Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
• • 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
  • B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
  • B29C48/154—Coating solid articles, i.e. non-hollow articles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • 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
  • C08J5/20—Manufacture of shaped structures of ion-exchange resins
  • C08J5/22—Films, membranes or diaphragms
• • 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
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/10—Coatings without pigments
  • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
  • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H19/28—Polyesters
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
  • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
  • D21H23/22—Addition to the formed paper
• • 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
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/02—2 layers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/02—Applications for biomedical use
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/16—Applications used for films
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/30—Applications used for thermoforming
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

• the present invention relates to a resin composition or film containing a poly(3-hydroxyalkanoate) resin, a laminate containing a laminate layer of the resin composition, and a method for producing the same.
• PHA polyhydroxyalkanoate
• P3HA poly(3-hydroxyalkanoate)
• P3HB poly(3-hydroxybutyrate) homopolymer resin
• P3HB3HV poly(3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer resin
• P3HB3HH poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) copolymer resin
• P3HB4HB poly(3-hydroxybutyrate-co-4-hydroxybutyrate) copolymer resin
• the lamination method can be selected from a method in which PHA resin is fed into an extruder equipped with a T-shaped die, processed into a film, and then the film is laminated onto the substrate, or an extrusion lamination method in which PHA resin molten using similar equipment is directly laminated onto a substrate that has been separately unwound, without first being made into a film.
• Patent Document 2 describes that a resin film having a reaction product of a resin component containing P3HB3HH(A) having a 3-hydroxyhexanoate unit content of 1 to 6 mol % and P3HB3HH(B) having a 3-hydroxyhexanoate unit content of 24 mol % or more with a specific amount of organic peroxide has good mechanical properties and blocking resistance, and can be manufactured with good productivity.
• the inventors have found through their research that when P3HA resin is turned into a film using an extruder equipped with a T-die (hereinafter sometimes referred to as T-die film making) or when extrusion lamination is performed to form a laminate layer of P3HA resin directly on a substrate, if the processing speed is increased to improve productivity, there is room for improvement, such as fluctuations in the thickness of the film or laminate layer in the flow direction (hereinafter sometimes referred to as the MD direction) and the length in the TD direction (perpendicular to the MD direction) becoming smaller relative to the die width (large neck-in).
• the present invention aims to provide a P3HA-based resin composition that can suppress thickness variations and neck-in in the TD direction of the film or laminate layer even when the production speed is increased during T-die film formation or extrusion lamination processing.
• the present invention provides a resin composition containing a poly(3-hydroxyalkanoate)-based resin component
• the poly(3-hydroxyalkanoate) resin component is A copolymer (A) of 3-hydroxybutyrate units and other hydroxyalkanoate units, in which the content of the other hydroxyalkanoate units is 24 mol % or more;
• the copolymer (C) contains 3-hydroxybutyrate units and other hydroxyalkanoate units, and the content of the other hydroxyalkanoate units is 5 mol % or more and less than 24 mol %,
• the weight average molecular weight of the copolymer (A) is 100,000 or more and 500,000 or less
• the present invention relates to a resin composition, wherein at least one or all of the
• the present invention also relates to a film containing the resin composition, and also to a laminate containing a laminate layer containing the resin composition and a substrate layer.
• the laminate may be a molded article.
• the present invention further relates to a method for producing a film, the method including a step of melt extrusion molding the resin composition using a T-die, and also to a method for producing the laminate, the method including a step of forming the laminate layer on at least one side of the base layer by an extrusion lamination method, and further to a method for producing a laminate, the method including a step of molding the resin composition into a film, and a step of placing the film on at least one side of the base layer and forming the laminate layer by any one of a dry lamination method, a non-solvent lamination method, or a thermal lamination method.
• the present invention even if the production speed is increased during T-die film formation or extrusion lamination, thickness variation and neck-in in the TD direction of the film or laminate layer can be suppressed. Therefore, a film with uniform thickness and width, or a laminate having a laminate layer with uniform thickness and width can be produced with high productivity. Furthermore, by using the laminate, films or laminates of consistent quality can be produced with good yield.
• the resin composition according to this embodiment is a resin composition containing a poly(3-hydroxyalkanoate) resin as an essential component.
• the poly(3-hydroxyalkanoate) resin contained in the resin composition according to this embodiment is a biodegradable aliphatic polyester (a polyester not containing an aromatic ring), and is a polyhydroxyalkanoate containing 3-hydroxyalkanoic acid repeating units represented by the general formula: [-CHR-CH 2 -CO-O-] (wherein R is an alkyl group represented by C n H 2n+1 , and n is an integer of 1 to 15). Of these, those containing this repeating unit in an amount of 50 mol % or more, more preferably 70 mol % or more, based on the total monomer repeating units (100 mol %).
• P3HA-based resins poly(3-hydroxybutyrate)-based resins (hereinafter sometimes referred to as "P3HB-based resins”) are preferably used because they are particularly easy to obtain and process.
• the P3HB-based resin is an aliphatic polyester resin that can be produced from microorganisms, and is a polyester resin that has 3-hydroxybutyrate (hereinafter, sometimes referred to as "3HB") as a repeating unit.
• the P3HB-based resin may be poly(3-hydroxybutyrate) that has only 3HB as a repeating unit, or it may be a copolymer of 3-hydroxybutyrate and another hydroxyalkanoate, but in this embodiment, it contains at least three types of copolymers that differ from each other in the content ratio of the constituent monomers.
• P3HA resin examples include poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (hereinafter sometimes referred to as "P3HB3HH"), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (hereinafter sometimes referred to as "P3HB3HV”), poly(3-hydroxybutyrate-co-4-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyoctanoate), poly(3-hydroxybutyrate-co-3-hydroxyoctadecanoate), etc.
• P3HB3HH poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)
• P3HB3HV poly(3-hydroxybutyrate-co-3-hydroxyvalerate)
• P3HB3HV poly(3-hydroxybutyrate-co-4-hydroxybutyrate)
• poly(3-hydroxybutyrate-co-3-hydroxyoctanoate) poly(3-hydroxybutyrate-
• 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.
• P3HB3HH is also preferred from the viewpoints that it is easy to produce industrially and is a physically useful plastic.
• P3HB3HH is preferred from the viewpoints that it can lower the melting point and enable molding processing at low temperatures.
• P3HB3HH Commercially available products of P3HB3HH include Kaneka Biodegradable Polymer Green Planet (registered trademark) from Kaneka Corporation.
• the melting point and Young's modulus of the P3HB3HV vary depending on the ratio of the 3-hydroxybutyrate and 3-hydroxyvalerate components, but because the two components co-crystallize, the degree of crystallinity is high at 50% or more, making it more flexible than poly(3-hydroxybutyrate), but the improvement in brittleness is insufficient.
• the average content ratio of each monomer unit in all monomer units constituting the P3HA-based resin component 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 P3HA-based resin component, and refers to the molar ratio of each monomer unit contained in the entire mixture of P3HA-based resins.
• the P3HA-based resin component contained in the resin composition according to this embodiment contains three types of P3HA-based resins having different content ratios of constituent monomers, as shown below.
• examples of the other hydroxyalkanoate units contained in copolymer (A), copolymer (B), and copolymer (C) include 3-hydroxyhexanoate units, 3-hydroxyvalerate units, 4-hydroxybutyrate units, 3-hydroxyoctanoate units, and 3-hydroxyoctadecanoate units. Only one type of other hydroxyalkanoate units may be contained, or two or more types may be contained.
• the other hydroxyalkanoate units contained in copolymer (A), copolymer (B), and copolymer (C) may be the same or different from each other.
• it is preferable that the other hydroxyalkanoate units in at least one or all of copolymer (A), copolymer (B), and copolymer (C) are 3-hydroxyhexanoate.
• Copolymer (A) is a low-crystalline P3HA-based resin
• copolymer (B) is a high-crystalline P3HA-based resin
• Copolymer (C) is a medium-crystalline P3HA-based resin whose crystallinity is intermediate between copolymers (A) and (B).
• highly crystalline P3HA-based resins have excellent productivity but poor mechanical strength, while low-crystalline P3HA-based resins have poor productivity but excellent mechanical properties. It is presumed that when both resins are used in combination, the highly crystalline P3HA-based resin forms fine resin crystal particles, while the low-crystalline P3HA-based resin forms tie molecules that crosslink the resin crystal particles.
• the strength and productivity of the laminate layer of the film or laminate can be improved.
• the content of 3-hydroxybutyrate units in the copolymer (A) is preferably lower than the average content of 3-hydroxybutyrate units in all monomer units constituting the P3HA resin component.
• the content of other hydroxyalkanoate units in the copolymer (A) is preferably 24 mol% or more and 99 mol% or less, more preferably 24 mol% or more and 50 mol% or less, even more preferably 24 mol% or more and 35 mol% or less, and particularly preferably 24 mol% or more and 30 mol% or less.
• copolymer (A) poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) is preferred, with poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) being more preferred.
• the content of 3-hydroxybutyrate units in copolymer (B) is preferably higher than the average content of 3-hydroxybutyrate units in all monomer units constituting the P3HA resin component.
• the content of other hydroxyalkanoate units in the copolymer (B) is preferably 1 mol % or more and less than 5 mol %, and more preferably 2 mol % or more and 4 mol % or less.
• copolymer (B) poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) is preferred, with poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) being more preferred.
• the ratio of each copolymer to the total of copolymer (A) and copolymer (B) is not particularly limited, but it is preferable that the ratio of copolymer (A) is 40% by weight or more and 90% by weight or less, and the ratio of copolymer (B) is 10% by weight or more and 60% by weight or less, and it is more preferable that the ratio of copolymer (A) is 55% by weight or more and 75% by weight or less, and the ratio of copolymer (B) is 25% by weight or more and 45% by weight or less.
• the content ratio of copolymer (A) relative to the total amount of P3HA-based resin components contained in the resin composition according to this embodiment is preferably 15% by weight or more and 45% by weight or less. Within this range, the action of copolymer (A) is more likely to be exhibited, and even if the production speed is increased, the effect of suppressing thickness fluctuations in the film or laminate layer and neck-in in the TD direction is more likely to be realized.
• the lower limit is more preferably 20% by weight or more, even more preferably 25% by weight or more, and particularly preferably 27% by weight or more, since thickness fluctuations and neck-in in the film or laminate layer can be further suppressed.
• the upper limit is more preferably 43% by weight or less.
• copolymer (C) in addition to copolymer (A) and copolymer (B), the solidification of the P3HA resin component is accelerated, so that the production speed of T-die film formation and extrusion lamination processing can be increased.
• the content of other hydroxyalkanoate units in the copolymer (C) is preferably 5 mol% or more and less than 24 mol%, more preferably 5 mol% or more and 22 mol% or less, even more preferably 6 mol% or more and 20 mol% or less, and particularly preferably 6 mol% or more and 18 mol% or less.
• the upper limit may be 15 mol% or less, or 10 mol% or less.
• copolymer (C) poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) or poly(3-hydroxybutyrate-co-4-hydroxybutyrate) is preferred, with poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) being more preferred.
• the ratio of copolymer (C) to the total of copolymer (A), copolymer (B), and copolymer (C) is not particularly limited, but is preferably 1% by weight or more and 99% by weight or less, more preferably 5% by weight or more and 90% by weight or less, and even more preferably 8% by weight or more and 85% by weight or less.
• the lower limit may be 20% by weight or more, 30% by weight or more, or 40% by weight or more.
• the upper limit may be 80% by weight or less, or 70% by weight or less. Since thickness fluctuation and neck-in of the film or laminate layer can be further suppressed, the ratio of copolymer (C) is preferably 60% by weight or less, more preferably 55% by weight or less, and even more preferably 50% by weight or less.
• the weight average molecular weight of the entire P3HA-based resin component is not particularly limited, but from the viewpoint of achieving both strength and productivity of the film or laminate layer, it is preferably from 100,000 to 2,000,000, more preferably from 150,000 to 1,000,000, and particularly preferably from 200,000 to 500,000.
• the upper limit may be 400,000 or less, or 300,000 or less.
• the weight average molecular weight of the copolymer (A), which is a low crystalline resin, is set to 100,000 or more and 500,000 or less.
• the weight average molecular weight of the copolymer (A) is set to 100,000 or more and 500,000 or less.
• the weight average molecular weight of the copolymer (A) is preferably 150,000 or more and 450,000 or less, and more preferably 200,000 or more and 400,000 or less.
• the lower limit may be 250,000 or more, or 300,000 or more.
• the weight average molecular weight of each of the copolymers (B) and (C) is not particularly limited. However, the weight average molecular weight of the copolymer (B) is preferably from 200,000 to 1,000,000, more preferably from 220,000 to 800,000, and even more preferably from 250,000 to 600,000. The upper limit may be 500,000 or less, or may be 400,000 or less.
• the weight average molecular weight of the copolymer (C) is preferably 100,000 or more and 2,500,000 or less, more preferably 150,000 or more and 2,000,000 or less, and even more preferably 200,000 or more and 1,500,000 or less.
• the upper limit may be 1,000,000 or less, 500,000 or less, 400,000 or less, or 300,000 or less.
• the weight average molecular weight of the P3HA resin described above is the value measured for the P3HA resin before it is reacted with the organic peroxide.
• the weight average molecular weight can be measured using gel permeation chromatography (GPC) (Shimadzu Corporation's "High Performance Liquid Chromatograph 20A System"), a polystyrene gel (Showa Denko KK's "K-G 4A” and “K806M”) column, chloroform as the mobile phase, and the molecular weight calculated as polystyrene.
• GPC gel permeation chromatography
• a polystyrene gel Showa Denko KK's "K-G 4A” and "K806M”
• chloroform as the mobile phase
• a calibration curve is prepared using polystyrene with weight average molecular weights of 31,400, 197,000, 668,000, and 1,920,000.
• the column used in the GPC can be a column appropriate for measuring the molecular weight.
• Copolymer (B) and copolymer (C) may each be a reaction product with an organic peroxide, or may be an unmodified product that has not been reacted with an organic peroxide. However, it is advantageous in terms of production of the resin composition that copolymer (B) and copolymer (A) are both reaction products with an organic peroxide.
• the copolymer (C) may be either a reactant or an unmodified product. From the viewpoint of improving the crack resistance of the film or laminate layer and suppressing neck-in in the TD direction, it is preferable that the copolymer (C) is a reactant. Also, from the viewpoint of suppressing the melt viscosity of the resin composition to improve processability and from the viewpoint of making it easier to suppress thickness fluctuations during high-speed production, it is preferable that the copolymer (C) is an unreacted product.
• the organic peroxides include, for example, diisobutyl peroxide, cumyl peroxyneodecanoate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, t-butyl peroxy 2-ethylhexanoate, 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, d
• t-butylperoxy 2-ethylhexyl carbonate t-butylperoxy isopropyl carbonate
• t-butylperoxy 2-ethylhexanoate t-butylperoxy 2-ethylhexanoate
• Only one type of organic peroxide may be used, or two or more types may be used in combination.
• the amount of the organic peroxide used can be appropriately set taking into consideration the effects of the invention, but the total amount of the organic peroxide used in the resin composition is preferably 1.0 part by weight or less, and particularly preferably 0.8 part by weight or less, relative to 100 parts by weight of copolymer (A).
• the lower limit is preferably 0.1 part by weight or more, more preferably 0.2 part by weight or more, and more preferably 0.3 part by weight or more. From the viewpoint of suppressing neck-in in the TD direction and improving the crack resistance of the film or laminate layer, it is preferably 0.35 part by weight or more, more preferably 0.40 part by weight or more, and particularly preferably 0.50 part by weight or more.
• the weight average molecular weight of the P3HA resin after reaction with the organic peroxide is preferably in the range of about 50,000 to 150,000 higher than the weight average molecular weight of the P3HA resin before the reaction as described above.
• the method for measuring the weight average molecular weight is as described above.
• the weight average molecular weight of the copolymer (A) after reaction with the organic peroxide is preferably about 150,000 to 650,000, more preferably about 200,000 to 600,000, and particularly preferably about 250,000 to 550,000.
• the lower limit may be 300,000 or more.
• the weight average molecular weight of the entire P3HA-based resin component including the copolymer after reaction with the organic peroxide is preferably 150,000 to 2,500,000, more preferably 200,000 to 1,500,000, and particularly preferably 250,000 to 600,000.
• the weight average molecular weight 150,000 or more the strength of the film or laminate layer tends to be further improved.
• weight average molecular weight 2,500,000 or less processability tends to be further improved and molding tends to be easier.
• the content of the P3HA-based resin component in the resin composition according to this embodiment is not particularly limited, but is preferably 20% by weight or more, more preferably 30% by weight or more, even more preferably 40% by weight or more, even more preferably 60% by weight or more, and particularly preferably 70% by weight or more.
• the upper limit of the content of the P3HA-based resin component is not particularly limited, but may be 100% by weight or less, or may be 99% by weight or less.
• the resin composition according to the present embodiment may contain a resin other than the P3HA resin (sometimes referred to as "other resin").
• the other resin is not particularly limited as long as it does not significantly reduce the compatibility, moldability, or mechanical properties when molded, but when the resin composition is used for an application requiring the biodegradability characteristic of the P3HA resin, it is preferable that the resin is a biodegradable resin.
• the other resin include an aliphatic polyester having a structure in which an aliphatic diol and an aliphatic dicarboxylic acid are polycondensed, and an aliphatic aromatic polyester having both an aliphatic compound and an aromatic compound as monomers.
• Examples of the former include polyethylene succinate, polybutylene succinate (PBS), polyhexamethylene succinate, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polybutylene succinate adipate (PBSA), polyethylene sebacate, and polybutylene sebacate.
• Examples of the latter include poly(butylene adipate-co-butylene terephthalate) (PBAT), poly(butylene sebacate-co-butylene terephthalate), poly(butylene azelate-co-butylene terephthalate), poly(butylene succinate-co-butylene terephthalate) (PBST), and the like.
• the other resins may be used alone or in combination of two or more.
• the content of other resins in the resin composition according to this embodiment is not particularly limited, but is preferably 250 parts by weight or less, more preferably 100 parts by weight or less, and even more preferably 50 parts by weight or less, relative to 100 parts by weight of the total amount of the P3HA-based resin components. It may be 30 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less. There is no particular lower limit for the content of other resins, and it may be 0 parts by weight.
• the resin composition according to the present embodiment may contain other components (additives).
• 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.
• the resin composition may also contain a crystal nucleating agent.
• crystal nucleating agents 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-hydroxyalkanoate)-based resins.
• the crystal nucleating agents may be used alone or in combination, and the ratio of their use may 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 the P3HA resin components.
• the resin composition may also contain a lubricant.
• 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 P3HA resin.
• the amount of the lubricant used is not particularly limited, but is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, and even more preferably 0.1 to 1.5 parts by weight, per 100 parts by weight of the total amount of the P3HA resin components.
• the resin composition may contain a filler.
• a filler By including a filler, the film or laminate layer can have a higher strength.
• 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 P3HA-based resin components.
• the resin composition does not have to contain a filler.
• the resin composition may contain a plasticizer.
• the plasticizer is not particularly limited, but from the viewpoint of compatibility with the P3HA-based resin, it is preferable to use an ester compound having an ester bond in the molecule.
• modified glycerin compounds, dibasic acid ester compounds, adipate compounds, polyether ester compounds, citrate compounds, sebacate compounds, and isosorbide ester compounds are preferred, and modified glycerin compounds are particularly preferred.
• the ester compounds can be used alone or in combination of two or more. When using two or more in combination, the mixing ratio of the ester compounds can be appropriately adjusted.
• Glycerin ester compounds are preferred as modified glycerin compounds.
• any of glycerin monoesters, diesters, and triesters can be used, but from the viewpoint of compatibility with the P3HA resin component, glycerin triesters are preferred.
• glycerin triesters are particularly preferred.
• Specific examples of glycerin diacetomonoesters include glycerin diacetomonolaurate, glycerin diacetomonooleate, glycerin diacetomonostearate, glycerin diacetomonocaprylate, and glycerin diacetomonodecanoate.
• the modified glycerin compounds include Riken Vitamin Co., Ltd.'s "Rikemal” (registered trademark) PL series and "BIOCIZER” (registered trademark).
• dibasic acid ester compounds include dibutyl adipate, diisobutyl adipate, bis(2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, bis[2-(2-butoxyethoxy)ethyl]adipate, bis[2-(2-butoxyethoxy)ethyl]adipate, bis(2-ethylhexyl)azelate, dibutyl sebacate, bis(2-ethylhexyl)sebacate, diethyl succinate, and mixed-group dibasic acid ester compounds.
• adipate ester compounds examples include diethylhexyl adipate, dioctyl adipate, and diisononyl adipate.
• polyether ester compounds examples include polyethylene glycol dibenzoate, polyethylene glycol dicaprylate, and polyethylene glycol diisostearate.
• citrate ester compound is acetyl tributyl citrate.
• An example of a sebacic acid ester compound is dibutyl sebacate.
• ester compound glycerin diester is preferred, glycerin diacetomonoester is more preferred, and glycerin diacetomonolaurate is more preferred, particularly from the viewpoint of compatibility with P3HA-based resins.
• the drawdown time (t) of the resin composition according to the present embodiment may be appropriately set and is not particularly limited.
• the upper limit of the drawdown time is preferably 45 (sec) or less, more preferably 40 (sec) or less, and particularly preferably 35 (sec) or less.
• the lower limit is preferably 10 (sec) or more, more preferably 14 (sec) or more, and particularly preferably 20 (sec) or more.
• the drawdown time can be controlled within the above range by adjusting the amount of organic peroxide used, the molecular weight of each copolymer or the entire P3HA-based resin component, the proportion of each copolymer used, and the like.
• the P3HA resin used in the melt-kneading step may be at least one or all of copolymer (A), copolymer (B) and copolymer (C).
• copolymer (A) and, optionally, copolymer (B) and/or (C).
• each copolymer that has not been reacted with an organic peroxide is preferable.
• the P3HA resin and organic peroxide are fed into an extruder and melt-kneaded, but in addition to these components, other components such as the crystal nucleating agent, external lubricant, filler, plasticizer, etc., as described above, may also be fed into the extruder to melt-knead.
• other components such as the crystal nucleating agent, external lubricant, filler, plasticizer, etc., as described above, may also be fed into the extruder to melt-knead.
• the P3HA resin, the organic peroxide, and other components as necessary may be fed into the extruder separately, or the components may be mixed together and then fed into the extruder. It is particularly preferable to feed the organic peroxide and the P3HA resin into the extruder separately.
• This feeding method has the advantage that the dispersibility of the organic peroxide is improved, making it less likely for lumps to form in the resulting molded product, and making it easier to perform T-die filming or extrusion lamination with good quality and stability.
• all of the P3HA-based resin components may be reacted with the organic peroxide.
• a portion of the P3HA-based resin components may be reacted with the organic peroxide to form a reaction product, and the remaining P3HA-based resin may be added to the reaction product and further melt-kneaded.
• the remaining P3HA-based resin added later does not react with the organic peroxide. From the standpoint of productivity and property improvement, it is preferable to react a portion of the P3HA-based resin components with the organic peroxide and then add the remaining P3HA-based resin.
• the upper limit of the resin temperature measured with a thermometer in the die is preferably 190°C or less, more preferably 180°C or less, and particularly preferably 170°C or less, and the lower limit is preferably 120°C or more, more preferably 125°C or more, and particularly preferably 130°C or more.
• the upper limit of the residence time in the extruder is preferably 700 seconds or less, more preferably 500 seconds or less, and particularly preferably 300 seconds or less, and the lower limit is preferably 40 seconds or more, more preferably 50 seconds or more, and particularly preferably 60 seconds or more.
• the resin temperature and residence time are affected by the set temperature of the extruder, the screw rotation speed, and the screw configuration.
• the resin temperature exceeds 180°C, deterioration of the P3HA resin may be accelerated, so it is preferable to set the barrel zone where the barrel temperature of the extruder is 120°C or more and 160°C or less in less than half of the extruder, so that the residence time at a resin temperature of 180°C is not 60 seconds or more.
• the die temperature In order to facilitate pelletization of the resin coming out of the die (for example, pelletization by strand cutting, underwater cutting, etc.), it is preferable to set the die temperature to, for example, 120°C or more and 160°C or less to reduce poor cutting due to insufficient solidification and adhesion of pellets to each other.
• the resin composition according to this embodiment can be further molded (molded) to obtain various molded articles (molded articles obtained by molding the lamination resin composition according to this embodiment).
• the resin composition according to this embodiment can be suitably used in the production of films for producing laminates, and in methods for producing laminates by directly extrusion laminating onto a substrate. Therefore, laminates produced by film attachment or extrusion lamination can be suitably produced.
• lamination method there are no particular limitations on the lamination method, but specific examples include an extrusion lamination method in which a resin composition containing molten P3HA-based resin is extruded from a T-die into a film, directly laminated onto a separately unwound substrate layer such as paper, and cooled and pressed using a cooling roll, and a lamination method in which a film containing P3HA-based resin that has been previously prepared by melt extrusion molding using a T-die is placed on the surface of a substrate layer and pressed (specifically, a thermal lamination method, a dry lamination method, or a non-solvent lamination method).
• the substrate layer is not particularly limited as long as it can laminate the resin composition according to the present embodiment. From the viewpoint of increasing the biodegradability of the entire laminate, the substrate layer is preferably a layer having biodegradability.
• biodegradability refers to the property that the material can be decomposed into water and carbon dioxide by the action of microorganisms.
• the biodegradable substrate layer include, but are not limited to, paper (mainly composed of cellulose), cellophane, cellulose ester; polyvinyl alcohol, polyamino acid, polyglycolic acid, pullulan, etc. Paper or cellophane is preferred, and paper is particularly preferred, because it is excellent in heat resistance and inexpensive.
• the substrate layer may be previously subjected to a surface treatment such as corona treatment, plasma treatment, frame treatment, anchor coat treatment, etc. These surface treatments may be performed alone or in combination with a plurality of surface treatments.
• a surface treatment such as corona treatment, plasma treatment, frame treatment, anchor coat treatment, etc.
• the heating temperature in the lamination method is preferably a temperature in the range of the temperature of the resin composition according to this embodiment at the time of lamination, which is equal to or higher than the melting point (Tm) of the resin composition and less than a temperature 30°C higher than the melting point (Tm).
• the melting point refers to the top temperature of the melting point peak on the highest temperature side in the crystal melting curve obtained by differential scanning calorimetry. If the lamination temperature is lower than the melting point, the resin cannot be sufficiently flowed, and the adhesive strength with the base material layer tends to be insufficient.
• the lamination temperature is preferably 160°C or higher, more preferably 165°C or higher, and particularly preferably 170°C or higher.
• the upper limit of the lamination temperature is preferably 180°C or lower. When the lamination temperature is 180°C or less, it tends to be possible to avoid a decrease in the mechanical strength of the laminate layer caused by thermal decomposition of the P3HA-based resin.
• the lamination temperature can be set so that the temperature of the resin composition containing the P3HA resin is within the above range during lamination.
• the temperature of the T-die can be adjusted, and in the case of thermal lamination, the temperature of the heating roll used when laminating the films can be adjusted.
• the surface temperature of the cooling roll in the extrusion lamination method is not particularly limited as long as it is a temperature at which the resin layer can be cooled and pressed, and can be determined appropriately.
• the surface temperature of the cooling roll may be, for example, 20 to 70°C, and is preferably 40 to 60°C. If it is within the above range, crystallization of the P3HA-based resin component is promoted, which results in reduced adhesion to the cooling roll and allows solidification to be achieved in a short period of time.
• the thickness of the film according to this embodiment, or the thickness of the laminate layer of the laminate according to this embodiment, is not particularly limited, but from the viewpoint of preventing water absorption into the paper base layer while ensuring sufficient flexibility, it is preferably 5 to 300 ⁇ m, and more preferably 10 to 200 ⁇ m.
• the laminate according to the present embodiment can be used to manufacture a molded article (hereinafter, also referred to as the present molded article).
• the present molded article is formed from a laminate having a uniform thickness or width of the laminate layer, and therefore has excellent productivity and is advantageous in various applications.
• the present molded article is not particularly limited as long as it contains the present laminate, but examples include paper, film, sheets, tubes, plates, rods, containers (e.g., bottle containers), bags, parts, etc. From the perspective of marine pollution countermeasures, the present molded article is preferably a bag or bottle container.
• the present molded article may be the present laminate itself, or may be a product that has been subjected to secondary processing using the present laminate. Since the laminate is subjected to secondary processing, the molded article containing it can be suitably used as various packaging container materials such as shopping bags, various bags, food and confectionery packaging materials, cups, trays, cartons, etc.
• the laminate contains a resin composition having high adhesion to substrates and good heat resistance, it is more suitable as a container for holding liquids, in particular, a container for holding hot contents such as food and drink cups for instant noodles, instant soup, coffee, etc., trays for prepared foods, lunch boxes, microwave foods, etc.
• the heat seal temperature of this laminate varies depending on the adhesion method.
• the heat seal temperature of this laminate is usually 250°C or less, preferably 200°C or less, and more preferably 180°C or less. If it is within the above range, melting of the resin near the sealed part can be avoided, and an appropriate resin layer thickness and seal strength can be ensured.
• the lower limit is usually 130°C or more, preferably 140°C or more, and more preferably 150°C or more. If it is within the above range, appropriate adhesion at the sealed part can be ensured.
• the heat seal pressure of this laminate varies depending on the adhesion method.
• the heat seal pressure of this laminate is usually 0.1 MPa or more, and preferably 0.3 MPa or more. If it is within the above range, appropriate adhesion at the sealed portion can be ensured.
• the upper limit is usually 0.5 MPa or less, and preferably 0.45 MPa or less. If it is within the above range, thinning of the film thickness at the sealed end can be avoided, and seal strength can be ensured.
• the molded product can also be composited with a molded product made of a material different from the molded product (e.g., fiber, thread, rope, woven fabric, knitted fabric, nonwoven fabric, paper, film, sheet, tube, plate, rod, container, bag, part, foam, etc.) in order to improve its physical properties. It is preferable that these materials are also biodegradable.
• a material different from the molded product e.g., fiber, thread, rope, woven fabric, knitted fabric, nonwoven fabric, paper, film, sheet, tube, plate, rod, container, bag, part, foam, etc.
• the poly(3-hydroxyalkanoate) resin component is A copolymer (A) of 3-hydroxybutyrate units and other hydroxyalkanoate units, in which the content of the other hydroxyalkanoate units is 24 mol % or more;
• the copolymer (C) contains 3-hydroxybutyrate units and other hydroxyalkanoate units, and the content of the other hydroxyalkanoate units is 5 mol % or more and less than 24 mol %,
• the weight average molecular weight of the copolymer (A) is 100,000 or more and 500,000 or less
• [Item 2] 2. The resin composition according to item 1, wherein the content of the copolymer (A) relative to the total amount of the poly(3-hydroxyalkanoate)-based resin component is 15% by weight or more and 45% by weight or less. [Item 3] 3. The resin composition according to item 1 or 2, wherein at least the copolymer (A) is a reaction product with the organic peroxide. [Item 4] 4. The resin composition according to any one of items 1 to 3, wherein the total amount of the organic peroxide used in the resin composition is 0.1 parts by weight or more and 1.0 parts by weight or less with respect to 100 parts by weight of the copolymer (A). [Item 5] 5.
• Melt viscosity The melt viscosity was measured using a capillary rheometer equipped with an orifice having a radius of 1 mm and a capillary length of 10 mm attached to the end of a barrel having a furnace diameter of 0.955 mm, at a barrel setting temperature of 170° C., a volumetric flow rate of 0.716 cm 3 /min, and a shear rate of 122 sec -1 [item 6] 6.
• Drawdown time The time required for a resin composition discharged from an orifice to fall 20 cm when measuring melt viscosity [Item 7] 7.
• Melt viscosity Melt viscosity measured using a capillary rheometer equipped with an orifice having a radius of 1 mm and a capillary length of 10 mm attached to the end of a barrel having a furnace diameter of 0.955 mm, at a barrel set temperature of 170° C., a volumetric flow rate of 0.716 cm 3 /min, and a shear rate of 122 sec -1.
• Drawdown time The time required for a resin composition discharged from an orifice to fall 20 cm when measuring the melt viscosity [Item 8]
• the other hydroxyalkanoate units in at least one or all of the copolymers (A), (B), and (C) are 3-hydroxyhexanoate.
• a film comprising the resin composition according to any one of items 1 to 8.
• a laminate comprising a laminate layer containing the resin composition according to any one of items 1 to 8, and a substrate layer.
• a substrate layer is biodegradable.
• Item 12 Item 12.
• a molded article comprising the laminate according to any one of items 10 to 12.
• Item 14 Item 9. A method for producing a film, comprising a step of melt-extrusion molding the resin composition according to any one of items 1 to 8 using a T-die.
• a pressure cooker tester HAST CHAMBER EHS-221M, manufactured by ESPEC Corporation
• A-2 P3HB3HH having a weight average molecular weight of 330,000 obtained by hydrolyzing P3HB3HH having a 3HH composition of 25.8 mol% and a weight average molecular weight of 680,000 in terms of standard polystyrene measured by GPC, obtained according to the method described in Example 9 of WO 2019/142845.
• A'-1 P3HB3HH obtained according to the method described in Example 9 of WO 2019/142845, having a 3HH composition of 25.8 mol% and a weight average molecular weight of 680,000 in terms of standard polystyrene measured by GPC
• B-1 P3HB3HH having a weight average molecular weight of 360,000 obtained by hydrolyzing P3HB3HH having a 3HH composition of 2.1 mol% and a weight average molecular weight of 700,000 in terms of standard polystyrene measured by GPC, obtained according to the method described in Example 2 of WO 2019/142845.
• P3HB3HH having a weight average molecular weight of 330,000 obtained by hydrolyzing P3HB3HH having a 3HH composition of 2.0 mol% and a weight average molecular weight of 680,000 in terms of standard polystyrene measured by GPC, obtained according to the method described in Example 2 of WO 2019/142845.
• P3HB3HH obtained according to the method described in Example 2 of WO 2019/142845, having a 3HH composition of 2.0 mol% and a weight average molecular weight of 680,000 in terms of standard polystyrene measured by GPC
• P3HB3HH having a weight average molecular weight of 220,000 obtained by hydrolyzing P3HB3HH having a 3-hydroxyhexanoate (3HH) composition of 6.0 mol% and a standard polystyrene-equivalent weight average molecular weight of 630,000 measured by GPC, obtained according to the method described in Example 1 of WO 2019/142845.
• C-2 P3HB3HH obtained according to the method described in Example 1 of WO 2019/142845, having a 3-hydroxyhexanoate (3HH) composition of 6.0 mol% and a weight average molecular weight of 630,000 in terms of standard polystyrene measured by GPC
• C-3 P3HB3HH obtained according to the method described in Example 1 of WO 2019/142845, having a 3-hydroxyhexanoate (3HH) composition of 6.0 mol% and a weight average molecular weight of 420,000 in terms of standard polystyrene measured by GPC.
• F-1 Pentaerythritol (manufactured by Mitsubishi Chemical Corporation: NeuRizer P)
• F-2 Behenamide (manufactured by Nippon Fine Chemicals Co., Ltd.: BNT-22H)
• melt viscosity The melt viscosity ( ⁇ ) was measured using a Shimadzu capillary rheometer equipped with an orifice having a radius of 1 mm and a capillary length of 10 mm at the end of a barrel having a furnace diameter of 0.955 mm, at a barrel set temperature of 170° C., a volumetric flow rate of 0.716 cm 3 /min, and a shear rate of 122 sec -1 .
• the film thickness fluctuation rate is less than 20% (excellent applicability)
• ⁇ The film thickness fluctuation rate is 20% or more and less than 25% (applicable)
• ⁇ The film thickness fluctuation rate is 25% or more and less than 30% (applicable, but may not be suitable depending on the application)
• ⁇ The film thickness fluctuation rate is 30% or more (not applicable)
• the width (length in the TD direction/mm) of the film obtained using a T-die with a die lip width T of 500 mm was measured at 20 points at 5 cm intervals along the MD direction, and the neck-in ratio was calculated from the median value using the following formula.
• Neck-in rate (%) [dice width (T) - median width of film] / die width (T) x 100
• the applicability of the laminate to the laminate layer was evaluated according to the following criteria. ⁇ : Neck-in rate is 25% or less (excellent applicability) ⁇ : Neck-in rate is 26% to 35% (applicable) ⁇ : Neck-in ratio is 36% or more and 45% or less (applicable, but may not be suitable depending on the application) ⁇ : Neck-in rate is 46% or more (not applicable)
• TEM26SS co-directional intermeshing twin-screw extruder
• P3HA (A-2 and B-2) fed from the main feeder is a reaction product with the organic peroxide.
• the strand obtained from the die was passed through a water tank filled with warm water at 40 to 45 ° C. to solidify, and cut with a pelletizer to obtain P3HA-based resin pellets 1.
• the resulting pellets were used to evaluate the melt viscosity and drawdown, and the results are shown in Table 1.
• Table 1 also shows the weight average molecular weight of each P3HA or the entire P3HA-based resin component before reaction with the organic peroxide.
• the P3HA resin pellets 1 were fed into a single-screw extruder equipped with a T-die, extruded from the T-die under conditions that the resin temperature immediately after extrusion was 163 to 167° C., and taken up with a cooling roll set at 60° C. at a take-up speed (film processing speed) of 22 m/min or 45 m/min to form a film, thereby obtaining a P3HA film.
• the films obtained at each processing speed were evaluated for the film thickness variation rate and neck-in rate, and the results are shown in Table 1.
• the P3HA film obtained above and a base paper having a basis weight of 210 g/ m2 were sandwiched so that the heating roll was in contact with the paper side and the cooling roll was in contact with the P3HA film side, and the conditions were adjusted so that the surface temperature of the P3HA film was 170° C., thereby obtaining a laminate including a paper base material and a laminate layer.
• the crack resistance of the obtained laminate was evaluated, and the results are shown in Table 1.
• Examples 2 to 5 P3HA resin pellets 2 to 5, a film, and a laminate were prepared in the same manner as in Example 1, except that the formulation was changed as shown in Table 1, and the evaluations were carried out in the same manner as in Example 1. The results are summarized in Table 1.
• Example 6 Except for feeding C-1 from the main feeder instead of the side feeder, P3HA resin pellets 6, a film, and a laminate were prepared in the same manner as in Example 1, and the same evaluations were carried out as in Example 1. The results are summarized in Table 1. Incidentally, the P3HA (A-2, B-2, and C-1) fed from the main feeder during the melt-kneading process is a reaction product with the organic peroxide.
• the P3HA resin pellets 7 were fed into a single-screw extruder equipped with a T-die, extruded from the T-die under conditions such that the resin temperature immediately after extrusion was 163 to 167°C, and taken up with a cooling roll set at 60°C at a take-up speed (film processing speed) of 22 m/min or 45 mm/min to form a film.
• film processing speed 22 m/min
• a film could be formed although there was a large variation in film thickness.
• the film thickness variation and neck-in rate during processing were extremely large, making it impossible to continuously obtain a film-shaped molded product.
• P3HA (A'-1, B-3, C-2, C-3) fed from the main feeder is a reaction product with the organic peroxide.
• the strand obtained from the die was passed through a water tank filled with warm water at 40 to 45° C. to solidify it, and then cut with a pelletizer to obtain P3HA resin pellets 8.
• the P3HA resin pellets 8 were fed into a single screw extruder equipped with a T-die, extruded from the T-die under conditions such that the resin temperature immediately after extrusion was 163 to 167°C, and taken up with a cooling roll set at 60°C at a take-up speed (film processing speed) of 22 m/min or 45 mm/min to form a film.
• film processing speed was 22 m/min and 45 m/min
• the film thickness fluctuation and neck-in ratio during processing were extremely large, making it impossible to continuously obtain a film-shaped molded product, and it was also impossible to obtain a good laminate.

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• 2024
  • 2024-03-07 JP JP2025506777A patent/JPWO2024190618A1/ja active Pending
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• 2025
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