JP5620866B2 - Method for producing plant-based biomass molding material, method for producing plant-based biomass molded body, and plant-based biomass molded body obtained by this method - Google Patents

Description

The present invention relates to a method for producing a plant biomass molding material Ru using plant biomass material, a method of manufacturing a plant-based biomass molded article using this plant biomass molding material, and to a plant-based biomass molded article obtained by this method.

  In recent years, plant-based biomass materials that are sustainable resources and carbon stock materials have attracted attention in place of petroleum-derived resources. In particular, technological development is underway to utilize biomass materials while reducing the use of petroleum-derived resources as much as possible. Among these, as a technique attracting attention, there is a method of obtaining a molding material, a molded body, or the like from plant-based biomass material in place of plastic. For example, in Patent Document 1, a wood-based material is finely pulverized into a fine powder, which is treated with water vapor to be softened to have fluidity, poured into a mold and hot-pressed, or the fine powder is molded into a mold. It is disclosed that a plastic-like woody molding material imparted with an arbitrary three-dimensional shape is obtained by putting it in a container, pressing it with steam treatment, molding, and then cooling and solidifying it.

  However, in the above prior art, even if the wood-based material is softened by treatment with water vapor, it is difficult to sufficiently improve the fluidity of the wood-based material, and a high molding pressure of about 150 MPa is required at the time of molding, In particular, there is a problem that a general-purpose facility cannot be used to obtain a molded body having a large volume. Furthermore, a complicated mold design becomes necessary because the supply port of the material to the mold needs to have a small diameter or the mold needs to withstand high pressure. Furthermore, since the molding pressure has to be high, there is a problem that only a molded body having a high density can be obtained, and variations of the molded body are limited.

  Moreover, the molded object obtained from plant-type biomass material also has the problem that characteristics, such as water resistance and intensity | strength, are not enough compared with the molded object obtained from petroleum origin resources.

JP 2003-11109 A

The present invention has been made in view of the above reasons, and is a plant-based biomass molding material for obtaining a plant-based biomass molding material that has good fluidity during molding and can form a molded article having high water resistance. A production method , a method for producing a plant biomass molded body for obtaining a molded article having high water resistance from the plant biomass molding material, and a plant biomass molded body having high water resistance formed from the plant biomass molding material The purpose is to provide.

  The plant-based biomass molding material according to the present invention includes a first material composed of a plant-based biomass material impregnated with a thermosetting main resin, a compound that undergoes a thermosetting reaction with the main resin, and thermosetting of the main resin. It contains one or more second materials consisting of a plant biomass material impregnated with one or more auxiliaries selected from compounds that promote the reaction.

The plant-based biomass molding material according to the present invention is
(A) a step of preparing a thermosetting main agent resin, one or more auxiliary agents selected from a compound that undergoes a thermosetting reaction with the main agent resin and a compound that promotes the thermosetting reaction of the main agent resin;
(B) a step of preparing the first material by impregnating the plant-based biomass material with the main resin,
(C) a step of preparing one or more second materials by impregnating the plant biomass material with the auxiliary agent; and (d) mixing the first material and the second material into a plant system. Obtaining a biomass molding material;
It is preferable to be obtained by a method comprising

  In the step (d), it is preferable to obtain the plant biomass molding material by mixing the first material and the second material and applying a shear stress to the resulting mixture.

  In the plant biomass molding material according to the present invention, the auxiliary agent preferably contains at least one selected from amines, imines, amides, imidazoles, acid anhydrides, and polyols.

  In the plant-based biomass molding material according to the present invention, the auxiliary agent preferably contains at least one of amines, amides, imines, imidazoles, and acid anhydrides that also act as a fluidizing agent.

  In the plant biomass molding material according to the present invention, the main resin preferably includes at least one selected from epoxy resins, isocyanates, and phenol resins.

  The plant biomass molding material according to the present invention is preferably capable of low pressure molding with a fluidization pressure of 25 MPa or less.

The method for producing a plant biomass molded body according to the present invention,
(E) a step of preparing the plant-based biomass molding material, and (f) a step of supplying the plant-based biomass molding material into a mold and performing heat flow molding.

  In the method for producing a plant biomass molded body according to the present invention, the main agent and the auxiliary agent are foamable materials that foam when they react, and heating in the mold in the step (f) It is preferable to cause the main agent and the auxiliary agent to react with each other at the time of fluid molding to cause foaming.

  In the method for producing a plant-based biomass molded body according to the present invention, it is preferable that the main resin contains an isocyanate and the auxiliary agent contains a polyol.

  In the method for producing a plant biomass molded body according to the present invention, it is also preferable that the main resin includes an epoxy resin and the auxiliary agent includes an acid anhydride.

  The plant-based biomass molded body according to the present invention is manufactured by the method for manufacturing a plant-based biomass molded body.

  The plant-based biomass molded body according to the present invention has water resistance such that the evaluation in a water resistance test immersed in water at a temperature of 20 ° C. for 24 hours has a water absorption rate of 1.78% or less and a volume expansion coefficient of 1.69% or less. It is preferable.

The plant biomass molded body according to the present invention preferably has a density of 1.1 g / cm ³ or less.

  The plant biomass molded body according to the present invention preferably has water resistance such that the evaluation in a water resistance test immersed in water at a temperature of 20 ° C. for 24 hours is a volume expansion coefficient of 0.42% or less.

  ADVANTAGE OF THE INVENTION According to this invention, the fluidity | liquidity at the time of shaping | molding is good, and in order to obtain a highly water-resistant molded object from this plant-based biomass molding material which can form a highly water-resistant molded object, A method for producing a plant biomass molded body and a highly water-resistant plant biomass molded body formed from the plant biomass molding material are obtained.

(A) thru | or (c) is the schematic which shows the process of applying a shear stress to the mixture in one Embodiment of this invention. (A) thru | or (d) is the schematic which shows the process of shape | molding a plant biomass shaping | molding material in one Embodiment of this invention. 2 is an appearance photograph of a plant biomass molding material obtained in Example 1. FIG.

  In the present embodiment, the plant biomass molding material contains a first material and a second material. The first material is a plant biomass material impregnated with a thermosetting main resin. The second material consists of a plant biomass material impregnated with an auxiliary agent. The auxiliary agent includes one or more compounds selected from a compound (curing agent, crosslinking agent, etc.) that undergoes thermosetting reaction with the main resin and a compound (curing accelerator, curing catalyst, etc.) that accelerates the thermosetting reaction of the main resin. included.

  The plant-based biomass material refers to a plant-derived material in the biomass. Biomass is a “renewable organic resource derived from living organisms excluding fossil resources”, that is, living organisms are generated by photosynthesis from water and carbon dioxide, which are inorganic substances, using the energy of the sun that falls on the earth. As long as there is life and solar energy, it is a resource that can be renewed continuously (see Biomass Nippon Comprehensive Strategy, Cabinet decision on March 31, 2006).

  As plant biomass materials, plant materials such as wood, bamboo, hemp, herbs, agricultural products, etc .; wastes of the plant materials, residues (skins, leaves, stems, fruits), etc .; obtained by processing the materials Paper, pulp, etc. are mentioned. Examples of the wood include conifers such as cedar, hinoki and pine, and broad-leaved trees such as beech, oak and hippopotamus. Examples of hemp include jute, kenaf, flax, hemp, ramie, and sisal. Plant materials other than these include straw, rice straw, rice husk, palm nuts and sugar cane squeezed dregs.

  Examples of the plant biomass material include a single plate shape, a chip shape, and a fiber shape. The size of the plant biomass material is not particularly limited.

  As plant biomass materials, a plurality of types of materials having different materials, shapes, sizes, etc. may be used in combination.

  The thermosetting main resin and auxiliary agent in the plant-based biomass molding material are not particularly limited as long as the thermosetting reaction of the main resin progresses, but cellulose which is the main component of the plant-based biomass material A compound having affinity for hemicellulose, lignin and the like is preferably used, and a compound having affinity for an OH group is particularly preferably used.

  Preferable specific examples of the main resin include epoxy resins, isocyanates, and phenol resins. Among these, only 1 type may be used or 2 or more types may be used together.

  Examples of the epoxy resin include alicyclic epoxy resins, hydantoin type epoxy resins, triglycidyl isocyanurate, aromatic epoxy resins and the like. Examples of the alicyclic epoxy resin include compounds having a cyclohexene oxide group, a tricyclodecene oxide group, a cyclopentene oxide group, etc., and an epoxy compound having a structure in which an aromatic ring of an aromatic epoxy compound is hydrogenated (for example, diglycidyl hexahydrophthalate). , Diglycidylcyclohexane 1,3-dicarboxylate (cis isomer or trans isomer), diglycidyl cyclohexane 1,4-dicarboxylate (cis isomer or trans isomer)) and the like. Examples of the hydantoin type epoxy resin include diglycidyl hydantoin, glycidylglycidoxyalkylhydantoin, and the like. Triglycidyl isocyanurate is obtained by reacting, for example, triallyl isocyanurate with hypochlorous acid to obtain a trichlorohydrin intermediate, and chloridyl is eliminated from this intermediate by removing chlorine hydrogen with an alkali, or cyanuric acid. And epichlorohydrin are reacted to obtain a trichlorohydrin intermediate, from which hydrogen chloride is eliminated and glycidylation is performed as described above. Furthermore, triglycidyl tris isocyanurate is also mentioned. Examples of the aromatic epoxy resin include bisphenol A epoxy resin, novolac epoxy resin, bisphenol F epoxy resin, brominated epoxy resin, and the like.

  Examples of the isocyanates include aliphatic, alicyclic, araliphatic and aromatic diisocyanate compounds. Aliphatic diisocyanate compounds include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate. 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate, and the like. Examples of the alicyclic diisocyanate compound include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis ( Cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, isophorone diisocyanate and the like. . Examples of the araliphatic diisocyanate compound include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis (1- Isocyanate-1-methylethyl) benzene or a mixture thereof. As aromatic diisocyanate compounds, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diene Isocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate and the like. Other diisocyanate compounds include diisocyanates containing sulfur atoms such as phenyl diisothiocyanate.

  Examples of the phenol resin include a resol type phenol resin.

  Preferable specific examples of the auxiliary agent include amines, imines, amides, imidazoles, acid anhydrides, and polyols. Among these, only 1 type may be used or 2 or more types may be used together.

  Examples of amines include aliphatic polyamines, aromatic amines, and modified amines. Examples of the aliphatic polyamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine and the like. Examples of the alicyclic polyamine include isophorone diamine, 1,3-bisaminomethylcyclohexane, bis (4-aminocyclohexyl) methane, norbornene diamine, 1,2-diaminocyclohexane, and laromine. Examples of the aromatic amine include diaminodiphenylmethane, metaphenylenediamine, and diaminodiphenylsulfone. Examples of modified amines include amine adducts and ketimines.

  Examples of imines include ethyleneimine, polyethyleneimine, pyridine and the like.

  Examples of amides include aliphatic polyamides, aromatic polyamides, and alicyclic polyamides.

  Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and the like.

  Examples of acid anhydrides include aromatic acid anhydrides, cycloaliphatic acid anhydrides, aliphatic acid anhydrides, and the like. Specific examples include phthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydro anhydride, methyl hexahydro phthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene tetra Examples thereof include carboxylic dianhydride, trimellitic anhydride, pyromellitic acid free, benzophenone tetracarboxylic dianhydride, aliphatic dibasic acid polyanhydride and the like.

  Examples of polyols include ethylene glycol, polyethylene glycol, polypropylene glycol, glycerin, pentanediol, hexanediol, and derivatives thereof. When an acid anhydride is used as an auxiliary agent, when a plant biomass molding material is molded, the hydroxyl group in the plant biomass material reacts with the acid anhydride group of the acid anhydride, thereby forming a plant biomass molding The amount of hydroxyl groups in the body is reduced. For this reason, the water resistance of a plant-type biomass molded object becomes still higher.

  Amines, amides, imines, imidazoles, and acid anhydrides also act as fluidizing agents. The auxiliary agent preferably contains at least one of amines, amides, imines, imidazoles, and acid anhydrides that also act as a fluidizing agent. When such an auxiliary agent is used, the fluidity during heating of the plant-based biomass molding material is improved, and therefore the molding pressure of the plant-based biomass molding material can be further reduced. The content of the auxiliary agent that also acts as a fluidizing agent in the plant-based biomass molding material is preferably 10% by mass or less with respect to the main resin.

  As auxiliary agents, sugars such as sucrose, xylitol, starch, glucomannan, pectin, chitosan and derivatives thereof; phenol / formaldehyde condensate having methylol group; melamine / formaldehyde condensate, urea, urea / formaldehyde condensate; tannin It is also preferred to use compounds having an OH group, such as acids. Further, it is also preferable to use a compound having a COOH group or a CHO group such as acids such as acetic acid, citric acid, oxalic acid, lactic acid and salts thereof, an aqueous solution of glyoxal, and the like as an auxiliary agent.

  In the first material, it is also preferable that the vegetable biomass material is impregnated with the solvent together with the main resin, and in the second material, it is also preferable that the vegetable biomass material is impregnated with the solvent together with the auxiliary agent. As such a solvent, it is preferable to use a solvent having an OH group, such as alcohols such as ethanol and methanol, and a water / alcohol mixed solution.

  When a plurality of types of main agent resins are used, one type of first material containing the plurality of types of main agent resins may be used, and a plurality of types of first materials each containing a plurality of types of main agent resins may be used. Materials may be used. Further, when a plurality of types of auxiliaries are used, one type of second material containing the plurality of types of auxiliaries may be used, and a plurality of types of second materials each containing a plurality of types of auxiliaries may be used. Two materials may be used.

  As an example of the combination of the main agent resin and the auxiliary agent, a combination of the main agent resin containing isocyanates and the auxiliary agent containing polyols can be mentioned. In this case, a light and low-density plant biomass molded body is obtained by foaming when the plant biomass material is molded. This foaming is considered to occur when water molecules contained in the plant biomass material react with isocyanate to generate carbon dioxide.

  As an example of the combination of the main agent resin and the auxiliary agent, a combination of the main agent resin containing the epoxy resin and the auxiliary agent containing the acid anhydride may be mentioned. In this case, when the plant-based biomass molding material is molded, the hydroxyl group in the plant-based biomass material reacts with the epoxy group of the epoxy resin and the acid anhydride group of the acid anhydride. The amount of hydroxyl groups is reduced. For this reason, the plant-type biomass molded object with very high water resistance is obtained.

  The first material is prepared by impregnating a plant-based biomass material with a main resin. For example, the main biomass resin is impregnated in the plant biomass material by applying the main agent resin to the plant biomass material or immersing the plant biomass material in the main agent resin.

  In preparing the first material, a plant biomass material may be impregnated with a mixed solution containing a main resin and an appropriate solvent. In this case, the plant biomass material can be easily impregnated with the main resin. As the solvent, those having high affinity with plant-based biomass materials are preferably used. For example, alcohols such as ethanol and methanol, ketones, a mixed solution of these solvents and water, and the like are used. preferable.

  The plant-based biomass material is placed in a pressure-resistant container in a state where the plant-based biomass material is coated with the main agent resin or the mixed solution containing the main agent resin, or the plant-based biomass material is immersed in the main agent resin or the mixed solution containing the main agent resin. In this state, the decompression and pressurization in the container may be repeated. In this case, the plant-based biomass material is more quickly impregnated with the main resin.

  When a mixed solution containing the main resin is used, the plant biomass material may be impregnated with the mixed solution, and then the plant biomass material may be dried to remove the solvent.

  The second material is prepared by impregnating a plant biomass material with an auxiliary agent. For example, the auxiliary agent is impregnated into the plant biomass material by applying the auxiliary agent to the plant biomass material or immersing the plant biomass material in the auxiliary agent.

  There is no particular limitation on the ratio of the plant biomass material in the first material and the main resin impregnated in the plant biomass material, but from the viewpoint of moldability, the ratio of the main resin is fluidity and water resistance. Is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more.

  In preparing the second material, a plant biomass material may be impregnated with a mixed solution containing an auxiliary agent and an appropriate solvent. In this case, the plant-based biomass material can be easily impregnated with the auxiliary agent. As the solvent, those having a high affinity with plant biomass materials are preferably used. For example, alcohols such as ethanol and methanol, and solvents having an OH group such as water / alcohol mixed solutions may be used. preferable. When the auxiliary agent is an acid anhydride, it is particularly preferable to use glycerin as a solvent.

  The plant biomass material is placed in a pressure-resistant container in a state where the plant biomass material is coated with an auxiliary agent or a mixed liquid containing the auxiliary agent or the plant biomass material is immersed in the auxiliary liquid or the mixed liquid containing the auxiliary agent. In this state, the decompression and pressurization in the container may be repeated. In this case, the plant biomass material is more quickly impregnated with the auxiliary.

  When a mixed solution containing an auxiliary agent is used, the plant biomass material may be impregnated with the mixed solution, and then the plant biomass material may be dried to remove the solvent.

  The ratio of the plant-based biomass material in the second material and the auxiliary agent impregnated in the plant-based biomass material is not particularly limited, but from the viewpoint of moldability, the ratio of the auxiliary agent is not limited to fluidity or water resistance. It is preferably 5% by mass or more, and more preferably 10% by mass or more, and further preferably 15% by mass or more.

  A plant biomass molding material is obtained by mixing the first material and the second material. The ratio of the first material and the second material is such that the ratio of the main resin and the auxiliary agent in the plant biomass molding material is such that the thermosetting reaction of the main resin can sufficiently proceed. Adjust as appropriate. The specific ratio depends on the types of the main resin and the auxiliary agent.

  When preparing a plant biomass molding material, prepare a mixture by mixing the first material and the second material, and then apply a shear stress to the mixture to obtain a plant biomass molding material. Is also preferable. In this case, the fluidity at the time of molding of the plant-based biomass molding material is improved. Furthermore, the dispersibility of the main resin and the auxiliary agent in the plant biomass molding material is improved. For this reason, when the plant-based biomass molded body is formed, the reaction between the main resin and the auxiliary agent occurs uniformly in the plant-based biomass molding material, and the reactivity is improved. For this reason, the homogeneity of the plant-based biomass molded body is enhanced and the water resistance of the plant-based biomass molded body is further improved. Furthermore, since the moldability is improved in this way, it is possible to reduce the molding temperature and molding pressure during molding, thereby suppressing the decomposition of hemicellulose, cellulose, etc. in the plant biomass material during molding. Is possible.

  Examples of the method of applying shear stress to the mixture include a method of applying the mixture to a compression molding machine, a method of applying the mixture to a pellet mill, and a method of applying the mixture to a roll molding machine. A plurality of methods may be applied in combination.

  FIG. 1 shows an example of a method for applying a shear stress to the mixture 2. In this example, a shear stress is applied to the mixture 2 by forcibly passing the small holes 8 while pressing the mixture 2. The apparatus shown in FIG. 1 includes a female mold 4, a male mold 6, and a plate 5. The female die 4 is a cylindrical member in which a hollow portion 7 having upper and lower openings is formed, and the opening diameter of the hollow portion 7 is, for example, 30 mm. The male mold 6 is a columnar member that matches the shape of the hollow portion 7. The plate 5 is a member that closes the lower opening of the hollow portion 7. A small hole 8 communicating with the hollow portion 7 is formed in the plate 5. Although the diameter of the small hole 8 should just be smaller than the diameter of the hollow part 7, it is preferable that it is the range of 1-30 mm especially.

  In the example shown in FIG. 1, when a shear stress is applied to the mixture 2, the mixture 2 is first supplied to the hollow portion 7 of the female mold 4 as shown in FIGS. 1 (a) and 1 (b). The lower opening of the mold 4 is closed with the plate 5, and the male mold 6 is inserted into the hollow portion 7 in this state. In this state, a compressive force is applied between the plate 5 and the male mold 6 as shown in FIG. Reference numeral 9 in the figure denotes a jig for applying a compressive force to the plate 5. Then, as shown in FIG. 1C, the mixture 2 passes through the small holes 8 while being compressed, and at this time, the mixture 2 is subjected to shear stress. Thereby, the plant-type biomass molding material 1 is obtained.

  It is also preferable to apply the above-described shear stress to the plant biomass material used for the preparation of the first material before impregnating the main component resin. In this case, the plant-based biomass material is easily impregnated with the main agent resin in a short time, and the plant-based biomass material is more easily impregnated with the main agent resin more uniformly. It is also preferable to apply the shear stress as described above to the plant biomass material used for the preparation of the second material before impregnating the auxiliary material. In this case, the plant-based biomass material is easily impregnated with the auxiliary agent in a short time, and the plant-based biomass material is more easily impregnated more uniformly.

  In this embodiment, the plant-based biomass material is composed of a plant-based biomass material impregnated with the main resin and a plant-based biomass material impregnated with the auxiliary agent. Therefore, the moldability is good.

  Furthermore, since the main agent resin and the auxiliary agent are impregnated separately into the plant biomass material, the curing reaction when the main agent resin is impregnated into the plant biomass material and when the auxiliary agent is impregnated into the plant biomass material is performed. It is suppressed. For this reason, the main component resin and the auxiliary agent are easily impregnated into the plant biomass material. Furthermore, the progress of the curing reaction is suppressed even in plant-based biomass materials. Thus, since progress of the hardening reaction before shaping | molding is suppressed, it is suppressed that the fluidity | liquidity at the time of shaping | molding of plant biomass material is inhibited by hardened | cured material.

  A plant-based biomass molded body is obtained by supplying a plant-based biomass molding material into a mold and performing heat flow molding.

  Heat flow molding means a processing method in which a plant-based biomass material with plasticity and fluidity imparted with heat and pressure is deformed by causing relative displacement between cells. Injection molding, extrusion molding Including insert molding, calendar molding, deep drawing and so on.

  An example of a specific method for forming a plant biomass molding material is shown in FIG. The apparatus shown in FIG. 2 includes a mold 10, a cylinder 11, and a pressing mold 12. The mold 10 includes two divided molds 101 and 102. When the divided molds 101 and 102 are clamped, a molding space 14 is formed inside the mold 10. The mold 10 is also formed with a supply hole 15 that communicates the molding space 10 with the outside. The cylinder 11 is a cylindrical member having a hollow portion 13 that opens up and down, and the opening of the hollow portion 11 matches the opening of the supply hole 15. The male mold 12 is a cylindrical member that matches the shape of the hollow portion 13 and the supply hole 15.

  In the example shown in FIG. 2, when the plant-based biomass molding material 1 is molded, the mold 10 is clamped and the cylinder 11 is supplied to the supply hole of the mold 10 as shown in FIGS. 2 (a) and 2 (b). The plant-based biomass molding material 1 is supplied into the cylinder 11 in this state. In this state, the pressing die 12 is inserted into the cylinder. A compression force is applied between the mold 10 and the pressing mold 12 while heating the mold 10 and the cylinder 11 in this state. Then, the plant-based biomass molding material 1 is supplied to the molding space 14 through the supply holes 15 while being heated and pressurized. Further, the plant-based biomass molding material 1 flows in the molding space 14 to fill the space 14, and the thermosetting reaction proceeds by mixing the main resin and the auxiliary agent in the plant-based biomass molding material 1. . Further, when the combination of the main resin and the auxiliary agent in the plant-based biomass molding material 1 constitutes a foamable material, foaming occurs. Thereby, the plant biomass molded body 3 is formed in the molding space 14. Subsequently, after the mold 10 is cooled as necessary, the mold 10 is opened as shown in FIG. 2 (c), so that the plant biomass as shown in FIG. 2 (d) is obtained. The molded body 3 is taken out.

  As molding conditions, depending on the molding method, the temperature and pressure for allowing the plant-based biomass molding material to flow and harden are appropriately set. Since the softening temperature of the lignin constituting the plant biomass material is about 80 ° C. (when containing water), the molding temperature is preferably 80 ° C. or higher in order to soften the lignin. Moreover, since decomposition | disassembly of the hemicellulose and cellulose which comprise a plant biomass material will arise at 200 degreeC or more, discoloration will arise in a molded object, or intensity | strength will fall, It is preferable that shaping | molding temperature is 200 degrees C or less. Although the temperature of the part which a plant biomass molding material contacts only for a short time may exceed 200 degreeC, it is preferable that the temperature of such part is 300 degrees C or less.

  The molding pressure may be any pressure that allows the plant-based biomass molding material to flow. In this embodiment, the plant-based biomass molding material is composed of a plant-based biomass material impregnated with the main resin and a plant-based biomass material impregnated with the auxiliary agent, so that the plant-based biomass can be obtained even if the molding pressure is small. The molding material can be fluidized. Low pressure molding with a fluidization pressure (molding pressure) of 25 MPa or less is also possible.

  When a plant biomass material or mixture is subjected to a shearing force when the plant biomass molding material is prepared, the fluidity of the plant biomass molding material is improved, thus reducing the molding temperature and molding pressure. Is possible.

  Since the cured product of the main resin is compounded in the plant biomass molded body thus obtained, the water resistance of the plant biomass molded body is high and its strength is also improved. For this reason, the water resistance is such that the water absorption rate is evaluated to be 1.78% or less and the volume expansion rate is 1.69% or less according to a water resistance test (24 hour water absorption test according to JIS A5905) immersed in water at a temperature of 20 ° C. It is also possible to obtain a plant-based biomass molded body having properties.

  In particular, when a plant-based biomass material hydrophobized by acetylation or the like is used as a base material, an epoxy resin is used as a main agent and maleic anhydride is used as an auxiliary agent, the water resistance of the plant-based biomass molded body is particularly improved, and a temperature of 20 It is also possible to obtain a plant-based biomass molded article having water resistance such that the water absorption rate is 0.96% or less and the volume expansion coefficient is 0.42% or less as evaluated by a water resistance test immersed in water at 24 ° C. for 24 hours. Become.

In addition, since it is possible to reduce the molding pressure when molding the plant-based biomass molding material, it is possible to obtain not only a high-density plant-based biomass molded body but also a low-density plant-based biomass molded body. Variations in density design for biomass compacts will expand. In particular, when the main resin contains isocyanates and the auxiliary contains polyols, a porous plant-based biomass molded body is formed when the combination of the main resin and auxiliary forms a foamable material. It is also possible to obtain a light and low-density plant biomass molded body having a density of 1.1 g / cm ³ or less.

[Example 1]
A wood chip obtained by cutting a 100 cm × 200 cm poplar single plate into about 4 cm square was prepared as a plant biomass material.

  A water-soluble epoxy resin (manufactured by Nagase ChemteX Corporation, trade name Denacol EX810) is prepared as a main resin, and propyl gallate as a crosslinking agent and imidazole (a product made by Shikoku Kasei Kogyo Co., Ltd.) as an auxiliary agent. Name cureazole 2E4MZ-CN).

  The wood chip was immersed in the main resin and then left to stand in an air-dried state in the atmosphere, thereby obtaining a first material. Another wood chip was immersed in a crosslinking agent and allowed to stand in the air until it was in an air-dried state, thereby obtaining a second material containing the crosslinking agent. Furthermore, another wood chip was immersed in the curing accelerator and allowed to stand until it was in an air-dried state, thereby obtaining a second material containing the curing accelerator. The impregnation amounts of the main resin, propyl gallate, and imidazole for each plant biomass material were all 15% by mass.

  25 g of the first material, 12.5 g of the second material containing the crosslinking agent, and 2.5 g of the second material containing the curing accelerator were mixed to obtain a mixture. A shearing force was applied to the mixture using the apparatus shown in FIG. In the apparatus shown in FIG. 1, the hollow portion 7 has an inner diameter of 30 mm, and the small hole 8 has an inner diameter of 10 mm. Thereby, a plant-based biomass molding material was obtained. An appearance photograph of this plant-based biomass molding material is shown in FIG.

  This plant-based biomass molding material was heat-flow molded using the apparatus shown in FIG. The molding pressure was 25 MPa and the molding temperature was 150 ° C. Thereby, the plant-type biomass molded object of the dimension of 100 mm x 10 mm x 4 mm was obtained.

  When the plant biomass molded body was subjected to a water absorption test at a water temperature of 20 ° C. according to JIS A5905 for 24 hours, the water absorption was 2.42% and the volume expansion rate due to water absorption was 1.5%. Moreover, when the bending strength of this plant-type biomass molded object was measured according to JISZ2101, it was 30 MPa.

[Example 2]
A wood chip obtained by cutting a 100 cm × 200 cm poplar single plate into about 4 cm square was prepared as a plant biomass material.

  An isocyanate resin (trade name KU primer # 3, manufactured by Konishi Co., Ltd.) was prepared as the main resin, and a polyol (polyethylene glycol 600) was prepared as an auxiliary agent.

  The wood chip was dipped in the main resin and allowed to stand until air-dried to obtain a first material. A second material was obtained by immersing another wood chip in the auxiliary agent and allowing it to stand until air-drying. The impregnation amounts of the main resin and the auxiliary agent for each plant biomass material were both 20% by mass.

  20 g of the first material and 20 g of the second material were mixed to obtain a plant-based biomass molding material.

  This plant-based biomass molding material was heat-flow molded using the apparatus shown in FIG. The molding pressure was 100 MPa and the molding temperature was 150 ° C. As a result, a porous plant-based biomass molded body having a size of 100 mm × 10 mm × 4 mm was obtained.

It was 1.1 g / cm < ³ > when the density of this plant-type biomass molded object was measured. When the plant biomass molded body was subjected to a water absorption test at a water temperature of 20 ° C. according to JIS A5905 for 24 hours, the water absorption was 3.28%, and the volume expansion coefficient due to water absorption was 4.5%. Moreover, it was 30 MPa when the bending strength of this plant-type biomass molded object was measured based on JISZ2101.

[Example 3]
A wood chip obtained by cutting a 100 cm × 200 cm acetylated poplar veneer into about 4 cm square was prepared as a plant biomass material.

  A water-soluble epoxy resin (manufactured by Nagase ChemteX Corporation, trade name Denacol EX-810) was used as a main resin, and maleic anhydride was used as an auxiliary agent.

  The wood chip was immersed in the main resin and then left to stand in an air-dried state in the atmosphere, thereby obtaining a first material. A second material was obtained by immersing another wood chip in the auxiliary agent and allowing it to stand until air-drying. The impregnation amounts of the main resin and the auxiliary agent for each plant biomass material were both 15% by mass.

  16 g of the first material and 24 g of the second material were mixed to obtain a plant-based biomass molding material.

  This plant-based biomass molding material was heat-flow molded using the apparatus shown in FIG. The molding pressure was 25 MPa and the molding temperature was 150 ° C. Thereby, the plant-type biomass molded object of the dimension of 100 mm x 10 mm x 4 mm was obtained.

  When this plant-based biomass molded body was subjected to a water absorption test at a water temperature of 20 ° C. according to JIS A5905 for 24 hours, the water absorption was 0.96% and the volume expansion coefficient due to water absorption was 0.42%. Moreover, it was 30 MPa when the bending strength of this plant-type biomass molded object was measured based on JISZ2101.

DESCRIPTION OF SYMBOLS 1 Plant biomass molding material 2 Mixture 3 Plant biomass molding

Claims (15)

(A) a step of preparing a thermosetting main agent resin, one or more auxiliary agents selected from a compound that undergoes a thermosetting reaction with the main agent resin and a compound that promotes the thermosetting reaction of the main agent resin;
(B) a step of preparing the first material by impregnating the plant-based biomass material with the main resin,
(C) a step of preparing one or more second materials by impregnating the plant biomass material with the auxiliary, and (d) mixing the first material and the second material , thereby Obtaining a plant-based biomass molding material by applying shear stress to the resulting mixture ,
Method for producing a plant biomass molding material containing. The method for producing a biomass molding material according to claim 1, wherein in the step (d), a shear stress is applied to the mixture by forcibly passing through a small hole while pressing the mixture. The method for producing a plant biomass molding material according to claim 1 or 2 , wherein the auxiliary agent contains at least one selected from amines, imines, amides, imidazoles, acid anhydrides, and polyols. The plant biomass according to any one of claims 1 to 3 , wherein the auxiliary agent contains at least one of amines, amides, imines, imidazoles, and acid anhydrides that also act as a fluidizing agent. Manufacturing method of molding material. The manufacturing method of the plant-type biomass molding material as described in any one of Claims 1 thru | or 4 in which the said main ingredient resin contains at least 1 type chosen from an epoxy resin, isocyanates, and a phenol resin. The method for producing a plant biomass molding material according to any one of claims 1 to 5 , wherein a plant biomass molding material capable of low pressure molding at a fluidization pressure of 25 MPa or less is obtained . (E) a step of preparing a plant biomass molding material manufactured by the method for manufacturing a plant biomass molding material according to any one of claims 1 to 6 , and (f) gold for the plant biomass molding material. A method for producing a plant-based biomass molded body, comprising a step of supplying the mold into a mold and performing heat flow molding. At the time of heat-fluid molding in the mold in the step (f), the plant-based biomass molding material is heated and pressurized to be supplied to the molding space for the mold, and further, the plant-based biomass molding The plant-based biomass molded body according to claim 7, wherein a material is caused to flow in the space so that the space is filled with the plant-based biomass molding material and a thermosetting reaction of the plant-based biomass molding material proceeds in the space. Production method. The main agent and the auxiliary agent are foamable materials that foam when they react,
The method for producing a plant biomass molded body according to claim 7 or 8, wherein the main agent and the auxiliary agent are reacted and foamed at the time of heat flow molding in the mold in the step (f). The manufacturing method of the plant-type biomass molded object of Claim 9 in which the said main ingredient resin contains isocyanates and the said adjuvant contains polyols. The method for producing a plant-based biomass molded article according to claim 7 or 8, wherein the main resin includes an epoxy resin and the auxiliary agent includes an acid anhydride. The plant-type biomass molded object manufactured by the manufacturing method of the plant-type biomass molded object as described in any one of Claims 7 thru | or 11. The plant-based biomass molded article according to claim 12, which has a water resistance of 1.78% or less and a volume expansion coefficient of 1.69% or less as evaluated by a water resistance test immersed in water at a temperature of 20 ° C for 24 hours. A plant-based biomass molded body having a density of 1.1 g / cm ³ or less, produced by the method for producing a plant-based biomass molded body according to claim 9 or 10. A plant having water resistance with a volume expansion coefficient of 0.42% or less evaluated by a water resistance test, which is produced by the method for producing a plant biomass molded body according to claim 11 and immersed in water at a temperature of 20 ° C. for 24 hours. -Based biomass compact.