WO2013108817A1 - 植物由来プラスチックブレンド物およびその製造方法 - Google Patents
植物由来プラスチックブレンド物およびその製造方法 Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
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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
- C08J3/005—Processes for mixing polymers
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/16—Biodegradable polymers
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Definitions
- the present invention relates to a plastic blend and a method for producing the same.
- the present invention relates to a plant-derived plastic blend using plant-derived raw materials and a method for producing the same.
- PLLA polylactic acid
- PE polyethylene
- HDPE high-density PE
- LDPE low-density PE
- HDPE high-density PE
- PLLA high elastic modulus plastic
- An object of the present invention is to provide a plant-derived plastic blend in which HDPE and PLLA are microscopically mixed to improve mechanical performance and a method for producing the same.
- a plant-derived plastic blend further comprising 1% by weight or more and 20% by weight or less of a compatibilizer is provided.
- the ratio of the domain size of the plant-derived polylactic acid is 1 ⁇ m or less is 60% or more, and the plant-derived polylactic acid is a matrix
- the ratio of the domain size of the plant-derived polyethylene of 1 ⁇ m or less may be 40% or more.
- the compatibilizer is an epoxy group-containing resin, is a copolymer having an epoxy group and containing a structure of an olefin compound, and (a) 60% by weight of ethylene units 99 wt% or less, (b) 0.1 to 30 wt% of unsaturated carboxylic acid glycidyl ester unit and / or unsaturated glycidyl ether unit, and (c) 0 wt% or more of ethylenically unsaturated ester compound
- An epoxy group-containing ethylene copolymer comprising 40% by weight or less may be used.
- the epoxy group-containing resin may be an ethylene-glycidyl methacrylate-methyl acrylate copolymer having a glycidyl methacrylate content of 0.1 wt% to 30 wt%.
- the plant-derived plastic blend may have a tensile modulus of 950 MPa or more and a breaking elongation of 4% or more.
- a raw material containing plant-derived high-density polyethylene, plant-derived polylactic acid, and a compatibilizer is melt-kneaded with the raw material sent in the screw tip direction.
- the product is supplied again to a melt-kneading apparatus equipped with an internal feedback screw that can move to the rear end direction.
- the rotational speed of the screw is 200 rpm to 3000 rpm, and the shear rate is 300 sec ⁇ 1.
- a method for producing a plant-derived plastic blend in which melt kneading is performed by circulating for a certain time under the condition of 4500 sec ⁇ 1 or less.
- the raw material may be transferred in the rear end direction through a hole provided in the screw.
- the total of 50% to 90% by weight of plant-derived high-density polyethylene and 10% to 50% by weight of plant-derived polylactic acid is 100% by weight.
- a compatibilizer of 1 to 10% by weight may be further added and kneaded.
- the container containing the plant-derived plastic blend as described in any one of the above is provided.
- the container for cosmetics containing the plant-derived plastic blend as described in any one of the above is provided.
- the packaging container containing the plant-derived plastic blend as described in any one of the above is provided.
- the automotive component containing the plant-derived plastic blend as described in any one of the above is provided.
- a plant-derived plastic blend in which HDPE and PLLA both derived from plants are microscopically mixed to improve mechanical performance, and a method for producing the same.
- the present invention examined a method of microscopically mixing plant-derived high-density PE and PLLA.
- the present inventors have found that not only adding a compatibilizing agent but also applying high shear molding to microscopically mix high-density PE and PLLA, the mechanical performance is greatly improved. It was.
- the plant-derived plastic blend according to an embodiment of the present invention includes plant-derived high-density PE, plant-derived PLLA, and a compatibilizer.
- the plant-derived plastic blend according to this embodiment is a plastic blend obtained by microscopically mixing high-density PE and PLLA by subjecting these raw materials to high shear molding.
- the plant-derived high-density polyethylene (plant-derived HDPE) according to this embodiment is a component that imparts high mechanical performance to the plant-derived plastic blend.
- the plant-derived HDPE according to the present embodiment can be a known plant-derived HDPE, and is commercially available.
- the plant-derived plastic blend according to this embodiment preferably contains 10% to 90% by weight of plant-derived HDPE.
- the plant-derived polylactic acid (plant-derived PLLA) according to this embodiment is a component that imparts a high elastic modulus, particularly a tensile elastic modulus, to a plant-derived plastic blend.
- the plant-derived PLLA according to the present embodiment can use a known plant-derived PLLA and is commercially available.
- the plant-derived plastic blend according to this embodiment preferably contains 10% by weight or more and 90% by weight or less of plant-derived PLLA.
- the compatibilizer according to the present embodiment is a component that compatibilizes plant-derived HDPE and plant-derived PLLA in a plant-derived plastic blend.
- the compatibilizer according to the present embodiment is an epoxy group-containing resin, a copolymer having an epoxy group and containing a structure of an olefinic compound, and (a) 60 wt% or more and 99 wt% of ethylene units.
- E-GMA-MA ethylene-glycidyl methacrylate-methyl acrylate copolymer
- E-GMA-MA ethylene-glycidyl methacrylate-methyl acrylate copolymer
- the E-GMA-MA according to this embodiment preferably has a glycidyl methacrylate content of 0.1 wt% or more and 30 wt% or less.
- the plant-derived plastic blend according to the present embodiment preferably contains 1 to 20% by weight of E-GMA-MA, with the total of plant-derived HDPE and plant-derived PLLA being 100 masses. By containing E-GMA-MA within this range, plant-derived HDPE and plant-derived PLLA can be suitably dispersed in the plant-derived plastic blend, and excellent mechanical performance can be exhibited.
- the plant-derived plastic blend according to this embodiment has a structure in which plant-derived HDPE and plant-derived PLLA are microscopically mixed, it has a tensile elastic modulus of 950 MPa or more and a breaking elongation of 4% or more.
- the plant-derived plastic blend according to this embodiment when the plant-derived polyethylene is a matrix, the ratio of the domain size of the plant-derived polylactic acid is 1 ⁇ m or less is 60% or more, and the plant-derived polylactic acid is a matrix. In this case, the proportion of the plant-derived polyethylene domain size of 1 ⁇ m or less is 40% or more.
- the plant-derived plastic blend according to this embodiment with improved mechanical performance can be used for containers such as cosmetic containers and packaging containers, and automobile parts.
- the cosmetic container, the packaging container, and the automobile part according to the present embodiment can be replaced with plant-derived materials by including the plant-derived plastic blend according to the present embodiment, and have excellent mechanical performance. it can.
- the plant-derived plastic blend according to the present invention is realized by microscopic mixing of HDPE and PLLA, which has conventionally been difficult. Such microscopic mixing requires not only the addition of a compatibilizer but also a high shear molding process. The high shear molding process according to the present embodiment will be described below.
- the screw rotation speed is 200 rpm to 3000 rpm
- the plant-derived HDPE the plant-derived PLLA
- melt-kneading agent and melt-kneading an extrudate of a plant-derived plastic blend in which one polymer component is used as a matrix and the dispersed phase size of the other polymer component is microscopically controlled is produced.
- the “extruded product” produced in the present invention is simply called an extrudate “kneaded product” in a kneaded state. Or an extrudate “molded product” formed into a sheet-like shape by molding. ).
- plant-derived high-density PE In order to knead a mixture of plant-derived high-density PE, plant-derived PLLA, and a compatibilizer, a method by dry blending in which the mixture is mixed in a granular state in advance can be used.
- plant-derived PLLA Prior to dry blending, for example, plant-derived PLLA may be dried in vacuum at 80 ° C. for 24 hours, and plant-derived HDPE and compatibilizer may be dried in vacuum at 45 ° C. for 24 hours.
- plant-derived PLLA and plant-derived HDPE are incompatible, and in order to obtain a blended product thereof, it is usual to use a biaxial melt kneader or the like at 170 ° C. to 250 ° C. near the melting point. Mix.
- the internal structure of those extrudates has a dispersed phase size of several microns when one component is a matrix. Since the so-called phase-separated structure is coarsened to a level of several tens of micrometers, the resulting melt-kneaded material cannot exhibit good mechanical performance.
- the apparatus used in the melt-kneading step for producing the plant-derived plastic blend of the present invention is not limited to the application of the shear flow field, and any apparatus that can also provide an extension field is suitable.
- a shear flow field is applied between the screw and the cylinder, and an extension field is applied when passing through the screw return hole 44. Any device that can provide such a field may be used.
- the inventors of the present invention have developed a blend comprising a plant-derived PLLA and a plant-derived HDPE, and a system to which a compatibilizer is added, in place of a conventional twin screw kneader.
- the screw rotation speed is 200 rpm to 3000 rpm
- the shear rate is 300 sec -1 or more 4500Sec -1 or less, under the following conditions heating temperature 250 ° C. 180 ° C. or higher, by melt kneading, novel never conventionally obtained, by uniformly and intimately finely plant derived HDPE matrix phase
- a plant-derived plastic blend in which a plant-derived PLLA phase is dispersed can be obtained.
- an object to be melt kneaded such as a plant-derived PLLA, a plant-derived HDPE, or a system to which a compatibilizing agent is added is used.
- Thorough blending is required before feeding to a high shear molding machine. This means that the insoluble resin is adjusted in advance to the respective weight composition and then dry blended so that it is not unevenly distributed and is made as uniform as possible.
- the scale of the apparatus does not use a large-scale apparatus that can be industrialized, but the amount of incompatible resin that is used when the scale is actually scaled for industrialization also increases. In this case, it is necessary to dry-blend the insoluble resin in advance after adjusting the weight composition in advance, and supply it without causing uneven distribution. In this embodiment, dry blending is adopted, but it is also necessary to adopt a more advanced blending method.
- FIG. A micro high-shear molding machine equipped with an internal feedback screw produced by the present inventors is shown in FIG. This trace type high shear molding machine itself is the same as the trace type high shear molding machine introduced in JP-A-2005-313608.
- a micro high shear molding machine 10 includes a melt-kneading unit 12 and a molding unit 14.
- the molding part 14 has an extrusion molding part or an injection molding part.
- the melt-kneading unit 12 includes a material charging unit 16, a cylinder 18, a feedback screw 20 mounted in the cylinder 18, and a shaft 24 connected to the cylinder 18 via a bearing 22.
- the cylinder 18 includes a heater 26 for melting the resin in the cylinder 18.
- the cylinder 18 includes a seal member 28 for sealing between the molding portion 14 and the shaft 24 of the cylinder 18 at the opposite end. As shown in FIGS. 2 and 3, the cylinder 18 includes a front end surface 29 of the screw 20 and a seal surface of the seal member 28 facing the front end surface 29 (hereinafter referred to as “seal surface 28”). Adjustment means for adjusting the gap (gap) 32 is provided on the screw rear side. The spacing 32 is adjusted within the range of about 0.5 to about 5 mm.
- the extrusion molding unit that is the molding unit 14 includes an extrusion unit heater 35 and a T-die 34 for film creation.
- the T die 34 includes a T die front end heater 36 and a T die rear end heater 38.
- the extruded film passes through the discharge port 40 between the heaters 36 and 38 at both ends.
- a thermocouple 42 is attached to the extrusion part and the T-die tip heater 36 to measure the temperature. The measurement result is sent to a control device (not shown) to adjust the temperature of the melt-kneading unit 12 and the temperature of the T die.
- Screw 20 has an inner diameter 1mm or 5mm or less, preferably has the following pore 44 about 2mm above 3 mm, the rotational speed of the screw is at 200rpm or 3000rpm less, shear rate, 300 sec -1 or more 4500Sec -1 below is there.
- the temperature in the cylinder 18 varies depending on the melt-kneaded resin, but for room temperature or amorphous resin, a temperature higher than the glass transition point is used as a guide, and for a crystalline resin, a temperature higher than its melting point is used as a guide. Set under conditions. The raw material passes through the holes 44 provided in the screw 20 and is moved toward the screw rear end.
- the screw 20 has a structure in which at least two types of incompatible blended resins are sufficiently melt-kneaded inside the screw 20.
- FIG. 3 shows a resin internal feedback structure 46 in the feedback screw 20.
- the internal feedback type structure 46 sufficiently kneads the mixed resin introduced from the screw rear stage 48 while feeding it to the screw front stage 50 by the screw 20, and opposes the kneaded resin to the most distal surface 29 of the screw 20 and the front end surface thereof.
- the resin confined in the space 32 with the seal surface 28 and further kneaded is put into a hole 44 provided in the longitudinal direction at substantially the center of the screw 20, and returned to the subsequent stage of the screw 20 again.
- the kneading time in the internal feedback type structure 46 can be arbitrarily changed depending on the time for circulating through the internal feedback type structure 46.
- the degree of kneading is adjusted by varying the distance 32 between the tip surface of the screw 20 and the seal surface 28 facing the tip surface and the inner diameter of the hole 44 of the screw 20.
- the degree of kneading increases as the interval 32 is narrowed and the inner diameter of the hole 44 of the screw 20 is decreased.
- the interval 32 and the inner diameter of the hole 44 of the screw 20 are optimized in consideration of the viscosity of the resin. There is a need.
- the mixing time of the resin in the cylinder 18 is 1 minute or more and 10 minutes or less.
- a compatibilizing agent is added to the plant-derived high-density PE and plant-derived PLLA to react at the interface between the blends.
- a high shear field can be applied and melt kneading can be performed.
- the molding process conditions include not only the setting of the specific temperature described above, but also the screw rotation speed and kneading time of the molding machine. Setting is important.
- the screw rotation speed can be set between 100 rpm and 3000 rpm
- the kneading time can be set between 0.5 minutes and 60 minutes, but the rotation speed and kneading time are 200 rpm and 3000 rpm, 1 minute and 10 respectively. Optimal results could be obtained by setting it to less than a minute.
- the production method according to the present invention is characterized in that high shear molding is performed under the specific temperature conditions described above, with the screw rotation speed and the kneading time being the optimum numerical conditions.
- good results can be obtained only by combining specific conditions. Even if one of the setting conditions such as the temperature setting or the screw rotation speed and the kneading time is not satisfied, a satisfactory result cannot be obtained.
- the tip 20 is opposed to the tip surface 29 of the screw 20.
- the strength of the shear flow field or the degree of kneading can be adjusted.
- the interval 32 can be set to an arbitrary value of 0.5 mm between 1 mm and 5 mm, and the inner diameter of the hole 44 of the screw 20 is similarly set to an arbitrary value of 0.5 ⁇ between 1 ⁇ and 5 ⁇ .
- the interval can be set, an optimum result can be obtained by setting the interval 32 and the inner diameter of the hole 44 of the screw 20 to 2 mm and 2.5 ⁇ , respectively.
- plant-derived high-density PE (bio-HDPE) (manufactured by Toyota Tsusho, SGE7252) was used.
- Plant-derived PLLA has a weight average molecular weight (Mw) of 1.7 ⁇ 10 5 g / mol and a D-form content of 1.2% (PLLA-1) and a weight average molecular weight (Mw) of 1.3.
- the one having ⁇ 10 5 g / mol and a D-form content of 1.2% (PLLA-2) was used.
- E-GMA-MA (Sumitomo Chemical, BF2C) was used as a compatibilizer.
- plant-derived HDPE: plant-derived PLLA-2: E-GMA-MA 75: 25: 10 were used in Examples 13 and 14, 50:50:10 were used in Examples 15 and 16, and 25:75:10 were used as examples. 17 and 18.
- the plant-derived PE is not limited to a high density (0.948 to 0.962 g / cm 3 ), but is almost the same even if a low density (0.916 to 0.920 g / cm 3 ) is used. Results were obtained. Further, the compatibilizer E-GMA-MA (manufactured by Sumitomo Chemical Co., Ltd.) gave almost the same results even when BF7L or BF20C was used.
- the plant-derived PLLA Prior to kneading, the plant-derived PLLA was dried in vacuum at 80 ° C. for 24 hours, and the plant-derived HDPE and the compatibilizer were dried in vacuum at 45 ° C. for 24 hours.
- the above-mentioned plant-derived HDPE, plant-derived PLLA, and E-GMA-MA were dry blended at a ratio of 5 wt% or 10 wt% with respect to 100 wt% of these blends at room temperature. About 5 g of this dry blend was put into a micro-type high shear molding machine (HSE3000mini manufactured by Imoto Seisakusho Co., Ltd.), and the gap (interval 32 in FIG. 3) and the inner diameter of the internal feedback screw hole (hole in FIG. 3).
- the inner diameter of 44 is set to 2 mm and 2.5 ⁇ , respectively, is heated and melted at 190 to 200 ° C., and the screw speed is 300 rpm (Examples 1, 3, 5, 7, 9, 11, 13, 15 and 17) and 600 rpm (Examples 2, 4, 6, 8, 10, 12, 14, 16 and 18), kneaded for 2 minutes, extruded from a T-die, and cooled and solidified by passing through a cooling water bath.
- NHSS2-28 fully automatic high shear molding apparatus manufactured by Niigata Machine Techno Co., Ltd. was used as the melt kneading apparatus.
- the temperature was controlled by using a cooling means for cooling the cylinder so that the resin temperature did not exceed 220 ° C.
- Comparative Example 1 is an extrudate of plant-derived high-density polyethylene (bio-HDPE) alone
- Comparative Example 2 is an extrudate of plant-derived polylactic acid (PLLA-1)
- Comparative Example 3 is plant-derived polylactic acid (PLLA-2). The extrudate is shown.
- FIG. 4 is a scanning electron microscope (SEM image) showing the microscopic structure of the extrudate of Comparative Example 4
- FIG. 5 is an SEM image showing the microscopic structure of the extrudate obtained in Example 7.
- the microscopic structure in this example was measured using an SEM (field emission type SEM XL-20 manufactured by Philips) at an acceleration voltage of 10 kV.
- the PLLA domain dispersed in the matrix (bio-HDPE phase) is coarsened to 20 to 30 ⁇ m, and it is clear that the phases are separated.
- Example 7 it was found that the interface state was very smooth at the resolution level shown in FIG. 5 and was refined to a size of 2 ⁇ m or less even where the PLLA domain was visible.
- 6 and 7 are transmission electron microscope (TEM) images showing the microscopic structure of the extrudate obtained in this example.
- 6 (a) shows the extrudate of Example 1
- FIG. 6 (b) shows the extrudate of Example 2.
- FIG. FIG. 7A shows the extrudate of Example 3
- FIG. 7B shows the extrudate of Example 4.
- the microscopic structure in this example was measured using TEM (JEM 1230, manufactured by JEOL Ltd.) at an acceleration voltage of 120 kV. The observed images were recorded with a Gatan CCD camera.
- the sample was embedded and double-stained with osmium tetroxide (OsO 4 ) and ruthenium tetroxide (RuO 4 ), and then an ultrathin section was prepared for TEM observation.
- OsO 4 osmium tetroxide
- RuO 4 ruthenium tetroxide
- the matrix is bio-HDPE (black background phase), and the dispersed matrix is PLLA (white background domain).
- the structure of Example 2 processed at 600 rpm has a finer dispersed phase size than Example 1 processed at 300 rpm, and the domain size distribution per unit area in the TEM image is 1 for the PLLA phase. It can be seen that the small domain of ⁇ m or less is 80% or more.
- Example 3 and 4 shown in FIG. 7 the major difference from Examples 1 and 2 shown in FIG. 6 is that the matrix and the dispersed phase are reversed. That is, in the microscopic structure of the blend sample with this composition, PLLA forms a matrix (white background phase), and bio-HDPE has a dispersed phase (black background domain). Moreover, the microstructure here depends greatly on the molding conditions, and as shown in FIG. 7 (a), in Example 3 where high shear processing was performed at a screw rotation speed of 300 rpm, the dispersed phase size was large, and a domain of several ⁇ m to 10 ⁇ m. However, as shown in FIG. 7B, in Example 4 processed at a screw rotation speed of 600 rpm, the dispersed phase size is very small, and the ratio of the domain size of 1 ⁇ m or less in the unit area is 50. It turns out that it is more than%.
- Tables 1 to 3 collectively show the tensile elastic modulus and elongation at break according to this example in the stress-strain characteristics shown in FIGS.
- the content of plant-derived PLLA is 25 to 75% by weight and the total is 100% by weight with respect to plant-derived HDPE. It is clear that the tensile modulus of plant-derived HDPE (932 MPa), which originally had a low elastic modulus, is remarkably improved by kneading at 600 rpm with a high shear molding apparatus by adding 5 to 10% by weight. It was. In other words, the plant-derived plastic blend material is subjected to high shear molding to increase the plant-derived PLLA content, so that the plant-derived HDPE and the plant-derived PLLA are microscopically dispersed to improve the tensile elastic modulus.
- plant-derived PLLAs used as Comparative Examples 2 and 3 differ only in molecular weight, but the PLLA alone has a very large elastic modulus, but the elongation at break is 4%, which is a very poor plastic.
- plant-derived HDPE (Comparative Example 1) is a plastic that extends by 997.7%. Therefore, as shown in the present example, when the plant-derived HDPE is microscopically dispersed with respect to the plant-derived PLLA, only 4%, which is a defect of the PLLA, is extended. The disadvantage of this is significantly improved.
- Example 8 corresponding to 136% of Example 2, it is 703.7%, in Example 10 corresponding to 13.6% of Example 4, it is 41.4%, and further in Example 6.
- Example 12 corresponding to 14.2%, the elongation at break increases to 27.6%.
- plant-derived PE and plant-derived PLLA are blended by high shear molding to perform fine mixing, and mechanical performance is dramatically improved.
- An improved blend of plant-derived plastics can be realized.
- containers and various members are created as materials having balanced mechanical performance that require higher elastic modulus than PE or higher elongation than PLLA, and use of plant-derived plastics. It is possible to accelerate further.
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Abstract
Description
本実施形態に係る植物由来高密度ポリエチレン(植物由来HDPE)は、植物由来プラスチックブレンド物に高い力学性能を付与する構成成分である。本実施形態に係る植物由来HDPEは、公知の植物由来HDPEを利用可能であり、商業的に入手可能である。本実施形態に係る植物由来プラスチックブレンド物は、植物由来HDPEを10重量%以上90重量%以下含有することが好ましい。
本実施形態に係る植物由来ポリ乳酸(植物由来PLLA)は、植物由来プラスチックブレンド物に高い弾性率、特に引張弾性率を付与する構成成分である。本実施形態に係る植物由来PLLAは、公知の植物由来PLLAを利用可能であり、商業的に入手可能である。本実施形態に係る植物由来プラスチックブレンド物は、植物由来PLLAを10重量%以上90重量%以下含有することが好ましい。
本実施形態に係る相容化剤は、植物由来プラスチックブレンド物において、植物由来HDPEと植物由来PLLAを相容化させる成分である。本実施形態に係る相容化剤は、エポキシ基含有樹脂であり、エポキシ基を有し、オレフィン系化合物の構造を含有する共重合体であり、(a)エチレン単位を60重量%以上99重量%以下、(b)不飽和カルボン酸グリシジルエステル単位および/または不飽和グリシジルエーテル単位を0.1重量%以上30重量%以下、(c)エチレン系不飽和エステル化合物を0重量%以上40重量%以下からなるエポキシ基含有エチレン共重合体であることが好ましい。例えば、エチレン-グリシジルメタクリレート-メチルアクリレート共重合体(E-GMA-MA)を用いることができる。本実施形態において好適に利用可能なE-GMA-MAとしては、例えば、住友化学(株)製のBF7LやBF2C、BF20Cなどがある。本実施形態に係るE-GMA-MAは、グリシジルメタクリレートの含有量が0.1重量%以上30重量%以下であることが好ましい。本実施形態に係る植物由来プラスチックブレンド物は、植物由来HDPEと植物由来PLLAとの合計を100質量として、さらに、E-GMA-MAを1重量%以上20重量%以下含有することが好ましい。この範囲でE-GMA-MAを含有することにより、植物由来プラスチックブレンド物において植物由来HDPEと植物由来PLLAを好適に分散させ、優れた力学性能を発揮させることができる。
上述したように、本発明に係る植物由来プラスチックブレンド物においては、従来困難であったHDPEとPLLAとの微視的な混合により実現される。このような微視的な混合は、相容化剤を添加するのみならず、高せん断成形加工を施す必要がある。以下に、本実施形態に係る高せん断成形加工について説明する。
本実施例においては、植物由来高密度PE(bio-HDPE)(豊田通商製、SGE7252)を用いた。植物由来PLLAとして、重量平均分子量(Mw)が1.7×105 g/molでD-体含有量が1.2%のもの(PLLA-1)と重量平均分子量(Mw)が1.3×105 g/molでD-体含有量が1.2%のもの(PLLA-2)とを用いた。また、相容化剤として、E-GMA-MA(住友化学製、BF2C)を用いた。各植物由来プラスチックブレンド物原料の混合比は、植物由来HDPE:植物由来PLLA-1:E-GMA-MA=75:25:5を実施例1および2、50:50:5を実施例3および4、25:75:5を実施例5および6とした。また、植物由来HDPE:植物由来PLLA-1:E-GMA-MA=75:25:10を実施例7および8、50:50:10を実施例9および10、25:75:10を実施例11および12とした。また、植物由来HDPE:植物由来PLLA-2:E-GMA-MA=75:25:10を実施例13および14、50:50:10を実施例15および16、25:75:10を実施例17および18とした。なお、植物由来PEは高密度(0.948~0.962 g/cm3)のものだけでなく、低密度(0.916~0.920 g/cm3)のものを用いてもほぼ同じ結果が得られた。また、相容化剤のE-GMA-MA(住友化学製)はBF7LあるいはBF20Cを用いてもほぼ同じ結果が得られた。
比較例1として、植物由来高密度ポリエチレン(bio-HDPE)単体の押出物、比較例2として植物由来ポリ乳酸(PLLA-1)の押出物、比較例3として植物由来ポリ乳酸(PLLA-2)の押出物を示す。
図4は比較例4の押出物の微視的構造を示す走査型電子顕微鏡(SEM像)であり、図5は実施例7で得られた押出物の微視的構造を示すSEM像である。本実施例での微視的構造は、SEM(Philips社製 フィールドエミッション型SEM XL-20)を使用し、加速電圧10 kVで測定した。
実施例及び比較例の植物由来プラスチックブレンド物のシートをカッターで打ち抜いて、ダンベル状試験片とした。引張特性の試験は、ASTM D638に規定された方法に準拠して行った。応力-ひずみ曲線は、オリエンテック社製引張試験機(テンシロンUTM-300)を用いて測定した。本試験は、23℃、相対湿度50%の雰囲気で、クロスヘッド速度500mm/minで行った。
Claims (12)
- 10重量%以上90重量%以下の植物由来ポリエチレンと、10重量%以上90重量%以下の植物由来ポリ乳酸との合計が100重量%となるように含有し、
1重量%以上20重量%以下の相容化剤をさらに含有することを特徴とする植物由来プラスチックブレンド物。 - 前記植物由来プラスチックブレンド物は、前記植物由来ポリエチレンがマトリクスの場合には、前記植物由来ポリ乳酸のドメインサイズが1 μm以下の割合が60%以上であること、前記植物由来ポリ乳酸がマトリクスの場合には、前記植物由来ポリエチレンのドメインサイズが1 μm以下の割合が40%以上であることを特徴とする請求項1に記載の植物由来プラスチックブレンド物。
- 前記相容化剤はエポキシ基含有樹脂であり、エポキシ基を有し、オレフィン系化合物の構造を含有する共重合体であり、(a)エチレン単位を60重量%以上99重量%以下、(b)不飽和カルボン酸グリシジルエステル単位および/または不飽和グリシジルエーテル単位を0.1重量%以上30重量%以下、(c)エチレン系不飽和エステル化合物を0重量%以上40重量%以下からなるエポキシ基含有エチレン共重合体であることを特徴とする請求項1に記載の植物由来プラスチックブレンド物。
- 前記エポキシ基含有樹脂は、グリシジルメタクリレートの含有量が0.1重量%以上30重量%以下であるエチレン-グリシジルメタクリレート-メチルアクリレート共重合体であることを特徴とする請求項1に記載の植物由来プラスチックブレンド物。
- 前記植物由来プラスチックブレンド物の引張弾性率が950MPa以上で、破断伸びが4%以上であることを特徴とする請求項1に記載の植物由来プラスチックブレンド物。
- シリンダー内で、植物由来ポリエチレンと、植物由来ポリ乳酸と、相容化剤とを含む原料を、スクリュー先端方向に送られた前記原料の溶融混練物を再度後端方向に移行できる内部帰還型スクリューを搭載した溶融混練装置に供給し、180℃以上250℃以下の加熱下、前記スクリューの回転数が200rpm以上3000rpm以下、せん断速度が300sec-1以上4500sec-1以下である条件下で、一定時間循環して溶融混練を行うことを特徴とする植物由来プラスチックブレンド物の製造方法。
- 前記原料を、前記スクリューに設けられた孔を通って前記後端方向に移行させることを特徴とする請求項6に記載の植物由来プラスチックブレンド物の製造方法。
- 10重量%以上90重量%以下の植物由来ポリエチレンと、10重量%以上90重量%以下の植物由来ポリ乳酸との合計が100重量%となるように含有し、
1重量%以上20重量%以下の相容化剤をさらに添加して、混練することを特徴とする請求項6に記載の植物由来プラスチックブレンド物の製造方法。 - 請求項1に記載の植物由来プラスチックブレンド物を含むことを特徴とする容器。
- 請求項1に記載の植物由来プラスチックブレンド物を含むことを特徴とする化粧品用容器。
- 請求項1に記載の植物由来プラスチックブレンド物を含むことを特徴とする包装容器。
- 請求項1に記載の植物由来プラスチックブレンド物を含むことを特徴とする自動車用部品。
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CN201380005661.7A CN104053718A (zh) | 2012-01-17 | 2013-01-17 | 植物源塑料掺混物及其制造方法 |
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KR102617471B1 (ko) * | 2021-11-01 | 2023-12-27 | 이폴리텍 주식회사 | 내열성이 강화된 폴리락트산 조성물 및 이로부터 제조되는 내열성이 강화된 생분해성 용기 |
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