WO2023157633A1 - 成形用樹脂組成物及び成形体 - Google Patents

成形用樹脂組成物及び成形体 Download PDF

Info

Publication number
WO2023157633A1
WO2023157633A1 PCT/JP2023/003113 JP2023003113W WO2023157633A1 WO 2023157633 A1 WO2023157633 A1 WO 2023157633A1 JP 2023003113 W JP2023003113 W JP 2023003113W WO 2023157633 A1 WO2023157633 A1 WO 2023157633A1
Authority
WO
WIPO (PCT)
Prior art keywords
poly
hydroxyalkanoate
weight
resin
molding
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.)
Ceased
Application number
PCT/JP2023/003113
Other languages
English (en)
French (fr)
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
Priority to JP2024501078A priority Critical patent/JPWO2023157633A1/ja
Publication of WO2023157633A1 publication Critical patent/WO2023157633A1/ja
Priority to US18/806,471 priority patent/US20240400822A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • B29C48/32—Extrusion nozzles or dies with annular openings, e.g. for forming tubular articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D35/00—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor
    • B65D35/02—Body construction
    • B65D35/04—Body construction made in one piece
    • B65D35/08—Body construction made in one piece from plastics material
    • 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
    • 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
    • B29K2867/00—Use of polyesters or derivatives thereof as mould material
    • B29K2867/04—Polyesters derived from hydroxycarboxylic acids
    • 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
    • B29L2023/00—Tubular articles
    • B29L2023/008—Drinking straws
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • 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
    • 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
    • C08L2205/24—Crystallisation aids

Definitions

  • the present invention relates to a molding resin composition and a molding containing a poly(3-hydroxyalkanoate)-based resin.
  • Poly(3-hydroxyalkanoate)-based resin is a thermoplastic polyester that is produced and accumulated as an energy storage substance in the cells of many microbial species, and is a material that can be biodegraded not only in soil but also in seawater. Therefore, it is attracting attention as a material that solves the above problems.
  • Patent Document 1 discloses a resin tube formed from a poly(3-hydroxybutyrate)-based resin and having a thickness of 0.1 to 0.6 mm as a resin tube that is flexible and can be suitably used as a straw.
  • An object of the present invention is to provide a resin composition for molding which contains a poly(3-hydroxyalkanoate)-based resin component and which is capable of reducing the thickness of the molded body. .
  • the present inventors have found that the poly(3-hydroxyalkanoate)-based resin component contained in the resin composition for molding is replaced with a poly(3-hydroxyalkanoate)-based resin ( A) and the reaction product (B) of the poly(3-hydroxyalkanoate)-based resin (b1) and the organic peroxide (b2) enables the molding to be thin. and completed the present invention.
  • the present invention provides a poly(3-hydroxyalkanoate) resin (A) containing at least one copolymer of 3-hydroxybutyrate units and other hydroxyalkanoate units, and A reaction product of a poly(3-hydroxyalkanoate) resin (b1) containing at least two copolymers of 3-hydroxybutyrate units and other hydroxyalkanoate units and an organic peroxide (b2) (B), the ratio of the poly(3-hydroxyalkanoate)-based resin (A) to the total of the poly(3-hydroxyalkanoate)-based resin (A) and the reaction product (B) is 20% by weight or more and 99% by weight or less, and the ratio of the reaction product (B) is 1% by weight or more and 80% by weight or less.
  • the present invention also relates to a molded article containing the resin composition for molding. Furthermore, the present invention provides a method for producing the molded article, a step of reacting the poly(3-hydroxyalkanoate)-based resin (b1) with the organic peroxide (b2) to obtain the reaction product (B); A step of mixing the reaction product (B) and the poly(3-hydroxyalkanoate)-based resin (A) to obtain a mixture; It also relates to a method for producing a molded body, comprising the step of molding said mixture into a molded body.
  • a resin composition for molding that contains a poly(3-hydroxyalkanoate)-based resin component and that can reduce the thickness of the molded body.
  • One embodiment of the present invention is a poly(3-hydroxyalkanoate)-based resin (A), and a reaction product of a poly(3-hydroxyalkanoate)-based resin (b1) and an organic peroxide (b2) (B), relates to a resin composition for molding containing.
  • the poly(3-hydroxyalkanoate) resin (A) (hereinafter also referred to as P3HA (A)) contained in the molding resin composition is a polymer containing 3-hydroxyalkanoate structural units (monomer units). be. P3HA(A) is substantially unreacted with the organic peroxide and does not contain a crosslinked structure formed by the reaction with the organic peroxide. By blending P3HA (A), the crystallinity of the entire poly(3-hydroxyalkanoate)-based resin component contained in the molding resin composition is improved, and the moldability is improved. molding is possible. As P3HA (A), one type of poly(3-hydroxyalkanoate)-based resin may be used, or two or more types of poly(3-hydroxyalkanoate)-based resins may be used in combination.
  • the 3-hydroxyalkanoate structural unit is preferably a structural unit represented by the following general formula (1). [-CHR-CH 2 -CO-O-] (1)
  • R represents an alkyl group represented by C p H 2p+1 , and p represents an integer of 1-15.
  • R include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, methylpropyl group, butyl group, isobutyl group, t-butyl group, pentyl group and hexyl group.
  • p 1 to 10 are preferable, and 1 to 8 are more preferable.
  • Poly(3-hydroxyalkanoate)-based resins produced from microorganisms are particularly preferred as the P3HA (A).
  • Poly(3-hydroxyalkanoate) resins produced from microorganisms contain all 3-hydroxyalkanoate structural units as (R)-3-hydroxyalkanoate structural units.
  • P3HA (A) preferably contains 3-hydroxyalkanoate structural units (especially structural units represented by the above general formula (1)) in an amount of 50 mol% or more, and preferably 60 mol% or more of all structural units. is more preferable, and it is even more preferable to contain 70 mol % or more.
  • P3HA (A) may contain only one or two or more 3-hydroxyalkanoate structural units as repeating units constituting the polymer, or may contain one or two or more 3-hydroxyalkanoate structures. In addition to the units, other structural units (eg, 4-hydroxyalkanoate structural units, etc.) may also be included.
  • P3HA (A) examples include poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxypropionate), poly(3-hydroxybutyrate-co-3 -hydroxyvalerate) (abbreviation: P3HB3HV), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) ate) (abbreviation: P3HB3HH), poly (3-hydroxybutyrate-co-3-hydroxyheptanoate), poly (3-hydroxybutyrate-co-3-hydroxyoctanoate), poly (3-hydroxybutyrate) late-co-3-hydroxynonanoate), poly(3-hydroxybutyrate-co-3-hydroxydecanoate), poly(3-hydroxybutyrate-co-3-hydroxyundecanoate), poly(3 -hydroxybutyrate-co-4-hydroxybutyrate) (abbreviation: P3HB4HB) and the like.
  • P3HA (A) contains at least one copolymer of 3-hydroxybutyrate units (hereinafter sometimes referred to as 3HB) and other hydroxyalkanoate units.
  • P3HA(A) may contain only one type of the copolymer, or may contain two or more types thereof.
  • P3HA (A) may consist of at least one of the above copolymers alone, or in addition to at least one of the above copolymers, poly(3-hydroxybutyrate), that is, 3 - may contain a homopolymer of hydroxybutyrate.
  • the copolymer of the 3-hydroxybutyrate unit and other hydroxyalkanoate unit contained in P3HA (A) is poly(3-hydroxybutyrate -co-3-hydroxyvalerate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) noate), and poly(3-hydroxybutyrate-co-4-hydroxybutyrate), preferably one or more selected from the group consisting of poly(3-hydroxybutyrate-co-3-hydroxy hexanoate) and/or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) are more preferred, and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) is even more preferred.
  • the average content ratio of 3-hydroxybutyrate units and other hydroxyalkanoate units in P3HA (A) is 3-hydroxybutyrate units/other hydroxyalkanoate units from the viewpoint of thinning, productivity, strength, etc.
  • the alkanoate unit ratio is preferably 99/1 to 94/6 (mol%/mol%), more preferably 98/2 to 94/6 (mol%/mol%).
  • the average content of each monomer unit in P3HA(A) can be determined by a method known to those skilled in the art, for example, the method described in paragraph [0047] of WO2013/147139.
  • the average content ratio means the ratio of each monomer unit to all monomer units contained in the entire P3HA(A).
  • P3HA (A) is a mixture of two or more poly(3-hydroxyalkanoate) resins, it refers to the ratio of each monomer contained in the mixture as a whole.
  • the weight average molecular weight of P3HA (A) is not particularly limited, but is preferably 200,000 to 2,000,000, more preferably 250,000 to 1,500,000, more preferably 300,000 to 300,000, from the viewpoint of thinning of the molded body, productivity, strength, etc. 1 million is more preferred.
  • the production method of P3HA (A) is not particularly limited, and may be a production method by chemical synthesis or a production method by microorganisms. Among them, the production method using microorganisms is preferable.
  • a known method can be applied to the production method using microorganisms.
  • 3-hydroxybutyrate and other hydroxyalkanoate copolymer-producing bacteria include Aeromonas caviae, which is a P3HB3HV and P3HB3HH-producing bacterium, Alcaligenes eutrophus, which is a P3HB4HB-producing bacterium, and the like. It has been known.
  • Alcaligenes eutrophus AC32 strain Alcaligenes eutrophus AC32, FERM BP-6038
  • T.Fukui, Y.Doi, J.Bateriol into which a P3HA synthase group gene was introduced in order to increase the productivity of P3HB3HH .
  • 179, p4821-4830 (1997) are more preferred, and microbial cells obtained by culturing these microorganisms under appropriate conditions and accumulating P3HB3HH in the cells are used.
  • genetically modified microorganisms into which various poly(3-hydroxyalkanoate) resin synthesis-related genes have been introduced may be used according to the poly(3-hydroxyalkanoate) resin to be produced. Optimization of culture conditions, including the type of With these, the content of 3-hydroxybutyrate units in the poly(3-hydroxyalkanoate) resin can be adjusted.
  • reaction product (B) The reaction product (B) contained in the molding resin composition is a reaction product of the poly(3-hydroxyalkanoate) resin (b1) and the organic peroxide (b2).
  • the reaction product has a structure in which a poly(3-hydroxyalkanoate)-based resin is crosslinked by reaction with an organic peroxide.
  • the resin composition for molding according to the present embodiment contains an organic peroxide-derived component (e.g., a decomposition product of the organic peroxide, a decomposition product-derived compounds, etc.).
  • an organic peroxide-derived component e.g., a decomposition product of the organic peroxide, a decomposition product-derived compounds, etc.
  • the amount of P3HA (A) out of the total of P3HA (A) and reaction product (B) It may be set so that the ratio is 20% by weight or more and 99% by weight or less, and the ratio of the reaction product (B) is 1% by weight or more and 80% by weight or less. From the viewpoint of productivity and thinning of the molded body, it is preferable that the proportion of P3HA (A) is 20% by weight or more and 90% by weight or less, and the proportion of the reaction product (B) is 10% by weight or more and 80% by weight or less. More preferably, the proportion of P3HA (A) is 20% by weight or more and 80% by weight or less, and the proportion of the reaction product (B) is 20% by weight or more and 80% by weight or less.
  • the poly(3-hydroxyalkanoate) resin (b1) (hereinafter also referred to as P3HA (b1)) constituting the reaction product (B) is a polymer containing 3-hydroxyalkanoate structural units (monomer units). be.
  • P3HA(b1) The details of P3HA(b1) are the same as those of P3HA(A), except for the items described below.
  • P3HA (b1) contains at least two copolymers of 3-hydroxybutyrate units and other hydroxyalkanoate units.
  • the copolymer is poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxybutyrate-co-3- from hydroxyvalerate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), and poly(3-hydroxybutyrate-co-4-hydroxybutyrate) It is preferably one or more selected from the group consisting of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and/or poly(3-hydroxybutyrate-co-4-hydroxybutyrate ) is more preferred, and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) is even more preferred.
  • the average content of each monomer unit in P3HA (b1) can be determined as described above for P3HA (A).
  • the average content ratio means the ratio of each monomer unit to all monomer units contained in the entire P3HA (b1). Since P3HA (b1) is a mixture of two or more poly(3-hydroxyalkanoate)-based resins, it refers to the ratio of each monomer contained in the mixture as a whole.
  • P3HA (b1) preferably contains two or more types of copolymers of 3-hydroxybutyrate units and other hydroxyalkanoate units with different content ratios of other hydroxyalkanoate units.
  • Other hydroxyalkanoate units contained in the two or more copolymers may be the same or different.
  • a highly crystalline copolymer (b1-1) having a relatively low content of other hydroxyalkanoate units is compared with a content of other hydroxyalkanoate units.
  • a combination with a highly effective low-crystalline copolymer (b1-2) can be mentioned. According to this aspect, the strength of the molded article to be manufactured can be increased.
  • the content of other hydroxyalkanoate units is preferably 1 mol% or more and 6 mol% or less, more preferably 2 mol% or more and 6 mol% or less.
  • poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) ) is preferred, and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) is more preferred.
  • the content of other hydroxyalkanoate units is preferably 24 mol% or more and 99 mol% or less, more preferably 24 mol% or more and 50 mol% or less. mol % or more and 35 mol % or less is more preferable, and 24 mol % or more and 30 mol % or less is particularly preferable.
  • poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) ) is preferred, and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) is more preferred.
  • the ratio of each resin to the total amount of both copolymers is not particularly limited. It is preferable that the coalescence (b1-1) is 10% by weight or more and 90% by weight or less, the copolymer (b1-2) is 90% by weight or more and 10% by weight or less, and the copolymer (b1-1) is 20% by weight. % to 80% by weight, more preferably 80% to 20% by weight of the copolymer (b1-2), and 30% to 70% by weight of the copolymer (b1-1) It is more preferable that the copolymer (b1-2) is 70% by weight or more and 30% by weight or less.
  • the weight average molecular weight of P3HA (b1) is not particularly limited, but is preferably 200,000 to 2,000,000, more preferably 250,000 to 1,500,000, and 300,000 to 300,000 to 1 million is more preferred.
  • P3HA(b1) can be produced in the same manner as P3HA(A).
  • the reaction product (B) may contain only P3HA (b1) as a resin component, but may further contain resins other than P3HA (b1) (especially biodegradable resins). Other resins described later can be used as such resins.
  • the content of the resin other than P3HA (b1) contained in the reaction product (B) is not particularly limited, but may be 0 parts by weight or more and less than 5 parts by weight with respect to 100 parts by weight of the resin composition for molding. , 0 to 3 parts by weight, or 0 to 1 part by weight.
  • Organic peroxide (b2) The organic peroxide (b2) to be reacted with P3HA (b1) is not particularly limited, but examples include diisobutyl peroxide, cumyl peroxyneodecanoate, di-n-propyl peroxydicarbonate, and diisopropyl peroxydicarbonate.
  • dibenzoyl peroxide dibenzoyl peroxide, t-butylperoxy-2-ethylhexyl carbonate, and t-butylperoxyisopropyl carbonate are preferred.
  • organic peroxide one type may be used alone, or two or more types may be used in combination.
  • the organic peroxide (b2) is used in various forms such as solid and liquid, and may be in a liquid form diluted with a diluent or the like.
  • an organic peroxide in a form that can be mixed with a poly(3-hydroxyalkanoate)-based resin is a poly(3-hydroxyalkanoate)-based It is preferable because it can be uniformly dispersed in the resin, and local modification reaction can be easily suppressed.
  • the amount of the organic peroxide (b2) used is 0.01 to 0.5 parts by weight with respect to 100 parts by weight of P3HA (b1) from the viewpoint of thinning, productivity, strength, etc. of the molded body. It is preferably 0.05 to 0.4 parts by weight, and even more preferably 0.1 to 0.3 parts by weight.
  • the reaction product (B) can be preferably obtained by charging the P3HA (b1) and the organic peroxide (b2) into an extruder and melt-kneading them. Thereby, the P3HA (b1) can be uniformly crosslinked.
  • other components such as a crystal nucleating agent, a lubricant, an organic or inorganic filler, etc., which will be described later, are put into the extruder and melt-kneaded. good too.
  • the P3HA (b1) and the organic peroxide (b2) may be individually charged into the extruder, or each component may be mixed and then charged into the extruder.
  • the melt-kneading can be carried out according to known or commonly used methods, and can be carried out, for example, using an extruder (single-screw extruder, twin-screw extruder), kneader, or the like.
  • the conditions for melt-kneading are not particularly limited and can be set as appropriate, but it is preferable to set the resin temperature and residence time at which the reaction with the organic peroxide (b2) can be completed during melt-kneading.
  • the melt-kneading is preferably performed at a resin temperature in the range of 155° C. or higher and 175° C. or lower as measured by a die thermometer.
  • it is preferable to carry out melt-kneading so that the residence time in the extruder is 60 seconds or more and 300 seconds or less.
  • the reaction product (B) can also be produced by reacting P3HA (b1) and organic peroxide (b2) in an aqueous dispersion. At this time, for efficient reaction, the aqueous dispersion of P3HA (b1) containing the organic peroxide (b2) should be heated to a temperature suitable for modification.
  • the resin component contained in the resin composition for molding may be composed only of P3HA (A) and the reaction product (B), but in addition to P3HA (A) and the reaction product (B), poly( 3-Hydroxyalkanoate) resins other than resins may be included.
  • examples of such other resins include aliphatic polyester resins such as polylactic acid, polybutylene succinate adipate, polybutylene succinate, and polycaprolactone; Aliphatic-aromatic polyester-based resins such as late terephthalate and the like are included.
  • the other resin only one kind may be contained, or two or more kinds may be contained.
  • the content of the other resins is not particularly limited, it is preferably as small as possible from the viewpoint of the seawater decomposability of the molded product.
  • the content of the other resin is preferably 35 parts by weight or less, more preferably 30 parts by weight or less, and It is more preferably not more than 10 parts by weight, and even more preferably not more than 10 parts by weight.
  • the lower limit of the content of the other resin is not particularly limited, and may be 0 parts by weight.
  • the resin composition for molding may not contain an inorganic filler, it preferably contains an inorganic filler from the viewpoint of improving the strength of the molded article.
  • the inorganic filler is not particularly limited as long as it can be used in the molded article, and examples thereof include quartz, fumed silica, silicic anhydride, fused silica, crystalline silica, amorphous silica, and a filler obtained by condensing alkoxysilane.
  • silica-based inorganic fillers such as ultrafine amorphous silica, alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass, silicone rubber, silicone resin, titanium oxide, carbon Fiber, mica, graphite, carbon black, ferrite, graphite, diatomaceous earth, clay, clay, talc, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, silver powder and the like. These may be used alone or in combination of two or more.
  • the inorganic filler may be surface-treated in order to increase dispersibility in the resin composition for molding.
  • Treatment agents used for surface treatment include higher fatty acids, silane coupling agents, titanate coupling agents, sol-gel coating agents, resin coating agents and the like.
  • the water content of the inorganic filler is preferably 0.01 to 10%, more preferably 0.01 to 5%, since it is easy to suppress hydrolysis of the poly(3-hydroxyalkanoate)-based resin. 0.01 to 1% is more preferred.
  • the water content can be determined according to JIS-K5101.
  • the average particle size of the inorganic filler is preferably 0.1 to 100 ⁇ m, more preferably 0.1 to 50 ⁇ m, and even more preferably 0.1 to 30 ⁇ m, in order to provide excellent properties and workability of the molded product. Particularly preferred is 0.1 to 15 ⁇ m.
  • the average particle size can be measured using a laser diffraction/scattering device such as "Microtrac MT3100II” manufactured by Nikkiso Co., Ltd.
  • inorganic fillers belonging to silicates are preferable because they can improve heat resistance and workability. Furthermore, since the effect of improving the strength of the molded body is large, the particle size distribution is small and it is difficult to inhibit surface smoothness and mold transferability, among silicates, talc, mica, kaolinite, montmorillonite, and smectite One or more selected from the group are preferred. Two or more kinds of silicates may be used in combination, and in that case, the kinds of silicates and the ratio of use thereof can be appropriately adjusted.
  • talc examples include general-purpose talc, surface-treated talc, and the like.
  • Talc manufactured by Kogyosha and Maruo Calcium is exemplified.
  • Examples of the mica include wet pulverized mica and dry pulverized mica, and specific examples include mica manufactured by Yamaguchi Mica Co. and Keiwa Rozai Co., Ltd.
  • Examples of the kaolinite include dry kaolin, calcined kaolin, and wet kaolin. , "ULTREX” (registered trademark), and kaolinite manufactured by Keiwa Rozai Co., Ltd. are exemplified.
  • the blending amount is the total of the resin components including P3HA (A) and the reaction product (B) from the viewpoint of improving the strength of the molded product and ensuring fluidity during melt molding. It is preferably 1 part by weight or more and 30 parts by weight or less per 100 parts by weight. 5 to 25 parts by weight is more preferred.
  • the resin composition for molding may contain additives other than the inorganic filler within a range that does not impair the effects of the invention.
  • Additives include, for example, crystal nucleating agents, lubricants, plasticizers, antistatic agents, flame retardants, conductive agents, heat insulating agents, cross-linking agents, antioxidants, ultraviolet absorbers, coloring agents, organic fillers, and hydrolysis inhibitors. agents and the like can be used depending on the purpose. In particular, biodegradable additives are preferred.
  • crystal nucleating agents examples include pentaerythritol, orotic acid, aspartame, cyanuric acid, glycine, zinc phenylphosphonate, and boron nitride.
  • Poly(3-hydroxybutyrate) can also be added as a crystal nucleating agent.
  • pentaerythritol is preferred because it has a particularly excellent effect of promoting the crystallization of poly(3-hydroxyalkanoate)-based resins.
  • the crystal nucleating agent may be used alone or in combination of two or more, and the mixing ratio can be appropriately adjusted according to the purpose.
  • the resin composition for molding may not contain a crystal nucleating agent (especially pentaerythritol).
  • the amount of the crystal nucleating agent added is not particularly limited, but the total weight of P3HA (A) and reaction product (B) is 100. parts, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8.5 parts by weight, still more preferably 0.7 to 6 parts by weight, and particularly preferably 0.8 to 3 parts by weight. be.
  • the amount added is not particularly limited. ) is preferably 0.1 to 15 parts by weight, more preferably 1 to 10 parts by weight, still more preferably 3 to 8 parts by weight, and particularly preferably 4 to 7 parts by weight, based on the total 100 parts by weight of the above.
  • lubricants include behenic acid amide, oleic acid amide, erucic acid amide, stearic acid amide, palmitic acid amide, N-stearylbehenic acid amide, N-stearyl erucic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, ethylenebiserucamide, ethylenebislaurylamide, ethylenebiscapricamide, p-phenylenebisstearicamide, polycondensates of ethylenediamine, stearic acid and sebacic acid.
  • behenic acid amide or erucic acid amide is preferable because of its particularly excellent lubricating effect on poly(3-hydroxyalkanoate)-based resins.
  • the lubricant may be used not only by one type but also by mixing two or more types, and the mixing ratio can be appropriately adjusted depending on the purpose.
  • the amount of the lubricant used is not particularly limited, but is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on the total of 100 parts by weight of P3HA (A) and reaction product (B). parts by weight, more preferably 0.1 to 1.5 parts by weight.
  • plasticizers include glycerin ester compounds, citrate compounds, sebacate compounds, adipate compounds, polyether ester compounds, benzoate compounds, phthalate compounds, isosol
  • plasticizers include bidester-based compounds, polycaprolactone-based compounds, and dibasic acid ester-based compounds.
  • glycerin ester-based compounds, citric acid ester-based compounds, sebacate-based compounds, and dibasic acid ester-based compounds are preferred because they have particularly excellent plasticizing effects on poly(3-hydroxyalkanoate)-based resins.
  • glycerin ester compounds include glycerin diacetomonolaurate and the like.
  • citrate compounds include acetyl tributyl citrate and the like.
  • sebacate-based compounds include dibutyl sebacate and the like.
  • dibasic acid ester compounds include benzylmethyldiethylene glycol adipate.
  • the plasticizer may be used in a mixture of two or more kinds as well as one kind, and the mixing ratio can be appropriately adjusted depending on the purpose.
  • the amount of the plasticizer to be used is not particularly limited, but is preferably 0 to 20 parts by weight, more preferably 0 to 15 parts by weight, more preferably 0 to 10 parts by weight, particularly preferably 0 to 5 parts by weight.
  • One embodiment of the present invention relates to a molded article composed of the resin composition for molding. Since the molded article is composed of the molding resin composition, it contains a poly(3-hydroxyalkanoate)-based resin component and can be made thin. Examples of such molded bodies include molded bodies having a hollow portion, such as resin tubes and bottles.
  • the term "tube” refers to an elongated cylindrical molded article having a substantially constant wall thickness, a substantially circular cross-sectional shape, and a hollow interior.
  • the tube can be used as a straw or pipe. Since the resin tube according to this embodiment can be made thin, it can be suitably used as a straw.
  • the thickness of the resin tube is such that it will not be crushed by suction when drinking a beverage as a straw, and because it has appropriate flexibility, it will not easily break, and it will not easily break when a fingertip or the like is poked.
  • 0.01 mm or more and 0.6 mm or less, more preferably 0.05 mm or more and 0.5 mm or less, and 0.1 mm or more and 0.4 mm More preferred are: According to this embodiment, it is possible to manufacture a resin tube having a thin wall thickness of 0.01 mm or more and less than 0.2 mm, or 0.01 mm or more and less than 0.1 mm.
  • the outer diameter of the resin tube is not particularly limited, but is preferably 2 to 10 mm, more preferably 4 to 8 mm, in terms of ease of use when drinking beverages as a straw. More preferably, 5 to 7 mm is even more preferable.
  • the cross-sectional shape of the resin tube is substantially circular, but from the viewpoint of usability as a straw, it is preferable that the cross-sectional shape is as close to a perfect circle as possible. Therefore, the flatness of the cross-sectional shape of the tube [100 x (maximum outer diameter - minimum outer diameter)/maximum outer diameter] is preferably 10% or less, more preferably 8% or less. , is more preferably 5% or less, and even more preferably 3% or less. A flatness of 0% means that the cross-sectional shape is a perfect circle.
  • the length of the resin tube is not particularly limited. However, when the resin tube is used as a straw, the length of the resin tube is preferably 50 to 350 mm, more preferably 70 to 300 mm, more preferably 90 to 270 mm, in terms of ease of use when drinking beverages as a straw. is more preferred.
  • the resin tube used as the straw may be a tube that has not been subjected to secondary processing, or may be a tube that has been subjected to secondary processing such as formation of a stopper portion or bellows portion.
  • secondary processing can be performed while heating the resin tube, it is preferably performed at room temperature.
  • the term "bottle” refers to a container having an inlet at the top and a hollow portion.
  • the bottle can be used as a container for holding beverages, liquid foods, liquid detergents, and the like. Since the bottle according to the present embodiment can be made thinner, it can be made lighter.
  • the resin composition for molding or the molded article according to the present embodiment has a Z-average molecular weight/weight average molecular weight (Mz/Mw) ratio measured by GPC of 10 or more and 300 or less. is preferred. Within this range, it is easier to produce compacts with a small wall thickness.
  • the ratio is preferably 20 or more and 290 or less, more preferably 30 or more and 270 or less, and even more preferably 40 or more and 250 or less.
  • both the weight average molecular weight (Mw) and the Z average molecular weight (Mz) are values obtained by GPC measurement.
  • Mw is a weighted average value calculated using the molecular weight as a weight
  • Mz is a weighted average value calculated using the square of the molecular weight as a weight. Therefore, Mz is more susceptible to the presence of high-molecular-weight components than Mw, and increases as the content of high-molecular-weight components increases.
  • the resin composition for molding or the molded article according to the present embodiment contains the reaction product (B) of the resin (b1) and the organic peroxide (b2), the content of the high molecular weight component is relatively high. Therefore, it is presumed that the Z-average molecular weight/weight-average molecular weight ratio may show a relatively high value.
  • the weight-average molecular weight of P3HA (A) or P3HA (b1), and the weight-average molecular weight and Z-average molecular weight of the molding resin composition or molded article were determined by gel permeation chromatography (HPLC manufactured by Shimadzu Corporation) using a chloroform solution. It can be measured by polystyrene conversion using GPC system).
  • gel permeation chromatography HPLC manufactured by Shimadzu Corporation
  • GPC system GPC system
  • the molding resin composition or molded article according to the present embodiment preferably has two or more peak tops in a GPC chart obtained by GPC measurement of the molding resin composition or molded article. These peak tops are considered to correspond to the peak top indicating the presence of P3HA (A) and the peak top indicating the presence of the reaction product (B). An example of such a GPC chart is shown in FIG.
  • the reaction product (B) is obtained by reacting the P3HA (b1) and the organic peroxide (b2) by the method described above.
  • P3HA (A), reaction product (B), and, if necessary, other resins, inorganic fillers, and other additives are added, and melt-kneaded using an extruder, kneader, Banbury mixer, rolls, etc.
  • the resulting resin composition is extruded into strands and then cut to obtain pellets in the form of particles such as cylindrical, cylindric, spherical, cubic, and rectangular parallelepipeds. It is desirable that the produced pellets are sufficiently dried at 40 to 80° C. to remove moisture, and then molded (especially, extruded).
  • the temperature at which the melt-kneading is carried out depends on the melting point, melt viscosity, etc. of the resin to be used, and cannot be categorically defined. 145 to 185°C is more preferred, and 150 to 180°C is even more preferred.
  • the resin temperature of the melt-kneaded product is 140° C. or higher, the resin component including the poly(3-hydroxyalkanoate)-based resin can be sufficiently melted, and when it is 190° C. or lower, poly( 3-Hydroxyalkanoate) can suppress thermal decomposition of resin components including resins.
  • the pellets thus produced are melted in an extruder, they can be molded into a tubular shape by extruding them through an annular die connected to the outlet of the extruder and putting them into water for solidification.
  • the blended product of each component may be melted in an extruder and then directly molded into a tubular shape without being pelletized.
  • the mold is closed to form the bottom part, and the plasticized resin By blowing air into the material, it can be molded into a bottle shape.
  • the blended product of each component may be melted in an extruder and then directly molded into a bottle shape without being pelletized.
  • the ratio of the poly(3-hydroxyalkanoate)-based resin (A) in the total of the poly(3-hydroxyalkanoate)-based resin (A) and the reaction product (B) is 20% by weight or more and 80% by weight. % or less, and the proportion of the reaction product (B) is 20% by weight or more and 80% by weight or less.
  • the poly(3-hydroxyalkanoate)-based resin (b1) is a copolymer (b1-1) containing 1 mol% or more and 6 mol% or less of other hydroxyalkanoate units, and another hydroxyalkanoate. 3.
  • the resin composition for molding according to item 1 or 2 comprising a copolymer (b1-2) having a unit content of 24 mol % or more and 99 mol % or less.
  • Item 4 Item 1, wherein the amount of the organic peroxide (b2) is 0.01 parts by weight or more and 0.5 parts by weight or less with respect to 100 parts by weight of the poly(3-hydroxyalkanoate) resin (b1). 4.
  • [Item 5] 5.
  • [Item 6] The molding resin composition according to any one of items 1 to 5, wherein two or more peak tops are present in the GPC chart of the molding resin composition.
  • [Item 7] The average content of the other hydroxyalkanoate units in the poly(3-hydroxyalkanoate) resin (A) is 1 to 6 mol%, 7.
  • the resin composition for molding according to any one of items 1 to 6, wherein the average content of the other hydroxyalkanoate units in the poly(3-hydroxyalkanoate) resin (b1) is 6 to 50 mol%. thing.
  • the poly(3-hydroxyalkanoate)-based resin (A) and the poly(3-hydroxyalkanoate)-based resin (b1) are respectively poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly (3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), and poly(3-hydroxybutyrate) 8.
  • the resin composition for molding according to any one of items 1 to 7, which is one or more selected from the group consisting of late-co-4-hydroxybutyrate).
  • the poly(3-hydroxyalkanoate)-based resin (A) and the poly(3-hydroxyalkanoate)-based resin (b1) are each poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) 9.
  • the content of the resin other than the poly(3-hydroxyalkanoate)-based resin (A) and the reaction product (B) is such that the content of the poly(3-hydroxyalkanoate)-based resin (A) and the reaction product ( 10.
  • a molded article comprising the molding resin composition according to any one of Items 1 to 12.
  • [Item 14] 14 14.
  • PBSA BioPBS (registered trademark) FD92PM manufactured by PTT MCC Biochem [polybutylene succinate adipate]
  • GPC measuring device Shimadzu Corporation high-performance liquid chromatograph 20A system Column: Showa Denko KG 4A (1 piece), K-806M (2 pieces) Sample concentration: 1 mg/ml Free liquid: chloroform solution Free liquid flow rate: 1.0 ml/min Sample injection volume: 100 ⁇ L Analysis time: 30 minutes Standard sample: standard polystyrene A chart obtained by the GPC measurement of the resin tube of Example 1 is shown in FIG.
  • Example 1 First, 1.75 kg of PHBH6, 1.75 kg of PHBH28, and 42 g of an organic peroxide were dry-blended for the production of the component (B) so that the resin composition shown in Table 1 was obtained.
  • the obtained resin material was put into a ⁇ 26 mm co-rotating twin-screw extruder set at a cylinder temperature of 150° C. and a die temperature of 150° C. and extruded.
  • the extruded resin material was passed through a water tank filled with hot water at 40° C. to solidify strands, which were cut with a pelletizer to obtain pellets of component (B).
  • the component (A) 1.5 kg of PHBH6, 50 g of Additive-1, 25 g of Additive-2 and 25 g of Additive-3 were mixed and dry-blended.
  • the obtained resin material ((A) component + additive) and the pellets of the (B) component obtained above are placed in a ⁇ 26 mm co-rotating twin-screw extruder with a cylinder temperature of 150 ° C. and a die temperature of 150 ° C. and extruded.
  • the resin composition pellets were obtained by passing the extruded resin material through a water tank filled with hot water at 40° C. to solidify strands and cutting them with a pelletizer.
  • the cylinder temperature and die temperature of a ⁇ 50 mm single-screw extruder connected to an annular die were set to 165 ° C., and the resin composition pellets were introduced and the screw rotation speed was 7.3 rpm. extruded into a tube as The extruded tube is passed through a water tank at 40°C at a distance of 100 mm from the annular die, and taken up at 10 m/min to obtain a resin tube with an outer diameter of 5 mm and a wall thickness of 0.08 mm. Met. Also, the weight average molecular weight and Z average molecular weight of the resin tube were evaluated.
  • Examples 2-7 Comparative Examples 1-3
  • Resin composition pellets were produced in the same manner as in Example 1 except that the formulation was changed as shown in Table 1, and the same evaluation as in Example 1 was performed. The results are summarized in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2023/003113 2022-02-15 2023-01-31 成形用樹脂組成物及び成形体 Ceased WO2023157633A1 (ja)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2024501078A JPWO2023157633A1 (https=) 2022-02-15 2023-01-31
US18/806,471 US20240400822A1 (en) 2022-02-15 2024-08-15 Resin composition for molding and molded article

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022021208 2022-02-15
JP2022-021208 2022-02-15

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US18/806,471 Continuation-In-Part US20240400822A1 (en) 2022-02-15 2024-08-15 Resin composition for molding and molded article

Publications (1)

Publication Number Publication Date
WO2023157633A1 true WO2023157633A1 (ja) 2023-08-24

Family

ID=87578507

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/003113 Ceased WO2023157633A1 (ja) 2022-02-15 2023-01-31 成形用樹脂組成物及び成形体

Country Status (3)

Country Link
US (1) US20240400822A1 (https=)
JP (1) JPWO2023157633A1 (https=)
WO (1) WO2023157633A1 (https=)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JP2021102669A (ja) * 2019-12-24 2021-07-15 株式会社カネカ 脂肪族ポリエステル系樹脂組成物およびその利用
WO2022014408A1 (ja) * 2020-07-17 2022-01-20 株式会社カネカ 脂肪族ポリエステル系樹脂組成物およびその利用
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
JP2021102669A (ja) * 2019-12-24 2021-07-15 株式会社カネカ 脂肪族ポリエステル系樹脂組成物およびその利用
WO2022014408A1 (ja) * 2020-07-17 2022-01-20 株式会社カネカ 脂肪族ポリエステル系樹脂組成物およびその利用
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

Also Published As

Publication number Publication date
US20240400822A1 (en) 2024-12-05
JPWO2023157633A1 (https=) 2023-08-24

Similar Documents

Publication Publication Date Title
CN115803381B (zh) 脂肪族聚酯系树脂组合物及其应用
WO2023100673A1 (ja) 樹脂チューブ
CN102056985B (zh) 生物可降解聚酯掺合物
EP4219628B1 (en) Resin composition for injection molding, and injection-molded object
CN113631657A (zh) 聚羟基烷酸酯系树脂组合物、其成型体及膜或片
JP6666328B2 (ja) ポリエステル樹脂組成物及び成形体の製造方法、並びにポリエステル樹脂組成物及び成形体
JP7755588B2 (ja) ブロー成形体
CN104662088A (zh) 聚酯树脂组合物及含有该树脂组合物的成形体
KR20110038642A (ko) 분지형 ｐｈａ 조성물, 그의 생성 방법 및 적용분야에서의 용도
JP2021102669A (ja) 脂肪族ポリエステル系樹脂組成物およびその利用
WO2023054388A1 (ja) ブロー成形体およびその製造方法
US12612488B2 (en) Resin composition for injection molding and injection-molded article
JP6401615B2 (ja) 樹脂組成物、樹脂成形体、およびこれらの製造方法
KR102787679B1 (ko) 바이오플라스틱 기반의 발포시트 및 그를 이용한 생분해 성형발포 제품
WO2024171795A1 (ja) ポリ（３－ヒドロキシアルカノエート）系樹脂組成物を含む成形体
JP7742845B2 (ja) 樹脂組成物、及びその成形体
JPWO2016114128A1 (ja) ポリエステル樹脂組成物およびポリエステル樹脂成形体
WO2023157633A1 (ja) 成形用樹脂組成物及び成形体
WO2024202634A1 (ja) 射出成形用樹脂組成物、射出成形体、及び射出成形体の製造方法
KR102029145B1 (ko) 기계적 물성이 개선된 바이오 플라스틱 및 이를 포함하는 정수기 필터 하우징
JP2016169374A (ja) ポリエステル樹脂成形体、およびその製造方法
WO2023140096A1 (ja) 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
JP7569311B2 (ja) 射出成形用樹脂組成物および射出成形体
JP6059991B2 (ja) マスターバッチ用脂肪族ポリエステル樹脂組成物及び成形用樹脂組成物
WO2025075152A1 (ja) 粉粒体、その製造方法、及び熱可塑性樹脂組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23756161

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2024501078

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 23756161

Country of ref document: EP

Kind code of ref document: A1