WO2014129293A1 - Composition de résine d'acide polylactique ainsi que procédé de fabrication de celle-ci, et article moulé - Google Patents

Composition de résine d'acide polylactique ainsi que procédé de fabrication de celle-ci, et article moulé Download PDF

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WO2014129293A1
WO2014129293A1 PCT/JP2014/052384 JP2014052384W WO2014129293A1 WO 2014129293 A1 WO2014129293 A1 WO 2014129293A1 JP 2014052384 W JP2014052384 W JP 2014052384W WO 2014129293 A1 WO2014129293 A1 WO 2014129293A1
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lactic acid
poly
polylactic acid
acid
resin composition
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PCT/JP2014/052384
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English (en)
Japanese (ja)
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高橋佳丈
直塚拓磨
大目裕千
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東レ株式会社
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Publication of WO2014129293A1 publication Critical patent/WO2014129293A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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 provides a polylactic acid resin composition, a molded article, and a polylactic acid resin composition that have improved molding processability, mechanical properties, durability, and stability during heating, and also excellent heat resistance and crystallization characteristics. It relates to a manufacturing method.
  • Polylactic acid is a polymer that can be melt-molded practically and has characteristics of biodegradability, so it is developed as a biodegradable plastic that is decomposed in the natural environment and released as carbon dioxide or water after use. Has been promoted.
  • polylactic acid itself is made from renewable resources (biomass) originating from carbon dioxide and water, so carbon that does not increase or decrease in the global environment even if carbon dioxide is released after use. Neutral properties have attracted attention and are expected to be used as environmentally friendly materials.
  • lactic acid which is a monomer of polylactic acid, is being produced at low cost by fermentation using microorganisms, and has been studied as an alternative material for general-purpose polymers made of petroleum-based plastics.
  • seat is performed by melt-kneading the unsaturated carboxylic acid alkylester polymer which uses acrylic acid ester as a raw material monomer with respect to polylactic acid resin. Yes.
  • a molded body can be obtained without bleeding out during the molding process of the polylactic acid resin composition, and the obtained molded body has characteristics of excellent flexibility and transparency.
  • Patent Document 2 the moldability of polylactic acid resin is improved by melt-kneading an acrylic resin-based modifier containing an epoxy group with respect to polylactic acid resin.
  • the epoxy group of the acrylic resin-based modifier reacts with the carboxyl group or hydroxyl group present at the end of the polylactic acid resin to form an appropriate cross-linked structure, thereby increasing the viscosity, which is suitable for molding. Is expressed.
  • Patent Document 3 describes that impact resistance of a polylactic acid resin composition can be improved by blending an acrylic resin with a polylactic acid resin composition composed of a polylactic acid resin and an ABS resin. Also in this technology, a reactive compound containing an epoxy group is exemplified as an acrylic resin, and the melt viscosity increases due to the reaction between the acrylic resin and the polylactic acid resin composition, in addition to impact resistance, thermal stability. Will also improve.
  • Patent Document 4 discloses that a polylactic acid stereocomplex composed of poly-L-lactic acid and poly-D-lactic acid is melt-kneaded with an acrylic resin containing an epoxy group to suppress a change in melt viscosity, and is stable against moisture and heat.
  • a polylactic acid resin composition excellent in properties and color tone is obtained.
  • polylactic acid composed of poly-L-lactic acid and poly-D-lactic acid is used as the polylactic acid resin, and therefore it has a stereocomplex crystal phase, so that it has higher heat resistance than poly-L-lactic acid alone.
  • polylactic acid has lower heat resistance and durability than petroleum-based plastics, and its crystallization speed is low, so it is inferior in productivity, and the range of practical use is greatly limited. .
  • polylactic acid stereocomplex is expected as a means to solve the disadvantages of polylactic acid.
  • the polylactic acid stereocomplex is formed by mixing optically active poly-L-lactic acid and poly-D-lactic acid.
  • the melting point of the polylactic acid stereocomplex reaches 220 ° C., which is 50 ° C. higher than the melting point 170 ° C. of the polylactic acid homopolymer.
  • a polylactic acid stereocomplex is formed by mixing poly-L-lactic acid and poly-D-lactic acid in a solution state or by heating and melt-mixing poly-L-lactic acid and poly-D-lactic acid.
  • a polylactic acid block copolymer is attracting attention as a new method for forming a polylactic acid stereocomplex.
  • This polylactic acid block copolymer is obtained by covalently bonding a poly-L-lactic acid segment containing L-lactic acid as a main component and a poly-D-lactic acid segment containing D-lactic acid as a main component. Even so, since the stereocomplex crystal formability is excellent and the melting point derived from the stereocomplex crystal is observed, it is possible to obtain a material having excellent thermal properties such as heat resistance and crystallization characteristics. For this reason, the application as a high melting point and highly crystalline fiber, film, and resin molded article is tried.
  • the molding process of polylactic acid In the molding process of polylactic acid, it is heated and melted above the melting point of the polymer and then shaped into the desired shape. However, when melted and retained at high temperatures, the melt viscosity generally decreases greatly, so for example in sheet film extrusion molding The thickness and width are not uniform, which may cause perforation of the sheet and poor stretching of the film. In thermoforming and blow molding, it tends to draw down during heating, so that the dimensional stability of the molded body is poor. Therefore, in the melt molding process of polylactic acid or stereocomplex, the molding conditions such as lowering the heating temperature are controlled to obtain a melt viscosity suitable for molding, but the molding temperature range is narrow and the molding processability is low. There's a problem.
  • Patent Documents 1 to 3 although the processability at the time of melting of the polylactic acid resin is improved, the crystallization speed of the polylactic acid is so slow that it does not show the temperature-falling crystallization temperature. However, productivity remains a problem. Furthermore, since the melting point of homopolylactic acid is around 170 ° C., there remains a problem in heat resistance in actual use.
  • the polylactic acid stereocomplex prepared by melt-mixing poly-L-lactic acid and poly-D-lactic acid in Patent Document 4 has a high melting point, but the crystallization speed is insufficient, so that it is the same as Patent Documents 1 to 3.
  • productivity remains a problem.
  • an organophosphate metal salt or the like is added, so that a large amount of gas is generated at the time of heating and melting, such as having moldability, heat resistance, and crystallization characteristics. None is available at present.
  • the present invention has been made in view of the above, and has improved mechanical properties, durability, retention stability during heating, and further forms polylactic acid stereocomplex having excellent heat resistance and crystallization characteristics. It is providing the manufacturing method of a resin composition, a molded object, and a polylactic acid resin composition.
  • the polylactic acid resin composed of a polylactic acid block copolymer is thickened with a polymer having a plurality of reactive groups per molecule, the crystallization characteristics do not deteriorate, and the molding processability, heat resistance, and crystallization characteristics The purpose is to achieve both.
  • the polylactic acid resin composition of the present invention has the following configuration. That is, (A) 100 parts by weight of a polylactic acid block copolymer composed of a poly-L-lactic acid segment containing L-lactic acid as a main component and a poly-D-lactic acid segment containing D-lactic acid as a main component (B ) A polylactic acid resin composition comprising 0.05 to 2 parts by weight of a polymer having a plurality of reactive groups per molecule, and (B) a weight average of the polymers having a plurality of reactive groups per molecule Crystallization when the molecular weight is 1,000 to 15,000 and the polylactic acid resin composition is heated to 250 ° C. and kept at a constant temperature for 3 minutes and then cooled at a cooling rate of 20 ° C./min in DSC measurement. A polylactic acid resin composition having a calorific value of 10 J / g or more.
  • the polymer having a plurality of reactive groups per molecule is preferably an epoxy group-containing acrylic resin-based reactive compound.
  • the polylactic acid resin composition of the present invention preferably has 2 to 30 epoxy groups per molecule of the epoxy group-containing acrylic resin reactive compound.
  • the polylactic acid resin composition of the present invention preferably has a stereocomplex formation rate (Sc) satisfying the following formula (1).
  • ⁇ Hh Amount of heat (J / g) based on the stereocomplex crystal when the polylactic acid resin composition is heated at a rate of temperature increase of 20 ° C./min in the DSC measurement.
  • the polylactic acid resin composition of the present invention is a ratio of the melt flow rate after 10 minutes (MFR10) to the melt flow rate after 20 minutes (MFR20) at 230 ° C. and 21.2 N load conditions of the polylactic acid resin composition. It is preferable that (MFR10 / MFR20) is 0.5 or more and 2 or less.
  • the polylactic acid resin composition of the present invention is a polylactic acid obtained when the polylactic acid resin composition is heated to 250 ° C. and kept at a constant temperature for 3 minutes in DSC measurement, and then cooled at a cooling rate of 20 ° C./min. It is preferable that the temperature-falling crystallization temperature of a resin composition is 130 degreeC or more.
  • the (A) polylactic acid block copolymer is prepared by mixing poly-L-lactic acid or poly-D-lactic acid under the conditions of the following combination 1 and / or the following combination 2.
  • a mixture satisfying the following formula (2) having a weight average molecular weight of 90,000 or more and a stereocomplex formation rate (Sc) is obtained, and then obtained by solid phase polymerization at a temperature lower than the melting point of the mixture. It is preferable.
  • the weight average molecular weight of either poly-L-lactic acid or poly-D-lactic acid is 60,000 to 300,000, and the other weight average molecular weight is 10,000 to 100,000 (Combination 2).
  • the (A) polylactic acid block copolymer is prepared by mixing poly-L-lactic acid or poly-D-lactic acid under the conditions of the following
  • a mixture satisfying the following formula (2) having a weight average molecular weight of 90,000 or more and a stereocomplex formation rate (Sc) is obtained, and then obtained by solid phase polymerization at a temperature lower than the melting point of the mixture. It is preferable.
  • the weight average molecular weight of either poly-L-lactic acid or poly-D-lactic acid is 120,000 to 300,000, and the other weight average molecular weight is 30,000 to 100,000
  • the ratio of the weight average molecular weight of poly-L-lactic acid to the weight average molecular weight of poly-D-lactic acid is 2 or more and less than 30.
  • the polylactic acid resin composition preferably has a weight average molecular weight of 100,000 to 500,000.
  • the polylactic acid resin composition of the present invention preferably further comprises (b) poly-L-lactic acid and / or (c) poly-D-lactic acid, relative to the polylactic acid resin composition. .
  • the molded object of this invention has the following structure. That is, It is the molded object which consists of the said polylactic acid resin composition.
  • the relative crystallinity of the molded article is preferably 90% or more, and the haze value of the molded article having a thickness of 1 mm is preferably 10% or less.
  • the method for producing a polylactic acid resin composition of the present invention has any one of the following configurations (I) to (III).
  • this polylactic acid resin contains a polylactic acid block copolymer as a constituent component, not only the molding processability of the polylactic acid resin composition and the retention stability during heating are improved, but also the crystallization characteristics are excellent. .
  • a polylactic acid block copolymer composed of a poly-L-lactic acid segment containing L-lactic acid as a main component and a poly-D-lactic acid segment containing D-lactic acid as a main component is an L-lactic acid unit.
  • a polylactic acid block copolymer in which a segment comprising D-lactic acid units is covalently bonded is an L-lactic acid unit.
  • the segment composed of L-lactic acid units is a polymer containing L-lactic acid as a main component, and means a polymer containing 70 mol% or more of L-lactic acid units.
  • the content is more preferably 80 mol% or more, further preferably 90 mol% or more, particularly preferably 95 mol% or more, and most preferably 98 mol% or more.
  • the segment composed of D-lactic acid units is a polymer containing D-lactic acid as a main component, and means a polymer containing 70 mol% or more of D-lactic acid units.
  • the content is more preferably 80 mol% or more, further preferably 90 mol% or more, particularly preferably 95 mol% or more, and most preferably 98 mol% or more.
  • the segment composed of L-lactic acid or D-lactic acid unit contains other components as long as the performance of the polylactic acid block copolymer and the polylactic acid resin composition containing the polylactic acid block copolymer is not impaired. Units may be included. Examples of component units other than L-lactic acid or D-lactic acid units include polycarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, and lactones.
  • succinic acid adipic acid, sebacic acid
  • Polycarboxylic acids such as fumaric acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, 5-tetrabutylphosphonium sulfoisophthalic acid or their derivatives, ethylene glycol, propylene glycol, butane Ethylene oxide or propylene oxide was added to diol, pentanediol, hexanediol, octanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, trimethylolpropane or pentaerythritol
  • Polyhydric alcohols aromatic polyhydric alcohols obtained by addition reaction of ethylene oxide with bisphenol, polyhydric alcohols such as diethylene glycol, triethylene glycol, polyethylene glycol
  • the polylactic acid block copolymer has a melting point based on a stereocomplex crystal in the range of 190 to 230 ° C. due to the formation of a stereocomplex, and therefore has excellent heat resistance as compared with a polylactic acid homopolymer.
  • a preferable range of the melting point derived from the stereocomplex crystal is 200 ° C. to 230 ° C., a temperature range of 205 ° C. to 230 ° C. is more preferable, and a temperature range of 210 ° C. to 230 ° C. is particularly preferable. Further, it may have a small melting peak based on a poly-L-lactic acid single crystal and / or a poly-D-lactic acid single crystal in the range of 150 ° C. to 185 ° C.
  • the polylactic acid block copolymer obtained in the present invention preferably has a stereocomplex formation rate (Sc) in the range of 80 to 100% from the viewpoint of heat resistance. More preferably, it is in the range of 85 to 100%, and particularly preferably 90 to 100%.
  • the stereocomplex formation rate is the ratio of the stereocomplex crystals in all the crystals in polylactic acid. Specifically, the crystal melting of poly-L-lactic acid single crystal and poly-D-lactic acid single crystal when the temperature is increased from 30 ° C. to 250 ° C. at a temperature rising rate of 20 ° C./min with a differential scanning calorimeter (DSC). It is possible to calculate by the following formula (4), where ⁇ H1 is the amount of heat based on and ⁇ Hh is the amount of heat based on crystal melting of the stereocomplex crystal.
  • the polylactic acid block copolymer preferably further satisfies the following formula (5).
  • Tm is a melting point when a polylactic acid block copolymer is heated from 30 ° C. to 250 ° C. at a temperature rising rate of 40 ° C./min by a differential scanning calorimeter (DSC)
  • Tms is a polylactic acid block
  • Tme is the differential scanning calorimeter of the polylactic acid block copolymer (DSC) shows the melting end temperature when the temperature is raised from 30 ° C.
  • a preferable range is 1 ⁇ (Tm ⁇ Tms) / (Tme ⁇ Tm) ⁇ 1.6, and a range of 1 ⁇ (Tm ⁇ Tms) / (Tme ⁇ Tm) ⁇ 1.4 is more preferable.
  • the polylactic acid block copolymer preferably has a temperature-falling crystallization temperature (Tc) of 130 ° C. or higher in terms of excellent moldability and heat resistance.
  • Tc temperature drop crystallization temperature
  • the temperature drop crystallization temperature (Tc) of the compact is a constant temperature state at 250 ° C. for 3 minutes after being heated from 30 ° C. to 250 ° C. at a temperature rising rate of 20 ° C./min by a differential scanning calorimeter (DSC). Is a crystallization temperature derived from polylactic acid crystals measured when the temperature is lowered at a cooling rate of 20 ° C./min.
  • the crystallization temperature (Tc) is not particularly limited, but is preferably 130 ° C. or higher, more preferably 132 ° C. or higher, and particularly preferably 135 ° C. or higher from the viewpoint of heat resistance and transparency.
  • the weight average molecular weight of the polylactic acid block copolymer of the present invention is not particularly limited, but is preferably 100,000 or more and less than 300,000 from the viewpoint of mechanical properties. More preferably, it is 120,000 or more and less than 280,000, more preferably 130,000 or more and less than 270,000, particularly preferably 140,000 or more and less than 260,000 from the viewpoint of moldability and mechanical properties.
  • the dispersion degree of the polylactic acid block copolymer is preferably in the range of 1.5 to 3.0 from the viewpoint of mechanical properties.
  • the range of the degree of dispersion is more preferably 1.8 to 2.7, and 2.0 to 2.4 is particularly preferable in terms of moldability and mechanical properties.
  • the weight average molecular weight and dispersity are values in terms of standard polymethyl methacrylate as measured by gel permeation chromatography (GPC) using hexafluoroisopropanol or chloroform as a solvent.
  • the average chain length of the polylactic acid block copolymer is preferably 20 or more. More preferably, it is 25 or more, and 30 or more is particularly preferable from the viewpoint of mechanical properties of the molded article.
  • the average chain length of the polylactic acid block copolymer was determined by 13 C-NMR measurement, and the integrated value of the peak existing in the vicinity of 170.1 to 170.3 ppm of the carbon peak attributed to carbonyl carbon is (a). , 169.8 to 170.0 ppm, where (b) is the integrated value of the peak, it can be calculated by the following equation (6).
  • the total number of segments consisting of L-lactic acid units and segments consisting of D-lactic acid units contained in one molecule of the polylactic acid block copolymer is 3 or more. It is preferable in that a polylactic acid block copolymer that easily forms can be obtained. More preferably, it is 5 or more, and it is especially preferable that it is 7 or more.
  • the total weight ratio of the segment composed of L-lactic acid units and the segment composed of D-lactic acid units is preferably 90:10 to 10:90. More preferably, it is 80:20 to 20:80, and particularly preferably 75:25 to 60:40 or 40:60 to 25:75.
  • the total weight ratio of the segment consisting of L-lactic acid units and the segment consisting of D-lactic acid units is within the above preferred range, a polylactic acid stereocomplex can be easily formed. As a result, the melting point of the polylactic acid block copolymer The rise of is sufficiently large.
  • the method for preparing the polylactic acid block copolymer is not particularly limited, and a general method for preparing polylactic acid can be used. Specifically, ring-opening polymerization is performed in the presence of a catalyst on either a cyclic dimer L-lactide or D-lactide produced from lactic acid as a raw material, and lactide which is an optical isomer of the polylactic acid is further obtained.
  • a lactide method in which a polylactic acid block copolymer is obtained by addition and ring-opening polymerization (preparation method 1 of a polylactic acid block copolymer), and the raw material is polymerized directly or by ring-opening polymerization via lactide.
  • the segment of the L-lactic acid unit is obtained by subjecting poly-L-lactic acid and poly-D-lactic acid to melt-kneading for a long time at a temperature higher than the melting end temperature of the component having the higher melting point.
  • D-lactic acid unit A method of obtaining a polylactic acid block copolymer obtained by transesterification with a polymentine (preparation method 3 of a polylactic acid block copolymer), and mixing a polyfunctional compound with poly-L-lactic acid and poly-D-lactic acid.
  • Any method may be used as a preparation method, but a method of solid-phase polymerization after mixing poly-L-lactic acid and poly-D-lactic acid is included in one molecule of polylactic acid block copolymer.
  • the total number of segments consisting of lactic acid units and segments consisting of D-lactic acid units is 3 or more, which is preferable in that a polylactic acid block copolymer having heat resistance, crystallinity and mechanical properties can be obtained.
  • poly-L-lactic acid is a polymer containing L-lactic acid as a main component, and means a polymer containing 70 mol% or more of L-lactic acid units. It is preferable to contain 80 mol% or more, more preferably 90 mol% or more, more preferably 95 mol% or more, and particularly preferably 98 mol% or more.
  • Poly-D-lactic acid is a polymer containing D-lactic acid as a main component, and means a polymer containing 70 mol% or more of D-lactic acid units. It is preferable to contain 80 mol% or more, more preferably 90 mol% or more, more preferably 95 mol% or more, and particularly preferably 98 mol% or more.
  • Preparation Method 1 As a method for preparing a polylactic acid block copolymer by ring-opening polymerization (Preparation Method 1), for example, either L-lactide or D-lactide is subjected to ring-opening polymerization in the presence of a catalyst, and then the other optical An example is a method of obtaining a polylactic acid block copolymer by carrying out ring-opening polymerization by adding lactide which is an isomer.
  • the ratio of the weight average molecular weight of the segment consisting of L-lactic acid units and the weight average molecular weight of the segment consisting of D-lactic acid units contained in one molecule of the polylactic acid block copolymer obtained by ring-opening polymerization is as follows. From the viewpoint of transparency, it is preferably 2 or more and less than 30. More preferably, it is 3 or more and less than 20, and particularly preferably 5 or more and less than 15.
  • the ratio of the weight average molecular weight of the segment consisting of L-lactic acid units to the weight average molecular weight of the segments consisting of D-lactic acid units is such that L-lactide and D-lactide used for polymerizing the polylactic acid block copolymer The weight ratio can be controlled.
  • the total number of segments composed of L-lactic acid units and segments composed of D-lactic acid units contained in one molecule of the polylactic acid block copolymer obtained by ring-opening polymerization is 3 or more, and the heat resistance and crystallinity are It is preferable in terms of improvement. More preferably, it is 5 or more, and it is especially preferable that it is 7 or more.
  • the weight average molecular weight per segment is preferably 2,000 to 50,000. More preferably, it is 4,000 to 45,000, and particularly preferably 5,000 to 40,000.
  • the optical purity of L-lactide and D-lactide used in the ring-opening polymerization method is preferably 90% ee or more from the viewpoint of improving the crystallinity and melting point of the polylactic acid block copolymer. More preferably, it is 95% ee or more, and it is especially preferable that it is 98% ee or more.
  • the water content in the reaction system is 4 mol% or less with respect to the total amount of L-lactide and D-lactide from the viewpoint of obtaining a high molecular weight product.
  • the water content is a value measured by a coulometric titration method using the Karl Fischer method.
  • Examples of the polymerization catalyst for preparing the polylactic acid block copolymer by the ring-opening polymerization method include a metal catalyst and an acid catalyst.
  • Examples of the metal catalyst include tin catalysts, titanium compounds, lead compounds, zinc compounds, cobalt compounds, iron compounds, lithium compounds, and rare earth compounds.
  • As the kind of the compound metal alkoxide, metal halogen compound, organic carboxylate, carbonate, sulfate, oxide and the like are preferable.
  • tin powder tin (II) chloride, tin (IV) chloride, tin (II) bromide, tin (IV) bromide, ethoxy tin (II), t-butoxy tin (IV), isopropoxy Tin (IV), tin (II) acetate, tin (IV) acetate, tin (II) octylate, tin (II) laurate, tin (II) myristate, tin (II) palmitate, tin stearate (II) ), Tin (II) oleate, tin (II) linoleate, tin (II) acetylacetone, tin (II) oxalate, tin (II) lactate, tin (II) tartrate, tin (II) pyrophosphate, p- Phenol sulfon
  • the acid catalyst may be a Bronsted acid as a proton donor, a Lewis acid as an electron pair acceptor, or an organic acid or an inorganic acid.
  • monocarboxylic acid compounds such as formic acid, acetic acid, propionic acid, heptanoic acid, octanoic acid, octylic acid, nonanoic acid, isononanoic acid, trifluoroacetic acid and trichloroacetic acid, oxalic acid, succinic acid, maleic acid, tartaric acid
  • dicarboxylic acid compounds such as malonic acid, tricarboxylic acid compounds such as citric acid and tricarivallic acid, benzenesulfonic acid, n-butylbenzenesulfonic acid, n-octylbenzenesulfonic acid, n-dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid 2,5
  • the shape of the acid catalyst is not particularly limited, and any of a solid acid catalyst and a liquid acid catalyst may be used.
  • the solid acid catalyst acidic clay, kaolinite, bentonite, montmorillonite, talc, zirconium silicate and Natural minerals such as zeolite, oxides such as silica, alumina, titania and zirconia or oxide composites such as silica alumina, silica magnesia, silica boria, alumina boria, silica titania and silica zirconia, chlorinated alumina, fluorinated alumina, positive Examples thereof include ion exchange resins.
  • a metal catalyst is preferable as the polymerization catalyst of the ring-opening polymerization method, among which a tin compound, a titanium compound, an antimony compound, and a rare earth compound are more preferable.
  • tin compounds and titanium compounds are more preferable.
  • a tin-based organic carboxylate or a tin-based halogen compound is preferable, and in particular, tin (II) acetate, tin (II) octylate, And tin (II) chloride is more preferred.
  • the addition amount of the polymerization catalyst in the ring-opening polymerization method is preferably 0.001 part by weight or more and 2 parts by weight or less with respect to 100 parts by weight of the raw material to be used (L-lactic acid, D-lactic acid, etc.). More preferred is 1 part by weight or more.
  • the catalyst amount is within the above preferred range, the effect of shortening the polymerization time can be obtained, while the molecular weight of the finally obtained polylactic acid block copolymer tends to increase.
  • the catalyst after heating and dissolving the lactide from the viewpoint of uniformly dispersing the catalyst in the system and increasing the polymerization activity.
  • Preparation Method 2 a method for preparing a polylactic acid block copolymer by solid phase polymerization after mixing poly-L-lactic acid and poly-D-lactic acid (Preparation Method 2) will be described.
  • Preparation Method 2 any of a ring-opening polymerization method and a direct polymerization method can be used.
  • poly-L-lactic acid and poly-D-lactic acid When a polylactic acid block copolymer is prepared by solid phase polymerization after mixing poly-L-lactic acid and poly-D-lactic acid, the weight average molecular weight and stereocomplex formation rate after solid phase polymerization are increased.
  • One of poly-L-lactic acid and poly-D-lactic acid has a weight average molecular weight of 60,000 to 300,000 or less, and the other has a weight average molecular weight of 10,000 to 100,000 or less. It is preferable. More preferably, one weight average molecular weight is 100,000 to 270,000 and the other weight average molecular weight is 15,000 to 80,000. Particularly preferably, one weight average molecular weight is 150,000 to 240,000 and the other weight average molecular weight is 20,000 to 50,000.
  • the combination of the weight average molecular weights of poly-L-lactic acid and poly-D-lactic acid is preferably selected as appropriate so that the weight average molecular weight after mixing is 90,000 or more.
  • the weight average molecular weight of the poly-L-lactic acid component and the poly-D-lactic acid component is such that the weight average molecular weight of either one of poly-L-lactic acid or poly-D-lactic acid is 120,000 or more. It is also a preferred embodiment that the weight average molecular weight is 300,000 or less and the other weight average molecular weight is 30,000 or more and 100,000 or less. More preferably, one weight average molecular weight is 100,000 or more and 270,000 or less, and the other weight average molecular weight is 35,000 or more and 80,000 or less. More preferably, it is 125,000 or more and 255,000 or less, and the other weight average molecular weight is 25,000 or more and 50,000 or less.
  • the ratio of the higher weight average molecular weight to the lower weight average molecular weight is preferably 2 or more and less than 30. More preferably, it is 3 or more and less than 20, and most preferably 5 or more and less than 15.
  • the combination of the weight average molecular weights of poly-L-lactic acid and poly-D-lactic acid is preferably selected as appropriate so that the weight average molecular weight after mixing is 90,000 or more.
  • the poly-L-lactic acid and poly-D-lactic acid used in the present invention have a weight average molecular weight of each of the poly-L-lactic acid component and the poly-D-lactic acid component within the above range, It is preferable that both the ratio of the weight average molecular weight of the L-lactic acid component and the poly-D-lactic acid component is 2 or more and less than 30.
  • the weight average molecular weight is a value in terms of standard polymethyl methacrylate as measured by gel permeation chromatography (GPC) using hexafluoroisopropanol or chloroform as a solvent.
  • the amount of lactide and oligomer contained in poly-L-lactic acid or poly-D-lactic acid is preferably 5% or less, respectively. More preferably, it is 3% or less, and particularly preferably 1% or less.
  • the amount of lactic acid contained in poly-L-lactic acid or poly-D-lactic acid is preferably 2% or less. More preferably, it is 1% or less, and particularly preferably 0.5% or less.
  • the acid value of poly-L-lactic acid or poly-D-lactic acid to be mixed is preferably 100 eq / ton or less for either one of poly-L-lactic acid or poly-D-lactic acid. More preferably, it is 50 eq / ton or less, More preferably, it is 30 eq / ton or less, Most preferably, it is 15 eq / ton or less.
  • the other acid value of the poly-L-lactic acid or poly-D-lactic acid to be mixed is preferably 600 eq / ton or less. More preferably, it is 300 eq / ton or less, More preferably, it is 150 eq / ton or less, Especially preferably, it is 100 eq / ton or less.
  • the water content in the reaction system is the sum of L-lactide and D-lactide from the viewpoint of obtaining a high molecular weight product. It is preferable that it is 4 mol% or less with respect to quantity. More preferably, it is 2 mol% or less, and 0.5 mol% or less is particularly preferable.
  • the water content is a value measured by a coulometric titration method using the Karl Fischer method.
  • the same metal catalyst and acid catalyst as in Preparation Method 1 can be mentioned.
  • the addition amount of the polymerization catalyst in the ring-opening polymerization method is preferably 0.001 part by weight or more and 2 parts by weight or less with respect to 100 parts by weight of the raw material used (L-lactic acid, D-lactic acid, etc.). More preferred is 0.001 part by weight or more and 1 part by weight or less.
  • the catalyst amount is within the above preferred range, the effect of shortening the polymerization time can be obtained, while the molecular weight of the finally obtained polylactic acid block copolymer tends to increase.
  • the catalyst after heating and dissolving the lactide from the viewpoint of uniformly dispersing the catalyst in the system and increasing the polymerization activity.
  • examples of the polymerization catalyst for polymerizing poly-L-lactic acid or poly-D-lactic acid by using a direct polymerization method include metal catalysts and acid catalysts.
  • the metal catalyst include tin catalysts, titanium compounds, lead compounds, zinc compounds, cobalt compounds, iron compounds, lithium compounds, and rare earth compounds.
  • the kind of the compound metal alkoxide, metal halogen compound, organic carboxylate, carbonate, sulfate, oxide and the like are preferable.
  • the metal compound described in the preparation method 1 as a metal catalyst, and the acid compound described in the preparation method 1 as an acid catalyst are mentioned.
  • tin compounds, titanium compounds, antimony compounds, rare earth compounds, and acid catalysts are preferred, and when considering the melting point of the produced polylactic acid, Tin compounds, titanium compounds, and sulfonic acid compounds are more preferred.
  • a tin-based organic carboxylate or a tin-based halogen compound is preferable, and in particular, tin (II) acetate, tin octylate (II ), And tin (II) chloride, and in the case of acid catalysts, mono and disulfonic acid compounds are preferred, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, propanedisulfonic acid, naphthalene disulfonic acid, and 2-amino More preferred is ethanesulfonic acid.
  • one type of catalyst may be used, or two or more types may be used in combination. However, in view of increasing the polymerization activity, it is preferable to use two or more types in combination, and it is possible to suppress coloring. In addition, it is preferable to use one or more selected from tin compounds and / or one or more selected from sulfonic acid compounds. Further, in terms of excellent productivity, tin (II) acetate and / or tin octylate ( II) and methanesulfonic acid, ethanesulfonic acid, propanedisulfonic acid, naphthalene disulfonic acid and 2-aminoethanesulfonic acid are more preferably used in combination.
  • the addition amount of the polymerization catalyst is preferably 0.001 part by weight or more and 2 parts by weight or less with respect to 100 parts by weight of the raw material to be used (L-lactic acid, D-lactic acid, etc.). More preferred are parts by weight or less.
  • the catalyst amount is within this preferred range, the effect of shortening the polymerization time can be obtained, while the molecular weight of the finally obtained polylactic acid block copolymer can be sufficiently increased.
  • the total addition amount is preferably within the above range, and one or more types selected from tin compounds and / or one or more types selected from sulfonic acid compounds are used in combination.
  • the weight ratio of the tin compound and the sulfonic acid compound is 1: 1 to 1:30 in that the high polymerization activity can be maintained and coloring can be suppressed. It is more preferable that the ratio is 1: 2 to 1:15.
  • the acid catalyst is added before the raw material or the raw material is dehydrated in terms of excellent productivity.
  • the addition of the raw material after dehydration is preferable from the viewpoint of increasing the polymerization activity.
  • the stereocomplex formation rate (Sc) is preferably in the range exceeding 60% immediately before the solid phase polymerization. More preferably, it is in the range of 70 to 99%, and particularly preferably in the range of 80 to 95%. That is, based on the above formula (4), the stereo complex formation rate (Sc) preferably satisfies the following formula (2).
  • ⁇ Hh calorific value (J / g) based on stereocomplex crystals when the temperature is raised at a rate of temperature rise of 20 ° C./min in DSC measurement of a mixture of poly-L-lactic acid and poly-D-lactic acid
  • ⁇ Hl Crystal melting of poly-L-lactic acid single crystal and poly-D-lactic acid single crystal when heated at a rate of temperature increase of 20 ° C./min in DSC measurement of a mixture of poly-L-lactic acid and poly-D-lactic acid Heat quantity based on (J / g)
  • the presence or absence of crystallization of poly-L-lactic acid and poly-D-lactic acid used for mixing is not particularly limited, and the crystallized poly-L-lactic acid and poly-D-lactic acid may be mixed.
  • molten poly-L-lactic acid and poly-D-lactic acid can be mixed.
  • a method of holding at a crystallization temperature in a gas phase or a liquid phase and a poly-L in a molten state A method of retaining lactic acid and poly-D-lactic acid in a melting machine having a melting point of ⁇ 50 ° C. to a melting point of + 20 ° C. while applying shear, and melting poly-L-lactic acid and poly-D-lactic acid with a melting point of ⁇ 50 ° C. For example, a method of staying while applying pressure in a melting point + 20 ° C. melting machine may be used.
  • the crystallization treatment temperature here is higher than the glass transition temperature and is lower than the melting point of polylactic acid having a low melting point among the poly-L-lactic acid or poly-D-lactic acid mixed above.
  • the temperature is within the range of the temperature rising crystallization temperature and the temperature falling crystallization temperature measured in advance by a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • any condition of reduced pressure, normal pressure or increased pressure may be used.
  • the time for crystallization in the gas phase or liquid phase is not particularly limited, but it is sufficiently crystallized within 3 hours, and preferably within 2 hours.
  • the melting machine is not limited as long as it can apply shear or pressure, and the polymerization can ,
  • a kneader, a Banbury mixer, a single screw extruder, a twin screw extruder, an injection molding machine, etc. can be used, and a single screw extruder and a twin screw extruder are preferred.
  • the crystallization temperature is from ⁇ 50 ° C. to melting point + 20 ° C. relative to the melting point of poly-L-lactic acid and poly-D-lactic acid to be mixed.
  • a range is preferred.
  • a more preferable range of the crystallization temperature is a melting point of ⁇ 40 ° C. to a melting point, and a particularly preferable temperature range is a melting point of ⁇ 30 ° C. to a melting point of ⁇ 5 ° C.
  • the temperature of the melting machine is usually set to a melting point + 20 ° C. or higher so that the resin melts and exhibits good fluidity. If the temperature of the melting machine is within the above preferred range, the crystallizing while maintaining appropriate fluidity.
  • the generated crystals are difficult to remelt.
  • the melting point is the crystal melting temperature when the temperature is raised from 30 ° C. to 250 ° C. at a rate of temperature rise of 20 ° C./min using differential thermal scanning measurement.
  • the crystallization treatment time is preferably 0.1 to 10 minutes, more preferably 0.3 to 5 minutes, and particularly preferably 0.5 to 3 minutes.
  • crystallization treatment time is within the above preferred range, crystallization occurs sufficiently, while thermal decomposition hardly occurs.
  • the shear rate at this time is preferably in the range of 10 to 400 (/ second). When the shear rate is within the above preferred range, the crystallization rate becomes sufficiently high, while thermal decomposition due to shear heat generation hardly occurs.
  • the mixing method of poly-L-lactic acid and poly-D-lactic acid is not particularly limited, and for example, the melting end temperature of the component having the higher melting point among poly-L-lactic acid and poly-D-lactic acid.
  • the method of melt kneading, the method of removing the solvent after mixing in the solvent, or at least one of the molten poly-L-lactic acid and poly-D-lactic acid is a temperature range from -50 ° C to 20 ° C in advance.
  • a method of mixing so that crystals of a mixture composed of poly-L-lactic acid and poly-D-lactic acid remain after being retained while applying shear in a melting machine.
  • the melting point refers to the temperature at the peak top of the polylactic acid single crystal melting peak measured by (DSC) with a differential scanning calorimeter, and the melting end temperature is determined with a differential scanning calorimeter (DSC). It means the peak end temperature in the polylactic acid single crystal melting peak measured by the above.
  • Examples of the method of melt-kneading at a temperature higher than the melting end temperature include a method of mixing poly-L-lactic acid and poly-D-lactic acid by a batch method or a continuous method.
  • Examples thereof include a single screw extruder, a twin screw extruder, a plast mill, a kneader, and a stirred tank reactor equipped with a decompression device.
  • a single screw extruder or a twin screw extruder may be used. preferable.
  • the temperature condition at the time of melting and kneading at a temperature higher than the melting end temperature it is preferable to carry out at a temperature higher than the melting end temperature of the higher melting point component of poly-L-lactic acid and poly-D-lactic acid.
  • the range is preferably 140 ° C to 250 ° C, more preferably 160 ° C to 230 ° C, and particularly preferably 180 ° C to 210 ° C.
  • mixing temperature is within the above-mentioned preferable range, mixing can be performed in a molten state, and the molecular weight of the mixture is hardly lowered during mixing. Furthermore, the fluidity of the mixture can be kept constant, and a significant decrease in fluidity hardly occurs.
  • the mixing time condition is preferably in the range of 0.1 minute to 10 minutes, more preferably in the range of 0.3 minute to 5 minutes, and particularly preferably in the range of 0.5 minute to 3 minutes.
  • the mixing time is in the above preferred range, poly-L-lactic acid and poly-D-lactic acid can be uniformly mixed, while thermal decomposition due to mixing hardly occurs.
  • the pressure condition for mixing at the melting end temperature or higher is not particularly limited, and may be any condition under an air atmosphere or an inert gas atmosphere such as nitrogen.
  • a specific method for mixing poly-L-lactic acid and poly-D-lactic acid crystallized by applying shear or pressure in a melting machine includes a batch method or a continuous method.
  • the melted poly-L-lactic acid and poly-D-lactic acid may be mixed into the melting point of polylactic acid having a lower melting point of poly-L-lactic acid and poly-D-lactic acid.
  • a method of staying while applying shear in a melting machine of ⁇ 50 ° C. to melting point + 20 ° C., or a poly-L-lactic acid and poly-D-lactic acid in a molten state are mixed with poly-L-lactic acid and poly-D-lactic acid.
  • the mixture of poly-L-lactic acid and poly-D-lactic acid is mixed by a method of staying while applying pressure in a melting machine having a melting point of ⁇ 50 ° C. to melting point + 20 ° C.
  • Stereo complex formation rate (Sc) It can be controlled.
  • the stereo complex formation rate (Sc) can be calculated by the above formula (4).
  • the mixing temperature condition is preferably in the range of -50 ° C. to melting point + 20 ° C. with respect to the melting point of the mixture of poly-L-lactic acid and poly-D-lactic acid.
  • a more preferable range of the mixing temperature is a melting point of ⁇ 40 ° C. to a melting point, and a particularly preferable range is a melting point of ⁇ 30 ° C. to a melting point of ⁇ 5 ° C.
  • the temperature of the melting machine is usually preferably set to a melting point + 20 ° C. or higher in order for the resin to melt and express good fluidity, but with such a preferred mixing temperature, the fluidity does not decrease too much, On the other hand, the generated crystals are difficult to remelt.
  • the melting point refers to the crystal melting temperature when the temperature is raised from 30 ° C. to 250 ° C. at a rate of temperature rise of 20 ° C./min using a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the shear rate when mixing poly-L-lactic acid and poly-D-lactic acid crystallized by applying shear or pressure in the melting machine is preferably in the range of 10 to 400 (/ sec).
  • shear rate is in the above preferred range, poly-L-lactic acid and poly-D-lactic acid can be uniformly mixed while maintaining fluidity and crystallinity, while heat is generated by shearing heat generated during mixing. It is difficult to cause decomposition.
  • the pressure applied during mixing is preferably in the range of 0.05 to 10 (MPa).
  • MPa 0.05 to 10
  • the method of supplying polylactic acid is not particularly limited, and a method of supplying poly-L-lactic acid and poly-D-lactic acid from a resin supply port in a lump or side supply as required.
  • a method of supplying poly-L-lactic acid and poly-D-lactic acid separately to the resin supply port and the side supply port by using the mouth is possible.
  • the supply of polylactic acid to the kneader can also be performed in a molten state directly from the polylactic acid production process.
  • the screw element in the extruder is preferably provided with a kneading element in the mixing part so that poly-L-lactic acid and poly-D-lactic acid can be uniformly mixed to form a stereo complex.
  • the mixing weight ratio of poly-L-lactic acid composed of L-lactic acid units and poly-D-lactic acid composed of D-lactic acid units is preferably 90:10 to 10:90. More preferably, it is 80:20 to 20:80, and particularly preferably 75:25 to 60:40 or 40:60 to 25:75.
  • a polylactic acid stereocomplex can be easily formed.
  • a polylactic acid block copolymer is formed. The rise in the melting point of is sufficiently large.
  • the mixing weight ratio of poly-L-lactic acid and poly-D-lactic acid is other than 50:50, a larger amount of poly-L-lactic acid or poly-D-lactic acid having a larger weight average molecular weight may be blended. preferable.
  • the catalyst may be a residual amount of the catalyst in producing poly-L-lactic acid and / or poly-D-lactic acid, or one or more selected from the above catalysts may be added in the mixing step. it can.
  • the content of the catalyst for efficiently proceeding with the solid-phase polymerization is preferably 0.001 part by weight or more and 1 part by weight or less with respect to 100 parts by weight of the mixture of poly-L-lactic acid and poly-D-lactic acid. More preferred is 0.001 part by weight or more and 0.5 part by weight or less.
  • the catalyst amount is within the above preferred range, the effect of shortening the reaction time of solid phase polymerization can be obtained, while the molecular weight of the finally obtained polylactic acid block copolymer tends to increase.
  • the weight average molecular weight (Mw) of the mixture of poly-L-lactic acid and poly-D-lactic acid after mixing is preferably 90,000 or more and less than 300,000 from the viewpoint of mechanical properties of the mixture. More preferably, it is 120,000 or more and less than 300,000, and it is especially preferable that it is 140,000 or more and less than 300,000.
  • the degree of dispersion of the mixture of poly-L-lactic acid and poly-D-lactic acid after mixing is preferably in the range of 1.5 to 4.0. A more preferred range is 2.0 to 3.7, and a particularly preferred range is 2.5 to 3.5.
  • the degree of dispersion means the ratio of the weight average molecular weight to the number average molecular weight of the mixture.
  • the standard polydispersity by gel permeation chromatography (GPC) measurement using hexafluoroisopropanol or chloroform as a solvent It is a value in terms of methyl methacrylate.
  • the amount of lactide and oligomer contained in poly-L-lactic acid or poly-D-lactic acid is preferably 5% or less, respectively. More preferably, it is 3% or less, and particularly preferably 1% or less.
  • the amount of lactic acid contained in poly-L-lactic acid or poly-D-lactic acid is preferably 2% or less. More preferably, it is 1% or less, and particularly preferably 0.5% or less.
  • the shape of the mixture of poly-L-lactic acid and poly-D-lactic acid is not particularly limited and may be any of agglomerates, films, pellets, and powders. From the viewpoint of efficiently proceeding the polymerization, it is preferable to use pellets or powder.
  • the method of pelletizing a mixture of poly-L-lactic acid and poly-D-lactic acid include a method of extruding the mixture into a strand and pelletizing, and a method of extruding the mixture into water and pelletizing with an underwater cutter. It is done.
  • examples of a method for making a mixture of poly-L-lactic acid and poly-D-lactic acid into powder include a method of pulverizing using a pulverizer such as a mixer, blender, ball mill, and hammer mill.
  • the method for carrying out this solid phase polymerization step is not particularly limited, and may be a batch method or a continuous method.
  • the reaction vessel may be a stirred tank reactor, a mixer reactor, a tower reactor, or the like. These reactors can be used in combination of two or more.
  • a mixture of poly-L-lactic acid and poly-D-lactic acid is crystallized.
  • the poly-L-lactic acid and poly-D are used in the solid phase polymerization step. -Crystallization of the mixture of lactic acid is not necessarily required, but the efficiency of solid phase polymerization can be further increased by crystallization.
  • the method for crystallization is not particularly limited, and a known method can be used.
  • a method of holding at a crystallization treatment temperature in a gas phase or a liquid phase or a method of cooling and solidifying a molten mixture of poly-L-lactic acid and poly-D-lactic acid while performing stretching or shearing operations.
  • a method of holding at the crystallization temperature in the gas phase or in the liquid phase is preferable.
  • the crystallization treatment temperature here is particularly limited as long as it is higher than the glass transition temperature and lower than the melting point of polylactic acid having a low melting point among the mixed poly-L-lactic acid and poly-D-lactic acid. Although it is not performed, it is more preferable that the temperature is within the range of the temperature-rise crystallization temperature and the temperature-fall crystallization temperature measured in advance by a differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • any of reduced pressure, normal pressure, and increased pressure may be used.
  • the time for crystallization is not particularly limited, but it is sufficiently crystallized within 3 hours, and within 2 hours is preferable.
  • the temperature condition for carrying out this solid phase polymerization step is preferably a temperature not higher than the melting point of the mixture of poly-L-lactic acid and poly-D-lactic acid.
  • the mixture of poly-L-lactic acid and poly-D-lactic acid has a melting point based on stereocomplex crystals in the range of 190 ° C. to 230 ° C. due to stereocomplex formation, and also has a poly-L in the range of 150 ° C. to 185 ° C. Since it has melting points based on -lactic acid single crystals and poly-D-lactic acid single crystals, it is preferable to carry out solid phase polymerization below these melting points. Specifically, it is preferably 100 ° C. or higher and 220 ° C.
  • the temperature conditions when the temperature is raised stepwise during the solid phase polymerization are as follows.
  • the first stage is 120 ° C. to 145 ° C. for 1 to 15 hours
  • the second stage is 135 ° C. to 160 ° C. for 1 to 15 hours
  • the third stage It is preferable that the temperature is raised from 150 ° C. to 175 ° C. for 10 to 30 hours, further, the first stage is from 130 ° C. to 145 ° C. for 2 to 12 hours, and the second stage is from 140 ° C. to 160 ° C. for 2 to 12 hours.
  • the temperature condition for continuous temperature increase during solid-phase polymerization is that the temperature is continuously increased from 150 ° C. to 175 ° C. at a rate of 1 to 5 (° C./min) from the initial temperature of 130 ° C. to 150 ° C. Is preferred. Further, combining stepwise temperature rise and continuous temperature rise is also preferable from the viewpoint of efficiently proceeding with solid phase polymerization.
  • this solid phase polymerization step is preferably carried out under a vacuum or an inert gas stream such as dry nitrogen.
  • the degree of vacuum when performing solid-phase polymerization under vacuum is preferably 150 Pa or less, more preferably 75 Pa or less, and particularly preferably 20 Pa or less.
  • the flow rate when solid-phase polymerization is performed under an inert gas stream is preferably in the range of 0.1 to 2,000 (mL / min), and 0.5 to 1,000 (mL / min) with respect to 1 g of the mixture. Is more preferable, and a range of 1.0 to 500 (mL / min) is particularly preferable.
  • the yield (Y) of the polymer after solid phase polymerization is preferably 90% or more. More preferably, it is 93% or more, and particularly preferably 95% or more.
  • the polymer yield (Y) here is the ratio of the weight of the polylactic acid block copolymer after solid phase polymerization to the weight of the mixture before solid phase polymerization. Specifically, when the weight of the mixture before solid phase polymerization is Wp and the weight of the polymer after solid phase polymerization is Ws, the yield (Y) of the polymer can be calculated by the following formula (7).
  • the degree of dispersion of the mixture is small.
  • the dispersion degree of the mixture before the solid phase polymerization is in the range of 1.5 to 4.0, and the dispersion degree of the polylactic acid block copolymer is in the range of 1.5 to 2.7 after the solid phase polymerization. It is preferable to become. More preferably, the dispersion degree of the mixture before the solid phase polymerization is in the range of 2.0 to 3.7, and the dispersion degree of the polylactic acid block copolymer is reduced to the range of 1.8 to 2.6 after the solid phase polymerization. Particularly preferably, the dispersion degree of the polylactic acid block copolymer is 2.0 to 2.5 after the solid phase polymerization from the range of the dispersion degree of the mixture 2.5 to 3.5 before the solid phase polymerization. It is to be in the range.
  • 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 the higher melting point, so that the L-lactic acid unit segment and the D-lactic acid unit segment
  • a method (Preparation Method 3) for obtaining a polylactic acid block copolymer obtained by transesterifying the lactic acid block copolymer will be described. Also in this preparation method, for the polymerization of poly-L-lactic acid and poly-D-lactic acid, any of the above-described ring-opening polymerization method and direct polymerization method can be used.
  • the weight average molecular weight of either one of poly-L-lactic acid and poly-D-lactic acid is high in that the stereocomplex formation rate becomes high after melt-kneading.
  • the weight average molecular weight is 60,000 to 300,000 or less, and the other weight average molecular weight is 10,000 to 100,000 or less. More preferably, one weight average molecular weight is 100,000 to 270,000 and the other weight average molecular weight is 15,000 to 80,000. Particularly preferably, one weight average molecular weight is 150,000 to 240,000 and the other weight average molecular weight is 20,000 to 50,000.
  • the combination of the weight average molecular weights of poly-L-lactic acid and poly-D-lactic acid is preferably selected as appropriate so that the weight average molecular weight after mixing is 90,000 or more. Further, in the present invention, the weight average molecular weight of the poly-L-lactic acid component and the poly-D-lactic acid component is such that the weight average molecular weight of either poly-L-lactic acid or poly-D-lactic acid is 60,000 or more. It is also a preferred embodiment that the weight average molecular weight is 300,000 or less and the other weight average molecular weight is 30,000 or more and 100,000 or less.
  • one weight average molecular weight is 100,000 or more and 270,000 or less, and the other weight average molecular weight is 20,000 or more and 80,000 or less. More preferably, it is 125,000 or more and 255,000 or less, and the other weight average molecular weight is 25,000 or more and 50,000 or less.
  • a method of melt kneading for a long time at a temperature higher than the melting end temperature a method of mixing poly-L-lactic acid and poly-D-lactic acid by a batch method or a continuous method may be mentioned, and any method may be used.
  • 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. From the viewpoint of uniform and sufficient kneading, a single screw extruder and a twin screw extruder are used. It is preferable to use it.
  • the mixing temperature condition it is important that the mixing is performed at a temperature higher than the melting end temperature of the component having a higher melting point among poly-L-lactic acid and poly-D-lactic acid.
  • the range is preferably 140 ° C. to 280 ° C., more preferably 160 ° C. to 270 ° C., and particularly preferably 180 ° C. to 260 ° C.
  • the mixing temperature is within the above preferred range, the fluidity does not decrease excessively, while the molecular weight of the mixture does not easily decrease.
  • the mixing time condition is preferably in the range of 0.1 to 30 minutes, more preferably in the range of 0.3 to 20 minutes, and particularly preferably in the range of 0.5 to 10 minutes.
  • the mixing time is within the above preferable range, the mixing of poly-L-lactic acid and poly-D-lactic acid becomes uniform, while thermal decomposition is hardly caused by mixing.
  • the pressure condition for mixing is not particularly limited, and may be any condition under an air atmosphere or an inert gas atmosphere such as nitrogen.
  • the mixing weight ratio of poly-L-lactic acid composed of L-lactic acid units and poly-D-lactic acid composed of D-lactic acid units is preferably from 80:20 to 20:80, and from 75:25 to The ratio is more preferably 25:75, further preferably 70:30 to 30:70, and particularly preferably 60:40 to 40:60.
  • the weight ratio of poly-L-lactic acid composed of L-lactic acid units is within the above preferred range, a polylactic acid stereocomplex is easily formed, and as a result, the resulting polylactic acid block copolymer has a sufficient melting point. growing.
  • the mixing step it is preferable to contain a catalyst in the mixture in order to promote transesterification of the L-lactic acid unit segment and the D-lactic acid unit segment efficiently.
  • the catalyst may be a residual amount of the catalyst when producing poly-L-lactic acid and / or poly-D-lactic acid, or a catalyst may be further added in the mixing step.
  • the catalyst content is preferably 0.001 part by weight or more and 1 part by weight or less with respect to 100 parts by weight of the mixture of poly-L-lactic acid and poly-D-lactic acid. More preferred are parts by weight or less.
  • the catalyst amount is in the above preferred range, the frequency of transesterification of the mixture is sufficiently high, while the molecular weight of the finally obtained polylactic acid block copolymer tends to increase.
  • the weight-average molecular weight of poly-L-lactic acid and poly-D-lactic acid used to obtain a polylactic acid block copolymer by this method is such that the formation rate of stereocomplexes is high. It is preferable that the weight average molecular weight of any one of -D-lactic acid is 30,000 to 100,000 or less and the other weight average molecular weight is 10,000 to 30,000 or less. More preferably, one weight average molecular weight is 35,000 to 90,000 and the other weight average molecular weight is 10,000 to 25,000. Particularly preferably, one weight average molecular weight is 40,000 to 80,000, and the other weight average molecular weight is 10,000 to 20,000.
  • the ratio of the weight average molecular weight of poly-L-lactic acid used in the above mixing to the weight average molecular weight of poly-D-lactic acid is 2 or more and less than 10 from the viewpoint of increasing the stereocomplex formation rate. Is preferred. More preferably, it is 3 or more and less than 10, and particularly preferably 4 or more and less than 10.
  • polyfunctional compound used here examples include polyvalent carboxylic acid anhydrides, polyvalent carboxylic acid halides, polyvalent carboxylic acids, polyvalent isocyanates, polyvalent amines, polyhydric alcohols, and polyvalent epoxy compounds. Specifically, 1,2-cyclohexanedicarboxylic acid anhydride, succinic acid anhydride, phthalic acid anhydride, trimellitic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, pyromellitic acid anhydride, etc.
  • Polycarboxylic acid anhydrides isophthalic acid chloride, terephthalic acid chloride, polyvalent carboxylic acid halides such as 2,6-naphthalenedicarboxylic acid chloride, succinic acid, adipic acid, sebacic acid, fumaric acid, terephthalic acid, isophthalic acid, 2 , 6-Polycarboxylic acids such as naphthalenedicarboxylic acid, hexamethylene diisocyanate, 4,4 ′ Polyvalent isocyanates such as diphenylmethane diisocyanate, toluene-2,4-diisocyanate, polyvalent amines such as ethylenediamine, hexanediamine, diethylenetriamine, ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, pentaerythritol, etc.
  • Polyhydric alcohol terephthalic acid diglycidyl ester, naphthalene dicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetraglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether , Glycerol triglycidyl ether, trimethylol B pan triglycidyl ether, polyvalent epoxy compounds such as pentaerythritol polyglycidyl ether and the like.
  • polyvalent carboxylic acid anhydrides polyvalent isocyanates, polyhydric alcohols and polyvalent epoxy compounds are preferred, and polyvalent carboxylic acid anhydrides, polyvalent isocyanates and polyvalent epoxy compounds are particularly preferred.
  • these can be used combining 1 type (s) or 2 or more types.
  • the mixing amount of the polyfunctional compound is preferably 0.01 parts by weight or more and 20 parts by weight or less, more preferably 0.1 parts by weight, with respect to 100 parts by weight of the total of poly-L-lactic acid and poly-D-lactic acid. More preferably, it is 10 parts by weight or less.
  • the addition amount of the polyfunctional compound is within the above preferable range, the effect of causing a covalent bond can be sufficiently exhibited.
  • a reaction catalyst may be added in order to promote the reaction between poly-L-lactic acid and poly-D-lactic acid and the polyfunctional compound.
  • the reaction catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, stearin.
  • Organic acids and Lewis acids such as boron trifluoride, aluminum tetrachloride, titanium tetrachloride, tin tetrachloride Etc. are exemplified, and these may be used in combination of one or two or more.
  • the amount of the catalyst added is preferably 0.001 part by weight or more and 1 part by weight or less with respect to 100 parts by weight of the total of poly-L-lactic acid and poly-D-lactic acid.
  • the catalyst amount is in the above preferred range, the reaction promoting effect is sufficient, while the molecular weight of the finally obtained polylactic acid block copolymer tends to increase.
  • the method for reacting poly-L-lactic acid or poly-D-lactic acid with a polyfunctional compound is not particularly limited.
  • poly-L-lactic acid and poly-D-lactic acid the one having the higher melting point.
  • the method include melt kneading at a temperature higher than the melting end temperature of the components.
  • Examples of the method of melt-kneading at a temperature higher than the melting end temperature include a method of mixing poly-L-lactic acid and poly-D-lactic acid by a batch method or a continuous method.
  • Examples include a single-screw extruder, a twin-screw extruder, a plastmill, a kneader, and a stirred tank reactor equipped with a decompression device.
  • a single-screw extruder or a twin-screw extruder should be used. Is preferred.
  • the temperature condition for melting and kneading it is preferable to carry out at a temperature higher than the melting end temperature of the component having a higher melting point among poly-L-lactic acid and poly-D-lactic acid.
  • the range is preferably 140 ° C to 250 ° C, more preferably 160 ° C to 230 ° C, and particularly preferably 180 ° C to 210 ° C.
  • the mixing temperature is within the above preferred range, the fluidity does not decrease excessively, while the molecular weight of the mixture does not easily decrease.
  • the time condition for melt kneading is preferably in the range of 0.1 to 30 minutes, more preferably in the range of 0.3 to 20 minutes, and particularly preferably in the range of 0.5 to 10 minutes.
  • the mixing time is within the above preferable range, the mixing of poly-L-lactic acid and poly-D-lactic acid becomes uniform, while thermal decomposition is hardly caused by mixing.
  • the pressure condition for melt kneading is not particularly limited, and may be any condition under an air atmosphere or an inert gas atmosphere such as nitrogen.
  • the mixing weight ratio of poly-L-lactic acid composed of L-lactic acid units and poly-D-lactic acid composed of D-lactic acid units is preferably from 90:10 to 10:90, and from 80:20 to More preferably, it is 20:80. Particularly preferred is 75:25 to 60:40 or 40:60 to 25:75.
  • the weight ratio of poly-L-lactic acid composed of L-lactic acid units is within the above preferred range, a polylactic acid stereocomplex is easily formed, and as a result, the melting point of the polylactic acid block copolymer finally obtained is increased. Become big enough.
  • a polylactic acid block copolymer obtained by mixing a polyfunctional compound with poly-L-lactic acid and poly-D-lactic acid is a polyfunctional compound in which poly-L-lactic acid and poly-D-lactic acid are covalently bonded. Therefore, it is possible to carry out solid phase polymerization by the method described above after mixing.
  • the polymer having a plurality of reactive groups per molecule is a polymer having a reactive group that undergoes an addition reaction with respect to the carboxyl group or hydroxyl group terminal of the polylactic acid resin composition.
  • the viscosity of the polylactic acid resin composition is improved, and as a result, molding processability, mechanical properties, durability, and stability during heating are improved.
  • a polymer having a plurality of reactive groups per molecule may be included when preparing a polylactic acid block copolymer in addition to the above-mentioned polylactic acid resin composition.
  • a polymer having a plurality of reactive groups per molecule may be included in advance with respect to poly-L-lactic acid or poly-D-lactic acid to be mixed.
  • the content of the polymer having a plurality of reactive groups per molecule will be described later.
  • the basic structure is a thermoplastic resin, and the weight average molecular weight (Mw) of the polymer is 1,000 to 15,000.
  • Mw weight average molecular weight
  • the compatibility in the polylactic acid resin composition can be increased.
  • the weight average molecular weight (Mw) of the polymer is 2,000 to 10,000, the compatibility in the polylactic acid resin composition is higher, and the polylactic acid resin composition has molding processability, mechanical properties, Durability and stability during heating are improved.
  • the weight average molecular weight (Mw) here is a weight average molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.
  • the reactive group that undergoes an addition reaction include a carbodiimide group, an epoxy group, an oxazoline group, an oxazine group, an aziridine group, and an isocyanate group.
  • an epoxy group is preferable from the viewpoint of reactivity.
  • the number of reactive groups contained in one molecule as a polymer having a plurality of reactive groups per molecule is preferably 2-30, more preferably 3-20, and even more preferably 4-10. .
  • the acrylic resin reactive compound when used as a polymer having a plurality of reactive groups in one molecule, is a polymer of a mixture of an epoxy group-containing acrylic monomer and a styrene monomer, Or it is preferable that it is a polymer of 3 types of mixtures of an epoxy-group containing acrylic monomer, a styrene monomer, and another vinyl monomer.
  • this acrylic resin-based reactive compound in the polylactic acid resin composition of the present invention, the viscosity of the polylactic acid resin composition is improved. As a result, molding processability, mechanical properties, durability, and stability during heating are stabilized. Will improve.
  • epoxy group-containing acrylic monomer constituting the acrylic resin-based reactive compound examples include (meth) acrylic acid glycidyl, cyclohexene oxide structure (meth) acrylic acid ester, and (meth) acrylic acid glycidyl ether.
  • glycidyl acrylate is preferably used in terms of radical polymerizability. These can be used alone or in combination of two or more.
  • styrene monomer constituting the acrylic resin reactive compound examples include styrene, ⁇ -methyl styrene, vinyl toluene, p-methyl styrene, t-butyl styrene, o-chlorostyrene, vinyl pyridine and the like. Of these, one or more of styrene and ⁇ -methylstyrene are preferably used from the viewpoint of affinity with the polylactic acid block copolymer.
  • vinyl monomers constituting the acrylic resin reactive compound include (meth) acrylic acid, (meth) methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) Butyl acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, lauryl (meth) acrylate, Stearyl (meth) acrylate, hydroxylethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylate ester of polyethylene glycol or polypropylene glycol, trimethoxysilylpropyl (meth) acrylate, (meth) acrylonitrile , N, N-dia
  • Examples include raw material monomers for forming
  • Acrylic acid methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, (meth) Preferred are 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and (meth) acrylonitrile.
  • the acrylic resin-based reactive compound preferably contains 2 to 30 average epoxy groups per molecule, more preferably 3 to 20, and still more preferably 4 to 10.
  • the average number of epoxy groups is within this preferred range, the polylactic acid resin composition has an excellent thickening effect, and the moldability, mechanical properties, durability, and stability during heating are sufficiently improved, while excess epoxy is used.
  • the group does not cause an excessive crosslinking reaction with the carboxyl group or hydroxyl group of the polylactic acid resin composition, and the moldability is not impaired.
  • the epoxy equivalent of the acrylic resin-based reactive compound containing an epoxy group is preferably 50 to 800 g / mol, more preferably 100 to 700 g / mol, and most preferably 150 from the viewpoint of reactivity and moldability. ⁇ 600 g / mol.
  • the epoxy equivalent and the carbodiimide equivalent represent the gram number of a polymer containing 1 equivalent of an epoxy group and the gram number of a polymer containing 1 equivalent of a carbodiimide group.
  • the weight average molecular weight (Mw) of the acrylic resin-based reactive compound containing an epoxy group is preferably 1,000 to 15,000, more preferably 2, from the viewpoint of reactivity and compatibility with the resin. 000 to 10,000.
  • the weight average molecular weight (Mw) here is a weight average molecular weight in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.
  • the acrylic resin-based reactive compound can be produced and used by a known technique, but a commercially available product can also be used.
  • a commercially available product Sumitomo Chemical Co., Ltd. "Bond First" (registered trademark) series, "Marproof” (registered trademark) series manufactured by NOF Corporation, "RESEDA” (registered trademark) series and “ARUFON” (registered trademark) series manufactured by Toagosei Co., Ltd. “JONCRYL” (registered trademark) series manufactured by BASF Japan Ltd. can be used preferably, but from the viewpoint of reactivity, “ARUFON” (registered trademark) series manufactured by Toagosei Co., Ltd.
  • the polylactic acid resin composition of the present invention comprises a polylactic acid block copolymer 100 comprising a poly-L-lactic acid segment containing L-lactic acid as a main component and a poly-D-lactic acid segment containing D-lactic acid as a main component.
  • a polylactic acid block copolymer 100 comprising a poly-L-lactic acid segment containing L-lactic acid as a main component and a poly-D-lactic acid segment containing D-lactic acid as a main component.
  • 0.05 to 2 parts by weight of a polymer having a plurality of reactive groups per molecule is contained with respect to parts by weight.
  • the amount is preferably 0.1 to 1.5 parts by weight, more preferably 0.3 to 1.0 parts by weight.
  • the viscosity of the polylactic acid resin composition is improved.
  • molding processability, mechanical properties, durability, Stability during heating is improved.
  • gelation accompanying the increase in viscosity does not occur.
  • the polylactic acid resin composition obtained in the present invention preferably has a stereocomplex formation rate (Sc) in the range of 80 to 100% from the viewpoint of heat resistance. More preferably, it is in the range of 85 to 100%, and particularly preferably 90 to 100%.
  • the stereocomplex formation rate is the ratio of the stereocomplex crystals in all the crystals in the polylactic acid resin composition. Specifically, the crystal melting of poly-L-lactic acid single crystal and poly-D-lactic acid single crystal when the temperature is increased from 30 ° C. to 250 ° C. at a temperature rising rate of 20 ° C./min with a differential scanning calorimeter (DSC). It is possible to calculate by the following formula (8), where ⁇ H1 is the amount of heat based on and ⁇ Hh is the amount of heat based on crystal melting of the stereocomplex crystal.
  • the temperature-falling crystallization temperature (Tc) is 130 degreeC or more at the point that a polylactic acid resin composition is excellent in a moldability and heat resistance.
  • the temperature drop crystallization temperature (Tc) of the compact is a constant temperature state at 250 ° C. for 3 minutes after being heated from 30 ° C. to 250 ° C. at a temperature rising rate of 20 ° C./min by a differential scanning calorimeter (DSC). Is a crystallization temperature derived from polylactic acid crystals measured when the temperature is lowered at a cooling rate of 20 ° C./min.
  • the crystallization temperature (Tc) is not particularly limited, but is preferably 130 ° C. or higher, more preferably 132 ° C. or higher, and particularly preferably 135 ° C. or higher from the viewpoint of heat resistance and transparency.
  • the amount of crystallization when the polylactic acid resin composition is heated to 250 ° C. and kept constant for 3 minutes and then cooled at a cooling rate of 20 ° C./min in DSC measurement. Is 10 J / g or more. From the viewpoint of crystallization characteristics, molding cycle, and transparency of the molded body, it is preferably 10 J / g or more, more preferably 20 J / g or more, and particularly preferably 40 J / g or more.
  • the temperature-falling crystallization temperature is 130 ° C. or higher, and the amount of crystallization during temperature-falling crystallization is 10 J / Since it is as high as g or more, it has not only excellent mechanical properties, durability and stability during heating, but also excellent heat resistance and crystallization characteristics.
  • the weight average molecular weight of the polylactic acid resin composition of the present invention is preferably 100,000 or more and less than 500,000 from the viewpoint of mechanical properties. More preferably, it is 120,000 or more and less than 450,000, and 130,000 or more and less than 400,000 is particularly preferable from the viewpoints of moldability, mechanical properties, and stability during heating.
  • the dispersity of the polylactic acid resin composition is preferably in the range of 1.5 to 4.5 from the viewpoint of mechanical properties.
  • the range of the degree of dispersion is more preferably from 1.8 to 3.7, and particularly preferably from 2.0 to 3.4 from the viewpoint of moldability and mechanical properties.
  • the weight average molecular weight and dispersity are values in terms of standard polymethyl methacrylate as measured by gel permeation chromatography (GPC) using hexafluoroisopropanol or chloroform as a solvent.
  • thermogravimetry TGA
  • the heat loss when the polylactic acid resin composition is maintained at a constant temperature of 240 ° C. for 30 minutes under a nitrogen atmosphere may be 3% or less. preferable. More preferably, it is preferably 2% or less, particularly preferably less than 1%. A low heating loss is preferred because of excellent residence stability.
  • the ratio (MFR10 / MFR20) of the melt flow rate (MFR10) after 10 minutes to the melt flow rate (MFR20) after 20 minutes under the condition of 230 ° C. and 21.2N load of the polylactic acid resin composition is 0.
  • a range of 5 or more and 2 or less is preferable in terms of moldability, mechanical properties, impact resistance, and stability during heating. More preferably, it is the range of 0.7 or more and 1.8 or less, More preferably, it is the range of 0.85 or more and 1.5 or less.
  • the melt flow rate here is a value measured at 190 ° C. and 21.2 N load conditions according to JIS K 7210 using “Melt Indexer” manufactured by Toyo Seiki Seisakusho.
  • any one of the following three methods (I) to (III) by using a heat-melt kneading apparatus such as an extruder or a kneader. Can be manufactured.
  • Examples of the method (I) for producing a polylactic acid resin composition include a method of melt-kneading a polylactic acid block copolymer and a polymer having a plurality of reactive groups in one molecule.
  • a method of melt kneading either a batch method or a continuous method may be used.
  • 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. From the viewpoint of uniform and sufficient kneading, a single screw extruder and a twin screw extruder are used. It is preferable to use it.
  • the temperature condition for melt kneading it is preferable to carry out at 180 ° C to 250 ° C.
  • the range is more preferably 200 ° C. to 240 ° C., and further preferably 205 ° C. to 235 ° C.
  • the mixing temperature is within the above preferred range, the fluidity does not decrease excessively, while the molecular weight of the mixture does not easily decrease.
  • the time condition for melt kneading is preferably in the range of 0.1 to 30 minutes, more preferably in the range of 0.3 to 20 minutes, and particularly preferably in the range of 0.5 to 10 minutes.
  • the mixing time is within the above preferable range, the polylactic acid block copolymer and the polymer having a plurality of reactive groups per molecule are uniformly mixed, while thermal decomposition is hardly caused by mixing.
  • the pressure condition for melt kneading is not particularly limited, and may be any condition under an air atmosphere or an inert gas atmosphere such as nitrogen.
  • poly-L-lactic acid and poly-D-lactic acid are mixed in advance, and then a polymer having a plurality of reactive groups per molecule is blended. And a method of subjecting the resulting mixture to solid phase polymerization at a temperature lower than the melting point of the mixture.
  • the method of melt kneading in this method may be a mixing method applied in the above-described method for producing a polylactic acid resin composition, and the above-mentioned polylactic acid resin composition is also used for the kneading apparatus, temperature conditions, time conditions, and pressure conditions during mixing. This is the same as described in the manufacturing method.
  • a method (III) for producing a polylactic acid resin composition three types of poly-L-lactic acid, poly-D-lactic acid and a polymer having a plurality of reactive groups in one molecule are mixed together and then mixed. And a method of solid-phase polymerization at a temperature lower than the melting point.
  • the method of melt kneading in this method may be a mixing method applied in the above-described method for producing a polylactic acid resin composition, and the above-mentioned polylactic acid resin composition is also used for the kneading apparatus, temperature conditions, time conditions, and pressure conditions during mixing. This is the same as described in the manufacturing method.
  • the polylactic acid resin composition of the present invention comprises a poly-L-lactic acid (segment consisting of L-lactic acid units) comprising L-lactic acid units of a polylactic acid resin finally obtained within a range not impairing the effects of the present invention,
  • a polyfunctional compound may be mixed.
  • the polyfunctional compound used here is not particularly limited, and polyvalent carboxylic acid anhydride, polyvalent carboxylic acid halide, polyvalent carboxylic acid, polyvalent isocyanate, polyvalent amine, polyhydric alcohol and Polyepoxy compounds and the like.
  • 1,2-cyclohexanedicarboxylic acid anhydride succinic acid anhydride, phthalic acid anhydride, trimellitic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, Polycarboxylic acid anhydrides such as pyromellitic acid anhydride, polycarboxylic acid halides such as isophthalic acid chloride, terephthalic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, succinic acid, adipic acid, sebacic acid, fumaric acid , Terephthalic acid, isophthalic acid, polyvalent carboxylic acids such as 2,6-naphthalenedicarboxylic acid, hexamethyle Polyisocyanates such as diisocyanate, 4,4'-diphenylmethane diisocyanate, toluene-2,4-diisocyanate, polyvalent amines such as ethylenediamine, hexanediamine
  • polyvalent carboxylic acid anhydrides polyvalent isocyanates, polyhydric alcohols and polyvalent epoxy compounds are preferred, and polyvalent carboxylic acid anhydrides, polyvalent isocyanates and polyvalent epoxy compounds are particularly preferred. These may be used alone or in combination of two or more.
  • the mixing amount of the polyfunctional compound is preferably 0.01 parts by weight or more and 20 parts by weight or less, more preferably 0.1 parts by weight, with respect to 100 parts by weight of the total of poly-L-lactic acid and poly-D-lactic acid. More preferably, it is 10 parts by weight or less.
  • the effect which uses a polyfunctional compound can be exhibited as the addition amount of a polyfunctional compound is the said preferable range.
  • a reaction catalyst may be added in order to promote the reaction between poly-L-lactic acid and poly-D-lactic acid and the polyfunctional compound.
  • the reaction catalyst include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, stearin.
  • the amount of the reaction catalyst added is preferably 0.001 part by weight or more and 0.5 part by weight or less with respect to 100 parts by weight of the total of poly-L-lactic acid and poly-D-lactic acid.
  • the catalyst amount is in the above preferred range, an effect of shortening the polymerization time can be obtained, while the molecular weight of the finally obtained polylactic acid resin can be increased.
  • polylactic acid resin composition of the present invention conventional additives such as a catalyst deactivator (hindered phenol compound, thioether compound, vitamin compound, triazole compound) are used as long as the object of the present invention is not impaired.
  • a catalyst deactivator hindered phenol compound, thioether compound, vitamin compound, triazole compound
  • Polyamine-based compounds, hydrazine derivative-based compounds, phosphorus-based compounds, etc. which may be used in combination, including at least one phosphorous-based compound, phosphate-based compound, phosphite-based More preferably, it is a compound or a metal phosphate inorganic compound.
  • the catalyst deactivator composed of a phosphorus compound examples include “ADEKA STAB” (registered trademark) AX-71 (dioftademil phosphate), PEP-8 (distearyl pentaerythritol diphosphite) manufactured by ADEKA, PEP -36 (cyclic neopentatetraylbis (2,6-t-butyl-4-methylphenyl) phosphite) or the like, or sodium dihydrogen phosphate, potassium dihydrogen phosphate, phosphoric acid Lithium dihydrogen, calcium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, calcium hydrogen phosphate, sodium hydrogen phosphite, potassium phosphite, calcium hydrogen phosphite, sodium hypophosphite, At least one gold phosphate selected from potassium hypophosphite and calcium hypophosphite Salts inorganic compounds.
  • plasticizer for example, polyalkylene glycol plasticizer, polyester plasticizer, polycarboxylic acid ester plasticizer, glycerin plasticizer, phosphate ester plasticizer, epoxy
  • plasticizers include plasticizers, fatty acid amides such as stearic acid amide and ethylenebisstearic acid amide, pentaerythritol, various sorbitols, polyacrylic acid esters, silicone oils and paraffins.
  • polyethylene glycol Polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, polytetramethylene glycol, ethylene oxide addition polymer of bisphenols, propylene of bisphenols
  • Polyalkylene glycols such as xoxide addition polymers, tetrahydrofuran addition polymers of bisphenols, or terminal end-capping compounds such as terminal epoxy-modified compounds, terminal ester-modified compounds, and terminal ether-modified compounds
  • polyalkylene glycol plasticizers bis ( Butyl diglycol) adipate, methyl diglycol butyl diglycol adipate, benzyl methyl diglycol adipate, acetyl tributyl citrate, methoxycarbonylmethyl dibutyl citrate, ethoxycarbonylmethyl dibutyl citrate, etc.
  • butadiene-based or acrylic core-shell elastomers examples include “Metablene” (registered trademark) manufactured by Mitsubishi Rayon Co., Ltd., “Kaneace” (registered trademark) manufactured by Kaneka Co., Ltd., and “Paralloid” manufactured by Rohm & Haas Japan Co., Ltd.
  • fillers fibrous, plate-like, powdery, granular, etc.
  • glass fiber PAN-based or pitch-based carbon fiber
  • Stainless steel fiber metal fiber such as aluminum fiber and brass fiber
  • organic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber
  • silica fiber titanium oxide fiber, silicon carbide fiber, rock wool , Potassium titanate whisker, barium titanate whisker, aluminum borate whisker, nitride nitride Fibrous, whisker-like filler, kaolin, silica, calcium carbonate, glass beads, glass flake, glass microballoon, molybdenum disulfide, wollastonite, montmorillonite, titanium oxide, zinc oxide, calcium polyphosphate, graphite, sulfuric acid Flame retardants (red phosphorus, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, magnesium
  • the polylactic acid resin composition used in the present invention may further contain poly-L-lactic acid and / or poly-D-lactic acid in addition to the above-mentioned polylactic acid block copolymer, as long as the object of the present invention is not impaired. it can.
  • poly-L-lactic acid is a polymer containing L-lactic acid as a main component, preferably containing 70 mol% or more of L-lactic acid units, and containing 90 mol% or more. Is more preferably 95 mol% or more, and particularly preferably 98 mol% or more.
  • Poly-D-lactic acid is a polymer containing D-lactic acid as a main component, and preferably contains 70 mol% or more of D-lactic acid units, more preferably 90 mol% or more. More preferably, it is more preferably 95 mol% or more, and particularly preferably 98 mol% or more.
  • poly-L-lactic acid and poly-D-lactic acid may contain other component units as long as the performance of the resulting polylactic acid resin composition is not impaired.
  • Component units other than the L-lactic acid or D-lactic acid unit are included for the segment containing L-lactic acid as the main component or the segment containing D-lactic acid as the main component that constitutes the polylactic acid block copolymer.
  • Examples of other component units that may be used include polycarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, and lactones.
  • the weight average molecular weight of poly-L-lactic acid or poly-D-lactic acid used in the present invention is not particularly limited, but is preferably 100,000 or more from the viewpoint of mechanical properties. 120,000 or more is more preferable, and 140,000 or more is particularly preferable in terms of moldability and mechanical properties.
  • the dispersity of poly-L-lactic acid or poly-D-lactic acid is preferably in the range of 1.5 to 3.0 from the viewpoint of mechanical properties.
  • the range of the degree of dispersion is more preferably 1.8 to 2.7, and 2.0 to 2.4 is particularly preferable in terms of moldability and mechanical properties.
  • the weight average molecular weight and dispersity are values in terms of standard polymethyl methacrylate as measured by gel permeation chromatography (GPC) using hexafluoroisopropanol or chloroform as a solvent.
  • poly-L-lactic acid and / or poly-D-lactic acid with respect to the polylactic acid resin composition is not particularly limited, and poly-L-lactic acid and / or poly with respect to the polylactic acid resin composition is not limited.
  • -D-lactic acid may be mixed, or poly-L-lactic acid and / or poly-D-lactic acid is mixed in advance to form a polylactic acid block copolymer and a polymer having a plurality of reactive groups in one molecule. You may mix.
  • the amount of poly-L-lactic acid and / or poly-D-lactic acid contained in the polylactic acid resin composition is preferably 10 parts by weight or more and 900 parts by weight or less with respect to 100 parts by weight of the polylactic acid resin composition. 30 to 400 parts by weight is preferable.
  • the poly-L-lactic acid and / or poly-D-lactic acid in the polylactic acid resin composition is in the above preferred range, the stereocomplex forming property can be improved, which is preferable.
  • the polylactic acid resin composition of the present invention includes other thermoplastic resins (for example, polyethylene, polypropylene, polystyrene, acrylic resin, acrylonitrile / butadiene / styrene copolymer, polyamide, and the like within a range not to impair the purpose of the present invention).
  • thermoplastic resins for example, polyethylene, polypropylene, polystyrene, acrylic resin, acrylonitrile / butadiene / styrene copolymer, polyamide, and the like within a range not to impair the purpose of the present invention.
  • thermosetting resin eg, phenol resin, melamine resin, polyester resin, silicone
  • Resin epoxy resin, etc.
  • soft thermoplastic resin for example, ethylene / glycidyl methacrylate copolymer, polyester elastomer, polyamide elastomer, ethylene / B pyrene
  • an acrylic resin having an alkyl (meth) acrylate unit having an alkyl group having 1 to 4 carbon atoms as a main component is preferably mentioned.
  • an alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms may be copolymerized with another alkyl acrylate having an alkyl group having 1 to 4 carbon atoms or an aromatic vinyl compound such as styrene. Good.
  • alkyl (meth) acrylate having the above alkyl group examples include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, cyclohexyl acrylate and cyclohexyl methacrylate. Can be mentioned.
  • polymethyl methacrylate composed of methyl methacrylate is particularly preferable.
  • the polylactic acid resin composition of the present invention has a characteristic that, when it is processed into a molded product as a molded body, it is easy to form a high melting point polylactic acid stereocomplex even after it is once melted by heat and solidified.
  • the molded product of the present invention preferably has a relative crystallinity of 90% or more and a molded product having a thickness of 1 mm has a haze value of 10% or less.
  • the relative crystallinity can be calculated by the following formula (9), where ⁇ Hm is the crystal melting enthalpy of the molded body and ⁇ Hc is the crystallization enthalpy at the time of temperature rising of the molded body.
  • Relative crystallinity [( ⁇ Hm ⁇ Hc) / ⁇ Hm] ⁇ 100 (9)
  • the relative crystallinity is preferably 90% or more, more preferably 92% or more, and particularly preferably 94% or more.
  • ⁇ Hc is the crystallization enthalpy of the molded body measured by a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min
  • ⁇ Hm is measured by DSC at a heating rate of 20 ° C./min. This is the crystal melting enthalpy of the molded body. After the temperature was increased from 30 ° C. to 250 ° C.
  • the temperature was cooled to 30 ° C. at a temperature decrease rate of 20 ° C./min. Furthermore, when the temperature is increased from 30 ° C. to 250 ° C. at a rate of temperature increase of 20 ° C./min in the second measurement (2nd RUN), it is preferably the crystal melting enthalpy measured at 2 nd RUN.
  • the haze value is a value obtained by measuring a 1 mm-thick molded body in accordance with JIS K 7105.
  • the haze value is preferably 10% or less, and more preferably 7% or less. preferable. Although a minimum is not specifically limited, If it is 0.1% or more, it can be used practically without a problem. Moreover, even if the molded object of this invention does not contain the crystal nucleating agent used in order to improve transparency, it can make haze value 10% or less by thickness 1mm or more.
  • Examples of the method for producing the molded product of the present invention include known molding methods such as injection molding, extrusion molding, blow molding, vacuum molding, and press molding. In terms of transparency and heat resistance, injection molding and blow molding are possible. Vacuum molding and press molding are preferred.
  • the mold temperature is a temperature range from the glass transition temperature of the polylactic acid resin composition to the melting point and below the melting point, preferably 60 in terms of transparency and heat resistance.
  • blow molding is performed as a method for producing a molded article of the present invention, for example, a polylactic acid resin composition is molded into a bottomed tubular product (parison) by injection molding using the above method, and then a polylactic acid resin is formed.
  • a polylactic acid resin composition is molded into a bottomed tubular product (parison) by injection molding using the above method, and then a polylactic acid resin is formed.
  • For blow molding set to a temperature range of not less than the glass transition point of the composition and a glass transition point of + 80 ° C. or less, preferably 60 ° C. or more and 140 ° C. or less, more preferably 70 ° C. or more and 130 ° C. or less.
  • There is a method of obtaining a molded body by moving to the mold and supplying compressed air from an air nozzle while stretching with a stretching rod.
  • the polylactic acid resin composition is heated at 60 to 150 ° C., preferably 65 to 120 ° C. with a heater such as a hot plate or hot air, in terms of transparency and heat resistance.
  • the sheet is heated at 70 ° C., more preferably 70 to 90 ° C., and the sheet is brought into close contact with the mold set at a mold temperature of 30 to 150 ° C., preferably 40 to 100 ° C., more preferably 50 to 90 ° C.
  • the polylactic acid resin composition is heated at 60 to 150 ° C., preferably 65 to 120 ° C. with a heater such as a hot plate or hot air, in terms of transparency and heat resistance.
  • a heater such as a hot plate or hot air
  • a mold comprising a male mold and a female mold, which is heated at 70 ° C., more preferably 70-90 ° C., and the sheet is set at a mold temperature of 30-150 ° C., preferably 40-100 ° C., more preferably 50-90 ° C.
  • pressure is applied in close contact with the mold and the mold is clamped.
  • the molded product made of the polylactic acid resin composition of the present invention is characterized by having transparency without being subjected to stretching treatment, it is not necessary to perform stretching treatment in order to impart transparency, but other necessity It is possible to perform a stretching process according to the above.
  • the shape of the formed body to be stretched is preferably a film or sheet shape.
  • the temperature range of the polylactic acid stereocomplex above the glass transition point and below the melting point preferably 60 ° C. or higher and 170 ° C. or lower, more preferably 70 ° C. or higher and 150 ° C. or lower. It is preferable to stretch in the temperature range.
  • the polylactic acid resin composition and the molded product containing the polylactic acid resin composition of the present invention include, for example, a film, a sheet, a fiber / cloth, a nonwoven fabric, an injection molded product, an extrusion molded product, a vacuum / pressure molded product, a blow molded product, and Can be used as a composite with other materials, such as agricultural materials, horticultural materials, fishery materials, civil engineering / building materials, stationery, medical supplies, automotive parts, electrical / electronic parts, optical films or other It is useful as an application.
  • mobile terminals such as relay cases, coil bobbins, optical pickup chassis, motor cases, notebook computer housings or internal parts, CRT display housings or internal parts, printer housings or internal parts, mobile phones, mobile PCs, handheld mobiles, etc.
  • VTR parts TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video cameras, video equipment parts such as projectors, "Laser Disk (registered trademark)", Compact Disc (CD), CD -ROM, CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, Home and office electrical product parts represented by word processor parts can be listed.
  • projectors "Laser Disk (registered trademark)", Compact Disc (CD), CD -ROM, CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates
  • lighting parts refrigerator parts, air conditioner parts, typewriter parts, Home and office electrical product parts represented by word processor parts
  • typewriter parts home and office electrical product parts represented by word processor parts
  • Tableware hot fill containers, microwave cooking containers, transparent heat-resistant containers for foods, cosmetic containers, wraps, foam buffer, paper lami, shampoo Bottles, beverage bottles, cups, candy packaging, shrink labels, lid materials, envelopes with windows, fruit baskets, hand cut tape, easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, electricity -Containers and packaging for wrapping films such as electronic parts, various apparel, interior goods, carrier tapes, print laminates, thermal stencil printing films, release films, porous films, container bags, credit cards, cash cards, ID cards , IC card, optical element, conductive embossed tape, IC tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, clear file, bag, chair, table, cooler box, kumade, hose reel, planter, Hose nozzle, table, desk surface Useful as furniture panels, kitchen cabinets, pen caps, gas lighters, etc.
  • the weight average molecular weight and dispersity of a polylactic acid resin composition are the values of standard polymethylmethacrylate conversion measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • a differential refractometer WATERS410 manufactured by Nippon Waters Co., Ltd. is used as a detector, a MODEL510 manufactured by Nippon Waters Co., Ltd.
  • the melting point refers to the peak top temperature in the crystal melting peak
  • the melting end temperature refers to the peak end temperature in the crystal melting peak.
  • Tm-Tms melting point derived from the stereocomplex crystal of the polylactic acid resin composition (peak top temperature at the crystal melting peak)
  • Tms stereocomplex crystal melting start temperature of the polylactic acid resin composition
  • Tme poly The melting point end temperature derived from the stereocomplex crystal of the lactic acid resin composition is shown, and each value is measured using a differential scanning calorimeter (DSC) manufactured by PerkinElmer Japan Co., Ltd., in a 5 mg sample under a nitrogen atmosphere. Value. The measured value was raised from 30 ° C. to 250 ° C.
  • DSC differential scanning calorimeter
  • ⁇ Hl indicates the amount of heat based on crystal melting of poly-L-lactic acid single crystal and poly-D-lactic acid single crystal appearing at 150 ° C. or more and less than 190 ° C.
  • ⁇ Hh is a stereocomplex crystal appearing at 190 ° C. or more and less than 250 ° C. The amount of heat based on the crystal melting of is shown.
  • the stereocomplex formation rate (Sc) of the polylactic acid resin composition in this example is calculated from the crystal melting peak measured at the second temperature rise of the differential scanning calorimeter (DSC).
  • DSC differential scanning calorimeter
  • the temperature-falling crystallization temperature of the polylactic acid resin composition was measured with a differential scanning calorimeter (DSC) manufactured by PerkinElmer Japan. Specifically, 5 mg of a sample was heated from 30 ° C. to 250 ° C. at a temperature rising rate of 20 ° C./min in a nitrogen atmosphere with a differential scanning calorimeter (DSC), and then kept at a constant temperature at 250 ° C. for 3 minutes.
  • Crystallization enthalpy ( ⁇ Hc) The peak area of the crystallization peak of the polylactic acid resin composition measured by a differential scanning calorimeter (DSC) is calculated.
  • Loss on heating The loss on heating of the polylactic acid resin composition was measured with a thermogravimetric measuring device (TGA) manufactured by PerkinElmer Japan. Specifically, 3 mg of the sample was maintained in a constant temperature state at 240 ° C.
  • melt viscosity ratio (MFR10 / MFR20) The melt viscosity ratio (MFR10 / MFR20) of the polylactic acid resin composition is in accordance with JIS K 7210, the melt flow rate after 10 minutes (MFR10) and the melt flow rate after 20 minutes (MFR20) at 230 ° C. and 21.2 N load conditions. ) was measured with a melt indexer manufactured by Toyo Seiki Seisakusho, and the ratio (MFR10 / MFR20) was calculated from each value.
  • the haze value was measured as an index of the transparency of the molded body made of the polylactic acid resin composition. Using a Nippon Denshoku Industries Co., Ltd. haze meter NDH-300A, a haze value was measured according to JIS K 7105 for a sheet-like molded body having a thickness of 0.1 mm. (9) Storage elastic modulus at 130 ° C. The storage elastic modulus was measured as an index of the heat resistance of the molded body made of the polylactic acid resin composition.
  • a center part of a sheet-like molded body having a thickness of 1 mm is cut into 40 mm ⁇ 2 mm to form a strip-like sample, and a temperature rise rate in a nitrogen atmosphere using a dynamic viscoelasticity measuring apparatus (DMS6100 manufactured by Seiko Instruments Inc.). Dynamic viscoelasticity measurement was performed at 2 ° C / min and a frequency of 3.5 Hz, and the storage elastic modulus at 130 ° C was measured. It can be said that the higher the elastic modulus, the higher the heat resistance.
  • DMS6100 dynamic viscoelasticity measuring apparatus
  • the poly-L-lactic acid and poly-D-lactic acid used in the present examples are as follows.
  • PLA1 had a weight average molecular weight of 50,000, a dispersity of 1.5, and a melting point of 157 ° C.
  • PLA2 had a weight average molecular weight of 140,000, a dispersity of 1.6, and a melting point of 165 ° C.
  • Reference Example 3 In a reaction vessel equipped with a stirrer and a reflux device, 50 parts of a 90% L-lactic acid aqueous solution was placed, the temperature was raised to 150 ° C., and the mixture was reacted for 3.5 hours while gradually reducing the pressure to distill off water.
  • PLA3 had a weight average molecular weight of 200,000, a dispersity of 1.7, and a melting point of 170 ° C.
  • PDA1 poly-D-lactic acid
  • PDA1 had a weight average molecular weight of 40,000, a dispersity of 1.5, and a melting point of 156 ° C.
  • Reference Example 5 In a reaction vessel equipped with a stirrer and a reflux apparatus, 50 parts of a 90% D-lactic acid aqueous solution was placed, the temperature was raised to 150 ° C., and the mixture was reacted for 3.5 hours while gradually reducing the pressure to distill off water.
  • poly-D-lactic acid was crystallized at 110 ° C. for 1 hour in a nitrogen atmosphere, and then at a pressure of 60 Pa, 140 ° C. for 3 hours, 150 ° C. for 3 hours, and 160 ° C. for 9 hours.
  • Solid phase polymerization was carried out to obtain poly-D-lactic acid (PDA2).
  • PDA2 had a weight average molecular weight of 7 million, a dispersity of 1.5, and a melting point of 161 ° C.
  • PDA3 poly-D-lactic acid
  • PDA3 had a weight average molecular weight of 130,000, a dispersity of 1.6, and a melting point of 164 ° C.
  • Reference Example 7 In a reaction vessel equipped with a stirrer and a reflux device, 50 parts of a 90% D-lactic acid aqueous solution was placed, the temperature was adjusted to 150 ° C., and the mixture was reacted for 3.5 hours while gradually reducing the pressure to distill off water.
  • poly-D-lactic acid was subjected to crystallization treatment at 110 ° C. for 1 hour in a nitrogen atmosphere, and then at a pressure of 60 Pa for 3 hours at 140 ° C., 3 hours at 150 ° C., and 18 hours at 160 ° C. Solid phase polymerization was carried out to obtain poly-D-lactic acid (PDA4).
  • A) Polylactic acid resin A-1: Polylactic acid stereocomplex obtained in Reference Example 8 (mixture of poly-L-lactic acid and poly-D-lactic acid) (Mw 110,000, dispersity 2.7)
  • A-2: Polylactic acid block copolymer obtained in Reference Example 9 (Mw 130,000, dispersity 2.4)
  • A-3: Polylactic acid stereocomplex obtained in Reference Example 10 (mixture of poly-L-lactic acid and poly-D-lactic acid) (Mw 130,000, dispersity 2.6)
  • A-4: Polylactic acid block copolymer obtained in Reference Example 11 (Mw 160,000, dispersity 2.3)
  • A-5: Polylactic acid stereocomplex obtained in Reference Example 12 (mixture of poly-L-lactic acid and poly-D-lactic acid) (Mw 40,000, dispersity 1.8)
  • polylactic acid stereocomplex (A-1) was melt-kneaded at a kneading temperature of 210 ° C. under reduced pressure to obtain polylactic acid stereocomplex (A-1).
  • the polylactic acid stereocomplex (A-1) had a weight average molecular weight of 110,000, a dispersity of 2.7, a melting point of 211 ° C., and a stereocomplex formation rate of 100%.
  • Reference Example 9 The polylactic acid stereocomplex (A-1) obtained in Reference Example 8 was subjected to crystallization treatment at 110 ° C. for 1 hour in a nitrogen atmosphere, and then at a pressure of 60 Pa at 140 ° C. for 3 hours and at 150 ° C. for 3 hours.
  • a polylactic acid block copolymer (A-2) had a weight average molecular weight of 130,000, a dispersity of 2.4, a melting point of 211 ° C., and a stereocomplex formation rate of 100%.
  • a polylactic acid stereocomplex (A-3) was obtained by melt kneading in the same manner as in Reference Example 8 except that 70 parts by weight of PLA3 and 30 parts by weight of PDA1 supplied to the twin screw extruder were used.
  • the polylactic acid stereocomplex (A-3) had a weight average molecular weight of 130,000, a dispersity of 2.6, melting points of 214 ° C and 151 ° C double peaks, and a stereocomplex formation rate of 95%.
  • the polylactic acid stereocomplex (A-3) obtained in Reference Example 10 was subjected to solid phase polymerization in the same manner as in Reference Example 9 to obtain a polylactic acid block copolymer (A-4).
  • the polylactic acid block copolymer (A-4) had a weight average molecular weight of 160,000, a dispersity of 2.3, melting points of double peaks of 215 ° C. and 171 ° C., and a stereocomplex formation rate of 97%.
  • a polylactic acid stereocomplex (A-5) is obtained by melt-kneading in the same manner as in Reference Example 10 except that PLA-1 is the poly-L-lactic acid to be melt-kneaded by a twin screw extruder and PDA1 is the poly-D-lactic acid.
  • the polylactic acid stereocomplex (A-5) had a weight average molecular weight of 40,000, a dispersity of 1.8, a melting point of 215 ° C., and a stereocomplex formation rate of 100%.
  • the polylactic acid stereocomplex (A-5) obtained in Reference Example 12 was subjected to solid phase polymerization in the same manner as in Reference Example 9 to obtain a polylactic acid block copolymer (A-6).
  • the polylactic acid block copolymer (A-6) had a weight average molecular weight of 60,000, a dispersity of 1.6, a melting point of 215 ° C., and a stereocomplex formation rate of 100%.
  • a polylactic acid stereocomplex (A-7) is obtained by melt-kneading in the same manner as in Reference Example 10 except that PLA-2 is used as the poly-L-lactic acid to be melt-kneaded by a twin screw extruder and PDA1 is used as the poly-D-lactic acid.
  • the polylactic acid stereocomplex (A-7) had a weight average molecular weight of 100,000, a degree of dispersion of 2.2, melting points of 213 ° C. and 152 ° C. double peaks, and a stereo complex formation rate of 96%.
  • the polylactic acid stereocomplex (A-7) obtained in Reference Example 14 was subjected to solid phase polymerization in the same manner as in Reference Example 9 to obtain a polylactic acid block copolymer (A-8).
  • the polylactic acid block copolymer (A-8) had a weight average molecular weight of 120,000, a dispersity of 2.0, melting points of 212 ° C. and 170 ° C. double peaks, and a stereocomplex formation rate of 98%.
  • a polylactic acid stereocomplex (A-9) was prepared by melt kneading in the same manner as in Reference Example 10 except that PLA-2 was used as the poly-L-lactic acid to be melt-kneaded by a twin screw extruder and PDA2 was used as the poly-D-lactic acid.
  • the polylactic acid stereocomplex (A-9) had a weight average molecular weight of 120,000, a dispersity of 2.4, melting points of 212 ° C and 160 ° C double peaks, and a stereocomplex formation rate of 93%.
  • the polylactic acid stereocomplex (A-9) obtained in Reference Example 16 was subjected to solid phase polymerization in the same manner as in Reference Example 9 to obtain a polylactic acid block copolymer (A-10).
  • the polylactic acid block copolymer (A-10) had a weight average molecular weight of 140,000, a degree of dispersion of 2.2, melting points of 212 ° C. and 171 ° C. double peaks, and a stereocomplex formation rate of 95%.
  • a polylactic acid stereocomplex (A-11) is obtained by melt-kneading in the same manner as in Reference Example 10 except that PLA-2 is used as the poly-L-lactic acid to be melt-kneaded by a twin screw extruder and PDA3 is used as the poly-D-lactic acid.
  • the polylactic acid stereocomplex (A-11) had a weight average molecular weight of 130,000, a dispersity of 2.5, melting points of 210 ° C and 165 ° C double peaks, and a stereocomplex formation rate of 55%.
  • a polylactic acid stereocomplex (A-13) is obtained by melt-kneading in the same manner as in Reference Example 10 except that PLA-3 is the poly-L-lactic acid to be melt-kneaded with a twin screw extruder and PDA2 is the poly-D-lactic acid.
  • the polylactic acid stereocomplex (A-13) had a weight average molecular weight of 150,000, a dispersity of 2.6, melting points of 211 ° C. and 161 ° C. double peaks, and a stereocomplex formation rate of 90%.
  • the polylactic acid stereocomplex (A-13) obtained in Reference Example 20 was subjected to solid phase polymerization in the same manner as in Reference Example 9 to obtain a polylactic acid block copolymer (A-14).
  • the polylactic acid block copolymer (A-14) had a weight average molecular weight of 170,000, a degree of dispersion of 2.4, melting points of 212 ° C. and 171 ° C. double peaks, and a stereocomplex formation rate of 95%.
  • a polylactic acid stereocomplex (A-15) was prepared by melt kneading in the same manner as in Reference Example 10 except that PLA3 was used as the poly-L-lactic acid to be melt-kneaded by a twin screw extruder and PDA3 was used as the poly-D-lactic acid.
  • the polylactic acid stereocomplex (A-15) had a weight average molecular weight of 170,000, a dispersity of 2.4, melting points of 212 ° C. and 168 ° C. double peaks, and a stereocomplex formation rate of 60%.
  • PLA4 had a weight average molecular weight of 80,000, a dispersity of 1.6, and a melting point of 168 ° C.
  • the ratio of the weight average molecular weight of the segment consisting of L-lactic acid units constituting the polylactic acid block copolymer A-17 to the weight average molecular weight of the segment consisting of D-lactic acid units was 2.7.
  • PLA 3 obtained in Reference Example 3 and PDA 4 obtained in Reference Example 7 were melt kneaded in the same manner as in Reference Example 8 to obtain a polylactic acid stereocomplex (A-19).
  • the polylactic acid stereocomplex (A-19) had a weight average molecular weight of 170,000, a dispersity of 1.7, melting points of 220 ° C. and 169 ° C. double peaks, and a stereocomplex formation rate of 55%.
  • B Polymer having a plurality of reactive groups per molecule
  • B-1 Acrylic resin-based reactive compound: Epoxy group-containing styrene / acrylic acid ester copolymer ("JONCRYL” (registered trademark) manufactured by BASF Japan Ltd.) ADR-4368, Mw (PMMA equivalent) 8,000, epoxy equivalent 285 g / mol)
  • B-2 Polycarbodiimide (“Carbodilite” (registered trademark) HMV-8CA, manufactured by Nisshinbo Chemical Co., Ltd.), Mw (PMMA conversion) 3,000, carbodiimide equivalent 278 g / mol)
  • B-3 Polycarbodiimide (manufactured by Nisshinbo Chemical Co., Ltd.
  • the pellet of the polylactic acid resin composition was heated at 240 ° C. for 2 minutes to melt, and then pressed at a press temperature of 80 ° C. to produce a 1 mm thick press sheet.
  • the press sheet was heat-treated at 110 ° C. for 30 minutes under a nitrogen atmosphere to obtain sheet-like molded bodies for various measurements.
  • the physical properties of the polylactic acid resin composition and the molded body obtained by melt kneading are as shown in Tables 1 and 2.
  • polylactic acid block copolymer A-2 was used as polylactic acid resin (A), and in Examples 5 to 8, polylactic acid block copolymer A-4 was used.
  • Acrylic resin-based reactive compounds (B-1) having different addition amounts were added as a polymer (B) having a plurality of reactive groups per molecule, and melt kneading was performed.
  • the amount of the acrylic resin-based reactive compound increased and the weight average molecular weight of the polylactic acid resin composition increased.
  • the polylactic acid resin composition had excellent crystallization characteristics with a temperature-falling crystallization temperature of 140 ° C.
  • melt viscosity ratio MFR10 / MFR20
  • Examples 9 to 14 the type of polylactic acid resin (A) was changed as shown in Table 1 to produce a polylactic acid resin composition.
  • any polylactic acid resin could be used as an acrylic resin.
  • the system reactive compound (B-1) the increase in molecular weight and the retention stability during heating were shown as in Examples 1-8.
  • thermophysical properties the temperature-falling crystallization temperature was 130 ° C. or higher, and it was found that the crystallization characteristics were excellent.
  • the haze value of the molded product was less than 10% and excellent in transparency, and showed good mechanical properties in terms of tensile strength and storage elastic modulus.
  • Example 15 a polylactic acid resin composition was prepared using polycarbodiimide (B-3) as a polymer (B) having a plurality of reactive groups per molecule, but by reaction with polycarbodiimide. Increased molecular weight and retention stability during heating were obtained.
  • polylactic acid was added to the polylactic acid resin (A-4) by adding crystal nucleating agents D-1 to D-3 in addition to the acrylic resin reactive compound (B-1).
  • Resin compositions were prepared, and any of the polylactic acid resin compositions showed an increase in molecular weight and a residence stability upon heating due to the reaction with the acrylic resin-based reactive compound (B-1). Further, in terms of thermophysical properties, since the temperature drop crystallization temperature was 130 ° C. or higher and the crystallization enthalpy ( ⁇ Hc) was 37 J / g or higher, it was found that heat resistance and crystallization characteristics were excellent.
  • haze value of the molded product was 12% or less and excellent transparency, and showed good mechanical properties in terms of tensile strength and storage elastic modulus.
  • a polylactic acid resin composition and a molded body pelletized by the same method as in Examples 1 to 18 were obtained.
  • the physical properties of the polylactic acid resin composition and the molded product obtained by melt kneading are as shown in Table 3 and Table 4.
  • Comparative Examples 1 to 4 the acrylic resin-based reactive compound (B-1) was added at 0.03 parts by weight and 2.5 parts by weight with respect to 100 parts by weight of the polylactic acid resin A-2 or A-4, respectively. Is. As a result, in Comparative Examples 1 and 3, the melt viscosity ratio (MFR10 / MFR20) was less than 0.5 even after the reaction with the acrylic resin-based reactive compound (B-1), compared with Examples 1 to 13. It was found that the residence stability during heating was low. On the other hand, in Comparative Examples 2 and 4, after the reaction with the acrylic resin-based reactive compound (B-1), the polylactic acid resin composition was gelled, and the melt viscosity ratio (MFR10 / MFR20) was 1 or more. . The polylactic acid resin compositions of Comparative Examples 2 and 4 could not be processed into molded articles due to gelation.
  • polylactic acid resin compositions were prepared using polylactic acid stereocomplexes or polylactic acid block copolymers shown in Tables 3 and 4 as polylactic acid resin (A).
  • polylactic acid resin (A) the weight average molecular weight increased due to the reaction with the acrylic resin-based reactive compound (B-1)
  • the melt viscosity ratio (MFR10 / MFR20) was 0.45 to 0,59, which was inferior in residence stability during heating as compared with the polylactic acid block copolymers shown in Examples 3, 7 and 9-11.
  • Comparative Examples 10 to 15 in any case, an increase in the weight average molecular weight is observed by adding the acrylic resin-based reactive compound (B-1) as the polymer (B) having a plurality of reactive groups in one molecule.
  • the crystallization enthalpy ⁇ Hc at the temperature-falling crystallization temperature was less than 10 J / g and the crystallization characteristics were poor.
  • the melt viscosity ratio (MFR10 / MFR20) is compared with the examples using the polylactic acid block copolymer. The result was low and the stability of the melt viscosity was poor.
  • the haze value of the molded products was 10% or more at any level of Comparative Examples 10 to 15, and the transparency was inferior to the Examples.
  • the polylactic acid stereocomplex A-19 was used for the polylactic acid resin (A), and in addition to the acrylic resin reactive compound (B-1), the crystal nucleating agent (D-1) to ( A polylactic acid resin composition was prepared by adding D-3).
  • the stereocomplex formation rate (Sc) of these polylactic acid resin compositions is less than 70%, the heat resistance is low compared to the examples, and the crystallization characteristics are also inferior as in the comparative examples 17-19.
  • the heat loss at 240 ° C. for 30 minutes was as high as 9% or more, and the residence stability was low.
  • the haze values of these molded products were also 10% or more, and the transparency was low as compared with the Examples.
  • the kneaded material kneaded as described above was subjected to crystallization treatment at 110 ° C. for 1 hour in a nitrogen atmosphere, followed by solid phase polymerization at 150 ° C. for 24 hours under a pressure of 60 Pa to obtain a polylactic acid resin composition. Obtained.
  • sheet-like molded bodies were produced in the same manner as in Examples 1 to 18.
  • Table 5 shows the physical properties of the polylactic acid resin composition and the molded body.
  • Example 21 The polylactic acid stereocomplex (A-3) obtained in Reference Example 10 and the acrylic resin-based reactive compound (B-1) were added from the resin supply port of the twin screw extruder and melt kneaded. The element configuration and temperature setting of the extruder are as described in Examples 19 and 20. Subsequently, the kneaded product after melt-kneading was subjected to solid phase polymerization by the method described in Examples 19 and 20. In addition, a sheet-like molded body was produced in the same manner as in Examples 1-18. Table 5 shows the physical properties of the polylactic acid resin composition and the molded body.
  • the resin supply port of the twin screw extruder was added in advance with the polylactic acid block copolymer (A-4) and the acrylic resin-based reactive compound (B-1) added in the amounts shown in Table 5.
  • the mixture was obtained by further adding and melt-kneading.
  • the polylactic acid resin composition was produced by adding the said mixture and PLA3 and PDA4 with the addition amount shown in Table 5 with respect to the resin supply port of a twin-screw extruder, and melt-kneading.
  • solid phase polymerization was not performed after kneading the polylactic acid resin composition.
  • sheet molded bodies were produced in the same manner as in Examples 1 to 18.
  • Table 5 shows the physical properties of the obtained polylactic acid resin composition and molded article.
  • a polylactic acid resin composition was prepared by preparing a kneaded material using a twin screw extruder in the same manner as in Examples 20 and 21. In Comparative Examples 24 and 25, the kneaded product was not subjected to solid phase polymerization.
  • sheet-like molded bodies were produced in the same manner as in Examples 1 to 19.
  • PLA3, PDA1 and the acrylic resin-based reactive compound (B-1) were solid-phase polymerized after melt kneading all together without preparing a polylactic acid block copolymer in advance as a polylactic acid resin.
  • the polylactic acid resin composition has a weight average molecular weight increased by reaction with the acrylic resin-based reactive compound (B-1), and the heat loss at 240 ° C. for 30 minutes is less than 1%, and the melt viscosity ratio (MFR10 / MFR20 ) was also less than 0.5 to 1 and was excellent in retention stability during heating.
  • the stereocomplex formation rate (Sc) was 90% or higher, and the heat resistance was high, and the temperature-falling crystallization temperature and crystallization enthalpy were also high, indicating that the crystallization characteristics were excellent.
  • the haze value of the molded product was also low, less than 10%, so that it was excellent in transparency and exhibited good mechanical properties in terms of tensile strength and storage elastic modulus.
  • Example 21 unlike Examples 1 to 18, when the acrylic resin-based reactive compound (B-1) was added before solid-phase polymerization, the polylactic acid resin composition was acrylic as in Examples 1 to 18.
  • the temperature-falling crystallization temperature was 130 ° C. or higher and the crystallization enthalpy was as high as 35 J / g or more, so that it was found that the crystallization characteristics were excellent.
  • the haze value of the molded product was 9%, which was excellent in transparency, and exhibited good mechanical properties in terms of tensile strength and storage elastic modulus.
  • the physical properties of the obtained polylactic acid resin compositions were increased by the reaction with the acrylic resin-based reactive compound (B-1) as in Examples 1 to 18, and the melt was melted.
  • the viscosity ratio (MFR10 / MFR20) was also 0.5 to less than 1, and the residence stability during heating was excellent.
  • the thermophysical properties the stereocomplex formation rate (Sc) was 90% or higher, and the heat resistance was high, and the temperature-falling crystallization temperature and crystallization enthalpy were also high, indicating that the crystallization characteristics were excellent.
  • the haze value of the molded product was also low, less than 10%, so that it was excellent in transparency and exhibited good mechanical properties in terms of tensile strength and storage elastic modulus.
  • the polylactic acid resin composition of the present invention has improved mechanical properties, durability, stability during heating, and heat resistance due to the thickening effect of the polymer having a plurality of reactive groups in one molecule. Also, since it has excellent crystallization characteristics, it can be suitably used in fields that require heat resistance, crystallization characteristics, and retention stability during heating.

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Abstract

L'invention concerne une composition de résine d'acide polylactique ainsi qu'un procédé de fabrication de cette composition qui est constituée par mélange d'un polymère possédant une pluralité de groupes réactifs par molécule, et d'un copolymère séquencé d'acide polylactique configuré par un segment poly-acide lactique L ayant un acide lactique L pour composant principal, et un segment poly-acide lactique D ayant un acide lactique D pour composant principal. Plus précisément, l'invention fournit une composition de résine d'acide polylactique ainsi qu'un procédé de fabrication de celle-ci et un article moulé. La composition de résine d'acide polylactique présente une amélioration des propriétés mécaniques, de la durabilité et de la stabilité au stockage en mode chauffage, et est excellente en termes de résistance à la chaleur et de caractéristiques de cristallisation.
PCT/JP2014/052384 2013-02-19 2014-02-03 Composition de résine d'acide polylactique ainsi que procédé de fabrication de celle-ci, et article moulé WO2014129293A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020144235A1 (fr) * 2019-01-09 2020-07-16 Purac Biochem B.V. Thermoformage d'articles à base de pla

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2906024T3 (es) * 2014-12-22 2022-04-12 Purac Biochem Bv Artículo de polilactida moldeado y procedimiento de preparación
TWI605069B (zh) * 2016-10-04 2017-11-11 Yan-Ru Zhou Polylactic acid foaming molding material, foamed molded article and manufacturing method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006265399A (ja) * 2005-03-24 2006-10-05 Toagosei Co Ltd 脂肪族ポリエステル樹脂組成物
JP2009079124A (ja) * 2007-09-26 2009-04-16 Unitika Ltd 生分解性ポリエステル樹脂組成物およびそれからなる成形体
JP2010222556A (ja) * 2009-02-24 2010-10-07 Kaneka Corp 熱可塑性樹脂組成物
JP2011052149A (ja) * 2009-09-03 2011-03-17 Osaka Gas Co Ltd ポリ乳酸樹脂組成物
JP2012177011A (ja) * 2011-02-25 2012-09-13 Toray Ind Inc ポリ乳酸組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006265399A (ja) * 2005-03-24 2006-10-05 Toagosei Co Ltd 脂肪族ポリエステル樹脂組成物
JP2009079124A (ja) * 2007-09-26 2009-04-16 Unitika Ltd 生分解性ポリエステル樹脂組成物およびそれからなる成形体
JP2010222556A (ja) * 2009-02-24 2010-10-07 Kaneka Corp 熱可塑性樹脂組成物
JP2011052149A (ja) * 2009-09-03 2011-03-17 Osaka Gas Co Ltd ポリ乳酸樹脂組成物
JP2012177011A (ja) * 2011-02-25 2012-09-13 Toray Ind Inc ポリ乳酸組成物

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020144235A1 (fr) * 2019-01-09 2020-07-16 Purac Biochem B.V. Thermoformage d'articles à base de pla
CN113286692A (zh) * 2019-01-09 2021-08-20 普拉克生化公司 基于pla的制品的热成型
CN113286692B (zh) * 2019-01-09 2023-12-26 普拉克生化公司 基于pla的制品的热成型

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