WO2023140096A1 - 変性された脂肪族ポリエステル系樹脂、及び、その組成物又は成形体 - Google Patents

変性された脂肪族ポリエステル系樹脂、及び、その組成物又は成形体 Download PDF

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WO2023140096A1
WO2023140096A1 PCT/JP2022/048664 JP2022048664W WO2023140096A1 WO 2023140096 A1 WO2023140096 A1 WO 2023140096A1 JP 2022048664 W JP2022048664 W JP 2022048664W WO 2023140096 A1 WO2023140096 A1 WO 2023140096A1
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aliphatic polyester
polyester resin
peroxide
weight
poly
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Ceased
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PCT/JP2022/048664
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English (en)
French (fr)
Japanese (ja)
Inventor
武宣 砂川
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Kaneka Corp
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Kaneka Corp
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Priority to EP22922246.8A priority Critical patent/EP4467589A4/en
Priority to US18/725,907 priority patent/US20250066538A1/en
Priority to JP2023575179A priority patent/JPWO2023140096A1/ja
Priority to CN202280088730.4A priority patent/CN118556095A/zh
Publication of WO2023140096A1 publication Critical patent/WO2023140096A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • 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
    • 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
    • C08G63/91—Polymers modified by chemical after-treatment
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/54—Aqueous solutions or dispersions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the present invention relates to a modified aliphatic polyester-based resin containing a poly(3-hydroxyalkanoate)-based resin, and a composition or molded article containing the resin.
  • plastic waste has become a cause of burden on the global environment, such as the impact on the ecosystem, the generation of toxic gases when burned, and global warming due to the large amount of combustion heat, and the development of biodegradable plastics is gaining momentum as a material that can solve this problem.
  • biodegradable plastics from the viewpoint of biodegradability and carbon neutrality, biodegradable plastics produced by microorganisms using plant-derived raw materials as carbon sources, especially aliphatic polyester resins, are attracting attention.
  • poly(3-hydroxybutyrate) homopolymer resins poly(3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer resins, poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) copolymer resins, and poly(3-hydroxybutyrate-co-4-hydroxybutyrate) copolymer resins, poly(3-hydroxyalkanoate) resins are attracting attention.
  • the poly(3-hydroxyalkanoate) resin is a biodegradable aliphatic polyester (preferably a polyester containing no aromatic ring), and is a polyhydroxyalkanoate containing a 3-hydroxyalkanoic acid repeating unit represented by the general formula: [-CHR-CH 2 -CO-O-] (wherein R is an alkyl group represented by C n H 2n+1 , and n is an integer of 1 or more and 15 or less) as an essential repeating unit.
  • the poly(3-hydroxyalkanoate)-based resin is also referred to as P3HA.
  • the P3HA preferably contains 50 mol % or more, more preferably 70 mol % or more, of 3-hydroxyalkanoic acid repeating units in all monomer repeating units (100 mol %).
  • the monomer composition ratio is preferably 80 to 99 mol%, more preferably 85 to 97 mol%, of the total monomer repeating units (100 mol%), from the viewpoint of a balance between flexibility and strength.
  • the composition ratio of the 3HB repeating unit is 80 mol % or more, the rigidity of P3HA is further improved, and the degree of crystallinity does not become too low, which tends to facilitate purification.
  • the composition ratio of 3HB repeating units is 99 mol % or less, the flexibility of P3HA tends to be further improved.
  • the monomer composition ratio of P3HA can be measured by gas chromatography or the like (see, for example, International Publication No. 2014/020838).
  • the microorganism that produces P3HA is not particularly limited as long as it has the ability to produce P3HA.
  • Bacillus megaterium which was discovered in 1925, was the first P3HB-producing bacterium.
  • Naturally occurring microorganisms such as Alcaligenes latus are known, in which P3HB accumulates intracellularly.
  • the weight-average molecular weight can be measured by gel permeation chromatography (GPC) ("High Performance Liquid Chromatograph 20A System” manufactured by Shimadzu Corporation), using polystyrene gel ("KG 4A” and "K-806M” manufactured by Showa Denko Co., Ltd.) as a column, using chloroform as a mobile phase, and calculating the molecular weight in terms of polystyrene.
  • GPC gel permeation chromatography
  • the modified aliphatic polyester resin according to this embodiment contains modified P3HA.
  • denatured means that a branched structure is formed in the P3HA molecule.
  • the branched structure can be formed by direct bonding of P3HA molecules through reaction of P3HA with radicals generated by decomposition of peroxides, which will be described later.
  • the drawdown time/melt viscosity ratio of the modified aliphatic polyester resin according to the present embodiment is preferably 2.0 ⁇ 10 ⁇ 2 to 1.0 ⁇ 10 ⁇ 1 (sec/[Pa s]), and more preferably 2.0 ⁇ 10 ⁇ 2 to 8.0 ⁇ 10 ⁇ 2 (sec/[Pa s]).
  • the lower limit may be 2.5 ⁇ 10 ⁇ 2 (sec/[Pa ⁇ s]) or more, or may be 3.0 ⁇ 10 ⁇ 2 (sec/[Pa ⁇ s]) or more.
  • the upper limit may be 7.0 ⁇ 10 ⁇ 2 (sec/[Pa ⁇ s]) or less, or may be 6.0 ⁇ 10 ⁇ 2 (sec/[Pa ⁇ s]) or less.
  • the drawdown time of the modified aliphatic polyester resin according to this embodiment is defined as follows. Drawdown time: The time required for the resin discharged from the orifice to drop 20 cm when measuring the melt viscosity.
  • the drawdown time exhibited by the modified aliphatic polyester resin according to the present embodiment is not particularly limited, but is preferably 30 to 200 (sec), more preferably 35 to 190 (sec), and even more preferably 40 to 180 (sec).
  • the drawdown time is set to 30 to 200 (sec)
  • the modified aliphatic polyester resin can be stably molded under practical processing conditions in various molding methods regardless of the amount used, and the production of a molded body with less foreign matter and excellent surface properties can be realized.
  • the lower limit of the drawdown time may be 50 (sec) or more, or may be 60 (sec) or more.
  • the upper limit may be 150 (sec) or less, or may be 100 (sec) or less.
  • the drawdown time exhibited by the modified aliphatic polyester resin according to the present embodiment can be controlled within the above range by the amount of peroxide added, the conditions during modification, the molecular weight of the P3HA used, etc., when the modified aliphatic polyester resin is produced by a method using a peroxide.
  • Mw weight average molecular weight
  • Mz Z average molecular weight
  • the modified aliphatic polyester resin according to this embodiment can be produced by modifying P3HA in the presence of a peroxide in an aqueous dispersion. In order to denature P3HA efficiently, it is preferable to heat an aqueous dispersion of P3HA containing a peroxide to a temperature suitable for denaturation.
  • the aqueous dispersion of P3HA can be prepared by adding powdered or pelletized P3HA to water.
  • the aqueous dispersion of P3HA may be obtained by culturing P3HA-producing microorganisms to accumulate P3HA in the cells, crushing the cells, and separating the components of the cells.
  • concentration of P3HA in the aqueous dispersion is not particularly limited and can be set as appropriate.
  • the peroxide is preferably a compound having a 1-minute half-life temperature of 200° C. or less, more preferably 170° C. or less, and even more preferably 140° C. or less.
  • the lower limit may be 50°C or higher, 60°C or higher, or 70°C or higher.
  • organic peroxides exhibiting such a one-minute half-life temperature include di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, bis(2-ethylhexyl)peroxydicarbonate, t-butylperoxy 2-ethylhexanoate, t-butylperoxyisobutyrate, and t-hexylperoxy 2-ethylhexanoate.
  • the inorganic peroxide includes, for example, hydrogen peroxide, potassium peroxide, calcium peroxide, sodium peroxide, magnesium peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, etc., considering the heating temperature and time during denaturation.
  • hydrogen peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate are preferable because they are easy to handle and have a decomposition temperature suitable for the heating temperature during denaturation.
  • One type of inorganic peroxide may be used alone, or two or more types may be used in combination.
  • an organic peroxide and an inorganic peroxide may be used in combination.
  • the amount of the peroxide used (based on the pure content of the peroxide) is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, and even more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of P3HA.
  • amount of peroxide used is within such a range, excessive reaction is suppressed, modification proceeds efficiently, and as a result, a modified aliphatic polyester resin in which the generation of high molecular weight components is suppressed can be produced.
  • the amount of the peroxide used (based on the pure content of the peroxide) is preferably 0.4 parts by weight or more, more preferably 0.6 parts by weight or more, still more preferably 0.8 parts by weight or more, and particularly preferably 0.9 parts by weight or more, relative to 100 parts by weight of the P3HA used for modification.
  • the content of the peroxide (pure content) in the aqueous-dispersed peroxide is usually 10 to 65% by weight, preferably 15 to 50% by weight, more preferably 20 to 40% by weight.
  • the peroxide is contained in such an amount, it is possible to obtain an aqueous-dispersed peroxide excellent in long-term stability while suppressing the transportation cost of the aqueous-dispersed peroxide.
  • the surfactant acts as an emulsifier. Inclusion of a surfactant in the aqueous-dispersed peroxide can enhance the dispersibility of the peroxide and enhance the long-term stability of the aqueous-dispersed peroxide.
  • As the surfactant generally known surfactants can be used, but surfactants that are liquid at room temperature are preferred. In particular, anionic surfactants or nonionic surfactants can be preferably used.
  • the specific type of surfactant may be appropriately selected in consideration of the type of peroxide, desired viscosity, and the like. Only one type of surfactant may be used, or two or more types may be used in combination.
  • the content of the surfactant in the aqueous-dispersed peroxide can be appropriately determined in consideration of the type of surfactant, the type and concentration of the peroxide, the storage temperature of the aqueous-dispersed peroxide, and the like.
  • the surfactant is used in such a content, the long-term stability of the aqueous-dispersed peroxide can be ensured while suppressing the effects on various physical properties of the resulting modified aliphatic polyester resin.
  • the surfactant may not be used.
  • the method for producing a modified aliphatic polyester resin described above does not include the process of introducing a foaming agent such as carbon dioxide, hydrocarbon, ether, etc. to foam the aliphatic polyester resin. Therefore, the modified aliphatic polyester resin produced does not substantially contain air bubbles inside the resin.
  • the aliphatic polyester resin composition containing the modified aliphatic polyester resin (A) and the unmodified P3HA (B) preferably exhibits a drawdown time/melt viscosity ratio of 2.0 ⁇ 10 ⁇ 2 to 5.0 ⁇ 10 ⁇ 1 (sec/[Pa ⁇ s]).
  • Drawdown time and melt viscosity values are each determined as described above.
  • the drawdown time/melt viscosity ratio of the resin composition is more preferably 2.0 ⁇ 10 -2 to 1.0 ⁇ 10 -1 (sec/[Pa s]), and more preferably 2.0 ⁇ 10 -2 to 8.0 ⁇ 10 -2 (sec/[Pa s]).
  • the content of the other resin is preferably 250 parts by weight or less, more preferably 100 parts by weight or less, further preferably 50 parts by weight or less, and particularly preferably 20 parts by weight or less, based on a total of 100 parts by weight of the modified aliphatic polyester-based resin (A) and the optional unmodified P3HA (B). Also, it may be 10 parts by weight or less, 5 parts by weight or less, or 1 part by weight or less.
  • the lower limit of the content of the other resin is not particularly limited, and may be 0 parts by weight.
  • plasticizer is not particularly limited, for example, modified glycerin compounds such as glycerin diacetomonolaurate, glycerin diacetomonocaprylate, and glycerin diacetomonodecanoate; adipate compounds such as diethylhexyl adipate, dioctyl adipate, and diisononyl adipate; polyether ester compounds such as polyethylene glycol dibenzoate, polyethylene glycol dicaprylate, and polyethylene glycol diisostearate; and benzoic acid ester compounds.
  • modified glycerin compounds such as glycerin diacetomonolaurate, glycerin diacetomonocaprylate, and glycerin diacetomonodecanoate
  • adipate compounds such as diethylhexyl adipate, dioctyl adipate, and diisononyl adipate
  • PO-4 di-sec-butyl peroxydicarbonate (“Luperox 225” manufactured by Arkema Yoshitomi Co., Ltd., 1 minute half-life temperature; 107° C.)
  • PO-5 An aqueous emulsion of t-butylperoxy 2-ethylhexanoate (“Luperox 26” manufactured by Arkema Yoshitomi Co., Ltd., 1 minute half-life temperature: 130° C.).
  • blow-up ratio film aperture/die lip aperture
  • Example 1 100 parts by weight of P3HA (PHBH-1) and 200 parts by weight of water (including various dilution waters) were added to a 6-necked flask equipped with a stirrer, baffle, reflux condenser, nitrogen inlet, peroxide addition port, and thermometer. After that, 2.0 parts by weight of t-butyl peroxy 2-ethylhexanoate (PO-1) was added as a peroxide over 0.5 hours, and the mixture was stirred at 60°C for 0.5 hours, then heated to 95°C and stirred for 5.5 hours. By spray-drying the aqueous suspension after the reaction, particles of the modified aliphatic polyester resin (A-1) were obtained.
  • P3HA PHBH-1
  • water including various dilution waters
  • FIG. 1 shows GPC charts obtained when GPC measurements were performed for Example 1, Comparative Example 1, and Comparative Example 4.
  • Comparative Example 4 (broken line) for the resin modified by melt kneading in the presence of peroxide shows a lower peak to the left of the maximum peak. The peak is considered to be due to the high-molecular-weight component produced by modification due to melt-kneading.
  • Example 1 solid line
  • Example 1 which relates to the resin modified in the aqueous dispersion
  • the left half of the maximum peak is slightly swollen, but no peak representing a high molecular weight component as in Comparative Example 4 is observed. It is considered that the values of the Z-average molecular weight/weight-average molecular weight ratio in Example 1 and Comparative Example 4 reflect such a difference in peak shape.
  • Example 14 10 parts by weight of the modified aliphatic polyester resin (A-1) obtained in Example 1, 90 parts by weight of PHBH-1 as unmodified P3HA (B), 0.5 parts by weight of lubricant (BA), and 0.5 parts by weight of lubricant (EA) were mixed to prepare a resin composition, and the melt viscosity and drawdown time were evaluated. Inflation film molding was also performed, and the blow-up ratio and foreign matter in the film were evaluated. Table 2 shows the evaluation results.
  • Comparative Example 8 relates to a resin composition that does not contain a modified aliphatic polyester resin and is composed only of unmodified poly(3-hydroxyalkanoate) (B).
  • Comparative Examples 9 to 11 relate to a resin composition containing an aliphatic polyester resin modified by melt kneading in the presence of a peroxide as described in Patent Documents 2 and 3. Although the blow-up ratio is high, the number of foreign substances found in the film was increased compared to Examples 13 to 21 and Comparative Example 8.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2022/048664 2022-01-20 2022-12-28 変性された脂肪族ポリエステル系樹脂、及び、その組成物又は成形体 Ceased WO2023140096A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP22922246.8A EP4467589A4 (en) 2022-01-20 2022-12-28 MODIFIED ALIPHATIC POLYESTER BASED RESIN AND ASSOCIATED MOLDED COMPOSITION OR OBJECT
US18/725,907 US20250066538A1 (en) 2022-01-20 2022-12-28 Modified aliphatic polyester resin and composition or molded article thereof
JP2023575179A JPWO2023140096A1 (https=) 2022-01-20 2022-12-28
CN202280088730.4A CN118556095A (zh) 2022-01-20 2022-12-28 经改性的脂肪族聚酯类树脂、以及其组合物或成型体

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JP2022-007157 2022-01-20

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EP (1) EP4467589A4 (https=)
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WO (1) WO2023140096A1 (https=)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026023582A1 (ja) * 2024-07-24 2026-01-29 株式会社カネカ ポリヒドロキシアルカノエート粉体、その製法及び利用

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6201083B1 (en) 1997-09-18 2001-03-13 Monsanto Company Modified polyhydroxyalkanoates for production of coatings and films
JP2008056851A (ja) * 2006-09-01 2008-03-13 Toyo Seikan Kaisha Ltd 脂肪族ポリエステル樹脂組成物及びその製造方法
US20080182193A1 (en) * 2007-01-25 2008-07-31 Xerox Corporation Polyester emulsion containing crosslinked polyester resin, process, and toner
WO2014020838A1 (ja) 2012-08-03 2014-02-06 株式会社カネカ ポリエステル樹脂組成物および該樹脂組成物を含む成形体
WO2019022008A1 (ja) * 2017-07-24 2019-01-31 株式会社カネカ ポリ（３－ヒドロキシアルカノエート）樹脂組成物
WO2019146555A1 (ja) 2018-01-26 2019-08-01 株式会社カネカ ポリ（３－ヒドロキシアルカノエート）系発泡粒子およびポリ（３－ヒドロキシアルカノエート）系発泡成形体
JP2020122062A (ja) 2019-01-30 2020-08-13 株式会社カネカ ポリ（３−ヒドロキシアルカノエート）樹脂組成物
WO2021002092A1 (ja) 2019-07-02 2021-01-07 株式会社カネカ ポリ（３－ヒドロキシアルカノエート）系発泡粒子およびポリ（３－ヒドロキシアルカノエート）系発泡成形体

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6201083B1 (en) 1997-09-18 2001-03-13 Monsanto Company Modified polyhydroxyalkanoates for production of coatings and films
JP2008056851A (ja) * 2006-09-01 2008-03-13 Toyo Seikan Kaisha Ltd 脂肪族ポリエステル樹脂組成物及びその製造方法
US20080182193A1 (en) * 2007-01-25 2008-07-31 Xerox Corporation Polyester emulsion containing crosslinked polyester resin, process, and toner
WO2014020838A1 (ja) 2012-08-03 2014-02-06 株式会社カネカ ポリエステル樹脂組成物および該樹脂組成物を含む成形体
WO2019022008A1 (ja) * 2017-07-24 2019-01-31 株式会社カネカ ポリ（３－ヒドロキシアルカノエート）樹脂組成物
WO2019146555A1 (ja) 2018-01-26 2019-08-01 株式会社カネカ ポリ（３－ヒドロキシアルカノエート）系発泡粒子およびポリ（３－ヒドロキシアルカノエート）系発泡成形体
JP2020122062A (ja) 2019-01-30 2020-08-13 株式会社カネカ ポリ（３−ヒドロキシアルカノエート）樹脂組成物
WO2021002092A1 (ja) 2019-07-02 2021-01-07 株式会社カネカ ポリ（３－ヒドロキシアルカノエート）系発泡粒子およびポリ（３－ヒドロキシアルカノエート）系発泡成形体

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
See also references of EP4467589A4
T. FUKUIY. DOI, J. BACTERIOL., vol. 179, 1997, pages 4821 - 4830

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026023582A1 (ja) * 2024-07-24 2026-01-29 株式会社カネカ ポリヒドロキシアルカノエート粉体、その製法及び利用

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US20250066538A1 (en) 2025-02-27
CN118556095A (zh) 2024-08-27
EP4467589A1 (en) 2024-11-27

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