WO2015146194A1 - ポリエステル樹脂組成物、並びに該樹脂組成物から形成される成形体およびその製造方法 - Google Patents
ポリエステル樹脂組成物、並びに該樹脂組成物から形成される成形体およびその製造方法 Download PDFInfo
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- WO2015146194A1 WO2015146194A1 PCT/JP2015/001794 JP2015001794W WO2015146194A1 WO 2015146194 A1 WO2015146194 A1 WO 2015146194A1 JP 2015001794 W JP2015001794 W JP 2015001794W WO 2015146194 A1 WO2015146194 A1 WO 2015146194A1
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- polyhydroxyalkanoate
- resin composition
- hydroxybutyrate
- melting point
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
- B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
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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
- B29C48/022—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
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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
- B29C48/30—Extrusion nozzles or dies
- B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
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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
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N15/00—Mutation or genetic engineering; DNA or RNA concerning genetic engineering, vectors, e.g. plasmids, or their isolation, preparation or purification; Use of hosts therefor
- C12N15/09—Recombinant DNA-technology
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/42—Hydroxy-carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/62—Carboxylic acid esters
- C12P7/625—Polyesters of hydroxy carboxylic acids
-
- 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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- 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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
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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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods
Definitions
- the present invention relates to a polyester resin composition, and in particular, a polyester resin composition for applying a biodegradable polyester resin decomposed by the action of microorganisms as various industrial materials, and a molded article formed therefrom. And a manufacturing method thereof.
- plastic waste has been able to solve the problems that have caused a great burden on the global environment, such as impact on the ecosystem, generation of harmful gases during combustion, global warming due to a large amount of combustion heat, Biodegradable plastics are actively developed.
- aliphatic polyester resins have attracted attention as plant-derived plastics, particularly polyhydroxyalkanoate (hereinafter sometimes referred to as PHA) resins, and among PHA resins.
- PHA polyhydroxyalkanoate
- Polymer resins, poly (3-hydroxybutyrate-co-4-hydroxybutyrate) copolymer resins, polylactic acid, and the like are attracting attention.
- Patent Documents 1 to 5 methods of adding polyhydroxybutyrate.
- Patent Document 1 a resin composition is produced by melt-kneading polyhydroxyalkanoate and polyhydroxybutyrate.
- the thermal decomposition of polyhydroxyalkanoate proceeds in a short time. there were. That is, in the method described in Patent Document 1, it is difficult to satisfactorily disperse polyhydroxybutyrate without causing deterioration of the polyhydroxyalkanoate due to heat, and the crystallization promoting effect tends to be insufficient.
- Patent Documents 2 to 5 describe a method of mixing polyhydroxybutyrate previously adjusted to a small particle size with polyhydroxyalkanoate, but there is a technique for reducing the particle size of polyhydroxybutyrate. Since there is a limit, the effect of promoting crystallization is limited as in Patent Document 1, and there is room for improvement.
- the present invention significantly improves the rate of crystallization, which is a disadvantage of polyhydroxyalkanoate, and improves the solidification property in melt molding processing.
- the purpose is to improve the processing speed.
- the inventors of the present invention have a resin composition containing a first polyhydroxyalkanoate and a second polyhydroxyalkanoate having specific thermal characteristics, which is rapidly solidified during molding and has excellent productivity. As a result, the present invention has been completed.
- the present invention is a polyester resin composition containing a first polyhydroxyalkanoate and a second polyhydroxyalkanoate, wherein the melting point of the second polyhydroxyalkanoate is
- the present invention relates to a polyester resin composition characterized by being observed at a temperature lower than the melting point measured with polyhydroxyalkanoate of 2 alone.
- the number of foreign matters in the sheet is 20/100 cm 2 or less.
- the melting point of the second polyhydroxyalkanoate is observed at a temperature 1 to 50 ° C. lower than the melting point measured by the second polyhydroxyalkanoate alone.
- the first polyhydroxyalkanoate and the second polyhydroxyalkanoate are co-produced by one kind of microorganism.
- the second polyhydroxyalkanoate is poly-3-hydroxybutyrate.
- the first polyhydroxyalkanoate is poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate), and poly It is at least one selected from the group consisting of (3-hydroxybutyrate-co-4-hydroxybutyrate).
- the present invention is also a molded body made of the resin composition.
- the present invention is also a method for producing the molded body, characterized by processing the resin composition.
- the speed of crystallization which is a disadvantage of polyhydroxyalkanoate, can be remarkably improved, and the solidification property in the melt molding process can be improved to increase the processing speed.
- the polyester resin composition of the present invention contains at least a first polyhydroxyalkanoate and a second polyhydroxyalkanoate, and is contained in the polyester resin composition when the melting point of the polyester resin composition is measured.
- the melting point of the second polyhydroxyalkanoate is characterized by being observed at a temperature lower than the melting point measured with the second polyhydroxyalkanoate alone.
- the melting point of the second polyhydroxyalkanoate contained in the conventional polyester resin composition is Observed at the same temperature as the melting point measured with two polyhydroxyalkanoates alone. Since the polyester resin composition of the present invention has the above-described characteristics, it has an effect that the solidification at the time of melt molding is quick and the productivity is excellent as compared with the conventional polyester resin composition.
- the second polyhydroxyalkanoate is dispersed in the resin composition of the present invention. Presumed to be derived. That is, the second polyhydroxyalkanoate is dispersed at the molecular level in the first polyhydroxyalkanoate, and the second polyhydroxyalkanoate has not grown to a crystal size enough to form a domain. Possible cause. Since the melting point generally correlates with the crystal size, the second polyhydroxyalkanoate does not grow into a sufficiently large crystal and is dispersed at the molecular level. It is assumed that the melting point of the second polyhydroxyalkanoate in the resin composition is observed at a temperature lower than the melting point measured with the second polyhydroxyalkanoate alone.
- the melting point in the present invention is a melting point measured by a general differential scanning calorimetry (DSC) method. Specifically, using a differential scanning calorimeter, the temperature was increased at a rate of 10 ° C./min, and the obtained endothermic peak was taken as the melting point.
- DSC differential scanning calorimetry
- the first PHA used in the present invention is represented by the formula (2): [—CHR—CH 2 —CO—O—] (wherein R is an alkyl group represented by C n H 2n + 1 , and n is 1 or more and 15). It is an aliphatic polyester containing a repeating unit represented by:
- the first PHA can be produced, for example, by microorganisms such as Alcaligenes eutrophus AC32 strain (J. Bacteriol., 179, 4821 (1997)) in which a PHA synthase gene derived from Aeromonas caviae is introduced into Alcaligenes eutrophus.
- microorganisms such as Alcaligenes eutrophus AC32 strain (J. Bacteriol., 179, 4821 (1997) in which a PHA synthase gene derived from Aeromonas caviae is introduced into Alcaligenes eutrophus.
- the first PHA used in the present invention is preferably at least one selected from microorganism-produced PHA produced from microorganisms.
- the first PHA is preferably a resin composed of 80 mol% or more of 3-hydroxybutyrate, more preferably a resin composed of 85 mol% or more, and is preferably a product produced by microorganisms.
- Specific examples include poly (3-hydroxybutyrate-co-3-hydroxypropionate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate), poly (3-hydroxybutyrate-co- 3-hydroxyvalerate-co-3-hydroxyhexanoate), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), poly (3-hydroxybutyrate-co-3-hydroxyheptanoate) ), Poly (3-hydroxybutyrate-co-3-hydroxyoctanoate), poly (3-hydroxybutyrate-co-3-hydroxynonanoate), poly (3-hydroxybutyrate-co-3-hydroxy) Decanoate), poly (3-hydroxybutyrate-co-3-hydroxyundecanoate), poly (3-hydro Xybutyrate-co-4-hydroxybutyrate) and the like.
- poly (3-hydroxybutyrate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate), poly (3-hydroxybutyrate-co-) 3-hydroxyvalerate-co-3-hydroxyhexanoate), poly (3-hydroxybutyrate-co-3-hydroxyhexanoate), poly (3-hydroxybutyrate-co-4-hydroxybutanoate) can be preferably used.
- the resin is composed of either one or both of (hydroxybutyrate).
- 3-hydroxybutyrate (hereinafter sometimes referred to as 3HB) and a comonomer copolymerized (for example, 3-hydroxyvalerate (hereinafter sometimes referred to as 3HV), 3
- 3HH 3-hydroxyhexanoate
- 4HB 4-hydroxybutyrate
- 3-hydroxybutyrate / comonomer 97/3 to 80/20 (mol% / mol%) is preferable, and 95/5 to 85/15 (mol% / mol%).
- the comonomer ratio is less than 3 mol%, the molding process temperature and the thermal decomposition temperature are close to each other, which may make molding difficult.
- the comonomer ratio exceeds 20 mol%, the crystallization of PHA is delayed, and thus productivity may be deteriorated.
- the said comonomer may be 1 type, 2 or more types can also be used for it. Even when two or more kinds of the comonomers are used, the preferred range of the monomer ratio (3-hydroxybutyrate / comonomer) in the resin is the same as described above.
- the ratio of each monomer in the resin that is the first PHA can be measured by gas chromatography as follows. To about 20 mg of dried PHA, 2 ml of a sulfuric acid / methanol mixture (15/85 (weight ratio)) and 2 ml of chloroform are added and sealed, and heated at 100 ° C. for 140 minutes to obtain the methyl ester of the PHA decomposition product. After cooling, 1.5 g of sodium hydrogen carbonate is added little by little to neutralize it, and the mixture is allowed to stand until the generation of carbon dioxide gas stops. After adding 4 ml of diisopropyl ether and mixing well, the monomer unit composition of the PHA decomposition product in the supernatant is analyzed by capillary gas chromatography to determine the ratio of each monomer in the resin.
- GC-17A manufactured by Shimadzu Corporation was used as the gas chromatograph
- NEUTRA BOND-1 manufactured by GL Science Co., Ltd.
- He is used as the carrier gas
- the column inlet pressure is 100 kPa
- 1 ⁇ l of the sample is injected.
- the temperature is raised from an initial temperature of 100 ° C. to 200 ° C. at a rate of 8 ° C./min, and further from 200 to 290 ° C. at a rate of 30 ° C./min.
- the weight average molecular weight (hereinafter sometimes referred to as Mw) of the first PHA is preferably 200,000 to 2,500,000, more preferably 250,000 to 2,000,000, and even more preferably 300,000 to 1,000,000.
- Mw weight average molecular weight
- mechanical properties and the like may be inferior, and when it exceeds 2.5 million, molding may be difficult.
- the weight average molecular weight was measured using gel permeation chromatography (“Shodex GPC-101” manufactured by Showa Denko KK), using polystyrene gel (“Shodex K-804” manufactured by Showa Denko KK) as the column, and moving chloroform. It can be determined as the molecular weight when converted to polystyrene. At this time, a calibration curve is prepared using polystyrene having a weight average molecular weight of 31400, 197000, 668000, and 1920,000.
- the second polyhydroxyalkanoate is a polyhydroxyalkanoate that acts as a nucleating agent that promotes crystallization of the first polyhydroxyalkanoate, that is, promotes solidification.
- the second polyhydroxyalkanoate is a polyhydroxyalkanoate containing a repeating unit represented by the formula (2), and is a polyhydroxyalkanoate having a structure different from that of the first polyhydroxyalkanoate.
- the content of the second polyhydroxyalkanoate in the present invention is not particularly limited as long as it is less than the first polyhydroxyalkanoate serving as a matrix. It is preferably 1 to 15 parts by weight. The content is more preferably 0.3 to 10 parts by weight, still more preferably 0.5 to 8 parts by weight. If the content of the second polyhydroxyalkanoate is less than 0.1 parts by weight, the effect of promoting crystallization is inferior, and if it exceeds 15 parts by weight, the tensile elongation of the molded product is lowered, and the surface appearance of the molded product is deteriorated. However, the physical properties tend to be low, for example, the transparency of the film is impaired.
- the second polyhydroxyalkanoate is a polyhydroxyalkanoate having a structure different from that of the first polyhydroxyalkanoate.
- the second PHA is preferably a resin composed of 80 mol% or more of 3-hydroxybutyrate, more preferably a resin composed of 85 mol% or more, and is preferably produced by a microorganism.
- poly-3-hydroxybutyrate can be particularly preferably used in terms of promoting crystallization and dispersibility.
- the poly-3-hydroxybutyrate is a resin mainly composed of 3-hydroxybutyrate.
- the term “main unit” means that 97.5 mol% or more, preferably 98 mol% or more, more preferably 98.5 mol% or more of the total monomer units constituting the resin is occupied by 3-hydroxybutyrate. It means that
- the poly-3-hydroxybutyrate in the present invention is most preferably a homopolymer (single resin) comprising 3-hydroxybutyrate units, but is not limited thereto, and mainly 3-hydroxybutyrate units and other hydroxyalkanoates. It may be a resin obtained by copolymerizing ate units.
- hydroxyalkanoate units examples include 3-hydroxypropionate, 3-hydroxyhexanoate, 3-hydroxyvalerate, 3-hydroxycaprolate, 3-hydroxyheptanoate, 3-hydroxy 3-hydroxyalkanoates such as octanoate, ⁇ -fluoro-3-hydroxyheptanoate, ⁇ -fluoro-3-hydroxynonanoate, ⁇ -chloro-3-hydroxyoctanoate; glycolic acid, lactic acid, 2- 2-hydroxyalkanoates such as hydroxybutyrate, 2-hydroxyisobutyrate, 2-hydroxy-2-methylbutyrate, 2-hydroxyvalerate, 2-hydroxycaproate, 2-hydroxy-2-ethylbutyrate ; 4-hydrido such as 4-hydroxybutyrate Carboxymethyl alkanoates; 5- hydroxyvalerate like 5-hydroxyalkanoate and the like.
- the weight average molecular weight of the second polyhydroxyalkanoate is not particularly limited as long as the crystallization of the first polyhydroxyalkanoate can be promoted, but the same range as the weight average molecular weight of the first polyhydroxyalkanoate described above. It is preferable that
- polyester resin composition When the melting point of the polyester resin composition of the present invention is measured, the melting point of the second polyhydroxyalkanoate is observed at a temperature lower than the melting point measured with the second polyhydroxyalkanoate alone.
- the polyester resin composition of the present invention is not particularly limited as long as the melting point of the second polyhydroxyalkanoate in the composition is observed at a temperature lower than the melting point measured by the second polyhydroxyalkanoate alone,
- the melting point of the second polyhydroxyalkanoate in the composition is 1 ° C. to 50 ° C. lower than the melting point measured with the second polyhydroxyalkanoate alone in that it is more excellent in promoting crystallization and appearance of the molded body. It is preferably observed at a temperature lower by 3 ° C. to 45 ° C., more preferably observed at a temperature lower by 5 ° C. to 35 ° C.
- the melting point of the poly-3-hydroxybutyrate measured in the polyester composition of the present invention is 120 ° C. to 169 ° C. ° C is preferable, 125 ° C to 167 ° C is more preferable, and 135 ° C to 165 ° C is still more preferable.
- the melting point in order to reduce measurement errors, it is preferable to obtain a plurality of measurement samples, measure the melting point of each sample, and adopt the average value as the measured value of the melting point.
- first polyhydroxyalkanoate and the second polyhydroxyalkanoate is particularly effective if it can promote crystallization of the first polyhydroxyalkanoate.
- poly-3-hydroxybutyrate, poly (3-hydroxybutyrate-co-4-hydroxybutyrate) / poly-3-hydroxybutyrate is preferred.
- the polyester resin composition of the present invention since the second polyhydroxyalkanoate is well dispersed in the first polyhydroxyalkanoate and its melting point is lowered, the polyester resin composition of the present invention Can be melted at the processing temperature of the first polyhydroxyalkanoate, and the effect of promoting crystallization can be obtained efficiently. Therefore, it is possible to reduce deterioration due to thermal decomposition during melt molding processing, and thereby it is possible to suppress a change with time in mechanical properties that occurs after solidification.
- the second polyhydroxyalkanoate is finely dispersed to such an extent that a molded product with a small number of foreign matters (foreign matters having a large particle diameter) can be obtained.
- the number of foreign matters in the polyester resin composition of the present invention is preferably 20 pieces / 100 cm 2 or less, and more preferably 10 pieces / 100 m 2 or less.
- 10/100 cm 2 is preferable, and 5/100 cm 2 is more preferable in that a molded body having a thickness of less foreign matter and less than 100 ⁇ m can be obtained.
- the number of foreign matters in the present invention is the number of foreign matters having a size of 100 ⁇ m or more observed on the surface of a 100 ⁇ m thick sheet obtained by molding a polyester resin composition.
- polyester resin composition of the present invention it is more preferable that no foreign matter having a size of 1 mm or more is present in the range of about 1,000 cm 2 .
- the foreign material in this application originates in the resin component of a large particle diameter with insufficient mixing or dispersion
- the processing temperature of the first polyhydroxyalkanoate means a temperature at which the first polyhydroxyalkanoate including the melting point of the first polyhydroxyalkanoate can be softened or fluidized to be plasticized.
- the polyester resin composition in the present invention may contain various additives as long as the effects of the present invention are not impaired.
- the additives are, for example, lubricants, crystal nucleating agents, plasticizers, hydrolysis inhibitors, antioxidants, release agents, UV absorbers, dyes, pigments and other colorants, inorganic fillers, and the like. These additives are preferably biodegradable, although they can be used accordingly.
- crystal nucleating agent means what acts as a nucleus when the first polyhydroxyalkanoate is crystallized, and excludes the second polyhydroxyalkanoate.
- additives include inorganic fibers such as carbon fibers and organic fibers such as human hair and wool.
- natural fibers such as bamboo fiber, pulp fiber, kenaf fiber, other similar plant substitute species, Mallow family annual plant, linden annual plant plant and the like can also be used. From the viewpoint of reducing carbon dioxide, plant-derived natural fibers are preferable, and kenaf fibers are particularly preferable.
- a first microorganism is used as the first method in that the second polyhydroxyalkanoate can be satisfactorily dispersed while suppressing thermal degradation without requiring a high-temperature process during production.
- a method in which the polyhydroxyalkanoate and the second polyhydroxyalkanoate are simultaneously produced, that is, co-produced, can be preferably used.
- Such microorganisms only need to have a gene encoding a PHA synthase that synthesizes the first PHA and a gene encoding a PHA synthase that synthesizes the second PHA.
- a microorganism has not been discovered in nature so far, but the host microorganism encodes a gene encoding a PHA synthase that synthesizes the first PHA or a PHA synthase that synthesizes the second PHA.
- Either or both of the genes to be produced can be produced by introducing them using genetic recombination techniques or the like.
- a known gene can be used as a gene to be introduced.
- the microorganism of the present invention has an expression regulation related to its expression upstream of a gene encoding a PHA synthase that synthesizes a first PHA and a gene encoding a PHA synthase that synthesizes a second PHA. It preferably has an “arrangement”.
- the first PHA and the second PHA are simultaneously produced in the cells of the microorganism, and both PHA are recovered from the microorganism, whereby the polyester resin composition of the present invention is obtained. Can be manufactured.
- the resin composition containing the first PHA and the second PHA co-produced from one kind of microorganism the resin composition produced by mixing the conventional first PHA and the second PHA.
- the melting point of the second polyhydroxyalkanoate can be characterized as being observed at a temperature lower than the melting point measured with the second polyhydroxyalkanoate alone.
- polyester resin composition of the present invention recovered from microorganisms may be used for molding as it is, but may be used for molding after adding an additive as necessary, melt-kneading to pelletize.
- a known apparatus such as a Banbury mixer, a roll mill, a kneader, a single-screw or multi-screw extruder is used, and the mixture is mechanically kneaded while heating at an appropriate temperature to be pelletized.
- the temperature at the time of kneading may be adjusted according to the melting temperature of the resin to be used, but in order to obtain the effect of the present invention that promotes crystallization of polyhydroxyalkanoate, the upper limit is about 185 ° C. It is preferable. Therefore, for example, it may be about 100 to 185 ° C., but is preferably 170 ° C. or less.
- the polyester resin composition of the present invention or pellets thereof can be sufficiently dried at 40 to 80 ° C. to remove moisture, and then molded by a known molding method to obtain an arbitrary molded body.
- the molding method include film molding, sheet molding, injection molding, blow molding, fiber spinning, extrusion foaming, and bead foaming.
- Examples of the method for producing a film molded body include T-die extrusion molding, calendar molding, roll molding, and inflation molding.
- the film forming method is not limited to these.
- the molding temperature during film molding is preferably 140 to 190 ° C, more preferably 140 to 170 ° C.
- the film obtained from the polyester resin composition of the present invention can be thermoformed by heating, vacuum formed, and press formed.
- an injection molding method such as an injection molding method, a gas assist molding method, or an injection compression molding method that is generally employed when molding a thermoplastic resin
- an injection molding method such as an injection molding method, a gas assist molding method, or an injection compression molding method that is generally employed when molding a thermoplastic resin
- in-mold molding method gas press molding method, two-color molding method, sandwich molding method, PUSH-PULL, SCORIM, etc. can also be adopted other than the above methods.
- the injection molding method is not limited to these.
- the molding temperature at the time of injection molding is preferably 140 to 190 ° C.
- the mold temperature is preferably 20 to 80 ° C., and more preferably 30 to 70 ° C.
- the molded article of the present invention can be suitably used in agriculture, fishery, forestry, horticulture, medicine, hygiene, food industry, clothing, non-clothing, packaging, automobiles, building materials, and other fields.
- Example 1 Preparation of PHA using KNK005 REP-phaJ4b / ⁇ phaZ1,2,6 / pCUP2-Plac-phaC Re strain (PHB2 wt% product)
- a plasmid for gene replacement was prepared for the purpose of disrupting the phaZ6 gene.
- PCR was performed using the genomic DNA of C. necator H16 strain as a template and the DNAs shown in SEQ ID NO: 1 and SEQ ID NO: 2 as primers.
- KOD-plus Toyobo Co., Ltd.
- PCR was performed using the DNAs shown in SEQ ID NO: 3 and SEQ ID NO: 4 as primers.
- PCR was performed using the two types of DNA fragments obtained by the above PCR as templates and the DNAs shown in SEQ ID NO: 1 and SEQ ID NO: 4 as primers, and the resulting DNA fragments were digested with the restriction enzyme SmiI.
- This DNA fragment was ligated with a DNA fragment obtained by digesting the vector pNS2X-sacB described in JP-A-2007-259708 with SmiI using DNA ligase (Ligation High, manufactured by Toyobo Co., Ltd.), upstream of the phaZ6 structural gene and A gene disruption plasmid pNS2X-phaZ6 (-+) having a downstream DNA sequence was prepared.
- the gene disruption plasmid pNS2X-phaZ6 (-+), in which the gene disruption strain was prepared, was introduced into Escherichia coli S17-1 strain (ATCC47055), KNK005 strain (see US7384766) and Nutrient Agar medium (manufactured by DIFCO) ) The mixed culture was carried out to carry out the joint transmission.
- the KNK005 strain is a strain having the gene encoding the PHA synthase described in SEQ ID NO: 5 as a host and the C. necator H16 strain.
- the KNK005 ⁇ phaZ6 strain is a strain having a full length deletion of the phaZ6 gene on the chromosome and a gene encoding the PHA synthetase described in SEQ ID NO: 5 on the chromosome.
- a plasmid for gene replacement was prepared for the purpose of disrupting the phaZ1 gene.
- PCR was performed using the genomic DNA of the C. necator H16 strain as a template and the DNAs shown in SEQ ID NO: 6 and SEQ ID NO: 7 as primers.
- KOD-plus was used as the polymerase.
- PCR was performed using the DNAs represented by SEQ ID NO: 8 and SEQ ID NO: 9 as primers.
- PCR was performed using the two kinds of DNA fragments obtained by the above PCR as templates and the DNAs shown in SEQ ID NO: 6 and SEQ ID NO: 9 as primers, and the resulting DNA fragments were digested with the restriction enzyme SmiI.
- This DNA fragment is ligated with a DNA fragment obtained by digesting pNS2X-sacB with SmiI using DNA ligase to create a plasmid pNS2X-phaZ1 (-+) for gene disruption having DNA sequences upstream and downstream of the phaZ1 structural gene did.
- KNK005 ⁇ phaZ1,6 strain is a strain having a full-length deletion of the phaZ1 and phaZ6 genes on the chromosome and a gene encoding the PHA synthase described in SEQ ID NO: 5 on the chromosome.
- a plasmid for gene replacement was prepared for the purpose of disrupting the phaZ2 gene.
- PCR was performed using the genomic DNA of the C. necator H16 strain as a template and the DNAs shown in SEQ ID NO: 10 and SEQ ID NO: 11 as primers.
- KOD-plus was used as the polymerase.
- PCR was performed using the DNAs represented by SEQ ID NO: 12 and SEQ ID NO: 13 as primers.
- PCR was performed using the two types of DNA fragments obtained by the above PCR as templates and the DNAs shown in SEQ ID NO: 10 and SEQ ID NO: 13 as primers, and the resulting DNA fragments were digested with the restriction enzyme SmiI.
- This DNA fragment is ligated with a DNA fragment obtained by digesting pNS2X-sacB with SmiI using DNA ligase to create a plasmid pNS2X-phaZ2 (-+) for gene disruption having DNA sequences upstream and downstream of the phaZ2 structural gene did.
- the phaZ2 gene was disrupted using pNS2X-phaZ2 (-+) with the KNK005 ⁇ phaZ1,6 strain as the parent strain.
- the obtained strain was named KNK005 ⁇ phaZ1,2,6 strain.
- the KNK005 ⁇ phaZ1,2,6 strain has a full-length deletion of the phaZ1 and phaZ6 genes on the chromosome, a deletion from the 16th codon to the stop codon of the phaZ2 gene, and PHA synthesis described in SEQ ID NO: 5 on the chromosome.
- an expression regulatory sequence insertion plasmid was prepared for the purpose of inserting an expression regulatory sequence upstream of the phaJ4b gene on the chromosome.
- PCR was performed using the genomic DNA of the C. necator H16 strain as a template and the DNAs shown in SEQ ID NO: 14 and SEQ ID NO: 15 as primers.
- KOD-plus was used as the polymerase.
- PCR was performed using the DNAs represented by SEQ ID NO: 16 and SEQ ID NO: 17 as primers.
- PCR was performed using the DNAs shown in SEQ ID NO: 18 and SEQ ID NO: 19 as primers.
- PCR was performed using the three types of DNA fragments obtained by the above PCR as templates and the DNAs shown in SEQ ID NOs: 14 and 17 as primers, and the resulting fragments were digested with SmiI.
- This DNA fragment was ligated with a DNA fragment obtained by digesting pNS2X-sacB with SmiI using DNA ligase, and a DNA sequence upstream of the phaJ4b structural gene, an expression regulatory sequence described in SEQ ID NO: 20 comprising a phaC1 promoter and a phaC1SD sequence, And a plasmid pNS2X-sacB + phaJ4bU-REP-phaJ4b for DNA insertion having the phaJ4b structural gene sequence.
- an expression regulatory sequence was inserted upstream of the phaJ4b gene using pNS2X-sacB + phaJ4bU-REP-phaJ4b with the KNK005 ⁇ phaZ1,2,6 strain as the parent strain.
- the obtained strain was named KNK005 REP-phaJ4b / ⁇ phaZ1,2,6 strain.
- the KNK005 REP-phaJ4b / ⁇ phaZ1,2,6 strain has a full-length deletion of the phaZ1 and phaZ6 genes on the chromosome, a deletion from the 16th codon to the stop codon of the phaZ2 gene, and a phaC1 gene immediately upstream of the phaJ4b gene.
- a plasmid pCUP2-Plac-phaC Re for production of PHB was prepared for the purpose of co-production of PHBH and PHB by introducing into KNK005 REP-phaJ4b / ⁇ phaZ1,2,6 strain.
- PCR was performed using genomic DNA of C. necator H16 strain as a template, DNAs represented by SEQ ID NO: 21 and SEQ ID NO: 22 as primers, and the resulting DNA fragment was digested with MunI and SpeI.
- KOD-plus was used as the polymerase.
- This DNA fragment was ligated with a DNA fragment obtained by digesting the pCUP2 vector with MunI and SpeI using DNA ligase, an expression regulatory sequence consisting of a phaC1SD sequence, and a plasmid pCUP2-SD- for PHB production having a phaC Re structural gene sequence phaC Re was produced.
- PCR was performed using pCR (R) 2.1-TOPO (R) (manufactured by Invitrogen) as a template, DNAs represented by SEQ ID NO: 23 and SEQ ID NO: 24 as primers, and the resulting DNA fragment was digested with MunI.
- KOD-plus was used as the polymerase.
- This DNA fragment was ligated with a DNA fragment obtained by digesting pCUP2-SD-phaC Re with MunI using DNA ligase, and an expression regulatory sequence described in SEQ ID NO: 25 consisting of a lac promoter and a phaC1SD sequence, and a phaC Re structural gene sequence
- SEQ ID NO: 25 consisting of a lac promoter and a phaC1SD sequence
- phaC Re structural gene sequence A plasmid for PHB production pCUP2-Plac-phaC Re having
- KNK005 REP-phaJ4b / ⁇ phaZ1,2,6 strain was cultured overnight in Nutrient Broth medium.
- 0.5 ml of the obtained culture solution was inoculated into 100 ml of Nutrient Broth medium and cultured at 30 ° C. for 3 hours.
- the obtained culture broth was quickly cooled on ice, and the cells were collected and washed thoroughly with ice-cooled distilled water, and the obtained cells were suspended in 2 ml of distilled water.
- the cell solution was mixed with the plasmid solution and injected into a cuvette for electroporation.
- Electroporation was performed using a MicroPulser electroporator (manufactured by Bio-Rad) under the conditions of a voltage of 1.5 kV, a resistance of 800 ⁇ , and a current of 25 ⁇ F.
- the bacterial cell solution was recovered, 5 ml of Nutrient Broth medium was added, and the mixture was cultured at 30 ° C. for 3 hours.
- the obtained culture broth was applied to a Nutrient Agar medium containing 100 mg / l kanamycin sulfate. After culturing at 30 ° C. for 3 days, a strain into which the plasmid was introduced was obtained from the obtained colonies.
- the obtained strain was named KNK005 REP-phaJ4b / ⁇ phaZ1,2,6 / pCUP2-Plac-phaC Re strain.
- the KNK005 REP-phaJ4b / ⁇ phaZ1,2,6 / pCUP2-Plac-phaC Re strain was cultured as follows.
- composition of the seed medium is 1% (w / v) Meat extract, 1% (w / v) Bacto Trypton, 0.2% (w / v) Yeast extract, 0.9% (w / v) Na 2 PO 4 ⁇ 12H 2 O 0.15% (w / v) KH 2 PO 4 (pH 6.8).
- composition of the preculture medium 1.1% (w / v) Na 2 PO 4 ⁇ 12H 2 O, 0.19% (w / v) KH 2 PO 4, 1.29% (w / v) (NH 4) 2 SO 4, 0.1% (w / v) MgSO 4 ⁇ 7H 2 O, 0.5% (v / v) trace metal salt solution (1.6% (w / v) FeCl 2 ⁇ 6H 2 O in 0.1N hydrochloric acid, 1% (w / v ) CaCl 2 ⁇ 2H 2 O, 0.02% (w / v) CoCl 2 ⁇ 6H 2 O, 0.016% (w / v) CuSO 4 ⁇ 5H 2 O, 0.012% (w / v) NiCl 2 ⁇ 6H 2 O Dissolved).), 5 ⁇ 10 ⁇ 6 % (w / v) kanamycin.
- palm double olein oil was used at a concentration of 2.5%
- composition of the PHA production medium 0.578% (w / v) Na 2 PO 4 ⁇ 12H 2 O, 0.101% (w / v) KH 2 PO 4, 0.437% (w / v) (NH 4) 2 SO 4, 0.15% (w / v) MgSO 4 ⁇ 7H 2 O, 0.75% (v / v) trace metal salt solution (1.6% (w / v) FeCl 2 ⁇ 6H 2 O in 0.1 N hydrochloric acid, 1% (w / v ) CaCl 2 ⁇ 2H 2 O, 0.02% (w / v) CoCl 2 ⁇ 6H 2 O, 0.016% (w / v) CuSO 4 ⁇ 5H 2 O, 0.012% (w / v) NiCl 2 ⁇ 6H 2 O It was melted.
- Carbon source is Palm fatty acid distillate (PFAD; MALAYSIAN BIOTECHNOLOGY CORPORATION SDN BDH. Free fatty acid content 95.0%; Fatty acid composition C12: 0 0.2%, C14: 0 1.2%, C16: 0 47.6%, C16: 1 0.3%, C18: 1 35.7%, C18: 2 9.7%, C18: 3 0.4%, C20: 0 0.4%; melting point 43.8 ° C) emulsified by the following procedure was used.
- PFAD and 450 g of water were weighed and heated to 60 ° C., respectively, and 4.7 g of Na 2 PO 4 .12H 2 O and 2.75 g of sodium caseinate were dissolved in water. After dissolution, it was mixed with PFAD and pre-emulsified with a homomixer (LABORATORY MIXER EMULSIFIER, manufactured by SILVERSON) at a stirring speed of 2500 rpm. Furthermore, this preliminary emulsified liquid was emulsified at a pressure of 10 barr with a high-pressure homogenizer (PAND2K type, manufactured by Niro Soabi) to obtain an emulsion.
- PAND2K type high-pressure homogenizer
- the operating conditions were a culture temperature of 30 ° C., a stirring speed of 500 ⁇ rpm, an aeration rate of 1.8 L / min, and a pH of 6.7 to 6.8 while controlling for 28 hours. A 7% aqueous ammonium hydroxide solution was used for pH control.
- PHA production culture 10 ⁇ L jar fermenter (MDL-1000 model manufactured by Maruhishi Bioengine) containing 2 ⁇ L of PHA production medium was inoculated with 25% (v / v) of the preculture seed.
- the operating conditions were a culture temperature of 32 ° C., a stirring speed of 450 ⁇ rpm, an aeration rate of 3.0 L / min, and a pH controlled between 6.7 and 6.8.
- a 7% aqueous ammonium hydroxide solution was used for pH control.
- the culture was performed for 45 to 54 hours.
- composition 1 The obtained resin composition containing PHBH and PHB was designated as Composition 1.
- Example 2 Preparation of PHA using KNK005 REP-phaJ4b / ⁇ phaZ1,2,6 / pCUP2-PJ4a-phaC Re strain (PHB3.5 wt% product)
- a plasmid pCUP2-PJ4a-phaC Re for production of PHB was prepared for the purpose of co-production of PHBH and PHB by introduction into KNK005 REP-phaJ4b / ⁇ phaZ1,2,6 strain.
- PCR was performed using genomic DNA of C. necator H16 strain as a template and DNAs represented by SEQ ID NO: 26 and SEQ ID NO: 27 as primers. Similarly, PCR was performed using the DNAs represented by SEQ ID NO: 22 and SEQ ID NO: 28 as primers. PCR was performed using the two types of DNA fragments obtained by the above PCR as templates and the DNAs shown in SEQ ID NO: 22 and SEQ ID NO: 26 as primers, and the resulting DNA fragments were digested with MunI and SpeI. As the polymerase, KOD-plus was used.
- This DNA fragment was ligated with a DNA fragment obtained by digesting the pCUP2 vector with MunI and SpeI using DNA ligase, the expression regulatory sequence PJ4a described in SEQ ID NO: 29, and the PHB production plasmid pCUP2- having the phaC Re structural gene sequence PJ4a-phaC Re was prepared.
- Purified PHA was obtained in the same manner as in Example 1 using KNK005 REP-phaJ4b / ⁇ phaZ1,2,6 / pCUP2-PJ4a-phaC Re strain.
- the obtained resin composition containing PHBH and PHB was designated as Composition 2.
- Example 3 Preparation of PHA using KNK005 REP-phaJ4b / ⁇ phaZ1,2,6 / pCUP2-PJ4a-phaC Re strain (PHB6.0 wt% product) Purified PHA was obtained in the same manner as in Example 1 using KNK005 REP-phaJ4b / ⁇ phaZ1,2,6 / pCUP2-PJ4a-phaC Re strain. However, palm double olein oil was used instead of emulsified PFAD as a carbon source during cultivation. The obtained resin composition containing PHBH and PHB was designated as Composition 3.
- Example 4 Preparation of PHA using KNK005 REP-phaJ4b / ⁇ phaZ1,2,6 / pCUP2-REP-phaC Re strain (PHB7.9 wt% product)
- a plasmid pCUP2-REP-phaC Re for production of PHB was prepared for the purpose of co-production of PHBH and PHB by introduction into KNK005 REP-phaJ4b / ⁇ phaZ1,2,6 strain.
- PCR was performed using genomic DNA of the C. necator H16 strain as a template and DNAs represented by SEQ ID NO: 22 and SEQ ID NO: 30 as primers, and the resulting DNA fragment was digested with EcoRI and SpeI.
- KOD-plus was used as the polymerase.
- This DNA fragment was ligated with a DNA fragment obtained by digesting the pCUP2 vector described in JP-A-2007-259708 with MunI and SpeI using DNA ligase, and an expression regulatory sequence described in SEQ ID NO: 20 comprising a phaC1 promoter and a phaC1SD sequence.
- a PHB production plasmid pCUP2-REP-phaC Re having the phaC Re structural gene sequence was prepared.
- Purified PHA was obtained in the same manner as in Example 1 using the KNK005 REP-phaJ4b / ⁇ phaZ1,2,6 / pCUP2-REP-phaC Re strain.
- the obtained resin composition containing PHBH and PHB was designated as Composition 4.
- PHBH Purification of PHBH from the culture broth was performed in the same manner as described in Example 1. The obtained PHBH was designated as Composition 5.
- composition analysis of the first precipitate fraction and the second precipitate fraction was measured by gas chromatography. After each separated fraction was dried at 80 ° C. for 4 hours, 2 ml of sulfuric acid-methanol mixture (15:85) and 2 ml of chloroform were added to 20 mg of each precipitated fraction and sealed, and heated at 100 ° C. for 140 minutes. To methyl esterify. After cooling, 1.5 g of sodium bicarbonate was added little by little to neutralize it, and the mixture was allowed to stand until the generation of carbon dioxide gas stopped. After adding 4 ml of diisopropyl ether and mixing well, the mixture was centrifuged, and the monomer unit composition in the supernatant was analyzed by capillary gas chromatography.
- the gas chromatograph used was Shimadzu Corporation GC-17A, and the capillary column used was GL Science's NEUTRA BOND-1 (column length 25 m, column inner diameter 0.25 mm, liquid film thickness 0.4 ⁇ m). He was used as the carrier gas, the column inlet pressure was 100 kPa, and 1 ⁇ l of the sample was injected. As temperature conditions, the temperature was raised from an initial temperature of 100 to 200 ° C. at a rate of 8 ° C./min, and further from 200 to 290 ° C. at a rate of 30 ° C./min.
- ⁇ Measurement of melting point of PHBH alone or PHB alone> For the measurement of the melting point, a differential scanning calorimeter (DSC7020) manufactured by Hitachi High-Tech Science Corporation was used. As a sample, PHBH or about 5 mg of PHB separated as described above was precisely weighed, and the endothermic peak obtained at a heating rate of 10 ° C./min was defined as the melting point. The average value measured three times is shown in Table 1 as the melting point.
- ⁇ Melting point measurement about composition> For the measurement of the melting point, a differential scanning calorimeter (DSC7020) manufactured by Hitachi High-Tech Science Corporation was used. As a sample, about 5 mg of any one of Compositions 1 to 7 was precisely weighed, and the endothermic peak obtained at a heating rate of 10 ° C./min was taken as the melting point. The endothermic peak on the low temperature side was the melting point of PHBH, and the endothermic peak on the high temperature side was the melting point of PHB. The average value measured three times is shown in Table 1 as the melting point.
- the solidification test was performed as follows. First, any one of Compositions 1 to 7 was dried at 80 ° C. for 5 hours. Next, each composition was melt kneaded at a preset temperature of 170 ° C., a screw rotation speed of 100 rpm, and a kneading time of 1 minute using a small kneader Xplore series MC5 manufactured by DSM Co. It was put into a warm bath and the time for setting was measured. The faster the crystallization, the shorter the setting time, that is, the smaller the number in the solidification test, the better the solidification characteristics. The measurement was performed 5 times in the same procedure, and the average value is shown in Table 1.
- the maximum strand speed that can be pelletized is defined as pellet productivity.
- Example 1 and Comparative Example 2 have almost the same PHB content, but Example 1 was superior to Comparative Example 2 in all of the solidification test, pellet productivity, and sheet productivity. Also, Example 4 was superior to Comparative Example 3 in which the PHB content was almost the same in all of the solidification test, pellet productivity, and sheet productivity.
- the solidification of the resin composition is improved by observing the melting point of the second polyhydroxyalkanoate in the resin composition at a temperature lower than the melting point measured by the second polyhydroxyalkanoate alone. It can be seen that the processing speed at the time of molding accompanied by melting and solidification is improved.
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Abstract
Description
本発明に用いる第1のPHAは、式(2):[-CHR-CH2-CO-O-](式中、RはCnH2n+1で表されるアルキル基で、nは1以上15以下の整数である。)で示される繰り返し単位を含む脂肪族ポリエステルである。
第2のポリヒドロキシアルカノエートは、第1のポリヒドロキシアルカノエートの結晶化を促進、即ち、固化を促進させる核剤として作用するポリヒドロキシアルカノエートである。
本発明のポリエステル樹脂組成物について融点を測定すると、第2のポリヒドロキシアルカノエートの融点が、第2のポリヒドロキシアルカノエート単独で測定した融点よりも低い温度で観測される。
本発明のポリエステル樹脂組成物の製造方法として、製造時に高温プロセスを必要とせず熱劣化を抑えて第2のポリヒドロキシアルカノエートを良好に分散させることができる点で、1種の微生物で第1のポリヒドロキシアルカノエートと第2のポリヒドロキシアルカノエートを同時に製造する、すなわち共生産する方法を好ましく用いることができる。
本発明のポリエステル樹脂組成物からなる成形体の製造方法を以下に例示する。
(PHB2 wt%品)
まずphaZ6遺伝子の破壊を目的とし、遺伝子置換用プラスミドの作製を行った。C. necator H16株のゲノムDNAを鋳型とし、配列番号1および配列番号2で示したDNAをプライマーとしてPCRを行った。ポリメラーゼはKOD-plus(東洋紡社製)を用いた。同様に配列番号3および配列番号4で示したDNAをプライマーとしてPCRを行った。さらに、上記PCRで得られた2種DNA断片を鋳型とし、配列番号1および配列番号4で示したDNAをプライマーとしてPCRを行い、得られたDNA断片を制限酵素SmiIで消化した。このDNA断片を、特開2007-259708号公報に記載のベクターpNS2X-sacBをSmiIで消化したDNA断片と、DNAリガーゼ(Ligation High、東洋紡社製)を用いて連結し、phaZ6構造遺伝子より上流および下流のDNA配列を有する遺伝子破壊用プラスミドpNS2X-phaZ6(-+)を作製した。
KNK005 REP-phaJ4b/ΔphaZ1,2,6/pCUP2-Plac-phaCRe株を以下のように培養した。
培養経時および培養終了時、培養ブロスをサンプリングし、遠心分離によって菌体を回収、エタノールで洗浄後真空乾燥し、乾燥菌体を取得した。
(PHB3.5 wt%品)
KNK005 REP-phaJ4b/ΔphaZ1,2,6株に導入し、PHBHとPHBを共生産することを目的とし、PHB生産用プラスミドpCUP2-PJ4a-phaCReを作製した。
(PHB6.0 wt%品)
KNK005 REP-phaJ4b/ΔphaZ1,2,6/pCUP2-PJ4a-phaCRe株を用いて、実施例1と同様の手法で精製PHAを取得した。ただし培養時の炭素源として乳化PFADの代わりに、パームダブルオレイン油を使用した。得られたPHBHとPHBを含む樹脂組成物を組成物3とした。
(PHB7.9 wt%品)
KNK005 REP-phaJ4b/ΔphaZ1,2,6株に導入し、PHBHとPHBを共生産することを目的とし、PHB生産用プラスミドpCUP2-REP-phaCReを作製した。
PHBHの培養生産にはKNK-631株(国際公開第2009/145164号参照)を用いた。培養は、実施例1記載の方法と同様に行った。ただし、炭素源は乳化PFADの代わりにパームダブルオレイン油を使用した。培養は60~70時間行った。
比較例1で得られたPHBHと次の製造例1で得られたPHBを表1に示す組成比でドライブレンドし、東芝機械社製の2軸押出機TEM26SSを用いて、シリンダー設定温度120~140℃で、スクリュー回転数を100rpmで溶融混錬することによって樹脂組成物を作製した。得られた樹脂組成物はそれぞれ、組成物6及び組成物7とした。
PHBの培養生産にはCupriavidus necator H16(ATCC17699)株を用いた。培養は、実施例1記載の方法と同様に行った。培養は45~54時間行った。
約1000mgの樹脂組成物を100mlのクロロホルムに約50℃で溶解させた。その後に、266.7mlのヘキサンを加えて10分間攪拌した後に析出してきた成分を第一析出画分として吸引ろ過で分別した。更に130mlのヘキサンを加えて5分間攪拌後、15分間静置して析出してきたものを第二析出画分として吸引ろ過した。それぞれ乾燥して重量を測定し、第一析出画分と第二析出画分の合計量に対する第一析出画分の重量比を、PHBの比率として表1に示した。
組成分析はガスクロマトグラフィーによって測定した。分別した各析出画分を80℃で4時間乾燥した後、各析出画分20mgに2mlの硫酸-メタノール混液(15:85)と2mlのクロロホルムを添加して密栓し、100℃で140分間加熱することによってメチルエステル化した。冷却後、これに1.5gの炭酸水素ナトリウムを少しずつ加えて中和し、炭酸ガスの発生がとまるまで放置した。4mlのジイソプロピルエーテルを添加してよく混合した後、遠心して、上清中のモノマーユニット組成をキャピラリーガスクロマトグラフィーにより分析した。ガスクロマトグラフは島津製作所GC-17A、キャピラリーカラムはGLサイエンス社製NEUTRA BOND-1(カラム長25m、カラム内径0.25mm、液膜厚0.4μm)を用いた。キャリアガスとしてHeを用い、カラム入口圧100kPaとし、サンプルは1μlを注入した。温度条件は、初発温度100から200℃まで8℃/分の速度で昇温、さらに200から290℃まで30℃/分の速度で昇温した。
融点の測定には日立ハイテクサイエンス社の示差走査熱量計(DSC7020)を用いた。試料として、上記で分別したPHBHまたはPHB約5mgを精秤し、昇温速度10℃/分で得られる吸熱ピークを融点とした。3回測定した平均値を融点として表1に示した。
融点の測定には日立ハイテクサイエンス社の示差走査熱量計(DSC7020)を用いた。試料として、組成物1~7のいずれかを約5mg精秤し、昇温速度10℃/分で得られる吸熱ピークを融点とした。低温側の吸熱ピークをPHBHの融点、高温側の吸熱ピークをPHBの融点とした。3回測定した平均値を融点として表1に示した。
固化試験は次のように実施した。まず、組成物1~7のいずれかを80℃で5時間乾燥した。次いで、DSM社製の小型混練機XploreシリーズMC5を用いて、各組成物を、設定温度170℃、スクリュー回転数100rpm、混錬時間1分で溶融混錬した後、溶融した樹脂を約50℃の温浴に投入し、固まる時間を計測した。結晶化が早いほど固まる時間が短い、すなわち、固化試験では数字が小さいほど固化特性は優れていることを意味する。同手順で測定を5回行い、その平均値を表1に示した。
ペレットの生産性は次のようにして評価した。東芝機械社製の2軸押出機TEM26SSを用いて、各組成物を、シリンダー設定温度120~140℃で溶融混錬し、φ4mm、3穴のストランドダイから溶融樹脂を吐出させ、設定60℃の温水で満たされた1.5m長の温浴槽内を通過して結晶化、固化して、ペレタイザーにてペレット状にカットする。
シートの生産性は次のように評価した。Tダイシート成形機(東洋精機製作所社製:ラボプラストミル)を用い、各組成物を、ダイスリップ厚=250μm、ダイスリップ幅=150mm、シリンダー設定温度=120~140℃、ダイス設定温度=150~160℃、冷却ロール設定温度60℃にて、100mm幅のシートに成形した。Tダイからシート状にでてきた溶融樹脂は冷却ロールに接触することで結晶化し固化され、厚さ100μmのシートに成形される。樹脂が十分に結晶化し固化される場合は、成形されたシートは冷却ロールから離型され、巻き取られるが、シートの線速が早まると冷却ロールに接触している時間が短くなるので結晶化せずに十分に固化しないので冷却ロールから離型できなくなる。シートが離型できる最大のシート線速をシート生産性と定義した。従い、線速値が高いほどシート生産性は優れることを意味する。結果は表1に示した。
異物の数は次のように評価した。上述したTダイ成形で得られた厚み約100μmのシートからおおよそ100mm四方を切り出し、当該シートを、倍率20倍の目盛り付拡大鏡を用いて観察し、大きさ100μm以上の異物(未溶融物)の数を計測した。面積100cm2あたりに存在する異物の数に換算した値を表1に示した。
Claims (8)
- 第1のポリヒドロキシアルカノエートと第2のポリヒドロキシアルカノエートを含有するポリエステル樹脂組成物であって、
前記ポリエステル樹脂組成物中で、第2のポリヒドロキシアルカノエートの融点は、第2のポリヒドロキシアルカノエート単独で測定した融点よりも低い温度で観測されることを特徴とするポリエステル樹脂組成物。 - 前記樹脂組成物を100μm厚のシートに成形した時、当該シート中の異物の数が20個/100cm2以下であることを特徴とする請求項1に記載のポリエステル樹脂組成物。
- 前記ポリエステル樹脂組成物中で、第2のポリヒドロキシアルカノエートの融点は、第2のポリヒドロキシアルカノエート単独で測定した融点よりも1~50℃低い温度で観測されることを特徴とする請求項1又は2に記載のポリエステル樹脂組成物。
- 第1のポリヒドロキシアルカノエートと第2のポリヒドロキシアルカノエートは1種の微生物で共生産されたものであることを特徴とする請求項1~3の何れかに記載のポリエステル樹脂組成物。
- 第2のポリヒドロキシアルカノエートが、ポリ-3-ヒドロキシブチレートであることを特徴とする請求項1~4の何れかに記載のポリエステル樹脂組成物。
- 第1のポリヒドロキシアルカノエートが、ポリ(3-ヒドロキシブチレート-コ-3-ヒドロキシヘキサノエート)、ポリ(3-ヒドロキシブチレート-コ-3-ヒドロキシバリレート)、及び、ポリ(3-ヒドロキシブチレート-コ-4-ヒドロキシブチレート)からなる群より選択される少なくとも1種であることを特徴とする請求項1~5の何れかに記載のポリエステル樹脂組成物。
- 請求項1~6の何れかに記載の樹脂組成物からなる成形体。
- 請求項1~6の何れかに記載の樹脂組成物を加工することを特徴とする請求項7に記載の成形体の製造方法。
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WO2020040093A1 (ja) | 2018-08-20 | 2020-02-27 | 株式会社カネカ | ポリ(3-ヒドロキシブチレート)系樹脂チューブ及びその製造方法 |
WO2020195477A1 (ja) | 2019-03-22 | 2020-10-01 | 株式会社カネカ | ポリ(3-ヒドロキシブチレート)系熱成形用樹脂シート、その成形体、及び製造方法 |
WO2021010327A1 (ja) * | 2019-07-16 | 2021-01-21 | 株式会社カネカ | 溶融加工用組成物の製造方法 |
WO2021010054A1 (ja) | 2019-07-16 | 2021-01-21 | 株式会社カネカ | 射出成形体の製造方法 |
WO2021251049A1 (ja) * | 2020-06-09 | 2021-12-16 | 株式会社カネカ | ポリヒドロキシアルカン酸の製造方法およびその利用 |
WO2022004637A1 (ja) * | 2020-06-29 | 2022-01-06 | 株式会社カネカ | 樹脂フィルム |
WO2022044836A1 (ja) * | 2020-08-25 | 2022-03-03 | 株式会社カネカ | 樹脂フィルム、及び、該樹脂フィルムから形成される袋、手袋、結束材 |
KR102431676B1 (ko) * | 2021-07-30 | 2022-08-11 | 씨제이제일제당(주) | 생분해성 수지 조성물, 이를 이용한 생분해성 필름 및 멀칭 필름, 및 이의 제조방법 |
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AU2022319131A1 (en) * | 2021-07-29 | 2024-03-07 | Danimer Ipco, Llc | Biopolymer compositions incorporating poly(3-hydroxypropionate) |
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JP7473551B2 (ja) | 2019-07-16 | 2024-04-23 | 株式会社カネカ | 溶融加工用組成物の製造方法 |
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WO2022044836A1 (ja) * | 2020-08-25 | 2022-03-03 | 株式会社カネカ | 樹脂フィルム、及び、該樹脂フィルムから形成される袋、手袋、結束材 |
KR102431676B1 (ko) * | 2021-07-30 | 2022-08-11 | 씨제이제일제당(주) | 생분해성 수지 조성물, 이를 이용한 생분해성 필름 및 멀칭 필름, 및 이의 제조방법 |
WO2023008903A1 (ko) * | 2021-07-30 | 2023-02-02 | 씨제이제일제당(주) | 생분해성 수지 조성물, 및 이를 이용한 생분해성 필름 및 생분해성 멀칭 필름 |
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