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WO2024014545A1 - Matériau à base de résine pour moulage, article moulé en résine et procédé destiné à produire un matériau à base de résine pour moulage - Google Patents

Matériau à base de résine pour moulage, article moulé en résine et procédé destiné à produire un matériau à base de résine pour moulage Download PDF

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Publication number
WO2024014545A1
WO2024014545A1 PCT/JP2023/026116 JP2023026116W WO2024014545A1 WO 2024014545 A1 WO2024014545 A1 WO 2024014545A1 JP 2023026116 W JP2023026116 W JP 2023026116W WO 2024014545 A1 WO2024014545 A1 WO 2024014545A1
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Prior art keywords
resin material
molding
molding resin
weight
resin
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English (en)
Japanese (ja)
Inventor
収二郎 矢野
忠孝 樋田
イスラム・モハメド・サイフル
真由美 田村
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SHOKOZAN MINING Co Ltd
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SHOKOZAN MINING Co Ltd
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Priority to JP2024533773A priority Critical patent/JPWO2024014545A1/ja
Publication of WO2024014545A1 publication Critical patent/WO2024014545A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable

Definitions

  • the present invention relates to a resin material for molding, a resin molded product, and a method for producing a resin material for molding.
  • bioplastics also called bioresins
  • bioresins which have a lower environmental impact
  • Bioplastics are broadly divided into biomass plastics (also called biomass resins), which are made from renewable organic resources such as plants, and biodegradable plastics, which can be broken down into carbon dioxide and water through the action of microorganisms.
  • biomass plastics also called biomass resins
  • biodegradable plastics which can be broken down into carbon dioxide and water through the action of microorganisms.
  • biodegradable plastics which can be broken down into carbon dioxide and water through the action of microorganisms.
  • Patent Document 1 For example, a biomass resin composition containing a biomass resin and a hydroxyalkyl (alkyl) cellulose compound has been developed (see Patent Document 1).
  • Patent Document 1 by including a biomass resin and a hydroxyalkyl (alkyl) cellulose compound, an attempt is made to realize a biomass resin composition that has excellent transparency, strength, and heat resistance without adding a non-biomass filler. .
  • strength is maintained by including cellulose nanofibers (hereinafter referred to as CNF) in this biomass resin composition.
  • CNF cellulose nanofibers
  • CNF is included to compensate for the lack of strength in biomass plastics, but in molding (e.g. injection molding) using biomass plastics mixed with CNF, the molding itself Problems have arisen in that it is difficult and the CNF is unevenly dispersed, which impairs the appearance of the molded product.
  • the present invention was made to solve these problems, and its purpose is to create a molding resin material that can realize bioplastics with improved moldability and good dispersibility without impairing the appearance. , a resin molded product, and a method for producing a resin material for molding.
  • the molding resin material according to the present disclosure contains biodegradable plastic and cellulose microfibers, and has a biomass ratio of 90% by mass or more.
  • the resin molded product according to the present disclosure is molded using the above molding resin material.
  • the method for producing a molding resin material according to the present disclosure includes a drying step of drying cellulose microfibers to a moisture content of 5% by weight or less, a cellulose microfiber dried in the drying step, and a biodegradable plastic. , and a kneading step of kneading with a pressure kneader.
  • a molding resin material a method for producing a molding resin material, and a method for producing a molding resin material that can realize a bioplastic with improved moldability and good dispersibility without impairing the appearance.
  • a method for producing a molding resin material that can realize a bioplastic with improved moldability and good dispersibility without impairing the appearance.
  • FIG. 1 is a schematic configuration diagram of a pellet manufacturing apparatus used for manufacturing a molding resin according to the present embodiment. It is a table showing manufacturing conditions of each example and each comparative example. It is a table showing the results of each example and each comparative example.
  • 3 is a photograph showing molded products using the molding resin materials of (a) Comparative Example 3, (b) Comparative Example 4, and (c) Comparative Example 5.
  • 3 is a photograph showing molded products using the molding resin materials of (a) Example 2, (b) Example 2, and (c) Comparative Example 1.
  • 3 is a photograph showing molded products using molding resin materials of (a) Example 5, (b) Example 6, and (c) Comparative Example 2.
  • 1 is a table showing evaluation of the appearance of molding resin materials using a scanning electron microscope (SEM). It is a table and a graph showing the biomass degree of CMF and molding resin material.
  • the molding resin of this embodiment is a molding resin material that contains biodegradable plastic and cellulose microfibers and has a biomass ratio of 90% by mass or more.
  • the biodegradable plastic is preferably a bio-based biomass plastic. Further, the molding resin material preferably has a biomass ratio of 100% by mass.
  • the plastic in this embodiment is a thermoplastic resin. In this specification, when a numerical range is expressed as A to B, it indicates a range of A or more and B or less.
  • Figure 1 shows a classification table of plastics.
  • plastics are classified according to whether they are biodegradable or not, and the material from which they are derived.
  • plastics made of fossil-derived materials that are not biodegradable are non-bioplastics, and representative examples include PE (polyethylene), PP (polypropylene), PET (polyethylene terephthalate), and PTT (polytrisate).
  • PE polyethylene
  • PP polypropylene
  • PET polyethylene terephthalate
  • PTT polytrisate
  • plastics made from biodegradable fossil-derived materials include PVA (polyvinyl alcohol), PGA (polyglycolic acid), PBS (polybutylene succinate), PBSA (polybutylene succinate-co-adipate), There are PBAT (polybutylene adipate terephthalate) and PETS (polyethylene terephthalate succinate).
  • PVA polyvinyl alcohol
  • PGA polyglycolic acid
  • PBS polybutylene succinate
  • PBSA polybutylene succinate-co-adipate
  • PBAT polybutylene adipate terephthalate
  • PETS polyethylene terephthalate succinate
  • plastics that are not biodegradable and are made of fossil-derived and bio-derived materials include bio-PET (polyethylene terephthalate), bio-PPT (polytrimethylene terephthalate), and bio-PA (polyamide) 610, 410, 510.
  • Bio PA Polyamide
  • 1012, 10T, Bio PA Polyamide
  • 11T MXD10 (Nylon MXD6)
  • Bio PA56 Polyamide 56
  • Bio PC Polystyrene
  • Bio PU Polyurethane
  • Aromatic Polyester Bio Unsaturated Polyester
  • biophenolic resin and bioepoxy resin.
  • biodegradable plastics made from fossil- and bio-derived materials include bio-PBS (polybutylene succinate), PBAT (polybutylene adipate terephthalate), PLA (polylactic acid) compounds, and starch polyester resins. There is.
  • plastics that are not biodegradable and are made of bio-derived materials include Bio-PE, Bio-PA11, and Bio-PA1010.
  • biodegradable plastics made from bio-derived materials include PLA (polylactic acid), PHA (polyhydroxyalkanoate) (PHBH (3-hydroxybutyric acid/3-hydroxyhexanoic acid copolymer polyester) ), etc.).
  • PLA polylactic acid
  • PHA polyhydroxyalkanoate
  • PHBH polyhydroxybutyric acid/3-hydroxyhexanoic acid copolymer polyester
  • the plastics surrounded by the dashed line in Figure 1 are biomass plastics, and the plastics surrounded by dotted lines are biodegradable plastics.
  • the binder of the molding resin of this embodiment is a biodegradable plastic, particularly a biomass plastic derived only from bio-based materials. Specifically, they are PLA, PHA type (PHBH), bio-PBS, PBAT/PLA (polylactic acid) compound, and starch polyester resin, and preferably PLA and PHA type (PHBH). Further, it is preferable to use a pellet-shaped binder.
  • the filler of the molding resin of this embodiment is cellulose micro fiber (hereinafter abbreviated as CMF).
  • CMF cellulose micro fiber
  • the fiber length is 20 to 50 ⁇ m, preferably 35 to 45 ⁇ m
  • the particle size distribution (D50) is 20 to 50 ⁇ m, preferably 30 to 40 ⁇ m.
  • the CMF is a cellulose fiber made from coniferous wood that has been subjected to pulverized and classified products, and has an average fiber length of 45 ⁇ m, an average fiber diameter of 35 ⁇ m, and a tentative ratio of 0.25.
  • CMF may be made from broad-leaved trees or other plants.
  • FIG. 2 shows a schematic explanatory diagram showing the manufacturing mechanism of the molding resin material of this embodiment, and the method for manufacturing the molding resin will be described below based on the diagram.
  • the method for producing molding resin of the present embodiment mainly uses a pellet manufacturing apparatus 1 having a kneader 2 for kneading a binder and a filler, and an extruder 3 for producing pellet-shaped molding resin from a kneaded material K. .
  • the kneader 2 is a pressure kneader.
  • the kneader 2 has a pair of kneader screws 21 rotatably installed in a barrel 20 with an open top that allows temperature adjustment.
  • the pressure press 22 of the kneader 2 can be moved up and down to open and close the upper opening, and during kneading, the pressure press 22 can be lowered to pressurize the inside of the barrel 20.
  • Materials to be kneaded can be introduced into the barrel 20 through an input port 23 .
  • the barrel 20 is rotatable as shown by the dotted line in FIG. 2 so as to discharge the kneaded material K.
  • a conveyor 4 is provided between the kneader 2 and the extruder 3.
  • the conveyor 4 has a bucket 40 that accommodates the kneaded material K discharged from the barrel 20 of the kneader 2.
  • the bucket 40 can be moved above the hopper 30 of the extruder 3, which will be described later, and the kneaded material K can be thrown into the hopper 30 from above the hopper 30.
  • the extruder 3 has a hopper 30 into which the kneaded material K is charged, and a hopper screw 31 is rotatably provided within the hopper 30.
  • the hopper 30 is connected to a horizontally extending hollow cylinder 32, and a straight screw 33 is rotatably provided within the cylinder 32.
  • the temperature of the cylinder 32 can be adjusted, and by rotating the straight screw 33 inside, the kneaded material K can be melted and extruded toward the tip side.
  • a pelletizer 34 is provided on the distal end side of the straight screw 33.
  • the pelletizer 34 has a die 34a that forms the molten resin into a small diameter rod, and a rotary cutter 34b that cuts the resin coming out of the die 34a into pellets.
  • a sorter or the like for sorting pellets may be provided downstream of the extruder 3.
  • the molding resin of this embodiment is granulated by the manufacturing apparatus 1 configured as described above in the following procedure.
  • step S1 CMF, which is a filler, is introduced into the barrel 20 from the input port 23 of the kneader 2.
  • step S2 the kneader screw 21 is driven to rotate while heating the barrel 20 in a non-pressurized state to reduce the water content of the CMF (drying step).
  • drying step it is preferable to dry the CMF to a moisture content of 5% by weight or less.
  • CMF generally contains a water content of about 7 to 10% by weight, but in order to improve its moldability as a molding resin material and to prevent steam explosions, the water content of CMF must be adjusted before kneading with the binder. It is effective to provide a drying step in which the amount of the carbon dioxide is dried to 5% by weight or less.
  • step S3 after the drying of the CMF in step S2 is completed, a resin material as a binder is charged into the barrel 20 from the input port 23.
  • step S4 the pressure press 22 is lowered to pressurize and heat the inside of the barrel 20, while rotating the kneader screw 21 to knead the CMF and the binder resin material (kneading step).
  • step S5 after the kneading in step S4 is completed, the kneaded material K is taken out from the barrel 20 and put into the bucket 40 of the conveyor 4.
  • step S6 the kneaded material K is transported by the conveyor 4 to the hopper 30 of the extruder 3, and the kneaded material K is introduced into the hopper 30.
  • step S7 the hopper screw 31 is driven to draw the kneaded material K into the cylinder 32.
  • step S8 the straight screw 33 rotates while heating the inside of the cylinder 32, thereby transferring the kneaded material K to the tip side while melting it.
  • step S9 in the pelletizer 34, the resin is extruded into a rod shape from the die 34a, and the resin coming out from the die 34a is cut by the rotary cutter 34b to form a pellet-shaped molding resin material.
  • the pellet-shaped molding resin material of this embodiment is produced using the pellet manufacturing apparatus 1 by the production method including steps S1 to S9.
  • the pellet manufacturing apparatus 1 of this embodiment uses a pressure kneader to knead the binder and filler, the kneader is not limited to this.
  • kneading may be performed using an extruder (for example, a twin-screw extruder).
  • a molded article using the molding resin material of this embodiment is formed by injection molding the above-mentioned pellet-shaped molding resin material. That is, although not shown, a pellet-shaped molding resin material is kneaded using a kneader, and then injection molded using an extruder for molded products. Existing kneaders and injection molding machines can be used.
  • Example> Examples of molded articles made of a molding resin material according to the present invention, comparative examples of molded articles made of a molding resin material whose filler is CNF, and molded articles made of a molding resin material made of bioplastics including those derived from fossils are shown below. Evaluations of moldability, appearance, and physical properties of a comparative example of a molded article and a comparative example of a molded article made of a conventional non-bioplastic molding resin material will be described with reference to FIGS. 3 to 9.
  • FIG. 3 shows the manufacturing conditions of each example and each comparative example.
  • the binder was PLA resin
  • the binder was PHA resin
  • Comparative Examples 3 to 5 the binder was bio-PBS.
  • the binder was PP resin.
  • a molding resin material is manufactured using the pellet manufacturing apparatus 1 described above, and a molded product is molded using an injection molding machine using the molding resin material.
  • the kneading conditions shown in FIG. 3 are the kneading conditions in the kneader 2 of the pellet manufacturing apparatus 1, and the molding conditions are the molding conditions in the injection molding machine.
  • CMF cellulose powder obtained by dry-pulverizing coniferous wood was used.
  • the CNF used as the filler was cellulose fiber obtained by pulverizing coniferous wood using the TEMPO oxidation method, and had a water content of 7.96% by weight, a tentative specific gravity of 0.35, and a top size of 209.3 ⁇ m.
  • the PLA resins of Examples 1 to 4 and Comparative Example 1 are plant-derived PLA resins made from starch contained in corn, etc., and have an MFR (melt flow rate) of 10 to 15 (g/10min) and a specific gravity. 1.25 and a melting point of 165-175°C was used.
  • Example 1 a molding resin material was manufactured using 100% by weight of PLA resin, that is, only PLA resin without mixing filler.
  • the molding conditions for a molded article using the molding resin material of Example 1 were injection time of 45 seconds, temperature of 180° C., and cooling time of 40 seconds.
  • Example 2 a molding resin material was produced by mixing 80% by weight of PLA resin with 20% by weight of CMF having a fiber length of 35 to 45 ⁇ m and a particle size distribution D50 of 33.09 ⁇ m as a filler.
  • the molding resin material of Example 2 was produced by kneading at 190° C. and 40 rpm for 27 minutes. Further, the molding conditions for the molded product using the molding resin material of Example 2 were: injection time 15 seconds, temperature 180° C., and cooling time 5 seconds.
  • Example 3 a molding resin material was produced by mixing 40% by weight of PLA resin with 60% by weight of CMF having a fiber length of 35 to 45 ⁇ m and a particle size distribution D50 of 33.09 ⁇ m as a filler.
  • the molding resin material of Example 3 was produced by kneading at 185° C. and a rotation speed of 40 rpm for 25 minutes.
  • Example 4 a molding resin material was produced by mixing 30% by weight of PLA resin with 70% by weight of CMF having a fiber length of 35 to 45 ⁇ m and a particle size distribution D50 of 33.09 ⁇ m as a filler.
  • the molding resin material of Example 4 was produced by kneading at 195° C. and a rotation speed of 40 rpm for 25 minutes.
  • Comparative Example 1 a molding resin material was produced by mixing 80% by weight of PLA resin with 20% by weight of CNF having a fiber length of 3 nm to 1 ⁇ m and a particle size distribution D50 of 26.30 ⁇ m as a filler.
  • the molding resin material of Comparative Example 1 was manufactured by kneading at 180° C. and a rotation speed of 40 rpm for 15 minutes. However, the quality of the molding resin material of Comparative Example 1 was poor, and a molded article could not be molded.
  • the PHA resins (PHBV resins) of Examples 5 to 7 and Comparative Example 2 are plastics produced in vivo by microorganisms using biomass such as vegetable oil as raw materials, and have an MFR (melt flow rate) of 8 to 15. , specific gravity 1.25, and melting point 175 to 180°C.
  • Example 5 a molding resin material was manufactured using 100% by weight of PHA resin, that is, only PHA resin without mixing filler.
  • the molding conditions for a molded article using the molding resin material of Example 5 were injection time of 12 seconds, temperature of 170° C., and cooling time of 40 seconds.
  • Example 6 a molding resin material was produced by mixing 80% by weight of PHA resin with 20% by weight of CMF having a fiber length of 35 to 45 ⁇ m and a particle size distribution D50 of 33.09 ⁇ m as a filler.
  • the molding resin material of Example 6 was produced by kneading at 160° C. and a rotation speed of 40 rpm for 20 minutes. Further, the molding conditions for the molded product using the molding resin material of Example 6 were: injection time 12 seconds, temperature 160° C., and cooling time 40 seconds.
  • Example 7 a molding resin material was produced by mixing 40% by weight of PHA resin with 60% by weight of CMF having a fiber length of 35 to 45 ⁇ m and a particle size distribution D50 of 33.09 ⁇ m as a filler.
  • the molding resin material of Example 7 was manufactured by kneading at 176° C. and a rotation speed of 40 rpm for 25 minutes.
  • a molding resin material was produced by mixing 80% by weight of PHA resin with 20% by weight of CNF having a fiber length of 3 nm to 1 ⁇ m and a particle size distribution D50 of 26.30 ⁇ m as a filler.
  • the molding resin material of Example 9 was produced by kneading at 145° C. and 40 rpm for 15 minutes.
  • the molding conditions for the molded product using the molding resin material of Comparative Example 2 were: injection time 12 seconds, temperature 170° C., and cooling time 40 seconds.
  • the bio-PBS of Comparative Examples 3 to 5 is a bioplastic with a biomass ratio of 50% by weight produced from biosuccinic acid and 1,4-butanediol from corn, cassava, sugarcane, etc., and has an MFR (melt flow rate) of 50% by weight. 5, a specific gravity of 1.26 and a melting point of 115°C was used.
  • the molding resin material was manufactured using 100% by weight of bio-PBS, that is, only bio-PBS without mixing filler.
  • the molding conditions for the molded article using the molding resin material of Comparative Example 3 were injection time of 30 seconds, temperature of 130° C., and cooling time of 40 seconds.
  • Comparative Example 4 a molding resin material was produced by mixing 80% by weight of bio-PBS with 20% by weight of CMF having a fiber length of 35 to 45 ⁇ m and a particle size distribution D50 of 33.09 ⁇ m as a filler.
  • the molding resin material of Comparative Example 2 was manufactured by kneading at 130° C. and a rotation speed of 40 rpm for 25 minutes.
  • the molding conditions for the molded article using the molding resin material of Comparative Example 4 are the same as in Example 1: injection time 30 seconds, temperature 130° C., and cooling time 40 seconds.
  • Comparative Example 5 66.2% by weight of bio-PBS was mixed with 28.4% by weight of CMF having a fiber length of 35 to 45 ⁇ m and a particle size distribution D50 of 33.09 ⁇ m as a filler, and 5.7% by weight of rubber and wax.
  • a resin material for molding was produced by adding % by weight.
  • the molding resin material of Comparative Example 5 was manufactured by kneading at 130° C. and a rotation speed of 40 rpm for 25 minutes. Further, the molding conditions for the molded product using the molding resin material of Example 2 were: injection time 12 seconds, temperature 190° C., and cooling time 40 seconds.
  • the PP resin used in Comparative Examples 6 to 10 was homopolypropylene F113G manufactured by Prime Polymer Co., Ltd., which had an MFR (melt flow rate) of 3, a specific gravity of 0.90, and a melting point of 165°C.
  • Comparative Example 6 a molding resin material was manufactured using 100% by weight of PP resin, that is, only PP resin without mixing filler.
  • the molding conditions for the molded article using the molding resin material of Comparative Example 6 were injection time of 14 seconds, temperature of 200° C., and cooling time of 40 seconds.
  • a molding resin material was produced by mixing 80% by weight of PP resin with 20% by weight of CMF having a fiber length of 35 to 45 ⁇ m and a particle size distribution D50 of 33.09 ⁇ m as a filler.
  • the molding resin material of Comparative Example 8 was manufactured by kneading at 200° C. and a rotation speed of 40 rpm for 26 minutes. Furthermore, the molding conditions for the molded product using the molding resin material of Comparative Example 8 were: injection time 14 seconds, temperature 200° C., and cooling time 60 seconds.
  • Comparative Example 8 59.2% by weight of PP resin was mixed with 39.5% by weight of CMF having a fiber length of 35 to 45 ⁇ m and a particle size distribution D50 of 33.09 ⁇ m as a filler, and 1.3% of wax was added as an additive.
  • a resin material for molding was produced by adding % by weight.
  • the molding resin material of Comparative Example 9 was manufactured by kneading at 175° C. and a rotation speed of 40 rpm for 45 minutes. Furthermore, the molding conditions for the molded product using the molding resin material of Comparative Example 9 were: injection time 14 seconds, temperature 200° C., and cooling time 60 seconds.
  • Comparative Example 9 39.2% by weight of PP resin was mixed with 58.8% by weight of CMF having a fiber length of 35 to 45 ⁇ m and a particle size distribution D50 of 33.09 ⁇ m as a filler, and 2.0% of wax was added as an additive. % was added to produce a molding resin material.
  • the molding resin material of Comparative Example 9 was manufactured by kneading at 175° C. and a rotation speed of 40 rpm for 45 minutes. Furthermore, the molding conditions for the molded product using the molding resin material of Comparative Example 9 were: injection time 14 seconds, temperature 200° C., and cooling time 60 seconds.
  • Comparative Example 10 19.6% by weight of PP resin was mixed with 78.4% by weight of CMF having a fiber length of 35 to 45 ⁇ m and a particle size distribution D50 of 33.09 ⁇ m as a filler, and 2.0% of wax was added as an additive.
  • a resin material for molding was produced by adding % by weight.
  • the molding resin material of Comparative Example 9 was manufactured by kneading at 176° C. and a rotation speed of 40 rpm for 44 minutes.
  • FIG. 4 shows the results of each example and each comparative example for each molding resin material and molded product manufactured under such manufacturing conditions.
  • Figures 5 to 7 show photographs of the molded products of each example and each comparison
  • Figure 8 shows a table showing the appearance of the resin material for molding using press sheets
  • Figure 9 shows the appearance of the molded products using a scanning electron microscope.
  • a table showing the appearance properties of the molding resin material by (SEM) is shown, and the characteristics of the molding resin material and molded product of this embodiment will be described below based on FIGS. 4 to 9.
  • the moldability will be explained based on FIGS. 4 to 7.
  • the moldability is based on the presence or absence of defects such as burrs, short shots, warping, sink marks, voids, flow marks, weld lines, and silver streaks in the molded product (test piece).
  • Comparative Examples 6 to 10 which use PP resin that has been commonly used, there is no problem in moldability. Furthermore, Comparative Examples 3 to 5, in which bio-PBS of which 50% is derived from fossils, have no problems in moldability. On the other hand, regarding Examples 1 to 7 and Comparative Examples 1 and 2, which are bioplastics with a biomass ratio of 100%, only Examples 3 to 7, in which CMF is mixed, meet the moldability as a product. It is.
  • Comparative Example 3 (Bio PBS 100% by weight) shown in FIG. 5(a)
  • Comparative Example 4 (Bio PBS 80% by weight, CMF 20%) shown in FIG. 5(b)
  • Comparative Example 4 shown in FIG. 5(c)
  • Comparative Example 5 Bio PBS 66, 2% by weight, CMF 28.4%, rubber, wax 5.7% by weight
  • Example 1 (100% by weight of PLA resin) shown in FIG. 6(a)
  • Example 2 PLA resin 80% by weight, CMF 20%
  • Example 2 PLA resin 80% by weight, CMF 20%
  • FIG. 6(c) Comparative Example 1 (PLA resin 80% by weight, CNF 20%)
  • the test piece broke during molding, and molding could not be performed.
  • Example 5 (PHA 100% by weight) shown in FIG. 7(a)
  • Example 6 (PHA 80% by weight, CMF 20%) shown in FIG. 7(b)
  • Comparative Example 2 (PHA 80% by weight) shown in FIG. 7(c).
  • CNF 20% there were no defects in the molded products (test pieces), and there was no problem in moldability.
  • Comparative Examples 6 to 11 using PP resin have no problems in appearance.
  • Examples 1 to 7 and Comparative Examples 1 and 2 which are bioplastics with a biomass ratio of 100%
  • Examples 2 to 4 in which CMF is mixed, satisfy the appearance as a product.
  • FIG. 8 shows the evaluation of the appearance of the molding resin material using a press sheet.
  • the heat press machine First, prepare the heat press machine, turn on the heat press machine, and raise the temperature for 2 hours.
  • the heat press machine is equipped with one pressure detection section and one heater at the top and bottom.
  • the set temperature was set at 200°C.
  • the Lumirror containing the sample was placed in a heat press machine, a load of 0.95 to 1 t was applied, and it was heated for 1 minute. After 1 minute had passed, a load of 8.95 to 9 t was applied and heating was continued for 1 minute. Thereafter, immediately remove the Lumirror from the heat press.
  • the molding resin materials of PLA resin (Comparative Example 1) and PHA resin (Comparative Example 2) mixed with CNF as a filler had many aggregates and poor dispersibility in the press sheet evaluation. Recognize.
  • the molding resin materials of PLA resin (Examples 2 to 4) and PHA resin (Examples 6 and 7) mixed with CMF as a filler had almost no agglomerates in the press sheet evaluation, and had excellent dispersibility. I know that there is. In Examples 3, 4, and 7, some color unevenness occurred on the surface, but there were no agglomerates and no major problem occurred in terms of appearance quality.
  • PP resin a similar press sheet evaluation was performed by mixing paper powder (actually measured particle size 55 to 65 ⁇ m) and paper pieces (catalog value particle size 1 to 2 mm, measured particle size 1000 to 2000 ⁇ m), but there were many aggregates. Dispersibility was poor.
  • the molding resin materials of bio-PBS resin (Comparative Examples 4 and 5) and PP resin (Comparative Examples 9 and 10) mixed with CMF (catalog value particle size 35 to 45 ⁇ m, measured particle size 25 to 35 ⁇ m) as a filler are as follows: In the press sheet evaluation, there were almost no agglomerates, indicating excellent dispersibility.
  • FIG. 9 shows a table showing the evaluation of the appearance of the molding resin material using a scanning electron microscope (SEM). Note that the molding resin material to be evaluated in FIG. 9 is obtained by observing pellets using an SEM.
  • SEM scanning electron microscope
  • the molding resin materials of PLA resin (Comparative Example 1) and PHA resin (Comparative Example 2) mixed with CNF as a filler have large variations in particle size and poor dispersibility as seen from the SEM images. I understand.
  • the molding resin materials of PLA resin (Example 2), PHA resin (Example 6), and bio-PBS (Example 2) mixed with CMF as a filler have small variations in particle size as seen from SEM images, and are dispersed. It turns out that he has excellent sex.
  • FIG. 9 also shows an SEM image of bio-PBS (comparative example 4) mixed with CMF as a filler, which also had small variations in particle size and excellent dispersibility.
  • the physical property evaluation will be explained based on FIG. 4.
  • the required physical properties and their values change depending on the use of the molded product. For example, strength is primarily required for molded products such as automobile parts. On the other hand, items that do not require much strength include so-called daily necessities. Indices for determining strength include bending strength and bending elasticity. IZOD impact strength is important for things that affect impact, such as car bumpers. Additionally, molding shrinkage is generally evaluated as dimensional formability.
  • Examples 2 and 6 which have a biomass ratio of 100% by weight (CMF 20% by weight) and satisfy moldability and appearance, have the bending strength and bending elasticity of the PP resin mixed with talc. It has been possible to achieve physical properties that are equivalent to or better than Comparative Example 7, which is a mixture of PP resin and CMF, and Comparative Example 8, which is a mixture of PP resin and CMF.For molded products that require strength, the biomass ratio of PP resin molded products is 100% by weight. It turns out that it can be replaced.
  • Examples 2 and 6 are superior in bending elasticity and bending strength to bio-PBS with a biomass ratio of 50% by weight and a mixture of 20% by weight of CMF. For this reason, Examples 2 and 6, for example, can be applied to molded products that require a certain strength, such as automobile parts.
  • the molding resin material of this embodiment achieves a biomass ratio of 100% by weight (a high biomass ratio of at least 90% by weight) while maintaining moldability and appearance. It is characterized by its ability to be molded while satisfying its properties.
  • biodegradable plastics as bioplastics made only from bio-derived materials, it is possible to realize molding resin materials with lower environmental impact.
  • the environmental load reduction effect can be maximized.
  • biodegradable plastic 30% by weight or more and the CMF to 20% by weight or more, it is possible to realize a bioplastic molding resin material with sufficient moldability and appearance.
  • PLA polylactic acid
  • PHA PHBV
  • CMF cellulose microfiber
  • the resin molded product molded using the molding resin material of this embodiment has excellent moldability and appearance.
  • the production method for resin materials for molding includes a drying process in which the moisture content of CMF is dried to 5% by weight or less, and a pressure kneading machine to mix the CMF dried in the drying process and biodegradable plastic.
  • a drying process in which the moisture content of CMF is dried to 5% by weight or less
  • a pressure kneading machine to mix the CMF dried in the drying process and biodegradable plastic.
  • the first sample is CMF (sample name: ARBOCEL FD600/30)
  • the second sample is a molding resin material (sample name: PHA(CMF60)-MB)
  • the third sample is a molding resin material.
  • a sample (sample name: PLA(CMF70)-MB) was prepared.
  • the second sample contained PHA resin and CMF in a weight percent ratio of 40:60.
  • the third sample contained PLA resin and CMF in a weight percent ratio of 30:70.
  • Carbon dioxide was generated by burning each sample without pretreatment, and the generated carbon dioxide was purified using a vacuum line.
  • graphite was produced by reducing purified carbon dioxide with hydrogen using iron as a catalyst. The produced graphite was packed into a cathode with an inner diameter of 1 mm using a hand press machine, which was fitted into a wheel and attached to a measuring device.
  • the measuring device used was a 14 C-AMS dedicated device (manufactured by NEC Corporation) based on a tandem accelerator, which counted 14 C, 13 C concentration ( 13 C/ 12 C), and 14 C concentration ( 14 C/ 12 C). C) was measured.
  • oxalic acid (HOxII) provided by the US National Institute of Standards (NIST) was used as a standard sample, and measurements of this standard sample and a background sample were also performed at the same time. The measurement results are shown in Table 1 below.
  • ⁇ 13 C is a value obtained by measuring the 13 C concentration ( 13 C/ 12 C) of sample carbon and expressing the deviation from the standard sample in thousandth deviation ( ⁇ ). This value is a value measured by an AMS device, and is also noted as “AMS” in Table 1 below.
  • pMC percent Modern Carbon
  • ⁇ 14 C is the deviation of the 14 C concentration of the sample carbon relative to standard modern carbon expressed in thousandths of a deviation ( ⁇ ), and the value obtained by correcting this with ⁇ 13 C is ⁇ 14 C.
  • the biomass degree of the sample calculated using ⁇ 13 C-corrected pMC according to ASTM D6866-22 is shown in FIG.
  • the standard value atmospheric correction factor REF (pMC)
  • REF atmospheric correction factor
  • the carbon contained in the sample is derived from terrestrial plants
  • the carbon-based biomass degree for each year of production is as shown in Figure 10. However, if the carbon source is not a terrestrial plant, or if it is terrestrial but is expected to be older than 2004, the calculation will be different.
  • the bar graph in FIG. 10 shows the ratio of biomass-derived carbon and petroleum-derived carbon to the total carbon contained in the sample. Note that the mixing weight ratio of the biomass raw material and the petroleum raw material does not necessarily match the above ratio. IAAA-220645 shows very high pMC values for modern atmospheres. There is a high possibility that the biomass used as raw material, such as wood, is old, and in that case, it is not suitable to use the 2022 REF (pMC) in ASTM D6866-22.
  • the biomass degree of each of the first sample, second sample, and third sample was 90% by mass or more.
  • a molding resin material containing biodegradable plastic and cellulose microfibers and having a biomass ratio of 90% by mass or more [2] The molding resin material according to [1], wherein the biodegradable plastic is a biomass plastic made only of bio-derived materials. [3] The molding resin material according to [1] or [2], wherein the biomass ratio is 100% by mass. [4] The molding resin material according to any one of [1] to [3], wherein the biodegradable plastic is 30% by weight or more, and the cellulose microfiber is 20% by weight or more. [5] The molding resin material according to any one of [1] to [4], wherein the biodegradable plastic is a polylactic acid resin.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne matériau à base de résine pour moulage qui contient des microfibres de plastique et de cellulose biodégradables et qui présente un rapport de biomasse supérieur ou égal à 90 % en masse.
PCT/JP2023/026116 2022-07-15 2023-07-14 Matériau à base de résine pour moulage, article moulé en résine et procédé destiné à produire un matériau à base de résine pour moulage Ceased WO2024014545A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001192401A (ja) * 2000-01-02 2001-07-17 Nippon Koonsutaac Kk 生分解性のモデル用ブロック材
JP2007112859A (ja) * 2005-10-19 2007-05-10 Nissan Motor Co Ltd 脂肪族ポリエステル樹脂組成物
JP2008150599A (ja) * 2006-12-13 2008-07-03 Cheil Industries Inc 天然繊維強化ポリ乳酸樹脂組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001192401A (ja) * 2000-01-02 2001-07-17 Nippon Koonsutaac Kk 生分解性のモデル用ブロック材
JP2007112859A (ja) * 2005-10-19 2007-05-10 Nissan Motor Co Ltd 脂肪族ポリエステル樹脂組成物
JP2008150599A (ja) * 2006-12-13 2008-07-03 Cheil Industries Inc 天然繊維強化ポリ乳酸樹脂組成物

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