JP2012177011A - Polylactic acid composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polylactic acid composition and a molding composed of the polylactic acid composition, and concretely, to feed a polylactic acid composition including a polylactic acid resin which has excellent fluidity and moldability, and to feed a molding composed of the polylactic acid composition.SOLUTION: The polylactic acid composition is obtained by blending (B) a fluidity modifier of 0.01 to 50 pts.wt. to (A) 100 pts.wt. of a polylactic acid resin composed of poly-L-lactic acid and poly-D-lactic acid. As the fluidity modifier, any one selected from a compound having three or more functional groups, an acrylic compound, a branched polymer, a liquid crystal polymer, low molecular weight linear polyester, low molecular weight linear polycarbonate and an aromatic series low molecular weight compound is preferable.

Description

  The present invention relates to a polylactic acid composition and a molded article comprising the same, and more particularly to a polylactic acid composition containing a polylactic acid resin excellent in fluidity and moldability and a molded article comprising the same.

  Polylactic acid is a polymer that is melt-moldable with excellent transparency and has characteristics of biodegradability. After use, it is decomposed in the natural environment and released as carbon dioxide or water. Development has been promoted. On the other hand, in recent years, 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. Furthermore, 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. However, 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. .

  As one means for solving such problems, attention has been paid to the use of a polylactic acid resin forming a stereocomplex. The polylactic acid resin forming the stereocomplex is formed by mixing optically active poly-L-lactic acid and poly-D-lactic acid, and this melting point is 50 ° C. higher than the melting point 170 ° C. of the polylactic acid homopolymer. It reaches 220 ° C. For this reason, application as a high melting point and highly crystalline fiber, film, and resin molded product is tried.

  However, since the polylactic acid resin forming the stereocomplex has a greatly improved melting point, it is necessary to set the molding processing temperature to be proportionally higher, which causes a new problem of thermal decomposition during the molding processing. The generation of gas and the decrease in molecular weight due to thermal decomposition may cause a decrease in the appearance and mechanical properties of the molded product. In addition, by reducing the processing temperature at the time of molding, thermal decomposition is suppressed, but due to an increase in melt viscosity, filling of the mold becomes insufficient, and the intended molded product cannot be obtained. There is a demand for improvement in fluidity due to a decrease in melt viscosity of a polylactic acid resin forming a stereocomplex.

  In Patent Document 1, as a fluidity improver, a branched polymer, a liquid crystal polymer, a low molecular weight linear polyester, a low molecular weight linear polycarbonate, an aromatic low molecular compound, an acrylic compound, or three or more hydroxyl groups or amino groups Although the description regarding the resin composition in which a functional group such as poly-L-lactic acid, poly-D-lactic acid, or a polylactic acid resin forming a stereocomplex is added is described in the text, the addition of a fluidity improver There is no description regarding the amount, and in all the examples, no fluidity improver was added, so the effect was unclear.

  Patent Document 2 describes a polylactic acid resin composition in which a liquid crystal polymer is added to a polylactic acid resin that forms a stereocomplex, but there is no description regarding fluidity and moldability. There is no suggestion of improvement.

  Patent Document 3 describes in the text a fiber in which 0.1 to 1.0% by weight of a dendritic polyester is added to a matrix composed of a polylactic acid resin forming a stereocomplex. Examples include PET and It only describes poly-L-lactic acid and does not describe any effect on polylactic acid resin forming a stereocomplex. Further, although there is a description regarding improvement in fluidity at the time of melt spinning, there is no description regarding moldability, and there is no suggestion about improvement of moldability.

  Patent Document 4 describes a polylactic acid resin composition in which fluidity is improved by adding a surface-treated flame retardant to a polylactic acid resin that forms a stereo complex. Although the fluidity is improved as compared with a flame retardant not subjected to the treatment, the effect is insufficient. In addition, the examples only describe poly-L-lactic acid, and do not describe any effect on the polylactic acid resin forming the stereocomplex.

JP 2009-155490 A JP 2010-180374 A JP 2009-52160 A JP 2010-70722 A

  The present invention relates to a polylactic acid composition and a molded article comprising the same, and more specifically, an object thereof is to supply a polylactic acid composition containing a polylactic acid resin having excellent fluidity and moldability and a molded article comprising the same. .

  As a result of intensive studies to solve the above problems, the present inventors have found that (A) 100 parts by weight of a polylactic acid resin composed of poly-L-lactic acid and poly-D-lactic acid is (B) a fluidity improver. It was found that by blending 0.01 to 50 parts by weight, a polylactic acid composition having excellent fluidity and excellent moldability, which could not be achieved by conventional knowledge, can be obtained. The invention has been reached.

That is, the present invention is as follows.
[1] A polylactic acid composition comprising (A) 0.01 to 50 parts by weight of a flow improver for 100 parts by weight of a polylactic acid resin comprising poly-L-lactic acid and poly-D-lactic acid. Product [2] In DSC measurement, the resin composition was heated to 250 ° C. and kept at a constant temperature for 3 minutes, and then the constant temperature crystallization temperature when the temperature was lowered at a cooling rate of 20 ° C./minute was 120 ° C. or higher, 30 The polylactic acid composition according to the above [1], wherein the stereocomplex crystal has a melting point of 200 ° C. or higher when the temperature is lowered to 250 ° C. at a temperature rising rate of 20 ° C./min. 3] (A) The polylactic acid resin has a weight average molecular weight of 100,000 or more, and (B) the melt viscosity after blending the fluidity improver is (B) the melt viscosity before blending the fluidity improver [1] [2] The polylactic acid composition according to any one of [4] (A), wherein the polylactic acid resin is a block copolymer composed of a segment composed of poly-L-lactic acid and a segment composed of poly-D-lactic acid. The polylactic acid composition [5] (A), wherein the polylactic acid resin according to any one of [1] to [3] is a segment composed of poly-L-lactic acid and poly-D-lactic acid In the block copolymer composed of the segment, the ratio of the weight average molecular weight of the segment composed of poly-L-lactic acid and the weight average molecular weight of the segment composed of poly-D-lactic acid is 1.5 or more and less than 30, The polylactic acid composition [6] (B) fluidity improver according to the above [4], wherein the molecular weight of the compound is a compound having three or more functional groups, an acrylic compound, Branched poly -The liquid crystal polymer, low molecular weight linear polyester, low molecular weight linear polycarbonate, or any one selected from aromatic low molecular weight compounds, the above-mentioned [1] to [5] The polylactic acid composition [7] according to any one of [1] to [6], wherein 1 to 100 parts by weight of (C) a crystallization accelerator is blended with 100 parts by weight of (A) polylactic acid resin. Any one of the above [1] to [7], wherein the polylactic acid composition [8] according to any one of (A) 1 to 100 parts by weight of the filler is blended with 100 parts by weight of the polylactic acid resin. [9] Any of the above [1] to [8], wherein the polylactic acid composition [9] (A) 100 parts by weight of the polylactic acid resin is blended with 1 to 100 parts by weight of the (E) impact modifier. The polylactic acid composition according to [10] (A) 100 parts by weight of the polylactic acid resin (G) The polylactic acid composition according to any one of [1] to [9] above, wherein 1 to 100 parts by weight of a flame retardant is blended [11] any one of [1] to [10] A molded article comprising the polylactic acid composition described in 1.

  According to the present invention, it is possible to supply a polylactic acid composition containing a polylactic acid resin excellent in fluidity and moldability, and a molded article comprising the same.

  Hereinafter, the polylactic acid composition of the present invention will be specifically described.

<Polylactic acid resin (A)>
The polylactic acid resin (A) of the present invention is a segment comprising poly-L-lactic acid in which poly-L-lactic acid and poly-D-lactic acid are melt-kneaded or the unit derived from L-lactic acid is 70% or more. It shows a block copolymer composed of segments composed of poly-D-lactic acid whose D-lactic acid-derived unit is 70% or more.

  Here, poly-L-lactic acid is a polymer containing L-lactic acid as a main component, and preferably contains 70 mol% or more of L-lactic acid units, and contains 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.

  In the present invention, poly-L-lactic acid or poly-D-lactic acid may contain other component units as long as the performance of the resulting polylactic acid resin is not impaired. Examples of component units other than L-lactic acid or D-lactic acid units include polycarboxylic acids, polyhydric alcohols, hydroxycarboxylic acids, lactones, and the like. Specifically, 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, polypropylene glycol or their derivatives, glycolic acid, 3-hydroxybutyric acid, 4-hydroxy Hydroxycarboxylic acids such as butyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid, and glycolide, ε-caprolactone glycolide, ε-caprolactone, β-propiolactone, δ-butyrolactone, β- or γ-butyrolactone, pivalolactone, and lactones such as δ-valerolactone.

  The weight average molecular weight of the polylactic acid resin used in the present invention is not particularly limited, but is preferably 90,000 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. Moreover, the dispersity 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 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.

  Furthermore, the polylactic acid resin used by this invention has melting | fusing point based on a stereocomplex crystal in the range of 190-230 degreeC by stereocomplex formation. 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. Moreover, it may have melting | fusing point based on a poly-L-lactic acid single crystal and a poly-D-lactic acid single crystal in the range of 150 to 185 ° C.

The polylactic acid resin preferably has a stereocomplex formation rate (Sc) of 60% or more, more preferably 70% or more, further preferably 75 to 100%, and more preferably 90 to 100%. It is particularly preferred. Here, the stereocomplex formation rate is the ratio of the stereocomplex crystals in all the crystals in polylactic acid. Specifically, the amount of heat based on crystal melting of poly-L-lactic acid single crystal and poly-D-lactic acid single crystal measured by a differential scanning calorimeter (DSC) is ΔHl, and the amount of heat based on crystal melting of stereocomplex crystals. Can be calculated by the following formula (1).
Sc = ΔHh / (ΔHl + ΔHh) × 100 (1)

  In the present invention, the total weight ratio of poly-L-lactic acid and poly-D-lactic acid is preferably 80:20 to 20:80, and more preferably 75:25 to 25:75. Further, it is preferably 70:30 to 30:70, and most preferably 60:40 to 40:60. When the weight ratio of the segment composed of L-lactic acid units is less than 20% by weight or more than 80% by weight, the increase in the melting point of the obtained polylactic acid resin becomes small and it becomes difficult to form a polylactic acid stereocomplex. Produces a trend.

  Next, the polymerization method of poly-L-lactic acid and poly-D-lactic acid will be described in detail.

  Examples of a method for obtaining poly-L-lactic acid and poly-D-lactic acid by ring-opening polymerization include a method of performing ring-opening polymerization in the presence of a catalyst for either L-lactide or D-lactide. it can.

  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.

  When obtaining a polylactic acid block copolymer by the ring-opening polymerization method, the amount of water in the reaction system is 4 mol% or less based on the total amount of L-lactide and D-lactide from the viewpoint of obtaining a high molecular weight product. preferable. 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.

  Examples of the polymerization catalyst for producing poly-L-lactic acid or poly-D-lactic acid by a 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. Specifically, 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 sulfonate tin (II), bis (methane sulfonate) tin (II), tin sulfate (II), tin oxide (II), tin oxide (IV), tin sulfide (II), tin sulfide (IV), oxidation Dimethyltin (IV), methylphenyltin (IV) oxide, dibuty oxide Tin (IV), dioctyl tin (IV) oxide, diphenyl tin (IV) oxide, tributyl tin oxide, triethyl tin hydroxide (IV), triphenyl tin hydroxide (IV), tributyl tin hydride, monobutyl tin (IV) Oxide, tetramethyltin (IV), tetraethyltin (IV), tetrabutyltin (IV), dibutyldiphenyltin (IV), tetraphenyltin (IV), tributyltin (IV) acetate, triisobutyltin (IV) acetate, Triphenyltin acetate (IV), dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin (IV) dilaurate, dibutyltin (IV) maleate, dibutyltin bis (acetylacetonate), tributyltin chloride (IV), Dibutyltin dichloride, monobutyltin trichloride, dioctyltin dichloride, triphenyltin (IV) chloride, sulfide Butyltin, tributyltin sulfate, tin (II) methanesulfonate, tin (II) ethanesulfonate, tin (II) trifluoromethanesulfonate, ammonium hexachlorotin (IV), dibutyltin sulfide, diphenyltin sulfide and triethyl sulfate Examples thereof include tin compounds such as tin and phthalocyanine tin (II). Also, titanium methoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium isobutoxide, titanium cyclohexyl, titanium phenoxide, titanium chloride, titanium diacetate, titanium triacetate, titanium tetraacetate, titanium (IV) oxide, etc. Titanium compounds, lead diisopropoxy (II), lead monochloride, lead acetate, lead (II) octylate, lead (II) isooctanoate, lead (II) isononanoate, lead (II) laurate, lead oleate (II), lead compounds such as lead (II) linoleate, lead naphthenate, lead (II) neodecanoate, lead oxide, lead (II) sulfate, zinc powder, methyl propoxy zinc, zinc chloride, zinc acetate, octylic acid Zinc (II), zinc naphthenate, zinc carbonate, zinc oxide, zinc sulfate and other zinc compounds, chloride Baltic, cobalt acetate, cobalt (II) octylate, cobalt (II) isooctanoate, cobalt (II) isononanoate, cobalt (II) laurate, cobalt (II) oleate, cobalt (II) linoleate, cobalt naphthenate , Cobalt compounds such as cobalt (II) neodecanoate, cobaltous carbonate, cobaltous sulfate, cobalt (II) oxide, iron (II) chloride, iron (II) acetate, iron (II) octylate, iron naphthenate Iron compounds such as iron carbonate (II), iron sulfate (II), iron oxide (II), propoxy lithium, lithium chloride, lithium acetate, lithium octylate, lithium naphthenate, lithium carbonate, dilithium sulfate, lithium oxide, etc. Lithium compounds, triisopropoxy europium (III), triisopropoxy neo (III), triisopropoxylantan, triisopropoxy samarium (III), triisopropoxy yttrium, isopropoxy yttrium, dysprosium chloride, europium chloride, lanthanum chloride, neodymium chloride, samarium chloride, yttrium chloride, dysprosium triacetate (III ), Europium triacetate (III), lanthanum acetate, neodymium triacetate, samarium acetate, yttrium triacetate, dysprosium carbonate (III), dysprosium carbonate (IV), europium carbonate (II), lanthanum carbonate, neodymium carbonate, samarium carbonate ( II), samarium carbonate (III), yttrium carbonate, dysprosium sulfate, europium (II) sulfate, lanthanum sulfate, neodymium sulfate, samarium sulfate, yttrium sulfate, yttrium dioxide Examples include rare earth compounds such as europium, lanthanum oxide, neodymium oxide, samarium (III) oxide, and yttrium oxide. In addition, potassium compounds such as potassium isopropoxide, potassium chloride, potassium acetate, potassium octylate, potassium naphthenate, tert-butyl potassium carbonate, potassium sulfate, potassium oxide, copper (II) diisopropoxide, copper chloride (II), copper acetate (II), copper octylate, copper naphthenate, copper sulfate (II), copper compounds such as dicopper carbonate, nickel chloride, nickel acetate, nickel octylate, nickel carbonate, nickel sulfate (II) Nickel compounds such as nickel oxide, tetraisopropoxyzirconium (IV), zirconium trichloride, zirconium acetate, zirconium octylate, zirconium naphthenate, zirconium carbonate (II), zirconium carbonate (IV), zirconium sulfate, zirconium oxide (II Zirconization , Antimony compounds such as triisopropoxyantimony, antimony fluoride (III), antimony fluoride (V), antimony acetate, antimony (III) oxide, magnesium, magnesium diisopropoxide, magnesium chloride, magnesium acetate, magnesium lactate , Magnesium compounds such as magnesium carbonate, magnesium sulfate, magnesium oxide, calcium compounds such as diisopropoxy calcium, calcium chloride, calcium acetate, calcium octylate, calcium naphthenate, calcium lactate, calcium sulfate, aluminum, aluminum isopropoxide, Aluminum compounds such as aluminum chloride, aluminum acetate, aluminum octylate, aluminum sulfate, aluminum oxide, germanium, tetri Germanium compounds such as propoxygermane and germanium (IV) oxide, manganese compounds such as triisopropoxymanganese (III), manganese trichloride, manganese acetate, manganese (II) octylate, manganese (II) naphthenate, and manganese sulfate And bismuth chloride (III), bismuth powder, bismuth oxide (III), bismuth acetate, bismuth octylate, bismuth neodecanoate, and the like. Also, sodium stannate, magnesium stannate, potassium stannate, calcium stannate, manganese stannate, bismuth stannate, barium stannate, strontium stannate, sodium titanate, magnesium titanate, aluminum titanate, potassium titanate, Compounds composed of two or more metal elements such as calcium titanate, cobalt titanate, zinc titanate, manganese titanate, zirconium titanate, bismuth titanate, barium titanate and strontium titanate are also preferred. 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. Specifically, 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 And 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-dimethylbenzenesulfonic acid, 2,5-dibutylbenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid , 5-amino-2 Methylbenzenesulfonic acid, 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, p-phenol Sulfonic acid, cumene sulfonic acid, xylene sulfonic acid, o-cresol sulfonic acid, m-cresol sulfonic acid, p-cresol sulfonic acid, p-toluene sulfonic acid, 2-naphthalene sulfonic acid, 1-naphthalene sulfonic acid, isopropyl naphthalene sulfone Acid, dodecylnaphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, 1,5-naphthalenedisulfonic acid, 2,7-naphthalenedisulfonic acid, 4,4-biphenyldisulfonic acid, anthraquinone-2-sulfonic acid, m- Benzene disulfonic acid, 2,5-diamino-1,3-benzenedisulfonic acid, aniline-2,4-disulfonic acid, anthraquinone-1,5-disulfonic acid, aromatic sulfonic acid such as polystyrene sulfonic acid, methanesulfonic acid, Ethanesulfonic acid, 1-propanesulfonic acid, n-octylsulfonic acid, pentadecylsulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, 1,2-ethanedisulfonic acid, 1,3-propanedisulfonic acid, aminomethanesulfone Acids, aliphatic sulfonic acids such as 2-aminoethanesulfonic acid, cyclopentanesulfonic acid, cyclohexanesulfonic acid and camphorsulfonic acid, sulfonic acid compounds such as alicyclic sulfonic acid such as 3-cyclohexylaminopropanesulfonic acid, aspartic acid And Acidic amino acids such as glutamic acid, phosphoric acid monoesters such as ascorbic acid, retinoic acid, phosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, monododecyl phosphate and monooctadecyl phosphate, didodecyl phosphate And phosphoric acid diesters such as dioctadecyl phosphate, phosphoric acid compounds such as phosphorous acid monoester and phosphite diester, boric acid, hydrochloric acid, sulfuric acid and the like. Further, 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. For example, as 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.

  In the present invention, when considering the molecular weight of the produced poly-L-lactic acid or poly-D-lactic acid, a metal catalyst is preferable as the polymerization catalyst, among which a tin compound, a titanium compound, an antimony compound, and a rare earth compound are more preferable. In consideration of the melting point of the polylactic acid produced, tin compounds and titanium compounds are more preferable. Further, in consideration of the thermal stability of the polylactic acid produced, a tin-based organic carboxylate or a tin-based halogen compound is preferable, and in particular, tin (II) acetate, tin (II) octylate, and tin chloride ( II) is more preferred.

  The addition amount of the polymerization catalyst is not particularly limited, and 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 0.001 part by weight or more and 1 part by weight or less. If the amount of the catalyst is less than 0.001 part by weight, the effect of shortening the polymerization time is lowered, and if it exceeds 2 parts by weight, the molecular weight of the finally obtained polylactic acid block copolymer tends not to increase. Moreover, when using 2 or more types of catalysts together, it is preferable that a total addition amount exists in said range.

  The addition timing of the polymerization catalyst is not particularly limited, but it is preferable to add the catalyst after heating and dissolving the lactide from the viewpoint of uniformly dispersing the catalyst in the system and increasing the polymerization activity.

  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.

  Moreover, as a polymerization catalyst at the time of manufacturing poly-L-lactic acid or poly-D-lactic acid using a direct polymerization method, the same metal catalyst and acid catalyst as the ring-opening polymerization method are mentioned.

  When considering the molecular weight of polylactic acid produced using a direct polymerization method, 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. Furthermore, in consideration of the thermal stability of the polylactic acid produced, in the case of a metal catalyst, 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, naphthalenedisulfonic acid, and 2-amino More preferred is ethanesulfonic acid. Further, 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 coloring can be suppressed. 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 one or more of methanesulfonic acid, ethanesulfonic acid, propanedisulfonic acid, naphthalene disulfonic acid, and 2-aminoethanesulfonic acid are more preferable. Tin (II) acetate and / or tin octylate (II) combined with any one of methanesulfonic acid, ethanesulfonic acid, propanedisulfonic acid, and 2-aminoethanesulfonic acid But more preferable.

  The addition amount of the polymerization catalyst is not particularly limited, and 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 0.001 part by weight or more and 1 part by weight or less. If the amount of the catalyst is less than 0.001 part by weight, the effect of shortening the polymerization time is lowered, and if it exceeds 2 parts by weight, the molecular weight of the finally obtained polylactic acid block copolymer tends not to increase. In addition, when two or more types of catalysts are used in combination, 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. In that case, it is preferable that the weight ratio of the tin compound and the sulfonic acid compound is 1: 1 to 1:30 in terms of maintaining high polymerization activity and suppressing coloration, and productivity. Is more preferably 1: 2 to 1:15.

  The timing for adding the polymerization catalyst is not particularly limited, but particularly when polylactic acid is polymerized by a direct polymerization method, adding the acid catalyst before dehydrating the raw material or the raw material is excellent in productivity. From the viewpoint of increasing the polymerization activity, it is preferable to add a metal catalyst after dehydrating the raw material.

  In order to further increase the molecular weight of poly-L-lactic acid or poly-D-lactic acid obtained by the direct polymerization method, it is preferable to carry out solid phase polymerization at a temperature lower than its melting point.

  When performing the solid phase polymerization step, it is necessary that the poly-L-lactic acid or poly-D-lactic acid is crystallized, and the crystallization treatment is performed after the melt polymerization step and before the solid phase polymerization step. Do.

  As a method for crystallization, a method of heat treatment at a crystallization temperature in a gas phase such as nitrogen or air or a liquid phase such as water or ethanol, a solution obtained by dissolving poly-L-lactic acid or poly-D-lactic acid in a solvent, And then evaporating the solvent, contacting poly-L-lactic acid or poly-D-lactic acid with the solvent, and performing a stretching or shearing operation on the molten poly-L-lactic acid or poly-D-lactic acid. The method of cooling and solidifying is mentioned. Among the above methods, there are a method of heat treatment at a crystallization temperature in a gas phase of nitrogen, and a method of cooling and solidifying molten poly-L-lactic acid or poly-D-lactic acid while performing stretching or shearing operations. preferable. Moreover, you may combine said several method.

  The cooling method for cooling and solidifying molten poly-L-lactic acid or poly-D-lactic acid while performing stretching or shearing operations is preferably water cooling, and the time of contact with water is preferably within 10 minutes. Within a minute is more preferable, and within 3 minutes is still more preferable. The time from cooling to solid phase polymerization is preferably within 12 hours, more preferably within 6 hours, and even more preferably within 3 hours.

  The crystallization temperature as used herein is not particularly limited as long as it is higher than the glass transition temperature of poly-L-lactic acid or poly-D-lactic acid that can be obtained in the melt polymerization step and lower than the melting point. However, 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), and it is possible to efficiently obtain a high molecular weight product. It is preferably 70 to 130 ° C, more preferably 75 to 130 ° C, and most preferably 80 to 130 ° C.

  Further, the temperature of the crystallization process may be one stage, but is preferably a multistage of two or more stages, more preferably the temperature is increased stepwise as the reaction proceeds, for example, a temperature of 80 to 100 ° C. And a method of reacting at a temperature of 100 to 130 ° C. In addition, the temperature increase width for each stage is preferably 30 ° C. or less, more preferably 25 ° C. or less, and further preferably 20 ° C. or less.

  The time for crystallization is preferably 1 to 7 hours, more preferably 1.5 to 5 hours. The pressure condition in the crystallization treatment may be any of reduced pressure, normal pressure and increased pressure, but normal pressure is preferable.

  Moreover, when performing the temperature of a crystallization process in two or more steps | paragraphs, for example, it is 1 to 4 hours at the temperature of 70-100 degreeC as a 1st stage, and the temperature of 100-130 degreeC as a 2nd stage. The method performed in 4 hours is mentioned, 1 to 3 hours at a temperature of 70 to 90 ° C. as the first stage, 1 to 3 hours at a temperature of 90 to 110 ° C. as the second stage, and 110 to 130 ° C. as the third stage. More preferably, it is carried out at a temperature for 1 to 3 hours. In addition, even if it is a case where temperature is performed by the multistage of 2 steps or more, the total of the reaction time of a crystallization process has preferable 1-7 hours.

  It should be noted that the temperature may be continuously raised instead of being raised in multiple stages in which the temperature is kept constant in each stage as described above. For example, a method of maintaining the temperature at 160 ° C. after raising the temperature from 140 ° C. to 160 ° C. over 20 hours, that is, at 1 ° C. per hour can be mentioned. When the temperature is continuously increased, the rate of temperature increase is preferably 10 ° C. or less per hour.

  In the present invention, the shape of poly-L-lactic acid or poly-D-lactic acid at the time of crystallization treatment is not particularly limited, and any shape such as a lump, a film, a pellet, and a powder may be used. It is preferable to use pellets or powders in that they can be made into a powder. As a method of forming pellets, molten poly-L-lactic acid or poly-D-lactic acid is extruded into strands, pelletized with a strand cutter, dropped into droplets using a dropping nozzle, gas or liquid And a method of pelletizing by contacting with a base, a method of cutting with extrusion from a die into a gas or liquid, and the like. Moreover, as a method of making into powder, the method of grind | pulverizing using a mixer, a blender, a ball mill, and a hammer grinder is mentioned. In the case of powder, the average particle size is preferably 0.01 to 5 mm, more preferably 0.1 to 1 mm, in that it can be efficiently crystallized.

Moreover, it is preferable to perform a solid phase polymerization process continuously on the conditions containing the following two steps at least.
Condition 1 130 ° C to 155 ° C
Condition 2 155 ° C to 165 ° C

  In the present invention, the solid phase polymerization step is preferably performed at a temperature not higher than the melting point of poly-L-lactic acid or poly-D-lactic acid after completion of direct polymerization, and a high molecular weight product can be obtained efficiently. Therefore, it is preferably performed at a temperature of 130 to 165 ° C, more preferably at a temperature of 135 to 165 ° C, and further preferably at a temperature of 140 to 165 ° C. Among these, the final temperature is preferably 155 to 165 ° C, more preferably 160 to 165 ° C.

  In addition, the temperature of the solid phase polymerization process may be one step or may be two or more steps, but it is preferably two or more steps in terms of easily increasing the molecular weight in a short time. It is more preferable to raise the temperature step by step as the process proceeds, for example, a method in which the reaction is performed at a temperature of 130 to 155 ° C and then the reaction is performed at a temperature of 155 to 165 ° C. In addition, the temperature rise width for each stage is preferably 15 ° C. or less, more preferably 10 ° C. or less, and further preferably 5 ° C. or less.

  In the present invention, the solid phase polymerization step is preferably performed with a reaction time of 1 to 100 hours, more preferably 5 to 50 hours in that a high molecular weight product can be obtained efficiently. The reaction time is preferably 10 to 30 hours, and more preferably.

  Moreover, when performing the temperature of a solid-phase polymerization process in two or more steps | paragraphs, for example, it is 1 to 50 hours at the temperature of 130-150 degreeC as a 1st stage, and the temperature of 150-165 degreeC as a 2nd stage. The method performed in -50 hours is mentioned, and it is easy to increase the molecular weight in a short time, so that the first stage is 5 to 20 hours at a temperature of 120 to 140 ° C, and the second stage is 5 to 5 at a temperature of 140 to 155 ° C. More preferably, it is carried out at a temperature of 155 to 165 ° C. for 10 to 30 hours as a third stage for 20 hours. In addition, even if it is a case where temperature is performed by the multistep of 2 steps or more, the total of the reaction time of a solid phase polymerization process is 1 to 100 hours.

  It should be noted that the temperature may be continuously raised instead of being raised in multiple stages in which the temperature is kept constant in each stage as described above. For example, a method of maintaining the temperature at 160 ° C. after raising the temperature from 140 ° C. to 160 ° C. over 20 hours, that is, at 1 ° C. per hour can be mentioned. When the temperature is continuously increased, the rate of temperature increase is preferably 10 ° C. or less per hour.

  In the present invention, in the solid phase polymerization step, the pressure condition is not particularly limited, and any of a reduced pressure condition, a normal pressure condition and a pressurized condition may be used, but a high molecular weight product can be obtained efficiently. Thus, it is preferable that the pressure is reduced or normal. When performed under reduced pressure conditions, it is preferably performed at a pressure of 0.13 to 1300 Pa. Moreover, it is preferable to carry out at the pressure of 1-1000 Pa, It is more preferable to carry out at the pressure of 10-900 Pa, It is further more preferable to carry out at the pressure of 100-800 Pa, It is especially preferable to carry out at the pressure of 500-700 Pa. Further, the pressure of the solid phase polymerization process may be one stage or may be two or more stages, but is preferably two or more stages, for example, after the reaction is performed at a pressure of 700 to 1300 Pa. And a method of performing the reaction at a pressure of 0.13 to 700 Pa. When carried out under normal pressure conditions, it is preferably carried out under an inert gas stream such as dry nitrogen, and the flow rate is 0.01 to 200 L per kg of poly-L-lactic acid or poly-D-lactic acid after completion of direct polymerization. / Min is preferred, 0.1 to 150 L / min is more preferred, and 0.5 to 100 L / min is particularly preferred.

  In the present invention, when performing the solid phase polymerization step, the shape of poly-L-lactic acid or poly-D-lactic acid is not particularly limited, and any of a lump, a film, a pellet, and a powder may be used. Pellets or powders are preferably used in that solid phase polymerization can be efficiently advanced. As a method of forming pellets, molten poly-L-lactic acid or poly-D-lactic acid is extruded into strands, pelletized with a strand cutter, dropped into droplets using a dropping nozzle, gas or liquid The method of making it pelletize by making it contact with is mentioned. Moreover, as a method of making into powder, the method of grind | pulverizing using a mixer, a blender, a ball mill, and a hammer grinder is mentioned. In the case of powder, the average particle diameter is preferably 0.01 to 5 mm, more preferably 0.1 to 1 mm, in that solid-phase polymerization can be efficiently performed.

  In the present invention, the solid phase polymerization step may be a batch method or a continuous method, and the reaction vessel may be a stirred vessel type reaction vessel, a mixer type reaction vessel, a tower type reaction vessel, or the like. Can be used in combination of two or more. Moreover, it is preferable to carry out by a continuous method from the point of productivity.

  The 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, or the molten poly-L-lactic acid may be mixed. -L-lactic acid and poly-D-lactic acid can also be mixed. In the case of crystallization of poly-L-lactic acid and poly-D-lactic acid used for mixing, as a specific method, a method of holding at a crystallization temperature in a gas phase or a liquid phase and a poly-L-lactic acid in a molten state And poly-D-lactic acid are retained in a melting machine having a melting point of −50 ° C. to melting point + 20 ° C. while applying shear, and the molten poly-L-lactic acid and poly-D-lactic acid are melted from −50 ° C. to melting point + 20. Examples thereof include a method of staying in a melting machine at 0 ° C. while applying pressure.

  The crystallization temperature here is particularly higher as long as it is higher than the glass transition temperature and is lower than the melting point of polylactic acid having a low melting point among poly-L-lactic acid or poly-D-lactic acid mixed as described above. Although not limited, 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).

  When crystallization is performed in a gas phase or a liquid phase, any of reduced pressure, normal pressure, and increased pressure may be used.

  Further, 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.

  In the method of crystallizing poly-L-lactic acid and poly-D-lactic acid by applying shear or pressure in the melter, the melter is not limited as long as it can apply shear or pressure, and a polymerization can, A kneader, a Banbury mixer, a single screw extruder, a twin screw extruder, an injection molding machine or the like can be used, and a single screw extruder or a twin screw extruder is preferable.

  In the method of crystallizing by applying shear or pressure in the melting machine, the crystallization temperature is preferably in the range of the melting point of poly-L-lactic acid and poly-D-lactic acid to be mixed from −50 ° C. to melting point + 20 ° C. 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, but if it stays at a temperature exceeding the melting point + 20 ° C., if crystals are temporarily formed However, it is not preferable because it melts again, and if it stays at a melting point of −50 ° C. or lower and crystallizes, the fluidity is remarkably lowered, which is not preferable. Here, the melting point is the crystal melting temperature when the temperature is raised from 30 ° C. to 240 ° C. at a rate of temperature rise of 20 ° C./minute using differential thermal scanning measurement.

  The crystallization time is preferably 0.1 minutes to 10 minutes, more preferably 0.3 to 5 minutes, and particularly preferably 0.5 minutes to 3 minutes. When the crystallization time is 0.1 minutes or less, the crystallization is insufficient, which is not preferable. When the crystallization time is longer than 10 minutes, thermal decomposition is easily caused by the treatment, which is not preferable.

  By applying shear in the melting machine, the molecules of the molten resin tend to be oriented, and as a result, the crystallization rate can be remarkably increased. The shear rate at this time is preferably in the range of 10 to 400 / second. A shear rate of less than 10 / sec is not preferred because the crystallization rate is reduced. On the other hand, when the shear rate exceeds 400 / sec, the resin temperature rises due to shear heat generation, and thermal decomposition tends to occur, which is not preferable.

  Even when a pressure is applied, crystallization tends to be promoted, and particularly in the range of 0.05 to 10 MPa, crystallized polylactic acid having both good fluidity and crystallinity can be obtained, which is preferable. When the pressure is less than 0.05 MPa and 10 MPa or more, the crystallization rate is low, which is not preferable.

  Furthermore, it is particularly preferable to perform treatment by simultaneously applying a shear rate of 10 to 400 / sec and a pressure of 0.05 to 10 MPa because the crystallization rate becomes higher.

  Next, a method for mixing poly-L-lactic acid and poly-D-lactic acid will be described in detail.

  The method for mixing poly-L-lactic acid and poly-D-lactic acid is not particularly limited. For example, the melting end temperature of the component having the higher melting point of poly-L-lactic acid and poly-D-lactic acid is higher than the melting end temperature. At least one of molten poly-L-lactic acid and poly-D-lactic acid within a temperature range of melting point −50 ° C. to melting point + 20 ° C. in advance. And 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 the melting machine.

  Here, 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. preferable.

  About the temperature condition at the time of melt-kneading above the melting end temperature, it is preferable to carry out at the melting end temperature or higher of the higher melting point component of poly-L-lactic acid and poly-D-lactic acid. Preferably it is the range of 140 to 250 degreeC, More preferably, it is 160 to 230 degreeC, Most preferably, it is 180 to 210 degreeC. When the mixing temperature exceeds 250 ° C., the molecular weight of the mixture is greatly decreased, which is not preferable. When the mixing temperature is 140 ° C. or lower, the fluidity is significantly decreased.

  Moreover, about the time conditions to mix, the range for 0.1 minute-10 minutes is preferable, 0.3 minute-5 minutes are more preferable, The range for 0.5-3 minutes is especially preferable. When the mixing time is 0.1 minutes or less, it is not preferable because the mixing of poly-L-lactic acid and poly-D-lactic acid is non-uniform. Therefore, it is not preferable.

  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.

  As a specific method of mixing poly-L-lactic acid and poly-D-lactic acid obtained by crystallizing poly-L-lactic acid and poly-D-lactic acid by applying shear or pressure in a melting machine, a batch method or A method of mixing by a continuous method may be mentioned, and any method may be used. Poly-L-lactic acid and poly-D-lactic acid in a molten state may be mixed with poly-L-lactic acid and poly-D-lactic acid. A method of retaining poly (L-lactic acid) and poly (D-lactic acid) in a melted state in a melting machine having a melting point of −50 ° C. to melting point + 20 ° C. Of the lactic acid and poly-D-lactic acid, the method of staying while applying pressure in the melting point of the melting point of -50 ° C. to melting point + 20 ° C. of the polylactic acid having the lower melting point is poly-L-lactic acid and poly -Controlling stereocomplex formation rate of D-lactic acid mixture A particularly preferred in terms of being able to.

Here, the stereocomplex formation rate is the ratio of the stereocomplex crystals in all the crystals in polylactic acid. Specifically, the amount of heat based on crystal melting of poly-L-lactic acid single crystal and poly-D-lactic acid single crystal measured by a differential scanning calorimeter (DSC) is ΔHl, and the amount of heat based on crystal melting of stereocomplex crystals. Can be calculated by the following equation (2).
Sc = ΔHh / (ΔHl + ΔHh) × 100 (2)

  The stereocomplex formation rate (Sc) can be calculated from the ratio of the polylactic acid single crystal and the stereocomplex crystal measured by X-ray diffraction, but in the present invention, from the crystal melting calorimetry measured by the DSC described above. Use the calculated value.

  About the temperature conditions to mix, the range of melting | fusing point-50 degreeC-melting | fusing point +20 degreeC of the mixture of poly-L-lactic acid and poly-D-lactic acid is preferable. A more preferable range of the mixing 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 in order to melt the resin and develop good fluidity. However, if processing is performed at a temperature exceeding the melting point + 20 ° C., if crystals are generated, However, it is not preferred because it will be re-melted, and when it is crystallized by treatment at a melting point of -50 ° C. or lower, the fluidity is remarkably lowered. Here, the melting point refers to a crystal melting temperature when the temperature is raised from 30 ° C. to 240 ° C. at a rate of temperature rise of 20 ° C./min using a differential scanning calorimeter (DSC).

  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.

  In kneading using an extruder, the method of supplying polylactic acid is not particularly limited, and a method of supplying poly-L-lactic acid and poly-D-lactic acid in a lump from a resin supply port, or a side supply port as necessary Can be used to separately supply poly-L-lactic acid and poly-D-lactic acid to the resin supply port and the side supply port, respectively. 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 stereocomplex.

  In the mixing step, 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 80:20 to 20:80, and 75:25 It is more preferably 25:75, further preferably 70:30 to 30:70, and particularly preferably 60:40 to 40:60. When the weight ratio of the poly-L-lactic acid composed of L-lactic acid units is less than 20% by weight or more than 80% by weight, the increase in the melting point of the finally obtained polylactic acid block copolymer becomes small. This tends to make it difficult to form a polylactic acid stereocomplex. When the mixing weight ratio of poly-L-lactic acid and poly-D-lactic acid is other than 50:50, it is preferable to blend a larger amount of poly-L-lactic acid or poly-D-lactic acid having a larger weight average molecular weight. .

  In this mixing step, it is preferable to contain a catalyst in the mixture in order to efficiently proceed with the next solid phase polymerization. At this time, the catalyst may be a residual amount of the catalyst in producing poly-L-lactic acid and / or poly-D-lactic acid, or a catalyst may be further added in the mixing step.

  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 from the viewpoint of mechanical properties of the mixture. It is more preferably 120,000 or more, and particularly preferably 140,000 or more.

  Moreover, the dispersion degree 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. More preferably, it is the range of 1.8-3.5, Most preferably, it is the range of 2.0-3.0. Here, the degree of dispersion means the ratio of the weight average molecular weight to the number average molecular weight of the mixture. Specifically, 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.

  A method for crystallizing a mixture of poly-L-lactic acid and poly-D-lactic acid is not particularly limited, and a known method can be used. For example, a method of holding at a crystallization temperature in a gas phase or a liquid phase, a method of cooling and solidifying a molten mixture of poly-L-lactic acid and poly-D-lactic acid while performing an operation of stretching or shearing, etc. From the viewpoint that the operation is simple, a method of holding at the crystallization temperature in a gas phase or a liquid phase is preferable.

  The crystallization temperature here is particularly higher as long as it is higher than the glass transition temperature and is lower than the melting point of polylactic acid having a low melting point among poly-L-lactic acid or poly-D-lactic acid mixed as described above. Although not limited, 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).

  When crystallizing, any of reduced pressure, normal pressure, and increased pressure may be used.

  Further, the time for crystallization is not particularly limited, but it is sufficiently crystallized within 3 hours, and preferably within 2 hours.

  Next, the polymerization method of the polylactic acid block copolymer will be described in detail.

  As a method for obtaining a polylactic acid block copolymer by ring-opening polymerization, for example, either L-lactide or D-lactide is subjected to ring-opening polymerization in the presence of a catalyst, and then lactide which is the other optical isomer. And a method for obtaining a polylactic acid block copolymer by carrying out ring-opening polymerization.

  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.

  When obtaining a polylactic acid block copolymer by the ring-opening polymerization method, the amount of water in the reaction system is 4 mol% or less based on the total amount of L-lactide and D-lactide from the viewpoint of obtaining a high molecular weight product. preferable. 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.

  Examples of the polymerization catalyst for producing poly-L-lactic acid or poly-D-lactic acid by a 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. Specifically, 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 sulfonate tin (II), bis (methane sulfonate) tin (II), tin sulfate (II), tin oxide (II), tin oxide (IV), tin sulfide (II), tin sulfide (IV), oxidation Dimethyltin (IV), methylphenyltin (IV) oxide, dibuty oxide Tin (IV), dioctyl tin (IV) oxide, diphenyl tin (IV) oxide, tributyl tin oxide, triethyl tin hydroxide (IV), triphenyl tin hydroxide (IV), tributyl tin hydride, monobutyl tin (IV) Oxide, tetramethyltin (IV), tetraethyltin (IV), tetrabutyltin (IV), dibutyldiphenyltin (IV), tetraphenyltin (IV), tributyltin (IV) acetate, triisobutyltin (IV) acetate, Triphenyltin acetate (IV), dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin (IV) dilaurate, dibutyltin (IV) maleate, dibutyltin bis (acetylacetonate), tributyltin chloride (IV), Dibutyltin dichloride, monobutyltin trichloride, dioctyltin dichloride, triphenyltin (IV) chloride, sulfide Butyltin, tributyltin sulfate, tin (II) methanesulfonate, tin (II) ethanesulfonate, tin (II) trifluoromethanesulfonate, ammonium hexachlorotin (IV), dibutyltin sulfide, diphenyltin sulfide and triethyl sulfate Examples thereof include tin compounds such as tin and phthalocyanine tin (II). Also, titanium methoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium isobutoxide, titanium cyclohexyl, titanium phenoxide, titanium chloride, titanium diacetate, titanium triacetate, titanium tetraacetate, titanium (IV) oxide, etc. Titanium compounds, lead diisopropoxy (II), lead monochloride, lead acetate, lead (II) octylate, lead (II) isooctanoate, lead (II) isononanoate, lead (II) laurate, lead oleate (II), lead compounds such as lead (II) linoleate, lead naphthenate, lead (II) neodecanoate, lead oxide, lead (II) sulfate, zinc powder, methyl propoxy zinc, zinc chloride, zinc acetate, octylic acid Zinc (II), zinc naphthenate, zinc carbonate, zinc oxide, zinc sulfate and other zinc compounds, chloride Baltic, cobalt acetate, cobalt (II) octylate, cobalt (II) isooctanoate, cobalt (II) isononanoate, cobalt (II) laurate, cobalt (II) oleate, cobalt (II) linoleate, cobalt naphthenate , Cobalt compounds such as cobalt (II) neodecanoate, cobaltous carbonate, cobaltous sulfate, cobalt (II) oxide, iron (II) chloride, iron (II) acetate, iron (II) octylate, iron naphthenate Iron compounds such as iron carbonate (II), iron sulfate (II), iron oxide (II), propoxy lithium, lithium chloride, lithium acetate, lithium octylate, lithium naphthenate, lithium carbonate, dilithium sulfate, lithium oxide, etc. Lithium compounds, triisopropoxy europium (III), triisopropoxy neo (III), triisopropoxylantan, triisopropoxy samarium (III), triisopropoxy yttrium, isopropoxy yttrium, dysprosium chloride, europium chloride, lanthanum chloride, neodymium chloride, samarium chloride, yttrium chloride, dysprosium triacetate (III ), Europium triacetate (III), lanthanum acetate, neodymium triacetate, samarium acetate, yttrium triacetate, dysprosium carbonate (III), dysprosium carbonate (IV), europium carbonate (II), lanthanum carbonate, neodymium carbonate, samarium carbonate ( II), samarium carbonate (III), yttrium carbonate, dysprosium sulfate, europium (II) sulfate, lanthanum sulfate, neodymium sulfate, samarium sulfate, yttrium sulfate, yttrium dioxide Examples include rare earth compounds such as europium, lanthanum oxide, neodymium oxide, samarium (III) oxide, and yttrium oxide. In addition, potassium compounds such as potassium isopropoxide, potassium chloride, potassium acetate, potassium octylate, potassium naphthenate, tert-butyl potassium carbonate, potassium sulfate, potassium oxide, copper (II) diisopropoxide, copper chloride (II), copper acetate (II), copper octylate, copper naphthenate, copper sulfate (II), copper compounds such as dicopper carbonate, nickel chloride, nickel acetate, nickel octylate, nickel carbonate, nickel sulfate (II) Nickel compounds such as nickel oxide, tetraisopropoxyzirconium (IV), zirconium trichloride, zirconium acetate, zirconium octylate, zirconium naphthenate, zirconium carbonate (II), zirconium carbonate (IV), zirconium sulfate, zirconium oxide (II Zirconization , Antimony compounds such as triisopropoxyantimony, antimony fluoride (III), antimony fluoride (V), antimony acetate, antimony (III) oxide, magnesium, magnesium diisopropoxide, magnesium chloride, magnesium acetate, magnesium lactate , Magnesium compounds such as magnesium carbonate, magnesium sulfate, magnesium oxide, calcium compounds such as diisopropoxy calcium, calcium chloride, calcium acetate, calcium octylate, calcium naphthenate, calcium lactate, calcium sulfate, aluminum, aluminum isopropoxide, Aluminum compounds such as aluminum chloride, aluminum acetate, aluminum octylate, aluminum sulfate, aluminum oxide, germanium, tetri Germanium compounds such as propoxygermane and germanium (IV) oxide, manganese compounds such as triisopropoxymanganese (III), manganese trichloride, manganese acetate, manganese (II) octylate, manganese (II) naphthenate, and manganese sulfate And bismuth chloride (III), bismuth powder, bismuth oxide (III), bismuth acetate, bismuth octylate, bismuth neodecanoate, and the like. Also, sodium stannate, magnesium stannate, potassium stannate, calcium stannate, manganese stannate, bismuth stannate, barium stannate, strontium stannate, sodium titanate, magnesium titanate, aluminum titanate, potassium titanate, Compounds composed of two or more metal elements such as calcium titanate, cobalt titanate, zinc titanate, manganese titanate, zirconium titanate, bismuth titanate, barium titanate and strontium titanate are also preferred. 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. Specifically, 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 And 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-dimethylbenzenesulfonic acid, 2,5-dibutylbenzenesulfonic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid , 5-amino-2 Methylbenzenesulfonic acid, 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, p-chlorobenzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, p-phenol Sulfonic acid, cumene sulfonic acid, xylene sulfonic acid, o-cresol sulfonic acid, m-cresol sulfonic acid, p-cresol sulfonic acid, p-toluene sulfonic acid, 2-naphthalene sulfonic acid, 1-naphthalene sulfonic acid, isopropyl naphthalene sulfone Acid, dodecylnaphthalenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, 1,5-naphthalenedisulfonic acid, 2,7-naphthalenedisulfonic acid, 4,4-biphenyldisulfonic acid, anthraquinone-2-sulfonic acid, m- Benzene disulfonic acid, 2,5-diamino-1,3-benzenedisulfonic acid, aniline-2,4-disulfonic acid, anthraquinone-1,5-disulfonic acid, aromatic sulfonic acid such as polystyrene sulfonic acid, methanesulfonic acid, Ethanesulfonic acid, 1-propanesulfonic acid, n-octylsulfonic acid, pentadecylsulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, 1,2-ethanedisulfonic acid, 1,3-propanedisulfonic acid, aminomethanesulfone Acids, aliphatic sulfonic acids such as 2-aminoethanesulfonic acid, cyclopentanesulfonic acid, cyclohexanesulfonic acid and camphorsulfonic acid, sulfonic acid compounds such as alicyclic sulfonic acid such as 3-cyclohexylaminopropanesulfonic acid, aspartic acid Or Acidic amino acids such as glutamic acid, phosphoric acid monoesters such as ascorbic acid, retinoic acid, phosphoric acid, metaphosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, monododecyl phosphate and monooctadecyl phosphate, didodecyl phosphate And phosphoric acid diesters such as dioctadecyl phosphate, phosphoric acid compounds such as phosphorous acid monoester and phosphorous acid diester, boric acid, hydrochloric acid, sulfuric acid and the like. Further, 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. For example, as 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.

  In the present invention, when considering the molecular weight of the produced polylactic acid, a metal catalyst is preferable as the polymerization catalyst, among which a tin compound, a titanium compound, an antimony compound, and a rare earth compound are more preferred, and the melting point of the produced polylactic acid is considered. In this case, a tin compound and a titanium compound are more preferable. Further, in consideration of the thermal stability of the polylactic acid produced, a tin-based organic carboxylate or a tin-based halogen compound is preferable, and in particular, tin (II) acetate, tin (II) octylate, and tin chloride ( II) is more preferred.

  The addition amount of the polymerization catalyst is not particularly limited, and 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 0.001 part by weight or more and 1 part by weight or less. If the amount of the catalyst is less than 0.001 part by weight, the effect of shortening the polymerization time is lowered, and if it exceeds 2 parts by weight, the molecular weight of the finally obtained polylactic acid block copolymer tends not to increase. Moreover, when using 2 or more types of catalysts together, it is preferable that a total addition amount exists in said range.

  The addition timing of the polymerization catalyst is not particularly limited, but it is preferable to add the catalyst after heating and dissolving the lactide from the viewpoint of uniformly dispersing the catalyst in the system and increasing the polymerization activity.

  Next, a method for obtaining a polylactic acid block copolymer by solid phase polymerization after mixing poly-L-lactic acid and poly-D-lactic acid will be described.

  When a polylactic acid block copolymer is produced 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 50,000 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 45,000. Particularly preferably, one weight average molecular weight is 150,000 to 240,000 and the other weight average molecular weight is 20,000 to 40,000. 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. Here, as a method for producing poly-L-lactic acid and poly-D-lactic acid, any of a ring-opening polymerization method and a direct polymerization method can be used.

  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 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.

  When a polylactic acid block copolymer is produced by solid-phase polymerization after mixing poly-L-lactic acid and poly-D-lactic acid, the shape of the mixture of poly-L-lactic acid and poly-D-lactic acid is particularly limited. It may be any of a lump, a film, a pellet and a powder, but from the viewpoint of efficiently proceeding solid phase polymerization, it is preferable to use a pellet or powder. Examples of the method for forming pellets include a method in which the mixture is extruded into a strand shape and pelletized, and a method in which the mixture is extruded into water and pelletized using an underwater cutter. Moreover, as a method of making into powder, the method of grind | pulverizing using grinders, such as a mixer, a blender, a ball mill, and a hammer mill, is mentioned. 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.

  When this solid phase polymerization step is carried out, it is preferable that a mixture of poly-L-lactic acid and poly-D-lactic acid is crystallized. In the present invention, when the mixture obtained in the mixing step of poly-L-lactic acid and poly-D-lactic acid is in a crystallized state, poly-L-lactic acid and poly-D are used when the solid phase polymerization step is performed. -Crystallization of the mixture of lactic acid is not necessarily required, but the efficiency of solid-phase polymerization can be further increased by performing crystallization.

  The method for crystallization is not particularly limited, and a known method can be used. For example, a method of holding at a crystallization temperature in a gas phase or a liquid phase, a method of cooling and solidifying a molten mixture of poly-L-lactic acid and poly-D-lactic acid while performing an operation of stretching or shearing, etc. From the viewpoint that the operation is simple, a method of holding at the crystallization temperature in a gas phase or a liquid phase is preferable.

  The crystallization temperature here is particularly higher as long as it is higher than the glass transition temperature and is lower than the melting point of polylactic acid having a low melting point among poly-L-lactic acid or poly-D-lactic acid mixed as described above. Although not limited, 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).

  When crystallizing, any of reduced pressure, normal pressure, and increased pressure may be used.

  Further, the time for crystallization is not particularly limited, but it is sufficiently crystallized within 3 hours, and preferably within 2 hours.

  The temperature condition for carrying out this solid phase polymerization step is a temperature not higher than the melting point of the mixture of poly-L-lactic acid and poly-D-lactic acid, and specifically, preferably 100 ° C. or higher and 220 ° C. or lower. Further, from the viewpoint of further promoting solid phase polymerization, it is more preferably 110 ° C. or more and 210 ° C. or less, and most preferably 120 ° C. or more and 200 ° C. or less.

  In order to shorten the reaction time of solid phase polymerization, it is preferable to raise the temperature stepwise or continuously as the reaction proceeds. As temperature conditions when the temperature is raised stepwise during solid phase polymerization, the first stage is 120 to 145 ° C. for 1 to 15 hours, the second stage is 135 to 160 ° C. for 1 to 15 hours, and the third stage is 150. It is preferable to raise the temperature at ˜175 ° C. for 10 to 30 hours, and further, as the first stage, 130 to 145 ° C. for 2 to 12 hours, as the second stage, 140 to 160 ° C. for 2 to 12 hours, as the third stage It is more preferable to raise the temperature at 155 to 175 ° C. for 10 to 25 hours. As a temperature condition when the temperature is continuously increased during solid-phase polymerization, it is preferable that the temperature is continuously increased from 150 to 150 ° C. to an initial temperature of 150 to 175 ° C. at a rate of 1 to 5 ° C./min. Further, combining stepwise temperature rise and continuous temperature rise is also preferable from the viewpoint of efficiently proceeding with solid phase polymerization.

  Moreover, when implementing this solid-phase polymerization process, it is preferable to carry out under vacuum or inert gas flow, 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 2000 ml / min, more preferably in the range of 0.5 to 1000 ml / min, and 1.0 to 1.0 g per 1 g of the mixture. A range of 500 ml / min is particularly preferred.

  Next, poly-L-lactic acid and poly-D-lactic acid are 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 are separated. A method for obtaining a transesterified polylactic acid block copolymer will be described.

  In order to obtain a polylactic acid block copolymer by this method, the weight average molecular weight of either poly-L-lactic acid or poly-D-lactic acid is high in that the stereocomplex formation rate is increased after melt-kneading. It is preferably 60,000 to 300,000 or less, and the other weight average molecular weight is preferably 10,000 to 50,000 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 45,000. Particularly preferably, one weight average molecular weight is 150,000 to 240,000 and the other weight average molecular weight is 20,000 to 40,000. 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. Here, as a method for producing poly-L-lactic acid and poly-D-lactic acid, any of a ring opening polymerization method and a direct polymerization method can be used.

  The method for mixing poly-L-lactic acid and poly-D-lactic acid is not particularly limited. For example, the melting end temperature of the component having the higher melting point of poly-L-lactic acid and poly-D-lactic acid is higher than the melting end temperature. And melt kneading.

  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. preferable.

  About the temperature conditions to mix, it is important to carry out more than the melting completion temperature of the component with a higher melting | fusing point among poly-L-lactic acid and poly-D-lactic acid. Preferably it is the range of 140 to 250 degreeC, More preferably, it is 160 to 230 degreeC, Most preferably, it is 180 to 210 degreeC. When the mixing temperature exceeds 250 ° C., the molecular weight of the mixture is greatly decreased, which is not preferable. When the mixing temperature is 140 ° C. or lower, the fluidity is significantly decreased.

  About the time conditions to mix, the range for 0.1 minute-30 minutes is preferable, 0.3 minute-20 minutes are more preferable, The range for 0.5 minute-10 minutes is especially preferable. When the mixing time is 0.1 minutes or less, the mixing of poly-L-lactic acid and poly-D-lactic acid is not preferable because it is non-uniform. Therefore, it is not preferable.

  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 to be mixed and poly-D-lactic acid composed of D-lactic acid units is preferably 80:20 to 20:80, and 75:25 to 25: 75 is more preferable, 70:30 to 30:70 is more preferable, and 60:40 to 40:60 is particularly preferable. When the weight ratio of the poly-L-lactic acid composed of L-lactic acid units is less than 20% by weight or more than 80% by weight, the increase in the melting point of the finally obtained polylactic acid block copolymer becomes small. This tends to make it difficult to form a polylactic acid stereocomplex.

  In this mixing step, it is preferable to contain a catalyst in the mixture in order to efficiently promote transesterification of the L-lactic acid unit segment and the D-lactic acid unit segment. At this time, the catalyst may be a residual amount of the catalyst in producing poly-L-lactic acid and / or poly-D-lactic acid, or a catalyst may be further added in the mixing step.

  The content of the catalyst is not particularly limited, and 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. 001 parts by weight or more and 0.5 parts by weight or less are more preferable. When the amount of catalyst is less than 0.001 part by weight, the frequency of transesterification of the mixture decreases. When the amount exceeds 1 part by weight, the frequency of transesterification of the mixture is large, so that the molecular weight of the finally obtained polylactic acid block copolymer is It tends to be lower.

  In the present invention, it is preferable to add a catalyst deactivator after obtaining a polylactic acid resin. When the polymerization catalyst remains, the polylactic acid block copolymer may be thermally decomposed during melt kneading and melt molding by the remaining catalyst, and thermal decomposition can be suppressed by adding a catalyst deactivator. , Thermal stability can be improved.

  Examples of the catalyst deactivator used in the present invention include hindered phenol compounds, thioether compounds, vitamin compounds, triazole compounds, polyvalent amine compounds, hydrazine derivative compounds, phosphorus compounds, and the like. You may use together. Among them, it is preferable to include at least one phosphorus compound, and it is more preferable to use a phosphate compound or a phosphite compound.

  Specific examples of the hindered phenol compound include n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl). -5'-t-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6-hexane Diol-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis- [3- (3,5-di-t-butyl- 4-hydroxyphenyl) -propionate], 2,2′-methylenebis- (4-methyl-t-butylphenol), triethylene glycol-bis- [3- (3-t-butyl) 5-methyl-4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) undecane, N, N′-bis-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionylhexamethylenediamine, N, N′-tetramethylene-bis-3- (3′-methyl-5) '-T-butyl-4'-hydroxyphenol) propionyldiamine, N, N'-bis- [3- (3,5-di-t-butyl-4-hydroxyphenol) propionyl] Dorazine, N-salicyloyl-N′-salicylidenehydrazine, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N′-bis [2- {3- (3,5-di- t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] oxyamide, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylene Bis- (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) and the like. Preferably, triethylene glycol-bis- [3- (3-t-butyl-5-methyl- 4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate Acid] methane, 1,6-hexanediol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], pentaerythrityl-tetrakis [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis- (3,5-di-t-butyl-4-hydroxy-hydrocinnamide). Specific product names of the hindered phenol compounds include “ADEKA STAB” AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, AO-330 manufactured by ADEKA. “Irganox” 245, 259, 565, 1010, 1035, 1076, 1098, 1222, 1330, 1425, 1520, 3114, 5057, manufactured by Ciba Specialty Chemicals, “Sumilyzer” BHT-R, MDP-S, manufactured by Sumitomo Chemical Co., Ltd. Examples include BBM-S, WX-R, NW, BP-76, BP-101, GA-80, GM, GS, “Sianox” CY-1790 manufactured by Cyanamid.

  Specific examples of the thioether compound include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-lauryl thiopropionate) Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3- Stearylthiopropionate). Specific product names of the thioether compounds include “ADEKA STAB” A0-23, AO-412S, AO-503A manufactured by ADEKA, “Irganox” PS802 manufactured by Ciba Specialty Chemicals, “Sumilyzer” TPL-R manufactured by Sumitomo Chemical, Examples thereof include TPM, TPS, TP-D, DSTP manufactured by API Corporation, DLTP, DLTOIB, DMTP, “Sinox” 412S manufactured by Cypro Kasei, and “Sianox” 1212 manufactured by Cyamide.

  Specific examples of the polyvalent amine compound include 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro. [5.5] Undecane, ethylenediamine-tetraacetic acid, alkali metal salt (Li, Na, K) of ethylenediamine-tetraacetic acid, N, N′-disalicylidene-ethylenediamine, N, N′-disalicylidene-1 , 2-propylenediamine, N, N ″ -disalicylidene-N′-methyl-dipropylenetriamine, 3-salicyloylamino-1,2,4-triazole and the like.

Specific examples of the hydrazine derivative-based compound include decamethylene dicarboxyl acid-bis (N′-salicyloyl hydrazide), bis (2-phenoxypropionyl hydrazide) isophthalate, N-formyl-N′-salicyloyl hydrazine. 2,2-oxamide bis- [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], oxalyl-bis-benzylidene-hydrazide, nickel-bis (1-phenyl-3- Methyl-4-decanoyl-5-pyrazolate), 2-ethoxy-2′-ethyloxanilide, 5-t-butyl-2-ethoxy-2′-ethyloxanilide, N, N-diethyl-N ′, N′-diphenyl oxamide, N, N′-diethyl-N, N′-diphenyl oxamide, oxalic acid (Benzylidene hydrazide), thiodipropionic acid-bis (benzylidene hydrazide), bis (salicyloyl hydrazine), N-salicylidene-N′-salicyloyl hydrazone, N, N′-bis [3- (3 5-Di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, N, N′-bis [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] Oxamide etc. are mentioned.

  Examples of phosphorus compounds include phosphite compounds and phosphate compounds. Specific examples of such phosphite compounds include tetrakis [2-t-butyl-4-thio (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -5-methylphenyl] -1, 6-hexamethylene-bis (N-hydroxyethyl-N-methylsemicarbazide) -diphosphite, tetrakis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -1,10-decamethylene-di-carboxylic acid-di-hydroxyethylcarbonylhydrazide-diphosphite, tetrakis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-) 5'-t-butylphenyl) -5-methylphenyl] -1,10-decamethylene-di-carboxylic acid- -Salicyloylhydrazide-diphosphite, tetrakis [2-tert-butyl-4-thio (2'-methyl-4'-hydroxy-5'-tert-butylphenyl) -5-methylphenyl] -di (hydroxyethylcarbonyl) ) Hydrazide-diphosphite, tetrakis [2-tert-butyl-4-thio (2′-methyl-4′-hydroxy-5′-tert-butylphenyl) -5-methylphenyl] -N, N′-bis (hydroxy) Ethyl) oxamide-diphosphite and the like, and at least one P—O bond is more preferably bonded to an aromatic group, and specific examples include tris (2,4-di-t-butylphenyl). Phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylene phosphonite, bis (2,4-di-t- Tilphenyl) pentaerythritol-di-phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-t-butyl) Phenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecylphos) Phyto-5-t-butyl-phenyl) butane, tris (mixed mono and di-nonylphenyl) phosphite, tris (nonylphenyl) phosphite, 4,4′-isopropylidenebis (phenyl-dialkyl phosphite), etc. Tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol di-phosphite, tetrakis (2,4-di-t -Butylphenyl) -4,4'-biphenylenephosphonite can be preferably used. Specific product names of phosphite compounds include “ADEKA STAB” C, PEP-4C, PEP-8, PEP-11C, PEP-24G, PEP-36, HP-10, 2112, 260, 522A, manufactured by ADEKA, 329A, 1178, 1500, C, 135A, 3010, TPP, “Irgaphos” 168 manufactured by Ciba Specialty Chemicals, “Smilizer” P-16 manufactured by Sumitomo Chemical, “Sand Stub” PEPQ manufactured by Clariant, “Weston” 618 manufactured by GE, 619G, 624 and the like.

  Specific examples of the phosphate compound include monostearyl acid phosphate, distearyl acid phosphate, methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, octyl acid phosphate, isodecyl acid phosphate, etc., among them monostearyl acid phosphate Distearyl acid phosphate is preferred. Specific product names of phosphate compounds include “Irganox” MD1024 from Ciba Specialty Chemicals, “Inhibitor” OABH from Eastman Kodak, “Adekastab” CDA-1, CDA-6, AX-71 from ADEKA, etc. Can be mentioned.

  As further preferred examples of specific examples, PEP-8 (distearyl pentaerythritol diphosphite), “ADEKA STAB” AX-71 (dioftademil phosphate) manufactured by ADEKA, PEP-36 (cyclic neopentatetrayl bis (2, 6-t-butyl-4-methylphenyl) phosphite).

  The addition amount of the catalyst deactivator is not particularly limited, but is preferably 0.001 to 2 parts by weight with respect to 100 parts by weight of the polylactic acid block copolymer in terms of excellent thermal stability. The amount is more preferably 0.01 to 1 part by weight, still more preferably 0.05 to 0.5 part by weight, and most preferably 0.08 to 0.3 part by weight.

  The catalyst deactivator is preferably added after the polylactic acid resin is obtained from the viewpoint of maintaining the high molecular weight.

<Flowability improver (B)>
The (B) fluidity improver used in the present invention has a function of greatly reducing the melt viscosity of the thermoplastic resin by blending with the (A) polylactic acid resin. Specifically, One selected from a compound having three or more functional groups, an acrylic compound, a branched polymer, a liquid crystal polymer, a low molecular weight linear polyester, a low molecular weight linear polycarbonate, and an aromatic low molecular compound Is included. In addition, these may be 1 type and may use 2 or more types together.

  The compound having three or more functional groups used in the present invention is a component necessary for improving the fluidity of the polylactic acid resin of the present invention. The component is not limited as long as it has three or more functional groups in the molecule, and may be a low molecular compound or a polymer. In addition, the component may be any compound as long as it has three or more functional groups such as a trifunctional compound, a tetrafunctional compound, and a pentafunctional compound, but in terms of excellent fluidity and mechanical properties. It is more preferably a trifunctional compound or a tetrafunctional compound, and further preferably a tetrafunctional compound.

  In the present invention, in terms of excellent fluidity and mechanical properties, the component is a polyfunctional compound having three or more functional groups, and at least one of the terminal structures having a functional group is represented by formula (1). The compound is preferably a compound having a structure represented, and in particular in terms of excellent fluidity and mechanical properties, the component is a polyfunctional compound having three or more functional groups, and has a terminal structure having a functional group It is more preferable that two or more of the compounds have a structure represented by the formula (1), and a compound in which three or more of the terminal structures having a functional group in the component are a structure represented by the formula (1) It is more preferable that all of the terminal structures having a functional group in the component are compounds represented by the formula (1).

  Here, R represents a hydrocarbon group having 1 to 15 carbon atoms, n represents an integer of 1 to 10, X represents a hydroxyl group, an aldehyde group, a carboxylic acid group, a sulfo group, an amino group, a glycidyl group, It represents at least one functional group selected from an isocyanate group, a carbodiimide group, an oxazoline group, an oxazine group, an ester group, an amide group, a silanol group, and a silyl ether group.

  In the present invention, R represents an alkylene group, n represents an integer of 1 to 7, and X represents a hydroxyl group, a carboxylic acid group, an amino group, or glycidyl in terms of excellent fluidity and mechanical properties. It is preferable to represent at least one functional group selected from a group, an isocyanate group, an ester group, and an amide group, R represents an alkylene group, n represents an integer of 1 to 5, X represents a hydroxyl group, More preferably, it represents at least one functional group selected from a carboxylic acid group, an amino group, a glycidyl group, and an ester group, R represents an alkylene group, n represents an integer of 1 to 4, and X represents More preferably, it represents at least one functional group selected from a hydroxyl group, an amino group, a glycidyl group and an ester group, R represents an alkylene group, n represents an integer of 1 to 3, and X represents Hydroxy It is particularly preferred is. In the present invention, when R is an alkylene group, the structure represented by the formula (1) indicates a structure containing an alkylene oxide unit.

  In the present invention, the functional group in the component is a hydroxyl group, aldehyde group, carboxylic acid group, sulfo group, amino group, glycidyl group, isocyanate group, carbodiimide group, oxazoline group, oxazine group, ester group, amide group, silanol group, It is preferable that there are at least one selected from silyl ether groups, and the functional group in the component preferably has three or more functional groups that are the same or different from these. In the present invention, the component is a polyfunctional compound having three or more functional groups, and two or more of the terminal structures having a functional group are structures represented by the formula (1). In this case, the functional groups may be the same or different from the above, but are preferably the same in terms of fluidity, mechanical properties, and productivity.

  As a preferable example of the compound having three or more functional groups, when the functional group is a hydroxyl group, 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,6-hexanetetrol, glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, triethanolamine, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tritrimethylolpropane, 2 -Methylpropanetriol, 2-methyl-1,2,4-butanetriol, pentaerythritol, dipentaerythritol, tripentaerythritol, methylglucoside, sorbitol, mannitol, sucrose, 1,3,5-trihydroxybenzene, 1, 2 Polymers such as polyhydric alcohol or a polyvinyl alcohol having a carbon number of 3 to 24, such as 4-trihydroxy benzene. Of these, glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol having a branched structure are preferable from the viewpoint of fluidity and mechanical properties.

  As a preferable example of a compound having three or more functional groups, when the functional group is a carboxylic acid group, propane-1,2,3-tricarboxylic acid, 2-methylpropane-1,2,3-triscarboxylic acid, Butane-1,2,4-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, benzenepentacarboxylic acid, cyclohexane-1,2 , 4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, naphthalene-1,2,4-tricarboxylic acid, naphthalene-2,5,7- Tricarboxylic acid, pyridine-2,4,6-tricarboxylic acid, naphthalene-1,2,7,8-tetracarboxylic acid, naphthalene-1,4,5,8-te Polycarboxylic acid or acrylic acid such as Rakarubon acid, include polymers such as methacrylic acid, it may be used acid anhydrides thereof. Of these, propane-1,2,3-tricarboxylic acid, trimellitic acid, trimesic acid and acid anhydrides having a branched structure are preferable from the viewpoint of fluidity.

  When the functional group of the compound having three or more functional groups is an amino group, at least one of the three or more substituents is preferably a primary or secondary amine, both of which are primary or secondary More preferred are amines, and particularly preferred are primary amines.

  As a preferred example of a compound having three or more functional groups, when the functional group is an amino group, 1,2,3-triaminopropane, 1,2,3-triamino-2-methylpropane, 1,2, 4-triaminobutane, 1,2,3,4-tetraminobutane, 1,3,5-triaminocyclohexane, 1,2,4-triaminocyclohexane, 1,2,3-triaminocyclohexane, 1,2 , 4,5-tetraminocyclohexane, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 1,2,3-triaminobenzene, 1,2,4,5-tetraminobenzene, 1 , 2,4-triaminonaphthalene, 2,5,7-triaminonaphthalene, 2,4,6-triaminopyridine, 1,2,7,8-tetraminonaphthalene, 1,4,5,8-tetrami Naphthalene, and the like. Of these, 1,2,3-triaminopropane, 1,3,5-triaminocyclohexane and 1,3,5-triaminobenzene having a branched structure are preferable from the viewpoint of fluidity.

  As a preferred example of a compound having three or more functional groups, when the functional group is a glycidyl group, a monomer such as triglycidyl triazolidine-3,5-dione, triglycidyl isocyanurate, poly (ethylene / ethylene Examples of the polymer include glycidyl methacrylate) -g-polymethyl methacrylate, glycidyl group-containing acrylic polymer, and glycidyl group-containing acrylic / styrene polymer.

  As a preferable example of the compound having three or more functional groups, when the functional group is an isocyanate group, nonane triisocyanate (for example, 4-isocyanatomethyl-1,8-octane diisocyanate (TIN)), decane triisocyanate, undecane Examples include triisocyanate and dodecane triisocyanate.

  As a preferred example of the compound having three or more functional groups, when the functional group is an ester group, the aliphatic acid ester or aromatic acid ester of the compound having three or more hydroxyl groups, or the three or more carboxylic acid groups An ester derivative of a compound having

  As a preferable example of the compound having three or more functional groups, when the functional group is an amide group, an amide derivative of the compound having three or more carboxylic acid groups is exemplified.

  From the viewpoint of fluidity and mechanical properties, it is preferable that the compound having three or more functional groups contains one or more alkylene oxide units. In the present invention, the component is a polyfunctional compound having three or more functional groups, and at least one of the terminal structures having a functional group is a compound represented by the formula (1), When R in the formula (1) is an alkylene group, the structure represented by the formula (1) shows a structure containing an alkylene oxide unit, and the component is particularly excellent in terms of fluidity. Most preferred is a polyfunctional compound having three or more functional groups, which is a polyfunctional compound containing an alkylene oxide unit. In the present invention, an aliphatic alkylene oxide unit having 1 to 4 carbon atoms is effective as a preferred example of the alkylene oxide unit. Specific examples include a methylene oxide unit, an ethylene oxide unit, a trimethylene oxide unit, a propylene oxide unit, Examples thereof include a tetramethylene oxide unit, a 1,2-butylene oxide unit, a 2,3-butylene oxide unit, and an isobutylene oxide unit. In the present invention, particularly as an alkylene oxide unit, it is excellent in fluidity. Preference is given to using compounds containing ethylene oxide units or propylene oxide units.

  In the component used in the present invention, the number of alkylene oxide units contained in the compound having three or more functional groups is 0.1 to 20 alkylene oxide units per functional group in terms of excellent fluidity. It is preferably 0.5-10, more preferably 1-5.

  As a preferred example of a compound having three or more functional groups containing one or more alkylene oxide units, when the functional group is a hydroxyl group, (poly) oxymethylene glycerin, (poly) oxyethylene glycerin, (poly) oxytrimethylene Glycerin, (poly) oxypropylene glycerin, (poly) oxyethylene- (poly) oxypropylene glycerin, (poly) oxytetramethylene glycerin, (poly) oxymethylene diglycerin, (poly) oxyethylene diglycerin, (poly) oxy Trimethylene diglycerin, (poly) oxypropylene diglycerin, (poly) oxymethylene trimethylolpropane, (poly) oxyethylenetrimethylolpropane, (poly) oxytrimethylenetrimethylolpropane, (poly) oxypropylene Trimethylolpropane, (poly) oxyethylene- (poly) oxypropylene trimethylolpropane, (poly) oxytetramethylenetrimethylolpropane, (poly) oxymethyleneditrimethylolpropane, (poly) oxyethyleneditrimethylolpropane, (poly) Oxytrimethylene ditrimethylolpropane, (poly) oxypropylene ditrimethylolpropane, (poly) oxymethylene pentaerythritol, (poly) oxyethylene pentaerythritol, (poly) oxytrimethylene pentaerythritol, (poly) oxypropylene pentaerythritol, ( Poly) oxyethylene- (poly) oxypropylene pentaerythritol, (poly) oxytetramethylene pentaerythritol, (poly) oxime Range pentaerythritol, (poly) oxyethylene dipentaerythritol, (poly) oxytrimethylene dipentaerythritol, (poly) oxypropylene dipentaerythritol, (poly) oxymethylene glucose, (poly) oxyethylene glucose, (poly) oxy Examples include trimethylene glucose, (poly) oxypropylene glucose, (poly) oxyethylene- (poly) oxypropylene glucose, and (poly) oxytetramethylene glucose.

  In addition, as a preferable example of a compound having three or more functional groups containing one or more alkylene oxide units, when the functional group is a carboxylic acid, propane-1,2,3-tricarboxylic acid containing (poly) methylene oxide units is used. Acid, Propane-1,2,3-tricarboxylic acid containing (poly) ethylene oxide units, Propane-1,2,3-tricarboxylic acid containing (poly) trimethylene oxide units, Propane containing (poly) propylene oxide units 1,2,3-tricarboxylic acid, propane-1,2,3-tricarboxylic acid containing (poly) tetramethylene oxide units, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) methylene oxide units Acid, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) ethylene oxide units, (poly 2-methylpropane-1,2,3-triscarboxylic acid containing trimethylene oxide units, 2-methylpropane-1,2,3-triscarboxylic acid containing (poly) propylene oxide units, (poly) tetramethylene oxide 2-methylpropane-1,2,3-triscarboxylic acid containing units, butane-1,2,4-tricarboxylic acid containing (poly) methylene oxide units, butane-1,2, containing (poly) ethylene oxide units 4-tricarboxylic acid, butane-1,2,4-tricarboxylic acid containing (poly) trimethylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly) propylene oxide units, (poly) tetramethylene oxide Butane-1,2,4-tricarboxylic acid containing units, butane-1, containing (poly) methylene oxide units, , 3,4-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid containing (poly) ethylene oxide units, butane-1,2,3,4-tetra containing (poly) trimethylene oxide units Carboxylic acid, butane-1,2,3,4-tetracarboxylic acid containing (poly) propylene oxide units, butane-1,2,3,4-tetracarboxylic acid containing (poly) tetramethylene oxide units, (poly ) Trimellitic acid containing methylene oxide units, trimellitic acid containing (poly) ethylene oxide units, trimellitic acid containing (poly) trimethylene oxide units, trimellitic acid containing (poly) propylene oxide units, (poly) tetra Trimellitic acid containing methylene oxide units, trimesic acid containing (poly) methylene oxide units, (poly) ethylene Trimesic acid containing lenoxide units, trimesic acid containing (poly) trimethylene oxide units, trimesic acid containing (poly) propylene oxide units, trimesic acid containing (poly) tetramethylene oxide units, including (poly) methylene oxide units Hemimellitic acid, Hemimellitic acid containing (poly) ethylene oxide units, Hemimellitic acid containing (poly) trimethylene oxide units, Hemimellitic acid containing (poly) propylene oxide units, Hemi containing (poly) tetramethylene oxide units Mellitic acid, pyromellitic acid containing (poly) methylene oxide units, pyromellitic acid containing (poly) ethylene oxide units, pyromellitic acid containing (poly) trimethylene oxide units, pyromellitic acid containing (poly) propylene oxide units , (Poly Pyromellitic acid containing tetramethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) methylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) ethylene oxide units, (poly) Cyclohexane-1,3,5-tricarboxylic acid containing trimethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly) propylene oxide units, cyclohexane-1,3 containing (poly) tetramethylene oxide units , 5-tricarboxylic acid and the like.

  Further, as a preferred example of a compound having three or more functional groups containing one or more alkylene oxide units, when the functional group is an amino group, 1,2,3-triaminopropane containing a (poly) methylene oxide unit, 1,2,3-triaminopropane containing (poly) ethylene oxide units, 1,2,3-triaminopropane containing (poly) trimethylene oxide units, 1,2,3-containing (poly) propylene oxide units Triaminopropane, 1,2,3-triaminopropane containing (poly) tetramethylene oxide units, 1,2,3-triamino-2-methylpropane containing (poly) methylene oxide units, (poly) ethylene oxide units 1,2,3-triamino-2-methylpropane containing, 1,2,3-toe containing (poly) trimethylene oxide units Amino-2-methylpropane, 1,2,3-triamino-2-methylpropane containing (poly) propylene oxide units, 1,2,3-triamino-2-methylpropane containing (poly) tetramethylene oxide units, 1,2,4-triaminobutane containing (poly) methylene oxide units, 1,2,4-triaminobutane containing (poly) ethylene oxide units, 1,2,4-containing (poly) trimethylene oxide units Triaminobutane, 1,2,4-triaminobutane containing (poly) propylene oxide units, 1,2,4-triaminobutane containing (poly) tetramethylene oxide units, 1 containing (poly) methylene oxide units , 2,3,4-tetraminobutane, 1,2,3,4-tetraminobutane containing (poly) ethylene oxide units, ) 1,2,3,4-tetraminobutane containing trimethylene oxide units, 1,2,3,4-tetraminobutane containing (poly) propylene oxide units, 1,2,4 containing (poly) tetramethylene oxide units 3,4-tetraminobutane, 1,3,5-triaminocyclohexane containing (poly) methylene oxide units, 1,3,5-triaminocyclohexane containing (poly) ethylene oxide units, (poly) trimethylene oxide units 1,3,5-triaminocyclohexane containing, 1,3,5-triaminocyclohexane containing (poly) propylene oxide units, 1,3,5-triaminocyclohexane containing (poly) tetramethylene oxide units, (poly ) 1,2,4-triaminocyclohexane containing methylene oxide units, (poly) ethylene 1,2,4-triaminocyclohexane containing lenoxide units, 1,2,4-triaminocyclohexane containing (poly) trimethylene oxide units, 1,2,4-triaminocyclohexane containing (poly) propylene oxide units 1,2,4-triaminocyclohexane containing (poly) tetramethylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly) methylene oxide units, 1,2,4 containing (poly) ethylene oxide units 4,5-tetraminocyclohexane, 1,2,4,5-tetraminocyclohexane containing (poly) trimethylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly) propylene oxide units, (poly) tetra 1,2,4,5-tetraminosi containing methylene oxide units Rhohexane, 1,3,5-triaminobenzene containing (poly) methylene oxide units, 1,3,5-triaminobenzene containing (poly) ethylene oxide units, 1,3 containing (poly) trimethylene oxide units 5-triaminobenzene, 1,3,5-triaminobenzene containing (poly) propylene oxide units, 1,3,5-triaminobenzene containing (poly) tetramethylene oxide units, (poly) methylene oxide units 1,2,4-triaminobenzene containing, 1,2,4-triaminobenzene containing (poly) ethylene oxide units, 1,2,4-triaminobenzene containing (poly) trimethylene oxide units, (poly) 1,2,4-triaminobenzene containing propylene oxide units, including (poly) tetramethylene oxide units , It may be mentioned 2,4-diaminobenzene and the like.

  In addition, as a preferable example of a compound having three or more functional groups containing one or more alkylene oxide units, when the functional group is an ester group, an aliphatic acid of a compound having three or more hydroxyl groups containing the alkylene oxide unit Examples thereof include esters or aromatic acid esters and ester derivatives of compounds having three or more carboxylic acid groups containing the alkylene oxide unit.

  In addition, as a preferred example of a compound having three or more functional groups containing one or more alkylene oxide units, when the functional group is an amide group, an amide of a compound having three or more carboxylic acid groups containing the alkylene oxide unit Derivatives and the like.

  As a particularly preferred example of a compound having three or more functional groups containing one or more alkylene oxide units from the viewpoint of fluidity, when the functional group is a hydroxyl group, (poly) oxyethylene glycerin, (poly) oxypropylene glycerin, (Poly) oxyethylene diglycerin, (poly) oxypropylene diglycerin, (poly) oxyethylene trimethylolpropane, (poly) oxypropylene trimethylolpropane, (poly) oxyethylene ditrimethylolpropane, (poly) oxypropylene ditrimethylol Examples include propane, (poly) oxyethylene pentaerythritol, (poly) oxypropylene pentaerythritol, (poly) oxyethylene dipentaerythritol, and (poly) oxypropylene dipentaerythritol. In the case of rubonic acid, propane-1,2,3-tricarboxylic acid containing (poly) ethylene oxide units, propane-1,2,3-tricarboxylic acid containing (poly) propylene oxide units, and (poly) ethylene oxide units are included. Trimellitic acid, trimellitic acid containing (poly) propylene oxide units, trimesic acid containing (poly) ethylene oxide units, trimesic acid containing (poly) propylene oxide units, cyclohexane-1,3 containing (poly) ethylene oxide units Examples include 5-tricarboxylic acid and cyclohexane-1,3,5-tricarboxylic acid containing a (poly) propylene oxide unit. When the functional group is an amino group, 1,2,3-triamino containing a (poly) ethylene oxide unit 1,2 containing propane, (poly) propylene oxide units 3-triaminopropane, 1,3,5-triaminocyclohexane containing (poly) ethylene oxide units, 1,3,5-triaminocyclohexane containing (poly) propylene oxide units, 1, containing (poly) ethylene oxide units Examples include 3,5-triaminobenzene and 1,3,5-triaminobenzene containing a (poly) propylene oxide unit.

  The compound having three or more functional groups used in the present invention may react with (A) the polylactic acid resin and be introduced into the main chain and side chain of the component (A). You may keep the structure at the time of mixing | blending, without reacting.

  The viscosity of the compound having three or more functional groups used in the present invention is preferably 15000 m · Pa or less at 25 ° C., more preferably 5000 m · Pa or less in terms of fluidity and mechanical properties, It is particularly preferably 2000 m · Pa or less. Although there is no particular lower limit, it is preferably 100 m · Pa or more from the viewpoint of bleeding property during molding. When the viscosity at 25 ° C. is larger than 15000 m · Pa, the fluidity improving effect is insufficient, which is not preferable.

  The molecular weight or weight average molecular weight (Mw) of the compound having three or more functional groups used in the present invention is preferably in the range of 50 to 10,000, and in the range of 150 to 8,000 in terms of fluidity. Is more preferable, and the range of 200 to 1000 is more preferable. In the present invention, Mw of a compound having three or more functional groups is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  The moisture content of the compound having three or more functional groups used in the present invention is preferably 1% or less. More preferably, the moisture content is 0.5% or less, and further preferably 0.1% or less. There is no particular lower limit for the moisture content of the components. A moisture content higher than 1% is not preferable because it causes a decrease in mechanical properties.

  In the present invention, the branched polymer refers to a polymer having a branched structure, and specifically refers to a polymer having a multi-branched structure. The branched structure includes a plurality of linear segments radially from a central core. A star polymer having a branched chain, a graft polymer having a structure in which a polymer having a plurality of branch points and a branch chain is introduced into the main linear polymer chain, and having a branch in three dimensions, Examples include hyperbranched polymers having a branched structure in the repeating unit, and dendrimers having a precisely controlled molecular weight distribution and degree of branching, and star polymers and hyperbranched polymers are preferred because they are easy to produce industrially. In this respect, a hyperbranched polymer is more preferable. The branched polymer of the present invention is preferably a polymer having a branched structure that does not have a crosslinked structure due to a chemical bond such as a covalent bond, in that the effect of improving fluidity is great.

  In the present invention, the branched polymer is not particularly limited as long as it is a polymer having a branched structure, but in terms of fluidity, polyamide, polyester, polyesteramide, polycarbonate, polyester polycarbonate, polyether, polystyrene, polyphenylene, polyimide, It is preferable that it contains any one selected from polyphenylene sulfide and polyurethane, polyesters and polycarbonates are more preferable in terms of mechanical properties, aromatic polymers having an aromatic ring are more preferable, and alkylene terephthalate structure It is particularly preferable that

  In the present invention, the method for producing the branched polymer is not particularly limited. In the case of a star polymer, after synthesizing a linear segment that becomes a branched chain, an arm-first method of grafting to the core and a multifunctional initiator as a component that becomes the core, and then a branched chain Any of the co-first methods for synthesizing a linear segment may be used. In the case of a dendrimer, either the Divergent method in which a stepwise reaction is repeated from the core to increase branching, or the Convergent method in which the outer shell components are repeatedly stepped and finally bonded to the core may be used. In the case of a hyperbranched polymer, a method of self-polycondensation using a compound having a total of 3 or more of two types of substituents in one molecule, a sequential reaction using a bifunctional compound and a trifunctional compound May be any one of a method of conducting polycondensation, a method of chain-reacting self-polycondensation using a vinyl monomer having an initiator site, and a method of chain-reacting ring-opening polymerization using a cyclic monomer. Preferred are a method of sequential self-polycondensation using a compound having a total of 3 or more of two kinds of substituents in the molecule and a method of successive reactive polycondensation using a bifunctional compound and a compound having a functionality of three or more. .

  In the present invention, when the branched polymer is a hyperbranched polymer, the raw material monomer is not particularly limited as long as the above production method can be carried out. As a specific example, the compound having a total of 3 or more of two kinds of substituents in one molecule includes diphenolic acid, 5- (2-hydroxyethoxy) isophthalic acid, 5-acetoxyisophthalic acid, 5-phenoxyisophthalic acid, 3,5-hydroxybenzoic acid, 3,5-acetoxybenzoic acid, 3,5-bis (2-hydroxyethoxy) benzoic acid, methyl 3,5-bis (2-hydroxyethoxy) benzoate, 3,5-bis (Trimethylsiloxy) benzoic acid chloride, 4,4- (4′-hydroxyphenyl) pentanoic acid, 4,4- (4′-hydroxyphenyl) pentanoic acid methyl, 3,5-dibromophenol, 5- (bromomethyl)- 1,3-dihydroxybenzene, 3,5-diaminobenzoic acid, 3,5-bis (4-aminophenoxy) benzoic acid, 5-aminoi Phthalic acid, phenol-3,5-diglycidyl ether, (3,5-dibromophenyl) boronic acid, 6-bromo-1- (4-hydroxy-4'-biphenylyl) -2- (4-hydroxyphenyl) Hexane, 13-bromo-1- (4-hydroxyphenyl) -2- (4-hydroxy-4 ″ -p-terphenylyl) tridecane, 13-bromo-1- (4-hydroxyphenyl) -2- [ 4- (6-Hydroxy-2-naphthalenylyl) phenyl] tridecane and the like, and in terms of fluidity and mechanical properties, 5- (2-hydroxyethoxy) isophthalic acid, 5-acetoxyisophthalic acid, 3,5-acetoxy Benzoic acid, 3,5-bis (2-hydroxyethoxy) benzoic acid, methyl 3,5-bis (2-hydroxyethoxy) benzoate, 3,5- Sus (trimethylsiloxy) benzoic acid chloride, 4,4- (4′-hydroxyphenyl) pentanoic acid, 3,5-bis (4-aminophenoxy) benzoic acid, 13-bromo-1- (4-hydroxyphenyl)- 2- (4-Hydroxy-4 ″ -p-terphenylyl) tridecane is preferred. Examples of the bifunctional compound include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′- Aromatic dicarboxylic acids such as diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, Dicarboxylic acid components such as aliphatic dicarboxylic acids such as dimer acid, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof, ethylene glycol, propylene glycol, 1, 4 Butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimer diol, or the like, or a long chain glycol having a molecular weight of 200 to 100,000, that is, polyethylene glycol, Diol components such as poly-1,3-propylene glycol, polytetramethylene glycol, 4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F and their ester-forming derivatives, Ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2-methylpentamethylenedia Diamine components such as min, p-phenylenediamine, and p-xylylenediamine, and trifunctional or higher compounds include trimesic acid, trimellitic acid, pyromellitic acid, mellitic acid, glycerin, trimethylolpropane, pentaerythritol, 1,3 , 5-benzenetriol, tris (4-aminophenyl) amine, 1,3,5-tris (4-aminophenoxy) benzene, etc., and at least one compound having an aromatic ring may be used. In terms of mechanical properties, one or more diol components selected from terephthalic acid and ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol and 1,6-hexanediol In this case, a branched polymer is preferably used. It can be obtained those having an alkylene terephthalate structure. Examples of the vinyl monomer having an initiator site include 3- (1-chloroethyl) styrene and 4-chloromethylstyrene. Examples of the cyclic monomer include 2- (3,5-dihydroxyphenyl) -1,3-oxazoline.

  The molecular weight of the branched polymer used in the present invention is not particularly limited, but in terms of fluidity, the number average molecular weight (Mn) is preferably in the range of 300 to 30,000, more preferably in the range of 500 to 10,000. Preferably, the range is from 800 to 5000, more preferably from 1000 to 3000, the weight average molecular weight (Mw) is preferably from 300 to 150,000, and from 500 to 50,000. More preferably, it is more preferably in the range of 800-30000, and particularly preferably in the range of 1000-10000.

  The molecular weight distribution (Mw / Mn) of the branched polymer used in the present invention is not particularly limited, but is preferably in the range of 1 to 5 and more preferably in the range of 1 to 4 in terms of fluidity. 1 to 3 is more preferable.

The molecular weight is a value measured by GPC (gel permeation chromatography) under the following conditions.
Column: K-806M (2), K-802 (1) (Showa Denko)
Solvent: pentafluorophenol / chloroform = 35/65 (% by weight)
Flow rate: 0.8mL / min
Sample concentration: 0.08% (wt / vol)
Injection volume: 0.200 mL
Temperature: 23 ° C
Detector: Differential refractive index (RI) detector (RI-8020 manufactured by Tosoh Corporation)
Calibration curve: A calibration curve using monodisperse polystyrene is used.

The degree of branching (DB) of the branched polymer used in the present invention is not particularly limited, but is preferably in the range of 0.1 to 1.0 and in the range of 0.2 to 0.9 in terms of fluidity. It is more preferable that it is in the range of 0.3 to 0.9. In the present invention, DB can be obtained from the following equation, and the number of each unit can be obtained from measurement by nuclear magnetic resonance (NMR).
DB = (D + T) / (D + L + T)
D: number of dendritic units L: number of linear units T: number of terminal units

  The glass transition temperature (Tg) of the branched polymer used in the present invention is not particularly limited, but is preferably in the range of −60 to 200 ° C. and in the range of 0 to 150 ° C. in terms of fluidity. More preferably, it is more preferable that it is the range of 50-120 degreeC. In the present invention, Tg can be determined from measurement by a differential scanning calorimeter (DSC).

  The melting point (Tm) of the branched polymer used in the present invention is not particularly limited, but is preferably in the range of 0 to 300 ° C., more preferably in the range of 30 to 250 ° C. in terms of fluidity. More preferably, it is in the range of 50 to 200 ° C. In the present invention, Tm can be determined from measurement by a differential scanning calorimeter (DSC).

  In the present invention, the liquid crystal polymer is a resin capable of forming a linear anisotropic molten phase, and preferably has an ester bond. For example, a liquid crystalline polyester comprising a structural unit selected from an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic and / or aliphatic dicarbonyl unit, an alkylenedioxy unit, etc., and forming an anisotropic melt phase Or, a liquid crystalline polyester amide that is composed of a structural unit selected from the above structural unit and an aromatic iminocarbonyl unit, an aromatic diimino unit, an aromatic iminooxy unit, and the like, and that forms an anisotropic melt phase, etc. Specifically, a liquid crystalline polyester comprising a structural unit produced from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, a structural unit produced from p-hydroxybenzoic acid, and 6-hydroxy-2-naphthoic acid. Generated structural units, aromatic dihydroxy compounds and / or aliphatic dicarboxylic acids Liquid crystalline polyester comprising a structural unit produced from the above, structural unit produced from p-hydroxybenzoic acid, structural unit produced from 4,4′-dihydroxybiphenyl, aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid and / or adipine Liquid crystalline polyester comprising a structural unit produced from an aliphatic dicarboxylic acid such as acid or sebacic acid, a structural unit produced from p-hydroxybenzoic acid, a structural unit produced from ethylene glycol, or a structural unit produced from terephthalic acid Polyester, structural unit generated from p-hydroxybenzoic acid, structural unit generated from ethylene glycol, liquid crystalline polyester composed of structural units generated from terephthalic acid and isophthalic acid, structural unit generated from p-hydroxybenzoic acid, ethylene Glico A liquid crystalline polyester comprising a structural unit formed from an aliphatic dicarboxylic such as terephthalic acid and / or adipic acid or sebacic acid, p-hydroxybenzoic acid, a structural unit formed from 4,4′-dihydroxybiphenyl, A structural unit generated from an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, a structural unit generated from ethylene glycol, a structural unit generated from ethylene glycol, a structural unit generated from an aromatic dihydroxy compound As the liquid crystalline polyester, and the liquid crystalline polyester amide resin, in addition to structural units selected from aromatic oxycarbonyl units, aromatic dioxy units, aromatic and / or aliphatic dicarbonyl units, alkylenedioxy units, etc. P-aminopheno Polyester amides that form an anisotropic melt phase containing p-iminophenoxy units produced from alcohol. Further, from the viewpoint of fluidity, the liquid crystal polymer preferably has a branched structure. Examples of the polymer having such characteristics can be obtained by the methods described in JP-T-8-503503, US Pat. No. 4,410,683, and the like.

  Of these liquid crystal polymers, linear liquid crystalline polyesters are preferable in terms of fluidity and mechanical properties, and liquid crystallinity composed of structural units formed from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid among others. Polyester, structural unit generated from p-hydroxybenzoic acid, structural unit generated from ethylene glycol, structural unit generated from 4,4′-dihydroxybiphenyl, aliphatic dicarboxylic such as terephthalic acid and / or adipic acid, sebacic acid, etc. Liquid crystalline polyester composed of the generated structural units, structural units generated from p-hydroxybenzoic acid, structural units generated from ethylene glycol, structural units generated from aromatic dihydroxy compounds, terephthalic acid, isophthalic acid, 2,6-naphthalene Aromatic dicals such as dicarboxylic acids A liquid crystalline polyester composed of a structural unit formed from an acid is more preferred. Among them, a liquid crystalline polyester composed of a structural unit formed from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and formed from p-hydroxybenzoic acid. Structural units, structural units generated from ethylene glycol, structural units generated from aromatic dihydroxy compounds, structural units generated from aromatic dicarboxylic acids such as terephthalic acid, structural units generated from p-hydroxybenzoic acid, More preferred are liquid crystalline polyesters having a structural unit produced from ethylene glycol and a structural unit produced from an aromatic dicarboxylic acid such as terephthalic acid.

The method for producing a liquid crystal polymer such as liquid crystalline polyester or liquid crystalline polyester amide used in the present invention is not particularly limited and can be produced by a known polycondensation method.
For example, the following production method is preferably exemplified as the production of the liquid crystalline polyester.

  (1) Diacylated products of p-acetoxybenzoic acid and aromatic dihydroxy compounds such as 4,4′-diacetoxybiphenyl and diacetoxybenzene, and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester by deacetic acid condensation polymerization reaction.

  (2) Reacting p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl and hydroquinone with aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid with acetic anhydride. Then, after acylating a phenolic hydroxyl group, a method for producing a liquid crystalline polyester by a deacetic acid polycondensation reaction.

  (3) From p-hydroxybenzoic acid phenyl ester and aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl and hydroquinone and diphenyl esters of aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester by dephenol polycondensation reaction.

  (4) After reacting p-hydroxybenzoic acid and aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid and the like with a predetermined amount of diphenyl carbonate to obtain diphenyl ester, 4,4 ′ A method for producing a liquid crystalline polyester by dephenol polycondensation reaction by adding an aromatic dihydroxy compound such as dihydroxybiphenyl or hydroquinone.

  (5) Polyester polymer such as polyethylene terephthalate, oligomer or liquid crystal by the method of (1) or (2) in the presence of bis (β-hydroxyethyl) ester of aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate For producing a conductive polyester.

  The liquid crystal starting temperature (TN) of the liquid crystal polymer used in the present invention is not particularly limited, but is preferably in the range of 0 to 300 ° C., more preferably in the range of 100 to 250 ° C. in terms of fluidity. More preferably, the temperature is in the range of 150 to 230 ° C. In the present invention, TN refers to the temperature at which the entire field of view starts to flow as measured by a shear stress heating device (CSS-450) at a shear rate of 1000 / s, a heating rate of 5 ° C./min, and an objective lens 60 times. .

  The melting point (Tm) of the liquid crystal polymer used in the present invention is not particularly limited, but is preferably 0 to 350 ° C. or less, more preferably 100 to 300 ° C. or less, and 180 to 250 from the viewpoint of fluidity. More preferably, it is not higher than ° C. In the present invention, Tm can be obtained from measurement by a differential scanning calorimeter (DSC), and is a value measured under a temperature rising rate of 20 ° C./min.

  The melt viscosity of the liquid crystal polymer used in the present invention is not particularly limited, but is preferably in the range of 0.5 to 200 Pa · s, more preferably in the range of 1 to 100 Pa · s in terms of fluidity. 1 to 50 Pa · s is more preferable. In the present invention, the melt viscosity of the liquid crystal polymer can be determined from the measurement by a capillograph, and is a value measured under the condition of Tm + 10 to 50 ° C. of the liquid crystal polymer and the shear rate of 1000 / s.

  The low molecular weight linear polyester used in the present invention is a linear polyester having a weight average molecular weight (Mw) in the range of 500 to 30,000. In terms of fluidity, mechanical properties, and bleed out, Mw is preferably in the range of 1000 to 25000, more preferably in the range of 1500 to 10,000, and even more preferably in the range of 3000 to 5000. In the present invention, Mw of the low molecular weight linear polyester is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  The low molecular weight linear polyester used in the present invention includes (a) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, (b) a hydroxycarboxylic acid or an ester-forming derivative thereof, ) A polymer or copolymer having at least one selected from lactone as a main structural unit, and (i) a dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming property in terms of fluidity and mechanical properties. A derivative is preferred. Moreover, as polyester, any of aromatic polyester, aliphatic polyester, and alicyclic polyester may be sufficient.

  The low molecular weight linear polycarbonate used in the present invention is a linear polycarbonate having a weight average molecular weight (Mw) in the range of 500 to 30,000. In terms of fluidity, mechanical properties and bleed out, Mw is preferably in the range of 1000 to 25000, more preferably in the range of 5000 to 20000, and still more preferably in the range of 7000 to 10,000. In the present invention, Mw of the low molecular weight linear polyester is a value in terms of polymethyl methacrylate (PMMA) measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as a solvent.

  The low-molecular-weight linear polycarbonate used in the present invention is a polymer or copolymer having a carbonate bond obtained by reacting a diol with a carbonic acid diester. From the viewpoint of fluidity, both ends are hydroxyl groups. A certain polycarbonate diol is preferable. In the present invention, the diol may be an aromatic diol, an aliphatic diol, or an alicyclic diol, and the carbonic acid diester may be any of dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like. The raw material diol is preferably used in a range of 0.5 to 5.0 times the mole of the carbonic acid diester so that both ends of the resulting polycarbonate are hydroxyl groups, and 0.8 to 2.0 times. Mole is more preferable, and 0.9 to 1.5 times mol is more preferable.

  The aromatic low molecular weight compound used in the present invention is a compound having an aromatic ring and having a number average molecular weight (Mn) of 50 or more and less than 1000. In the present invention, in terms of fluidity, it is preferably a compound having a carboxylic acid having an aromatic ring or an ester bond, and Mn is preferably in the range of 100 to 900, and in the range of 300 to 800. It is more preferable.

  The acrylic compound used in the present invention is a linear compound in which 30 mol% or more of the constituent components are composed of a (meth) acrylic acid monomer. In the present invention, in terms of fluidity, the (meth) acrylic acid monomer is preferably 50 mol% or more, and more preferably 70 mol% or more. In the present invention, specific examples of the (meth) acrylic acid monomer include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) allylate, (meth) acrylic. Examples include isopropyl acid, butyl (meth) acrylate, ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, and the like.

  The weight average molecular weight (Mw) of the acrylic compound used in the present invention is not particularly limited, but Mw is preferably in the range of 1000 to 300,000 in terms of fluidity, mechanical properties, and bleed out. More preferably, it is in the range of 10,000, more preferably in the range of 1,000 to 100,000.

  As a method for producing the acrylic compound used in the present invention, a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization or the like can be used. Although the temperature conditions at the time of superposition | polymerization are not specifically limited, -30-100 degreeC is preferable at a heat resistant point, 0-90 degreeC is more preferable, and 30-80 degreeC is further more preferable.

  In the present invention, the blending amount of the (B) fluidity improver is 0.01 to 50 parts by weight with respect to 100 parts by weight of the (A) polylactic acid resin, and 0.1 in terms of fluidity and moldability. -30 parts by weight is preferred, 0.5-20 parts by weight is more preferred, and 1-10 parts by weight is even more preferred.

<Crystal Accelerator (C)>
In the present invention, as the type of (C) crystallization accelerator, those known for thermoplastic resins can be used. Specifically, synthetic mica, clay, talc, zeolite, magnesium oxide, sulfide Examples thereof include inorganic crystallization accelerators such as calcium, boron nitride, and neodymium oxide. In order to improve dispersibility in the composition, it is preferably modified with an organic substance. Organic crystallization accelerators include sodium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum dibenzoate, potassium dibenzoate Organic carboxylic acid metal salts such as lithium dibenzoate, sodium β-naphthalate and sodium cyclohexanecarboxylate, organic sulfonates such as sodium p-toluenesulfonate and sodium sulfoisophthalate, sorbitol compounds, metal salts of phenylphosphonate, Phosphorus compound metal salts such as sodium-2,2′-methylenebis (4,6-di-t-butylphenyl) phosphate, ethylenebislauric acid amide, ethyl And the like organic amide compounds such as bis-12-dihydroxy stearic acid amide and trimesic acid tri cyclohexyl amide. By blending these crystallization accelerators, a polylactic acid resin composition and a molded product excellent in mechanical properties and moldability can be obtained.

  In this invention, the compounding quantity of (C) crystallization accelerator is 0.1-100 weight part with respect to 100 weight part of (A) polylactic acid resin, and the point of fluidity | liquidity and a moldability is 0.5. -50 parts by weight is preferred, 0.5-40 parts by weight is more preferred, and 0.5-30 parts by weight is even more preferred.

<Filler (D)>
In the present invention, as the type of (D) filler, any filler such as a fibrous shape, a plate shape, a powder shape, and a granular shape can be used. Specifically, glass fibers, PAN-based and pitch-based carbon fibers, stainless steel fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers, gypsum fibers, ceramic fibers, asbestos fibers, zirconia fibers , Alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, etc., whisker-like filler, mica, kaolin, Silica, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, montmorillonite, titanium oxide, zinc oxide, calcium polyphosphate, graphite, barium sulfate, etc. It includes plate-like filler, among others glass fibers are preferred. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from, for example, a long fiber type, a short fiber type chopped strand, a milled fiber, or the like. Moreover, said (D) filler can also be used in combination of 2 or more types. The (D) filler used in the present invention is used by treating the surface thereof with a known coupling agent (for example, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agents. You can also. The glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, or a thermosetting resin such as an epoxy resin.

  The filler (D) used in the present invention may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, such as aminosilane or epoxysilane. It may be treated with a coupling agent or the like.

  In the present invention, the blending amount of (D) filler is 1 to 100 parts by weight with respect to 100 parts by weight of (A) polylactic acid resin, and 5 to 50 parts by weight is preferable in terms of fluidity and moldability. 5 to 40 parts by weight is more preferable, and 5 to 30 parts by weight is further preferable.

<Impact resistance improver (E)>
In the present invention, it is preferable to blend (E) an impact resistance improver in order to impart (A) the mechanical strength and other properties of the polylactic acid resin. (E) The blending amount of the impact modifier is preferably in the range of 1 to 100 parts by weight per 100 parts by weight of the (A) polylactic acid resin from the viewpoint of fluidity and mechanical properties, and preferably 1 to 70 parts by weight. More preferably, it is mix | blended in the range of 1 part by weight, and it is still more preferable to mix | blend in the range of 1-50 weight part.

  In the present invention, as the (E) impact resistance improver, those known for thermoplastic resins can be used. Specifically, natural rubber, polyethylene such as low density polyethylene and high density polyethylene, Polypropylene, impact modified polystyrene, polybutadiene, styrene / butadiene copolymer, ethylene / propylene copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / vinyl acetate copolymer, ethylene / Polyester elastomers such as glycidyl methacrylate copolymer, polyethylene terephthalate / poly (tetramethylene oxide) glycol block copolymer, polyethylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymer, MB Include butadiene-based core shell elastomers or acrylic core shell elastomers such as these may be used alone or in combination. Examples of the butadiene-based or acrylic-based core-shell elastomer include “Metablene” manufactured by Mitsubishi Rayon, “Kaneace” manufactured by Kaneka, “Paralloid” manufactured by Rohm & Haas, and the like.

<Flame retardant (F)>
In the present invention, it is preferable to blend (F) a flame retardant in order to impart flame retardancy and other properties of (A) polylactic acid resin. (F) It is preferable from the point of fluidity | liquidity and a mechanical physical property that the compounding quantity of a flame retardant is 1-100 weight part with respect to 100 weight part of (A) polylactic acid resin, The range of 1-70 weight part is preferable. It is more preferable to mix | blend with 1 to 50 weight part, and it is still more preferable to mix | blend.

  In the present invention, as the flame retardant (F), those known for thermoplastic resins can be used. Specifically, red phosphorus, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, water Examples thereof include magnesium oxide, melamine and cyanuric acid or a salt thereof, and a silicon compound, and these can be used alone or in combination.

  Conventional additives can be added to the polylactic acid resin composition used in the present invention as long as the object of the present invention is not impaired.

  Examples of additives that can be added to the polylactic acid resin composition used in the present invention include ultraviolet absorbers (resorcinol, salicylate, benzotriazole, benzophenone, etc.), heat stabilizers (hindered phenols, hydroquinones, phosphites, and the like). Substitutes, etc.), lubricants, release agents (such as montanic acid and salts thereof, esters thereof, half esters thereof, stearyl alcohol, stearamide and polyethylene wax), dyes (such as nigrosine) and pigments (such as cadmium sulfide, phthalocyanine) Containing colorants, anti-coloring agents (phosphites, hypophosphites, etc.), conductive agents or coloring agents (carbon black, etc.), slidability improvers (graphite, fluororesins, etc.), antistatic agents, etc. 1 type (s) or 2 or more types can be added.

  In the polylactic acid resin composition used in the present invention, other thermoplastic resins (for example, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene copolymer, polyamide, polycarbonate, Polyphenylene sulfide resin, polyether ether ketone resin, polyester, polysulfone, polyphenylene oxide, polyacetal, polyimide, polyetherimide, cellulose ester, etc.) or thermosetting resin (for example, phenol resin, melamine resin, polyester resin, silicone resin, epoxy) Resin) or soft thermoplastic resin (for example, ethylene / glycidyl methacrylate copolymer, polyester elastomer, polyamide elastomer, ethylene / propylene ter Rimmer, ethylene / butene-1 copolymer) can further contain at least one or more of such.

  In the polylactic acid resin composition of the present invention, in terms of fluidity, (A) the melting viscosity of the polylactic acid resin at + 15 ° C. and the shear rate of 100 mm / min is preferably in the range of 50 to 150 Pa · s. More preferably, it is in the range of 50 to 140 Pa · s, more preferably in the range of 50 to 130 Pa · s, and particularly preferably in the range of 50 to 120 Pa · s. In the present invention, the melt viscosity of the resin composition can be measured by a capillograph.

  In the polylactic acid resin composition of the present invention, in terms of fluidity and mechanical properties, (A) Melting viscosity / weight average molecular weight × 10000 at a melting point + 15 ° C. and a shear rate of 100 mm / min of the polylactic acid resin is 4-9. It is preferable that it is the range of 4-8, It is more preferable that it is the range of 4-8, It is more preferable that it is the range of 4-7, It is especially preferable that it is the range of 4-6.

  The polylactic acid resin composition of the present invention can be molded by any known method such as injection molding, extrusion molding, blow molding, press molding, and spinning, and can be processed into various molded products and used. As molded products, it can be used as injection molded products, extrusion molded products, blow molded products, films, sheets, fibers, etc., as films, as various films such as unstretched, uniaxially stretched, biaxially stretched, as fibers, It can be used as various fibers such as undrawn yarn, drawn yarn, and super-drawn yarn. In particular, in the present invention, taking advantage of the excellent fluidity, it can be processed into an injection molded product having a thin part having a thickness of 0.01 to 1.0 mm, and fluidity and appearance are required. It can also be processed into large molded products.

  In the present invention, the above-mentioned various molded products can be used for various applications such as automobile parts, electrical / electronic parts, building members, various containers, daily necessities, household goods and sanitary goods.

  EXAMPLES Hereinafter, although an Example demonstrates the structure and effect of this invention further in detail, this invention is not limited to these. Here, the number of parts in the examples represents parts by weight. Moreover, the raw material used and the code | symbol in a table | surface are shown below.

(A) Polylactic acid resin A-1: Production Example 1 (mixed resin of poly-L-lactic acid and poly-D-lactic acid)
A-2: Production Example 2 (block copolymer of poly-L-lactic acid and poly-D-lactic acid)
A-3: Production Example 3 (mixed resin of poly-L-lactic acid and poly-D-lactic acid)
A-4: Production Example 4 (poly-L-lactic acid).

(B) Fluidity improver B-1: Compound having three or more functional groups (trimethylolpropane: molecular weight 134, ALDRICH)
B-2: Compound having three or more functional groups (pentaerythritol: molecular weight 136, Tokyo Kasei)
B-3: Compound having three or more functional groups (polyoxyethylene diglycerin, molecular weight 410, number of alkylene oxide units per functional group 1.5, Sakamoto Pharmaceutical SC-E450)
B-4: Compound having three or more functional groups (oxyethylenetrimethylolpropane: molecular weight 266, manufactured by Nippon Emulsifier TMP-30U)
B-5: A compound having three or more functional groups (polyoxyethylene pentaerythritol: molecular weight 400, PNT-60U manufactured by Nippon Emulsifier)
B-6: Production Example 5 (Branched polymer: Hyperbranched aromatic polyester)
B-7: Production Example 6 (Liquid Crystalline Polymer: Liquid Crystalline Polyester)
B-8: Production Example 7 (low molecular weight linear polyester: aliphatic polyester)
B-9: Production Example 8 (low molecular weight linear polycarbonate: aliphatic polycarbonate)
B-10: Aromatic low molecular weight compound (trimellitic acid tree 2-ethylhexyl, TOHA manufactured by Daihachi Chemical Industry, molecular weight 547, Tm-30 ° C.)
B-11: (Acrylic compound: Polybutyl acrylate (“Act Flow” UMB-1001, manufactured by Soken Chemical Co., Ltd., weight average molecular weight 1500)
B-12: Production Example 9 (acrylic compound: triblock copolymer (polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate, weight average molecular weight 62,000, polybutyl acrylate content 50 wt%)).

(C) Crystallization accelerator C-1: Talc (Nippon Talc "Microace" P-6)
C-2: Ethylene bis stearic acid amide ("Kao wax" EB-FF made by Kao)
C-3: Metal phosphate ("ADEKA STAB" NA-11 manufactured by ADEKA).

(D) Filler D-1: Glass fiber (Nittobo CS3J948).

(E) Impact modifier E-1: Core-shell type rubber containing glycidyl group in outermost layer ("Roid and Haas" Paraloid EXL2314 "(core: butyl acrylate rubber, shell: methyl methacrylate / glycidyl methacrylate co-polymer) Coalescing)).

(F) Flame retardant F-1: Magnesium hydroxide (ALDRICH).

[Production Example 1] (Production Example of A-1)
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 adjusted to 150 ° C., and the reaction was carried out for 3.5 hours while gradually reducing the pressure to distill off water. Thereafter, the pressure was brought to normal pressure in a nitrogen atmosphere, 0.02 part of tin (II) acetate was added, and then the polymerization reaction was performed for 7 hours while gradually reducing the pressure to 170 Pa at 170 ° C. to obtain poly-L-lactic acid ( PLLA1) was obtained. PLA1 had a weight average molecular weight of 18,000, a dispersity of 1.5, a melting point of 149 ° C., and a melting end temperature of 163 ° C. The obtained PLLA1 was subjected to crystallization treatment at 110 ° C. for 1 hour in a nitrogen atmosphere, followed by solid phase polymerization under a pressure of 60 Pa for 3 hours at 140 ° C., 3 hours at 150 ° C., and 18 hours at 160 ° C., Poly-L-lactic acid (PLLA2) was obtained. PLA2 had a weight average molecular weight of 203,000, a temperature drop crystallization temperature of 96 ° C., and a melting point of 170 ° C. Next, 50 parts of a 90% D-lactic acid aqueous solution is placed in a reaction vessel equipped with a stirrer and a reflux device, and the temperature is adjusted to 150 ° C., and then the pressure is gradually reduced to distill off water for 3.5 hours. Reacted. Thereafter, the pressure was increased to normal pressure in a nitrogen atmosphere, 0.02 part of tin (II) acetate was added, and then the polymerization reaction was performed for 7 hours while gradually reducing the pressure to 170 Pa at 13 ° C. to obtain poly-D-lactic acid ( PDLA1) was obtained. PLA1 had a weight average molecular weight of 17,000, a melting point of 148 ° C., and a melting end temperature of 161 ° C. The obtained PDLA1 was subjected to crystallization treatment at 110 ° C. for 1 hour in a nitrogen atmosphere, followed by solid phase polymerization under a pressure of 60 Pa for 3 hours at 140 ° C., 3 hours at 150 ° C., and 14 hours at 160 ° C., Poly-L-lactic acid (PDLA2) was obtained. PLA3 had a weight average molecular weight of 1580, a temperature-falling crystallization temperature of 97 ° C, and a melting point of 168 ° C.

  Next, PLLA2 and PDLA2 are preliminarily crystallized under a nitrogen atmosphere at a temperature of 110 ° C. for 2 hours, and the raw materials are blended so that PLLA2 / PDLA2 = 50/50 parts by weight. After dry blending 0.5 parts by weight of “ADEKA STAB” AX-71, manufactured by Adeka, to 100 parts by weight of PLLA2 and PDLA2, the cylinder temperature was set to 240 ° C. and the screw rotation speed was set to 100 rpm. Pellets of polylactic acid resin A are melt-kneaded with a PCM30 twin-screw extruder having a kneading block at several locations, and the strand discharged from the die is cooled in a cooling bath and then pelletized with a strand cutter. -1 was obtained. The polylactic acid resin A-1 had a weight average molecular weight of 182,000, a melt viscosity of 135 Pa · s, a temperature-falling crystallization temperature of 121 ° C., and a stereocomplex melting point of 214 ° C. The physical properties were measured after crystallization treatment at a pressure of 13.3 Pa and 110 ° C. for 2 hours.

[Production Example 2] (Production Example of A-2)
The PDLA1 obtained in Production Example 1 was subjected to crystallization treatment at 110 ° C. for 1 hour in a nitrogen atmosphere, and then a solid phase under a pressure of 60 Pa for 3 hours at 140 ° C., 3 hours at 150 ° C., and 6 hours at 160 ° C. Polymerization was performed to obtain poly-D-lactic acid (PDLA3). PDLA3 had a weight average molecular weight of 42,000, a falling crystallization temperature of 98 ° C., and a melting point of 158 ° C.

  The PLLA2 and PDLA3 obtained in Production Example 1 are preliminarily crystallized under a nitrogen atmosphere at a temperature of 110 ° C. for 2 hours, and PLLA2 is added from the resin supply port of the TEX30α twin screw extruder (manufactured by Nippon Steel). Then, PDLA3 was added from the side supply port provided in the portion of L / D = 30, and melt kneading was performed. The twin screw extruder is provided with a plasticizing part set at a temperature of 180 ° C. at a part where L / D = 10 from the resin supply port, and a kneading disk is provided at a part where L / D = 30 as a screw capable of applying shear. The structure can be mixed under shearing, and PLLA2 and PDLA3 were mixed at a mixing temperature of 200 ° C. under shearing. After cooling the strand discharged from the die in the cooling bath, pelletized polylactic acid melt-kneaded resin a-1 was obtained by pelletizing with a strand cutter. The obtained polylactic acid melt-kneaded resin was dried in a vacuum dryer at 110 ° C. and a pressure of 13.3 Pa for 2 hours, then subjected to solid phase polymerization at 140 ° C. and a pressure of 13.3 Pa for 4 hours, and then raised to 150 ° C. The mixture was heated for 4 hours, and further heated to 160 ° C. and subjected to solid phase polymerization for 10 hours to obtain a polylactic acid block copolymer. Next, after dry blending 0.5 parts by weight with respect to 100 parts by weight of the polylactic acid block copolymer obtained as a catalyst deactivator (manufactured by ADEKA, “ADEKA STAB” AX-71), the cylinder temperature was adjusted to 240 ° C. , Melt-kneaded with a PCM30 twin screw extruder with two kneading block sections set at a screw speed of 100 rpm, cool the strand discharged from the die in a cooling bath, and then pelletize it with a strand cutter By doing so, pellet-shaped polylactic acid resin A-2 was obtained. The polylactic acid resin A-2 had a weight average molecular weight of 16,000, a melt viscosity of 121 Pa · s, a temperature-falling crystallization temperature of 137 ° C., and a stereocomplex melting point of 213 ° C. The physical properties were measured after crystallization treatment at a pressure of 13.3 Pa and 110 ° C. for 2 hours.

[Production Example 3] (Production Example of A-3)
The PLLA1 obtained in Production Example 1 was subjected to crystallization treatment at 110 ° C. for 1 hour in a nitrogen atmosphere, and then a solid phase under a pressure of 60 Pa for 3 hours at 140 ° C., 3 hours at 150 ° C., and 10 hours at 160 ° C. Polymerization was performed to obtain poly-L-lactic acid (PLLA3). PLA2 had a weight average molecular weight of 103,000, a temperature drop crystallization temperature of 98 ° C., and a melting point of 171 ° C. Next, the PDLA 1 obtained in Production Example 1 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 10 hours. Solid phase polymerization was performed for time to obtain poly-D-lactic acid (PDLA4). PLA3 had a weight average molecular weight of 98,000, a falling crystallization temperature of 97 ° C., and a melting point of 168 ° C. Next, PLLA3 and PDLA4 are preliminarily crystallized under a nitrogen atmosphere at a temperature of 110 ° C. for 2 hours. The raw materials are blended so that PLLA3 / PDLA4 = 50/50 parts by weight, and a catalyst deactivator ( After dry blending 0.5 parts by weight of “ADEKA STAB” AX-71, manufactured by Adeka, with respect to a total of 100 parts by weight of PLLA3 and PDLA4, the cylinder temperature was set to 240 ° C. and the screw rotation speed was set to 100 rpm. Pellets of polylactic acid resin A are melt-kneaded with a PCM30 twin-screw extruder having a kneading block at several locations, and the strand discharged from the die is cooled in a cooling bath and then pelletized with a strand cutter. -3 was obtained. The polylactic acid resin A-3 had a weight average molecular weight of 92,000, a melt viscosity of 59 Pa · s, a temperature-falling crystallization temperature of 127 ° C., and a stereocomplex melting point of 225 ° C. The physical properties were measured after crystallization treatment at a pressure of 13.3 Pa and 110 ° C. for 2 hours.

[Production Example 4] (Production Example of A-4)
The PLLA2 obtained in Production Example 1 was preliminarily crystallized in a nitrogen atmosphere at a temperature of 60 ° C. for 2 hours, and a catalyst deactivator (manufactured by ADEKA, “ADEKA STAB” AX-71) was added to 100 of PLLA4. After dry blending 0.5 parts by weight with respect to parts by weight, the mixture was melt-kneaded in a PCM30 twin screw extruder having two kneading block parts with a cylinder temperature set to 190 ° C. and a screw rotation speed set to 100 rpm. After cooling the strand discharged from the inside of a cooling bath, pelletized polylactic acid resin A-3 was obtained by pelletizing with a strand cutter. The polylactic acid resin A-3 had a weight average molecular weight of 198,000, a melt viscosity of 163 Pa · s, and a temperature-falling crystallization temperature of 97 ° C. The physical properties were measured after crystallization treatment at a pressure of 13.3 Pa and 60 ° C. for 2 hours.

[Production Example 5] (Production Example of B-6)
In a 500 mL reaction vessel equipped with a stirring blade and a distillation tube, 66.3 g (0.48 mol) of p-hydroxybenzoic acid, 8.38 g (0.045 mol) of 4,4′-dihydroxybiphenyl, and terephthalic acid 7. 48 g (0.045 mol), 14.41 g (0.075 mol) of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, 31.52 g (0.15 mol) of trimesic acid and acetic anhydride 62.48 g (1.00 equivalent of the total phenolic hydroxyl groups) was charged and reacted at 145 ° C. for 2 hours with stirring in a nitrogen gas atmosphere. Thereafter, the temperature was raised to 280 ° C., and the mixture was stirred for 3 hours. When 91% of acetic acid was distilled, the heating and stirring were stopped, and the contents were discharged into cold water.

  The obtained dendritic polyester was dried at 110 ° C. for 5 hours using a dryer and then pulverized using a blender, and the obtained dendritic polyester powder was used for 12 hours at 100 ° C. using a vacuum heat dryer. Heated to vacuum dry.

  The dried dendritic polyester powder (70 g) and ethyl orthoacetate (31.4 g, 0.19 mol) were charged into a 500 mL reaction vessel equipped with a stirring blade and heated to 200 ° C. After stirring at 200 ° C. for 20 minutes, the contents are discharged into cold water, and heated and vacuum dried at 100 ° C. for 12 hours using a vacuum heat dryer, so that an aromatic hyperbranched aromatic polyester ( B-6) was obtained. As a result of analyzing B-6, the number average molecular weight was 2200 and the weight average molecular weight was 4900.

[Production Example 6] (Production Example of B-7)
A reaction vessel equipped with a stirring blade and a distillation tube was charged with 90 parts of p-acetoxybenzoic acid and 110 parts of polyethylene terephthalate having an intrinsic viscosity of 0.6 dl / g and reacted at 280 ° C. for 1 hour in a nitrogen stream. After that, polycondensation was performed at 290 ° C. and 67 kPa for 2 hours to obtain a liquid crystalline polyester (B-4) as a liquid crystal polymer. As a result of analyzing B-7, the liquid crystal starting temperature was 170 ° C. and the melting point was 200 ° C.

[Production Example 7] (Production Example of B-8)
A reaction vessel equipped with a stirring blade and a condenser was purged with nitrogen, and then 65 parts of adipic acid, 20 parts of 1,4-cyclohexanedimethanol, 20 parts of 1,4-butanediol and 10 parts of ethylene glycol were charged under a nitrogen stream. The mixture was reacted at 200 ° C. and 150 kPa for 1 hour, and further reacted at 220 ° C. and 40 kPa for 3 hours to obtain an aliphatic polyester (B-8) as a low molecular weight linear polyester. As a result of analyzing B-8, it was the weight average molecular weight 5750.

[Production Example 8] (Production Example of B-9)
The reaction vessel equipped with a stirring blade and a condenser was purged with nitrogen, and then charged with 56 parts of 1,6-hexanediol and 43 parts of dimethyl carbonate, held at 120 ° C. for 15 minutes in a nitrogen stream, and then tetrabutoxy 0.1 g of titanium was added, reacted at 190 ° C. and 10 kPa for 5 hours under a nitrogen stream, and further reacted at 200 ° C. and 67 Pa for 5 hours to obtain an aliphatic polycarbonate (B-9) as a low molecular weight linear polycarbonate. . As a result of analyzing B-9, it was found that the weight average molecular weight was 2850, the hydroxyl end group amount was 95 mol%, and the methyl carbonate end group amount was 5 mol%.

[Production Example 9] (Production Example of B-12)
Insert a stirrer coated with Teflon (registered trademark), etc. into a 2L three-necked flask equipped with a three-way cock, degass it with a vacuum pump while swirling with a dryer, and then replace with argon gas Repeated three times, the water in the flask was removed. To the three-necked flask were added 600 g of toluene, 56 g of 1,2-dimethoxyethane, 16.8 mmol of isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, and 3.2 mmol of sec-butyllithium. Stirring was performed with a magnetic stirrer for 10 minutes in an atmosphere. Thereafter, 32 g of methyl methacrylate was added, and a polymerization reaction was carried out at room temperature for 90 minutes (first block). Subsequently, the internal temperature of the polymerization solution was set to −40 ° C., and 64 g of n-butyl acrylate previously cooled to −40 ° C. was continuously dropped over 360 minutes (second block). Subsequently, 32 g of methyl methacrylate was added to return the internal temperature of the polymerization solution to room temperature, and stirring was continued for 600 minutes to carry out the polymerization reaction (third block). This polymerization solution was put into 15 L of methanol, and the polymer was reprecipitated as the polymerization was stopped. The polymer after reprecipitation was collected, and dried for a whole day and night in a vacuum dryer set at 60 ° C. to obtain an acrylic compound (B-12) having a block structure. As a result of measuring GPC of the obtained acrylic compound (B-12), the weight average molecular weight was 62,000. Further, as a result of composition analysis by 1H-NMR, methyl methacrylate polymer (PMMA) = 50% by weight and n-butyl acrylate polymer (PnBA) = 50% by weight. From these results, it was found that the acrylic compound (B-12) was a triblock copolymer of PMMA (25 wt%)-PnBA (50 wt%)-PMMA (25 wt%).

  Moreover, the evaluation methods used in Examples and the like are summarized below.

(1) Weight average molecular weight A weight average molecular weight is the value of the weight average molecular weight of standard polymethylmethacrylate measured by gel permeation chromatography (GPC). GPC measurement was performed using a WATERS differential refractometer WATERS 410 as a detector, a WATERS MODEL 510 as a pump, and a column in which Shodex GPC HFIP-806M and Shodex GPC HFIP-LG were connected in series. The measurement conditions were a flow rate of 0.5 mL / min, hexafluoroisopropanol was used as a solvent, and 0.1 mL of a solution having a sample concentration of 1 mg / mL was injected.

The weight average molecular weight and number average molecular weight of the branched polymer were measured by GPC (gel permeation chromatography) method under the following conditions.
Column: K-806M (2), K-802 (1) (Showa Denko)
Solvent: pentafluorophenol / chloroform = 35/65 (% by weight)
Flow rate: 0.8mL / min
Sample concentration: 0.08% (wt / vol)
Injection volume: 0.200 mL
Temperature: 23 ° C
Detector: Differential refractive index (RI) detector (RI-8020 manufactured by Tosoh Corporation)
Calibration curve: A calibration curve using monodisperse polystyrene is used.

(2) Melt Viscosity Using a Capillograph Type 1C (die diameter φ1 mm, die length 5 mm) manufactured by Toyo Seiki Co., Ltd., the melting point was + 10 ° C. and the shear rate was 100 / min.

(3) Melt Viscosity Reduction Rate The melt viscosity reduction rate was measured by the following general formula (melt viscosity before adding fluidity improver-melt viscosity after adding fluidity improver) / (melt before adding fluidity improver) Viscosity) x 100 (%)

(4) Thermal characteristics The temperature-falling crystallization temperature and the stereocomplex melting point were measured by a differential scanning calorimeter (DSC) manufactured by PerkinElmer. The measurement conditions are a sample 10 mg, a nitrogen atmosphere, and a temperature raising / lowering rate of 20 ° C./min.

  However, the melting point of the stereo complex is the crystal melting temperature of the stereo complex crystal that appears at 190 ° C. or higher and lower than 250.

(5) Formability 12.7 mm × 127 mm × 3 mm strips were molded and judged according to the following criteria.
A: A molded product can be obtained without any problem.
A: A molded product with a slight burr or unfilled can be obtained.
X: Burr or unfilled is large, and a molded product cannot be obtained.

(6) Impact resistance According to ASTM D256, the Izod impact strength of a molded product with a 3 mm thick notch was measured.

[Examples 1-21, Comparative Examples 1-3]
As shown in Tables 1 and 2, (A) polylactic acid resin and (B) fluidity improver were blended and melt kneaded using a PCM30 twin screw extruder under conditions of a cylinder temperature of 240 ° C. and a rotation speed of 100 rpm. A pellet-shaped resin composition was obtained.

  The moldability of the obtained resin composition was evaluated using an injection molding machine SG75H-MIV manufactured by Sumitomo Heavy Industries at a cylinder temperature of + 15 ° C. and a mold temperature of 90 ° C.

[Comparative Examples 4 and 5]
As shown in Table 2, (A) polylactic acid resin and (B) fluidity improver were blended and melt-kneaded under the conditions of a cylinder temperature of 190 ° C. and a rotation speed of 100 rpm using a PCM30 twin screw extruder. A polylactic acid composition was obtained.

  The moldability of the obtained resin composition was evaluated using an injection molding machine SG75H-MIV manufactured by Sumitomo Heavy Industries at a cylinder temperature of + 15 ° C. and a mold temperature of 90 ° C.

  The evaluation results are shown in Table 2.

  From the results of Tables 1 and 2, the following is clear.

  From the comparison between Examples 1-21 and Comparative Examples 1-5, the polylactic acid composition formed by blending (A) polylactic acid resin and (B) fluidity improver is excellent in fluidity and moldability. I understand that. In particular, (A) the polylactic acid resin is composed of poly-L-lactic acid and poly-D-lactic acid, and (B) the fluidity improver is a compound having three or more functional groups, an acrylic compound, a branched polymer, It can be seen that the liquid crystal polymer, the low molecular weight linear polyester, the low molecular weight linear polycarbonate, or the aromatic low molecular compound is preferable.

[Examples 22 to 39, Comparative Examples 6 to 11]
As shown in Tables 3 and 4, (A) polylactic acid resin and (B) fluidity improver were blended and melt kneaded using a PCM30 twin screw extruder under conditions of a cylinder temperature of 240 ° C. and a rotation speed of 100 rpm. A pellet-shaped resin composition was obtained.
The moldability of the obtained polylactic acid resin composition was evaluated using an injection molding machine SG75H-MIV manufactured by Sumitomo Heavy Industries at a cylinder temperature of + 15 ° C. and a mold temperature of 90 ° C.

  The evaluation results are shown in Tables 3 and 4.

  From the results of Tables 3 and 4, the following is clear.

  From the comparison between Examples 22 to 39 and Comparative Examples 1 to 5, a polylactic acid composition comprising (A) a polylactic acid resin, (B) a fluidity improver, and (C) a crystallization accelerator, It turns out that it is excellent in fluidity | liquidity and a moldability. In particular, (A) the polylactic acid resin is composed of poly-L-lactic acid and poly-D-lactic acid, and (B) the fluidity improver is a compound having three or more functional groups, an acrylic compound, a branched polymer, It can be seen that the liquid crystal polymer, the low molecular weight linear polyester, the low molecular weight linear polycarbonate, or the aromatic low molecular compound is preferable.

[Examples 40 to 45, Comparative Examples 12 to 17]
As shown in Table 5, in addition to (A) polylactic acid resin, (B) fluidity improver, (C) crystallization accelerator, (D) filler, (E) impact resistance improver, (F) difficulty A flame retardant was appropriately blended, and melt-kneading was performed using a PCM30 twin-screw extruder under conditions of a cylinder temperature of 240 ° C. and a rotation speed of 100 rpm to obtain a pellet-shaped resin composition.

The moldability of the obtained resin composition was evaluated using an injection molding machine SG75H-MIV manufactured by Sumitomo Heavy Industries at a cylinder temperature of + 15 ° C. and a mold temperature of 90 ° C.
The evaluation results are shown in Table 5.

From the results in Table 5, the following is clear.
From comparison between Examples 40 to 45 and Comparative Examples 12 to 17, (A) polylactic acid resin, (B) fluidity improver, (C) crystallization accelerator, (D) filler, (E) impact resistance It can be seen that the polylactic acid composition obtained by blending the property improver and (F) the flame retardant is excellent in fluidity and moldability.

Claims (11)

(A) A polylactic acid composition obtained by blending 0.01 to 50 parts by weight of a fluidity improver with 100 parts by weight of a polylactic acid resin composed of poly-L-lactic acid and poly-D-lactic acid. In DSC measurement, the temperature of the resin composition was raised to 250 ° C. and kept at a constant temperature for 3 minutes, and then the constant temperature crystallization temperature when the temperature was lowered at a cooling rate of 20 ° C./minute was 120 ° C. or higher. The polylactic acid composition according to claim 1, wherein the stereocomplex crystal has a melting point of 200 ° C. or higher when the temperature is further increased to 250 ° C. at a rate of temperature increase of 20 ° C./min. (A) The polylactic acid resin has a weight average molecular weight of 100,000 or more, and (B) the melt viscosity after blending the fluidity improver is 10 from the melt viscosity before blending (B) the fluidity improver. The polylactic acid composition according to claim 1, wherein the polylactic acid composition decreases by at least%. The (A) polylactic acid resin is a block copolymer composed of a segment composed of poly-L-lactic acid and a segment composed of poly-D-lactic acid. Polylactic acid composition. (A) In a block copolymer in which a polylactic acid resin is composed of a segment composed of poly-L-lactic acid and a segment composed of poly-D-lactic acid, the weight-average molecular weight of the segment composed of poly-L-lactic acid and poly-L 5. The polylactic acid composition according to claim 4, wherein the ratio of the weight average molecular weight of the segment comprising D-lactic acid is 1.5 or more and less than 30, and the total molecular weight is 100,000 or more. (B) The fluidity improver is a compound having three or more functional groups, an acrylic compound, a branched polymer, a liquid crystal polymer, a low molecular weight linear polyester, a low molecular weight linear polycarbonate, an aromatic low molecular compound. The polylactic acid composition according to claim 1, comprising any one selected from the group consisting of: The polylactic acid composition according to any one of claims 1 to 6, wherein 1 to 100 parts by weight of (C) a crystallization accelerator is blended with 100 parts by weight of (A) polylactic acid resin. The polylactic acid composition according to any one of claims 1 to 7, wherein (A) 1 to 100 parts by weight of the filler is blended with 100 parts by weight of the polylactic acid resin. The polylactic acid composition according to any one of claims 1 to 8, wherein (A) 1 to 100 parts by weight of an impact resistance improver is blended with 100 parts by weight of the polylactic acid resin. The polylactic acid composition according to any one of claims 1 to 9, wherein (A) 1 to 100 parts by weight of a flame retardant is blended with 100 parts by weight of the polylactic acid resin. The molded article which consists of a polylactic acid composition of any one of Claims 1-10.