producing the chemical product, wherein the chemical product is a cosmetic, a pharmaceutical product, a quasi-drug, a film, a sheet, a paint, an adhesive, or a food additive. [Effects of the Invention]

[0020] According to the method for producing a cellulose derivative disclosed herein, waste mushroom beds, which have conventionally been disposed of as industrial waste at enormous expense, can be effectively utilized as a cellulose raw material, and the method does not require complicated processes such as defibration and bleaching or large amounts of chemicals, allowing for derivatization in a simple, environmentally friendly manner, and enabling the production of a cellulose derivative with excellent solubility. Furthermore, according to the method for producing a cellulose derivative of the present disclosure, since defibration treatment is not required, a cellulose derivative having a high molecular weight and excellent film-forming properties can be produced.

[0021] For example, in the case of cellulose esters among cellulose derivatives, since cellulose is shredded by defibration treatment and its molecular weight is reduced, cellulose esters with excellent solubility and film-forming properties have been produced by reacting them with high-molecular-weight acid halides in the derivatization process. Furthermore, since the acid halides corrode the reactor, it has been necessary to use a corrosion-resistant reactor. However, the method of the present disclosure does not require defibration treatment, and therefore high-molecular-weight cellulose that has not been shredded by defibration treatment can be subjected to the derivatization step, and a cellulose derivative with excellent solubility and film-forming properties can be produced simply by reacting with acetic anhydride in the derivatization step. Therefore, the method of the present disclosure does not require the use of an acid halide in the derivatization step, and corrosion of the reactor due to the acid halide can be avoided. [Brief explanation of the drawings]

[0022] [Figure 1] FIG. 1 shows the results of NMR analysis of the acetyl cellulose obtained in Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0023] [Method of producing cellulose derivatives] The method for producing a cellulose derivative according to the present disclosure is a method for obtaining a cellulose derivative having a repeating unit represented by the following formula (1) by using lignin-decomposed biomass, in which at least a portion of the lignin has been decomposed by a white-rot fungus, as a cellulose raw material and subjecting the cellulose raw material to a derivatization step. [ka] (In the formula, R 1 ~R 3 are the same or different and are a hydrogen atom, an R group, a COR group, or a COOR group, and R 1 ~R 3 At least one of the groups is an R group, a COR group, or a COOR group. The R group is a hydrocarbon group or a group in which two or more hydrocarbon groups are linked via a linking group.

[0024] The hydrocarbon group (monovalent hydrocarbon group) for R includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and groups formed by combining these groups.

[0025] The hydrocarbon group is preferably an aliphatic hydrocarbon group from the viewpoint of solubility.

[0026] The aliphatic hydrocarbon group may be a group having 1 to 20 carbon atoms (=C 1-20 The aliphatic hydrocarbon group includes saturated aliphatic hydrocarbon groups and unsaturated aliphatic hydrocarbon groups.

[0027] Examples of the saturated aliphatic hydrocarbon group include alkyl groups (e.g., linear or branched alkyl groups) having about 1 to 20 carbon atoms (preferably 1 to 10, particularly preferably 1 to 3), such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, decyl group, and dodecyl group.

[0028] Examples of the unsaturated aliphatic hydrocarbon group include alkenyl groups (e.g., linear or branched alkenyl groups) having about 2 to 20 carbon atoms (preferably 2 to 10, particularly preferably 2 to 3), such as a vinyl group, an allyl group, or a 1-butenyl group; and alkynyl groups (e.g., linear or branched alkynyl groups) having about 2 to 20 carbon atoms (preferably 2 to 10, particularly preferably 2 to 3), such as an ethynyl group or a propynyl group.

[0029] Of the hydrocarbon groups, saturated aliphatic hydrocarbon groups are preferred, alkyl groups having 1 to 10 carbon atoms are preferred, alkyl groups having 1 to 3 carbon atoms are particularly preferred, and methyl groups are particularly preferred.

[0030] The linking group is a divalent group having one or more atoms, and examples thereof include a carbonyl group (-CO-), an ether bond (-O-), a thioether bond (-S-), an ester bond (-COO-), an amide bond (-CONH-), and a carbonate bond (-OCOO-).

[0031] The R includes a (poly)oxyalkylene group represented by the following formula (r1): In the formula, n represents an integer of 1 or more, R' represents an alkylene group (e.g., methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group, etc.), and R" represents hydrogen or an alkyl group. The bond coming out from the left end of the formula below bonds to an oxygen atom at the 2-, 3-, or 6-position in the repeating unit represented by the above formula (1). -(R'O)nR” (r1)

[0032] The average degree of substitution (DSa) of the cellulose derivative is, for example, 0.5 or more. From the viewpoint of high solubility and excellent handleability, the average degree of substitution is preferably 0.9 or more. The upper limit of the average degree of substitution is 3.0.

[0033] The average degree of substitution is the average number of groups in which hydrogen atoms constituting hydroxyl groups are substituted with hydrocarbon groups, COR groups, or COOR groups per repeating unit represented by the above formula (1) in the cellulose derivative. In this specification, the average degree of substitution can be measured by a known or conventional method, for example, 1 H-NMR and 13 It can be analyzed and measured by C-NMR. Specifically, the average degree of substitution of the hydrocarbon group, COR group, or COOR group can be calculated from the integral ratio of the proton peak in the cellulose skeleton to the proton peak of the terminal methyl group in the hydrocarbon group, COR group, or COOR group. In addition, when the peaks of hydrocarbon groups, COR groups, or COOR groups of the cellulose derivative overlap with the peaks derived from the cellulose skeleton in the NMR spectrum, all hydrogen atoms of the hydroxyl groups remaining in the cellulose derivative are replaced with benzoyl groups, and then 1 The average degree of substitution of the hydrocarbon group, COR group, or COOR group can be calculated from the integral ratio of the peak of the proton of the terminal methyl group of the hydrocarbon group in the hydrocarbon group, COR group, or COOR group to the characteristic peak of the benzoyl group by H-NMR analysis.

[0034] The cellulose derivative has excellent solubility in solvents, for example, 24 mg / 0.7 mL or more (for example, 24 to 40 mg / 0.7 mL) in DMSO, and is therefore easy to handle.

[0035] (lignin decomposition biomass) Lignin-decomposing biomass is biomass in which at least a portion of the lignin has been decomposed by white-rot fungi.

[0036] In biomass (i.e., biomass before lignin is decomposed by white-rot fungi), cellulose is partially bound to lignin via hemicellulose to form a lignin-cellulose complex, and it is extremely difficult to extract cellulose from this complex. Extracting cellulose requires complicated processes such as defibration and bleaching, as well as large amounts of chemicals, resulting in high energy consumption and a significant environmental impact. However, when at least a portion of the lignin is decomposed by white-rot fungi, cellulose becomes easier to extract, and the complicated processes such as defibration and bleaching are no longer necessary, and the use of large amounts of chemicals is also eliminated, making it possible to produce cellulose derivatives while reducing the environmental impact.

[0037] Cellulose is a polysaccharide that forms the backbone of plant cell walls and is composed of [C6H 10 O5] are polymers in which glucose-derived structural units are linked in a linear chain via β-(1-4) bonds. In plant cell walls, several dozen cellulose molecules are bundled together to form microfibrils, and multiple microfibrils then associate in rope-like formations to form macrofibrils.

[0038] Hemicellulose is a general term for cross-linking polysaccharides that cross-link cellulose microfibrils. Hemicellulose is composed of monosaccharides such as xylose, arabinose, mannose, and galactose, and has the effect of increasing the strength of cell walls by cross-linking cellulose microfibrils to form a mesh structure.

[0039] Lignin is a polymeric compound that forms a three-dimensional network structure by highly polymerizing phenolic compounds (e.g., cinnamyl alcohol, coniferyl alcohol, p-coumaryl alcohol, etc.).

[0040] The biomass is, for example, herbaceous biomass, and the lignin-decomposing biomass is, for example, biomass in which at least a portion of the lignin contained in the herbaceous biomass has been decomposed by white-rot fungi.

[0041] Examples of plant biomass that can be used include wood (conifers such as cedar, broad-leaved trees such as eucalyptus, etc.), seed hairs (cotton linters, bombax cotton, kapok, etc.), gin bark (e.g., hemp, kozo, mitsumata, etc.), leaves (e.g., Manila hemp, New Zealand hemp, etc.), rice straw, rice husks, bamboo, garden tree prunings, grass clippings, sugarcane, corn residue, etc., which can be cut or crushed (e.g., chips, sawdust, etc.).

[0042] White rot fungi are fungi that have enzymes that decompose lignin contained in biomass, and include edible mushrooms such as shiitake, nameko, enokitake, oyster mushroom, maitake, and tamogitake.

[0043] Lignin-decomposing biomass can be produced, for example, by adding nutrients to biomass as needed, attaching a seed culture of white-rot fungi to the biomass, and culturing the resulting mixture. The lignin-decomposing biomass may contain cultured white-rot fungi.

[0044] As the lignin-decomposing biomass, for example, waste mushroom beds can be used.

[0045] Edible mushroom cultivation on a mushroom bed is carried out using a medium obtained by, for example, shredding or crushing plants such as wood or leaves (chips, sawdust, etc.) and adding nutrients necessary for mushroom growth as needed. The medium after the grown edible mushrooms are harvested is called a waste mushroom bed. The lignin contained in the medium has been partially or completely decomposed by the edible mushrooms. Therefore, the lignin content of the waste mushroom bed is significantly reduced compared to the medium before mushroom cultivation, making it easier to extract cellulose.

[0046] Using waste mushroom beds as a cellulose raw material reduces the disposal costs of waste mushroom beds, and at the same time, it eliminates the need for mechanical or chemical defibration treatments that have traditionally been used to make cellulose easier to extract, and also eliminates the need to use large amounts of chemicals, thereby reducing the environmental burden and simplifying the manufacturing process.

[0047] <Derivatization process> This is a step of derivatizing the cellulose contained in the cellulose raw material to obtain a cellulose derivative having a repeating unit represented by the above formula (1).

[0048] An example of a method for derivatizing cellulose is to dissolve a cellulose raw material in a solvent, add a derivatizing agent thereto, and react the dissolved cellulose with the derivatizing agent.

[0049] The reaction temperature is, for example, 50 to 120°C, preferably 60 to 90°C. If the reaction temperature exceeds this range, depolymerization of cellulose occurs, and the molecular weight tends to decrease. If the reaction temperature is below this range, the reaction time tends to be longer.

[0050] (Derivatizing agent) The derivatizing agent can be selected and used depending on the type of the desired cellulose derivative.

[0051] The desired cellulose derivative is a cellulose ester, i.e., R1 ~R 3 When the cellulose derivative has a repeating unit in which at least one of the repeating units is a COR group, it is preferable to use an esterifying agent as the derivatizing agent.

[0052] Examples of the esterifying agent include acid halides, acid anhydrides, etc. These may be used alone or in combination of two or more.

[0053] Examples of acid halides include compounds represented by the following formula (c1): Examples of acid anhydrides include compounds represented by the following formula (c2): R in the following formulas (c1) and (c2) is the same as R in the above formula (1): 1 ~R 3 It is a hydrocarbon group corresponding to R in the COR group in the formula below, and is preferably a saturated aliphatic hydrocarbon group. Furthermore, X in the formula below represents a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom). RCOOX (c1) (RCO)2O (c2)

[0054] Specific examples of acids (i.e., organic carboxylic acids) that constitute the acid halides include saturated aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, enanthocaproic acid, caprylic acid, capric acid, lauric acid, myristic acid, and palmitic acid.

[0055] Specific examples of the acid halide include halides of the above organic carboxylic acids.

[0056] Specific examples of acid anhydrides (that is, organic carboxylic acid anhydrides) include saturated aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, and valeric anhydride.

[0057] The esterification reaction can be terminated by adding an alcohol (eg, methanol, ethanol) to the reaction system.

[0058] The desired cellulose derivative is a cellulose ether, i.e., R 1 ~R 3 In the case of a cellulose derivative having a repeating unit in which at least one of the repeating units is an R group, it is preferable to use an etherifying agent as the derivatizing agent.

[0059] The etherification agent can be selected and used depending on the type of the target cellulose ether.For example, when the target cellulose ether is cellulose methyl ether, examples of the etherification agent include methyl halides such as methyl chloride and methyl iodide; monochloroacetic acid; etc.When the target cellulose ether is cellulose ethyl ether, examples of the etherification agent include ethyl halides such as ethyl chloride and ethyl iodide; ethylene oxide; etc.

[0060] The target cellulose derivative is cellulose carbonate, that is, R 1 ~R 3 When the cellulose derivative has a repeating unit in which at least one of the repeating units is a COOR group, it is preferable to use a carbonating agent as the derivatizing agent.

[0061] The carbonating agent may, for example, be a carbamic acid ester represented by the following formula (c3): R in the following formula (c3) is the same as R in the above formula (1). 1 ~R 3 is a hydrocarbon group corresponding to R in the COOR group in ROCO-NH2(c3)

[0062] Examples of the carbamic acid ester include methyl carbamate, ethyl carbamate, propyl carbamate, and butyl carbamate.

[0063] The amount of the derivatizing agent used is, for example, 1 to 30 equivalents relative to 1 equivalent of glucose in cellulose (ie, 3 equivalents of hydroxyl groups).

[0064] (solvent) As the solvent, an ionic liquid can be preferably used.

[0065] Ionic liquids are salts consisting of anions and cations, and are liquid substances at room temperature (25°C).

[0066] Examples of anions that constitute ionic liquids include acetate anion, RfOSO3 - , p-CH3C6H4SO3 - (tosylate anion), RfSO3 - , (RfSO2)2N - , BF4 - , PF6 - , (RfSO2)3C - , (CN)2N - , (RfO)2PO2 - The Rf represents a halogenated alkyl group having 1 to 12 carbon atoms.

[0067] Among these, acetate anion is preferred as the anion because it has excellent solubility for the cellulose raw material.

[0068] Examples of cations constituting the ionic liquid include organic nitrogen-based cations such as imidazolium cation, pyridinium cation, pyrrolidinium cation, and ammonium cation; organic phosphorus-based cations such as phosphonium cation; and organic sulfur-based cations such as sulfonium cation.

[0069] Of the cations constituting the ionic liquid, imidazolium cations are particularly preferred because they have excellent solubility for the cellulose raw material.

[0070] Therefore, the ionic liquid is preferably an imidazolium salt represented by the following formula (i): [ka] (In the above formula, R 1 , R 3are the same or different and represent a monovalent hydrocarbon group; R 2 , R 4 , R 5 are the same or different and represent a hydrogen atom or a monovalent hydrocarbon group. - indicates the counter anion)

[0071] The amount of solvent (for example, ionic liquid) used is, for example, 10 to 50 parts by weight per 1 part by weight of the cellulose raw material.

[0072] (Compatibilizer) In the reaction, a compatibilizer may be added to improve the solubility of the cellulose raw material in the solvent (for example, an ionic liquid).

[0073] Examples of compatibilizers include aprotic polar solvents such as dimethyl sulfoxide (DMSO), acetonitrile, and N,N-dimethylformamide; and polyhydric alcohols such as ethylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, erythritol, erythritol, and dipentaerythritol. These may be used alone or in combination of two or more.

[0074] The amount of the compatibilizer used is, for example, 20 to 60 parts by weight, and preferably 20 to 30 parts by weight, per part by weight of the cellulose raw material.

[0075] <Other processes> The method for producing a cellulose derivative according to the present disclosure may include other steps in addition to the above-described derivatization step, as necessary.

[0076] The method for producing a cellulose derivative may include a pretreatment step of removing components other than cellulose from the cellulose raw material prior to the derivatization step.

[0077] For example, when using waste mushroom beds as the cellulose raw material, it is preferable to remove nutrients, lignin, etc. remaining in the waste mushroom beds in the pretreatment step.

[0078] Nutrients contained in cellulosic raw materials can be removed by extraction with a solvent.

[0079] Examples of the solvent include alcohols such as methanol, ethanol, propanol, and butanol; aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aliphatic hydrocarbons such as hexane, heptane, and octane; esters such as ethyl acetate and butyl acetate, etc. These can be used alone or in combination of two or more.

[0080] The solvent preferably contains at least an alcohol, and it is particularly preferable to use a mixture of an alcohol and an aromatic hydrocarbon [the former / latter (mixing weight ratio) is, for example, 40 / 60 to 60 / 40].

[0081] Lignin contained in cellulose raw materials can be removed by decomposing it with a bleaching agent and then washing it (for example, with water and acetone).

[0082] Examples of the bleaching agent include sodium hypochlorite, sodium dichloroisocyanurate, hydrogen peroxide, sodium percarbonate, sodium perborate, ozone, chlorine dioxide, persulfates such as monopersulfuric acid, potassium permanganate, ammonium peroxodipersulfate, sodium persulfate, and potassium monopersulfate (potassium monopersulfate), hydrosulfite, and thiourea dioxide. These may be used alone or in combination of two or more.

[0083] Furthermore, in the method for producing a cellulose derivative, a step of purifying the reaction product obtained after the derivatization step by general treatments such as precipitation, washing, and filtration may be provided.

[0084] Conventionally, mechanical or chemical defibration treatments have been performed to facilitate extraction of cellulose that has formed a complex with lignin, but the method disclosed herein uses lignin-decomposed biomass, in which at least a portion of the lignin has been decomposed by white-rot fungi, as the cellulose raw material, eliminating the need for mechanical or chemical defibration treatments.By not performing mechanical or chemical defibration treatments, cellulose that has high molecular weight and crystallinity can be subjected to the derivatization step.

[0085] In the past, the molecular weight of cellulose was reduced by mechanical or chemical defibration treatment, and thus a cellulose derivative with a high molecular weight and excellent solubility was produced by adding a high molecular weight substituent in the derivatization process. However, in the method of the present disclosure, as described above, high molecular weight cellulose can be subjected to the derivatization process, and therefore a cellulose derivative with a high molecular weight and excellent solubility can be produced simply by adding a low molecular weight substituent (e.g., an acetyl group) in the derivatization process.

[0086] [Chemical product manufacturing method] The method for producing a chemical product according to the present disclosure is a method for producing a cellulose derivative having a repeating unit represented by formula (1) by the above-described method for producing a cellulose derivative, and using the produced cellulose derivative to produce a chemical product containing the cellulose derivative.

[0087] There are no particular limitations on the method for producing a chemical product containing the cellulose derivative using the produced cellulose derivative. For example, the chemical product can be produced by mixing the cellulose derivative with necessary components depending on the application of the chemical product, and then subjecting the mixture to a forming process such as granulation, molding, or film formation as necessary.

[0088] Examples of components required depending on the application of chemical products include plasticizers (e.g., dimethyl phthalate, triethyl citrate, triacetin, etc.), oils, powders, surfactants, lower alcohols, polyhydric alcohols, polymeric compounds other than cellulose derivatives, ultraviolet absorbers, antioxidants, dyes, fragrances, coloring materials, antifouling agents, moisturizing agents, fillers, volatile organic solvents, leveling agents, water, etc. These can be used alone or in combination of two or more.

[0089] The formulation of the chemical product may be any of solid, semi-solid, gel, liquid, and the like.

[0090] Examples of the chemical products include cosmetics, pharmaceuticals, quasi-drugs, films, sheets, paints, adhesives, food additives, tableware, packaging containers, trays, agricultural materials, fishing materials, office automation parts, construction materials, home appliance parts, automotive components, daily necessities, stationery, and eyeglass frames.

[0091] Examples of the cosmetics include lip cosmetics such as lipstick, lip gloss, and lip liner; makeup cosmetics such as mascara, eyeliner, eye shadow, cheek color, foundation (cream foundation, pressed foundation, liquid foundation, etc.), and concealer; cream, emulsion, lotion, all-in-one gel, serum, facial cleanser, solid soap, massage agent, deodorant, sunscreen, hair growth agent, shampoo, conditioner, hair color, hair oil, hair wax, hair styling spray, hair foam, waterproof cosmetics, etc. The cosmetics may be in a liquid, semi-solid, or solid form at room temperature.

[0092] Examples of the pharmaceuticals include applications as bases and film coating agents (for example, film coating agents for drug delivery).

[0093] Examples of the film include a liquid crystal film, a protective film for a polarizing plate, a photographic film, and a protective film for a liquid crystal display.

[0094] The paint is, for example, paint used for automobiles, wood, plastics, metals, etc.

[0095] According to the method of the present disclosure, chemical products are produced using cellulose derivatives produced in an environmentally friendly manner, and therefore the resulting chemical products are environmentally friendly products.

[0096] The above-described configurations and combinations thereof of the present disclosure are merely examples, and additions, omissions, substitutions, and modifications of the configurations are possible as appropriate without departing from the spirit of the present disclosure. Furthermore, each aspect disclosed in this specification can be combined with any other feature disclosed in this specification. Furthermore, the present disclosure is not limited by the embodiments. [Example]

[0097] The present disclosure will be explained in more detail below using examples, but the present disclosure is not limited to these examples.

[0098] Example 1 (Pretreatment process) Waste mushroom beds (15 g) used after mushroom cultivation were stirred with an alcohol / benzene mixed solution [mixing ratio: 1 / 1 (g)] at room temperature for 6 hours to extract impurities, and the mixture was filtered to obtain a residue. Alcohol (100 g) was added to the residue obtained, and the mixture was stirred at room temperature for 4 hours to re-extract impurities, followed by filtration to obtain a residue. The resulting residue was air-dried overnight. 2.5 g of the dried sample was mixed with 150 mL of water, 1.0 g of sodium hypochlorite, and 0.2 mL of acetic acid, and the mixture was heated at 70°C for 1 hour. Thereafter, the mixture was subjected to suction filtration, and the resulting residue was washed with water and acetone, thereby obtaining a white powder.

[0099] (Esterification step) To 0.14 g of the obtained white powder, 2.71 g of an ionic liquid (1-ethyl-3-methylimidazolium acetate) and 3.43 g of DMSO were added, and the temperature was raised to 80° C. Next, 0.5 g of acetic anhydride was added dropwise at a rate of 1 to 2 drops per second. Thirty minutes after the completion of the dropwise addition, methanol was added to react the remaining acetic anhydride and precipitate a white powder, which was separated by suction filtration and dried overnight in a vacuum (10 mmTorr or less) at room temperature to obtain a white powder (0.1 g). The obtained white powder was analyzed by NMR ( 1 The NMR analysis results of the acetyl cellulose were shown in Figure 1. As a result, the production of acetyl cellulose (average substitution degree of hydrogen atoms constituting hydroxyl groups with CHCO groups: 2.27) was confirmed. The solubility of the obtained acetyl cellulose in DMSO at room temperature was 24 to 40 mg / 0.7 mL.

[0100] Example 2 The same procedure as in Example 1 was carried out except that lauric acid chloride was used instead of acetic anhydride in the esterification step. As a result, cellulose laurate (C of hydrogen atoms constituting hydroxyl groups) was 11 H 23 The formation of CO groups (average substitution degree: 2.25) was confirmed. The solubility of the obtained cellulose laurate in DMSO at room temperature was 24 to 40 mg / 0.7 mL.

[0101] Variations of the invention according to the present disclosure are described below. [1] Using lignin-decomposed biomass in which at least a portion of the lignin has been decomposed by white-rot fungi as a cellulose raw material, The method for producing a cellulose derivative comprises subjecting the cellulose raw material to a derivatization step to obtain a cellulose derivative having a repeating unit represented by the following formula (1): [ka] (In the formula, R 1 ~R3 are the same or different and are a hydrogen atom, an R group, a COR group, or a COOR group, and R 1 ~R 3 At least one of the groups is an R group, a COR group, or a COOR group. The R group is a hydrocarbon group or a group in which two or more hydrocarbon groups are linked via a linking group. [2] The method for producing a cellulose derivative according to [1], wherein the cellulose raw material is first subjected to an impurity removal step and then to the derivatization step. [3] The method for producing a cellulose derivative according to [2], wherein the impurity removal step includes a step of removing impurities using alcohol. [4] The method for producing a cellulose derivative according to [2] or [3], wherein the impurity removal step includes a step of removing impurities using sodium hypochlorite. [5] The method for producing a cellulose derivative according to any one of [1] to [4], wherein the lignin-decomposed biomass is a waste mushroom bed. [6] The method for producing a cellulose derivative according to any one of [1] to [5], wherein the impurities are residual lignin. [7] The method for producing a cellulose derivative according to any one of [1] to [6], which does not include a step of subjecting the cellulose raw material to mechanical or chemical defibration treatment. [8] A method for producing a chemical product, comprising producing a cellulose derivative having a repeating unit represented by the following formula (1) by the method for producing a cellulose derivative according to any one of [1] to [7], and using the produced cellulose derivative to produce a chemical product containing the cellulose derivative: [ka] (In the formula, R 1 ~R 3 are the same or different and are a hydrogen atom, an R group, a COR group, or a COOR group, and R 1 ~R 3 At least one of the groups is an R group, a COR group, or a COOR group, wherein R represents a hydrocarbon group. [9] The method for producing a chemical product according to [8], wherein the chemical product is a cosmetic, a pharmaceutical, a quasi-drug, a film, a sheet, a paint, an adhesive, or a food additive.

Claims

1. using lignin-decomposed biomass in which at least a portion of lignin has been decomposed by white-rot fungi as a cellulose raw material; The method for producing a cellulose derivative comprises subjecting the cellulose raw material to a derivatization step to obtain a cellulose derivative having a repeating unit represented by the following formula (1): 【Chemistry 1】 (In the formula, R 1 ~R 3 are the same or different and are a hydrogen atom, an R group, a COR group, or a COOR group, and R 1 ~R 3 At least one of is an R group, a COR group, or a COOR group. The R is a hydrocarbon group or a group in which two or more hydrocarbon groups are linked via a linking group.

2. The method for producing a cellulose derivative according to claim 1, wherein the cellulose raw material is first subjected to an impurity removal step and then subjected to the derivatization step.

3. The method for producing a cellulose derivative according to claim 2 , wherein the impurity removal step comprises a step of removing impurities using an alcohol.

4. The method for producing a cellulose derivative according to claim 2 or 3, wherein the impurity removal step comprises a step of removing impurities using sodium hypochlorite.

5. The method for producing a cellulose derivative according to claim 1 or 2, wherein the lignin-decomposed biomass is a waste mushroom bed.

6. The method for producing a cellulose derivative according to claim 1 or 2, wherein the impurities are residual lignin.

7. The method for producing a cellulose derivative according to claim 1 or 2, which does not include a step of subjecting the cellulose raw material to mechanical or chemical defibration treatment.

8. A method for producing a chemical product, comprising producing a cellulose derivative having a repeating unit represented by the following formula (1) by the method for producing a cellulose derivative according to claim 1 or 2, and using the produced cellulose derivative to produce a chemical product containing the cellulose derivative: 【Chemistry 2】 (In the formula, R 1 ~R 3 are the same or different and are a hydrogen atom, an R group, a COR group, or a COOR group, and R 1 ~R 3 At least one of the groups is an R group, a COR group, or a COOR group, wherein R represents a hydrocarbon group.

9. The method for producing a chemical product according to claim 8, wherein the chemical product is a cosmetic, a pharmaceutical, a quasi-drug, a film, a sheet, a paint, an adhesive, or a food additive.

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