JP2018178012A - Resin modifier, resin composition, solid electrolyte, lithium ion secondary battery, and method for producing resin modifier - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel resin modifier that facilitates improved heat resistance and/or antiplasticization of resin.SOLUTION: The present invention provides a resin modifier for improved heat resistance and/or antiplasticization that contains low modified lignin.SELECTED DRAWING: None

Description

  The present invention relates to a modifier for resin, a resin composition, a solid electrolyte, a lithium ion secondary battery, and a method for producing a modifier for resin.

  Additives for improving the heat resistance of organic polymers have been studied for a long time, and, for example, phosphorus / halogen flame retardants, metal hydrates, inorganic flame retardants such as red phosphorus, triazine flame retardants, organophosphorus flame retardants Flame retardants are being considered.

JP 2011-92151 A

  With phosphorus and halogen-based flame retardants, health damage and environmental impact due to the generation of harmful gases at the time of combustion have become problems. Also in the inorganic flame retardant, the triazine flame retardant, and the organophosphorus flame retardant, there is a problem that the flame retardancy is not sufficient.

  In recent years, clay minerals have been proposed as heat-resistant fillers for organic polymers. However, clay minerals require various organic treatments to improve the compatibility with resins, and the addition process is complicated.

  Lignin is a polymer having a phenylpropane unit as a basic unit, and is contained in woody plants and herbaceous plants. Lignin is present in plant bodies in a form in which it is complexly bound to polysaccharides such as cellulose and hemicellulose. It is not easy to take out lignin alone from the plant without denaturation, and lignin extracted under severe conditions using conventional strong acids, strong bases, strong heat, etc. is denatured by condensation, depolymerization etc. . Therefore, the application of conventional lignin is limited to the field of concrete dispersant, fuel and the like. Also, conventional over-modified lignin is difficult to blend into organic polymers without chemical treatments such as alkylation.

  An object of the present invention is to provide a novel resin modifier which can easily improve the heat resistance of a resin and / or anti-plasticization.

  The inventors of the present invention have newly found that the heat resistance improvement and / or anti-plasticization of the resin can be easily performed by applying the low-modified lignin to the resin.

  The present invention provides a modifier for resin, which contains low-denatured lignin, for improving heat resistance and / or anti-plasticizing.

  In the above-mentioned resin modifier, the nitrobenzene oxidative decomposition rate of the low-modified lignin may be 15% or more.

  The present invention also provides a resin composition comprising a phase containing low-denaturing lignin and a resin, wherein the phase forms a single phase. The said resin composition is excellent in heat resistance.

  In the resin composition, the resin may be a thermoplastic resin.

  In the resin composition, the thermoplastic resin is preferably polyethylene carbonate.

  In the above-mentioned resin composition, the above-mentioned resin may be cellulose nanofibers.

  The present invention also provides a solid electrolyte comprising the above resin composition and an alkali metal salt. Since the said resin composition is excellent in heat resistance, it can be used suitably for a solid electrolyte.

  In the solid electrolyte, the alkali metal salt is preferably a lithium salt.

  The present invention also provides a lithium ion secondary battery comprising the above solid electrolyte.

  The present invention also comprises the steps of wet-grinding a plant material containing lignin and a polysaccharide in the presence of a saccharifying enzyme to obtain a liquid containing a ground product, solid-liquid separating the liquid containing the ground product, and containing low-modified lignin. A process for producing a modifier for resin, which contains low-modified lignin, for improving heat resistance and / or antiplasticizing, comprising the steps of obtaining a solid component.

  According to the present invention, a novel resin modifier is provided which can easily improve the heat resistance and / or anti-plasticization of the resin.

It is a graph which shows the X-ray scattering intensity profile of simultaneous saccharification grinding | pulverization lignin. It is a graph which shows the particle size distribution of simultaneous saccharification grinding | pulverization lignin. It is a graph which shows the thermogravimetric measurement result of a PEC lignin complex. It is a graph which shows 5% mass loss temperature of PEC lignin complex. It is a graph which shows the weight loss of PEC single-piece | unit and PEC lignin complex. It is a graph which shows the glass transition temperature of PEC lignin complex. It is a graph which shows the tension test result of PEC lignin complex. It is a graph which shows the tension test result of PEC lignin complex. It is a graph which shows the Young's modulus of PEC lignin complex.

  Hereinafter, modes for carrying out the present invention will be described in detail. The present invention is not limited to the following embodiments.

  The modifier for resin according to the present embodiment contains low-modified lignin. The low-modified lignin has the function of improving the heat resistance of the resin and / or antiplasticizing the resin by being applied to the resin. Therefore, the modifier for resin which concerns on this embodiment can be suitably used in order to improve the heat resistance of resin, and / or to antiplasticize resin by containing low modified lignin.

  In the present specification, to deplasticize a resin means, for example, to reduce the rigidity of the resin, and specifically to, for example, to increase the Young's modulus in a molded article such as a film of the resin.

  The low-modified lignin used in the present embodiment is obtained from a plant containing lignin and polysaccharides, for example, by simultaneous saccharification and grinding described later, compared to sulfite lignin and kraft lignin obtained in the conventional pulp production process It is characterized in that the degree of degeneration is extremely low. In general, sulfite lignin is lignin obtained by high temperature boiling treatment of a raw material containing lignin and polysaccharide in a sulfite aqueous solution, and kraft lignin is high temperature boiling treatment of the above raw material with alkali and sodium sulfide Lignin obtained by

  The degree of modification of lignin can be evaluated, for example, by the nitrobenzene oxidative decomposition rate. The low-modified lignin used in this embodiment has a higher nitrobenzene oxidative decomposition rate than conventional sulfite lignin and kraft lignin. The nitrobenzene oxidative decomposition of lignin produces an aldehyde when it has a certain structure, and the more the condensed-type structure having a carbon-carbon bond, the lower the amount of aldehyde produced. Therefore, the higher the value of the nitrobenzene oxidative decomposition rate in lignin, the lower the proportion of condensed lignin, and the lower the degree of denaturation.

  The nitrobenzene oxidative decomposition rate of the low-modified lignin used in this embodiment may be, for example, 15% or more, and 18% or more, 20% or more, 22% or more, 25% or more, 27% or more, 30% or more, 35 %, 40% or more, or 45% or more. When lignin is derived from coniferous trees, the nitrobenzene oxidative decomposition rate may be, for example, 15% or more, 18% or more, 20% or more, 22% or more, 25% or more, or 27% or more. When lignin is derived from a broadleaf tree, the nitrobenzene oxidative decomposition rate is, for example, 15% or more, 18% or more, 20% or more, 22% or more, 25% or more, 27% or more, 30% or more, 35% or more , 40% or more, 45% or 50% or more.

  Further, the nitrobenzene oxidative decomposition rate of the low-modified lignin used in the present embodiment is, for example, 1 of the nitrobenzene oxidative decomposition rate in the raw material of the unmodified lignin having the same origin as the low-modified lignin, It may be 1 to 1.8 times, or 1.2 to 1.6 times.

  The degradation rate of nitrobenzene is determined by adding wood flour or lignin to an aqueous solution previously made alkaline with a reagent such as sodium hydroxide, adding nitrobenzene to the equivalent of 0.1 to 2.0 times the amount of lignin, and using an autoclave It is a decomposition method of heating while stirring at an arbitrary temperature of 100 to 200 ° C. for 1 to 3 hours. Monomer aromatic compounds such as vanillin, vanillic acid, syringaldehyde and syringic acid in the reaction product to be obtained are quantified, and the ratio of the amount of the above monomer aromatic compound to the amount of lignin used is the nitrobenzene oxidation decomposition rate Calculated as

  The low-modified lignin used in the present embodiment is obtained from non-edible plant biomass which is abundant in nature, and has an aromatic network structure and is excellent in compatibility with organic polymers, so its application range Is wide. The low-modified lignin tends to retain β-ether bonds better and to reduce condensed carbon-carbon bonds as compared to conventional sulfite lignin and kraft lignin. Moreover, the said low modified | denatured lignin is excellent in the dispersibility to aqueous solvents, such as water.

  The low-modified lignin used in the present embodiment can be obtained as plate-like particles. The diameter of the low-denaturing lignin may be 10 nm to 2 μm, and may be 10 nm to 1 μm, 10 to 500 nm, 10 to 100 nm, 10 to 80 nm.

  The reason why the low-modified lignin used in the present embodiment has the effect of improving the heat resistance of the resin is the possibility that the plate-like lignin particles are stacked to prevent physical heat transfer. Is considered. In addition, it is also possible that the low-denatured lignin supplements radicals generated in the thermal decomposition process.

  The modifier for resin according to the present embodiment may be made of only low-modified lignin, or may be low-modified lignin. The modifier for resin may partially contain polysaccharides such as cellulose and hemicellulose derived from plant raw materials. The resin modifier may be used in combination with other additives such as a compatibilizer.

  The modifier for resin which concerns on this embodiment can be applied to arbitrary resin, and can be used for heat resistance improvement and / or antiplasticization. The above-mentioned modifier for resin can be used as a flame retardant for resin because it can improve the heat resistance of the resin. By blending the resin improver with the resin, for example, in an arbitrary ratio, the plasticity of the resin and the composition containing the resin improver can be adjusted to any degree.

  The modifier for resin according to the present embodiment can be used, for example, in a ratio of 0.5 to 99.5% by mass with respect to the total amount of resin, and 1 to 99% by mass, 5 to 95% by mass, 10 You may use in the ratio of -90 mass%, 20-90 mass%, 30-70 mass%, and 40-60 mass%.

  When the resin modifier according to the present embodiment is used to improve the heat resistance of the resin, the resin to which the resin modifier is applied may be either a thermoplastic resin or a thermosetting resin. When the resin modifier is used to deplasticize the resin, the applied resin may be either a thermoplastic resin or a thermosetting resin, but when applied to a thermoplastic resin, the present invention It is preferable because the effect of The specific aspect of the resin applied to the modifier for resin is the same as that of the resin in the resin composition described later.

<Method for producing low-denatured lignin>
The low-denatured lignin used in this embodiment is, for example, a step of wet-grinding a plant material containing lignin and a polysaccharide in the presence of a saccharifying enzyme to obtain a liquid containing a ground material, and solid-liquid separation of the liquid containing a ground material And obtaining a solid component containing low-denatured lignin. The low-modified lignin can be produced, for example, by the method disclosed in Patent Document 1.

  The plant material is not particularly limited as long as it contains lignin and polysaccharides, and may be, for example, plants such as conifers such as cedar, broad-leaved trees and grasses, and may be woody plants or herbaceous plants. The polysaccharide is, for example, cellulose, hemicellulose or the like. The hemicellulose is, for example, xylan, arabinoxylan, xyloglucan, glucomannan or the like. The plant material may be coarsely ground beforehand before being subjected to wet grinding. Coarse grinding can be performed, for example, using a grinder such as a cutter mill, chipper, rotary cutter or the like.

  The saccharifying enzyme may be any enzyme capable of saccharifying polysaccharides such as cellulose and hemicellulose contained in plant raw materials, and examples thereof include cellulase, hemicellulase, pectinase and the like, and it is preferable to use cellulase and hemicellulase in combination. The amount of saccharifying enzyme used at the time of wet pulverization is not particularly limited, and can be appropriately set according to the amount of plant material to be used.

  Cellulase is an enzyme that hydrolyzes glucosidic bonds of β-1,4-glucan, for example, endoglucanase that cleaves from the inside of the molecule of cellulose, degrades from the reducing end or non-reducing end of cellulose, and releases cellobiose There are exoglucanase, β-glucosidase which cleaves glucosidic bond of cellobiose and converts it to glucose. Pectinase is an enzyme having a catalytic function of degrading pectin, and examples include polygalacturonase, pectin lyase, pectin esterase, pectin methyl esterase and the like. The hemicellulase is an enzyme that degrades polysaccharides other than cellulose and pectin among polysaccharides that constitute the cell wall of a plant body. In wet grinding, in addition to the saccharifying enzyme, for example, an enzyme such as a proteolytic enzyme may be used in combination.

  Wet grinding is performed in a state in which the plant material to be ground is suspended in a liquid. Wet grinding can be performed, for example, using a ball mill or bead mill. In the present specification, wet grinding in the presence of saccharifying enzymes is also referred to as "simultaneous saccharification grinding".

  The medium at the time of wet-grinding is not particularly limited as long as it can maintain the liquid containing the plant raw material in the state of suspension without inactivating the saccharifying enzyme, for example, aqueous solvent, organic solvent, ionic solvent Etc.

  As conditions for wet grinding, medium pH 2.0 to 11.0, weight ratio of medium to object to be ground 1: 1 to 100: 1, bead diameter of grinding machine 0.1 to 20 mm, bead peripheral speed 0.3 The flow rate may be appropriately selected within the range of 50 m / sec, slurry flow rate of 0.1 to 10 L / min, and the temperature in the vessel of 0 to 100 ° C. The grinding time may be such that the particle size of the obtained pulverized material is an arbitrary value or less, for example, an average particle size of 1 μm or less. Wet grinding may be performed while measuring the particle size of the ground product, the slurry viscosity, etc. over time.

  After completion of the wet pulverization, the resulting pulverized material is separated into a liquid component and a solid component by solid-liquid separation means such as centrifugation, to obtain a solid component. Sugars mainly elute in the liquid component and lignin mainly remains in the solid component. The amount of sugar eluted in the liquid component can be measured, for example, by the somogie Nelson method or the like. If it is considered that the decomposition of the sugar in the plant material is insufficient as a result of the measurement, the saccharifying enzyme and the solvent may be added to the solid component again to carry out additional saccharification. That is, simultaneous saccharification grinding may include an additional saccharification step. Saccharification can be carried out, for example, with stirring. When additional saccharification is performed, the resulting solid-liquid mixture is subjected to solid-liquid separation again to obtain solid components.

  The solid component obtained by simultaneous saccharification and grinding may be used as the low-modified lignin as it is, or the solid component dried or the solid component washed with a liquid such as water and then dried may be the low-modified lignin It may be used as

  The present invention can also be said to be a method of improving the heat resistance of the resin and / or antiplasticizing the resin, which comprises the step of blending the low-modified lignin into the resin.

<Resin composition>
The present invention also provides a resin composition comprising a phase containing low modified lignin and a resin. At least a portion of the low-denaturing lignin and resin-containing phase forms a single phase. The resin composition concerning this embodiment may contain components other than low denaturation lignin and resin, and may have a portion which is not single phase. The resin composition may further contain a compatibilizer.

  As resin which forms a resin composition with low denaturation lignin concerning this embodiment, it may be thermoplastic resin and thermosetting resin, for example. One type of resin may be used alone, or two or more types may be used in combination.

  The low-modified lignin used in the present embodiment is excellent in compatibility with the thermoplastic resin. Therefore, when the resin in the resin composition is a thermoplastic resin, it is possible to obtain a resin composition containing a phase which is a compatible single phase and which contains a low-modified lignin and a thermoplastic resin. In addition, compatibility means that two or more types of polymers are mixed at a molecular level or substantially at a level close to the molecular level, and specifically, for example, the resin composition is pulled by hand Even when it is possible to form a film to be held, it can be said that the resin composition is substantially compatible when, for example, the glass transition temperature of the resin composition is one. When the resin is a thermoplastic resin, the resin composition according to the present embodiment is also referred to as a “resin complex” of low-denaturing lignin and a thermoplastic resin.

  Examples of the thermoplastic resin include polycarbonate such as polyalkylene carbonate, polyolefin resin, polystyrene resin, polyester resin, polyamide resin, polyurethane resin, acrylic resin, polyether resin such as polyethylene oxide, cellulose resin, polyvinyl alcohol, ethylene- Examples thereof include vinyl alcohol copolymers.

  Polyalkylene carbonate is a polymer having an alkylene carbonate structure consisting of an alkylene group and a carbonate group as a constitutional unit, and examples thereof include polyethylene carbonate, polypropylene carbonate, poly (1,2-dimethyl ethylene carbonate), polybutene carbonate, polyisobutene carbonate, Polypentene carbonate, polyhexene carbonate, polycyclopentene carbonate, polycyclohexene carbonate, polycycloheptene carbonate, polycyclooctene carbonate, polylimonene carbonate and the like.

  As a cellulose resin, cellulose ester, cellulose ether, etc. are mentioned, for example. The cellulose-based resin may be cellulose nanofibers. Cellulose nanofibers are cellulose fibers disintegrated to nano order. The cellulose nanofiber may be one in which a hydroxyl group derived from cellulose is substituted by a substituent.

  As a thermosetting resin, an epoxy resin, a phenol resin, a melamine resin, a urea resin etc. are mentioned, for example. The thermosetting resin is preferably a resin having a functional group crosslinkable with low-modified lignin. When the resin is a thermosetting resin, the resin composition according to the present embodiment may be in an uncured state or in a cured state.

  The content mass ratio of the low-modified lignin to the resin in the resin composition according to the present embodiment can be any ratio according to the property of the desired product, for example, 0.5: 99.5 to 99.5. May be 0.5: 1: 99 to 99: 1, 5: 95 to 95: 5, 10: 90 to 90: 10, 20: 80 to 80: 20, 30: 70 to 70:30, or It can be 40:60 to 60:40. The heat resistance of the resin composition is improved and the rigidity tends to be increased as the content ratio of low modified lignin in the resin composition is higher.

  The weight average molecular weight of the resin is not particularly limited, but may be, for example, 10,000 to 1,000,000, 10,000 to 500,000, 30,000 to 200,000. The weight average molecular weight is measured by gel permeation chromatography.

  The 5% mass decomposition temperature of the resin composition according to the present embodiment may be, for example, 235 to 280 ° C., and may be 260 to 280 ° C. The 5% mass decomposition temperature of the resin composition may be, for example, 15 to 100 ° C. higher or 30 to 60 ° C. higher as compared to the case where the low denatured lignin is not contained. The thermal decomposition residual rate at 500 ° C. of the resin composition according to the present embodiment may be, for example, 2 to 80%, and may be 5 to 55%, or 10 to 40%. The thermal decomposition residual rate at 500 ° C. of the resin composition according to the present embodiment may be, for example, 2 to 80% higher than that in the case of not containing low-denatured lignin, 5 to 55%, 10 to 40 % May be high. The resin composition according to the present embodiment may have a glass transition temperature higher by, for example, 5 to 20 ° C. and 7 to 15 ° C., as compared to the case where the low-denatured lignin is not contained.

  The Young's modulus of the resin composition according to the present embodiment may be, for example, 5 to 250 MPa, 10 to 230 MPa, or 50 to 200 MPa.

  The resin composition according to the present embodiment is excellent in various properties such as heat resistance, mechanical properties, and antibacterial properties, as compared with the case where low modified lignin is not contained, since low modified lignin is blended. Specifically, in the resin composition according to the present embodiment, for example, the rigidity is improved. Further, the low-modified lignin used in the resin composition according to the present embodiment is also advantageous in that it can be obtained by a method in which the load on the human body and the environment from the plant raw material is small.

<Method for Producing Resin Composition>
The resin composition concerning this embodiment can be manufactured using low denaturation lignin and arbitrary resin. The low-modified lignin can be used as it is for the production of a resin composition without further chemical treatment or the like, and the resin composition can be produced conveniently.

  When the resin is a thermoplastic resin, the resin composition according to the present embodiment can be produced, for example, by blending low-modified lignin and a thermoplastic resin in an arbitrary ratio and melt-kneading. The heating temperature during kneading is equal to or higher than the melting temperature of the thermoplastic resin to be used. The heating temperature may be 20 to 90 ° C. higher than the melting temperature of the thermoplastic resin used. Kneading can be performed, for example, using an apparatus such as a kneading injection molding machine (18D0, manufactured by Imoto Machinery Co., Ltd.). Kneading conditions can be, for example, 120 ° C. and 100 rpm.

  When the resin is a thermoplastic resin, the obtained resin composition (resin composite) can be further molded as a molded body, for example, by a method such as extrusion molding, injection molding, compression molding and the like.

  When the resin is a thermosetting resin, the resin composition according to the present embodiment can be obtained, for example, by mixing low-modified lignin and a thermosetting resin. Additives such as a curing accelerator may be added to the resin composition. The resin composition may be cured.

  As a use of the resin composition concerning this embodiment, or its molded object, a surface protective film, an interfacial bonding agent, etc. are mentioned, for example.

<Solid electrolyte>
Since the said resin composition is excellent in heat resistance, it can be used suitably for a solid electrolyte. The solid electrolyte is a lightweight and flexible electrolyte membrane without a fear of liquid leakage, and is expected to be applied to a secondary battery using lithium ion or the like. The solid electrolyte according to the present embodiment includes the resin composition and an alkali metal salt.

  The content of the resin composition in the solid electrolyte may be, for example, 5 to 99% by mass or 10 to 95% by mass with respect to the total amount of the solid electrolyte.

  The resin in the resin composition used for the solid electrolyte is preferably a thermoplastic resin, more preferably a polyalkylene carbonate.

  In the above-mentioned solid electrolyte, examples of the alkali metal salt include lithium salt, sodium salt, potassium salt and the like. The alkali metal salt is preferably a lithium salt.

In the solid electrolyte, the alkali metal salt may be present as a cation such as an alkali metal and as a counter ion of the cation. When the alkali metal salt is a lithium salt, the energy density is higher. Examples of the lithium _{salt, LiClO 4, LiBF 4, LiI} , LiPF 6, LiCF 3 SO 3, LiCF 3 COO, LiNO 3, LiAsF 6, LiSbF 6, LiAlCl 4, LiCl, LiBr, LiB (C 2 H 5) _{4, LiCH 3 SO 3, LiC} 4 F 9 SO 3, Li (CF 3 SO 2) 2 N, Li (C 2 F 5 SO 2) N, Li (FSO 2) 2 N, Li [(CO 2) 2 ₂ B etc. can be mentioned. Among these, from the viewpoint of ionic conductivity, Li (CF ₃ SO ₂ ) ₂ N (lithium bis (trifluoromethanesulfonyl) imide: LiTFSI), and Li (FSO ₂ ) ₂ N (lithium bis (fluorosulfonyl) imide: It is preferred to include at least one of LiFSI). The solid electrolyte may contain an alkali metal salt singly or in combination of two or more.

  The solid electrolyte according to the present embodiment may be solid (solvent-free solid electrolyte) containing no solvent, or may be gel (polymer gel electrolyte) containing a solvent. When the solid electrolyte is a polymer gel electrolyte, the content of the solvent in the polymer gel electrolyte is usually 30 to 99% by mass of the whole solid electrolyte.

  The solid electrolyte according to this embodiment may contain, in addition to the above resin composition, a known resin as a resin used for the electrolyte. Further, the electrolyte may contain a filler, an additive and the like.

  As the filler, for example, talc, kaolin, clay, calcium silicate, alumina, zirconia, zinc oxide, antimony oxide, indium oxide, tin oxide, titanium oxide, iron oxide, iron oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, silica, Examples include calcium carbonate, potassium titanate, barium titanate, mica, montmorillonite, glass fiber and the like. Among these, it is preferable to contain at least one of alumina, zirconia, magnesium oxide, and barium titanate.

  The method for producing the solid electrolyte according to the present embodiment is not particularly limited. For example, an alkali metal salt and a solvent are added to and dissolved in the resin composition according to the present embodiment, and the solid electrolyte is removed by removing the solvent. You can get it.

  The form, configuration, and the like of the solid electrolyte according to this embodiment are not particularly limited, and may be, for example, a membrane-like solid electrolyte membrane. The solid electrolyte membrane is preferably self-supporting. The solid electrolyte membrane having self-supporting property is excellent in handleability. The self-supporting membrane is a membrane that can be peeled off and handled while keeping the shape of the solid electrolyte membrane from the support.

  The solid electrolyte membrane can be manufactured as follows. For example, a mixed solution containing the resin composition according to the present embodiment, an alkali metal salt and a solvent is applied to the surface of a support to form a coating, and the solvent in the coating is removed to form a film-like solid. An electrolyte membrane can be obtained. At this time, when it is necessary to peel off the solid electrolyte membrane from the support, it is preferable that the surface of the support is subjected to a peeling treatment.

<Lithium ion secondary battery>
The solid electrolyte according to the present embodiment can be suitably used for a lithium ion secondary battery. The lithium ion secondary battery according to the present embodiment includes the solid electrolyte according to the present embodiment. The lithium ion secondary battery preferably includes the above-described solid electrolyte as a constituent material of the electrolyte layer. A lithium ion secondary battery comprises an anode, a cathode, and an electrolyte layer disposed between the anode and the cathode. With this configuration, a battery with excellent characteristics can be obtained.

  A solid electrolyte membrane may be formed directly on the electrode by applying a mixed solution containing the above resin composition, an alkali metal salt and a solvent to the electrode and removing the solvent. The various members included in the lithium ion secondary battery according to the present embodiment are not particularly limited, and for example, materials generally used for the battery can be used.

  Hereinafter, the present invention will be more specifically described based on examples. However, the present invention is not limited by the following examples.

<Preparation of Simultaneous Saccharification Pulverized Lignin>
Sugi wood was crushed to about 2 to 5 mm by a cutter mill to obtain wood powder. After immersing 500 g of wood flour in 4.5 L of 100 mM phosphate buffer (pH 5.0) overnight, it was added to a wet pulverizer LMZ4 (manufactured by Ashizawa Finetech Co., Ltd.) together with a buffer, and cellulase hemic manufactured by Genencor Co. The cellulase mixture (50 mL each of Optimash XL and Optimash BG) was added, and wet grinding was started while maintaining at 50 ° C. The bead used for LMZ4 used a 0.5 mm diameter thing made of zirconia metal. After the wood flour was introduced into LMZ4, the particle size of the wood flour was measured and when the average particle size became 10 μm, the beads were changed to a diameter of 0.1 mm, and wet grinding was performed for a total of 4 hours. The viscosity of the wood flour suspension decreased as the wet milling proceeded. The average primary particle size of the obtained powder was about 30 nm.

  After grinding, the supernatant and the residue were separated by centrifugation. The sugar in the supernatant was quantified by the somogie Nelson method. After washing the residue with water, the mixture of cellulase and hemicellulase mixed solution and 1 L of phosphate buffer was again added to the residue, and the saccharification reaction was performed by stirring at 50 ° C. for 12 hours. After completion of the reaction, the supernatant and the residue were separated by centrifugation to obtain lignin (simultaneous saccharified and crushed lignin) as a residue. The amount of sugar was similarly quantified for the obtained supernatant. The total amount of sugars in the obtained supernatant was about 85%. It was confirmed that about 85% of cellulose and hemicellulose contained in wood was degraded and eluted as sugar in the supernatant.

<Measurement of nitrobenzene oxidative decomposition rate>
100 mg of air-dried simultaneously saccharified ground lignin powder, 7 mL of 1N NaOH solution, and 0.4 mL of nitrobenzene were charged into a 10 mL stainless steel autoclave and reacted at 170 ° C. with stirring for 2.5 hours. After completion of the reaction, 15 mg of p-hydroxybenzoic acid was added as an internal standard. The mixture was extracted three times with an equal volume of diethyl ether to remove nitrobenzene and by-products such as aniline and azobenzene. Hydrochloric acid was added to the remaining aqueous layer to adjust to pH 1.0, and then extracted three times with equal volumes of diethyl ether. The obtained extract was dried under reduced pressure to obtain an aromatic compound produced from the simultaneous saccharification and grinding lignin. The obtained aromatic compound was dissolved in a 10 mM phosphoric acid solution containing 10% acetonitrile, and high-performance liquid chromatography was performed to characterize and quantify the generated aromatic compound. As aromatic compounds, 20.926 mg of vanillin, 1.72 mg of vanillic acid and 1.87 mg of syringaldehyde were obtained, and a monomeric aromatic compound was obtained at a ratio of 24.5% from the simultaneous saccharified and ground lignin used. It was done. That is, the nitrobenzene oxidative degradation rate of simultaneous saccharified ground lignin was 24.5%. On the other hand, when the nitrobenzene oxidation decomposition rate was similarly measured about the sulfite lignin and kraft lignin obtained by the conventional pulp manufacturing process, it was 7 to 11%. Moreover, the nitrobenzene oxidation decomposition rate of cedar wood flour was about 27%. Simultaneous saccharified ground lignin was confirmed to be close to the state of untreated native lignin.

<X-ray scattering intensity measurement of simultaneous saccharified ground lignin>
About simultaneously saccharified ground lignin obtained by the above-mentioned method, X-ray scattering intensity profile was acquired by BL45XU of SPring-8 in the state of aqueous solution (6.8 mass%). The results are shown in FIG. The molecular shape (fractal dimension) can be grasped by calculating the power E of the wave number q (nm ⁻¹ ) at the scale of lignin minor axis (R) to major axis (L). The power E of the wave number q of simultaneous saccharified ground lignin was 2, indicating that the co-saccharified ground lignin particles were thin plate-like (tabular). Moreover, the particle size distribution (volume basis) of simultaneous saccharification grinding | pulverization lignin measured by the dynamic-light-scattering method is shown in FIG. Simultaneous saccharified ground lignin was shown to be a plate-like molecule with a diameter of several tens of nm.

<Preparation of PEC lignin complex>
A complex of PEC and simultaneous saccharified ground lignin as follows using polyethylene carbonate (PEC, Empower Materials) and the simultaneous saccharified ground lignin obtained by the method described above (hereinafter, “PEC lignin complex” Also referred to as The simultaneously saccharified and ground lignin was fed into a kneading injection molding machine (manufactured by Imoto Machinery Co., Ltd., trade name: 18D0) so as to be sandwiched by polyethylene carbonate from above and below. The first-stage melt-kneading was performed for about 90 minutes under the conditions of 120 ° C. and 100 rpm for simultaneously saccharified ground lignin and PEC (4 g in total). Next, the second stage melt kneading was performed for about 120 minutes under the same conditions to obtain a PEC lignin complex. What changed the compounding quantity of simultaneous saccharification grinding | pulverization lignin between 0-100% was produced, respectively, and it used for the following evaluation.

<Heat resistance: Thermogravimetric measurement>
Thermogravimetric measurement was performed on a PEC lignin complex using TG / DTA 7200 (manufactured by Hitachi High-Tech Science Co., Ltd.) at a temperature rising rate of 10 ° C./minute under a nitrogen atmosphere. The change in weight when the temperature is raised from 30 ° C. to 500 ° C. is shown in FIG. It was confirmed that, as the addition rate of the simultaneous saccharified ground lignin is higher, the weight loss due to heat is suppressed and the heat resistance is excellent.

The 5% mass loss temperature (Td ₅ ) of the complex of PEC with co-saccharified ground lignin is shown in FIG. The addition of co-saccharified ground lignin increased the 5% mass loss temperature by up to about 60 ° C. In addition, even when only 1% by mass of simultaneous saccharified ground lignin was added, a 5% mass decrease temperature increase was confirmed, and a further remarkable increase was confirmed when 5% by mass was added.

  The weight loss when the heating temperature was fixed at 180 ° C. was measured for the PEC lignin complex in which the mixing ratio of simultaneous saccharified ground lignin was 10% by mass, and the PEC alone (the simultaneous addition of saccharified ground lignin was 0% by mass). The results are shown in FIG. In the case of PEC alone, about 95% by mass was decomposed in 15 minutes, while in the PEC lignin complex with 10% by mass simultaneous saccharified lignin addition rate, about 12% by mass was decomposed in 12 hours.

Suggested Scanning Calorimetry
The glass transition temperature (Tg) of the PEC lignin complex was measured using DSC 7020 (manufactured by Hitachi High-Tech Science Co., Ltd.). What arranged the graph which shows each calorie | heat amount change in the case of 0-100 mass% of lignin contents on the same graph for convenience is shown in FIG. As the lignin content increased, the glass transition temperature of the complex increased. Also, all PEC lignin complexes had a single glass transition temperature, suggesting that the complexes form a single phase and are compatible.

<FT-IR measurement>
About PEC lignin complex, FT / IR measurement was performed using FT / IR-4100 (manufactured by JASCO Corporation). The absorption peaks of C の O group and OH group derived from PEC were also measured in the PEC lignin complex as well, which indicates that PEC does not interact with the simultaneous saccharified ground lignin. The

<GPC>
The number average molecular weight of PEC in PEC alone and PEC lignin complex was calculated by gel permeation chromatography (GPC) method. GPC analysis was performed using a high-speed GPC apparatus (HLC-8320GPC, manufactured by Tosoh Corporation) and TSK gel GMHHR-H column (manufactured by Tosoh Corporation) at 25 ° C., mobile phase chloroform, at a flow rate of 1.0 mL / min. The The results are shown in Table 1. As a result of GPC analysis, two PEC molecular weight peaks were confirmed, but none of them was confirmed to be changed by the addition of lignin. This suggested that copolymerization did not occur between PEC and co-saccharified ground lignin.

<Tension test>
The PEC lignin complex was hot pressed at 20 MPa and 120 ° C. using a hot press (MINI TEST PRESS-10, manufactured by Toyo Seiki Seisakusho Co., Ltd.) to obtain a film of the complex. A sample of 0.5 cm × 2 cm was cut out, and a tensile test was performed using an OZ 502 system (manufactured by Sentech Co., Ltd.) at 25 ° C. and a tensile speed of 10 mm / min to calculate tensile stress and Young's modulus. The tensile stress is shown in FIGS. 7 and 8, and the Young's modulus is shown in FIG. FIG. 8 is a graph in which spots in the case of the lignin addition rate of 60 to 80% in FIG. 7 are enlarged. It was confirmed that as the content of the simultaneous saccharified ground lignin increases, the rigidity of the film increases and the plasticity decreases.

Claims (10)

  A modifier for resin, containing low-denatured lignin, for improving heat resistance and / or anti-plasticizing.   The modifier for resin according to claim 1, wherein the nitrobenzene oxidative decomposition rate of the low-modified lignin is 15% or more.   A resin composition comprising a phase containing low denatured lignin and a resin, wherein the phase forms a single phase.   The resin composition according to claim 3, wherein the resin is a thermoplastic resin.   The resin composition according to claim 4, wherein the thermoplastic resin is polyethylene carbonate.   The resin composition according to claim 3, wherein the resin is cellulose nanofibers.   A solid electrolyte comprising the resin composition according to any one of claims 3 to 6 and an alkali metal salt.   The solid electrolyte according to claim 7, wherein the alkali metal salt is a lithium salt.   A lithium ion secondary battery comprising the solid electrolyte according to claim 8. Wet-grinding a plant material containing lignin and a polysaccharide in the presence of a saccharifying enzyme to obtain a liquid containing a ground product;
Solid-liquid separating the liquid containing the pulverized product to obtain a solid component containing low-denatured lignin,
The manufacturing method of the modifier for resin for improving heat resistance and / or antiplasticizing which contains low modified | denatured lignin.