Classifications

• • 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
• • 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
• • 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
  • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
  • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/20—Carboxylic acid amides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

• the present invention relates to an extruded film containing a poly(3-hydroxyalkanoate) resin.
• Poly(3-hydroxyalkanoate) resins such as poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), are attracting attention as materials with this type of compost-degradability and marine-degradability.
• Patent Document 1 discloses an inflation film that contains poly(3-hydroxyalkanoate) resin as the main resin component.
• Patent Document 2 also discloses that a resin film is made using two types of poly(3-hydroxyalkanoate) resins with melting temperatures differing by 5°C or more, and that the film can be manufactured by extrusion molding using a T-die.
• Patent Documents 1 and 2 make it possible to produce extruded films containing poly(3-hydroxyalkanoate) resins.
• poly(3-hydroxyalkanoate) resins tend to solidify slowly after melting, which can result in insufficient productivity. It has been found that it tends to be difficult to increase production speed, particularly when attempting to perform continuous extrusion molding using a T-die.
• the molten resin raw material is extruded from the T-die onto a casting roll and formed into a film while being cooled.
• the resin raw material containing poly(3-hydroxyalkanoate) resin tends to stick to the casting roll and become impossible to remove.
• Patent Document 1 uses pentaerythritol, which is known as a crystal nucleating agent for poly(3-hydroxyalkanoate) resins.
• pentaerythritol which is known as a crystal nucleating agent for poly(3-hydroxyalkanoate) resins.
• solidification becomes even slower, resulting in a noticeable tendency for productivity to decrease.
• the present invention aims to provide an extruded film containing poly(3-hydroxyalkanoate)-based resin that can be manufactured with good productivity.
• the inventors discovered that by using a combination of poly(3-hydroxyalkanoate) copolymer and poly(3-hydroxybutyrate) resin to form an extruded film, the resin raw material is less likely to stick to the casting roll, and the production speed of film molding can be significantly improved, which led to the completion of the present invention.
• the present invention relates to an extruded film containing poly(3-hydroxyalkanoate)-based copolymer (A) and poly(3-hydroxybutyrate) (B).
• an extruded film containing a poly(3-hydroxyalkanoate) resin which can be produced with good productivity.
• a poly(3-hydroxyalkanoate) resin-containing extruded film having good physical properties such as elongation and strength can be continuously produced with good productivity.
• the resin raw material is less likely to stick to the casting roll, and the production speed of film molding can be significantly improved. Therefore, the problem of sugar alcohols bleeding out from the film and the problem of contamination of the production equipment (especially the casting roll surface) due to bleeding out can be avoided.
• a poly(3-hydroxyalkanoate)-based resin-containing extruded film can be produced continuously at a high production rate by a molding method in which a molten resin material is extruded from a T-die onto a casting roll.
• a poly(3-hydroxyalkanoate)-based resin-containing film that can achieve both high film molding productivity and good stretchability can be provided, and a poly(3-hydroxyalkanoate)-based resin-containing stretched film having good physical properties such as elongation and strength can be continuously produced with good productivity.
• a poly(3-hydroxyalkanoate)-based resin-containing stretched film can be produced continuously at a high production rate by continuously stretching a molten resin material from a molding method in which the molten resin material is extruded from a T-die onto a casting roll.
• the present embodiment relates to an extruded film containing a poly(3-hydroxyalkanoate)-based copolymer (A) and a poly(3-hydroxybutyrate) (B).
• the poly(3-hydroxyalkanoate) copolymer (A) may be a single poly(3-hydroxyalkanoate) copolymer or a mixture of two or more poly(3-hydroxyalkanoate) copolymers. However, it is preferable to contain at least two types of poly(3-hydroxyalkanoate) copolymers having different types of constituent monomers and/or different content ratios of the constituent monomers, since this makes it easier to achieve both productivity and physical properties of the film and can also improve stretchability.
• the poly(3-hydroxyalkanoate) copolymer (A) is preferably a polymer having a 3-hydroxyalkanoate unit, specifically a polymer containing a 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 to 15.
• R include linear or branched alkyl groups such as methyl, ethyl, propyl, methylpropyl, butyl, isobutyl, t-butyl, pentyl, and hexyl.
• p is preferably an integer of 1 to 10, and more preferably an integer of 1 to 8.
• poly(3-hydroxyalkanoate) copolymer (A) a poly(3-hydroxyalkanoate) copolymer produced from a microorganism is particularly preferred.
• a poly(3-hydroxyalkanoate) copolymer produced from a microorganism all of the 3-hydroxyalkanoate units are contained as (R)-3-hydroxyalkanoate units.
• the poly(3-hydroxyalkanoate) copolymer (A) preferably contains 3-hydroxyalkanoate units (particularly units represented by general formula (1)) in an amount of 50 mol% or more of all constituent units, more preferably 60 mol% or more, and even more preferably 70 mol% or more.
• the poly(3-hydroxyalkanoate) copolymer (A) may contain only two or more types of 3-hydroxyalkanoate units as the constituent units of the polymer, or may contain other units (e.g., 4-hydroxyalkanoate units, etc.) in addition to one or more types of 3-hydroxyalkanoate units.
• the poly(3-hydroxyalkanoate) copolymer (A) is preferably a copolymer of 3-hydroxybutyrate (hereinafter sometimes referred to as 3HB) units and other hydroxyalkanoate units (hereinafter also referred to as "poly(3-hydroxybutyrate) copolymer").
• 3HB 3-hydroxybutyrate
• poly(3-hydroxybutyrate) copolymer it is preferable that all of the 3-hydroxybutyrate units are (R)-3-hydroxybutyrate units.
• poly(3-hydroxybutyrate) copolymers include 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) (abbreviation: P3HB3HH), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (abbreviation: P3HB3HH), Examples of suitable poly(3-hydroxybutyrate-co-3-hydroxyheptanoate), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxynonanoate), poly(3-hydroxybutyrate-co-3-hydroxydecanoate), poly(3-hydroxybutyrate-co-3-hydroxyundecanoate), poly(3-hydroxybutyrate
• composition ratio of the repeating units By changing the composition ratio of the repeating units, it is possible to change the melting point and degree of crystallinity, and thus physical properties such as Young's modulus and heat resistance, making it possible to impart physical properties between those of polypropylene and polyethylene.
• poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) is particularly preferred from the viewpoints that it is easy to produce industrially and is a physically useful plastic.
• poly(3-hydroxybutyrate)-based copolymers which have the property of being easily thermally decomposed when heated to 180°C or higher
• poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) is preferred from the viewpoints that it is possible to lower the melting point and mold it at low temperatures.
• poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) products include Kaneka Biodegradable Polymer Green Planet (registered trademark) from Kaneka Corporation.
• the average content ratio of each monomer unit in all monomer units constituting the poly(3-hydroxyalkanoate)-based copolymer (A) can be determined by a method known to those skilled in the art, for example, the method described in paragraph [0047] of WO 2013/147139.
• the average content ratio means the molar ratio of each monomer unit in all monomer units constituting the poly(3-hydroxyalkanoate)-based copolymer (A), and when the poly(3-hydroxyalkanoate)-based copolymer (A) is a mixture of two or more poly(3-hydroxyalkanoate)-based copolymers, it means the molar ratio of each monomer unit contained in the entire mixture.
• the poly(3-hydroxyalkanoate) copolymer (A) preferably contains at least two types of poly(3-hydroxyalkanoate) copolymers that differ from each other in the type of constituent monomers and/or the content ratio of the constituent monomers.
• at least one type of highly crystalline poly(3-hydroxyalkanoate) copolymer and at least one type of low crystalline poly(3-hydroxyalkanoate) copolymer can be used in combination.
• the content ratio of 3-hydroxybutyrate units contained in the highly crystalline poly(3-hydroxyalkanoate) copolymer is preferably higher than the average content ratio of 3-hydroxybutyrate units in all monomer units constituting the poly(3-hydroxyalkanoate) copolymer (A).
• the content ratio of 3-hydroxybutyrate units contained in the low crystalline poly(3-hydroxyalkanoate) copolymer is preferably lower than the average content ratio of 3-hydroxybutyrate units in all monomer units constituting the poly(3-hydroxyalkanoate) copolymer (A).
• the method for obtaining a blend of two or more poly(3-hydroxyalkanoate) copolymers is not particularly limited, and may be a method for obtaining a blend by microbial production or a method for obtaining a blend by chemical synthesis.
• a blend may be obtained by melt-kneading two or more copolymers using an extruder, kneader, Banbury mixer, roll, etc., or a blend may be obtained by dissolving two or more copolymers in a solvent, mixing, and drying.
• the weight average molecular weight of the entire poly(3-hydroxyalkanoate) copolymer (A) is not particularly limited, but from the viewpoint of achieving both the physical properties of the film and productivity, it is preferably 200,000 to 2,000,000, more preferably 300,000 to 1,500,000, and even more preferably 400,000 to 1,000,000.
• the weight average molecular weight of the poly(3-hydroxyalkanoate) copolymer can be measured in terms of polystyrene using gel permeation chromatography (Shimadzu Corporation HPLC GPC system) using a chloroform solution. A column suitable for measuring the weight average molecular weight can be used as the column for the gel permeation chromatography.
• the weight average molecular weight of each poly(3-hydroxyalkanoate) copolymer described below can also be measured in the same manner.
• the method for producing poly(3-hydroxyalkanoate) copolymers is not particularly limited, and may be a production method by chemical synthesis or a production method using microorganisms. Among these, production methods using microorganisms are preferred. Known methods can be applied to the production method using microorganisms.
• known bacteria that produce copolymers of 3-hydroxybutyrate and other hydroxyalkanoates include Aeromonas caviae, which produces P3HB3HV and P3HB3HH, and Alcaligenes eutrophus, which produces P3HB4HB.
• genetically modified microorganisms into which various poly(3-hydroxyalkanoate) copolymer synthesis-related genes have been introduced may be used according to the poly(3-hydroxyalkanoate) copolymer to be produced, and the culture conditions, including the type of substrate, may be optimized.
• an unmodified poly(3-hydroxyalkanoate) copolymer can be used as the poly(3-hydroxyalkanoate) copolymer (A).
• a copolymer obtained by modifying an unmodified poly(3-hydroxyalkanoate) copolymer with a raw material that reacts with the copolymer, such as a peroxide (hereinafter referred to as a "modifying raw material") may also be used.
• a peroxide hereinafter referred to as a "modifying raw material”
• the modified copolymer obtained by reacting the copolymer with the modifying raw material in advance may be molded into a film, or the copolymer may be mixed with the modifying raw material and reacted at the time of film molding.
• the entire copolymer may be reacted with the modifying raw material, or a part of the copolymer may be reacted with the modifying raw material to obtain a modified copolymer, and the remaining unmodified copolymer may be added to the modified copolymer.
• the raw material for modification is not particularly limited as long as it is a compound that can react with poly(3-hydroxyalkanoate)-based copolymers, but organic peroxides are preferably used because of their ease of handling and the ease of controlling the reaction with poly(3-hydroxyalkanoate)-based copolymers.
• organic peroxides are preferably used because of their ease of handling and the ease of controlling the reaction with poly(3-hydroxyalkanoate)-based copolymers.
• the compounds described below can be used as appropriate as the organic compound.
• the poly(3-hydroxyalkanoate) copolymer (A) contains at least a copolymer (A-1) of 3-hydroxybutyrate units and other hydroxyalkanoate units, the content of which is 24 mol % or more.
• the poly(3-hydroxyalkanoate)-based copolymer (A) preferably further contains, in addition to the copolymer (A-1), a copolymer (A-2) of 3-hydroxybutyrate units and other hydroxyalkanoate units, in which the content of other hydroxyalkanoate units is 1 mol % or more and less than 5 mol %.
• a copolymer (A-2) which has a higher crystallinity than the copolymer (A-1), in combination with the copolymer (A-1), it is possible to improve the productivity and physical properties of the film in a well-balanced manner.
• the content of the other hydroxyalkanoate units is preferably 24 to 99 mol%, more preferably 24 to 50 mol%, further preferably 24 to 35 mol%, and particularly preferably 24 to 30 mol%.
• the content of the other hydroxyalkanoate units is preferably from 2 to 4 mol %, more preferably from 2 to 3 mol %.
• copolymer (A-1) and the copolymer (A-2) poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) is preferable, and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) is particularly preferable.
• the weight average molecular weight of copolymer (A-1) and copolymer (A-2) is preferably from 200,000 to 2,500,000, more preferably from 220,000 to 2,300,000, and even more preferably from 250,000 to 2,000,000, from the viewpoint of achieving both the physical properties of the film and productivity.
• the content of copolymer (A-1) is preferably 5% by weight or more and 85% by weight or less of the total weight of poly(3-hydroxyalkanoate)-based copolymer (A) and poly(3-hydroxybutyrate) (B) from the viewpoint of the balance between productivity and physical properties of the film, and from the viewpoint of improving the elongation of the film.
• the lower limit is more preferably 15% by weight or more, even more preferably 20% by weight or more, and particularly preferably 25% by weight or more, from the viewpoint of elongation.
• the upper limit is more preferably 70% by weight or less, even more preferably 60% by weight or less, even more preferably 50% by weight or less, and particularly preferably 40% by weight or less, from the viewpoint of productivity of the film.
• copolymer (A) contains copolymer (A-1) and copolymer (A-2)
• the weight ratio (A-1/A-2) of copolymer (A-1) to copolymer (A-2) is preferably 20/80 to 80/20, more preferably 30/70 to 70/30, and even more preferably 40/60 to 60/40, from the viewpoint of achieving both the physical properties of the film and productivity, and from the viewpoint of improving the elongation of the film.
• the poly(3-hydroxyalkanoate)-based copolymer (A) preferably further contains, in addition to the copolymers (A-1) and (A-2), a copolymer (A-3) of 3-hydroxybutyrate units and other hydroxyalkanoate units, in which the content of other hydroxyalkanoate units is 5 mol % or more and less than 24 mol %.
• the crystallinity of the copolymer (A-3) is intermediate between that of the copolymers (A-1) and (A-2).
• the content of other hydroxyalkanoate units is preferably 6 mol% or more.
• the upper limit is more preferably 20 mol% or less, even more preferably 15 mol% or less, and particularly preferably 10 mol% or less.
• copolymer (A-3) poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) is preferred, with poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) being particularly preferred.
• the weight average molecular weight of the copolymer (A-3) is preferably from 200,000 to 2,500,000, more preferably from 250,000 to 2,300,000, and even more preferably from 300,000 to 2,000,000, from the viewpoint of achieving both the physical properties of the film and productivity.
• the content of copolymer (A-3) is preferably 0% by weight or more and 50% by weight or less of the total weight of poly(3-hydroxyalkanoate)-based copolymer (A) and poly(3-hydroxybutyrate) (B) from the viewpoint of achieving both the physical properties of the film and productivity.
• the lower limit is preferably 10% by weight or more, and more preferably 20% by weight or more.
• the upper limit is more preferably 45% by weight or less, and even more preferably 40% by weight or less.
• the weight average molecular weight of the entire poly(3-hydroxyalkanoate) copolymer (A) is not particularly limited, but from the viewpoint of achieving both the physical properties of the film and productivity, it is preferably 200,000 to 2,000,000, more preferably 300,000 to 1,500,000, and even more preferably 400,000 to 1,000,000.
• the poly(3-hydroxyalkanoate)-based copolymer (A) contains a reaction product (A') of a poly(3-hydroxyalkanoate)-based copolymer and an organic peroxide.
• the reaction product is a modified resin in which a crosslinked structure has been introduced into the poly(3-hydroxyalkanoate)-based copolymer by reaction with an organic peroxide.
• the poly(3-hydroxyalkanoate) copolymer before reacting with the organic peroxide may be a single poly(3-hydroxyalkanoate) copolymer or a mixture of two or more poly(3-hydroxyalkanoate) copolymers.
• the reactant (A') preferably contains at least a reaction product of a copolymer (A-1) of 3-hydroxybutyrate units and other hydroxyalkanoate units, the content of which is 24 mol% or more, with an organic peroxide.
• a copolymer (A-1) of 3-hydroxybutyrate units and other hydroxyalkanoate units the content of which is 24 mol% or more
• an organic peroxide the copolymer having a high content of other hydroxyalkanoate units and low crystallinity with an organic peroxide and using it in combination with poly(3-hydroxybutyrate) (B)
• the poly(3-hydroxyalkanoate) copolymer (A) preferably contains a copolymer (A-2) of 3-hydroxybutyrate units and other hydroxyalkanoate units, the content of which is 1 mol% or more and less than 5 mol%.
• the copolymer (A-2) may be a reactant (A') with an organic peroxide or an unreacted product, but is preferably a reactant (A').
• the copolymer (A-2) which has higher crystallinity than the copolymer (A-1), it is possible to improve the balance between the productivity and the stretchability of the film, and further to easily achieve good film properties.
• the copolymer (A-2) is preferably used in combination with the copolymer (A-1).
• the content of the other hydroxyalkanoate units is preferably 24 to 99 mol%, more preferably 24 to 50 mol%, further preferably 24 to 35 mol%, and particularly preferably 24 to 30 mol%.
• the content of the other hydroxyalkanoate units is preferably from 2 to 4 mol %, more preferably from 2 to 3 mol %.
• copolymer (A-1) and the copolymer (A-2) poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) is preferable, and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) is particularly preferable.
• the weight average molecular weight of copolymer (A-1) and copolymer (A-2) is preferably from 200,000 to 2,300,000, more preferably from 220,000 to 2,000,000, and even more preferably from 250,000 to 1,500,000, from the viewpoint of achieving both film productivity and stretchability.
• the amount of copolymer (A-1) used is preferably 5% by weight or more and 60% by weight or less based on the total weight of the poly(3-hydroxyalkanoate)-based copolymer (A) and poly(3-hydroxybutyrate) (B) from the viewpoint of the balance between film productivity and stretchability, and from the viewpoint of improving film elongation.
• the lower limit is more preferably 7% by weight or more, even more preferably 10% by weight or more, and particularly preferably 20% by weight or more, from the viewpoint of film elongation.
• the upper limit is more preferably 50% by weight or less, and even more preferably 40% by weight or less, from the viewpoint of film productivity.
• the weight ratio (A-1/A-2) of copolymer (A-1) to copolymer (A-2) is preferably 20/80 to 80/20, more preferably 30/70 to 70/30, and even more preferably 40/60 to 60/40, from the viewpoint of achieving both productivity and stretchability of the film and improving the elongation of the film.
• the poly(3-hydroxyalkanoate) copolymer (A) preferably contains a copolymer (A-3) of 3-hydroxybutyrate units and other hydroxyalkanoate units, the content of which is 5 mol% or more and less than 24 mol%.
• the copolymer (A-3) may be a reactant (A') with an organic peroxide or an unreacted product, but is preferably a reactant (A').
• the crystallinity of the copolymer (A-3) is intermediate between the copolymers (A-1) and (A-2).
• the content of other hydroxyalkanoate units is preferably 6 mol% or more.
• the upper limit is more preferably 20 mol% or less, even more preferably 15 mol% or less, and particularly preferably 10 mol% or less.
• copolymer (A-3) poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) is preferred, with poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) being particularly preferred.
• the weight average molecular weight of the copolymer (A-3) is preferably from 200,000 to 2,500,000, more preferably from 250,000 to 2,300,000, and even more preferably from 300,000 to 2,000,000, from the viewpoint of achieving both film productivity and stretchability.
• the content of copolymer (A-3) is preferably 0% by weight or more and 85% by weight or less of the total weight of poly(3-hydroxyalkanoate)-based copolymer (A) and poly(3-hydroxybutyrate) (B) from the viewpoint of achieving both film productivity and stretchability, and from the viewpoint of film physical properties.
• the lower limit is preferably 5% by weight or more, more preferably 10% by weight or more, even more preferably 20% by weight or more, even more preferably 30% by weight or more, and particularly preferably 40% by weight or more.
• the upper limit is more preferably 80% by weight or less, and even more preferably 75% by weight or less.
• the weight average molecular weight of the entire poly(3-hydroxyalkanoate) copolymer (A) is not particularly limited, but from the viewpoint of achieving both productivity and stretchability of the film, it is preferably 200,000 to 2,000,000, more preferably 300,000 to 1,500,000, and even more preferably 400,000 to 1,000,000.
• the weight average molecular weight described here is the value measured for the copolymer before it is reacted with the organic peroxide.
• Organic peroxides are not particularly limited, but examples thereof include diisobutyl peroxide, cumyl peroxyneodecanoate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, bis(4-t-butylcyclohexyl)peroxydicarbonate, bis(2-ethylhexyl)peroxydicarbonate, t-hexyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxyneoheptanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, di(3,5,5-trimethylhexanoyl)peroxide, dilauroyl peroxide ...
• peroxyalkylene oxide examples include oxy-2-ethylhexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane, t-hexylperoxy-2-ethylhexanoate, di(4-methylbenzoyl)peroxide, dibenzoyl peroxide, t-butylperoxy 2-ethylhexyl carbonate, t-butylperoxy isopropyl carbonate, 1,6-bis(t-butylperoxycarbonyloxy)hexane, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy acetate, t-butylperoxybenzoate, t-amylperoxy, 3,5,5-trimethylhexanoate, 2,2-bis(4,4-di-t-butylperoxycyclohexyl
• dibenzoyl peroxide t-butylperoxy 2-ethylhexyl carbonate, and t-butylperoxy isopropyl carbonate are preferred.
• organic peroxide one type may be used alone, or two or more types may be used in combination.
• Organic peroxides are used in various forms, such as solid and liquid, and may be liquid forms diluted with a diluent or the like. Among them, organic peroxides in a form that can be mixed with poly(3-hydroxyalkanoate)-based copolymers (particularly organic peroxides that are liquid at room temperature (25°C)) are preferred because they can be uniformly dispersed in the poly(3-hydroxyalkanoate)-based copolymer and make it easier to suppress localized denaturation reactions.
• the amount of organic peroxide used is preferably 0.01 to 3 parts by weight per 100 parts by weight of the poly(3-hydroxyalkanoate) copolymer to be reacted with the organic peroxide. More preferably, it is 0.03 to 2 parts by weight, even more preferably, it is 0.05 to 1 part by weight, and particularly preferably, it is 0.1 to 0.5 parts by weight.
• the reaction product (A') of the poly(3-hydroxyalkanoate) copolymer and the organic peroxide can be preferably obtained by feeding the poly(3-hydroxyalkanoate) copolymer and the organic peroxide into an extruder and melt-kneading them. This allows the poly(3-hydroxyalkanoate) copolymer to be uniformly crosslinked.
• other components such as a crystal nucleating agent and a lubricant, as described below, may also be fed into the extruder to perform melt-kneading.
• Poly(3-hydroxybutyrate) (B) may also be fed into the extruder to perform melt-kneading.
• the melt kneading can be carried out according to known or conventional methods, for example, using an extruder (single-screw extruder or twin-screw extruder), kneader, etc.
• the conditions for melt kneading are not particularly limited and can be set as appropriate, but it is preferable to set a resin temperature and residence time that can complete the reaction with the organic peroxide during melt kneading. Specifically, it is preferable to melt knead when the resin temperature measured with a die thermometer is in the range of 130°C to 190°C. It is also preferable to melt knead so that the residence time in the extruder is 60 seconds to 300 seconds.
• the resin material can be extruded into strands and cut to obtain pellets with particle shapes such as cylinders, elliptical cylinders, spheres, cubes, and rectangular parallelepipeds.
• the pellets produced are preferably thoroughly dried at 40 to 80°C to remove moisture before use. However, the pelletizing process may be omitted, and the film molding process may be carried out following the melt kneading process.
• the poly(3-hydroxyalkanoate)-based copolymer (A) contains a copolymer (A-3') of 3-hydroxybutyrate units and other hydroxyalkanoate units, the content of which is 5 mol% or more and less than 24 mol% and has a weight-average molecular weight of 700,000 or more.
• the copolymer (A-3') having a medium crystallinity and a high molecular weight in combination with the poly(3-hydroxybutyrate) (B) the stretchability of the poly(3-hydroxyalkanoate)-based resin-containing extruded film can be improved.
• the content of other hydroxyalkanoate units is 5 mol% or more and less than 24 mol%, but the lower limit is preferably 6 mol% or more, more preferably 8 mol% or more, and even more preferably 10 mol% or more.
• the upper limit is preferably 20 mol% or less, more preferably 17 mol% or less, and even more preferably 14 mol% or less.
• copolymer (A-3') poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) is preferred, with poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) being particularly preferred.
• the weight average molecular weight of the copolymer (A-3') is 700,000 or more, preferably 750,000 or more. There is no particular upper limit, but from the viewpoint of productivity, it is preferably 2,000,000 or less, more preferably 1,500,000 or less, and even more preferably 1,000,000 or less.
• the content of the copolymer (A-3') is 20% by weight or more and 80% by weight or less of the total weight of the poly(3-hydroxyalkanoate)-based copolymer (A) and poly(3-hydroxybutyrate) (B) from the viewpoint of the balance between the stretchability of the film, the productivity, and the strength. This makes it possible to obtain the effect of improving the stretchability by blending the copolymer (A-3'), and to produce the extruded film with good productivity.
• the lower limit is preferably 30% by weight or more, more preferably 40% by weight or more, even more preferably 45% by weight or more, even more preferably 50% by weight or more, particularly preferably 60% by weight or more, and most preferably 70% by weight or more.
• the upper limit is preferably 75% by weight or less, and more preferably 70% by weight or less.
• the copolymer (A-3') preferably includes a copolymer (A-3'-1) of 3-hydroxybutyrate units and other hydroxyalkanoate units, in which the content of other hydroxyalkanoate units is 5 mol% or more and less than 10 mol% and the weight average molecular weight is 700,000 or more, and a copolymer (A-3'-2) of 3-hydroxybutyrate units and other hydroxyalkanoate units, in which the content of other hydroxyalkanoate units is 10 mol% or more and less than 24 mol% and the weight average molecular weight is 700,000 or more.
• the ratio of the copolymer (A-3'-2) to the total of the copolymer (A-3'-1) and the copolymer (A-3'-2) is preferably 30 to 90% by weight, more preferably 50 to 85% by weight, and even more preferably 60 to 83% by weight.
• the poly(3-hydroxyalkanoate) copolymer (A) may further contain a copolymer (A-3") of 3-hydroxybutyrate units and other hydroxyalkanoate units, in which the content of other hydroxyalkanoate units is 5 mol% or more and less than 24 mol% and the weight average molecular weight is less than 700,000.
• the content of other hydroxyalkanoate units is 5 mol% or more and less than 24 mol%, but the lower limit is preferably 6 mol% or more, more preferably 8 mol% or more, and even more preferably 10 mol% or more.
• the upper limit is preferably 20 mol% or less, more preferably 17 mol% or less, and even more preferably 14 mol% or less.
• copolymer (A-3") poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) is preferred, with poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) being particularly preferred.
• the weight average molecular weight of the copolymer (A-3") is less than 700,000, but from the viewpoint of film productivity, it is preferably 600,000 or less, and more preferably 500,000 or less. There is no particular lower limit, but from the viewpoint of the physical properties of the film, it is preferably 200,000 or more, and more preferably 300,000 or more.
• the copolymer (A) may be composed of only the copolymer (A-3'), or may be composed of only the copolymer (A-3') and the copolymer (A-3"). However, it may further contain a poly(3-hydroxyalkanoate)-based copolymer that does not fall into either the copolymer (A-3') or the copolymer (A-3").
• Examples of such poly(3-hydroxyalkanoate)-based copolymers include a copolymer (A-2) of 3-hydroxybutyrate units and other hydroxyalkanoate units, in which the content of the other hydroxyalkanoate units is 1 mol% or more and less than 5 mol%, and a copolymer (A-1) of 3-hydroxybutyrate units and other hydroxyalkanoate units, in which the content of the other hydroxyalkanoate units is 24 mol% or more.
• the amount of copolymer (A-3') relative to the total amount of copolymer (A), or, when copolymer (A-3") is contained, the total amount of copolymer (A-3') and copolymer (A-3") relative to the total amount of copolymer (A), is, for example, preferably 70 to 100% by weight, more preferably 80 to 100% by weight, and even more preferably 90 to 100% by weight.
• the weight average molecular weight of the entire poly(3-hydroxyalkanoate) copolymer (A) is not particularly limited, but from the viewpoint of the stretchability of the film, it is preferably 500,000 to 2,000,000, more preferably 600,000 to 1,500,000, and even more preferably 700,000 to 1,000,000.
• the extruded film according to this embodiment contains poly(3-hydroxybutyrate) (B).
• Poly(3-hydroxybutyrate) (B) exhibits higher crystallinity than poly(3-hydroxyalkanoate)-based copolymer (A) and has the property of being easily solidified. Therefore, by using a formulation containing this resin, the solidification of poly(3-hydroxybutyrate) (B) proceeds rapidly when the molten resin material is cooled by a cast roll, so that the entire resin material is less likely to stick to the cast roll, and the productivity of the extruded film containing poly(3-hydroxyalkanoate)-based resin can be increased.
• Poly(3-hydroxybutyrate) (B) refers to a homopolymer of 3-hydroxybutyrate, or a polymer that contains a small amount of hydroxyalkanoate units other than 3-hydroxybutyrate units in addition to 3-hydroxybutyrate units. Specifically, it is preferable that poly(3-hydroxybutyrate) (B) contains 3-hydroxybutyrate units in a proportion of more than 99 mol% and not more than 100 mol% of the total constituent monomers.
• Hydroxyalkanoate units other than 3-hydroxybutyrate units that may be contained in poly(3-hydroxybutyrate) (B) are not particularly limited as long as they are copolymerizable with 3-hydroxybutyrate units, but examples include 3-hydroxyalkanoate units other than 3-hydroxybutyrate units and hydroxyalkanoate units other than 3-hydroxyalkanoate units (e.g., 4-hydroxyalkanoate units). In particular, 3-hydroxyhexanoate units are preferred.
• the weight average molecular weight of poly(3-hydroxybutyrate) (B) is not particularly limited, but from the viewpoint of improving the productivity of the film, it is preferably 200,000 to 2,000,000, and more preferably 300,000 to 1,500,000.
• the upper limit is more preferably 1,000,000 or less, and particularly preferably 500,000 or less.
• the weight average molecular weight can be measured by the method described above.
• Poly(3-hydroxybutyrate) (B) may be an unmodified resin, or may be a resin modified by reaction with an organic peroxide.
• the type and amount of organic peroxide that can be used, and the method of modification are as described above for the poly(3-hydroxyalkanoate)-based copolymer (A) of the second embodiment, and therefore will not be described here.
• the modification of the poly(3-hydroxyalkanoate)-based copolymer (A) and the modification of the poly(3-hydroxybutyrate) (B) may be carried out separately and then the two may be mixed, or the poly(3-hydroxyalkanoate)-based copolymer (A) and the poly(3-hydroxybutyrate) (B) may be mixed before modification and then both may be modified simultaneously.
• the content of poly(3-hydroxybutyrate) (B) is preferably 2% by weight or more and 75% by weight or less of the total weight of poly(3-hydroxyalkanoate)-based copolymer (A) and poly(3-hydroxybutyrate) (B) from the viewpoint of achieving both productivity and physical properties of the film.
• the lower limit is more preferably 3% by weight or more, even more preferably 10% by weight or more, and particularly preferably 15% by weight or more, from the viewpoint of improving productivity.
• the upper limit is more preferably 70% by weight or less, even more preferably 60% by weight or less, even more preferably 50% by weight or less, particularly preferably 40% by weight or less, and most preferably 30% by weight or less, from the viewpoint of film physical properties.
• the content of poly(3-hydroxybutyrate) (B) is preferably 5% by weight or more and 60% by weight or less of the total weight of poly(3-hydroxyalkanoate)-based copolymer (A) and poly(3-hydroxybutyrate) (B) from the viewpoint of achieving both film productivity and stretchability.
• the lower limit is more preferably 10% by weight or more, and even more preferably 12% by weight or more, from the viewpoint of improving film productivity.
• the upper limit is more preferably 50% by weight or less, even more preferably 40% by weight or less, even more preferably 30% by weight or less, particularly preferably 25% by weight or less, and most preferably 20% by weight or less, from the viewpoint of film physical properties.
• the extruded film according to this embodiment is a resin film mainly composed of poly(3-hydroxyalkanoate) copolymer (A) and poly(3-hydroxybutyrate) (B).
• the total proportion of poly(3-hydroxyalkanoate) copolymer (A) and poly(3-hydroxybutyrate) (B) in the total amount of the extruded film may be 50% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, and even more preferably 90% by weight or more. It may be 95% by weight or more, or 98% by weight or more.
• the extruded film according to this embodiment may contain other resins in addition to the poly(3-hydroxyalkanoate) copolymer (A) and poly(3-hydroxybutyrate) (B) within the scope of the invention.
• other resins include aliphatic polyester resins such as polylactic acid, polybutylene succinate adipate, polybutylene succinate, and polycaprolactone, and aliphatic aromatic polyester resins such as polybutylene adipate terephthalate, polybutylene sebate terephthalate, and polybutylene azelate terephthalate. Only one type of other resin may be contained, or two or more types may be contained.
• the content of the other resin is not particularly limited, but is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, and even more preferably 30 parts by weight or less, relative to 100 parts by weight of the total of poly(3-hydroxyalkanoate) copolymer (A) and poly(3-hydroxybutyrate) (B). It may be 10 parts by weight or less, 5 parts by weight or less, or 1 part by weight or less. There is no particular lower limit for the content of the other resin, and it may be 0 parts by weight or more.
• the extruded film according to the present embodiment may contain additives that can be used together with the poly(3-hydroxyalkanoate) copolymer (A) and the poly(3-hydroxybutyrate) (B) to the extent that the effects of the invention are not impaired.
• additives include colorants such as pigments and dyes, odor absorbents such as activated carbon and zeolite, fragrances such as vanillin and dextrin, fillers, plasticizers, antioxidants, weather resistance improvers, ultraviolet absorbers, crystal nucleating agents, lubricants, release agents, water repellents, antibacterial agents, and sliding property improvers. Only one type of additive may be contained, or two or more types may be contained. The content of these additives can be appropriately set by a person skilled in the art depending on the purpose of use. The crystal nucleating agent, lubricant, filler, and plasticizer will be described in more detail below.
• crystal nucleating agent The extruded film according to the present embodiment may contain a crystal nucleating agent.
• crystal nucleating agents include sugar alcohols such as pentaerythritol, galactitol, and mannitol; talc; fatty acid amides; orotic acid, aspartame, cyanuric acid, glycine, zinc phenylphosphonate, and boron nitride.
• sugar alcohols are preferred, and pentaerythritol is particularly preferred, because they are particularly effective in promoting the crystallization of the poly(3-hydroxyalkanoate)-based copolymer (A) and the poly(3-hydroxybutyrate) (B).
• the crystal nucleating agent may be used alone or in combination with two or more other agents, and the ratio of use may be appropriately adjusted depending on the purpose.
• a crystal nucleating agent When a crystal nucleating agent is used, its amount is not particularly limited, but is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, and even more preferably 0.7 to 1.5 parts by weight, per 100 parts by weight of the total of poly(3-hydroxyalkanoate) copolymer (A) and poly(3-hydroxybutyrate) (B).
• the extruded film according to this embodiment may be substantially free of sugar alcohols such as pentaerythritol.
• Substantially free of sugar alcohols means that the amount of sugar alcohols is less than 0.1 parts by weight per 100 parts by weight of the total of poly(3-hydroxyalkanoate) copolymer (A) and poly(3-hydroxybutyrate) (B). It may be less than 0.01 parts by weight.
• sugar alcohols are substantially free of sugar alcohols, it is possible to avoid the problems of bleeding out of sugar alcohols from the film and the associated contamination of the cast roll surface.
• talc and/or a fatty acid amide as a crystal nucleating agent, and it is particularly preferable to blend both talc and a fatty acid amide.
• these crystal nucleating agents in combination with poly(3-hydroxybutyrate) (B), even when sugar alcohols are not substantially blended, the productivity of the extruded film can be improved, and further, the problem of blocking, in which films stick to each other after the extruded film is wound up, can be suppressed.
• Specific examples of the fatty acid amide are as follows: The fatty acid amide blended in the extruded film according to the present embodiment can function as both a crystal nucleating agent and a lubricant.
• the extruded film according to the present embodiment may contain a lubricant.
• the lubricant include behenamide, oleamide, erucamide, stearamide, palmitamide, N-stearylbehenamide, N-stearylerucamide, ethylenebisstearamide, ethylenebisoleamide, ethylenebiserucamide, ethylenebislauramide, ethylenebiscapricamide, p-phenylenebisstearamide, and polycondensates of ethylenediamine, stearic acid, and sebacic acid.
• behenamide or erucamide is preferred because of its particularly excellent lubricant effect on the poly(3-hydroxyalkanoate)-based copolymer (A) and poly(3-hydroxybutyrate) (B).
• One type of lubricant may be used, or two or more types may be used, and the ratio of use may be appropriately adjusted depending on the purpose.
• the amount used is not particularly limited, but is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, and even more preferably 0.1 to 1.5 parts by weight, per 100 parts by weight of the total of the poly(3-hydroxyalkanoate) copolymer (A) and poly(3-hydroxybutyrate) (B).
• the extruded film according to this embodiment preferably contains a lubricant, but does not have to contain one.
• the extruded film according to the present embodiment may contain a filler.
• a filler By including a filler, a film with higher strength can be obtained.
• the filler may be either an inorganic filler or an organic filler, or both may be used in combination.
• the inorganic filler is not particularly limited, but examples thereof include talc, silicate, carbonate, sulfate, phosphate, oxide, hydroxide, nitride, carbon black, and the like. Only one type of inorganic filler may be used, or two or more types may be used in combination.
• the filler When the filler is used, its content is not particularly limited, but is preferably 0.5 to 100 parts by weight, more preferably 1 to 80 parts by weight, even more preferably 3 to 70 parts by weight, and even more preferably 5 to 60 parts by weight, per 100 parts by weight of the total of the poly(3-hydroxyalkanoate)-based copolymer (A) and poly(3-hydroxybutyrate) (B).
• the extruded film according to this embodiment may not substantially contain a filler.
• “Substantially no filler” means that the amount of filler is less than 0.5 parts by weight per 100 parts by weight of the total of the poly(3-hydroxyalkanoate)-based copolymer (A) and poly(3-hydroxybutyrate) (B). It may be less than 0.1 parts by weight.
• the extruded film according to the present embodiment may contain a plasticizer.
• the plasticizer include glycerin ester compounds, citrate ester compounds, sebacic acid ester compounds, adipate compounds, polyether ester compounds, benzoic acid ester compounds, phthalic acid ester compounds, isosorbide ester compounds, polycaprolactone compounds, and dibasic acid ester compounds.
• glycerin ester compounds, citrate ester compounds, sebacic acid ester compounds, and dibasic acid ester compounds are preferred because of their particularly excellent plasticizing effect on the poly(3-hydroxyalkanoate) copolymer (A).
• Examples of the glycerin ester compounds include glycerin diacetomonolaurate.
• Examples of the citrate compounds include acetyl tributyl citrate.
• Examples of the sebacic acid ester compounds include dibutyl sebacate.
• Examples of the dibasic acid ester compounds include benzyl methyl diethylene glycol adipate.
• the plasticizer may be used alone or in combination of two or more kinds, and the ratio of use can be appropriately adjusted depending on the purpose.
• the amount used is not particularly limited, but is preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight, and even more preferably 3 to 10 parts by weight, per 100 parts by weight of the poly(3-hydroxyalkanoate) copolymer (A) and poly(3-hydroxybutyrate) (B) combined.
• the extruded film according to this embodiment may be substantially free of plasticizer.
• Substantially no plasticizer is blended means that the amount of plasticizer blended is less than 1 part by weight per 100 parts by weight of the poly(3-hydroxyalkanoate) copolymer (A) and poly(3-hydroxybutyrate) (B) combined. It may be less than 0.1 part by weight.
• extruded film refers to a film produced by an extrusion process.
• the extruded film according to the present embodiment may be an unstretched film that has not been subjected to a stretching process, or may be a stretched film that has been stretched in the MD direction and/or TD direction after film formation.
• the "extruded film” in this application may include both an unstretched film and a stretched film. From the viewpoint of strength, a stretched film is preferred. In particular, according to the second and third aspects, the stretched film can be produced with high productivity.
• the thickness of the extruded film according to this embodiment is preferably 10 to 200 ⁇ m, more preferably 15 to 150 ⁇ m, and even more preferably 20 to 100 ⁇ m, from the viewpoints of the uniform thickness, appearance, strength, light weight, etc. of the film.
• the extruded film according to this embodiment is preferably a long film that is produced industrially, and is particularly preferably a strip-shaped film wound into a roll.
• the length of such a film is not particularly limited, but may be, for example, 5,000 m or more, or 10,000 m or more. In this embodiment, such long films can be produced continuously and stably.
• An extruded film is produced by melting a film raw material containing the poly(3-hydroxyalkanoate) copolymer (A), the poly(3-hydroxybutyrate) (B), and, if necessary, other components, and extruding the molten film raw material, i.e., by carrying out an extrusion molding method.
• a film having a uniform thickness can be easily and continuously produced.
• a single screw extruder, a twin screw extruder, or the like can be appropriately used.
• extrusion molding methods include the T-die method, in which molten raw materials are extruded from a T-die into a flat film, and the inflation method, in which molten resin is extruded from a ring-shaped die and gas is blown into the inside to expand it into a bag shape.
• films produced by extrusion molding from a T-die are called T-die films.
• the present invention can be suitably applied to the production of T-die films. The production of T-die films will be explained in detail below.
• the conditions for melting the film raw materials may be any conditions under which the poly(3-hydroxyalkanoate) copolymer (A) and poly(3-hydroxybutyrate) (B) melt, and the temperature of the molten film raw materials may be, for example, about 140 to 210°C.
• the molten film material is then extruded onto a casting roll to form a film.
• the molten film material comes into contact with the casting roll and moves along the surface of the casting roll, causing it to cool and solidify.
• This step may be a step of extruding a molten material onto one or more casting rolls, or a step of opposing a touch roll to a casting roll and sandwiching the molten material extruded onto the casting roll between the touch rolls.
• an air knife or an air chamber may be used.
• the casting roll may be placed in a water tank or an air chamber may be used.
• the lower limit of the set temperature of the casting roll is preferably 0°C or higher, more preferably 10°C or higher, and even more preferably 15°C or higher, in order to suppress the adhesion of the poly(3-hydroxyalkanoate)-based copolymer (A) and improve its releasability from the casting roll.
• the temperature is preferably higher than the glass transition temperature (Tg) of the poly(3-hydroxyalkanoate)-based copolymer (A) + 10°C.
• the upper limit of the temperature setting of the cast roll is not particularly limited, but from the viewpoint of promoting solidification of the poly(3-hydroxyalkanoate)-based copolymer (A), it is preferably 80°C or less, and more preferably 60°C or less.
• the film cooled on the casting roll is transported while the casting roll is rotating, and the film is peeled off from the casting roll. This produces an unstretched film.
• the MD direction is also called the machine direction, flow direction, or longitudinal direction.
• the TD direction which will be described later, is the direction perpendicular to the MD direction, and is also called the perpendicular direction or width direction.
• the stretching process in the MD direction can be carried out continuously from the peeling off of the cast roll within one production line.
• This process is not particularly limited, but can be carried out, for example, by using a roll longitudinal stretching machine to create a difference in the rotation speed between multiple rolls that transport the film.
• the heating temperature is preferably 70°C or higher, more preferably 90°C or higher, and even more preferably 100°C or higher. If a reaction product (A') with an organic peroxide or a high molecular weight substance (A-3') is used as the poly(3-hydroxyalkanoate) copolymer, it is difficult to break even when stretched at such high temperatures, and stretching at a high ratio is possible.
• the upper limit of the heating temperature is preferably below the melting point of the poly(3-hydroxyalkanoate) resin.
• the heating method is not particularly limited, but examples include a method in which an air current adjusted to a predetermined temperature is applied to the film, a method in which the film temperature is controlled by setting a roll to a predetermined temperature, a method in which the film temperature is controlled to a predetermined temperature by heating the film using an auxiliary heating means such as an IR heater, and a method in which the film is passed through an oven adjusted to a predetermined temperature. These methods may be used alone or in combination.
• the stretching ratio in the MD direction is not particularly limited, but in order to improve the strength and elongation of the film, it is desirable that it be 1.5 times or more. It is preferably 2 times or more, and more preferably 2.5 times or more.
• Such a high stretching ratio can be achieved by using the reaction product (A') of a poly(3-hydroxyalkanoate)-based copolymer and an organic peroxide, or a high molecular weight poly(3-hydroxyalkanoate)-based copolymer (A-3').
• the upper limit of the stretching ratio is usually 8 times or less, but may be 6 times or less.
• a biaxially stretched film with high strength in both the MD and TD directions can be obtained.
• the stretching process in the TD direction can be carried out continuously from the stretching process in the MD direction in one production line. This process is not particularly limited, but can be carried out, for example, by using a transverse stretching machine such as a clip-type tenter to clamp both widthwise ends of the film and pull it in the TD direction.
• the stretching process in the TD direction is also preferably carried out while heating the film.
• heating method There are no particular limitations on the heating method, and examples include those described above for the stretching process in the MD direction.
• the temperature during the TD stretching process may be the same as the temperature during MD stretching described above, but such a temperature is preferably 35 to 150°C, more preferably 45 to 140°C, and even more preferably 55 to 130°C.
• the stretching ratio in the TD direction is not particularly limited, but it is desirable that it be 1.5 times or more in order to improve the strength and elongation of the film in the TD direction. It is preferably 2 times or more, and more preferably 2.5 times or more.
• the upper limit of the stretching ratio is usually 8 times or less, but may be 6 times or less.
• the stretched film is heated to a temperature at which high-melting point crystals grow. This increases the crystallinity of the film, increases the strength of the stretched film, and stabilizes the physical properties of the stretched film.
• the heating temperature during heat setting is preferably 80 to 150°C, more preferably 90 to 135°C, and most preferably 100 to 130°C. If the heating temperature is 80°C or higher, the crystallization degree of the stretched film increases, and the crystals formed may have a high melting point. If the heating temperature is 150°C or lower, breakage due to melting of the film can be avoided.
• This heating can be carried out, for example, by heating the film while maintaining its stretched state after the stretching process. At this time, heat shrinkage occurs in the opposite direction to the stretching direction, so it is preferable to relax it to prevent breakage. Relaxation is an operation in which tension is released in the opposite direction to the stretching direction, and it is preferable to appropriately adjust the amount of relaxation between 5 and 30%.
• a step of cooling the film may be carried out as appropriate. After this, it is preferable to carry out a step of winding the film onto a winding roll.
• the manufacturing method for the extruded film according to this embodiment is preferably carried out while continuously transporting the film from melt extrusion to the final step. This makes it possible to manufacture the extruded film with good productivity through an industrially simple process.
• the manufacturing method according to this embodiment can be carried out while continuously winding up the manufactured extruded film on a winding roll.
• the transport speed is not particularly limited, but from the viewpoint of film productivity, it is preferable that the transport speed be 5 m/min or more before the start of stretching. Also, from the viewpoint of production stability, it is preferable that the transport speed be 50 m/min or less before the start of stretching.
• the extruded film according to the present embodiment may be a resin film composed of an independent single layer, but may also be a laminate in which other layers are laminated on one or both sides of the film. Such a laminate also constitutes one aspect of the present invention.
• the other layer include a resin layer, an inorganic layer, a metal layer, a metal oxide layer, a printed layer, etc. These other layers may be laminate layers, coating layers, or vapor deposition layers.
• the resin layer which is one of the other layers in the laminate, is not particularly limited, but from the viewpoint of enhancing the biodegradability of the entire laminate, it is preferable that it is a layer containing a poly(3-hydroxyalkanoate)-based resin (C).
• a poly(3-hydroxyalkanoate)-based resin (C) As the poly(3-hydroxyalkanoate)-based resin (C), the poly(3-hydroxyalkanoate)-based copolymer (A) and poly(3-hydroxybutyrate) (B) described above can be used as appropriate, but there is no particular limitation. There is also no particular limitation on the components other than the poly(3-hydroxyalkanoate)-based resin (C), and components known as additives to the resin layer can be used as appropriate.
• This resin layer may function as a heat seal layer.
• the film according to this embodiment can be suitably used as a packaging film, a heat sealable film, a twist film, and the like.
• the content of poly(3-hydroxybutyrate) (B) is 2 to 75% by weight based on the total weight of the poly(3-hydroxyalkanoate)-based copolymer (A) and the poly(3-hydroxybutyrate) (B).
• [Item 5] 5 5.
• the reactant (A') comprises a reactant of an organic peroxide with a copolymer (A-1) of 3-hydroxybutyrate units and other hydroxyalkanoate units, the content of the other hydroxyalkanoate units being 24 mol % or more.
• the reactant (A') comprises a reactant of an organic peroxide with a copolymer (A-1) of 3-hydroxybutyrate units and other hydroxyalkanoate units, the content of the other hydroxyalkanoate units being 24 mol % or more.
• the poly(3-hydroxyalkanoate)-based copolymer (A) comprises a copolymer (A-3) of 3-hydroxybutyrate units and other hydroxyalkanoate units, the content of which is 5 mol% or more and less than 24 mol%.
• reactant (A') comprises a reaction product of copolymer (A-3) and an organic peroxide.
• the poly(3-hydroxyalkanoate) copolymer (A) contains a copolymer (A-3') of 3-hydroxybutyrate units and other hydroxyalkanoate units, the content of the other hydroxyalkanoate units being 5 mol% or more and less than 24 mol% and having a weight average molecular weight of 700,000 or more;
• the content of the copolymer (A-3') is 20 to 80% by weight based on the total weight of the poly(3-hydroxyalkanoate)-based copolymer (A) and the poly(3-hydroxybutyrate) (B); 3.
• the extruded film according to item 19 wherein the poly(3-hydroxyalkanoate) copolymer (A) further comprises a copolymer (A-3′′) of 3-hydroxybutyrate units and other hydroxyalkanoate units, the content of other hydroxyalkanoate units being 5 mol% or more and less than 24 mol% and having a weight average molecular weight of less than 700,000.
• the poly(3-hydroxyalkanoate) copolymer (A) further comprises a copolymer (A-3′′) of 3-hydroxybutyrate units and other hydroxyalkanoate units, the content of other hydroxyalkanoate units being 5 mol% or more and less than 24 mol% and having
• extruded film of any of the preceding claims wherein the other hydroxyalkanoate units include 3-hydroxyhexanoate units.
• item 23 23.
• item 24 24.
• PHB Poly(3-hydroxybutyrate) (B) As P3HB(B), the following PHB was used.
• PHB Poly(3-hydroxybutyrate) (weight average molecular weight: 350,000 g/mol) It was produced according to the method described in Comparative Example 1 of WO 2004/041936.
• (Inorganic filler) C-1 Talc [SG-200N15, manufactured by Nippon Talc]
• T-die film formability The T-die film formability was evaluated according to the following evaluation criteria based on the take-up speed of the T-die film during production. ⁇ : Take-up speed is 3 m/min or more ⁇ : Take-up speed is 1 m/min or more ⁇ : Take-up speed is less than 1 m/min
• ⁇ Film tear strength> The film to be evaluated was stored at 50° C. for 3 days, and then the tear strength was measured using the Elmendorf tear method based on JIS K-7128-2. The measurement was carried out five times, and the average value was recorded in the table as the tear strength.
• Example 1 (Method for producing resin composition) 30 parts by weight of poly(3-hydroxyalkanoate) resin PHBH-1, 30 parts by weight of PHBH-2, 20 parts by weight of PHBH-3, 7 parts by weight of PHBH-4, and 13 parts by weight of PHB were dry-blended with 1 part by weight of C-1 as an inorganic filler and 1 part by weight of C-2 as a lubricant.
• the resulting resin material was charged into the hopper of a ⁇ 26 mm co-rotating twin-screw extruder with the cylinder temperature and die temperature set to 160° C., melt-kneaded, extruded from the die into strands, passed through a water tank filled with 45° C. hot water to solidify the strands, and cut with a pelletizer to obtain resin pellets P-1.
• T-die film (Production of T-die film)
• the cylinder temperature and die temperature of a single screw extruder having a diameter of 40 mm and connected to a T-die having a width of 350 mm were set to 170°C.
• the resin pellets P-1 were put into the single screw extruder and extruded into a film shape through a T-die.
• the formed film was cooled with a cooling roll ( ⁇ 250 mm) set at 60° C., and then taken up with a take-up roll to produce a T-die film having a thickness of 60 ⁇ m.
• the T-die film moldability was evaluated during the production of the T-die film, and the results are shown in Table 1.
• the obtained T-die film was evaluated for elastic modulus, tensile strength, breaking elongation, and tear strength, and the results are shown in Table 1.
• Example 2 Resin pellets were produced in the same manner as in Example 1, except that the composition was changed as shown in Table 1. Films were produced in the same manner as in Example 1, and the T-die film moldability, elastic modulus, breaking stress, breaking elongation, and tear strength were evaluated. The evaluation results are shown in Table 1.
• Example 1 film formation was possible at a take-up speed of 3.5 m/min without the resin material sticking to the cooling roll.
• Example 4 the forming speed could only be increased to 1 m/min, but continuous film production was possible.
• Comparative Example 1 Resin pellets were produced in the same manner as in Example 1, except that the composition was changed as shown in Table 1. Also, an attempt was made to produce a film in the same manner as in Example 1, but a T-die film could not be obtained because the film stuck to a cooling roll or the like.
• Example 5 (Method for producing resin composition) Poly(3-hydroxyalkanoate) resin PHBH-1 7.5 parts by weight, PHBH-2 7.5 parts by weight, PHBH-3 65 parts by weight, PHBH-4 7 parts by weight, PHB 13 parts by weight, C-1 1.0 parts by weight as an inorganic filler, C-2 1.0 parts by weight as a lubricant, E-1 0.2 parts by weight as an organic peroxide were dry blended.
• the obtained resin material was put into a ⁇ 26mm co-rotating twin screw extruder hopper with a cylinder temperature and a die temperature set to 160 ° C., melt-kneaded, extruded onto a strand from the die, passed through a water tank filled with hot water at 45 ° C. to solidify the strand, and cut with a pelletizer to obtain resin pellets P-2.
• the reaction between the P3HA copolymer (A) and the organic peroxide proceeded to form a reactant (A').
• the cylinder temperature and die temperature of a single screw extruder having a diameter of 40 mm and connected to a T-die having a width of 350 mm were set to 170°C.
• the resin pellets P-2 were put into the single screw extruder and extruded into a film shape using a T-die.
• the formed film was cooled using a cooling roll set at a temperature of 60°C, and then taken up using a take-up roll to produce a T-die film.
• the film was then continuously stretched 2.5 times in the machine direction (MD) at a stretching temperature of 135°C using a roll longitudinal stretching machine to produce a stretched film having a thickness of 30 ⁇ m.
• the T-die film moldability was evaluated based on the take-up speed of the T-die film during production, and the results are shown in Table 2.
• the elastic modulus, breaking stress, breaking elongation, and tear strength of the obtained stretched film were evaluated, and the results are shown in Table 2.
• Example 6 Resin pellets were produced in the same manner as in Example 5, except that the composition was changed as shown in Table 2. Films were produced in the same manner as in Example 5, and the T-die film moldability, elastic modulus, breaking stress, breaking elongation, and tear strength were evaluated. At that time, the film stretching temperature was appropriately changed between 60 and 140°C. The evaluation results are shown in Table 2.
• Example 8 The elastic modulus, breaking stress, breaking elongation, and tear strength of the T-die film before the stretching step in Example 5 were evaluated, and the results are shown in Table 2.
• Example 9 Resin pellets were produced in the same manner as in Example 5, except that the composition was changed as shown in Table 2. Film production was also carried out in the same manner as in Example 5, and T-die film moldability was evaluated. Furthermore, an attempt was made to produce a stretched film in the same manner as in Example 5, but the film broke during stretching, and so a stretched film could not be produced.
• Comparative Example 2 Resin pellets were produced in the same manner as in Example 5, except that the composition was changed as shown in Table 2. Also, an attempt was made to produce a film in the same manner as in Example 5, but a T-die film could not be obtained because the film stuck to a cooling roll or the like.
• Example 10 (Method for producing resin composition) 30 parts by weight of poly(3-hydroxyalkanoate) resin PHBH-3, 7 parts by weight of PHBH-4, 50 parts by weight of PHBH-5, and 13 parts by weight of PHB were dry-blended with 1 part by weight of C-1 as an inorganic filler and 1 part by weight of C-2 as a lubricant.
• the resulting resin material was charged into a hopper of a ⁇ 26 mm co-rotating twin-screw extruder with a cylinder temperature and a die temperature set to 160° C., melt-kneaded, extruded from the die into strands, passed through a water tank filled with hot water at 45° C. to solidify the strands, and cut with a pelletizer to obtain resin pellets P-3.
• the cylinder temperature and die temperature of a single screw extruder having a diameter of 40 mm and connected to a T-die having a width of 350 mm were set to 170°C.
• the resin pellets P-3 were put into the single screw extruder and extruded into a film shape using a T-die.
• the formed film was cooled using a cooling roll set at a temperature of 50°C, and then taken up using a take-up roll to produce a T-die film.
• the film was then continuously stretched in the machine direction (MD) at a stretching temperature of 135°C using a roll longitudinal stretching machine to produce a stretched film having a thickness of 30 ⁇ m.
• the T-die film moldability was evaluated based on the take-up speed of the T-die film during production, and the results are shown in Table 3.
• the elastic modulus, breaking stress, breaking elongation, and tear strength of the obtained stretched film were evaluated, and the results are shown in Table 3.
• Example 11 to 12 Resin pellets were produced in the same manner as in Example 10, except that the composition was changed as shown in Table 3. Films were produced in the same manner as in Example 10, and the T-die film moldability, elastic modulus, breaking stress, breaking elongation, and tear strength were evaluated. At that time, the film stretching temperature and cooling roll temperature were appropriately adjusted. The evaluation results are shown in Table 3.
• Example 13 to 16 Resin pellets were produced in the same manner as in Example 10, except that the composition was changed as shown in Table 3. Film production was also carried out in the same manner as in Example 10, and T-die film moldability was evaluated. Furthermore, an attempt was made to produce a stretched film in the same manner as in Example 10, but the film broke during stretching, and so the stretched film could not be produced.

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