WO2021246434A1 - 加熱による前処理を伴う高分子成形物の製造方法 - Google Patents

加熱による前処理を伴う高分子成形物の製造方法 Download PDF

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WO2021246434A1
WO2021246434A1 PCT/JP2021/020957 JP2021020957W WO2021246434A1 WO 2021246434 A1 WO2021246434 A1 WO 2021246434A1 JP 2021020957 W JP2021020957 W JP 2021020957W WO 2021246434 A1 WO2021246434 A1 WO 2021246434A1
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temperature
melting
sample
mol
melt
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French (fr)
Japanese (ja)
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晃 前原
忠久 岩田
拓 大村
泰三 加部
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Mitsubishi Gas Chemical Co Inc
University of Tokyo NUC
Japan Synchrotron Radiation Research Institute
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Mitsubishi Gas Chemical Co Inc
University of Tokyo NUC
Japan Synchrotron Radiation Research Institute
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Priority to CN202180039544.7A priority Critical patent/CN115698398B/zh
Priority to EP21816826.8A priority patent/EP4159901A4/en
Priority to JP2022528860A priority patent/JP7766302B2/ja
Priority to KR1020227045045A priority patent/KR20230018416A/ko
Priority to US18/000,446 priority patent/US12605875B2/en
Publication of WO2021246434A1 publication Critical patent/WO2021246434A1/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D01F6/625—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters derived from hydroxy-carboxylic acids, e.g. lactones
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0059—Degradable
    • B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible

Definitions

  • the present invention is characterized by expanding the temperature range that can be used for subsequent thermoforming by partial melting by reconstructing the thickness of the lamella crystal of crystalline polyhydroxyalkanoate. Regarding the method.
  • Polyhydroxyalkanoate (Polyhydroxyalkanoate, hereafter abbreviated as PHA) is a thermoplastic polyester in which microorganisms accumulate, and has attracted attention as a biodegradable, biocompatible, and bioabsorbable plastic, and has undergone many studies. Has been done (Non-Patent Document 1). More than 100 types of monomer units constituting PHA are known.
  • a typical PHA is poly-3-hydroxybutyrate (hereinafter, P (3HB)) composed of (R) -3-hydroxybutyrate (also referred to as (R) -3-hydroxybutyric acid, hereinafter abbreviated as 3HB). (Abbreviated) (Non-Patent Document 1).
  • the melting point of P (3HB) is about 175 to 180 ° C., and has a melting point as high as that of polypropylene (hereinafter abbreviated as PP).
  • the fracture strength of P (3HB) is similar to that of PP, but the fracture elongation is 5% or less, and the glass transition point is 4 ° C. (room temperature or less).
  • P (3HB) is a highly crystalline, hard and brittle material, it is often not used as a molded product such as a single film.
  • methods for improving its physical properties include a method of introducing a second component monomer unit to form a copolymer, a method of increasing the molecular weight, and a method of increasing the molecular weight. And a method of compounding with a dissimilar polymer material is known.
  • the crystallization rate of PHA is significantly slower than that of traditional industrial polymers, and the glass transition point is below room temperature.
  • PHA is molded after being heated and melted, it takes a long time to cool for solidification and productivity is poor.
  • melt spinning crystallization is slow, so it is wound in an amorphous state and the yarn sticks.
  • thermoplastic polymer materials such as polyester
  • various crystal nucleating agents are being studied for the purpose of improving the crystallization rate.
  • crystal nucleating agents include, for example, for a specific polyester. Elemental substances such as Zn powder, Al powder, graphite, and carbon black; Metal oxides such as ZnO, MgO, A12O3, TiO2, MnO2, SiO2, Fe3O4; Nitridees such as aluminum nitride, silicon nitride, titanium nitride, and boron nitride; Inorganic salts such as Na2CO3, CaCO3, MgCo3, CaSO4, CaSiO3, BaSO4, Ca3 (PO4) 3; Clays such as talc, kaolin, clay and clay; Organic salts such as calcium oxalate, sodium oxalate, calcium benzoate, calcium phthalate, calcium tartrate, magnesium stearate, polyacrylic acid salt; Polymer compounds such as polyester, polyethylene and polypropylene: It is known to add such substances (Patent Document 1).
  • particulate matter such as talc, atomized mica, boron nitride, and calcium carbonate has been tried as a crystal nucleating agent for PHA.
  • organic phosphonic acids such as cyclohexylphosphonic acid or organic phosphinic acids or esters thereof, or derivatives of the acids or esters thereof, and groups IA-VA or IB-VB of the periodic table.
  • Patent Document 2 There is known a method of closely mixing a metal oxide, a hydroxide and a metal compound such as a saturated or unsaturated carponate, together.
  • Patent Document 3 Sugar alcohols such as erythritol, D-arabitol, rivitol, xylitol, galactitol, D-mannitol, L-mannitol, D-sorbitol, myo-inositol, scyllo-inositol (Patent Document 4); Polyvinyl alcohol, chitin, chitosan (Patent Document 5); Polyalkylene oxides such as polyethylene oxide, polypropylene oxide, and polybutylene oxide (Patent Document 6); Fatty alcohols such as polylactic acid and PHA, aliphatic carboxylic acid amides, aliphatic carboxylic acid salts, fatty alcohols and aliphatic carboxylic acid esters (Patent Documents 7 to 9); Fatty acid esters such as dimethyl adipate, di-2-ethylhexy
  • nuclear agents consisting of non-toxic fatty acids and amino acids that are easily decomposed, absorbed or metabolized in vivo are also included in the above, but they are substantially effective. At present, no crystal nucleating agent has been found yet.
  • Patent Documents 27 to 29 describe a P (3HB-co-3HV) copolymer composed of 3HB and 3-hydroxyvalerate (3-hydroxyvaleric acid, hereinafter abbreviated as 3HV), 3HB and 3-hydroxyhexanoate. From a P (3HB-co-3HHx) copolymer consisting of (3-hydroxyhexanoic acid, hereinafter abbreviated as 3HHx), or from 3HB and 3-hydroxyoctanoate (3-hydroxyoctanoic acid, hereinafter abbreviated as 3HO). It is disclosed that P (3HB) having a higher melting point is added as a crystal nucleating agent (nucleating material) to the P (3HB-co-3HO) copolymer.
  • Patent Documents 27 to 29 Dry mixing of blended dry powder PHA as is or in the presence of dry ice; Solution mixing in which the polymer is precipitated by evaporating the solvent after stirring and mixing while dissolving a part or all in a solvent such as chloroform; and P (3HB) on the melting point side to be added. ) Is not melted, and the added PHA (P (3HB-co-3HV), P (3HB-co-3HHx) or P (3HB-co-3HO)) on the low melting point side is in a melted state.
  • PHA P (3HB-co-3HV), P (3HB-co-3HHx) or P (3HB-co-3HO
  • the method of mixing by raising the temperature above the melting point of P (3HB) is a general melt mixing method, but P (3HB) is used in the vicinity of the melting point of P (3HB). PHA is inevitably deteriorated by thermal decomposition and stirring, and its molecular weight is lowered.
  • P (3HB) or 3HB-rich PHA that can become crystal nuclei is used as another PHA copolymer.
  • a method has also been reported in which P (3HB) and PHA do not have to be blended after being produced as a blend in the cells during culture and the PHA is taken out from the cells.
  • P (3HB) or P (3HB-co-3HHx) having a low 3HHx ratio is changed to P (3HB-co-3HHx) having an increased 3HHx ratio by changing the supply of the carbon source during the culture. The method of producing with is described.
  • Patent Document 31 and Patent Document 32 describe a method for producing a blend of PHA having different melting points in the same cell by holding a plurality of PHA polymerizing enzymes having different substrate specificities in the same cell by gene recombination technology. Is disclosed. There is a description that it is possible to perform molding at a temperature of 170 ° C or lower, but it is unclear in what temperature range it can be molded, and in known molding, it is molded after melting above the melting point of the polymer. In this document, the purpose is to improve the solidification rate (crystallization rate) of the PHA blend once melted.
  • Non-Patent Documents 2 to 4 do not aim at allowing P (3HB) to become a crystal nucleus, but describe a PHA-producing wild strain in which P (3HB) and a PHA copolymer are blended and produced in the same bacterium. Describes the blend production of P (3HB) homopolymers and C4 to C12 PHA copolymers by naturally retaining PHA polymerizing enzymes with different substrate specificities in the same cell.
  • ultra-high molecular weight body P (3HB) there are reports using ultra-high molecular weight body P (3HB) and reports on controlling crystal formation to increase the strength without depending on the molecular weight.
  • recombinant Escherichia coli is used to biosynthesize an ultrahigh molecular weight P (3HB) having a number average molecular weight of 1.5 million (weight average molecular weight 3 million) or more, and this ultrahigh molecular weight P (3HB) is used to improve physical properties.
  • the obtained P (3HB) film has been obtained (Patent Document 33 and Non-Patent Document 5).
  • P (3HB) is melt-extruded, rapidly cooled to a glass transition temperature of + 15 ° C. or lower, and solidified to produce amorphous fibers, which are amorphous.
  • P (3HB) fibers are obtained by cold-stretching the fibers of the above to align the molecular chains of the amorphous fibers and heat-treating them (hereinafter, also referred to as "cold-stretching method”) (Patent Document 34 and Patent Document 35). Further, the melt-extruded fiber is rapidly cooled to a glass transition temperature of PHA of + 15 ° C.
  • a method for producing a fiber which comprises producing a formed (isothermally crystallized) crystallized fiber, stretching the crystallized fiber, and further subjecting it to tension heat treatment (hereinafter, also referred to as "microcrystal nuclei stretching method"). Is also disclosed (Patent Document 36).
  • a super high molecular weight P (3HB) having a weight average molecular weight of 2.7 million made of recombinant Escherichia coli is added to P (3HB) having a weight average molecular weight of 520,000 derived from a normal microorganism, dissolved in chloroform, and then cast film is prepared. After molding, hot-pressing at 200 ° C, quenching with ice water, and cold-stretching the ultra-high molecular weight body P (3HB) film after reheating at 200 ° C., the ultra-high molecular weight body P ( It has been suggested that 3HB) behaves like a nuclear agent and promotes nucleation (Non-Patent Document 6).
  • the blended P (3HB) fiber to which 5% by weight of ultra-high molecular weight P (3HB) was added showed a strength of 740 MPa by cooling to 4 ° C. after melt spinning and applying two-step cold stretching.
  • the amount of molecular weight P (3HB) used can be small, it requires two-step cold stretching in a cooling state of 4 ° C., which is complicated to operate and is not suitable for industrialization.
  • melt-molded product is produced by melt-molding a molding material mainly composed of biodegradable polyester having a melting point in a specific range at a heating temperature in a specific range
  • the heat of cold crystallization and the heat of melting thereof are combined with the heat of cold crystallization. It has been reported that a melt-molded product is produced by setting the sum of the heat of cold crystallization and the heat of cold crystallization as a specific range as an index of the crystallization ability of the obtained melt-molded product and the degree of crystallization thereof (Patent). Document 37).
  • Non-Patent Document 8 a copolymer of 3HB and 3-hydroxyhexanoate is processed at a temperature (around 160 ° C.) at which crystals are not completely melted.
  • the tube is made of a poly (3-hydroxybutyrate) resin, and the difference between the melting point peak temperature and the ending temperature of the melting point peak in the differential scanning calorimetry of the poly (3-hydroxybutyrate) resin is 10 ° C. As described above, a tube has been reported (Patent Document 38).
  • the temperature of the melt molding is higher than the outflow start temperature by the flow tester heating method, and the temperature indicating that the crystal melting measured by the differential scanning calorimeter is completely completed (particularly, from the external melting end temperature). There is no mention of setting it to a low temperature).
  • the conventional method is to rapidly form primary nuclei after melting a slow-crystallizing crystalline polymer (polyester), to prevent the formation of large defective spherulites, and to crystallize to increase the strength. It has been developed from the viewpoint of making it solidify and crystallize it so that it can be easily processed. In melt molding of biodegradable crystalline polymers, various attempts have been made to promote crystallization for the purpose of improving the poor processability due to the slow crystallization rate and increasing the strength. There is room for improvement.
  • the temperature is lower than the temperature at which the entire polymer can be melted, and the temperature is high at a temperature at which fine lamella crystals and amorphous regions having a relatively thin melting point and a lower melting point are fluidized.
  • a method of melt-molding a fine but thick lamella crystal in a state where it is not melted by melting (that is, partially melting) the molecule is being studied.
  • the temperature range that can be used for partial melting may be narrow.
  • An object of the present invention is to provide a method for producing a polymer molded product, which can expand the temperature range that can be used for partial melting.
  • the present inventor has used it for thermoforming by partial melting by heat-treating crystalline polyhydroxyalkanoate at a temperature equal to or higher than the glass transition point and then performing partial melting molding. We have found that it is possible to expand the temperature range that can be achieved.
  • the present invention has been completed based on these findings.
  • the following inventions are provided.
  • the crystalline polyhydroxy alkanoate is heat-treated at a temperature equal to or higher than the glass transition point; and the polyhydroxy alkanoate containing lamella crystals having different lamella thickness obtained by the above heat treatment is used for some lamella crystals.
  • a method for producing a polymer molded product which comprises melt-molding in a temperature range in which the remaining lamella crystals are melted and fluidized and the remaining lamella crystals are not melted and remain.
  • the heat treatment is a heat treatment mediated by a gas, a liquid, or a solid.
  • ⁇ 3> The method according to ⁇ 1> or ⁇ 2>, wherein the heat treatment is a liquid-mediated heat treatment in which the polyhydroxyalkanoate is not completely dissolved in the liquid in a heated state.
  • the temperature range is higher than the outflow start temperature by the flow tester heating method and lower than the temperature indicating that the crystal melting measured by the differential scanning calorimeter is completely completed.
  • ⁇ 1 > To the method according to any one of ⁇ 3>.
  • ⁇ 5> The method according to any one of ⁇ 1> to ⁇ 4>, wherein the temperature range is higher than the outflow start temperature by the flow tester heating method and lower than the extrapolation melting end temperature.
  • thermoforming is molding by melt extrusion.
  • ⁇ 9> The method according to any one of ⁇ 1> to ⁇ 8>, wherein the crystalline polyhydroxy alkanoate is a copolymer containing 3-hydroxybutyric acid and 4-hydroxybutyric acid as a monomer unit.
  • the crystalline polyhydroxy alkanoate is a copolymer containing 3-hydroxybutyric acid and 4-hydroxybutyric acid as a monomer unit, and the ratio of 4-hydroxybutyric acid is 5 mol% or more and 40 mol% or less.
  • the temperature range that can be used for partial melting can be expanded.
  • FIG. 1 shows a flow curve (solid line) and a DSC curve (broken line) of sample S1 (P (3HB) homopolymer) by a flow tester heating method.
  • FIG. 2 shows a flow curve (solid line) and a DSC curve (broken line) of sample S2 (P (3HB) homopolymer) by the flow tester heating method.
  • FIG. 3 shows a flow curve (solid line) and a DSC curve (broken line) of sample S3 (P (3HB) homopolymer) by the flow tester heating method.
  • FIG. 4 shows the superposition of the DSC curves of the sample S1 (solid line), the sample S2 (broken line), and the sample S3 (rough broken line).
  • FIG. 1 shows a flow curve (solid line) and a DSC curve (broken line) of sample S1 (P (3HB) homopolymer) by a flow tester heating method.
  • FIG. 2 shows a flow curve (solid line) and a DSC curve (broken line) of sample
  • FIG. 5 shows a flow curve (solid line) and a DSC curve (broken line) of sample S4 (P (3HB-co-13.1 mol% 4HB)) by the flow tester heating method. The extrapolation melting end temperature of sample S4 and the temperature at which the DSC curve returns to the baseline are shown.
  • FIG. 6 shows a flow curve (solid line) and a DSC curve (broken line) of sample S5 (P (3HB-co-13.1 mol% 4HB)) by the flow tester heating method. The extrapolation melting end temperature of sample S5 and the temperature at which the DSC curve returns to the baseline are shown.
  • FIG. 6 shows a flow curve (solid line) and a DSC curve (broken line) of sample S5 (P (3HB-co-13.1 mol% 4HB)) by the flow tester heating method. The extrapolation melting end temperature of sample S5 and the temperature at which the DSC curve returns to the baseline are shown.
  • FIG. 7 shows a flow curve (solid line) and a DSC curve (broken line) of sample S6 (P (3HB-co-13.1 mol% 4HB)) by the flow tester heating method.
  • the extrapolation melting end temperature of sample S6 and the temperature at which the DSC curve returns to the baseline are shown.
  • FIG. 8 shows the superposition of the DSC curves of the sample S4 (solid line), the sample S5 (broken line), the sample S6 (dashed line), and the sample S7 (rough dashed line).
  • FIG. 9 shows a flow curve (solid line) and a DSC curve (broken line) of sample S8 (P (3HB-co-61.5 mol% 3HV)) by the flow tester heating method.
  • FIG. 10 shows a flow curve (solid line) and a DSC curve (broken line) of sample S9 (P (3HB-co-61.5 mol% 3HV)) by the flow tester heating method.
  • FIG. 11 shows a flow curve (solid line) and a DSC curve (broken line) of the sample S10 (P (3HB-co-61.5 mol% 3HV)) by the flow tester heating method.
  • FIG. 12 shows the superposition of the DSC curves of the sample S8 (solid line), the sample S9 (broken line), and the sample S10 (rough broken line).
  • FIG. 13 shows changes in the DSC curve for various pretreatments of sample S11.
  • FIG. 14 shows the change in the DSC curve with respect to the in-liquid heat treatment of the sample S11.
  • the method for producing a polymer molded product according to the present invention comprises heat-treating crystalline polyhydroxyalkanoate (PHA) at a temperature above the glass transition point; and lamella crystals having different lamella thicknesses obtained by the above heat treatment.
  • PHA crystalline polyhydroxyalkanoate
  • Polyhydroxyalkanoates include melt molding in a temperature range in which some lamella crystals are melted and fluidized, and the rest of the lamella crystals remain unmelted.
  • the crystalline polyhydroxy alkanoate is heat-treated at a temperature equal to or higher than the glass transition point.
  • the thickness of the lamella crystals can be reconstructed, thereby expanding the temperature range that can be used for melt molding.
  • the solid which is as hard as crystals and has no fluidity at low temperatures, rapidly decreases in rigidity and viscosity in a narrow temperature range and increases in fluidity. This temperature is the glass transition point.
  • the heating temperature is preferably in a temperature range in which the crystalline polyhydroxy alkanoate is above the glass transition point and does not melt all the crystals, and generally, the crystalline polyhydroxy alkanoate is 20 from the glass transition point.
  • the heat treatment can be performed at a temperature higher by about 170 ° C. (preferably a temperature higher by 40 to 120 ° C.).
  • the heating time is not particularly limited, but in general, heating can be performed for 1 hour to 72 hours, preferably 6 hours to 48 hours, and more preferably 12 hours to 36 hours.
  • the means of heat treatment is not particularly limited, and the heat treatment may be any of gas, liquid, or solid-mediated heat treatment.
  • Gas-mediated heat treatment refers to heat treatment of crystalline polyhydroxy alkanoates in gas.
  • gas examples include air and an inert gas (nitrogen, etc.).
  • Liquid-mediated heat treatment refers to heat treatment of crystalline polyhydroxyalkanoates in a liquid.
  • the liquid include water, lower alcohols (methanol, ethanol, etc.), polyhydric alcohols (glycerin, propylene glycol, etc.), organic solvents such as hexane, acetone, and mixtures thereof.
  • the polyhydroxyalkanoates are not completely dissolved in the liquid in the heated state.
  • the heat treatment mediated by a solid means, for example, a heat treatment in which a crystalline polyhydroxyalkanoate is brought into contact with a solid medium (for example, a plate or the like).
  • a solid medium for example, a plate or the like.
  • the solid include metals (aluminum, copper, silver, iron, stainless steel, etc.), ceramics, glass, and the like.
  • a polyhydroxy alkanoate Homopolymers of hydroxyalkanoic acid (eg, poly 3-hydroxypropionic acid, poly 3-hydroxybutyric acid, poly 3-hydroxyvaleric acid, poly 4-hydroxybutyric acid, poly 3-hydroxyhexanoic acid, poly 3-hydroxyoctanoic acid, poly 4-Hydroxyvaleric acid, poly4-hydroxyhexanoic acid, poly5-hydroxyvaleric acid, poly2-hydroxybutyric acid, poly2-hydroxyvaleric acid, poly2-hydroxyhexanoic acid, etc.); Copolymers of hydroxyalkanoic acid (eg, copolymers of 3-hydroxypropionic acid and 3-hydroxybutyric acid, copolymers of 3-hydroxypropionic acid and 3-hydroxyvaleric acid, copolymers of 3-hydroxypropionic acid and 4-hydroxybutyric acid, 3- Copolymer of hydroxypropionic acid and 3-hydroxyhexanoic acid, copolymer of 3-
  • polyhydroxyalkanoate may be used alone, or two or more types may be used in combination.
  • a highly crystalline continuous monomer is used to form a polymer structure of crystalline segments such as lamella crystals, tufted micelle structures, spherical crystals, dendrites, shishikabab structures, and stretched chain crystals.
  • Unit chains such as 3-hydroxypropionic acid chain, 3-hydroxybutyric acid chain, 3-hydroxyvaleric acid chain, 4-hydroxybutyric acid chain, 3-hydroxyhexanoic acid chain, 3-hydroxyhexanoic acid chain.
  • 3-Hydroxyoctanoic acid chain 4-hydroxyvaleric acid chain, 4-hydroxyhexanoic acid chain, 5-hydroxyvaleric acid chain, 2-hydroxybutyric acid chain, 2-hydroxyvaleric acid chain, 2- It is desirable that a chain structure sufficient to form a crystalline microstructure, such as a chain of hydroxyhexanoic acid, repeatedly exists in the polymer chain.
  • a stereoisomer or an optical isomer is present as a monomer unit, a crystalline segment consisting of a chain made of the same stereoisomer is required, for example, a chain of R-3-hydroxybutyric acid, S-3-.
  • the same stereoisomers such as hydroxybutyric acid chain, R-3-hydroxyvaleric acid chain, S-3-hydroxyvaleric acid chain, R-3-hydroxyhexanoic acid chain, S-3-hydroxyhexanoic acid chain, etc.
  • the chain structure of is an important factor for constructing the crystal structure. In the case of a polyhydroxyalkanoate containing a monomer unit in which a stereoisomer or an optical isomer is present, the crystallinity is lowered and it becomes difficult to obtain a crystalline segment.
  • a binary copolymer or a ternary copolymer having a chain of R-3-hydroxybutyric acid and incorporating other monomer units as a second component is used.
  • the above copolymer is more preferable.
  • the polyhydroxy alkanoate may be produced by either a chemical synthesis method or a biosynthetic method, but in order to secure a crystalline segment due to a chain structure, for example, when a monomer unit having a steric isomer is contained, for example.
  • a copolymer composed of either stereoisomer such as a copolymer of R-3-hydroxybutyric acid and 4-hydroxybutyric acid, or a copolymer of S-3-hydroxybutyric acid and 4-hydroxybutyric acid. Is desirable.
  • the ratio of 4-hydroxybutyric acid units to the total monomer units is preferably 5 mol% or more and 40 mol% or less.
  • the ratio of 4-hydroxybutyric acid units to all monomer units is 6 mol% or more, 7 mol% or more, 8 mol% or more, 9 mol% or more, 10 mol% or more, 11 mol% or more, 12 mol% or more, 13 mol. % Or more, 14 mol% or more, 15 mol% or more, or 16 mol% or more, 17 mol% or more, 18 mol% or more, 19 mol% or more, 20 mol% or more.
  • the ratio of 4-hydroxybutyric acid units to all monomer units is 35 mol% or less, 34 mol% or less, 33 mol% or less, 32 mol% or less, 31 mol% or less, 30 mol% or less, 29 mol% or less, 28 mol. % Or less, 27 mol% or less, 26 mol% or less, 25 mol% or less, 24 mol% or less, 23 mol% or less, 22 mol% or less, or 21 mol% or less.
  • the ratio of 3-hydroxyvaleric acid unit to the total monomer unit is preferably 5 mol% or more and 90 mol% or less.
  • the ratio of 3-hydroxyvaleric acid units to all monomer units is 5 mol% or more, 6 mol% or more, 7 mol% or more, 8 mol% or more, 9 mol% or more, 10 mol% or more, 15 mol% or more, 20. It may be mol% or more, 25 mol% or more, 30 mol% or more, 35 mol% or more, or 40 mol% or more, and may be 45 mol% or more, 50 mol% or more, 55 mol% or more, 60 mol% or more.
  • the ratio of 3-hydroxyvalerate units to all monomer units may be 90 mol% or less, 85 mol% or less, 80 mol% or less, 75 mol% or less, 70 mol% or less, 65 mol% or less.
  • the weight average molecular weight measured by polystyrene conversion gel permeation chromatography is preferably 100,000 or more, more preferably 200,000 or more, and further may be 300,000 or more, 400,000 or more, or 500,000 or more. ..
  • the weight average molecular weight measured by polystyrene conversion gel permeation chromatography is 600,000 or more, 700,000 or more, 800,000 or more, 900,000 or more, 1 million or more, 1.1 million or more, 1.2 million or more, 1.3 million or more, 1.4 million or more, 150. It may be 10,000 or more, 2 million or more, 3 million or more, or 4 million or more.
  • the upper limit of the weight average molecular weight measured by polystyrene conversion gel permeation chromatography is not particularly limited, but is generally 20 million or less, 10 million or less, 8 million or less, 7 million or less, 6 million or less, 5 million or less, It may be 4 million or less, or 3 million or less.
  • the weight average molecular weight by polystyrene conversion gel permeation chromatography measurement is 400,000 or more and 2.5 million or less, considering that the molecular weight decreases due to thermal decomposition and the viscosity at the time of melting does not become too high. It is more preferably 500,000 or more and 2.2 million or less, and further preferably 600,000 or more and 2 million or less.
  • the molecular weight of the polymer used may be lower than that at the time of melt molding from the viewpoint that the decrease in molecular weight due to thermal decomposition is easily suppressed, and the weight average molecular weight measured by polystyrene-equivalent gel permeation chromatography is 200,000 or more and 2.5 million or less. It is desirable, more preferably 400,000 or more and 2 million or less, and further preferably 600,000 or more and 1.5 million or less.
  • the polymer of the present invention may be a random polymer, a block polymer, an alternating polymer, or a graft polymer, but is preferably a random polymer.
  • the polyhydroxy alkanoate may be a thermoplastic resin.
  • the polyhydroxy alkanoate is preferably a biodegradable polymer, more preferably a bioabsorbable polymer.
  • Biodegradability means that it can be degraded by microorganisms or enzymes in the natural environment (eg soil, compost, lakes, seawater, etc.) or can be degraded in vivo to non-toxic components.
  • Bioabsorbability means that it can be metabolized by a living body such as a human or an animal.
  • the melting point of the polyhydroxy alkanoate is not particularly limited, but is preferably 180 ° C. or lower, more preferably 175 ° C. or lower (or less than 175 ° C.), and further preferably 170 ° C. or lower.
  • the melting point of the polyhydroxy alkanoate may be 160 ° C. or lower, 150 ° C. or lower, 140 ° C. or lower, or 130 ° C. or lower.
  • the lower limit of the melting point of the polyhydroxy alkanoate is not particularly limited, but is generally 40 ° C. or higher, 50 ° C. or higher, 60 ° C. or higher, 70 ° C. or higher, 80 ° C. or higher, 90 ° C. or higher, or 100 ° C. or higher. good.
  • the melting point of the main component may be within the above range.
  • the fluidity of the crystalline polyhydroxyalkanoate is equal to or higher than the outflow start temperature measured by the flow tester heating method, and the crystal melting measured by the differential scanning calorimeter (DSC) is completely completed.
  • DSC differential scanning calorimeter
  • the "temperature indicating that the crystal melting measured by the differential scanning calorimeter (DSC) is completely completed” is preferably the extrapolation melting end temperature of the melting peak.
  • the extrapolation melting end temperature of the melting peak can be determined as described in the examples below. That is, when the melting peak is sharp, it conforms to JIS-K7121, and the external melting end temperature of the melting peak is the intersection of the tangent line drawn at the point of the maximum slope before the peak end and the baseline after the peak. Temperature (recognized by Rigaku, Thermo plus EVO software). When a plurality of melting peak shapes overlap, the tangent line is manually redrawn for the peak on the higher temperature side, and the intersection with the baseline is set as the extrapolation melting end temperature.
  • melt molding is generally performed by melting at a temperature higher than the melting point such as melting point + 20 ° C., melting point + 10 ° C., melting point + 5 ° C., and then molding.
  • a temperature higher than the melting point such as melting point + 20 ° C., melting point + 10 ° C., melting point + 5 ° C.
  • the temperature of melting in the partially melted state is lower than that of complete melting, not only the thermal decomposition of the polymer but also the molecular chain of polyhydroxyalkanoate in which a small amount of water is involved in the heated state is involved. Since it is presumed that hydrolysis can also be reduced, it is generally desirable that the water content of the raw material is low, but the need to reduce and maintain the weight so as to have a particularly low concentration is reduced. It is also expected that this will eliminate the need for special equipment for strictly maintaining the dry state of the dry raw material polyhydroxyalkanoate, which causes moisture in the atmosphere to transfer to the raw material polymer in spinning and molding equipment. Will be done.
  • the present invention improves the molding processability of polyester having slow melt crystallization and improves productivity without adding a crystal nucleating agent, it does not prevent the use of the crystal nucleating agent.
  • the method of the present invention is the temperature at which crystals and amorphous regions, including relatively thin lamella crystals composed of 3HB segments inside the polymer, begin to melt and fluidize when P (3HB-co-4HB) is melted. Therefore, it is characterized by including a step of melt-extruding during a temperature at which a relatively thick lamella crystal composed of 3HB segments melts.
  • the present invention relates to a method for producing a biodegradable polyester molded product, which is characterized in that it can be molded without waiting for formation.
  • the poor molding processability of crystalline thermoplastic polyhydroxyalkanoate which has a slow crystallization, can be improved, and unlike the case of complete melting, molding can be performed immediately after partial melting without waiting for the formation of primary crystal nuclei, resulting in high productivity. improves.
  • the undissolved lamella crystals are oriented, the amorphous polymer chains are highly oriented, and the monomer is easy to form crystals. Unit continuous segments gather to promote crystallization.
  • the decrease in molecular weight due to thermal decomposition is suppressed, which leads to the maintenance of the molecular weight of the molded product, that is, the prevention of deterioration due to heat.
  • the temperature can be lowered by partial melt molding, so water that involves heat and moisture is more involved than complete melt molding.
  • the degree of decomposition can also be reduced, and the decrease in the molecular weight of polyhydroxyalkanoate is suppressed, leading to the maintenance of the molecular weight of the molded product.
  • polyhydroxyalkanoate is melt-molded.
  • an additive may be further added as long as the effect of the present invention is not impaired.
  • Additives include antioxidants, heat stabilizers (eg, hindered phenols, hydroquinones, phosphites and their substitutes, etc.), UV absorbers (eg, resorcinol, salicylate), anticolorants (phosphoric acid, etc.).
  • the method of blending the additive with the polyhydroxy alkanoate is not particularly limited, and examples thereof include dry blending, solution blending, and addition of the polyhydroxy alkanoate during chemical polymerization.
  • the polyhydroxy alkanoate can perform known melt molding such as injection molding, injection compression molding, compression molding, extrusion molding (melt extrusion molding), blow molding, press molding, and spinning (melt extrusion spinning).
  • melt molding such as injection molding, injection compression molding, compression molding, extrusion molding (melt extrusion molding), blow molding, press molding, and spinning (melt extrusion spinning).
  • the number of times of melt molding is not particularly limited, but preferably it can be performed only once.
  • the step of solidifying after molding can be performed in a molding die, in a gas (for example, air, nitrogen, etc.), or in a liquid (for example, water, alcohol, glycerin, or a mixture thereof). That is, the polyhydroxyalkanoate partially melted by the method of the present invention can be solidified by cooling in a molding die, a gas or a liquid.
  • the partially melted polyhydroxyalkanoate can be cooled in a molding die, in air or in water. More preferably, the partially melted polyhydroxyalkanoate can be cooled in a molding die or in the air.
  • Examples of the polyhydroxyalkanoate molded product manufactured by the method of the present invention include various films such as injection molded products, extrusion molded products, press molded products, sheets, pipes, unstretched films, uniaxially stretched films, and biaxially stretched films. Examples thereof include various fibers such as undrawn yarn and super drawn yarn.
  • the polymer molded product produced by the method of the present invention may be a tube-shaped product or a product other than the tube-shaped product.
  • P (3HB) poly 3-hydroxybutyric acid
  • Biogreen Mw 940,000, melting point about 175 ° C., glass transition point about 2 ° C.
  • the P (3HB-co-4HB) copolymer can be produced by a culture method according to the method described in WO2019 / 044837.
  • P (3HB-co-4HB) copolymers having various 4HB ratios can be produced by appropriately changing the type of carbon source used and the supply ratio.
  • P (3HB-co-61.5 mol% 3HV) was produced by a culture method according to the method described in JP-A No. 01-069622.
  • a method for extracting PHA from cells is extracted using a halogenated hydrocarbon solvent such as chloroform, and a solvent extraction method is used in which precipitation is performed with a poor solvent such as hexane or methanol.
  • aqueous-based extraction method may be used as described in Tokushu Kohei 04-061638, JP-A-07-177894, and WO2004209266.
  • the PHA molecular weight was measured by the gel permeation chromatography method as follows. Chloroform was added so that the PHA was about 0.5 mg / ml, and the mixture was dissolved at 60 ° C. for 4 hours, then returned to room temperature and filtered through a PTFE filter having a pore size of 0.2 ⁇ m to remove insoluble matters, and used as a measurement sample. ..
  • the GPC conditions are as follows.
  • PHA is measured using a flow tester CFT-500D (Capillary Rheometer Flowtester, manufactured by Shimadzu Corporation) or CFT-500EX (manufactured by Shimadzu Corporation).
  • the amount of the sample used for the measurement is about 1.2 g of PHA in the form of pellets, powder, film, etc., and is filled in a cylinder for measurement.
  • a powdery polymer When a powdery polymer is used, it may be molded using an appropriate granulator or press and filled in a cylinder.
  • a die with a diameter of 1.0 mm and a thickness of 1.0 mm, apply an extrusion load of 5 kg, and preheat at an initial set temperature of 30 ° C to 140 ° C (appropriately selected according to the type and melting point of the polymer).
  • the stroke length (mm) and the temperature curve when the temperature is raised to 130 to 260 ° C. (appropriately selected according to the type and melting point of the polymer) at a rate of 3 ° C./min are obtained.
  • the PHA heats up and the polymer begins to flow out of the die.
  • the temperature at this time is defined as the outflow start temperature.
  • ⁇ Measurement of melting behavior of PHA Measurement of thermal properties by differential scanning calorimeter (DSC)> The melting behavior of PHA was measured using a differential scanning calorimeter (Rigaku, Thermo plus EVO DSC8230). The measurement atmosphere was nitrogen (30 ml / min), and the temperature was raised from 30 ° C to 130 to 260 ° C (appropriately selected according to the type and melting point of PHA) at 20 ° C / min. The sample was around 1 mg, and an aluminum sample pan was used. Indium was used for temperature calibration.
  • the melting peak is sharp, it conforms to JIS-K7121, and the external melting end temperature of the melting peak is the temperature of the intersection of the tangent line drawn at the point of maximum slope before the peak end and the baseline after the peak. (Recognized by Rigaku, Thermo plus EVO software), but if multiple melting peak shapes overlap, manually redraw the tangent to the higher temperature peak and remove the intersection with the baseline. The melting end temperature was used.
  • the glass transition point (Tg) of each sample was measured under a nitrogen atmosphere (20 mL / min) using a differential scanning calorimetry (DSC) model: DSC 8500 (PerkinElme, USA) equipped with an intracooler. 1 st the run is heated from 50 ° C. to 200 ° C. at a heating rate of 10 ° C. / min, were isothermally for 1 minute at 200 ° C. to melt the sample. Then, rapidly cooled to -50 ° C. at 200 ° C. / min, after 1 minute isothermal treatment at -50 ° C., the temperature was raised from -50 ° C. to 200 ° C. at 10 ° C. / min, to measure a T g in 2 nd the run ..
  • the sample pan was made of aluminum. Indium was used for temperature calibration.
  • the aqueous purified P (3HB) powder was used as sample S1.
  • the Mw of sample S1 was 940,000.
  • Sample S1 was analyzed by CFT (Capillary Flowtester) and DSC.
  • the CFT outflow start temperature was 181.0 ° C.
  • the width of the crystal melting peak by DSC was about 140 to 189 ° C.
  • the apex of the crystal melting peak was 175.0 ° C.
  • the DSC extrapolation melting end temperature was 179.5 ° C.
  • the temperature at which the melting point peak reached the baseline was 188.7 ° C. It was found that the DSC extrapolation melting end temperature was lower than the CFT outflow start temperature, and the outflow did not occur unless it was in a completely melted state.
  • FIG. 1 shows the measurement results of CFT and DSC.
  • the temperature at which the melting point peak reaches the baseline is higher than the CFT outflow start temperature, and if attention is paid to this, it is possible to consider that the sample S1 can be partially melted in terms of measured values, but it is a polymer.
  • the molten state can be affected not only by the temperature but also by other factors such as the heating time, and if the pressure at the time of melt extrusion is high, partial melt extrusion becomes easier, so there are points to consider, so CFT.
  • the temperature from the outflow start temperature to the DSC external melting end temperature is shown in the table as the partial melt extrudable temperature.
  • Example 1 P (3HB) powder, 70 ° C. water bath heat treatment sample S2
  • the P (3HB) powder of the water-purified sample S1 was immersed in water, treated with a hot bath at 70 ° C. for 24 hours, and then vacuum dried to obtain sample S2.
  • the Mw of sample S2 was 940,000.
  • Sample S2 was analyzed by CFT and DSC.
  • the CFT outflow start temperature was 178.6 ° C.
  • the width of the crystal melting peak by DSC was about 140 to 188 ° C.
  • the apex of the crystal melting peak was 175.1 ° C.
  • the DSC external melting end temperature was 182.0 ° C.
  • the temperature at which the melting point peak reached the baseline was 188.0 ° C.
  • the DSC external melting end temperature is higher than the CFT outflow start temperature, and it is possible to flow out in a partially melted state, but the CFT outflow start temperature and the DSC external melting end temperature are in the same temperature range (temperature difference 3.4 ° C). Therefore, it seems that strict temperature control is required for molding in a substantially partially melted state.
  • FIG. 2 shows the measurement results of CFT and DSC.
  • Example 2 P (3HB) powder, 70 ° C. dry heat treatment sample S3
  • the P (3HB) powder of the aqueous-purified sample S1 was dry-heat-treated in a dry-heat oven at 70 ° C. for 24 hours, and then returned to room temperature to obtain sample S3.
  • the Mw of sample S3 was 940,000.
  • the CFT outflow start temperature was 178.6 ° C.
  • the width of the crystal melting peak by DSC was about 140 to 187 ° C.
  • the apex of the crystal melting peak was 174.9 ° C
  • the DSC extrapolation melting end temperature was 180.5 ° C
  • the temperature at which the melting point peak reached the baseline was 186.9 ° C.
  • the DSC external melting end temperature is higher than the CFT outflow start temperature, and it is possible to flow out in a partially melted state, but the CFT outflow start temperature and the DSC external melting end temperature are in the same temperature range (temperature difference 1.9 ° C). Therefore, it seems that strict temperature control is required for molding in a substantially partially melted state.
  • FIG. 3 shows the measurement results of CFT and DSC.
  • FIG. 4 shows the superposition of the DSC curves of Sample S1, Sample S2, and Sample S3 of Comparative Example 1, Example 1, and Example 2.
  • P (3HB) consists of a highly crystalline (R) -3HB continuous monomer unit chain, and unlike the PHA copolymer, the peak top position of the main melting point peak does not change significantly depending on the presence or absence of heat treatment, and is almost the same. DSC curve.
  • the outflow start temperature of CFT was slightly shifted to the lower temperature side than 181.0 ° C by the water bath / dry heat heat treatment of bulk P (3HB) at 70 ° C (178.6 ° C).
  • sample S4 P (3HB-co-13.1 mol% 4HB) powder
  • sample S4 P (3HB-co-13.1 mol% 4HB) purified by an aqueous system after undergoing an aqueous reaction at 70 ° C. for 35 hours was used as sample S4.
  • the Mw of sample S4 was 1 million, and the glass transition point (Tg) was about -4 ° C.
  • Sample S4 was analyzed by CFT and DSC.
  • the CFT outflow start temperature was 125.1 ° C.
  • the width of the crystal melting peak by DSC was about 49 to 157 ° C.
  • the peaks of the crystal melting peak were 63.7 ° C.
  • FIG. 5 shows the measurement results of CFT and DSC.
  • Melt spinning was performed at 126 ° C., 130 ° C., 135 ° C. as the temperature at which partial melting was possible, and at 150 ° C., 160 ° C., and 170 ° C. as the temperatures at which the material was almost melted.
  • the Mw before melt spinning was 1 million, while the Mw after partial melt spinning at 126 ° C was 950,000 and the Mw after partial melt spinning at 130 ° C was 970,000 and partial melting at 135 ° C.
  • the Mw after spinning was 970,000, the Mw after melting at 150 ° C was 820,000, the Mw after melting at 160 ° C was 650,000, and the Mw after melting at 170 ° C was 540,000. rice field.
  • the residual ratio of the molecular weight Mw after melt spinning at each temperature is 95% at 126 ° C, 97% at 130 ° C, 97% at 135 ° C, and 91 at 140 ° C, assuming that the molecular weight Mw before melt spinning is 100%. %, 82% at 150 ° C and 65% at 160 ° C, whereas it was 53% at 170 ° C, and it was clarified that the ability to spin at a lower temperature is effective in suppressing the decrease in molecular weight. In particular, the suppression of the decrease in molecular weight was remarkable in the partial melting spinning at 135 ° C. or lower, which is clearly not in a completely melted state.
  • sample S5 A sample S4 of water-purified dried P (3HB-co-13.1 mol% 4HB) was again immersed in water, treated with a hot bath at 70 ° C. for 24 hours, and then vacuum dried to obtain a sample S5.
  • the Mw of sample S5 was 1 million.
  • Sample S5 was analyzed by CFT and DSC.
  • the CFT outflow start temperature was 109.8 ° C.
  • the width of the crystal melting peak by DSC was about 88 to 159 ° C.
  • the peaks of the crystal melting peak were 95.0 ° C.
  • the DSC extrapolated melting end temperature was 139.1 ° C., and the temperature at which the melting point peak reached the baseline was 158.5 ° C. It was found that the DSC extrapolation melting end temperature was higher than the CFT outflow start temperature, and partial melt extrusion was possible in the range of 109.8 ° C or higher and lower than 139.8 ° C.
  • FIG. 6 shows the measurement results of CFT and DSC.
  • sample S4 partial melt extrusion was possible in the range of 125.1 ° C or higher and lower than 140.2 ° C, but in sample S5 that had been heat-treated with water at 70 ° C, partial melt extrusion was possible in the range of 109.8 ° C or higher and lower than 139.8 ° C.
  • the temperature range that can be melt-extruded and partially melt-extruded by heat treatment has expanded to the low temperature side by about 15 ° C.
  • sample S6 A sample S4 of water-purified dried P (3HB-co-13.1 mol% 4HB) was dried and heat-treated in an oven at 70 ° C. for 24 hours, and then returned to room temperature to obtain a sample S6.
  • the Mw of sample S6 was 1 million.
  • Sample S6 was analyzed by CFT and DSC. The CFT outflow start temperature was 110.0 ° C., and the width of the crystal melting peak by DSC was about 75 to 160 ° C.
  • the peaks of the crystal melting peak were 81.9 ° C and 119.1 ° C, the DSC extrapolated melting end temperature was 137.8 ° C, and the temperature at which the melting point peak reached the baseline was 158.8 ° C. It was found that the DSC extrapolation melting end temperature was higher than the CFT outflow start temperature, and partial melt extrusion was possible in the range of 110.0 ° C or higher and lower than 137.8 ° C.
  • FIG. 7 shows the measurement results of CFT and DSC.
  • FIG. 8 shows the superposition of the DSC curves of Sample S4, Sample S5, and Sample S6 of Example 3, Example 4, and Example 5. Further, a cast film was prepared by dissolving sample S4 in chloroform, and the DSC curve of the film (sample S7) aged at room temperature for 1 week or longer was also shown. Unlike the DSC curve of P (3HB) shown in FIG. 4, the DSC curve of the P (3HB-co-4HB) copolymer has a large melting peak due to the method of giving its thermal history, dissolution in a solvent, and evaporation of the solvent. The shape of the has changed.
  • sample S4 partial melt extrusion was possible in the range of 125.1 ° C or higher and lower than 140.2 ° C, but in sample S5 that had been heat-treated with water at 70 ° C, partial melt extrusion was possible in the range of 109.8 ° C or higher and lower than 139.8 ° C.
  • Sample S6 that could be melt-extruded and heat-treated at 70 ° C. was partially melt-extruded in the range of 110.0 ° C. or higher and lower than 139.1 ° C.
  • the temperature range that can be partially melt-extruded by heat treatment has expanded to the low temperature side by about 15 ° C.
  • Sample S8 P (3HB-co-61.5 mol% 3HV) purified by solvent extraction precipitation (chloroform extraction-hexane precipitation system) without solvent extraction without heat treatment was used as sample S8.
  • the Mw of sample S8 was 730,000, and the glass transition point (Tg) was about -11 ° C.
  • Sample S8 was analyzed by CFT and DSC.
  • the CFT outflow start temperature was 84.5 ° C.
  • the width of the crystal melting peak by DSC was about 56 to 179 ° C.
  • the apex of the crystal melting peak was 90.5 ° C., and there was also a peak of a small melting peak at 166.3 ° C., which was considered to be derived from a 3HB rich crystal.
  • the DSC external melting end temperature of the main melting peak is 97.5 ° C
  • the DSC external melting end temperature of the melting peak on the high temperature side is 173.2 ° C
  • the temperature at which the melting point peak reaches the baseline is 178.5 ° C. there were. It was found that the DSC extrapolation melting end temperature was higher than the CFT outflow start temperature, and partial melting extrusion was possible in the range of 84.5 or more and less than 173.2 ° C. Even if it is assumed that a component showing a small melting peak on the high temperature side, which is considered to be derived from 3HB rich crystals, is not mixed, the extrapolation melting end temperature of the melting peak on the low temperature side is 97.5 ° C., in which case. It can be seen that partial melt extrusion can be performed in the range of 84.5 ° C or higher and lower than 97.5 ° C.
  • FIG. 9 shows the measurement results of CFT and DSC.
  • Sample S9 Solvent-extracted water 70 ° C. heat treatment Soak P (3HB-co-61.5 mol% 3HV) of sample S8 purified by solvent-extraction precipitation in water and heat-bath at 70 ° C. for 24 hours. , Vacuum dried to obtain sample S9.
  • the Mw of sample S9 was 720,000.
  • Sample S9 was analyzed by CFT and DSC. The CFT outflow start temperature was 80.8 ° C., and the width of the crystal melting peak by DSC was about 49 to 178 ° C. The apex of the crystal melting peak was 90.7 ° C., and at 165.6 ° C., there was a peak of a small melting peak probably derived from a 3HB rich crystal.
  • the DSC external melting end temperature of the main melting peak is 96.9 ° C
  • the DSC external melting end temperature of the melting peak on the high temperature side is 172.6 ° C
  • the temperature at which the melting point peak reaches the baseline is 176.2 ° C. there were. It was found that the DSC extrapolation melting end temperature was higher than the CFT outflow start temperature, and partial melt extrusion was possible in the range of 80.8 ° C or higher and lower than 172.6 ° C. Even if it is assumed that a component showing a small melting peak on the high temperature side, which is considered to be derived from 3HB rich crystals, is not mixed, the extrapolation melting end temperature of the melting peak on the low temperature side is 96.9 ° C., in which case. It can be seen that can be partially melt-extruded in the range of 80.8 ° C or higher and lower than 96.9 ° C.
  • FIG. 10 shows the measurement results of CFT and DSC.
  • Sample S10 Solvent extraction Dry heat 70 ° C. heat treatment P (3HB-co-61.5 mol% 3HV) of sample S8 purified by solvent extraction precipitation is dried and heat-treated again in an oven at 70 ° C. for 24 hours. , The temperature was returned to room temperature to obtain sample S10. The Mw of sample S10 was 730,000. Sample S10 was analyzed by CFT and DSC. The CFT outflow start temperature was 79.8 ° C., and the width of the crystal melting peak by DSC was about 75 to 178 ° C.
  • the apex of the crystal melting peak was 88.9 ° C., and at 167.0 ° C., there was a peak of a small melting peak probably derived from a 3HB rich crystal.
  • the DSC external melting end temperature of the main melting peak is 97.5 ° C
  • the DSC external melting end temperature of the melting peak on the high temperature side is 173.3 ° C
  • the temperature at which the melting point peak reaches the baseline is 177.3 ° C. there were. It was found that the DSC extrapolation melting end temperature was higher than the CFT outflow start temperature, and partial melting extrusion was possible in the range of 79.8 ° C or higher and lower than 173.3 ° C.
  • FIG. 11 shows the measurement results of CFT and DSC.
  • FIG. 12 shows the superposition of the DSC curves of Sample S8, Sample S9, and Sample S10 of Comparative Example 2, Example 6, and Example 7.
  • the DSC curve of the P (3HB-co-3HV) copolymer changed the shape of the melting peak greatly depending on how the thermal history was given.
  • sample S8 partial melt extrusion was possible in the range of 84.5 ° C or higher and lower than 173.2 ° C, but in sample S9 that had been heat-treated with water at 70 ° C, partial melt extrusion was possible in the range of 80.8 ° C or higher and lower than 172.6 ° C.
  • sample S10 which was melt-extruded and heat-treated at 70 ° C., partial melt-extrusion was possible in the range of 79.8 ° C. or higher and lower than 173.3 ° C.
  • the temperature range that can be partially melt-extruded by heat treatment has expanded to the low temperature side by about 5 ° C.
  • sample S11 A water-based purified P (3HB-co-16.0 mol% 4HB) powder having a glass transition point (Tg) of about ⁇ 5 ° C. was used as sample S11.
  • Sample S11 was treated in air at 70 ° C. for 24 hours, 50 ° C. in water for 24 hours, 60 ° C. in water for 24 hours, 70 ° C. in water for 24 hours, 80 ° C. in water, and the PHA heat-treated in water was freeze-dried. Obtained a dry body.
  • Each heat-treated sample was evaluated by DSC, and the DSC curve (thermogram) of the temperature rise first cycle was overwritten in FIG. 13. Further, the same sample S11 was treated in water at 50 ° C.

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