WO2014189021A1 - Feuille de polylactide et son procédé de fabrication - Google Patents

Feuille de polylactide et son procédé de fabrication Download PDF

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Publication number
WO2014189021A1
WO2014189021A1 PCT/JP2014/063272 JP2014063272W WO2014189021A1 WO 2014189021 A1 WO2014189021 A1 WO 2014189021A1 JP 2014063272 W JP2014063272 W JP 2014063272W WO 2014189021 A1 WO2014189021 A1 WO 2014189021A1
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WIPO (PCT)
Prior art keywords
polylactic acid
sheet
poly
lactic acid
acid
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Ceased
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PCT/JP2014/063272
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English (en)
Japanese (ja)
Inventor
山内英幸
新崎盛昭
坂本純
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Toray Industries Inc
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Toray Industries Inc
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Priority to JP2014525649A priority Critical patent/JPWO2014189021A1/ja
Publication of WO2014189021A1 publication Critical patent/WO2014189021A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • B29C48/03—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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/69—Filters or screens for the moulding 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
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/76—Venting, drying means; Degassing means
    • 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
    • B29C48/92—Measuring, controlling or regulating
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92714—Degree of crosslinking, solidification, crystallinity or homogeneity
    • 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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • 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
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B29K2067/046—PLA, i.e. polylactic acid or polylactide
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable

Definitions

  • the present invention relates to a polylactic acid-based sheet having excellent transparency, heat resistance, and high-temperature formability.
  • Polylactic acid is a polymer that can be practically melt-molded and has biodegradable characteristics. Therefore, after use, development as a biodegradable polymer that is decomposed in the natural environment and released as carbon dioxide or water has been promoted.
  • the properties of carbon neutral have attracted attention and are expected to be used as environmentally friendly materials.
  • the nature of carbon neutral is that polylactic acid itself is made from renewable resources (biomass) originating from carbon dioxide and water, so even if polylactic acid is used and carbon dioxide is released, Carbon dioxide does not increase or decrease.
  • lactic acid which is a monomer of polylactic acid, is being produced at a low cost by fermentation using microorganisms. Therefore, polylactic acid has been studied as an alternative material for general-purpose petroleum plastics.
  • polylactic acid has been tried for practical use in a wide range as a melt-molded product.
  • heat resistance and durability are low compared with petroleum plastics, and the range of practical use is greatly limited.
  • a crystallization treatment such as heat treatment is performed in order to improve the heat resistance of the polylactic acid molded article, there is a problem that it becomes white turbid and transparency is lowered. Therefore, a polylactic acid molded article having excellent heat resistance and transparency even in a crystallized state is desired.
  • the polylactic acid stereocomplex is formed by mixing optically active poly-L-lactic acid (hereinafter referred to as PLLA) and poly-D-lactic acid (hereinafter referred to as PDLA).
  • PLLA optically active poly-L-lactic acid
  • PDLA poly-D-lactic acid
  • Patent Document 1 a resin sheet containing stereocomplex polylactic acid that defines the breaking elongation and stress during heating is studied.
  • a sheet made of polylactic acid stereocomplex exhibits excellent heat resistance.
  • it since it has a rigid structure and has high rigidity, there has been a problem that in molding applications, it is necessary to mold in a high temperature region.
  • draw down a draw down phenomenon in which the sheet hangs down in a heating process before forming has been a problem.
  • Patent Document 1 Although the polylactic acid-based sheet described in Patent Document 1 is excellent in moldability, the drawdown is large in the heating process before molding because of high elongation at the time of heating. Therefore, there is a problem that the sheet breaks at the time of molding or the sheet becomes defective in molding.
  • an object of the present invention is to provide a polylactic acid-based sheet that is excellent in transparency and heat resistance, and further excellent in moldability at high temperatures.
  • the polylactic acid-based sheet of the present invention employs the following means in order to solve the above problems.
  • the polylactic acid includes a polylactic acid block copolymer composed of a segment composed of poly-L-lactic acid and a segment composed of poly-D-lactic acid, (1) to (3) The polylactic acid-based sheet according to any one of the above.
  • the polylactic acid-based sheet of the present invention is a sheet mainly composed of polylactic acid, and has a heat shrinkage rate at 160 ° C. of 0% to 30% and a crystallinity of 1% to 30%. To do.
  • a heat shrinkage rate at 160 ° C. of 0% to 30%
  • a crystallinity of 1% to 30% To do.
  • Polylactic acid means that the lactic acid component is 70 mol% or more and 100 mol% or less in 100 mol% of all monomer components constituting polylactic acid.
  • the polylactic acid in the present invention is not particularly limited, but is preferably polylactic acid selected from the group consisting of poly-L-lactic acid, poly-D-lactic acid, and a polylactic acid block copolymer described later.
  • poly-L-lactic acid means that when the lactic acid component in polylactic acid is 100 mol%, the L-lactic acid component is contained in an amount of 70 mol% to 100 mol%.
  • poly-D-lactic acid means that when the lactic acid component in the polylactic acid is 100 mol%, the D-lactic acid component is contained in an amount of 70 mol% to 100 mol%.
  • the poly-L-lactic acid preferably contains 90 to 100 mol% of the L-lactic acid component when the lactic acid component in the polylactic acid is 100 mol%. More preferably, the content is 95 mol% or more and 100 mol% or less. The content is particularly preferably 98 mol% or more and 100 mol% or less.
  • the poly-D-lactic acid preferably contains 90 to 100 mol% of the D-lactic acid component when the lactic acid component in the polylactic acid is 100 mol%. Moreover, it is more preferable to contain 95 mol% or more and 100 mol% or less. The content is particularly preferably 98 mol% or more and 100 mol% or less.
  • the polylactic acid may contain components other than the lactic acid component (L-lactic acid component or D-lactic acid component) as long as the performance of the present invention is not impaired.
  • other components include polycarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, and lactones.
  • polysuccinic acids such as succinic acid, adipic acid, sebacic acid, fumaric acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, and 5-tetrabutylphosphonium sulfoisophthalic acid.
  • Carboxylic acids or their derivatives ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, neopentylglycol, glycerin, trimethylolpropane, pentaerythritol, trimethylolpropane or pentaerythritol with ethylene oxide or propylene oxide
  • Added polyhydric alcohol aromatic polyhydric alcohol obtained by addition reaction of bisphenol with ethylene oxide, diethylene glycol, triethylene glycol
  • Polyhydric alcohols such as liethylene glycol and polypropylene glycol or derivatives thereof, hydroxycarboxylic acids such as glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid, and glycolide, ⁇ -Caprolactone glycolide, ⁇ -caprolactone, ⁇ -propiolactone,
  • the polylactic acid-based sheet is mainly composed of polylactic acid means that when all the components in the polylactic acid-based sheet are 100% by mass, the polylactic acid is contained in an amount of 50% by mass to 100% by mass.
  • the polylactic acid-based sheet preferably contains 80% by mass or more and 100% by mass or less of polylactic acid when all components in the polylactic acid-based sheet are 100% by mass.
  • polylactic acid-based sheet of the present invention can contain various additives as long as the performance of the present invention is not impaired.
  • the polylactic acid-based sheet of the present invention can contain one or more crystal nucleating agents as long as the performance of the present invention is not impaired as required.
  • the crystal nucleating agent suitably contained in the polylactic acid-based sheet of the present invention include inorganic nucleating agents such as talc, ethylene bislauric acid amide, ethylene bis-12-dihydroxystearic acid amide, and trimesic acid tricyclohexyl amide.
  • Organic amide compounds such as copper phthalocyanine and pigment yellow 110, organic carboxylic acid metal salts, zinc phenylphosphonate and the like.
  • the polylactic acid-based sheet of the present invention can contain a moldability improving agent as long as it does not impair the performance of the present invention.
  • a moldability improver a multilayer structure polymer composed of a core layer and one or more shell layers covering it, a polyether block copolymer composed of a segment composed of polyether and a segment composed of polylactic acid And at least one selected from the group consisting of polyester-based block copolymers composed of polyester segments and polylactic acid segments, aliphatic polyesters (excluding polylactic acid), and aliphatic aromatic polyesters. Can be used.
  • the weight average molecular weight of polylactic acid is not particularly limited, but is preferably in the range of 100,000 to 300,000 in terms of moldability and mechanical properties. More preferably, the polylactic acid has a weight average molecular weight of 120,000 to 280,000. More preferably, it is 130,000 to 270,000. It is especially preferable that they are 140,000 or more and 260,000 or less.
  • the polylactic acid-based sheet of the present invention is mainly composed of polylactic acid.
  • polylactic acid for example, the following method A) or B) is preferable.
  • A) As polylactic acid a mixture of poly-L-lactic acid and poly-D-lactic acid is used.
  • B) As the polylactic acid a polylactic acid block copolymer (hereinafter referred to as a polylactic acid block copolymer) composed of a segment composed of poly-L-lactic acid and a segment composed of poly-D-lactic acid is used.
  • the method A) is that the polylactic acid contains poly-L-lactic acid and poly-D-lactic acid.
  • the polylactic acid contains a polylactic acid block copolymer composed of a segment composed of poly-L-lactic acid and a segment composed of poly-D-lactic acid.
  • the heat shrinkage rate of the polylactic acid-based sheet at 160 ° C. can be set to 0% to 30%, and the crystallinity can be further set to 1% to 30%. From the viewpoint that excellent transparency and heat resistance can be obtained when the sheet is formed, it is preferable to use a polylactic acid block copolymer as the method B), that is, polylactic acid.
  • melt kneading is not particularly limited. For example, there is a method of melt-kneading at a melting end temperature or higher of a component having a higher melting point among poly-L-lactic acid and poly-D-lactic acid. There is also a method of removing the solvent after mixing in the solvent.
  • At least one of molten poly-L-lactic acid and poly-D-lactic acid is allowed to stay in the melting machine in advance within the temperature range of melting point ⁇ 50 ° C. to melting point + 20 ° C. while being sheared, and then poly- There is a method of mixing so that crystals of a mixture of L-lactic acid and poly-D-lactic acid remain.
  • the method of melt-kneading at a temperature higher than the melting end temperature of the component having the higher melting point is poly-L-lactic acid and poly-D-lactic acid batchwise or continuously.
  • the method of mixing by a method is mentioned. You may mix by any method.
  • the kneading apparatus include a single screw extruder, a twin screw extruder, a plast mill, a kneader, and a stirred tank reactor equipped with a pressure reducing device. In view of uniform and sufficient kneading, it is preferable to use a twin screw extruder.
  • the mass ratio of poly-L-lactic acid to poly-D-lactic acid is 80:20 to 20:80. Is preferred. More preferably, it is 75:25 to 25:75. Further, it is preferably 70:30 to 30:70. In particular, it is most preferably 60:40 to 40:60.
  • the method for producing a polylactic acid block copolymer is particularly limited when a polylactic acid block copolymer composed of a segment composed of poly-L-lactic acid and a segment composed of poly-D-lactic acid is used as the polylactic acid.
  • a general method for producing polylactic acid can be used.
  • the polylactic acid block copolymer is prepared by mixing poly-L-lactic acid and poly-D-lactic acid in a twin screw extruder, and subsequently solid-phase polymerizing the mixture. This is preferable in that the resulting sheet has excellent heat resistance and transparency.
  • either of the cyclic dimer L-lactide or D-lactide generated from the raw lactic acid component is subjected to ring-opening polymerization in the presence of a catalyst, and lactide which is an optical isomer of the polylactic acid is added.
  • lactide method for producing a polylactic acid block copolymer by ring-opening polymerization is a lactide method for producing a polylactic acid block copolymer by ring-opening polymerization.
  • poly-L-lactic acid and poly-D-lactic acid are melt-kneaded for a long time at a temperature equal to or higher than the melting end temperature of the component having a higher melting point, whereby the L-lactic acid component segment and the D-lactic acid component segment are esterified.
  • poly-L-lactic acid and poly-D-lactic acid are covalently bonded with polyfunctional compound by mixing polyfunctional compound with poly-L-lactic acid and poly-D-lactic acid and reacting them.
  • polyfunctional compound by mixing polyfunctional compound with poly-L-lactic acid and poly-D-lactic acid and reacting them.
  • block copolymer There is a method for producing a block copolymer.
  • a segment composed of poly-L-lactic acid and a segment composed of poly-D-lactic acid is used as polylactic acid
  • the mass ratio of the segments made of lactic acid is preferably 80:20 to 20:80. More preferably, it is 75:25 to 25:75. Further, it is preferably 70:30 to 30:70. In particular, it is most preferably 60:40 to 40:60.
  • the heat shrinkage rate of the polylactic acid sheet of the present invention at 160 ° C. is 0% to 30%.
  • the heat shrinkage rate at 160 ° C. of the polylactic acid-based sheet is more preferably 5% to 30%, which has a great effect on suppressing drawdown. More preferably, it is 5% to 20%. If the heat shrinkage rate at 160 ° C. is less than 0%, the drawdown may increase because the sheet stretches. On the other hand, if the heat shrinkage rate at 160 ° C. exceeds 30%, the moldability may deteriorate in the subsequent molding step.
  • the heat shrinkage rate of the polylactic acid-based sheet of the present invention at 160 ° C. is 0.
  • a polylactic acid-based sheet is produced by a production method having a step of forming a sheet-like material mainly composed of polylactic acid, a step of heat treatment at 90 ° C. to 200 ° C., and a step of stretching. The method of doing can be mentioned.
  • the step of heat treatment and the step of stretching can be preferably employed either by a continuous method or by a step of winding and then stretching the sheet after the step of heat treatment.
  • the crystallinity of the polylactic acid sheet of the present invention is 1% to 30%.
  • the degree of crystallinity of the polylactic acid-based sheet is more preferably 5% to 25%. If the crystallinity is less than 1%, drawdown may increase, and if it exceeds 30%, moldability may be poor.
  • the polylactic acid-based sheet of the present invention is preferably produced by a production method having a step of forming a sheet-like material mainly composed of polylactic acid, a step of heat treatment at 90 ° C. to 200 ° C., and a step of stretching.
  • the step of forming a sheet-like material mainly composed of polylactic acid is not particularly limited.
  • the polymer is filtered.
  • a method is preferably employed in which the material is filtered, extruded from a mouthpiece having a tip-shaped shape, and wound onto the cast drum after closely contacting the cast drum.
  • the method of heating in the heat treatment step is not particularly limited, but heating in a heating oven or a tenter heating oven or heating with a heating roll is preferable.
  • non-adhesive such as a silicon rubber coated roll, a silicone-treated roll, a fluorine-treated roll, and a roll whose surface is roughened by sandblasting
  • the roll is preferably used as a heating roll.
  • a method of heating with a heating oven or a tenter type heating oven a method using hot air, a method using a far infrared heater, a method using a combination of these, or the like can be preferably employed.
  • a guide roll or the like when a guide roll or the like is installed in the oven, it is preferable to employ a non-adhesive roll as the guide roll. From the concern of sticking to the guide roll in the oven, it is particularly preferable to use a floating dryer in which no guide roll is installed in the oven.
  • the heat treatment temperature in the heat treatment step is preferably 90 ° C. to 200 ° C., more preferably 100 ° C. to 180 ° C. in order to suppress drawdown. If the heat treatment temperature is lower than 90 ° C., a sufficient crystallinity cannot be obtained, that is, the crystallinity cannot be made 1% to 30%, so that drawdown may be increased. Further, if the heat treatment temperature exceeds 200 ° C., the sheet is softened, so that sufficient crystallinity cannot be obtained, that is, the crystallinity cannot be made 1% to 30%, and the drawdown becomes large. There is.
  • the heat treatment time in the heat treatment step is preferably 5 seconds to 5 minutes, and more preferably 5 seconds to 3 minutes in order to control the crystallinity of the polylactic acid sheet to 1% to 30%. If the heat treatment time is less than 5 seconds, sufficient crystallinity may not be obtained, and if it exceeds 5 minutes, productivity may be inferior.
  • the stretching method in the stretching step after the heat treatment is not particularly limited, but stretching with a heating roll or a tenter type stretching machine is preferable. Among these, it is preferable to carry out with a tenter type stretching machine.
  • a heating roll it is performed in the length direction due to the peripheral speed difference of the heating roll.
  • stretching machine the width
  • the stretching temperature in the stretching step is preferably 70 ° C. to 200 ° C., more preferably 70 ° C. to 180 ° C., and further preferably 70 ° C. to 160 ° C. in order to suppress drawdown. If the stretching temperature is lower than 70 ° C., the stretching stress may be increased, and the sheet exceeding 200 ° C. may be softened to increase the drawdown.
  • the stretching ratio in the stretching step is preferably 1.1 to 3.0 times in order to suppress drawdown. More preferably, it is 1.1 times to 2.0 times. More preferably, it is 1.1 times to 1.5 times. If the draw ratio is less than 1.1 times, the drawdown may increase. If it exceeds 3.0 times, the shrinkage amount becomes too large, and the subsequent formability may deteriorate.
  • the preheating step in the stretching step is understood as a heat treatment step if it is heated to 90 ° C to 200 ° C. Further, if the draw ratio is slight and the film is heated to 90 ° C. to 200 ° C., it is understood as a heat treatment step.
  • the plane orientation coefficient fn of the polylactic acid based sheet is preferably 0.1 ⁇ 10 ⁇ 2 to 5 ⁇ 10 ⁇ 2 . More preferably, it is 0.5 ⁇ 10 ⁇ 2 to 3 ⁇ 10 ⁇ 2 . When the plane orientation coefficient is less than 0.1 ⁇ 10 ⁇ 2 , drawdown may increase. If it exceeds 5 ⁇ 10 ⁇ 2 , moldability may be poor.
  • the stereoification rate of the polylactic acid sheet is preferably 80% to 100%. More preferably, it is 90% to 100%. If the stereo ratio is less than 80%, the drawdown may increase.
  • the method of setting the stereo ratio to 80% to 100% can be achieved by providing a drawing step after the step of heat-treating a sheet mainly composed of polylactic acid at 90 ° C. to 200 ° C.
  • Thermal shrinkage at 160 ° C. (%) A strip-like sample having a width of 4 mm is cut out from the sheet in the longitudinal direction of the sheet, and using a thermomechanical analyzer (TMA6100 manufactured by SII), a load is set to 29.6 mN / mm 2 , a temperature rising rate is 10 K / min, and a sample length is set to 20 mm. Was measured to determine the amount of shrinkage at 160 ° C. And the thermal contraction rate in 160 degreeC was calculated
  • Thermal shrinkage rate (%) Shrinkage amount at 160 ° C./Sample length at 25 ° C. ⁇ 100 Expression (1) (2) Crystallinity (%) With respect to a diffraction peak obtained by a wide-angle X-ray diffraction method (2 ⁇ - ⁇ scan method) with an X-ray diffractometer (D8 ADVANCE manufactured by Bruker AXS), 2 ⁇ is 10 based on the diffraction curve associated with the amorphous portion. The total area (Stotal) of ⁇ 30 degrees was determined, the area of the diffraction curve associated with the amorphous part was determined, and the crystallinity was determined from the following formula.
  • Crystallinity (%) Total / (Stotal + area of diffraction curve associated with amorphous part) ⁇ 100
  • X-ray source CuK ⁇ ray output: 40 kV, 40 mA
  • RS 0.6 mm
  • RSm 1 mm
  • Plane orientation coefficient (fn) Refractive indexes (Nx, Ny, and Nz) in the sheet longitudinal direction, width direction, and thickness direction were measured with an Abbe refractometer, and calculated by the following equations.
  • the melting point of polylactic acid was measured with a differential scanning calorimeter (DSC) manufactured by PerkinElmer. The measurement conditions are 5 mg of the sample, a nitrogen atmosphere, and a heating rate of 20 ° C./min.
  • the melting point refers to the temperature of the peak top in the crystal melting peak.
  • the melting point shown here is the first measurement (1stRUN), the temperature is increased from 30 ° C. to 250 ° C. at a temperature increase rate of 20 ° C./min, and then cooled to 30 ° C. at a temperature decrease rate of 999 ° C./min.
  • the melting point was measured when the temperature was increased from 30 ° C. to 250 ° C. at a temperature increase rate of 20 ° C./min.
  • the sheet stereoization rate is determined by the melting enthalpy ( ⁇ Hsc) of the endothermic curve having a peak at 190 ° C. or higher and lower than 230 ° C. measured by the method for measuring the melting point of the sheet under the same conditions as the above-described melting point measurement method. It refers to the value obtained from the equation (2) using the melting enthalpy ( ⁇ Homo) of an endothermic curve having a peak at a temperature of from °C to 185 ° C.
  • Sheet moldability S (very good): The sheet is molded so as to sufficiently follow the bottom surface of the tray-shaped molded body.
  • B Molding failure: The sheet is not sufficiently track-formed to the bottom surface of the tray, or even if the sheet is track-formed, breakage of the sheet at the bottom surface is confirmed.
  • the weight average molecular weight of polylactic acid is a standard polymethyl methacrylate conversion value measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • a differential refractometer WATERS410 manufactured by WATERS is used as a detector
  • a MODEL510 manufactured by WATERS is used as a pump
  • Shodex (registered trademark) GPC HFIP-806M and Shodex (registered trademark) manufactured by Showa Denko KK are used as a column.
  • GPC HFIP-LG was used in series.
  • the measurement conditions were a flow rate of 0.5 mL / min, and in the measurement, hexafluoroisopropanol was used as a solvent, and 0.1 mL of a solution having a sample concentration of 1 mg / mL was injected.
  • A1 Production Example 1 (mixture of poly-L-lactic acid and poly-D-lactic acid)
  • A2 Production Example 2 (polylactic acid block copolymer composed of a segment composed of poly-L-lactic acid and a segment composed of poly-D-lactic acid)
  • [Production Example 1] (Production Example of A1)
  • a reaction vessel equipped with a stirrer and a reflux device 50 parts by mass of a 90% by mass L-lactic acid aqueous solution was added, the temperature was raised to 150 ° C., and the reaction was continued for 3.5 hours while gradually reducing the pressure to distill off water.
  • PLLA1 had a weight average molecular weight of 18,000 and a melting point of 149 ° C.
  • PLLA1 was subjected to crystallization treatment at 110 ° C. for 1 hour in a nitrogen atmosphere, followed by solid phase polymerization under a pressure of 60 Pa for 3 hours at 140 ° C., 3 hours at 150 ° C., and 18 hours at 160 ° C.
  • Poly-L-lactic acid (PLLA2) was obtained.
  • PLLA2 had a weight average molecular weight of 203,000 and a melting point of 170 ° C.
  • a 90% by mass D-lactic acid aqueous solution is placed in a reaction vessel equipped with a stirrer and a reflux apparatus, and the temperature is set to 150 ° C. Then, the pressure is gradually reduced and water is distilled off. Reacted for 5 hours. Thereafter, the pressure is brought to normal pressure in a nitrogen atmosphere, 0.02 part by mass of tin (II) acetate is added, and then a polymerization reaction is carried out for 7 hours while gradually reducing the pressure to 170 Pa at 13 ° C. to obtain poly-D-lactic acid. (PDLA1) was obtained. PDLA1 had a weight average molecular weight of 17,000 and a melting point of 148 ° C.
  • the obtained PDLA1 was subjected to a heat treatment for crystallization in a nitrogen atmosphere at 110 ° C. for 1 hour, followed by solid state polymerization under a pressure of 60 Pa for 3 hours at 140 ° C., 3 hours at 150 ° C., and 14 hours at 160 ° C.
  • PDLA2 poly-L-lactic acid
  • PDLA2 had a weight average molecular weight of 1580,000 and a melting point of 168 ° C.
  • PLLA2 and PDLA2 are preliminarily subjected to heat treatment for crystallization at a temperature of 110 ° C. for 2 hours in a nitrogen atmosphere, and PLLA2 / PDLA2 is blended to a mass ratio of 70/30 to deactivate the catalyst.
  • 0.5 parts by mass of an agent manufactured by Adeka, “Adeka Stub” AX-71
  • Adeka “Adeka Stub” AX-71
  • the cylinder temperature was set to 240 ° C. and the screw rotation speed was set to 100 rpm.
  • the strand discharged from the die is cooled in a cooling bath, and then pelletized with a strand cutter, so that the pellet-shaped polylactic acid A1 is obtained. Obtained.
  • the weight average molecular weight and melting point of polylactic acid A1 were as shown in Table 1. The obtained A1 was subjected to crystallization treatment at a pressure of 13.3 Pa, 110 ° C. for 2 hours, and 140 ° C. for 6 hours.
  • A2 was a step of producing a mixture by mixing poly-L-lactic acid and poly-D-lactic acid in a twin screw extruder, and the polylactic acid block copolymer was produced by solid-phase polymerization of the mixture.
  • PDLA1 obtained in Production Example 1 was subjected to a heat treatment for crystallization in a nitrogen atmosphere at 110 ° C. for 1 hour, and then at a pressure of 60 Pa, 140 ° C. for 3 hours, 150 ° C. for 3 hours, Solid phase polymerization was performed at 160 ° C. for 6 hours to obtain poly-D-lactic acid (PDLA3).
  • PDLA3 had a weight average molecular weight of 42,000 and a melting point of 158 ° C.
  • the twin screw extruder is provided with a plasticizing part set at a temperature of 180 ° C.
  • the structure can be mixed under shearing, and PLLA2 and PDLA3 were mixed at a mixing temperature of 200 ° C. under shearing.
  • the strand discharged from the die was cooled in a cooling bath, and then pelletized by a strand cutter to obtain pellet-shaped melt-kneaded polylactic acid.
  • the obtained melt-kneaded polylactic acid was dried in a vacuum dryer at 110 ° C. and a pressure of 13.3 Pa for 2 hours, then subjected to solid state polymerization at 140 ° C. and a pressure of 13.3 Pa for 4 hours, and then heated to 150 ° C. Then, the temperature was further raised to 160 ° C. for 4 hours and solid phase polymerization was performed for 10 hours to obtain a polylactic acid block copolymer. Next, 0.5 parts by mass of 100 parts by mass of the polylactic acid block copolymer obtained from the catalyst deactivator (manufactured by ADEKA, “ADEKA STAB” AX-71) was dry-blended, and the cylinder temperature was 240 ° C.
  • pellet-shaped polylactic acid A2 was obtained.
  • the weight average molecular weight and melting point of polylactic acid A2 were as shown in Table 1.
  • the crystallization treatment was performed at a pressure of 13.3 Pa, 110 ° C. for 2 hours, and 140 ° C. for 6 hours.
  • Examples 1-21 and Comparative Examples 1-3 Process for forming a sheet-like material mainly composed of polylactic acid After melt melting and kneading polylactic acid at 230 ° C. while degassing the vacuum vent part, the polymer is filtered with a 200 mesh wire mesh filter. The sheet was wound up after extruding from a mouthpiece with a tip set at a temperature of 0 ° C. and brought into close contact with a cast drum having a diameter of 30 cm heated to 40 ° C. using an air chamber. At this time, the thickness of the sheet was 250 ⁇ m.
  • Step of heat treatment The sheet thus obtained was heated by a heating roll comprising four silicon rubber coated rolls having a diameter of 20 cm under the conditions shown in Table 2 for heat treatment.
  • the heat-treated sheet is subjected to the conditions shown in Table 2 with a preheating portion comprising a ceramic coating roll having a diameter of 20 cm, a stretching roll comprising a nip roll comprising a ceramic coating roll having a diameter of 12 cm and a silicon coating roll having a diameter of 12 cm, and a diameter of 12 cm. It extended
  • the characteristics of the obtained sheet are as shown in Table 5.
  • the amount of drawdown was small and the moldability was good.
  • the drawdown amount was large and the moldability was poor.
  • Example 22-29 The sheet before heat treatment obtained by the same procedure as in Example 1 was subjected to heat treatment in a floating dryer consisting of a first (heating) zone having a length of 5 m and a second (cooling) zone having a length of 3 m under the conditions shown in Table 3. It was. The heat treatment was performed in the first zone, the heat treatment temperature was the temperature of the first zone, and the heat treatment time was the time from when the sheet was supplied to the first zone until it was discharged.
  • the heat-treated sheet was subjected to a preheating portion composed of a ceramic coating roll having a diameter of 20 cm, a stretching roll composed of a nip roll composed of a ceramic coating roll having a diameter of 12 cm and a silicon coating roll having a diameter of 12 cm, and Hcr plating having a diameter of 12 cm. Then, the film was drawn into a drawing machine composed of a cooling part made of a roll. The properties of the obtained sheet are as shown in Table 6. The drawdown amount was small and the moldability was good.
  • Examples 30-35 The heat-treated sheets obtained in Examples 3 and 5 were subjected to the conditions shown in Table 4 with a first (preheating) zone having a length of 1.5 m, a second (stretching) zone having 3 m, and a third (cooling) zone having 1.5 m. Stretching was performed in a tenter oven. The properties of the obtained sheet are as shown in Table 6. The drawdown amount was small and the moldability was good.

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Abstract

Le problème décrit par la présente invention est d'obtenir une feuille de polylactide présentant une transparence et une résistance à la chaleur excellentes, ainsi qu'une excellente aptitude au moulage à haute température. La solution selon l'invention consiste en une feuille de polylactide qui possède du polylactide en tant que constituant principal et qui est caractérisée en ce que son retrait thermique à 160 °C est compris entre 0 % et 30 % et son taux de cristallinité est compris entre 1 % et 30 %.
PCT/JP2014/063272 2013-05-24 2014-05-20 Feuille de polylactide et son procédé de fabrication Ceased WO2014189021A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2016186075A1 (ja) * 2015-05-21 2018-03-01 三井化学東セロ株式会社 ガスバリア性積層体の製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005089002A (ja) * 1995-09-22 2005-04-07 Jsp Corp 容器
WO2008126581A1 (fr) * 2007-03-16 2008-10-23 Toray Industries, Inc. Feuille de polyester aliphatique et corps moulé la comprenant
JP2009179773A (ja) * 2008-02-01 2009-08-13 Toray Ind Inc 脂肪族ポリエステル系成形体
JP2011231240A (ja) * 2010-04-28 2011-11-17 Teijin Ltd 樹脂フィルム、それよりなる加飾フィルム並びに加飾成形品
WO2012029393A1 (fr) * 2010-08-31 2012-03-08 東レ株式会社 Copolymère séquencé d'acide polylactique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005089002A (ja) * 1995-09-22 2005-04-07 Jsp Corp 容器
WO2008126581A1 (fr) * 2007-03-16 2008-10-23 Toray Industries, Inc. Feuille de polyester aliphatique et corps moulé la comprenant
JP2009179773A (ja) * 2008-02-01 2009-08-13 Toray Ind Inc 脂肪族ポリエステル系成形体
JP2011231240A (ja) * 2010-04-28 2011-11-17 Teijin Ltd 樹脂フィルム、それよりなる加飾フィルム並びに加飾成形品
WO2012029393A1 (fr) * 2010-08-31 2012-03-08 東レ株式会社 Copolymère séquencé d'acide polylactique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2016186075A1 (ja) * 2015-05-21 2018-03-01 三井化学東セロ株式会社 ガスバリア性積層体の製造方法
JP7002935B2 (ja) 2015-05-21 2022-01-20 三井化学東セロ株式会社 ガスバリア性積層体の製造方法

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