Classifications

• • 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
• • 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
  • B29C48/001—Combinations of extrusion moulding with other shaping operations
  • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
• • 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
  • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
  • B29C48/911—Cooling
  • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
  • B29C48/914—Cooling drums
• • 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
  • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2007/00—Flat articles, e.g. films or sheets
• • 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
  • C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
  • C08J2329/12—Homopolymers or copolymers of unsaturated ketones

Definitions

• the present invention relates to a method for producing a stretched film containing a poly(3-hydroxybutyrate)-based resin.
• plastics that has been dumped in the ocean or has flowed into the ocean via rivers, are drifting in the oceans on a global scale. Because such plastics retain their shape for long periods of time, they can have an impact on the ecosystem, including the so-called ghost fishing that traps and captures marine life, and if ingested by marine life, they can remain in the digestive tract and cause eating disorders.
• microplastics which are plastics that break down and break down into tiny particles due to ultraviolet rays, adsorb harmful compounds in seawater, and are then ingested by marine organisms, resulting in the ingestion of harmful substances into the food chain.
• biodegradable plastics are expected to combat marine pollution caused by such plastics, but a report compiled by the United Nations Environment Programme in 2015 pointed out that plastics that can be biodegraded through composting, such as polylactic acid, cannot be expected to decompose in a short period of time in the cold ocean waters, and therefore cannot be used to combat marine pollution.
• poly(3-hydroxybutyrate) resins are attracting attention as a material that can solve the above problems, as they can biodegrade even in seawater.
• a method of stretching a film is known as a technique for producing a thin, high-strength film.
• a method of stretching a film is known as a technique for producing a thin, high-strength film.
• the molten resin is cooled and solidified using a cast roll to form a roll of raw material, which is then preheated to a temperature at which it can be stretched and then stretched, allowing the stretched film to be produced continuously and with good productivity.
• Patent Document 1 discloses a method for producing biaxially stretched films containing poly(3-hydroxybutyrate)-based resin with good productivity.
• a stretched film made primarily of poly(3-hydroxybutyrate) resin is used as a packaging film, for example, it is heated to bond the stretched films together to seal the contents, or the ink is heated to fix the ink after it has been applied to the stretched film for printing.
• this type of heating can cause the stretched film to shrink, distorting the seal and printing.
• the present invention aims to provide a manufacturing method that can produce stretched films containing poly(3-hydroxybutyrate)-based resins with low heat shrinkage with good productivity.
• the present invention relates to a method for producing a stretched film containing a poly(3-hydroxybutyrate)-based resin, the method comprising the steps of melting a film raw material containing the poly(3-hydroxybutyrate)-based resin in an extruder and then forming the material into a film, stretching the formed film, and heat-treating the stretched film, the heat treatment including a process of raising the film to a temperature T1 and then to a temperature T2, and the temperature T1 and the temperature T2 satisfy all of the conditions of the following formulas (1) to (3).
• the present invention provides a method for producing stretched films containing poly(3-hydroxybutyrate)-based resins with low heat shrinkage and high productivity.
• This embodiment relates to a method for producing a stretched film containing a poly(3-hydroxybutyrate)-based resin, which includes a process for melting a film raw material containing the poly(3-hydroxybutyrate)-based resin in an extruder and then forming it into a film, a process for stretching the formed film, and a process for heat-treating the stretched film, in which the heat treatment includes a process for bringing the film to a temperature T1 and then to a temperature T2, and in which the temperatures T1 and T2 satisfy specific conditions.
• the poly(3-hydroxybutyrate)-based resin is an aliphatic polyester resin that can be produced from a microorganism, and is a polyester resin having 3-hydroxybutyrate as a repeating unit.
• the poly(3-hydroxybutyrate)-based resin may be a poly(3-hydroxybutyrate) having only 3-hydroxybutyrate as a repeating unit, or may be a copolymer of 3-hydroxybutyrate and another hydroxyalkanoate.
• the poly(3-hydroxybutyrate)-based resin may be a mixture of a homopolymer and one or more types of copolymers, or a mixture of two or more types of copolymers.
• poly(3-hydroxybutyrate) resin examples include poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [hereinafter, may be referred to as P3HB3HH], poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [hereinafter, may be referred to as P3HB3HV], poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [hereinafter, may be referred to as P3HB4HB], poly(3-hydroxybutyrate-co-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxyoctadecanoate), etc.
• poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate), and poly(3-hydroxybutyrate-co-4-hydroxybutyrate) are preferred because they are easy to produce industrially.
• 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 preferred.
• poly(3-hydroxybutyrate)-based resins 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 can lower the melting point and enable molding processing at low temperatures.
• poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) products include Kaneka Biodegradable Polymer PHBH (registered trademark) from Kaneka Corporation.
• the average content ratio of each monomer unit in all monomer units constituting the poly(3-hydroxybutyrate)-based resin 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-hydroxybutyrate)-based resin, and when the poly(3-hydroxybutyrate)-based resin is a mixture of two or more poly(3-hydroxybutyrate)-based resins, it means the molar ratio of each monomer unit contained in the entire mixture.
• the poly(3-hydroxybutyrate) resin may be a mixture of at least two types of poly(3-hydroxybutyrate) resins that differ from each other in the type of constituent monomers and/or the content ratio of the constituent monomers.
• the weight average molecular weight of the entire poly(3-hydroxybutyrate) resin is not particularly limited, but from the viewpoint of achieving both strength and productivity of the stretched film, it is preferably 200,000 to 2,000,000 g/mol, more preferably 250,000 to 1,500,000 g/mol, and even more preferably 300,000 to 1,000,000 g/mol.
• the weight-average molecular weight of poly(3-hydroxybutyrate) resins can be measured in polystyrene equivalent terms using gel permeation chromatography (Shimadzu Corporation HPLC GPC system) with a chloroform solution.
• a column suitable for measuring weight-average molecular weights can be used as the column for the gel permeation chromatography.
• the method for producing poly(3-hydroxybutyrate) resins 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.
• Aeromonas caviae which produces P3HB3HV and P3HB3HH
• Alcaligenes eutrophus which produces P3HB4HB.
• the poly(3-hydroxybutyrate) resin may be an unmodified resin, or an unmodified poly(3-hydroxybutyrate) resin may be modified with a raw material that reacts with the resin, such as a peroxide (hereinafter referred to as a "modifying raw material").
• a raw material such as a peroxide (hereinafter referred to as a "modifying raw material").
• a film raw material containing a poly(3-hydroxybutyrate) resin that has already been reacted with a modifying raw material may be molded into a film, or a film raw material containing an unmodified poly(3-hydroxybutyrate) resin and a modifying raw material may be reacted with the modifying raw material during molding.
• the entire resin may be reacted with the modifying raw material, or a portion of the resin may be reacted with the modifying raw material to obtain a modified resin, and the remaining unmodified resin may then be added to the modified resin.
• the raw material for modification is not particularly limited as long as it is a compound that can react with the poly(3-hydroxybutyrate)-based resin, but organic peroxides are preferably used because of their ease of handling and the ease of controlling the reaction with the poly(3-hydroxybutyrate)-based resin.
• the organic peroxides include, for example, 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, 1,1,3,3-tetramethylbuty
• the organic peroxide may be used in various forms, such as solid or liquid, and may be in liquid form diluted with a diluent or the like.
• organic peroxides in a form that can be easily mixed with the poly(3-hydroxybutyrate)-based resin are preferred because they can be more uniformly dispersed in the poly(3-hydroxybutyrate)-based resin and are more likely to suppress localized modification reactions in the resin composition.
• the content of poly(3-hydroxybutyrate) resin in the stretched film may be 50% by weight or more, 55% by weight or more, 60% by weight or more, 70% by weight or more, or 80% by weight or more. There is no upper limit to the content of poly(3-hydroxybutyrate) resin, and it may be 100% by weight or less.
• the stretched film may contain additives that can be used with the poly(3-hydroxybutyrate) resin to the extent that the effect of the invention is 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, UV absorbers, crystal nucleating agents, lubricants, release agents, water repellents, antibacterial agents, and sliding improvers.
• the film may contain only one type of additive, or may contain two or more types. The content of these additives can be appropriately set by a person skilled in the art depending on the purpose of use. Even if the poly(3-hydroxybutyrate) resin contains these additives, its melting point is approximately the same as the melting point of the poly(3-hydroxybutyrate) resin.
• crystal nucleating agent examples include polyhydric alcohols such as pentaerythritol, galactitol, and mannitol; orotic acid, aspartame, cyanuric acid, glycine, zinc phenylphosphonate, and boron nitride.
• pentaerythritol is preferred because of its particularly excellent effect of promoting the crystallization of poly(3-hydroxybutyrate)-based resins.
• One type of crystal nucleating agent may be used, or two or more types may be used, and the ratio of use can be appropriately adjusted depending on the purpose.
• the amount of the crystal nucleating agent used 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 amount of poly(3-hydroxybutyrate) resin.
• lubricant examples 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 poly(3-hydroxybutyrate)-based resins.
• One type of lubricant may be used, or two or more types may be used, and the ratio of use can be appropriately adjusted depending on the purpose.
• the amount of 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, and even more preferably 0.1 to 1.5 parts by weight, per 100 parts by weight of the total amount of poly(3-hydroxybutyrate) resin.
• 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 silicates, carbonates, sulfates, phosphates, oxides, hydroxides, nitrides, and carbon black. Only one type of inorganic filler may be used, or two or more types may be used in combination.
• the amount of the filler is not particularly limited, but is preferably 1 to 100 parts by weight, more preferably 3 to 80 parts by weight, even more preferably 5 to 70 parts by weight, and even more preferably 10 to 60 parts by weight, per 100 parts by weight of the total amount of the poly(3-hydroxybutyrate) resin.
• the stretched film does not have to contain a filler.
• plasticizer examples include glycerin ester compounds, citrate 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 compounds, sebacic acid ester compounds, and dibasic acid ester compounds are preferred because of their particularly excellent plasticizing effect on poly(3-hydroxyalkanoate) resins.
• the glycerin ester compounds include glycerin diacetomonolaurate.
• citrate compounds include acetyl tributyl citrate.
• sebacic acid ester compounds examples include dibutyl sebacate.
• dibasic acid ester compounds examples 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 of plasticizer 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 total amount of poly(3-hydroxybutyrate) resin.
• the stretched film does not have to contain a plasticizer.
• the stretched film may contain other resins besides the poly(3-hydroxybutyrate) resin, so long as the effects of the invention are not impaired.
• other resins include aliphatic polyester resins such as poly(3-hydroxypropionate), poly(4-hydroxybutyrate), polybutylene succinate adipate, polybutylene succinate, polycaprolactone, and polylactic acid, and aliphatic aromatic polyester resins such as polybutylene adipate terephthalate (hereinafter sometimes referred to as PBAT), polybutylene sebate terephthalate, and polybutylene azelate terephthalate. Only one type of other resin may be contained, or two or more types may be contained.
• PBAT polybutylene adipate terephthalate
• PBAT polybutylene sebate terephthalate
• polybutylene azelate terephthalate Only one type of other resin may be contained, or two or more types may be contained.
• the amount of the other resin is not particularly limited, but may be 100 parts by weight or less, 80 parts by weight or less, 70 parts by weight or less, 50 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, 10 parts by weight or less, 5 parts by weight or less, or 1 part by weight or less, relative to 100 parts by weight of the poly(3-hydroxybutyrate) resin.
• the lower limit of the amount of the other resin is not particularly limited, and may be 0 parts by weight or more.
• the lower limit may be 10 parts by weight or more, 20 parts by weight or more, 50 parts by weight or more, or 65 parts by weight or more per 100 parts by weight of the poly(3-hydroxybutyrate)-based resin.
• the upper limit may be less than 100 parts by weight per 100 parts by weight of the poly(3-hydroxybutyrate)-based resin.
• the stretched film containing the poly(3-hydroxybutyrate)-based resin of the present disclosure can be produced by the following production method, which includes the steps of melting a film raw material containing the poly(3-hydroxybutyrate)-based resin in an extruder, forming the film into a film, stretching the formed film, and heat-treating the stretched film, the heat treatment including a process of raising the film to a temperature T1 and then to a temperature T2, and the temperatures T1 and T2 satisfy all of the conditions of the following formulas (1) to (3).
• the method of forming it into a film is not particularly limited, and a known manufacturing method can be appropriately used.
• Specific examples include an inflation molding method, a T-die extrusion molding method using an extruder equipped with a T-die, a calendar molding method, and a rolling method.
• the inflation molding method or the T-die extrusion molding method is preferable because it can produce a strip-shaped film with good productivity.
• a single screw extruder also called a single screw extruder
• a twin screw extruder, etc. can be appropriately used as the extruder.
• the molding temperature is not particularly limited as long as it is a temperature at which the resin can be properly melted, but for example, 130 to 200°C is preferable.
• the molding temperature here refers to the resin temperature from the extruder until it is discharged from the die.
• the resin temperature can generally be measured, for example, by a thermometer installed in the adapter.
• the inflation molding method is a molding method in which a molten resin is extruded into a tube shape from an extruder equipped with a cylindrical die at the tip, and immediately after that, gas is blown into the tube to inflate it into a balloon shape to form a film.
• the inflation molding is not particularly limited, but can be performed, for example, using a general inflation molding machine used when molding a thermoplastic resin into a film.
• a typical inflation molding machine is one in which a cylindrical die is attached to a single-screw extruder.
• the single-screw extruder may be any machine that melts and kneads the input raw resin and obtains a constant discharge while maintaining the raw resin at the desired temperature.
• extruders equipped with mixing elements are preferred from the viewpoint of kneading properties.
• structure of the cylindrical die but a spiral mandrel die is preferred, as it produces fewer welds and is easy to obtain uniform thickness.
• the take-up speed in inflation molding is determined by the film thickness, width, and resin discharge amount, but can be adjusted within a range that maintains bubble stability. Generally, 1 to 100 m/min is preferable.
• an air ring that is blown from the outside of the bubble can be used to solidify the extruded molten resin and stabilize the bubble.
• the most suitable air ring blowing structure is a slit type that has multiple annular slits through which air is blown out, and the chambers between each slit promote bubble stabilization.
• the blow-up ratio (hereinafter sometimes referred to as BUR) in inflation molding is the circumferential length of the bubble cross section divided by the diameter of the die.
• the lower limit of BUR is preferably 1.5 times or more, more preferably 1.7 times or more, even more preferably 1.9 times or more, and particularly preferably 2 times or more.
• the upper limit of BUR is preferably 5.5 times or less, more preferably 4.5 times or less, even more preferably 4.0 times or less, and particularly preferably 3.5 times or less.
• the T-die extrusion molding method is a molding method in which a resin molten by an extruder is extruded from a slit-shaped discharge port onto a cast roll in a film shape to form a film.
• the T-die is not particularly limited, and any known T-die can be used as appropriate.
• the T-die is preferably one having a discharge port shaped to extrude a film-shaped raw material, but the shape is not particularly limited.
• the shape of the discharge port is also not particularly limited.
• a film-like raw material is extruded from the discharge port of the T-die.
• the shape of the raw material needs to be film-like, and there are no particular limitations on its thickness or width.
• the thickness is preferably approximately 20 ⁇ m to 600 ⁇ m, as this reduces thickness unevenness and allows for easy cooling after extrusion.
• the melt viscosity of the raw material extruded from the outlet of the T-die is not particularly limited, but it is preferably 1500 Pa ⁇ sec or less, as this reduces thickness unevenness and prevents the occurrence of die lines.
• the melt viscosity can be measured according to a known method.
• the thickness of the film before stretching is not particularly limited, and may be set appropriately taking into consideration the desired thickness of the stretched film, the stretching ratio, strength, etc. For example, 20 to 600 ⁇ m is preferable, 40 to 500 ⁇ m is more preferable, and 50 to 300 ⁇ m is even more preferable.
• the thickness of the film can be measured using a vernier caliper.
• the method is not particularly limited as long as the film can be stretched to a degree that allows it to be stretched, and any known production method can be used as appropriate.
• the stretching direction in the stretching process is not particularly limited, and the film can be stretched in any direction in the plane direction.
• the stretching direction may be either the MD direction or the TD direction of the film, or both the MD and TD directions. Stretching in either the MD or TD direction is called uniaxial stretching, and stretching in both the MD and TD directions is called biaxial stretching.
• the MD direction is also called the machine direction, flow direction, or longitudinal direction.
• the TD direction is perpendicular to the MD direction, and is also called the perpendicular direction or width direction.
• the specific stretching method is not particularly limited, but a method of stretching the film by stretching it in the stretching direction is preferred. Stretching the film in the stretching direction means pulling the film in the stretching direction. On the other hand, when stretching the film by applying pressure in the thickness direction of the film, such as roll rolling in which the film is sandwiched between two rolls, the film tends to adhere to the rolling rolls, which may reduce the productivity of the stretched film.
• the film can be stretched by gripping the ends and pulling them in the stretching direction.
• a roll longitudinal stretching machine can be used to stretch the film in the MD direction by varying the rotation speed of the rolls that transport the film.
• the stretch ratio in the MD direction can be determined by the ratio of the rotation speed of the rolls after stretching to the rotation speed of the rolls before stretching.
• the film When stretching a film in the TD direction while it is being transported continuously, the film can be stretched in the TD direction by, for example, clamping both widthwise ends of the film using a transverse stretching machine such as a clip-type tenter and pulling it in the TD direction.
• the stretch ratio in the TD direction can be determined by the ratio of the distance between both widthwise ends of the clamped film after stretching to the distance between both widthwise ends of the film clamped before stretching.
• the stretching ratio achieved in the process of stretching the molded film is not particularly limited, but is preferably 1.1 times or more, more preferably 1.3 times or more, even more preferably 1.5 times or more, and particularly preferably 2 times or more. There is no particular upper limit and it may be determined appropriately, but it may be, for example, 8 times or less, 7 times or less, 5 times or less, or 3 times or less.
• the stretching temperature is not particularly limited as long as the film can be stretched appropriately, and can be changed according to the mechanical strength, surface properties, thickness accuracy, etc. required for the stretched film to be produced.
• the stretching temperature is preferably 40°C or higher, more preferably 50°C or higher, and even more preferably 60°C or higher.
• the upper limit is sufficient as long as it is equal to or lower than the melting point of the poly(3-hydroxybutyrate) resin, and is preferably 150°C or lower, more preferably 145°C or lower, and even more preferably 140°C or lower. If the stretching temperature is within the above temperature range, the thickness unevenness of the resulting stretched film can be reduced, and furthermore, mechanical properties such as elongation, tear propagation strength, and fatigue resistance can be improved. Furthermore, problems such as the film sticking to the roll can be prevented.
• the stretching temperature here refers to the temperature of the film during stretching.
• the stretching temperature can generally be measured by measuring the temperature of the film itself or the ambient temperature near the film using an infrared thermometer, thermo label, thermocouple, etc.
• the means for adjusting the film temperature during stretching is not particularly limited, but examples include non-contact heating methods such as a method in which hot air heated to within the above temperature range is applied to the film being stretched, a method in which the film is heated while being stretched using an auxiliary heating means such as an infrared heater, and a method in which the film is stretched in a heating furnace whose temperature is adjusted to within the above temperature range; and contact heating methods such as a method in which the film is brought into contact with a roll heated to within the above temperature range. These may be used alone or in combination.
• hot air may be applied to the film between the upstream stretching roll and the downstream stretching roll in the MD direction.
• a floating heating method as a method for applying hot air heated to within the above temperature range to the film being stretched.
• Floating heating is a method in which hot air is blown onto both sides of the film from upper and lower nozzles to heat it. Multiple upper nozzles and multiple lower nozzles are arranged alternately toward the film surface, and the film can be heated by the hot air blown out from each of the upper and lower nozzles without the film coming into contact with either the upper or lower nozzle.
• the film surface and inside can be heated to the same temperature in a short period of time, making it possible to stretch the entire film uniformly.
• the infrared rays to be irradiated can be electromagnetic waves in the general infrared range, and can be any of the following: near infrared: wavelength 0.74 ⁇ m to 1.5 ⁇ m; mid infrared: wavelength 1.5 ⁇ m to 3.0 ⁇ m; far infrared: wavelength 3.0 ⁇ m to 1 mm.
• the upstream stretching roll in the MD direction of the two adjacent stretching rolls can be heated to within the above temperature range.
• the stretching temperature i.e., the temperature of the film during stretching, can be controlled by setting the temperature of the rolls to the desired stretching temperature.
• the method of adjusting the film temperature during stretching is preferably a method of contacting the film with a roll heated to within the above temperature range, from the viewpoint of excellent productivity and easy heating, particularly in the case of mass production.
• This is suitable for uniaxial stretching, particularly when stretching in the MD direction using multiple rolls of a roll longitudinal stretching machine.
• the step of heat-treating the stretched film includes a process of heating the film to a temperature T1 and then to a temperature T2, and the temperatures T1 and T2 satisfy all of the conditions of the following formulas (1) to (3).
• T1 melting point of poly(3-hydroxybutyrate)-based resin ⁇ 70
• T2 melting point of poly(3-hydroxybutyrate)-based resin ⁇ 20
• the temperature T2 is higher than (the melting point of poly(3-hydroxybutyrate) resin - 20) °C, the molecular orientation obtained by stretching will be lost, and the mechanical strength of the resulting stretched film may decrease, or the film may stick to the heating tool, or if multiple films are stacked, the films may stick to each other.
• temperature T1 is lower than (melting point of poly(3-hydroxybutyrate) resin - 70) °C and temperature T2 is higher than (melting point of poly(3-hydroxybutyrate) resin - 20) °C, the temperature difference between temperature T1 and temperature T2 will be too large, resulting in a rapid temperature rise, which may cause the film to stick to the heating tool or, if multiple films are stacked, the films to stick to each other.
• the temperatures T1 and T2 satisfy the conditions of the following expressions (4) and (5). (melting point of poly(3-hydroxybutyrate)-based resin - 70) ° C. ⁇ T1 ⁇ (melting point of poly(3-hydroxybutyrate)-based resin - 30) ° C. (4) (melting point of poly(3-hydroxybutyrate)-based resin - 60) ° C. ⁇ T2 ⁇ (melting point of poly(3-hydroxybutyrate)-based resin - 20) ° C. (5)
• the melting point of poly(3-hydroxybutyrate) resin refers to the apex temperature of the melting point peak in the DSC curve obtained by differential scanning calorimetry. Details of differential scanning calorimetry are described in the Examples section.
• temperatures T1 and T2 satisfy the relationship 0°C ⁇ T2-T1 ⁇ 40°C, and it is even more preferable that temperatures T1 and T2 satisfy the relationship 10°C ⁇ T2-T1 ⁇ 30°C.
• the heat treatment may include a process of raising the temperature to T2 and then to T3, and it is preferable that the temperatures T1, T2 and T3 satisfy the conditions of the following formulas (6) and (7).
• temperatures T2 and T3 satisfy the relationship 0°C ⁇ T3-T2 ⁇ 40°C, and it is even more preferable that temperatures T2 and T3 satisfy the relationship 10°C ⁇ T3-T2 ⁇ 20°C.
• the amount of heat shrinkage in the stretching direction is preferably 15% or less, more preferably 10% or less, even more preferably 8% or less, and particularly preferably 6% or less.
• the film may be relaxed when it is brought to the temperatures T1, T2, and T3. Of these, relaxing the film when it is brought to the first temperature T1 is preferred because it effectively prevents the stretched film from suddenly shrinking due to heat and from breaking during its manufacture and processing.
• the amount of relaxation is preferably 0 to 10%, and more preferably 5 to 10%. In particular, by relaxing in the stretching direction in the process of stretching the film, it is possible to reduce heat shrinkage.
• relaxation means reducing the film dimensions in the stretched direction in order to remove the stress in the stretched direction that exists in the film.
• the film dimensions refer to the distance between two points in an arbitrarily specified film plane, and may be the distance from one end of the film to the other end.
• the stretched film of the present disclosure is a strip-shaped film
• the film dimensions in the MD direction may be the distance between two points in the MD direction in an arbitrarily specified film plane
• the film dimensions in the TD direction may be the distance between both ends of the film in the width direction.
• the film dimensions are the straight-line distance between two points in an arbitrarily specified film plane, and may be the straight-line distance from one end of the film to the other end, and in particular, the film dimensions in the TD direction may be the straight-line distance between both ends of the film in the width direction.
• the film dimensions in the MD direction can be adjusted by varying the rotation speed of the two adjacent rolls.
• the film dimensions in the TD direction can be adjusted by clamping both widthwise ends of the film using a transverse stretching machine such as a clip-type tenter and changing the distance between the clamps.
• the amount of relaxation [%] in the MD direction during the heat treatment step can be calculated by the following formula (i-i), and the amount of relaxation [%] in the TD direction can be calculated by the following formula (i-ii).
• Relaxation amount in MD direction [%] ⁇ (Rotational speed of roll immediately before the roll for bringing the temperature to Tn) - (Rotational speed of roll for bringing the temperature to Tn) ⁇ / (Rotational speed of roll immediately before the roll for bringing the temperature to Tn) x 100, where n is 1, 2, or 3
• Relaxation amount in TD direction [%] ⁇ (distance between both ends of the film in the width direction just before the temperature is lowered to Tn) ⁇ (distance between both ends of the film in the width direction when the temperature is lowered to Tn) ⁇ /(distance between both ends of the film in the width direction just before the temperature is lowered to Tn) ⁇ 100, where n is 1, 2, or 3 (i-ii
• the times for bringing the film to temperatures T1, T2, and T3 are not particularly limited, but from the viewpoint of productivity, 0.5 to 30 seconds is preferable, 0.5 to 10 seconds is more preferable, and 0.5 to 5 seconds is even more preferable.
• Methods for adjusting the film temperature during heat treatment are not particularly limited, but examples include non-contact heating methods such as a method of applying hot air heated to within the above temperature range to the film, a method of heating the film using auxiliary heating means such as an infrared heater, and a method of heating the film by placing it in a heating furnace whose temperature is adjusted to within the above temperature range; and contact heating methods such as a method of contacting the film with a roll heated to within the above temperature range. These may be used alone or in combination.
• the means for adjusting the film temperature during heat treatment can be the same as those for adjusting the film temperature during stretching, so a description of each method will be omitted.
• a method of contacting the film with a roll heated to within the above temperature range is preferred as a means of adjusting the film temperature during heat treatment, from the viewpoint of excellent productivity and easy heating, particularly in mass production.
• This is preferable in that the film can be continuously transported and is highly productive when uniaxial stretching, particularly when stretching in the MD direction of the film using multiple rolls of a roll longitudinal stretching machine.
• the process of sequentially bringing the film to temperatures T1, T2, and T3 may involve contacting the film with rolls. Specifically, the film may be contacted in sequence with roll R1, which has been brought to temperature T1, roll R2, which has been brought to temperature T2, and roll R3, which has been brought to temperature T3.
• the time for bringing the film to temperatures T1, T2, and T3 refers to the time for which the film is in contact with roll R1 at temperature T1, roll R2 at temperature T2, and roll R3 at temperature T3, respectively.
• Roll R1 at temperature T1 may be composed of not only one roll, but also two or more rolls.
• roll R2 at temperature T2 and roll R3 at temperature T3 may each be composed of one or two or more rolls.
• the time for bringing the film to temperatures T1, T2, and T3 can be adjusted by increasing or decreasing the rotation speed of rolls R1, R2, and R3, or the number of rolls.
• the rotational speeds of roll R1, which brings the film to temperature T1, roll R2, which brings the film to temperature T2, and roll R3, which brings the film to temperature T3, are not particularly limited. From the viewpoint of adjusting the aforementioned relaxation amount to 0-10% or 5-10% and reducing heat shrinkage after stretching, the ratio of the rotational speed of roll R1 to the rotational speed of the roll immediately preceding roll R1, the ratio of the rotational speed of roll R2 to the rotational speed of roll R1, and the ratio of the rotational speed of roll R3 to the rotational speed of roll R2 are each preferably 90-100%, more preferably 90-95%.
• the manufacturing method of the present disclosure may include a step of cooling the film after the step of heat-treating the film.
• the film temperature in the film cooling step may be 60°C or less, and preferably 40°C or less.
• the film temperature can be lowered to a temperature lower than the heat treatment temperature, there are no particular limitations on the means for doing so, but an example is a method in which the film is brought into contact with a roll that has been cooled to 60°C or less, preferably 40°C or less. More specifically, the film may be cooled on one or more rolls, or by sandwiching the film between two rolls.
• a continuous process refers to obtaining a stretched film by sequentially carrying out the steps from melting the film raw material in an extruder, forming it into a film, to stretching the formed film, to heat-treating the stretched film, and further up to cooling the film as necessary.
• the thickness of the stretched film is not particularly limited and may be appropriately set to a desired thickness. From the viewpoints of the uniform thickness, appearance, strength, lightness, etc. of the film, the thickness is preferably 10 to 200 ⁇ m, more preferably 15 to 150 ⁇ m, and even more preferably 20 to 100 ⁇ m. The thickness of the film can be measured using a vernier caliper.
• the stretched film disclosed herein is thin yet strong, making it suitable for use as a packaging film, for example, packaging films for food products that require heat sealability.
• a method for producing a stretched film containing a poly(3-hydroxybutyrate)-based resin comprising the steps of: A step of melting the film raw material containing the poly(3-hydroxybutyrate)-based resin in an extruder and then forming it into a film; stretching the formed film; heat-treating the stretched film; The heat treatment includes a process of heating the film to a temperature T1 and then to a temperature T2, and the temperatures T1 and T2 satisfy all of the conditions of the following formulas (1) to (3).
• the treatment of bringing the film to a temperature T1 comprises: The manufacturing method according to any one of items 1 to 3, wherein the treatment of bringing the film into contact with a roll R1 having a temperature T1, and the treatment of bringing the film into temperature T2 is a treatment of bringing the film into contact with a roll R2 having a temperature T2.
• the method of any one of items 1 to 4 wherein the film is brought to a temperature T1 with a relaxation amount of 0 to 10% in the stretching direction.
• the time for bringing the film to temperature T1 is 0.5 to 30 seconds.
• Weight average molecular weight The weight average molecular weight of the resin was measured in terms of polystyrene using the above-mentioned gel permeation chromatography (HPLC GPC system manufactured by Shimadzu Corporation).
• the glass transition temperature (Tg) of the resin was determined by differential scanning calorimetry in accordance with JIS K-7121. Specifically, first, about 5 mg of the sample to be measured was precisely weighed, and the temperature was raised from -20°C to 200°C at a heating rate of 10°C/min using a differential scanning calorimeter (SSC5200, manufactured by Seiko Instruments Inc.) to obtain a DSC curve.
• SSC5200 differential scanning calorimeter
• the glass transition temperature (Tg) in a portion where the baseline changes stepwise due to the glass transition, the baselines before and after the change were extended, and a center line was drawn equidistant in the vertical direction from these two straight lines, and the temperature at the point where this center line intersects with the curve of the stepwise change due to the glass transition was determined as the glass transition temperature (Tg).
• the melting point was determined by differential scanning calorimetry in accordance with JIS K-7121. Specifically, first, about 4 to 5 mg of the sample to be measured was precisely weighed, and the temperature was raised from 0°C to 180°C at a heating rate of 10°C/min using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., SSC5200) to obtain a DSC curve. In the obtained DSC curve, the apex temperature of the melting point peak was taken as the melting point.
• the thickness was measured at 10 points at 10 cm intervals along the TD direction of the film using a vernier caliper, and the arithmetic mean value of the thicknesses at the 10 points was calculated to be the film thickness.
• MD longitudinal
• a 100mm x 210mm test piece was cut out from the stretched film (cut so that the short side was in the MD direction), and while holding all four sides (0% relaxation in the MD direction), it was placed in a hot air oven and held at 90°C for 10 seconds, and then removed to obtain the first stage of heat-treated stretched film. After that, while holding all four sides (0% relaxation in the MD direction), it was placed in a hot air oven and held at 120°C for 10 seconds, and then removed to obtain the second stage of heat-treated stretched film. Furthermore, while holding all four sides (0% relaxation in the MD direction), it was placed in a hot air oven and held at 130°C for 10 seconds, and then removed to obtain the third stage of heat-treated stretched film. The stretched film obtained did not stick to the roll or to each other. Furthermore, the amount of heat shrinkage was 4% in the MD direction and 0% in the TD direction. The evaluation results of the stretched film are shown in Table 1.
• Example 2 A stretched film was obtained in the same manner as in Example 1, except that the first heat treatment conditions were a film temperature of 90°C and a relaxation amount in the MD direction of 10%, the second heat treatment conditions were a film temperature of 110°C, and the third heat treatment conditions were a film temperature of 120°C.
• the obtained stretched film did not stick to the roll or to each other. Furthermore, the heat shrinkage was 4% in the MD direction and 0% in the TD direction.
• the evaluation results of the stretched film are shown in Table 1.
• Example 3 the stretched film was obtained in the same manner as in Example 1, except that the first heat treatment conditions were a film temperature of 80°C and a relaxation amount in the MD direction of 5%, the second heat treatment conditions were a film temperature of 90°C, and the third heat treatment conditions were a film temperature of 110°C and a relaxation amount in the MD direction of 10%.
• the stretched film obtained did not stick to the roll or to each other.
• the heat shrinkage was 3% in the MD direction and 1% in the TD direction.
• the evaluation results of the stretched film are shown in Table 1.
• Example 4 A stretched film was obtained in the same manner as in Example 1, except that the third heat treatment was not performed. The obtained stretched film did not stick to the roll or to other films. Furthermore, the amount of heat shrinkage was 6% in the MD direction and 0% in the TD direction. The evaluation results of the stretched film are shown in Table 1.
• Example 1 A stretched film was obtained in the same manner as in Example 1, except that the heat treatment was not performed. However, the film stuck to the roll and stuck to itself. The heat shrinkage was 20% in the MD direction and 3% in the TD direction. The evaluation results of the stretched film are shown in Table 1.
• the heat treatment conditions include a process in which the film is heated to temperature T1 and then to temperature T2.
• the amount of heat shrinkage in the TD direction is 1% or less
• the amount of heat shrinkage in the MD direction, which is the stretching direction is also small at less than 10%, and there is no sticking to the roll or between films, which shows that production can be performed with good productivity.

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