JP6561537B2 - MOLDING MATERIAL AND METHOD FOR PRODUCING MOLDING MATERIAL - Google Patents

Description

  The present invention relates to a molding material using woody biomass as a raw material and a method for producing the same.

  Biomass materials represented by wood are attracting attention as industrial resources. The biomass material means a material derived from a living organism such as a plant. Since the biomass material is organic, carbon dioxide is emitted when it is burned. However, the carbon contained in this is derived from carbon dioxide absorbed from the atmosphere by photosynthesis during the growth process, so using biomass materials does not increase the amount of carbon dioxide in the atmosphere as a whole It can be considered that. This property is called carbon neutral.

  Against the backdrop of global environmental issues such as global warming issues, there is an urgent need to conserve resources, material recycling aiming at raw materials for waste, and promotion of the environmental circulation cycle represented by biodegradable plastics. However, the revised Recycling Law and the Green Purchasing Law have been put in place, and the need for products that respond to these laws is increasing.

  Under these circumstances, blending biomass materials into resin molded products that are widely used from automotive parts materials to daily necessities promotes the practice of the carbon neutral philosophy. Use as a molding material or blending with other resin materials is in line with the promotion of environmental circulation cycles in recent years.

  However, if the wood is pulverized as it is without being treated, the moldability is insufficient and mixing with other thermoplastic resins is difficult. Therefore, in Patent Document 1, a woody material is heated and pressurized in the presence of water vapor and then mixed with a powdery explosion material, a resin, and a powdery woody material obtained by abrupt decompression and explosion. Patent Document 2 discloses a method for producing a wood-based molded body by performing steam treatment (including explosive treatment) on a lignocellulose-containing material to obtain a powder having a particle size of 45 μm or more and 180 μm or less. The materials are listed.

JP 2006-272696 A JP 2003-165844 A

  However, since Patent Document 1 contains a large amount of untreated powdery woody material, the moldability is insufficient, and the lignocellulosic thermoplastic material of Patent Document 2 is also insufficient in terms of moldability.

  Then, the subject of this invention is providing the molding material which is excellent in a moldability from wood.

  The inventors obtained a wood by steaming at a temperature of 170 to 230 ° C. and a pressure of 0.8 to 3 MPa for 5 to 20 minutes, and then instantaneously releasing the pressure to perform a blasting treatment. It has been found that an explosion-treated product having a size of 30 μm or less becomes a molding material having good moldability.

  According to the present invention, a molding material having good moldability can be obtained using woody biomass as a raw material.

  The present invention is a molding material comprising a blasted product obtained by blasting wood. In the blasting treatment of the present invention, the wood is steam-treated at a temperature of 170 to 230 ° C. and a pressure of 0.8 to 3 MPa at a holding time of 5 to 20 minutes, and then the pressure is instantaneously released. By performing the blasting treatment under such conditions, lignin and hemicellulose in the wood are partially decomposed and / or modified, so that pulverization is improved, and as a result, micronization becomes easy. Suitable as a material.

  When the temperature is lower than 170 ° C., the lignin is not sufficiently decomposed and the pulverization property is not sufficiently improved. Moreover, when it exceeds 230 degreeC, decomposition | disassembly of a cellulose will become excessive and a yield will fall.

  When the holding time is within 5 minutes, the lignin is not sufficiently decomposed and the grindability is not sufficiently improved. On the other hand, if it exceeds 20 minutes, the lignin is condensed, so that the lignin is hardly decomposed and the grindability is not sufficiently improved.

  In the present invention, it is preferable to add 0 to 1000 parts by mass of water to 1 part by mass of wood to perform steam treatment.

  As the raw material wood, for example, either hardwood or softwood can be used. From the viewpoint of digestibility, hardwood is preferable. Specifically, the broad-leaved trees include beech, china, birch, poplar, eucalyptus, acacia, oak, itayaka maple, senoki, elm, giraffe, honoki, willow, sen, basamushi, konara, kunugi, tochinoki, zelkova, mizume, mizuzuki Aodamo etc. are exemplified. As conifers, cedar, spruce, larch, black pine, todomatsu, himekomatsu, yew, neko, spruce, iramimi, fir, sawara, togasawara, asunaro, hiba, tsuga, kotsutsuga, hinoki, yew, yellowtail, spruce (Beihiba), Lawson Hinoki (Beihi), Douglas Fir (Beimatsu), Sitka Spruce (Beisuhi), Radiata Pine, Eastern Spruce, Eastern White Pine, Western Larch, Western Fir, Western Hemlock, Tamarack and the like.

  In the present invention, the raw material wood is preferably a pulverized product pulverized to a size of 0.1 to 100 mm, more preferably 0.1 to 50 mm. In the present invention, the size of the pulverized product of wood is a size that is sieved according to the size of the circular hole of the sieve. As an apparatus for pulverizing wood, it is preferable to perform pulverization with a knife cutting type biomass fuel chipper. Moreover, the bark may be mixed.

  As a device for performing the explosion treatment, a batch type explosion treatment device of Valmet, Nitto High Pressure Co., Ltd., Nippon Electric Heat Co., Ltd., Yasima Co., Ltd., Nippon Chemical Machinery Manufacturing Co., Ltd., or Valmet, Andritz Examples include a continuous explosion treatment apparatus.

  In the present invention, it is necessary that the average particle size of the blasted product is 30 μm or less. The average particle diameter is a 50% volume average particle diameter (D50) measured by a laser light scattering method (laser diffraction method), and is a laser diffraction / scattering type particle size distribution measuring instrument (Malvern Co., Ltd., product name). : Mastersizer 2000) or the like. If the average particle size of the blasted product exceeds 30 μm, the moldability is lowered.

  As an apparatus for pulverizing the average particle size of the crushed material to 30 μm or less, as a wet pulverizer, a mass colloider (manufactured by Masuko Sangyo Co., Ltd.), etc. Etc.).

  The molding material of the present invention may be used by mixing with a thermoplastic resin. Examples of the thermoplastic resin include, but are not limited to, polyethylene, polypropylene, and L-LDPE, and any resin that can be plasticized and molded by heat can be used. Among these, polyethylene and polypropylene are preferable from the viewpoint of moldability.

  Moreover, you may mix with the biodegradable resin which has thermoplasticity, for example, polylactic acid (PLA), polybutylene succinate, polyethylene succinate, polyglycol, polycaprolactone, polyvinyl alcohol etc. can be used.

  Further, it may be mixed with a thermosetting resin, for example, a thermosetting resin such as phenol resin, urea resin, melamine resin, unsaturated polyester resin, epoxy resin, diallyl phthalate resin, polyurethane resin, silicon resin, polyimide resin, etc. Etc., can be used.

  Various molded articles can be produced using the molding material of the present invention. The molding can be performed by a usual method used for molding a thermoplastic resin. For example, but not limited to, injection molding, extrusion molding, blow molding and the like can be performed.

  The molding material of the present invention can be used for various films, building materials, containers, automobile interior parts, and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to these. In addition, unless otherwise indicated, a part and% show a mass part and mass%.

[Example 1]
Eucalyptus Eurograndis chips were pulverized to 6 mm or less with a cutter mill (trade name: P-15, manufactured by Fritsch). After adding 800 g of water to 100 g of the solid content of the pulverized product and heating it to 200 ° C. using a steam explosion device (manufactured by Nitto High Pressure Co., Ltd.), maintaining the pressure at 1.6 MPa for 10 minutes and steaming, The pressure was released immediately and the blasting process was performed. Water was added to the obtained crushed material to obtain a slurry having a concentration of 5%, and pulverized with a wet pulverizer (trade name: Mascolloider MKG-C # 80, manufactured by Masuko Sangyo Co., Ltd., clearance 60 μm). The average particle size of the obtained pulverized product was measured by the following method, and the results are shown in Table 1.
Next, the pulverized product was diluted with ultrapure water to a concentration of 0.2% and filtered with a membrane filter (filter used: ADVANTEC H020A047A (hydrophilic PTFE), pore 0.2 μm, Φ47 mm). The obtained filtrated material is sandwiched between filter papers and subjected to two hot presses at a first time: 120 ° C., 2 kgf / cm ² , 10 minutes, second time: 180 ° C., 5 kgf / cm ² , 10 minutes. A molded product was obtained. The moldability and density of the obtained molded product were measured by the following methods, and the results are shown in Table 1.
-Average particle diameter of pulverized product: Laser diffraction / scattering particle size distribution analyzer (trade name: Mastersizer 2000, manufactured by Malvern Co., Ltd.) was used, and the 50% point of the volume cumulative distribution was defined as the average particle diameter.
Moldability: The moldability was evaluated by visual observation of the molded product according to the following criteria. A: Can be formed into a uniform sheet, Δ: Can be formed into a sheet, but non-uniform, x: Cannot be formed into a sheet.
Density: The thickness was measured with a caliper of the molded product, and the density was calculated from the weight.

[Example 2]
A molded product was obtained in the same manner as in Example 1 except that water was added to the explosion-treated product obtained in Example 1 and pulverized as a slurry having a concentration of 10%. Table 1 shows the average particle diameter of the pulverized product, the moldability and the density of the molded product.

[Comparative Example 1]
Water was added to the crushed material obtained in Example 1 and the mixture was pulverized as a slurry having a concentration of 5% with a wet pulverizer (trade name: Mascolloider MK-E # 46, manufactured by Masuko Sangyo Co., Ltd., clearance 100 μm). The obtained pulverized product was obtained in the same manner as in Example 1. Table 1 shows the average particle diameter of the pulverized product, the moldability and the density of the molded product.

[Comparative Example 2]
Water was added to the crushed material obtained in Example 1, and the mixture was pulverized as a slurry having a concentration of 10% with a wet pulverizer (trade name: Mascolloider MK-E # 46, manufactured by Masuko Sangyo Co., Ltd., clearance 100 μm). The obtained pulverized product was obtained in the same manner as in Example 1. Table 1 shows the average particle diameter of the pulverized product, the moldability and the density of the molded product.

[Comparative Example 3]
Eucalyptus Eurograndis chips were pulverized to 6 mm or less with a cutter mill (trade name: P-15, manufactured by Fritsch). Water was added to the pulverized product, and the mixture was pulverized as a slurry having a concentration of 5% with a wet pulverizer (trade name: Mascolloider MKG-C # 80, manufactured by Masuko Sangyo Co., Ltd., clearance 60 μm). The obtained pulverized product was obtained in the same manner as in Example 1. Table 1 shows the average particle diameter of the pulverized product, the moldability and the density of the molded product.

[Comparative Example 4]
Eucalyptus Eurograndis chips were pulverized to 6 mm or less with a cutter mill (trade name: P-15, manufactured by Fritsch). Water was added to the pulverized product, and the mixture was pulverized as a slurry having a concentration of 10% with a wet pulverizer (trade name: Mascolloider MKG-C # 80, manufactured by Masuko Sangyo Co., Ltd., clearance 60 μm). The obtained pulverized product was obtained in the same manner as in Example 1. Table 1 shows the average particle diameter of the pulverized product, the moldability and the density of the molded product.

[Comparative Example 5]
Kraft pulp manufactured using Eucalyptus Eurograndis as a raw material was pulverized to 6 mm or less with a cutter mill (trade name: P-15, manufactured by Fritsch). Water was added to the pulverized product, and the mixture was pulverized as a slurry having a concentration of 5% with a wet pulverizer (trade name: Mascolloider MKG-C # 80, manufactured by Masuko Sangyo Co., Ltd., clearance 60 μm). The obtained pulverized product was obtained in the same manner as in Example 1. Table 1 shows the average particle diameter of the pulverized product, the moldability and the density of the molded product.

  As shown in Table 1, the explosive treatment product having an average particle size of Examples 1 and 2 of 30 μm or less had good moldability. The explosive treatment product in which the average particle size of Comparative Examples 1 and 2 exceeded 30 μm was inferior in moldability. Moreover, the unprocessed ground material of Comparative Examples 3 to 4 and the kraft pulp of Comparative Example 4 were also inferior in moldability. Moreover, the power consumption at the time of a grinding | pulverization process was reduced by carrying out a blasting process.

Claims (1)

Woody biomass temperature 170 to 230 ° C., at a pressure 0.8～3MPa, 5 to 20 minutes, after steaming, instantaneously and pressure release to steam explosion treatment, and grinding the resulting blasting material laser light scattering method A method for producing a molding material having a 50% volume average particle diameter (D50) measured by (laser diffraction method) of 30 μm or less.