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WO2025177971A1 - Procédé de fabrication de corps moulé - Google Patents

Procédé de fabrication de corps moulé

Info

Publication number
WO2025177971A1
WO2025177971A1 PCT/JP2025/005076 JP2025005076W WO2025177971A1 WO 2025177971 A1 WO2025177971 A1 WO 2025177971A1 JP 2025005076 W JP2025005076 W JP 2025005076W WO 2025177971 A1 WO2025177971 A1 WO 2025177971A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
poly
hydroxyalkanoate
mol
producing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/005076
Other languages
English (en)
Japanese (ja)
Inventor
朋晃 橋口
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kaneka Corp
Original Assignee
Kaneka Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kaneka Corp filed Critical Kaneka Corp
Publication of WO2025177971A1 publication Critical patent/WO2025177971A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—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
    • B29C48/14—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the particular extruding conditions, e.g. in a modified atmosphere or by using vibration
    • 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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/63—Screws having sections without mixing elements or threads, i.e. having cylinder shaped sections
    • 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
    • B29C48/80—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling at the plasticising zone, e.g. by heating cylinders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a method for producing a molded article containing a poly(3-hydroxyalkanoate) resin.
  • Poly(3-hydroxyalkanoate) resins are thermoplastic polyesters that are produced and accumulated as energy storage substances within the cells of many microbial species. They are also biodegradable in soil and seawater, making them attractive as a material that can solve the above problems.
  • poly(3-hydroxyalkanoate) resins have a slow crystallization rate, so after the resin is heated and melted during molding, it takes time for it to crystallize and solidify, posing the issue of low productivity for molded articles produced by melt processing.
  • Patent Document 1 describes how a melt-processable composition with excellent solidification properties can be produced by heating and extruding a poly(3-hydroxybutyrate) resin that exhibits specific melting characteristics within a specific temperature range.
  • Patent Document 2 discloses that the crystallization rate of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) can be increased by blending 0.1 to 20 parts by weight of poly(3-hydroxyalkanoate) with 100 parts by weight of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), which has a melting point 20°C or more higher than that of the resin.
  • the present invention aims to provide a method for producing a molded article containing a poly(3-hydroxyalkanoate) resin that can improve molding speed.
  • molding speed can be improved by melt-kneading a first poly(3-hydroxyalkanoate)-based resin-containing composition, then adding a second poly(3-hydroxyalkanoate)-based resin-containing composition with a higher melting point in an unmolten state to the molten composition, and then maintaining the temperature between the melting points of both compositions before cooling and solidifying, thereby completing the present invention.
  • the present invention provides a method for producing a poly(3-hydroxyalkanoate)-based resin-containing molded article, comprising the steps of: A step of melt-kneading a poly(3-hydroxyalkanoate)-based resin-containing composition (A) having a melting point Tm1; a step of adding a non-molten poly(3-hydroxyalkanoate)-based resin-containing composition (B) having a melting point Tm2 (provided that Tm2 is higher than Tm1) to the molten composition (A) having a composition temperature lower than Tm2, thereby obtaining a poly(3-hydroxyalkanoate)-based resin-containing composition (C); maintaining the temperature of the composition (C) at a temperature equal to or higher than Tm1 and equal to or lower than Tm2; and extruding the composition (C) after the maintaining step, and cooling and solidifying the composition (C) to obtain a molded body.
  • the present invention provides a method for producing molded articles containing poly(3-hydroxyalkanoate) resins that can improve molding speed.
  • the present embodiment relates to a method for producing a poly(3-hydroxyalkanoate)-based resin-containing molded article, which includes the steps of melt-kneading a poly(3-hydroxyalkanoate)-based resin-containing composition (A) having a melting point Tm1, adding a non-molten poly(3-hydroxyalkanoate)-based resin-containing composition (B) having a melting point Tm2 to the molten composition (A) having a composition temperature lower than Tm2 to obtain a poly(3-hydroxyalkanoate)-based resin-containing composition (C), maintaining the temperature of the composition (C) at a temperature of Tm1 or higher and Tm2 or lower, and extruding the composition (C) after the maintaining step, and cooling and solidifying it to obtain a molded article.
  • the poly(3-hydroxyalkanoate) resin which is the main component of the composition
  • R represents an alkyl group represented by C p H 2p+1 , and p represents an integer of 1 to 15.
  • R include linear or branched alkyl groups such as methyl, ethyl, propyl, methylpropyl, butyl, isobutyl, t-butyl, pentyl, and hexyl.
  • p is preferably 1 to 10, and more preferably 1 to 8.
  • poly(3-hydroxyalkanoate) copolymer (a) a poly(3-hydroxyalkanoate) copolymer produced by a microorganism is particularly preferred.
  • a poly(3-hydroxyalkanoate) copolymer produced by a microorganism all of the 3-hydroxyalkanoate units are contained as (R)-3-hydroxyalkanoate units.
  • Poly(3-hydroxyalkanoate) copolymer (a) preferably contains 3-hydroxyalkanoate units (particularly units represented by general formula (1)) in an amount of 50 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more of all structural units (monomer units).
  • Poly(3-hydroxyalkanoate) copolymer (a) may contain only two or more types of 3-hydroxyalkanoate units as structural units of the polymer, or it may contain other units (e.g., 4-hydroxyalkanoate units) in addition to one or more types of 3-hydroxyalkanoate units.
  • the poly(3-hydroxyalkanoate) copolymer (a) preferably contains a copolymer (a1) of 3-hydroxybutyrate units and other hydroxyalkanoate units, in which the content of other hydroxyalkanoate units is 1 to 5 mol %, and a copolymer (a2) of 3-hydroxybutyrate units and other hydroxyalkanoate units, in which the content of other hydroxyalkanoate units is 24 mol % or more.
  • a resin composition can impart a good elastic modulus to molded articles and increase the productivity of molded articles.
  • the copolymer may further contain copolymer (a3) of 3-hydroxybutyrate units and other hydroxyalkanoate units, in which the content of other hydroxyalkanoate units is 6 mol% or more and less than 24 mol%. This makes it easier to achieve better elastic modulus and productivity.
  • copolymer (a1) poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) is preferred, with poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) being more preferred.
  • the content of other hydroxyalkanoate units in copolymer (a2) is 24 mol% or more.
  • the lower limit of this ratio is preferably 26 mol% or more, and more preferably 28 mol% or more.
  • the upper limit of this ratio is preferably 99 mol% or less, more preferably 50 mol% or less, even more preferably 40 mol% or less, and particularly preferably 30 mol% or less.
  • Poly(3-hydroxybutyrate) (b) refers to a homopolymer of 3-hydroxybutyrate, but may contain small amounts of monomer units other than 3-hydroxybutyrate units. Specifically, it is preferable that poly(3-hydroxybutyrate) (b) have an average content of 3-hydroxybutyrate units of more than 99 mol% and not more than 100 mol% out of 100 mol% of all constituent monomer units. The lower limit may be 99.5 mol% or more.
  • the content of poly(3-hydroxybutyrate) (b) may be set as appropriate, but it is preferable that the proportion of poly(3-hydroxybutyrate) (b) be 1% by weight or more and 20% by weight or less out of a total of 100% by weight of poly(3-hydroxyalkanoate) copolymer (a) and poly(3-hydroxybutyrate) (b).
  • a content of 1% by weight or more can increase the solidification rate of the entire poly(3-hydroxyalkanoate) resin, improving the productivity of molded articles.
  • the lower limit of the content is more preferably 3% by weight or more, and even more preferably 5% by weight or more.
  • a content of 20% by weight or less can easily suppress the generation of foreign matter caused by poly(3-hydroxybutyrate) (b).
  • the upper limit is more preferably 15% by weight or less.
  • the P3HA contained in the P3HA-containing composition (C) preferably has an average content of 3-hydroxybutyrate units out of 100 mol% of all constituent monomer units contained in the entire P3HA, of 80 mol% or more and 98.5 mol% or less, more preferably 85 mol% or more and 96 mol% or less, and even more preferably 88 mol% or more and 95 mol% or less, from the viewpoint of achieving both strength and productivity of the molded article.
  • the weight-average molecular weight of the poly(3-hydroxyalkanoate) resin is not particularly limited, but from the perspective of achieving both strength and productivity of the molded body, it is preferably between 200,000 and 2,000,000, more preferably between 250,000 and 1,500,000, and even more preferably between 300,000 and 1,000,000.
  • the weight-average molecular weight of poly(3-hydroxyalkanoate) resin, copolymer (a1), copolymer (a2), copolymer (a3), or poly(3-hydroxybutyrate) (b) can be measured in polystyrene terms using gel permeation chromatography (HPLC GPC system manufactured by Shimadzu Corporation) with a chloroform solution.
  • a column suitable for measuring weight-average molecular weights can be used as the column for gel permeation chromatography.
  • the method for producing poly(3-hydroxyalkanoate) resins is not particularly limited, and may be a chemical synthesis method or a microbial production method. Of these, microbial production methods are preferred. Known methods can be applied to microbial production methods.
  • known bacteria that produce copolymers of 3-hydroxybutyrate and other hydroxyalkanoates include Aeromonas caviae, which produces P3HB3HV and P3HB3HH, and Alcaligenes eutrophus, which produces P3HB4HB.
  • Aeromonas caviae which produces P3HB3HV and P3HB3HH
  • Alcaligenes eutrophus which produces P3HB4HB.
  • P3HB3HH in order to increase the productivity of P3HB3HH, Alcaligenes eutrophus AC32 strain (FERM BP-6038) (T. Fukui, Y.
  • the P3HA-containing composition (C) may contain other resins besides the poly(3-hydroxyalkanoate)-based resin, as long as the effects of the invention are not impaired.
  • other resins include aliphatic polyester-based resins such as polybutylene succinate adipate, polybutylene succinate, polycaprolactone, and polylactic acid, and aliphatic aromatic polyester-based resins such as polybutylene adipate terephthalate, polybutylene sebacate terephthalate, and polybutylene azelate terephthalate. Only one type of other resin may be contained, or two or more types may be contained.
  • the plasticizer is not particularly limited, but from the standpoint of compatibility with poly(3-hydroxyalkanoate) resins, it is preferable to use an ester compound having an ester bond within the molecule.
  • lubricants examples include behenamide, oleamide, erucamide, stearamide, palmitamide, N-stearylbehenamide, N-stearylerucamide, ethylenebisstearamide, ethylenebisoleamide, ethylenebiserucamide, ethylenebislauricamide, ethylenebiscapricamide, p-phenylenebisstearamide, and polycondensates of ethylenediamine, stearic acid, and sebacic acid.
  • behenamide and erucamide are preferred because of their particularly excellent lubricating effect on poly(3-hydroxyalkanoate) resins.
  • the P3HA-containing composition (A) preferably contains at least one or more poly(3-hydroxyalkanoate) copolymers (a). In addition, it may further contain other resins, plasticizers, additives, etc., as described above. It may or may not contain poly(3-hydroxybutyrate) (b).
  • the melt-kneading step and the holding step may be carried out sequentially in separate devices, but since this simplifies the manufacturing method, it is preferable to carry out the steps from melt-kneading of composition (A) to extrusion of composition (C) sequentially in the same extruder. In this case, it is preferable to provide a kneading section in the first half of the extruder to carry out the melt-kneading, and not provide a kneading section in the second half of the extruder to carry out the holding step.
  • the molded article produced by the manufacturing method according to this embodiment is not particularly limited, and may be any of pellets, injection molded articles, extrusion molded articles, blow molded articles, inflation molded articles, fibers, extruded foams, and bead foams. Such molded articles can be obtained at an improved molding speed. The obtained molded article can be further subjected to thermoforming by heating, vacuum molding, press molding, etc.
  • composition (B) was not added to composition (A) in a molten state, but was dry-blended with composition (A) in a non-molten state and then melted. Therefore, the effect of carrying out the holding step was not fully exerted, and the tube molding speed was less than 50 m/min.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Selon l'invention, le procédé de fabrication d'un corps moulé à teneur en résine à base de poly(3-hydroxyalcanoate), inclut : une étape au cours de laquelle une composition à teneur en résine à base de poly(3-hydroxyalcanoate) (A) présentant un point de fusion (Tm1), est malaxée à l'état fondu ; une étape au cours de laquelle une composition à teneur en résine à base de poly(3-hydroxyalcanoate) (B) à l'état non fondu présentant un point de fusion (Tm2) (Tm2 correspond à une température plus élevée que Tm1) est incorporée dans la composition à teneur en résine à base de poly(3-hydroxyalcanoate) (A) dont la température est inférieure à Tm2, et une composition à teneur en résine à base de poly(3-hydroxyalcanoate) (C) est obtenue ; une étape au cours de laquelle la température de la composition (C) est maintenue supérieure ou égale à Tm1 et inférieure ou égale à Tm2 ; et une étape au cours de laquelle la composition (C) après étape de maintien de température, est soumise à une extrusion, et le corps moulé est obtenu par refroidissement et solidification.
PCT/JP2025/005076 2024-02-21 2025-02-17 Procédé de fabrication de corps moulé Pending WO2025177971A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024-024242 2024-02-21
JP2024024242 2024-02-21

Publications (1)

Publication Number Publication Date
WO2025177971A1 true WO2025177971A1 (fr) 2025-08-28

Family

ID=96847145

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2025/005076 Pending WO2025177971A1 (fr) 2024-02-21 2025-02-17 Procédé de fabrication de corps moulé

Country Status (1)

Country Link
WO (1) WO2025177971A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010106272A (ja) * 2008-10-02 2010-05-13 Nitto Denko Corp ポリ乳酸系フィルムまたはシート
CN115157478A (zh) * 2022-09-02 2022-10-11 北京蓝晶微生物科技有限公司 一种可降解材料的造粒加工方法及其制备的成型体

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010106272A (ja) * 2008-10-02 2010-05-13 Nitto Denko Corp ポリ乳酸系フィルムまたはシート
CN115157478A (zh) * 2022-09-02 2022-10-11 北京蓝晶微生物科技有限公司 一种可降解材料的造粒加工方法及其制备的成型体

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