Method for separating cellulose, method for producing modified cellulose-based resin, modified cellulose-based resin, and molded product

Abstract

To provide a method for easily and rapidly separating cellulose from woody waste discharged from a construction site and / or a civil engineering site; a method for producing a modified cellulose-based resin by reacting cellulose, a polyisocyanate compound and a polyol compound in the presence of an ionic liquid; and a molded product obtained by using the modified cellulose-based resin.SOLUTION: There is provided a method for separating cellulose from woody waste discharged from a construction site and / or a civil engineering site, comprising: mixing the woody waste discharged from the construction site and / or the civil engineering site with an ionic liquid; and extracting the cellulose into the ionic liquid. There is further provided a method for producing a modified cellulose-based resin, comprising reacting, in the presence of an ionic liquid: an ionic liquid solution of cellulose obtained by mixing an ionic liquid with a woody waste discharged from a construction site and / or a civil engineering site; a polyisocyanate compound; and a polyol compound.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to a method for separating cellulose, a method for producing a modified cellulose-based resin using the separated cellulose, a modified cellulose-based resin obtained from the separated cellulose, and a molded product obtained from the modified cellulose-based resin. [Background technology]

[0002] Regarding wood waste generated from construction sites and / or civil engineering sites, disposal methods, including reuse, are an issue. For example, disposal methods for wood waste such as used cement formwork generated from construction sites and / or civil engineering sites, and wood waste generated during the construction of buildings with wooden designs, which have become widespread in recent years, are an issue. These wood wastes contain materials other than wood, for example concrete in concrete formwork, making it difficult to separate them during disposal.

[0003] The main components of wood that make up woody materials are lignin and cellulose, and if the cellulose could be separated and converted into useful substances, it would be a useful method for treating wood waste discharged from construction sites and / or civil engineering sites. However, the cellulose extraction methods known to date require treatment with strong acids or strong alkalis, which are harsh conditions and require large-scale equipment, making them disadvantageous in terms of cost and process. Furthermore, no method has been known to date for molding cellulose into molded products of any shape, and although resins obtained by chemically modifying cellulose are known, the molding conditions, etc. required for producing molded products using such resins are unknown, and improvements have been desired.

[0004] The following techniques are known as prior art relating to resins obtained by chemically modifying cellulose and separation of cellulose.

[0005] Patent Document 1 describes a resin composition obtained by blending (A) an olefin resin, (B) one or more members selected from the group consisting of cellulose and cellulose derivatives, and (C) a copolymer containing a monomer unit having a functional group capable of reacting with a hydroxyl group (monomer unit (1)) and a polypropylene macromer unit having a double bond at its terminal (macromer unit (1)).

[0006] Patent Document 2 describes a method for producing a functional product using biomass, which is characterized by using all dried substances of biomass, which may be crosslinked with a crosslinking agent, and allowing a modifying agent to act under conditions of high substrate concentration in which the biomass particles are subjected to shear stress under conditions that substantially suppress swelling and thickening of the biomass, and describes that diisocyanates can be used as crosslinking agents.

[0007] Patent Document 3 describes a method for producing polyurethane elastic yarn by mixing a solution in which polyurethane obtained by polymerizing polymer diol and diisocyanate as main components is dissolved in a solvent with a dispersion containing a polymeric compound dispersant (e.g., cellulose ester) having a thermal softening point of 100°C to 200°C, functional mineral particles (e.g., tourmaline stone, germanium ore, malt porphyry) and a solvent to prepare a spinning dope, and then spinning the solution.

[0008] Patent Document 4 describes a method for decomposing cellulose by dissolving cellulose in an ionic liquid and treating it with an acid, optionally with the addition of water.

[0009] Patent Document 5 describes a method for removing lignin from lignocellulosic biomass material, which comprises treating the lignocellulosic biomass with a mixed treatment liquid containing at least one of a hydroxyl group-containing compound and water, a delignification reaction catalyst, and a solvent containing an ionic liquid and an organic solvent, and dissolving the lignin in the lignocellulosic material in the mixed treatment liquid and removing it, thereby separating cellulose and lignin from lignocellulosic biomass.

[0010] Patent Document 6 describes a method for producing a cellulose solution using a cellulose-dissolving solvent consisting of an imidazolium-based ionic liquid and a nitrogen-based organic solvent or DMSO to dissolve cellulose at room temperature to 120° C. Furthermore, it describes passing the obtained cellulose solution through a solvent capable of extracting the imidazolium-based ionic liquid, the nitrogen-based organic solvent, and DMSO to obtain a cellulose fiber or film molded product. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] Patent Publication No. 2021-17528 [Patent Document 2] JP 2007-237026 A [Patent Document 3] JP 2006-169677 A [Patent Document 4] Special Publication No. 2009-531024 [Patent Document 5] JP 2010-84104 A [Patent Document 6] JP 2009-203467 A Summary of the Invention [Problem to be solved by the invention]

[0012] One of the problems to be solved by the present invention is to provide a method for easily and quickly separating cellulose from wood waste discharged from construction sites and / or civil engineering sites. One of the problems to be solved by the present invention is to provide a method for producing a modified cellulose-based resin, which comprises reacting cellulose, a polyisocyanate compound, and a polyol compound in the presence of an ionic liquid. One of the problems to be solved by the present invention is to provide a modified cellulose-based resin obtained by reacting cellulose, a polyisocyanate compound, and a polyol compound in the presence of an ionic liquid. One of the problems to be solved by the present invention is to provide a molded article obtained using a modified cellulose-based resin obtained by reacting cellulose, a polyisocyanate compound, and a polyol compound in the presence of an ionic liquid, and a method for producing the molded article. [Means for solving the problem]

[0013] The present inventors have conducted intensive research to solve the above problems. As a result, they have found that when an ionic liquid is mixed with wood waste discharged from a construction site and / or a civil engineering site, cellulose can be efficiently extracted into the ionic liquid, and cellulose can be efficiently separated from wood waste discharged from a construction site and / or a civil engineering site. They have also found that a modified cellulose-based resin can be easily produced by reacting the cellulose extracted in the ionic liquid with a polyisocyanate compound and a polyol compound in the presence of the ionic liquid, and that a molded product can be obtained by molding the obtained modified cellulose-based resin under heat and pressure in a mold, thereby completing the present invention.

[0014] That is, the present invention for solving the above problems mainly includes the following configurations. [Item 1] A method for separating cellulose from wood waste discharged from a construction site and / or a civil engineering site, comprising mixing an ionic liquid with wood waste discharged from the construction site and / or a civil engineering site and extracting cellulose into the ionic liquid. [Item 2] A method for producing a modified cellulose resin, comprising reacting (a) an ionic liquid solution of cellulose obtained by mixing an ionic liquid with wood waste discharged from a construction site and / or a civil engineering site, (b) a polyisocyanate compound, and (c) a polyol compound in the presence of the ionic liquid. [Item 3] A method for producing a modified cellulose-based resin, comprising reacting (p) cellulose, (q) a polyisocyanate compound, and (r) a polyol compound in the presence of an ionic liquid. [Item 4] (x) an ionic liquid solution of cellulose obtained by mixing an ionic liquid with wood waste discharged from construction sites and / or civil engineering sites, (y) a polyisocyanate compound, and (z) a polyol compound, in the presence of an ionic liquid, to obtain a modified cellulose resin. [Item 5] A modified cellulose-based resin obtained by reacting cellulose, a polyisocyanate compound, and a polyol compound in the presence of an ionic liquid. [Item 6] A molded product obtained by molding the modified cellulose resin according to item 4 or 5. [Item 7] A method for producing a molded product, comprising heating and pressurizing the modified cellulose resin according to item 4 or 5 in a mold. Effect of the Invention

[0015] The present invention provides a method for easily and quickly separating cellulose from wood waste discharged from construction sites and / or civil engineering sites. The present invention provides a method for producing a modified cellulose-based resin, which comprises reacting cellulose, a polyisocyanate compound, and a polyol compound in the presence of an ionic liquid. According to the present invention, there is provided a modified cellulose-based resin obtained by reacting cellulose, a polyisocyanate compound, and a polyol compound in the presence of an ionic liquid. The present invention provides a molded article obtained using a modified cellulose-based resin obtained by reacting cellulose, a polyisocyanate compound, and a polyol compound in the presence of an ionic liquid, and a method for producing the molded article.

[0016] According to the present invention, it is possible to effectively utilize wood waste, particularly wood waste discharged from construction sites and / or civil engineering sites, and to obtain a modified cellulose-based resin from the wood waste, which is a resin useful for producing molded products, etc. The modified cellulose-based resin obtained can be reused as a building material or a product such as a case or curved design, which was not possible with wood products, and is therefore very useful. [Brief description of the drawings]

[0017] [Figure 1] 3 is a scanning electron microscope photograph of the modified cellulose-based resin of the present invention according to Example 2. [Diagram 2] 3 is a differential scanning calorimetry (DSC) chart of the modified cellulose-based resin of the present invention in Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The method for separating cellulose, the method for producing a modified cellulose resin, the modified cellulose resin, and the molded product of the present invention will be described below.

[0019] [Cellulose separation method] The method for separating cellulose according to the present invention is a method for separating cellulose from wood waste discharged from a construction site and / or a civil engineering site, which comprises mixing an ionic liquid with wood waste discharged from a construction site and / or a civil engineering site and extracting cellulose into the ionic liquid. <Wood waste> The wood waste is not particularly limited as long as it is wood waste discharged from a construction site and / or a civil engineering site, and examples thereof include at least one selected from the group consisting of wooden construction waste generated during the demolition of buildings, wood waste such as sawdust, planer chips, short pieces, and scraps generated during construction and civil engineering work, wooden concrete formwork, weeds, pruning materials, and discarded wooden packaging materials. The wood waste is preferably pulverized as necessary in order to improve the solubility in the ionic liquid.

[0020] <Ionic liquid> The ionic liquid is not particularly limited as long as it is a salt that is liquid at room temperature (25° C.) and normal pressure (1 atm) and can dissolve cellulose at room temperature and normal pressure. For example, one or more types selected from the group consisting of imidazolium-based ionic liquids, pyridinium-based ionic liquids, ammonium-based ionic liquids, phosphonium-based ionic liquids, and cyclic amidinium-based ionic liquids can be mentioned.

[0021] The imidazolium ionic liquid is a salt of an imidazolium cation and an anion. Examples of the imidazolium cation include imidazolium ion, N-isobutylimidazolium ion, 2-methylimidazolium ion, 2-ethylimidazolium ion, 2-n-propylimidazolium ion, 2-isopropylimidazolium ion, 2-n-butylimidazolium ion, 4-methylimidazolium ion, 4-ethylimidazolium ion, 4,5-dimethylimidazolium ion, 1-butyl-3-methylimidazolium ion, 1-ethyl-3-methylimidazolium ion, 1-isobutyl-2-methylimidazolium ion, 1-isobutyl-2,3-dimethylimidazolium ion, and 2,4,5-trimethylimidazolium ion. From the viewpoint of availability, 1-butyl-3-methylimidazolium, 1-isobutyl-2-methylimidazolium ion, and 1-isobutyl-2,3-methylimidazolium ion are mentioned. From the viewpoint of cellulose solubility, 1-butyl-3-methylimidazolium ion or 1-ethyl-3-methylimidazolium ion is preferred. Examples of anions include halogen ions (fluoride ion, chloride ion, bromide ion, iodide ion), carboxylate ion (acetate ion, trifluoroacetate ion, methoxyacetate ion, etc.), phosphate ion, alkyl phosphate ion (dimethyl phosphate ion, diethyl phosphate ion, etc.), hydroxide ion, nitrate ion, sulfate ion, bisulfate ion, sulfonate ion, tosylate ion, perchlorate ion, aluminate ion, dialuminate ion, borate ion, amide ion, dicyanamide ion, succinate ion, and thiocyanate ion.

[0022] The pyridinium-based ionic liquid is a salt of a pyridinium cation and an anion. Examples of pyridinium ions include pyridinium ions, 1-n-butyl-3-methylpyridinium ions, 2-isobutylpyridinium ions, 3-isobutylpyridinium ions, 3-methylpyridinium ions, 4-methylpyridinium ions, 2-ethylpyridinium ions, 3-ethylpyridinium ions, 4-ethylpyridinium ions, 4-propylpyridinium ions, 2-n-hexylpyridinium ions, 3-n-hexylpyridinium ions, 3,5-dimethylpyridinium ions, 3,5-diethylpyridinium ions, 2,6-di-tert-butylpyridinium ions, 2-vinylpyridinium ions, 4-vinylpyridinium ions, 3 -hydroxymethylpyridinium ion, 4-hydroxymethylpyridinium ion, 2-(2-hydroxyethyl)pyridinium ion, 2-ethenylpyridinium ion, 2-ethynylpyridinium ion, 2-methyl-5-ethylpyridinium ion, 4-ethyl-2-methylpyridinium ion, 5-butyl-2-methylpyridinium ion, 2-ethyl-6-isopropylpyridinium ion, 3-ethyl-4-methylpyridinium ion, 2-methyl-5-vinylpyridinium ion, 2-methyl-3-ethylpyridinium ion, 2-methyl-5-(iso)propylpyridinium ion, 2,6-bis(hydroxymethyl)pyridinium ion, etc. From the viewpoint of cellulose solubility, 1-n-butyl-3-methylpyridinium ion is preferred. As the anion, the same anion as that constituting the imidazolium-based ionic liquid can be mentioned.

[0023] The ammonium-based ionic liquid is a salt of an ammonium cation and an anion. Examples of the ammonium ion include dimethylammonium ion, trimethylammonium ion, tetramethylammonium ion, diethylammonium ion, triethylammonium ion, tetraethylammonium ion, monopropylammonium ion, dipropylammonium ion, tripropylammonium ion, tetrapropylammonium ion, monobutylammonium ion, dibutylammonium ion, tributylammonium ion, tetrabutylammonium ion, monopentylammonium ion, dipentylammonium ion, tripentylammonium ion, tetrapentylammonium ion, monohexylammonium ion, dihexylammonium ion, methyl(ethyl)ammonium ion, methyl(propyl)ammonium ion, methyl(butyl)ammonium ion, methyl(pentyl)ammonium ion, methyl(hexyl)ammonium ion, ethyl(propyl)ammonium ion, ethyl(butyl)ammonium ion, ethyl(pentyl)ammonium ion, ethyl(ethyl ... (hexyl)ammonium ion, dimethyl(ethyl)ammonium ion, dimethyl(propyl)ammonium ion, dimethyl(butyl)ammonium ion, trimethyl(ethyl)ammonium ion, trimethyl(propyl)ammonium ion, trimethyl(butyl)ammonium ion, trimethyl(pentyl)ammonium ion, trimethyl(hexyl)ammonium ion, monovinylammonium ion, divinylammonium ion, trivinylammonium ion, monopropenylammonium ion, dipropenylammonium ion, tripropenylammonium ion, monobutenylammonium ion, dibutenylammonium ion, tributenylammonium ion, monopentenylammonium ion, dipentenylammonium ion, tripentenylammonium ion, monohexenylammonium ion, dihexenylammonium ion, dimethyl(vinyl)ammonium ion, dimethyl(propenyl)ammonium ion, dimethyl(butenyl)ammonium ion, dimethyl(pentenyl)ammonium ion,Dimethyl(hexenyl)ammonium ion, bis(2-methoxyethyl)monoethylammonium ion, trimethyl(vinyl)ammonium ion, bis(2-methoxyethyl)monomethylammonium ion, monocyclopentylammonium ion, dicyclopentylammonium ion, tricyclopentylammonium ion, monocyclohexylammonium ion, dicyclohexylammonium ion, dimethyl(cyclopentyl)ammonium ion, dimethyl(cyclohexyl)ammonium ion, (methylcyclopentyl)ammonium ion, bis(methylcyclopentyl)ammonium ion, (dimethylcyclopentyl)ammonium ion, bis(dimethylcyclopentyl)ammonium ion, (ethylcyclopentyl)ammonium ion, bis(ethylcyclopentyl)ammonium ion, (methylethylcyclopentyl)ammonium ion, bis(methylethylcyclopentyl)ammonium ion, (diethylcyclopentyl)ammonium ion, (methylcyclohexyl)ammonium ion, bis(methylcyclohexyl)ammonium ion, (dimethylcyclopentyl)ammonium ion, (ethylcyclohexyl)ammonium ion, bis(dimethylcyclohexyl)ammonium ion, (ethylcyclohexyl)ammonium ion, bis(ethylcyclohexyl)ammonium ion, (methylethylcyclohexyl)ammonium ion, (diethylcyclohexyl)ammonium ion, monomethanol ammonium ion, dimethanol ammonium ion, trimethanol ammonium ion, monoethanol ammonium ion, diethanol ammonium ion, triethanol ammonium ion, mono(n-propanol)ammonium ion, di(n-propanol)ammonium ion, tri(n-propanol)ammonium ion, monoisopropanol ammonium ion, diisopropanol ammonium ion, triisopropanol ammonium ion, monobutanol ammonium ion, dibutanol ammonium ion, tribetanol ammonium ion, monopentanol ammonium ion, dipentanol ammonium ion, tripentanol ammonium ion, monohexanol ammonium ion, dihexanol ammonium ion,Monomethyl monoethanol ammonium ion, Monoethyl monoethanol ammonium ion, Monoethyl monopropanol ammonium ion, Monoethyl monobutanol ammonium ion, Monoethyl monopentanol ammonium ion, Monopropyl monoethanol ammonium ion, Monopropyl monopropanol ammonium ion, Monopropyl monobutanol ammonium ion, Monopropyl monopentanol ammonium ion, Monobutyl monoethanol ammonium ion, Monobutyl monopropanol ammonium ion, Monobutyl monobutanol ammonium ion, Monobutyl monopentanol ammonium ion, Dimethyl monoethanol ammonium ion, Diethyl monoethanol ammonium ion, Diethyl monopropanol ammonium ion, Diethyl monobutanol ammonium ion, Diethyl monopentanol ammonium ion, Dipropyl monoethanol ammonium ion, Dipropyl monopropanol ammonium ion, Dipropyl monobutanol ammonium ion, Dipropyl monopentanol ammonium ion, dibutyl monoethanol ammonium ion, dibutyl monopropanol ammonium ion, dibutyl monobutanol ammonium ion, dibutyl monopentanol ammonium ion, monomethyl diethanol ammonium ion, monomethyl dipropanol ammonium ion, monomethyl dibutanol ammonium ion, monomethyl dipentanol ammonium ion, monoethyl diethanol ammonium ion, monoethyl dipropanol ammonium ion, monoethyl dibutanol ammonium ion, monoethyl dipentanol ammonium ion, monopropyl diethanol ammonium ion, monopropyl dipropanol ammonium ion, monopropyl dibutanol ammonium ion, monopropyl dipentanol ammonium ion, monobutyl diethanol ammonium ion, monobutyl dipropanol ammonium ion, monobutyl dibutanol ammonium ion, monobutyl dipentanol ammonium ion, monocyclohexyl monoethanol ammonium ion, monocyclohexyl diethanol ammonium ion,Monocyclohexyl monopropanol ammonium ion, monocyclohexyl dipropanol ammonium ion, mono (β-aminoethyl) monoethanol ammonium ion, mono tert-butyl monoethanol ammonium ion, mono tert-butyl diethanol ammonium ion, mono (β-aminoethyl) isopropanol ammonium ion, diethyl monoisopropanol ammonium ion, trimethyl monoethanol ammonium ion (choline ion), triethyl monoethanol ammonium ion, triethyl monopropanol ammonium ion, triethyl monobutanol ammonium ion, triethyl monopentanol ammonium ion, tripropyl monoethanol ammonium ion, tripropyl monopropanol ammonium ion, tripropyl monobutanol ammonium ion, tripropyl monopentanol ammonium ion, diethyl monomethylethanol ammonium ion, diethyl mono (2-methoxyethyl) monomethyl ammonium ion, bis (2-methoxyethyl) monoethyl monomethyl ammonium ion, monoethyl monomethyl diethanol ammonium ion, diethyl monomethyl monoethanol ammonium ion, and the like. From the viewpoint of solubility of cellulose, diethylmono(2-methoxyethyl)monomethylammonium ion and trimethylmonoethanolammonium ion (choline ion) are preferred. Examples of anions include the same anions as those constituting the imidazolium-based ionic liquid.

[0024] The phosphonium-based ionic liquid is a salt of a phosphonium cation and an anion. Examples of the phosphonium-based ion include tetramethylphosphonium ion, ethyltrimethylphosphonium ion, diethyldimethylphosphonium ion, triethylmethylphosphonium ion, methyltripropylphosphonium ion, tributylmethylphosphonium ion, tetraethylphosphonium ion, trimethylpropylphosphonium ion, diallyldimethylphosphonium ion, tetra-n-propylphosphonium ion, and tetra-n-butylphosphonium ion. From the viewpoint of cellulose solubility, tetra-n-butylphosphonium ion is preferred. Examples of the anion include the same anion as that constituting the imidazolium-based ionic liquid.

[0025] The cyclic amidinium ionic liquid is a salt of a cyclic amidinium cation and an anion. Examples of the cyclic amidinium ion include a diazabicycloundecenium ion and a diazabicyclononenium ion. Examples of the anion include the same anion as that constituting the imidazolium ionic liquid.

[0026] In the present invention, it is preferable to use at least one selected from the group consisting of 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium acetate, 1-ethyl-3-methylimidazolium methyl phosphate, 1-ethyl-3-methylimidazolium diethyl phosphate, diethylmono(2-methoxyethyl)monomethylammonium methoxyacetate, 1-butyl-3-methylpyridinium chloride, trimethylmonoethanolammonium acetate, and tetrabutylphosphonium chloride.

[0027] <Solvent> In the cellulose separation method according to the present invention, a solvent can be used in addition to the ionic liquid. Examples of the solvent include nitrogen-containing organic solvents (N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, etc.), sulfur-containing organic solvents (dimethyl sulfoxide, etc.), alcohol-based solvents (methanol, ethanol, propanol, butanol, etc.), ether-based solvents (butyl carbitol, diglyme, dimethyl ether, diethyl ether, tetrahydrofuran, etc.), ester-based solvents (ethyl acetate, butyl acetate, etc.), ketone-based solvents (acetone, methyl ethyl ketone), halogenated hydrocarbon-based solvents, aromatic hydrocarbon-based solvents, aliphatic hydrocarbon-based solvents, water, etc. The content of the solvent is 0% by mass or more, and can be 2% by mass or more, for example, 90% by mass or less, preferably 70% by mass or less, and more preferably 50% by mass or less, based on the total of the ionic liquid and the solvent being 100% by mass.

[0028] <Cellulose separation> The method for separating cellulose is not particularly limited. Examples of the method include a method of mixing wood waste with an ionic liquid, further mixing a solvent as necessary, dissolving cellulose in the ionic liquid, filtering the resulting mixture, and separating the cellulose as a filtrate, and a method of mixing wood waste with an ionic liquid, further mixing a solvent as necessary, dissolving cellulose in the ionic liquid, centrifuging the resulting mixture, and separating the cellulose as a supernatant. The amount of the ionic liquid or the mixture of the ionic liquid and the solvent used relative to the wood waste is not particularly limited. It can be appropriately determined depending on the content of the wood waste, etc. For example, the amount of the ionic liquid or the mixture of the ionic liquid and the solvent can be 1 part by mass or more, preferably 5 parts by mass or more, and preferably 8 parts by mass or more relative to 1 part by mass of the wood content in the wood waste. When dissolving cellulose in an ionic liquid, dissolution promoting means such as heating, stirring, ultrasonic vibration, etc. can be used as necessary.

[0029] The cellulose-containing ionic liquid solution obtained as the filtrate or supernatant can be used as is in the next reaction. Alternatively, the cellulose can be extracted using a coagulant that coagulates the cellulose in the ionic liquid solution. Examples of coagulants that can be used include water, ketone-based solvents (acetone, methyl ethyl ketone, etc.), alcohol-based solvents (methanol, ethanol, propanol, heptanol, butanol, etc.), nitrile-based solvents (acetonitrile, etc.), organic carboxylic acid-based solvents (acetic acid, formic acid, etc.), sulfur-containing organic solvents (dimethyl sulfoxide, etc.), ester-based solvents (methyl acetate, ethyl acetate, etc.), and nitrogen-containing organic solvents (dimethylacetamide, N,N-dimethylformamide, etc.).

[0030] [Method of manufacturing modified cellulose resin] The method for producing a modified cellulose-based resin of the present invention comprises reacting (i) an ionic liquid solution of cellulose or cellulose obtained by mixing an ionic liquid with wood waste discharged from a construction site and / or a civil engineering site, (ii) a polyisocyanate compound, and (iii) a polyol compound in the presence of an ionic liquid.

[0031] <Cellulose> Cellulose is represented by the following formula (A); [ka] (In the formula, n is the number of repeating units.) and is contained in coniferous wood in an amount of about 23% by mass to about 33% by mass, and in broadleaf wood in an amount of about 16% by mass to about 25% by mass or more. The number of repeating units n in formula (A) is not particularly limited, and is, for example, 100 or more, preferably 500 or more, more preferably 1,000 or more, and is, for example, 10,000 or less, preferably 6,000 or less, more preferably 4,000 or less.

[0032] The cellulose used in the method for producing a modified cellulose resin of the present invention may be cellulose itself or a cellulose-containing material such as wood, or an ionic liquid solution of cellulose obtained by mixing an ionic liquid with wood waste discharged from a construction site and / or civil engineering site. The "wood waste discharged from a construction site and / or civil engineering site" and the "ionic liquid" are the same as those described in the above [Method for separating cellulose].

[0033] <Polyisocyanate compounds> The polyisocyanate compound is at least one selected from the group consisting of an aliphatic polyisocyanate compound, an alicyclic polyisocyanate compound, an aromatic polyisocyanate compound, an araliphatic polyisocyanate compound, and derivatives of these polyisocyanate compounds.

[0034] Examples of the aliphatic polyisocyanate compound include 1,3-trimethylene diisocyanate, 1,2-propylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,6-diisocyanatohexanoic acid. and aliphatic diisocyanate compounds such as 2-isocyanatoethyl 2,6-diisocyanatohexanoate, 1,6-diisocyanato-3-isocyanatomethylhexane, 1,4,8-triisocyanatooctane, 1,6,11-triisocyanatoundecane, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6-triisocyanatohexane, and 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane.

[0035] Examples of the alicyclic polyisocyanate compound include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 4-methyl-1,3-cyclohexylene diisocyanate (hydrogenated TDI), 2-methyl-1,3-cyclohexylene diisocyanate, alicyclic diisocyanate compounds such as 1,3-bis(isocyanatomethyl)cyclohexane (hydrogenated 1,3-xylylene diisocyanate), 1,4-bis(isocyanatomethyl)cyclohexane (hydrogenated 1,4-xylylene diisocyanate), methylene bis(4,1-cyclohexanediyl) diisocyanate (hydrogenated MDI), and norbornane diisocyanate; 1,3,5-triisocyanatocyclohexane, 1,3,5-trimethylisocyanatocyclohexane, 2-(3 -isocyanatopropyl)-2,5-di(isocyanatomethyl)-bicyclo(2.2.1)heptane, 2-(3-isocyanatopropyl)-2,6-di(isocyanatomethyl)-bicyclo(2.2.1)heptane, 3-(3-isocyanatopropyl)-2,5-di(isocyanatomethyl)-bicyclo(2.2.1)heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane, 6-(2-isocyanatopropyl)-2,5-di(isocyanatomethyl)-bicyclo(2.2.1)heptane, alicyclic triisocyanate compounds such as 2-isocyanatoethyl)-2-isocyanatomethyl-3-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane, 5-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane, and 6-(2-isocyanatoethyl)-2-isocyanatomethyl-2-(3-isocyanatopropyl)-bicyclo(2.2.1)heptane; and the like.

[0036] Examples of aromatic polyisocyanate compounds include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, tolylene diisocyanate (crude TDI; a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate), 4,4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and 1,5-naphthalene. One or more selected from the group consisting of aromatic diisocyanate compounds such as diisocyanate; aromatic triisocyanate compounds such as triphenylmethane-4,4',4"-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6-triisocyanatotoluene; aromatic tetraisocyanate compounds such as 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate; and aromatic polyisocyanate compounds such as polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI).

[0037] Examples of the aromatic aliphatic polyisocyanate compound include one or more selected from the group consisting of aromatic aliphatic diisocyanate compounds such as 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ω,ω'-diisocyanato-1,4-diethylbenzene, 1,3-bis(1-isocyanato-1-methylethyl)benzene, and 1,4-bis(1-isocyanato-1-methylethyl)benzene; and aromatic aliphatic triisocyanate compounds such as 1,3,5-triisocyanatomethylbenzene.

[0038] Examples of derivatives of polyisocyanate compounds include at least one selected from the group consisting of dimer acid diisocyanates, polyisocyanate compound polymers (e.g., dimers, trimers (isocyanurate derivatives, iminooxadiazinedione derivatives, etc.), pentamers, heptamers, etc.), biuret bodies, allophanate bodies, uretdione bodies, uretoimine bodies, isocyanurate bodies, oxadiazinetrione bodies, carbodiimide bodies, adduct bodies (prepolymers), and blocked polyisocyanate compounds. Examples of adduct bodies (prepolymers) include prepolymers obtained by reacting the polyisocyanate compounds or derivatives thereof with active hydrogen-containing compounds having active hydrogen groups (hydroxyl groups, amino groups, etc.) that can react with isocyanate groups under conditions of excess isocyanate groups. Examples of the active hydrogen-containing compound include one or more selected from the group consisting of polyhydric alcohols, polyamines, water, and active hydrogen group-containing resins (acrylic polyols, polyolefin polyols, polyurethane polyols, polyether polyols, and polyester polyols).

[0039] The blocking agent for the isocyanate group in the blocked polyisocyanate compound is not particularly limited as long as it reacts with the isocyanate group and is easily released to regenerate (generate) the isocyanate group when heated to a temperature in the range of, for example, 70° C. or higher, preferably 100° C. or higher, more preferably 130° C. or higher, for example, 250° C. or lower. Examples of blocking agents include phenolic compounds such as phenol, cresol, xylenol, nitrophenol, ethylphenol, hydroxydiphenyl, butylphenol, isopropylphenol, nonylphenol, octylphenol, and methyl hydroxybenzoate; lactam compounds such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; aliphatic alcohol compounds such as methanol, ethanol, propyl alcohol, butyl alcohol, amyl alcohol, and lauryl alcohol; glycol ether compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and methoxymethanol; benzyl alcohol, Alcoholic hydroxyl group-containing compounds such as choline, glycolic acid, methyl glycolate, ethyl glycolate, butyl glycolate, lactic acid, methyl lactate, ethyl lactate, butyl lactate, methylol urea, methylol melamine, diacetone alcohol, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate; oxime compounds such as formamide oxime, acetamide oxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, and cyclohexane oxime; active methylene compounds such as dimethyl malonate, diethyl malonate, diisopropyl malonate, di-n-butyl malonate, diethyl methylmalonate, benzyl methyl malonate, diphenyl malonate, methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, n-propyl acetoacetate, benzyl acetoacetate, phenyl acetoacetate, and acetylacetone;Mercaptan compounds such as butyl mercaptan, t-butyl mercaptan, hexyl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol, and ethylthiophenol; acid amide compounds such as acetanilide, acetaniside, acetotoluide, acrylamide, methacrylamide, acetate amide, stearic acid amide, and benzamide; imide compounds such as succinimide, phthalic acid amide, and maleic acid amide; amine compounds such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine, and butylphenylamine; imidazole compounds such as imidazole and 2-ethylimidazole; urea, thiourea, ethylene urea, Examples of the compound include at least one selected from the group consisting of urea compounds such as ethylenethiourea and diphenylurea; carbamic acid esters such as N-phenyl phenyl carbamate; imine compounds such as ethyleneimine and propyleneimine; sulfite compounds such as sodium bisulfite and potassium bisulfite; pyrazole compounds such as pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, and 3-methyl-5-phenylpyrazole; imidazole compounds such as imidazole, benzimidazole, 2-methylimidazole, 2-ethylimidazole, and 2-phenylimidazole; and imidazoline compounds such as 2-methylimidazoline and 2-phenylimidazoline.

[0040] The blocked polyisocyanate compound can be produced by a known method. For example, the blocked polyisocyanate compound can be produced by reacting a polyisocyanate compound or a derivative thereof with a blocking agent in the presence of a solvent as needed. The solvent that is added as needed is not particularly limited as long as it is not reactive with the isocyanate compound. For example, one or more solvents selected from the group consisting of ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate and butyl acetate, and nitrogen-containing solvents such as N-methyl-2-pyrrolidone can be used.

[0041] <Polyol compound> The polyol compound is not particularly limited as long as it is a compound having two or more hydroxyl groups, and at least one of a low molecular weight polyol compound and a polymer polyol compound can be used.

[0042] The low molecular weight polyol compound is a compound having two or more hydroxyl groups in the molecule and a molecular weight of 42 or more and less than 400. Examples of the low molecular weight polyol compound include at least one selected from the group consisting of diol compounds such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, and dipropylene glycol; triol compounds such as glycerin and trimethylolpropane; polyol compounds such as pentaerythritol, diglycerin, and dipentaerythritol; and polyol compounds in which alkylene oxides having 2 to 4 carbon atoms are added to these low molecular weight compounds.

[0043] The polymer polyol compound is a compound having two or more hydroxyl groups at the molecular terminals and a number average molecular weight of 400 or more, preferably 500 or more, more preferably 1,000 or more, and 50,000 or less, preferably 10,000 or less, more preferably 5,000 or less. Examples of the polymer polyol compound include one or more selected from the group consisting of polyether polyol compounds, polyester polyol compounds, polycarbonate polyol compounds, polyurethane polyol compounds, epoxy polyol compounds, polyolefin polyol compounds, and acrylic polyol compounds. Preferably, the polymer polyol compound is one or more selected from the group consisting of polyether polyol compounds, polyester polyol compounds, and (meth)acrylic polyol compounds.

[0044] Examples of the polyether polyol compound include polyoxyalkylene polyol compounds. Examples of the polyoxyalkylene polyol compound include one or more compounds selected from the group consisting of polyol compounds obtained from polyoxyalkylenes having 2 to 4 carbon atoms.

[0045] The polyester polyol compound may be, for example, one or more selected from the group consisting of condensation polyester polyol compounds and ring-opening polyester polyol compounds. The condensation polyester polyol compound may be, for example, one or more selected from the group consisting of adipate polyester polyol compounds and phthalic acid polyester polyol compounds. The ring-opening polyester polyol compound may be, for example, polycaprolactone polyol compound.

[0046] The ratio of the amount of low molecular weight polyol compound to the amount of polymer polyol compound is not particularly limited.For example, the amount of polymer polyol compound is 0 parts by mass or more, for example 100 parts by mass or less, preferably 50 parts by mass or less, with respect to 100 parts by mass of low molecular weight polyol compound.In the present invention, it is preferable to use only low molecular weight polyol compound as polyol compound.

[0047] <Reaction of each component> In the method for producing a modified cellulose resin of the present invention, the reaction of cellulose, a polyisocyanate compound, and a polyol compound is carried out in the presence of an ionic liquid. Specifically, the reaction can be carried out by mixing the polyisocyanate compound and the polyol compound with the cellulose dissolved in the ionic liquid or a solvent containing the ionic liquid (cellulose ionic liquid solution).

[0048] Cellulose has strong hydrogen bonds between hydroxyl groups in and / or within a molecule, and the reactivity of the hydroxyl groups is low, so that it is chemically low and difficult to react with an isocyanate compound under normal conditions. However, since the method for producing a modified cellulose resin of the present invention requires a reaction in the presence of an ionic liquid, it is presumed that the hydrogen bonds formed between hydroxyl groups in and / or within a molecule are relaxed by the ionic liquid being solvated in cellulose, which makes it possible to react with a polyisocyanate compound. It is presumed that the polyisocyanate compound is added to the hydroxyl group of cellulose, and the hydroxyl group of cellulose or the hydroxyl group of a polyol compound reacts with the advantageous isocyanate group derived from the polyisocyanate compound to form a crosslinked polymer. Note that the present invention is not bound by such presumption.

[0049] In the method for producing a modified cellulose resin of the present invention, when the reaction of cellulose, a polyisocyanate compound, and a polyol compound is carried out in the presence of an ionic liquid, a catalyst for promoting the reaction of a hydroxyl group with an isocyanate group can be used as necessary, which can increase the polymerization rate and allow the reaction to take place at a low temperature.

[0050] Examples of catalysts that promote the reaction between hydroxyl groups and isocyanate groups include amine-based catalysts and metal-based catalysts, such as tin-based catalysts, bismuth-based catalysts, zinc-based catalysts, titanium-based catalysts, and zirconium-based catalysts.

[0051] Examples of the amine catalyst include triethylamine, tributylamine, benzyldimethylamine, triethylenediamine, tetramethylbutanediamine, 2-methyl-triethylenediamine, 1,8-diaza-bicyclo[5.4.0]-7-undecene (DBU), DBU salts (phenol salts, organic acid salts (stearates, oleates, formates, etc.)), 1,5-diaza-bicyclo[4.3.0]-5-nonene (DBN), DBN salts (phenol salts, organic acid salts (stearates, oleates, formates, etc.)), 1,5-diaza-bicyclo[4.4.0]-5-decene (DBD), DBD salts (phenol salts, organic acid salts (stearates, oleates, formates, etc.)), N-methylimidazole, 1,2-dimethylimidazole, 1 N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N'-trimethylaminoethyl-ethanolamine, bis(2-dimethylaminoethyl)ether, N,N-dimethylcyclohexylamine, tetramethylhexamethylenediamine, tripropylamine, and the like.

[0052] Examples of tin catalysts include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutyltin diacetate, dibutyltin dimaleate, dioctyltin diacetate, dioctyltin dineodecane, dibutyltin dichloride, dioctyltin dichloride, dibutyltin diacetate, dibutyltin di-2-ethyl-hexoate, dilauryltin diacetate, tin diacetate, tin dioctoate, tin dioleate, tin dilaurate, tin di-2-ethyl-1-hexoate, tin diethyl caproate, tin dipalmitate, metastannic acid, stannic oxide, trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide, and the like.

[0053] Examples of the bismuth catalyst include one or more selected from the group consisting of bismuth octoate, bismuth neodecanoate, bismuth stearate, bismuth oleate, bismuth naphthenate, bismuth tris(acetate), bismuth tris(octanoate), bismuth tris(2-ethylhexanoate), bismuth tris(neodecanoate), bismuth bis(neodecanoate-oxinate), bismuth neodecanoate-bis-(oxinate), and bismuth tris(N,N-diethyl-3-oxo-butanamidate).

[0054] Examples of the zinc-based catalyst include one or more selected from the group consisting of zinc acetate, zinc octoate, zinc neodecanoate, zinc stearate, zinc oleate, zinc naphthenate, zinc chelate complexes, and the like.

[0055] Examples of the titanium catalyst include one or more selected from the group consisting of tetraisopropyloxytitanate, dibutyltitanium dichloride, tetrabutyltitanium, butoxytitanium trichloride, titanium chelate complexes, and the like.

[0056] Examples of the zirconium catalyst include one or more selected from the group consisting of zirconium complexes (zirconium tetrakis(acetate), zirconium tetrakis(octanoate), zirconium tetrakis(2-ethylhexanoate), zirconium tetrakis(neodecanoate), zirconium tetrakis(acetylacetonate), zirconium tetrakis(1,3-diphenylpropane-1,3-dionate), zirconium tetrakis(ethylacetoacetate), zirconium tetrakis(N,N-diethyl-3-oxobutanamidate), etc.).

[0057] The amount of catalyst used to promote the reaction between hydroxyl groups and isocyanate groups is not particularly limited. For example, it is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass or more, and for example, 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 5 parts by mass or less, relative to 100 parts by mass of polyisocyanate compound. If the amount of catalyst used to promote the reaction between hydroxyl groups and isocyanate groups is less than 0.1 parts by mass, the reaction of forming urethane bonds may be slow, and if it exceeds 30 parts by mass, the reaction rate may be too fast and the reaction may become uncontrollable.

[0058] <Reaction ratio of each component> In the method for producing a modified cellulose-based resin of the present invention, the reaction ratio of cellulose, polyisocyanate compound and polyol compound is not particularly limited and can be appropriately adjusted depending on the properties required of the modified cellulose-based resin. For example, the reaction ratio can be set so that the equivalent ratio NCO / OH of the isocyanate group (NCO) to the total hydroxyl group (OH) in the cellulose and polyol compound is, for example, 0.4 or more, preferably 0.5 or more, more preferably 0.6 or more, and is, for example, 1.5 or less, preferably 1.2 or less, more preferably 1.1 or less.

[0059] The ratio of the amount of cellulose to the polyol compound is not particularly limited and can be appropriately adjusted depending on the properties required for the modified cellulose resin, etc. For example, the amount of the polyol compound is, for example, 20 parts by mass or more, preferably 30 parts by mass or more, and for example, 250 parts by mass or less, preferably 200 parts by mass or less, relative to 100 parts by mass of cellulose.

[0060] [Modified cellulose resin] The modified cellulose-based resin of the present invention is a modified cellulose-based resin obtained by reacting cellulose, a polyisocyanate compound, and a polyol compound in the presence of an ionic liquid. The cellulose may be an ionic liquid solution of cellulose obtained by mixing an ionic liquid with wood waste discharged from a construction site and / or a civil engineering site.

[0061] The cellulose, the ionic liquid solution of cellulose, the polyisocyanate compound, the polyol compound and the ionic liquid may be the same as the cellulose, the ionic liquid solution of cellulose, the polyisocyanate compound, the polyol compound and the ionic liquid described above in [Method for producing modified cellulose-based resin], respectively. The modified cellulose resin may be produced by the same method as that described above in [Production method of modified cellulose resin].

[0062] The modified cellulose resin of the present invention has a structural unit represented by formula (A1), and R 31 ~R 36 each independently has hydrogen or a group represented by formula (B1), formula (B2), or formula (B3), and R 31 ~R 36 At least one of the above is represented by formula (B1), and both ends of formula (B1) form a urethane bond with formula (A1), which is a crosslinked polymer compound. [ka] (In the formula, n1 is the number of repeating units.)

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] (In formulas (B1), (B2) and (B3), each R 1 are each independently a diisocyanate compound residue, and each R 2 each independently represents a residue of a diol compound. In formulae (B1), (B2) and (B3), m1, m2 and m3 each represent the number of repeating units.

[0067] The repeating unit represented by formula (A1) is derived from cellulose having the repeating unit represented by formula (A) described in the above [Production method of modified cellulose resin], and the number of repeating units n1 is not particularly limited as long as it is the number of repeating units of cellulose obtained from wood. For example, it is 100 or more, preferably 500 or more, more preferably 1,000 or more, and for example, 10,000 or less, preferably 6,000 or less, more preferably 4,000 or less.

[0068] R in formulas (B1), (B2) and (B3) 1 is derived from the diisocyanate compound described in the above [Method for producing modified cellulose-based resin]. 1 When there are multiple R, they may be the same or different. 1is a group selected from the group consisting of an aromatic diisocyanate compound residue, an araliphatic diisocyanate compound residue, an aliphatic diisocyanate compound residue, and an alicyclic diisocyanate compound residue, preferably an aromatic diisocyanate compound residue, more preferably a tolylene diisocyanate compound residue or a diphenylmethane diisocyanate compound residue.

[0069] R in formulas (B1), (B2) and (B3) 2 is derived from the diol compound described in the above [Method for producing modified cellulose-based resin]. 2 When there are a plurality of, they may be the same or different. Preferred are alkylene diol compound residues, and more preferred are ethylene glycol residues, propylene glycol residues, trimethylene glycol residues, butylene glycol residues, tetramethylene glycol residues and hexamethylene glycol residues.

[0070] The number m1 of repeating units in formula (B1) is not particularly limited as long as it is an integer of 0 or more, and is, for example, 5,000 or less, preferably 3,000 or less, and more preferably 1,000 or less. The number m2 of repeating units in formula (B2) is not particularly limited as long as it is an integer of 0 or more, and is, for example, 2,000 or less, preferably 1,000 or less, and more preferably 500 or less. The number m3 of repeating units in formula (B3) is not particularly limited as long as it is an integer of 0 or more, and is, for example, 2,000 or less, preferably 1,000 or less, and more preferably 500 or less.

[0071] The ratio of the amounts of formulae (B1), (B2) and (B3) present in the modified cellulose resin is not particularly limited. When the amount of formula (B1) present is taken as 100, the amount of formula (B2) present is 0 to 30, and the amount of formula (B3) present is 0 to 5.

[0072] The ratio of the cellulose residue, the polyisocyanate compound residue, and the polyol compound residue in the modified cellulose resin is not particularly limited, and may be the same as the reaction ratio of the cellulose, the polyisocyanate compound, and the polyol compound described in the above [Method for producing modified cellulose resin].

[0073] [Molded products and their manufacturing methods] The molded product of the present invention is obtained by molding one or more of the modified cellulose resins, or a modified cellulose resin composition containing 1 to 100 mass %, preferably 10 to 100 mass %, and more preferably 50 to 100 mass % of the modified cellulose resin. Examples of components other than the modified cellulose resin that may be contained in the modified cellulose resin composition include one or more selected from the group consisting of resins other than modified cellulose resins, fillers, various additives, etc.

[0074] The resin other than the modified cellulose-based resin is not particularly limited, but examples thereof include one or more types selected from the group consisting of polyolefin-based resins, polyester-based resins, polyether resins, acrylic-based resins, polyamide-based resins, polyimide-based resins, urethane-based resins, cellulose-based resins, and the like. The filler is not particularly limited, but examples thereof include one or more types selected from the group consisting of silica, talc, clay, calcium carbonate, barium sulfate, titanium oxide, glass flakes, carbon fibers, glass fibers, metal fibers, organic fibers, organic nanofibers, inorganic nanofibers, and metal nanofibers. The various additives are not particularly limited, but examples thereof include one or more selected from the group consisting of colorants such as organic pigments, inorganic pigments, and dyes, adsorbents such as zeolite and activated carbon, plasticizers, antibacterial agents, conductive materials, antioxidants, and gas storage and release compounds other than the gas storage and release compounds described above.

[0075] The shape of the molded product may be any shape, such as particles, fibers, films, porous bodies, molded bodies, etc. In the case of particles, the average particle diameter can be arbitrarily adjusted within the range of, for example, 0.1 μm to 20 mm. The average particle diameter of the gas storage and release material in the present invention is the volume-based cumulative particle diameter D50 value at a cumulative volume of 50% by volume measured by a laser diffraction scattering type particle size distribution measurement method. In the case of fibers, the length can be adjusted arbitrarily within the ranges of 1 mm to 3 m, the diameter of 0.1 mm to 5 mm, and the denier number of 0.5d to 20d. In the case of a film, the thickness can be adjusted to any value within the range of, for example, 2 μm to 5 mm. The width and length of the film can be any value. In the case of a porous body, for example, the apparent density is 0.1 g / cm 3 ~1.2g / cm 3 The porosity can be adjusted arbitrarily within the range of 5 to 80 vol %.

[0076] The method for producing the molded product is not particularly limited. For example, any molding means such as hot-press molding, extrusion molding, injection molding, etc. may be used to prepare a molded product of any shape. In the present invention, a method of filling a mold with the modified cellulose resin or modified cellulose resin composition and molding it under hot-press is preferably used. EXAMPLES

[0077] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0078] [Separation of cellulose] <Example 1> 50 mL of an ionic liquid (1-Butyl-3-methylimidazolium Chloride) was placed in a 500 mL separable flask, and 4 g of sawdust (wood powder), which is a wood waste, was added in three portions. After stirring at 200 rpm for 1 hour at 25°C, 100 mL of N-methyl-2-pyrrolidone was mixed, and centrifugation was performed at 10,000 rpm for 10 minutes at 25°C using a centrifuge, separating into a precipitate and a supernatant. The supernatant was a mixed solution of an ionic liquid and cellulose. From this, it was found that cellulose could be selectively separated from wood waste by using an ionic liquid.

[0079] [Production of Modified Cellulose-based Resin] <Example 2> To the supernatant obtained in Example 1, 15 g of tolylene diisocyanate (TDI: a mixture of 80% 2,4-tolylene diisocyanate and 20% 2,6-tolylene diisocyanate), 6.5 g of 1,3-propanediol, and 100 mg of diazabicycloundecene were added, and then stirred at 80°C for 2 hours. Next, 500 mL of methanol was added, and filtration was performed, separating into a supernatant and a precipitate. The precipitate was filtered off and dried at 60°C for 20 hours to obtain the target modified cellulose-based resin.

[0080] <Example 3> A modified cellulose-based resin was obtained in the same manner as in Example 2, except that 5.3 g of ethylene glycol was used instead of 6.5 g of 1,3-propanediol.

[0081] [Measurement, Observation, and Analysis of Modified Cellulose-based Resin] Regarding the modified cellulose-based resin obtained in Example 2, FT-IR measurement, transmission electron microscope observation, Raman spectroscopic analysis, and differential scanning calorimeter (DSC) behavior observation were performed as follows.

[0082] <FT-IR Measurement> The FT-IR of the modified cellulose-based resin obtained in Example 2 was measured by the single reflection ATR method using a Fourier transform infrared spectrophotometer ("FT / IR-6800" manufactured by JASCO Corporation) to analyze the molecular structure. The results are as follows. C=O:1738cm -1 , 1782cm -1 Phe-CH3: 1490cm -1 , 2928cm -1 , 2990cm -1 Height: 929cm -1 , 1082cm -1 , 3134cm -1 , 3416cm -1 Aromatic ring: 3053cm -1 , 3079cm -1 , 3096cm -1

[0083] <Transmission electron microscope observation> Equipment: Atomic resolution analytical electron microscope (JEOL "JEM-ARM200F Dual X") TEM measurement conditions: Acceleration voltage 300 kV, measurement temperature -100°C The results of observation of the modified cellulose resin obtained in Example 2 under a transmission electron microscope are shown in FIG. Observation using a transmission electron microscope confirmed the presence of numerous pores of approximately 1 to 5 nm on the surface of the polymer particles, and revealed that the interior of the polymer formed a microphase-separated structure consisting of two phases, hard segments and soft segments.

[0084] <Raman spectroscopy> Equipment used: Laser Raman spectrometer (JASCO Corporation "NRS-3300") Excitation laser wavelength: 532 nm Observed peak: 998 cm -1 , 1341cm -1 , 1436cm -1 , 1599cm -1 , 1652cm -1 , 2962cm -1 , 3073cm -1 From the peaks observed by Raman spectroscopic analysis of the modified cellulose resin obtained in Example 2, it was found that TDI and 1,3-propanediol were bonded to the cellulose via urethane bonds.

[0085] <Differential scanning calorimeter (DSC) behavior observation> Regarding the thermal properties of the modified cellulose resin obtained in Example 2, the behavior was observed by a differential scanning calorimeter (DSC), and the results are shown in FIG. As a result of the differential scanning calorimetry (DSC) behavior observation, endothermic peaks were observed around 75℃ and 260℃. Therefore, it was found that the phase transition occurred twice with increasing temperature.

[0086] <Structure of modified cellulose resin> From the results of the measurement, observation and analysis of the modified cellulose resin, it was found that the modified cellulose resin obtained in the examples has a structural unit represented by formula (A), 31 ~R 36 are each independently any one of hydrogen and a group represented by formula (B1), formula (B2) and formula (B3), and R in formula (A) 31 ~R 36 It was confirmed that at least one of the above was a crosslinked polymer compound represented by formula (B1), and both ends of formula (B1) formed urethane bonds with formula (A). [ka] (In the formula, n is the number of repeating units and is about 1,500.)

[0087] [ka] (In the formula, m1 is the number of repeating units and is an integer of 0 or more.)

[0088] [ka] (In the formula, m2 is the number of repeating units and is an integer of 0 or more.)

[0089] [ka] (In the formula, m3 is the number of repeating units and is an integer of 0 or more.)

[0090] (In the formulas (B1), (B2) and (B3), Each R 1 each independently represents formula (c1) or (c2); [ka] is a group represented by R 2 teeth, -CH2CH2CH2- It is a group represented by the following formula:

[0091] [Molded product manufacturing] <Example 4> The modified cellulose resin obtained in Example 2 was filled into a mold and heated and pressurized at 200°C using a hydraulic molding machine to obtain a rectangular parallelepiped (plate) molded product measuring 30 mm in length, 40 mm in width, and 1 mm in thickness.

[0092] <Example 5> Molding was carried out in the same manner as in Example 4, except that the modified cellulose resin obtained in Example 3 was used, to obtain a rectangular parallelepiped (plate-like) molded product having a length of 30 mm, a width of 40 mm and a thickness of 1 mm.

[0093] INDUSTRIAL APPLICABILITY The cellulose separation method according to the present invention is capable of efficiently separating only cellulose, and is an extremely useful invention for recycling cellulose. The modified cellulose resin according to the present invention has excellent moldability and can be used to produce molded products in various shapes, making it an extremely useful invention. The method for producing a modified cellulose resin according to the present invention involves reacting cellulose, a polyisocyanate compound, and a polyol compound in an ionic liquid, and it is presumed that the solvation effect of the ionic liquid relaxes the strong hydrogen bonds between / intramolecularly cellulose molecules, thereby increasing the reactivity of the hydroxyl groups in the cellulose with the isocyanate groups in the polyisocyanate compound. However, the present invention is not bound by this presumption. The present invention makes it possible to reuse wood waste discharged from construction sites and / or civil engineering sites as resin without complex operations, and is an extremely useful and meaningful method for treating wood waste compared to conventional methods.

Claims

1. A method for separating cellulose from wood waste discharged from a construction site and / or a civil engineering site, comprising mixing an ionic liquid with wood waste discharged from the construction site and / or a civil engineering site and extracting cellulose in the ionic liquid.

2. A method for producing a modified cellulose resin, comprising reacting (a) an ionic liquid solution of cellulose obtained by mixing an ionic liquid with wood waste discharged from a construction site and / or a civil engineering site, (b) a polyisocyanate compound, and (c) a polyol compound in the presence of an ionic liquid.

3. A method for producing a modified cellulose-based resin, comprising reacting (p) cellulose, (q) a polyisocyanate compound, and (r) a polyol compound in the presence of an ionic liquid.

4. (x) an ionic liquid solution of cellulose obtained by mixing an ionic liquid with wood waste discharged from a construction site and / or a civil engineering site; (y) a modified cellulose resin obtained by reacting a polyisocyanate compound and (z) a polyol compound in the presence of an ionic liquid.

5. A modified cellulose-based resin obtained by reacting cellulose, a polyisocyanate compound, and a polyol compound in the presence of an ionic liquid.

6. A molded product obtained by molding the modified cellulose resin according to claim 4 or 5.

7. A method for producing a molded product, comprising molding the modified cellulose resin according to claim 4 or 5 under heat and pressure in a mold.

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