WO2024111463A1 - Méthode de fabrication d'un corps moulé en résine à base de poly(3-hydroxyalcanoate) - Google Patents

Méthode de fabrication d'un corps moulé en résine à base de poly(3-hydroxyalcanoate) Download PDF

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Publication number
WO2024111463A1
WO2024111463A1 PCT/JP2023/040843 JP2023040843W WO2024111463A1 WO 2024111463 A1 WO2024111463 A1 WO 2024111463A1 JP 2023040843 W JP2023040843 W JP 2023040843W WO 2024111463 A1 WO2024111463 A1 WO 2024111463A1
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Prior art keywords
p3ha
resin composition
resin
poly
based resin
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English (en)
Japanese (ja)
Inventor
郁弥 迫
拓 野村
信雄 中村
遼 大橋
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Kaneka Corp
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Kaneka Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • 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

Definitions

  • the present invention relates to a method for producing molded bodies of poly(3-hydroxyalkanoate)-based resins (hereinafter sometimes referred to as "P3HA-based resins").
  • Biodegradable resins such as P3HA-based resins (for example, polyhydroxyalkanoic acid (hereinafter, sometimes referred to as "PHA” or “P3HA”)) are being increasingly used in various environmentally friendly applications due to their biodegradability.
  • P3HA-based resins When using P3HA-based resins, they may be molded into pellets for transportation or processing.
  • Patent Document 1 describes a method for producing polyester resin molded products by melt extruding a polyester resin composition, in which immediately after melt extrusion, the polyester resin composition is cooled in a medium in which PHA fine particles are dispersed to produce PHA pellets, etc.
  • the present invention aims to provide a technology that can suppress adhesion of molded bodies to each other and to the cutter, and can efficiently manufacture molded bodies of P3HA-based resin.
  • the inventors conducted extensive research to solve the above problems, and discovered that by adding water to the strands (hereinafter sometimes simply referred to as "strands") obtained from a resin composition containing a P3HA-based resin (hereinafter sometimes referred to as a "P3HA-based resin composition”) when cutting the strands, the molded bodies can be prevented from sticking to each other and to the cutter and the molded body discharge section.
  • strands a resin composition containing a P3HA-based resin
  • P3HA-based resin composition a resin composition containing a P3HA-based resin
  • the inventors also discovered that by holding the molded bodies after cutting in a holding tank (agitation tank), the molded bodies can be prevented from sticking to each other more reliably, and this led to the completion of the present invention.
  • one aspect of the present invention is a method for producing a molded product of a P3HA-based resin (hereinafter referred to as "this manufacturing method"), comprising: (i) a melt extrusion step in which a resin composition containing a P3HA-based resin is melted and extruded in an extruder; (ii) a stranding step in which the molten resin composition obtained in step (i) is cooled in a water bath to obtain strands; (iii) a cutting step in which the strands obtained in step (ii) are cut while adding water to a cutter; and (iv) a holding step in which the cut molded product obtained in step (iii) is held at Tc-25°C to Tc+15°C (where Tc represents the crystallization temperature of the resin composition containing the P3HA-based resin).
  • One aspect of the present invention provides a technology that can suppress adhesion of molded bodies to each other and to the cutter, and can efficiently manufacture molded bodies of P3HA-based resin.
  • the inventors therefore conducted extensive research to solve the above problems, and have succeeded in obtaining the following findings.
  • adding water to the strands and cutter can prevent the molded bodies from adhering to each other and to the cutter or the molded body discharge section.
  • This manufacturing method is extremely advantageous in the manufacture of molded bodies of P3HA-based resin, since it suppresses adhesion between the molded bodies and adhesion to the cutter, and allows molded bodies of P3HA-based resin to be manufactured with high productivity. Furthermore, this manufacturing method does not require the addition of an agent to prevent adhesion between the molded bodies, and therefore molded bodies with high biodegradability can be obtained. Therefore, with the above-mentioned configuration, the amount of plastic waste generated can be reduced, which can contribute to the achievement of Sustainable Development Goals (SDGs), such as Goal 12 "Ensure sustainable consumption and production patterns" and Goal 14 "Conserve and sustainably use the oceans and marine resources for sustainable development".
  • SDGs Sustainable Development Goals
  • Tc indicates the crystallization temperature of the resin composition containing the P3HA-based resin.
  • the "crystallization temperature of the resin composition” is a temperature measured by the method described in the Examples).
  • the production method preferably includes the following step in addition to the above steps (i) to (iv).
  • this manufacturing method can suppress adhesion of the molded bodies to each other and to the cutter, and can produce molded bodies of P3HA-based resin with high productivity.
  • Step (i) is a melt extrusion step in which a resin composition containing a P3HA-based resin (hereinafter, sometimes referred to as "the resin composition") is melted in an extruder and extruded.
  • the resin composition a resin composition containing a P3HA-based resin
  • P3HA-based resin refers to a P3HA-based resin having the following formula (1): [—O—CHR—CH 2 —CO—] (1) (wherein R is an alkyl group represented by C n H 2n+1 , and n is an integer of 1 to 15.) means a copolymer having one or more 3-hydroxyalkanoate repeating units as essential structural units.
  • R is an alkyl group represented by C n H 2n+1 , and n is an integer of 1 to 15.
  • P3HA-based resin may also be referred to as "P3HA”.
  • the P3HA-based resin is not particularly limited as long as it is included in the above formula (1).
  • the P3HA-based resin may be a copolymer consisting of two or more types of 3-hydroxyalkanoate repeating units, or a copolymer consisting of a 3-hydroxyalkanoate repeating unit and other repeating units.
  • the "P3HA-based resin” means a polymer (copolymer) containing 50 mol % or more of the 3-hydroxyalkanoate repeating units out of the total monomer repeating units (100 mol %).
  • the P3HA-based resin may be a copolymer consisting of only 3-hydroxyalkanoate repeating units, or a copolymer containing a 3-hydroxyalkanoate repeating unit and other repeating units.
  • the P3HA resin according to the present production method preferably contains a 3-hydroxybutyrate repeating unit (a repeating unit in which R is CH3 in the above formula (1)) as the 3-hydroxyalkanoate repeating unit.
  • the P3HA resin according to the present production method may be a poly(3-hydroxybutyrate) containing only 3-hydroxybutyrate as a repeating unit, or may be a copolymer of 3-hydroxybutyrate and another hydroxyalkanoate.
  • the P3HA-based resin may be a homopolymer, a mixture of a homopolymer and one or more types of copolymers, or a mixture of two or more types of copolymers.
  • the type of copolymerization is not particularly limited, and may be random copolymerization, alternating copolymerization, block copolymerization, graft copolymerization, etc.
  • examples of P3HA-based resins include poly(3-hydroxybutyrate) (P3HB), poly(3-hydroxybutyrate-co-3-hydroxypropionate) (P3HB3HP), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB3HH), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (P3HB3HV), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), and poly(3-hydroxybutyrate-co-4-hydroxybutyrate).
  • P3HB poly(3-hydroxybutyrate)
  • P3HB3HP poly(3-hydroxybutyrate-co-3-hydroxypropionate)
  • P3HB3HH poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)
  • P3HB3HH poly(3-hydroxybutyrate-co-3-hydroxyvalerate)
  • P3HB3HV poly(3-hydroxybutyrate-co-4-hydroxybutyrate)
  • Poly(3-hydroxybutyrate-co-3-hydroxyoctanoate) (P3HB3HO), poly(3-hydroxybutyrate-co-3-hydroxyoctadecanoate) (P3HB3HOD), poly(3-hydroxybutyrate-co-3-hydroxydecanoate) (P3HB3HD), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) (P3HB3HV3HH), etc.
  • P3HB3HH, P3HB4HB, and P3HB3HP are preferred.
  • P3HB3HH and P3HB4HB are particularly preferred because they are easy to produce industrially. From the viewpoint of industrial productivity, in addition to the above, P3HB and P3HB3HV are also preferred.
  • the P3HA resin is preferably produced by a microorganism.
  • the microorganism that produces the P3HA resin is not particularly limited as long as it is a microorganism capable of producing the P3HA resin.
  • the first P3HB3HH-producing bacterium was Bacillus megaterium, which was discovered in 1925, and other natural microorganisms include Cupriavidus necator (formerly classified as Alcaligenes eutrophus and Ralstonia eutropha) and Alcaligenes latus. It is known that P3HB3HH accumulates within the cells of these microorganisms.
  • Aeromonas kiabiei which produces P3HB3HH
  • Aeromonas kiabiei which produces P3HB3HH
  • P3HB4HB-producing bacterium Alcaligenes eutrophus.
  • Alcaligenes eutrophus AC32 (FERM BP-6038) (T. Fukui, Y. Doi, J. Bateriol., 179, pp.
  • P3HB3HH can also be produced by the method described in, for example, International Publication No. 2010/013483.
  • Commercially available products of P3HB3HH include Kaneka Biodegradable Polymer PHBH (registered trademark) manufactured by Kaneka Corporation.
  • the P3HA resin contains 3-hydroxybutyrate units (hereinafter also referred to as "3HB units"), and the content of 3HB units out of 100 mol% of all repeating units in the P3HA resin is preferably 82 mol% or more, more preferably 84 mol% or more, and even more preferably 86 mol% or more.
  • 3HB units 3-hydroxybutyrate units
  • the P3HA resin contains 3HB units, and the content of 3HB units in 100 mol% of all repeating units in the P3HA resin is preferably 99 mol% or less, more preferably 97 mol% or less, and even more preferably 95 mol% or less.
  • the content of 3HB units in the P3HA resin is 99 mol% or less, excellent effects are achieved in terms of the physical properties of the resin composition containing the P3HA resin. Note that when the resin composition is a blend of multiple P3HA resins, it is intended that the average 3HB unit content of all the P3HA resins contained in the resin composition be within this range.
  • the weight average molecular weight (hereinafter sometimes referred to as Mw) of the P3HA resin is not particularly limited, but is preferably 50,000 to 3 million, more preferably 100,000 to 2.5 million, even more preferably 150,000 to 2 million, and most preferably 150,000 to 1 million.
  • Mw weight average molecular weight
  • the mechanical properties such as strength are sufficient and the moldability is excellent.
  • the method for measuring the weight-average molecular weight of P3HA-based resin is not particularly limited, but for example, the weight-average molecular weight can be calculated as polystyrene equivalent by using chloroform as the mobile phase, a Waters GPC system as the system, and Showa Denko Shodex K-804 (polystyrene gel) as the column.
  • the P3HA-based resin may be, for example, any of those described above in the section P3HA-based resin.
  • the above-mentioned resins may be used alone or in combination of two or more kinds.
  • the content of the P3HA-based resin in the resin composition is preferably 80 parts by weight or more, more preferably 85 parts by weight or more, and even more preferably 90 parts by weight or more, per 100 parts by weight of the resin composition.
  • the content of the P3HA-based resin in the resin composition is 80 parts by weight or more, the effect of having high biodegradability is achieved.
  • the upper limit is not particularly limited, and may be, for example, 100 parts by weight.
  • the resin composition may contain a biodegradable resin other than the P3HA-based resin.
  • a biodegradable resin other than the P3HA-based resin examples include, but are not limited to, polybutylene adipate terephthalate (PBAT), polybutylene succinate adipate (PBSA), polybutylene succinate (PBS), polybutylene succinate terephthalate (PBST), polybutylene succinate adipate terephthalate (PBSAT), polybutylene sebacate terephthalate (PBSeT), polybutylene azelate terephthalate (PBAzT), polycaprolactone (PCL), polylactic acid (PLA), etc.
  • PBAT polybutylene adipate terephthalate
  • PBSA polybutylene succinate adipate
  • PBS polybutylene succinate terephthalate
  • PBSAT polybutylene succinate adipate terephthalate
  • PBSeT poly
  • the content of biodegradable resins other than P3HA-based resins in the resin composition is, for example, 30 parts by weight or less, preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, relative to 100 parts by weight of the resin composition.
  • the content of biodegradable resins other than P3HA-based resins in the resin composition is 30 parts by weight or less, an effect of exhibiting good moldability is achieved.
  • the lower limit is not particularly limited, and may be, for example, 0 parts by weight.
  • the amounts of both resins can be adjusted so that the sum of the P3HA-based resin and the biodegradable resin other than the P3HA-based resin is 100 parts by weight.
  • the resin composition may further contain a crystal nucleating agent and/or a lubricant.
  • a crystal nucleating agent the molding processability, productivity, etc. are improved.
  • the resin composition contains a lubricant, the surface smoothness of the molded product is improved.
  • the crystal nucleating agent and/or lubricant are incorporated into the aliphatic polyester resin composition by melt-kneading with the P3HA resin.
  • the crystal nucleating agent is not particularly limited as long as it has the above-mentioned effect, but examples thereof include inorganic substances such as pentaerythritol, boron nitride, titanium oxide, talc, layered silicates, calcium carbonate, sodium chloride, and metal phosphates; sugar alcohol compounds derived from natural products such as erythritol, galactitol, mannitol, and arabitol; polyvinyl alcohol, chitin, chitosan, polyethylene oxide, aliphatic carboxylic acid amides, aliphatic carboxylic acid salts, aliphatic alcohols, aliphatic carboxylic acid esters, dimethyl adipate, dibutyl adipate, and diisodecyl ether.
  • inorganic substances such as pentaerythritol, boron nitride, titanium oxide, talc, layered silicates, calcium carbonate, sodium chloride,
  • the content of the crystal nucleating agent is not particularly limited as long as it can promote the crystallization of the P3HA resin, but is preferably 0.1 to 2.0 parts by weight, more preferably 0.6 to 1.8 parts by weight, even more preferably 0.7 to 1.6 parts by weight, and particularly preferably 0.8 to 1.5 parts by weight, per 100 parts by weight of the resin composition.
  • the content of the crystal nucleating agent is 0.5 parts by weight or more per 100 parts by weight of the resin composition, a sufficient effect as a crystal nucleating agent can be obtained.
  • the content of the crystal nucleating agent is 2.0 parts by weight or less per 100 parts by weight of the resin composition, an appropriate viscosity is maintained during processing, and the effect on the physical properties of the molded product is also reduced.
  • the lubricant contains at least one selected from the group consisting of behenic acid amide, stearic acid amide, erucic acid amide, and oleic acid amide.
  • This provides the resulting molded article with lubricity (particularly external lubricity).
  • behenic acid amide, stearic acid amide, erucic acid amide, and oleic acid amide it is preferable to contain behenic acid amide or erucic acid amide from the viewpoint of improving processability and productivity.
  • the lubricant may be behenic acid amide, stearic acid amide, erucic acid amide, oleic acid amide, or a combination of two or more of these, or may be a combination with a lubricant other than behenic acid amide, stearic acid amide, erucic acid amide, or oleic acid amide (hereinafter referred to as "other lubricants").
  • other lubricants for example, those described in WO 2022/014408 can be used.
  • the amount of lubricant (the total amount when multiple lubricants are used) is not particularly limited as long as it can provide lubricity, but is preferably 0.1 to 2.0 parts by weight, more preferably 0.2 to 1.6 parts by weight, even more preferably 0.3 to 1.4 parts by weight, and particularly preferably 0.4 to 1.2 parts by weight, per 100 parts by weight of the resin composition.
  • the amount of lubricant is 0.1 part by weight or more per 100 parts by weight of the resin composition, a sufficient effect as a lubricant can be obtained.
  • the amount of lubricant is 2.0 parts by weight or less per 100 parts by weight of the resin composition, bleeding out onto the surface of the molded product is avoided, and a molded product with excellent appearance can be obtained.
  • the resin composition may contain other components such as plasticizers, inorganic fillers, antioxidants, ultraviolet absorbers, colorants such as dyes and pigments, and antistatic agents, as long as the effects of the present invention are not impaired.
  • plasticizers such as plasticizers, inorganic fillers, antioxidants, ultraviolet absorbers, colorants such as dyes and pigments, and antistatic agents, as long as the effects of the present invention are not impaired.
  • inorganic fillers such as plasticizers, inorganic fillers, antioxidants, ultraviolet absorbers, colorants such as dyes and pigments, and antistatic agents, as long as the effects of the present invention are not impaired.
  • antioxidants such as antioxidants, ultraviolet absorbers, colorants such as dyes and pigments, and antistatic agents
  • the resin composition does not contain an anti-adhesion agent.
  • the melt extrusion in step (i) may be carried out by any apparatus known in the art, including, but not limited to, a twin-screw extruder (e.g., TEM-26SX manufactured by Toshiba Machine Co., Ltd.), a single-screw extruder, and the like.
  • a twin-screw extruder e.g., TEM-26SX manufactured by Toshiba Machine Co., Ltd.
  • a single-screw extruder e.g., TEM-26SX manufactured by Toshiba Machine Co., Ltd.
  • the melting temperature in step (i) may vary depending on the composition of the resin composition, the type of P3HA-based resin contained in the resin composition, etc., but is, for example, 120 to 200°C, and preferably 140 to 180°C.
  • Step (ii) is a stranding step in which the molten resin composition obtained in step (i) is cooled in a water bath to obtain strands.
  • the resin composition is cooled in a water bath in a strand bath to promote crystallization of the resin composition and obtain strands.
  • step (ii) lowering the temperature of the strand bath enables more efficient (space-saving) strand cutting in step (iii).
  • step (iii) allows the strands coming out of the extruder to be rapidly cooled, and the residence time in the strand bath can be shortened (the size of the strand bath can be reduced).
  • the temperature of the water bath in step (ii) is preferably 20 to 60°C, more preferably 22 to 50°C, and even more preferably 25 to 40°C.
  • the temperature of the water bath in step (ii) is set to a low temperature of 20 to 60°C, molded bodies of P3HA-based resin can be manufactured with good productivity.
  • the temperature of the water bath is 20 to 60°C, the residence time in the water bath can be shortened, which has the advantage of allowing the strand bath to be made smaller.
  • the diameter of the strand obtained in step (ii) is preferably 0.5 to 10.0 mm, more preferably 0.6 to 5.0 mm, and even more preferably 0.8 to 3.0 mm.
  • the diameter of the strand is 0.5 to 10.0 mm, the strand can be cooled efficiently in step (ii) without being broken.
  • Step (iii) is a cutting step in which the strand obtained in step (ii) is cut while adding water to the cutter.
  • step (iii) by adding water to the cutter when cutting the strand, adhesion of the molded bodies to each other and to the cutter or the molded body discharge part can be suppressed.
  • while adding water to the cutter means that cutting is performed while water is applied to at least the strand and the blade of the cutter. More preferably, in addition to the above, cutting is performed while water is also applied to the formed body discharge section. Even more preferably, water is continued to be added from the strand cutter to the holding tank. This has the effect of preventing adhesion to the formed body discharge section and suppressing clogging of the formed body discharge section.
  • step (iii) it is preferable that the addition of water in step (iii) is performed on all of the strands, the cutter, and the molded body discharge section.
  • the temperature of the water added to the cutter is preferably Tc-25°C to Tc+15°C, more preferably Tc-20°C to Tc+10°C, and even more preferably Tc-10°C to Tc+5°C.
  • Tc indicates the crystallization temperature of the resin composition containing the P3HA-based resin.
  • the absolute temperature of the water added in step (iii) is preferably 50 to 90°C, and more preferably 60 to 80°C. When the absolute temperature of the water added is 50 to 90°C, sufficient crystallization occurs.
  • Step (iv) is a holding step in which the cut molded bodies obtained in step (iii) are held at Tc-25°C to Tc+15°C (wherein Tc represents the crystallization temperature of the resin composition containing the P3HA resin).
  • Tc represents the crystallization temperature of the resin composition containing the P3HA resin.
  • the holding temperature in step (iv) is Tc-25°C to Tc+15°C, preferably Tc-20°C to Tc+10°C, and more preferably Tc-10°C to Tc+5°C.
  • Tc indicates the crystallization temperature of the resin composition containing the P3HA-based resin. If the holding temperature is Tc-25°C to Tc+15°C, sufficient crystallization occurs.
  • the absolute temperature of the holding temperature in step (iv) is preferably 50 to 90°C, and more preferably 60 to 80°C. When the absolute temperature of the holding temperature is 50 to 90°C, sufficient crystallization occurs.
  • step (iv) is preferably carried out while stirring the cut molded body obtained in step (iii).
  • the stirring speed during the stirring is not particularly limited, but is, for example, 50 to 800 rpm, and preferably 200 to 600 rpm.
  • the mixing time is not particularly limited, but is, for example, 1 to 10 minutes, and preferably 1.5 to 5 minutes.
  • the device used for the stirring is not particularly limited, but for example, a vertical stirrer, a horizontal stirrer, etc. may be used.
  • Step (v) is a drying step in which the molded body obtained in step (iv) is dried at 40 to 120° C. By this step, a molded body can be obtained as a dried product.
  • the drying temperature in step (v) is preferably 40 to 120°C, more preferably 60 to 100°C, and even more preferably 70 to 90°C. If the drying temperature is 40 to 120°C, moisture can be sufficiently removed.
  • the drying time in step (v) can be changed as appropriate depending on the drying temperature, etc., but is, for example, 3 to 10 hours, and preferably 4 to 6 hours.
  • the device used for drying in step (v) is not particularly limited, but for example, a box dryer, a hopper dryer, etc. may be used.
  • the molded articles obtained by this manufacturing method can be used, for example, as paper, films, sheets, tubes, plates, rods, containers (e.g., bottle containers), food trays, bags, parts, etc.
  • one embodiment of the present invention is as follows. ⁇ 1> (i) a melt extrusion step of melting and extruding a resin composition containing a P3HA-based resin in an extruder; (ii) a stranding step in which the molten resin composition obtained in the step (i) is cooled in a water bath to obtain strands; (iii) a cutting step of cutting the strand obtained in the step (ii) while adding water to a cutter; and (iv) a holding step of holding the cut molded body obtained in the step (iii) at Tc-25°C to Tc+15°C (wherein Tc represents the crystallization temperature of the resin composition containing the P3HA-based resin).
  • a method for producing a molded article of a P3HA resin having the above structure ⁇ 2> The manufacturing method according to ⁇ 1>, wherein in the step (iii), the temperature of the water added to the cutter is Tc-25°C to Tc+15°C (wherein Tc represents the crystallization temperature of the resin composition containing the P3HA-based resin).
  • Tc represents the crystallization temperature of the resin composition containing the P3HA-based resin.
  • the temperature of the water bath is 20 to 60° C.
  • ⁇ 4> The manufacturing method according to any one of ⁇ 1> to ⁇ 3>, wherein the P3HA resin contains 3HB units and the content of 3HB units in the P3HA resin is 82 mol% or more.
  • ⁇ 5> The method according to any one of ⁇ 1> to ⁇ 4>, wherein the P3HA-based resin is one or more selected from poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), and poly(3-hydroxybutyrate-co-3-hydroxypropionate).
  • ⁇ 6> The method according to any one of ⁇ 1> to ⁇ 5>, wherein the strand has a diameter of 0.5 to 10.0 mm.
  • ⁇ 7> The method according to any one of ⁇ 1> to ⁇ 6>, further comprising: (v) drying the molded body obtained in the step (iv) at 40 to 120° C.
  • molecular weight 480,000 P3HA-1 was prepared by the method described in Example 1 of WO2022 / 091685, and P3HA-2 was prepared by the method described in Example 1 of WO2021 / 085534.
  • Lubricant Behenic acid amide (Nippon Fine Chemical Co., Ltd.) - Nucleating agent: pentaerythritol (Nippon Synthetic Chemical Industry Co., Ltd.).
  • the crystallization temperature of the P3HA resin composition is a temperature measured using the following apparatus, conditions and method.
  • Measurement method Differential Scanning Calorimetry (DSC) Measurement equipment: Hitachi Hightech Science, EXSTAR6000 series DSC6200 Measurement sample: 5 to 10 mg of P3HA was placed in an aluminum pan, the lid was placed on and crimped.
  • Measurement conditions The temperature is increased from 25° C. to 180° C. at 10° C./min, and then decreased at 10° C./min to 25° C. During the measurement, nitrogen gas is flowed at 50 mL/min. Identification of crystallization temperature: The exothermic peak observed during the temperature drop is taken as the crystallization peak, and the peak top is taken as the crystallization temperature.
  • the compacts discharged from the pelletizer or the mixing tank were extracted and their weights were measured. Among the extracted compacts, those that were not cut were selected and their weights were measured. Then, the mutual adhesion rate (%) of the compacts was calculated based on [weight of the uncut compacts among the extracted compacts]/[weight of all the extracted compacts] ⁇ 100.
  • Example 1 (Melt Extrusion (Step (i))) A twin-screw extruder (TEM-26SX manufactured by Toshiba Machine Co., Ltd.) was used for melt-kneading the P3HA-based resin composition. 60 parts by weight of P3HA-1, 40 parts by weight of P3HA-2, 0.5 parts by weight of behenic acid amide, and 1 part by weight of pentaerythritol were weighed and dry-blended to prepare a P3HA-based resin composition. The adjusted P3HA-based resin composition was fed to the twin-screw extruder, and the P3HA-based resin composition was melt-kneaded at a cylinder temperature of 175°C. The melt-kneaded P3HA-based resin composition at 185°C (crystallization temperature: 70°C) was discharged from the nozzle of the die attached to the tip of the extruder.
  • TEM-26SX manufactured by Toshiba Machine Co., Ltd.
  • the P3HA-based resin composition discharged from the extruder was immersed in a strand bath adjusted to a water temperature of 55° C. for 5 seconds, and then supplied to a wet pelletizer (Tanaka Corporation) (step (ii)).
  • the strands (diameter 3 mm) of the wet pelletizer were cut while supplying water at 60° C. to the blades and strands (diameter 3 mm) of the wet pelletizer (step (iii)).
  • the cut molded body was supplied to a holding tank (stirring tank) and retained in water at 60° C. (step (iv)). After that, the molded body was dehydrated and dried at 80° C. to obtain a molded body (step (v)).
  • the adhesion to the blades and the mutual adhesion rate of the molded body were measured and evaluated.
  • Example 2 A molded article was produced in the same manner as in Example 1, except that the water temperature in the strand bath was 33° C. and the residence time was 1.5 seconds.
  • Comparative Example 1 A molded body was produced in the same manner as in Example 1, except that in the production of the molded body, water was not added to the blades and strands of the wet pelletizer, and retention in the holding tank was not performed.
  • Comparative Example 2 A molded body was produced in the same manner as in Example 1, except that retention in a holding tank was not performed in the production of the molded body.
  • Comparative Example 3 The molded bodies were produced in the same manner as in Example 1, except that the temperature of water added to the blades and strands of the wet pelletizer and the retention temperature in the holding tank were 30°C.
  • Comparative Example 4 A molded body was produced in the same manner as in Example 2, except that retention in a holding tank was not performed in the production of the molded body.
  • Comparative Example 5 The molded bodies were produced in the same manner as in Example 2, except that the temperature of water added to the blades and strands of the wet pelletizer and the retention temperature in the holding tank were set to 30°C.
  • Comparative Example 6 The molded bodies were produced in the same manner as in Example 2, except that the temperature of water added to the blades and strands of the wet pelletizer and the retention temperature in the holding tank were 40°C.
  • the above shows that the method for producing molded bodies of P3HA-based resin according to one embodiment of the present invention can suppress adhesion of the molded bodies to each other and to the cutter, and can produce molded bodies of P3HA-based resin with high productivity.
  • Example 2 Furthermore, a comparison of Example 2 with Comparative Examples 4 to 6 showed that even if the residence time in the strand bath was shortened, there was no adhesion to the blades and the adhesion rate of the molded bodies was also reduced.
  • the manufacturing method of the present invention can be suitably used in the fields of agriculture, fishing, forestry, horticulture, medicine, hygiene products, clothing, non-clothing, packaging, automobiles, building materials, and other fields.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • 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 aborde le problème de suppression de l'adhérence mutuelle de corps moulés et d'adhérence d'un corps moulé à un dispositif de coupe et de fabrication d'un corps moulé en résine à base de P3HA avec une productivité élevée. Le problème est résolu par une méthode de fabrication d'un corps moulé en résine à base de P3HA, la méthode comprenant : (i) une étape de fusion et d'extrusion d'une composition de résine ; (ii) une étape de refroidissement de la composition de résine fondue avec un bain d'eau pour obtenir un brin ; (iii) une étape de coupe du brin tout en ajoutant de l'eau à un dispositif de coupe ; et (iv) une étape de maintien d'un corps moulé coupé à une température spécifique.
PCT/JP2023/040843 2022-11-25 2023-11-14 Méthode de fabrication d'un corps moulé en résine à base de poly(3-hydroxyalcanoate) Ceased WO2024111463A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019034987A (ja) * 2017-08-10 2019-03-07 地方独立行政法人京都市産業技術研究所 脂肪族ポリエステル樹脂組成物および成形体
JP2022104869A (ja) * 2021-09-03 2022-07-12 三菱ケミカル株式会社 生分解性に優れた３次元造形用材料およびその造形物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019034987A (ja) * 2017-08-10 2019-03-07 地方独立行政法人京都市産業技術研究所 脂肪族ポリエステル樹脂組成物および成形体
JP2022104869A (ja) * 2021-09-03 2022-07-12 三菱ケミカル株式会社 生分解性に優れた３次元造形用材料およびその造形物

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