+

WO2008075775A1 - Composition de résine à base d'acide polylactique et procédé de production d'un corps moulé en résine à base d'acide polylactique - Google Patents

Composition de résine à base d'acide polylactique et procédé de production d'un corps moulé en résine à base d'acide polylactique Download PDF

Info

Publication number
WO2008075775A1
WO2008075775A1 PCT/JP2007/074767 JP2007074767W WO2008075775A1 WO 2008075775 A1 WO2008075775 A1 WO 2008075775A1 JP 2007074767 W JP2007074767 W JP 2007074767W WO 2008075775 A1 WO2008075775 A1 WO 2008075775A1
Authority
WO
WIPO (PCT)
Prior art keywords
polylactic acid
acid resin
resin composition
plasticizer
ester
Prior art date
Application number
PCT/JP2007/074767
Other languages
English (en)
Japanese (ja)
Inventor
Akira Takenaka
Hiroaki Kishimoto
Original Assignee
Kao Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kao Corporation filed Critical Kao Corporation
Publication of WO2008075775A1 publication Critical patent/WO2008075775A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/18—Plasticising macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a polylactic acid resin composition and a polylactic acid resin molded article.
  • the present invention relates to a method for producing a polylactic acid resin molded article.
  • polylactic acid resin is made from a sugar that can be taken from corn, straw, etc., and a large amount of L-monolactic acid is produced by fermentation. The amount of resin obtained is extremely small, and the resulting resin is characterized by its high rigidity and good transparency.
  • polylactic acid resin is brittle, hard, and lacks flexibility, all of which are limited to the field of hard molded products. When molded into injection molded articles, flexibility and impact resistance are insufficient. There are problems such as whitening and inferior hinge characteristics when bent, and it is currently not used in the soft or semi-rigid field.
  • polylactic acid resin has a slow crystallization rate and is in an amorphous state after molding unless mechanical processes such as stretching are performed.
  • T g glass transition temperature
  • WO-A 200 3 0423 02 discloses an amide compound having a specific structure, a plasticizer, a lactic acid polymer composition containing a lactic acid polymer, and a method for producing a molded body thereof.
  • JP-A 200 6- 1 7 6747 discloses a method for producing a polylactic acid resin molded article having excellent heat resistance and impact resistance and good moldability, but the mold temperature is lowered. As a result, the moldability was still not fully satisfactory.
  • the present invention is a polylactic acid resin composition containing a polylactic acid resin and a plasticizer, wherein the polylactic acid resin has an optical purity of 99% or more, and the plasticizer has two or more ester groups in the molecule.
  • a polylactic acid resin composition which is a compound obtained by adding an average of 0.5 to 5 moles of an alkylene oxide having 2 to 3 carbon atoms per hydroxyl group to at least one of the alcohol components constituting the ester, and this A polylactic acid resin molded article obtained by molding a polylactic acid resin composition is provided.
  • a polylactic acid resin composition containing a polylactic acid resin having an optical purity of 99% or more and a plasticizer is melt-kneaded, and then the obtained melt is filled into a mold of 70 ° C or lower.
  • a method for producing a molded product of polylactic acid resin having a relative crystallinity of 60% or more is provided.
  • the present invention provides a polylactic acid resin composition having excellent heat resistance and impact resistance, good moldability, and particularly excellent moldability at a low mold temperature.
  • the present invention relates to a method for producing a polylactic acid resin molded article that can obtain a polylactic acid resin molded article having sufficient crystallinity even when the mold temperature is lowered and having excellent heat resistance and impact resistance. I will provide a.
  • the polylactic acid resin composition of the present invention is excellent in heat resistance and impact resistance, and exhibits excellent moldability even at a lower mold temperature.
  • a polylactic acid resin molded article having excellent heat resistance and impact resistance can be obtained even when the mold temperature is lowered, and the safety and productivity of the work are further improved. be able to.
  • the polylactic acid resin used in the present invention has an optical purity of 99% or more, that is, each unit of L monolactic acid or D_lactic acid is 99 mol% or more.
  • the lactic acid unit is preferably 1 mol% or less, and the L monolactic acid unit content is preferably 99 mol% or more.
  • the polylactic acid resin in the present invention includes polylactic acid (A) composed of 99 to 100 mol% of L monolactic acid units and 0 to 1 mol% of units such as D-lactic acid, and D_ It consists of a mixture of polylactic acid (B) composed of 9 9 to 100 mol% of lactic acid units and 0 to 1 mol% of units such as L-lactic acid, and (A) / (B) (weight ratio) It is also possible to use stereocomplex polylactic acid having a valence of 10 90 to 90 10.
  • the copolymer components other than lactic acid that can be used in each of the polylactic acids (A) and (B) constituting the stereocomplex polylactic acid are dicarboxylic acids having a functional group capable of forming two or more ester bonds, polyvalent Examples include alcohol, hydroxycarboxylic acid, lactone, and various other components, and examples include polyesters, polyethers, and polybodies that have two or more unreacted carboxyl groups and two or more hydroxyl groups in the molecule. It is done.
  • the weight average molecular weight of the polylactic acid resin is preferably 100,000 or more from the viewpoint of mechanical properties of the molded article, and is preferably 400,000 or less from the viewpoint of fluidity during molding. Preferably, it is 300, 00 or less, more preferably 200, 00 or less.
  • the weight average molecular weight of the polylactic acid resin was determined using gel permeation chromatograph (GPC), the solvent was black mouth form, the column was high temperature SEC column (GMHHR-H series) manufactured by Tosoh Corporation, and the flow rate was 1. It can be obtained by conversion using OmLZmin, column temperature 40 using a differential refractive index detector (RI) as a detector and styrene having a known molecular weight as a reference.
  • GPC gel permeation chromatograph
  • RI differential refractive index detector
  • polylactic acid resins can be obtained by dehydrating polycondensation using L monolactic acid or D-lactic acid having a necessary structure as a raw material.
  • lactide which is a cyclic dimer of lactic acid.
  • Lactide includes L-lactide, which is a cyclic dimer of L-lactic acid, D-lactide, which is a cyclic dimer of D-lactic acid, meso-monolactide and D-, which are cyclic dimerization of D-lactic acid and L-lactic acid.
  • DL-lactide is a racemic mixture of lactide and L-lactide
  • ring-opening polymerization is preferably performed using D-lactide or L-lactide.
  • the amount of residual monomer related to the polylactic acid resin is preferably 500 00 ppm or less, more preferably 2000 ppm or less, 1 000 It is more preferably p pm or less, and particularly preferably 500 p pm or less.
  • the amount of residual monomer in the polylactic acid resin is the lactide amount described in “Voluntary Standards for Food Containers and Packaging Made of Synthetic Resins such as Polyolefins, Third Edition Revised Edition 20 June 2004 Supplement, Part 3 Sanitation Test Method P13”. It can be determined according to the measurement method. Specifically, the polylactic acid resin is uniformly dissolved in dichloromethane, and the supernatant obtained by reprecipitation of the polymer by adding an acetone-cyclohexane mixed solution is applied to a gas chromatograph (GC) with a hydrogen flame detector (FID). The residual monomer amount in the polylactic acid resin can be measured by separating the residual monomer (lactide) and quantifying it by an internal standard method.
  • GC gas chromatograph
  • FID hydrogen flame detector
  • GC measurement can be performed under the following conditions.
  • a commercially available polylactic acid resin having an optical purity of 99% or more can be used.
  • examples of such a polylactic acid resin include a product name Eco-Plastic U'z S-1 2 (optical purity 99.6%), a product name Eco-Plastic U'z S, manufactured by Toyoyu Motor Co., Ltd. -1 7 (optical purity 99.7%).
  • the optical purity of polylactic acid resin is as follows: “Voluntary Standard for Food Containers and Packaging Made of Synthetic Resins such as Polyolefin, etc. Third Edition Revised Edition 2 0 June 2004 Supplement Part 3 Sanitation Test Method It can be determined according to the method for measuring D content in P12-13J. Specifically, the method for measuring the optical purity of the polylactic acid resin is as follows.
  • the measurement of HP LC can be performed under the following conditions.
  • UV detector UV detector (UV 2 ⁇ 4nm)
  • the plasticizer used in the polylactic acid resin composition of the present invention has two or more ester groups in the molecule, and at least one alcohol component constituting the ester is an alkylene having 2 to 3 carbon atoms per hydroxyl group. It is a compound with an average addition of 0.5 to 5 moles of oxaside.
  • the plasticizer used in the method for producing the polylactic acid resin molded product of the present invention is not particularly limited.
  • the plasticizer used in the method for producing the polylactic acid resin molded body of the present invention has two or more ester groups in the molecule from the viewpoint of plasticization efficiency, and at least one of the alcohol components constituting the ester is a hydroxyl group.
  • a compound in which an average of 0.5 to 5 moles of an alkylene oxide having 2 to 3 carbon atoms per one is added is preferable.
  • the carbon atom per hydroxyl group of the alcohol component having two or more ester groups in the molecule and constituting the ester A compound in which 0.5 to 5 moles of an average of 0.5 to 5 moles of an alkylene oxide of several to three is added is more preferable.
  • a compound is even more preferable, and a compound obtained by adding 1 to 4 moles of ethylene oxide is more preferable.
  • the alcohol component constituting the ester is preferably an average of 1 to 4 moles of alkylene oxide having 2 to 3 carbon atoms, more preferably 2 from the viewpoints of compatibility with polylactic acid resin, plasticization efficiency, and volatility resistance. ⁇ 3 mol added compound.
  • the alkylene oxide is preferably ethylene oxide.
  • the number of carbon atoms of the hydrocarbon group such as an alkyl group or alkylene group contained in the plasticizer for example, the number of carbon atoms of the hydrocarbon group of the polyhydric alcohol or polyvalent carboxylic acid constituting the ester compound is determined. 1-8 are preferred, 1-6 are more preferred, and 1-4 are even more preferred Yes.
  • the carbon number of the monocarboxylic acid and monoalcohol constituting the ester compound of the plasticizer is preferably 1 to 8, more preferably 1 to 6, more preferably 1 to 4, more preferably 1 to 2, from the viewpoint of compatibility. More preferred.
  • the method for producing the plasticizer used in the present invention is not particularly limited.
  • the plasticizer used in the present invention is a polyvalent carboxylic acid ether ester
  • an acid catalyst such as paratoluenesulfonic acid monohydrate or sulfuric acid.
  • a metal catalyst such as dibutyltin oxide
  • a saturated dibasic acid having 3 to 5 carbon atoms or an anhydride thereof and a polyalkylene glycol monoalkyl ether are directly reacted, or a saturated dibasic acid having 3 to 5 carbon atoms. It is obtained by ester exchange between a lower alkyl ester of a basic acid and a polyalkylene glycol monoalkyl ether.
  • polyethylene glycol monoalkyl ether, saturated dibasic acid, and paratoluenesulfonic acid monohydrate as a catalyst polyethylene glycol monoalkyl ether Z saturated dibasic acid noparatoluenesulfonic acid monohydrate.
  • (Molar ratio) 2 to 4/1 0. 0 0 1 to 0.0 ⁇ is charged into the reaction vessel, and in the presence or absence of a solvent such as toluene, at normal pressure or reduced pressure, temperature 1 It can be obtained by performing dehydration at 0 0 to 1 3 0. A method of performing the reaction under reduced pressure without using a solvent is preferred.
  • the plasticizer used in the present invention is a polyhydric alcohol ester
  • the plasticizer used in the present invention is a hydroxycarboxylic acid ether ester.
  • carboxylic acid such as lactic acid
  • an autoclave is used and an alkylene oxide having 2 to 3 carbon atoms at a temperature of 1.20 to 160 is added to 2 to 1 mole of hydroxycarboxylic acid. Add 5 moles.
  • 1 mol of acetic anhydride is added dropwise at 1 10 to 1 mol of the obtained lactic acid alkylene oxide adduct, and after completion of the addition, aging is carried out for 2 hours at 110 t: for acetylation.
  • the product is subjected to steam distillation under reduced pressure to distill off the acetic acid and unreacted acetic anhydride.
  • the product Z polyalkylene glycol monoalkyl ether Z paratoluene sulfonic acid monohydrate (catalyst) (molar ratio) 1 Z 1-2 / 0.0 0 1-0.05 It can be obtained by charging in a reaction vessel and dehydrating at a temperature of 100 to 130 under normal pressure or reduced pressure in the presence or absence of a solvent such as toluene.
  • the plasticizer used in the polylactic acid resin composition of the present invention has two or more ester groups in the molecule, the plasticizer is excellent in compatibility with the polylactic acid resin, and 2 to 4 ester groups in the molecule.
  • the plasticizer used in the present invention has good moldability when used in combination with a polylactic acid resin having an optical purity of 99% or more, and excellent moldability at a particularly low mold temperature. It can be expressed.
  • the plasticizer used in the method for producing the polylactic acid resin molded body of the present invention is preferably used from the viewpoint of excellent compatibility with the polylactic acid resin as long as it has two or more ester groups in the molecule. It is more preferable to have 2 to 4 ester groups. If at least one of the alcohol components constituting the ester has an average of 0.5 mol or more of an alkylene oxide having 2 to 3 carbon atoms per hydroxyl group, It is preferable from the viewpoint of imparting sufficient plasticity to the acid resin, and an average of 5 mol or less is preferable from the viewpoint of improving the predure resistance effect. Although not certain, by using the plasticizer in combination with a polylactic acid resin having an optical purity of 99% or more, the moldability is good, and excellent moldability can be exhibited particularly at a low mold temperature. preferable.
  • the plasticizer used in the present invention has two or more ester groups in the molecule from the viewpoint of the moldability and plasticity of the polylactic acid resin molded article, and also the bleed resistance of the plasticizer, and the average of ethylene oxide Compounds having 3 to 9 addition moles are preferred, selected from the group consisting of esters of succinic acid or adipic acid and polyethylene glycol monomethyl ether, and esters of acetic acid and dalyserin or ethylene glycol adducts of ethylene glycol. At least one is more preferable, and an ester of succinic acid or adipic acid and polyethylene dallicol monomethyl ether is more preferable.
  • the average number of moles added of ethylene oxide or propylene oxide can be measured by 1 H 1 NMR method.
  • an average of 0 to 1.5 of the two or more ester groups in the plasticizer used in the present invention may contain an ester group composed of an aromatic alcohol.
  • Aromatic alcohols are more compatible with polylactic acid resins than aliphatic alcohols with the same carbon number, so that the molecular weight can be increased while maintaining bleed resistance. From the viewpoint of plasticizing efficiency, it is preferable that an average of 0 to 1.2, more preferably 0 to 1, is an ester group composed of an aromatic alcohol.
  • the aromatic alcohol include benzyl alcohol
  • the average molecular weight of the plasticizer used in the present invention is preferably 2500 to 700, more preferably 300 to 600, more preferably from the viewpoint of bleed resistance and volatility resistance. Is 3 5 0 to 5 5 0, particularly preferably 4 0 0 to 5 0 0.
  • the average molecular weight can be obtained by calculating the hatching value by the method described in JISK 0 70 and calculating from the following formula.
  • plasticizer used in the present invention include esters of acetic acid and glycerin ethylene oxide average 3 to 9 mol adduct, acetic acid, from the viewpoint of excellent moldability and impact resistance of the polylactic acid resin molded article.
  • Alkyl ethers of polyhydric alcohols such as esters of diglycerin with an average of 4 to 12 moles of propylene oxide adduct, and esters of acetic acid and ethylene oxide with an average addition mole number of polyethylene glycol of 4 to 9 Esters, esters of succinic acid and ethylene oxide with an average addition mole number of polyethylene glycol monomethyl ether of 2 to 4, polyethylene glycol monomethyl ether with an average addition mole number of adipic acid and ethylene oxide of 2 to 3
  • the average number of moles of 1,3,6-hexanetricarboxylic acid and ethylene oxide added is 2 Esters of polyvalent carboxylic acids such as esters of polyethylene glycol monomethyl ether to 3 and polyethylene dallicol monomethyl ether are more preferred.
  • esters of succinic acid, adipic acid or 1,3,6-hexanetricarboxylic acid and polyethylene glycol monomethyl ether At least one selected from the group consisting of an ester of acetic acid and an ethylene oxide adduct of glycerin or ethylene glycol, an ester of an acetic acid and glycerin ethylene oxide average adduct of 3 to 6 mol, Esters of acetic acid and ethylene oxide with polyethylene dallicol having an average addition mole number of 4-6, succinic acid An ester of polyethylene glycol monomethyl ether with an average addition mole number of ethylene oxide of 2 to 3, an ester of adipic acid and diethylene glycol monomethyl ether, 1,3,6_hexanetricarboxylic acid and diethylene glycol More preferred are esters with monomethyl ether. From the viewpoint of the moldability and impact resistance of the
  • the ester of the present invention is preferably a fully esterified saturated ester from the viewpoint of sufficiently exerting the function as a plasticizer.
  • the plasticizer has two or more ester groups in the molecule, At least one of the constituent alcohol components is a compound in which an average of 0.5 to 5 moles of an alkylene oxide having 2 to 3 carbon atoms per hydroxyl group is added, preferably having two or more ester groups in the molecule. Further, a compound having a polyoxyethylene chain having an average addition mole number of ethylene oxide of 3 to 9 (more preferably having a methyl group, more preferably 2 or more). When it is, the heat resistance and compatibility with the polylactic acid resin are improved.
  • the bleed resistance is improved and the softening effect of the polylactic acid resin is improved.
  • the softening of the polylactic acid resin it is considered that when the polylactic acid resin is crystallized, its growth rate is also improved.
  • the polylactic acid resin retains flexibility even at a low mold temperature, crystallization of the polylactic acid resin progresses in a short mold holding time, and good moldability is expected.
  • the composition of the present invention further contains an organic nucleating agent.
  • the organic nucleating agent used in the present invention includes a hydroxy fatty acid ester and a hydroxyl group and an amide in the molecule from the viewpoints of moldability, heat resistance, impact resistance, and bloom resistance of the organic nucleating agent. At least selected from the group consisting of compounds having a group
  • crystal nucleating agent (1) One type (hereinafter referred to as crystal nucleating agent (1)) is preferred.
  • the hydroxy fatty acid ester is preferably a hydroxy fatty acid ester having 12 to 22 carbon atoms in the fatty acid from the viewpoint of improving the crystallization speed and compatibility with the polylactic acid resin. More preferred is a hydroxy fatty acid ester having at least two and having two or more ester groups.
  • the melting point of the hydroxy fatty acid ester is preferably 65 or more, and more preferably 70 to ⁇ 200 ”from the viewpoint of improving the crystallization speed.
  • the melting point of the hydroxy fatty acid ester is JIS-K 7 1 21 Calculated from the crystal melting endothermic peak temperature by differential scanning calorimetry (DSC) temperature rise method based on 21.
  • hydroxy fatty acid ester examples include 12-hydroxystearic acid triglyceride, 12-hydroxystearic acid diglyceride, 12-hydroxystearic acid monoglyceride, pen erythritol mono-mono 1 2-hydroxy Examples thereof include hydroxy fatty acid esters such as stearate, pen erythritol di-di-2-hydroxy stearate, pen erythritol monotri-l 2-hydroxy stearate and the like. From the viewpoint of moldability of the polylactic acid resin molding, heat resistance, impact resistance, and bloom resistance of the organic nucleating agent, 12-hydroxystearic acid glyceride is preferable.
  • an aliphatic amide having a hydroxyl group is preferable from the viewpoint of improving the compatibility with the polylactic acid resin, and the amide group has two or more hydroxyl groups.
  • An aliphatic amide having two or more of them is more preferable.
  • the melting point of a compound having a hydroxyl group and an amide group in the molecule is determined by the dispersibility of the organic nucleating agent during kneading. From the viewpoint of improving the crystallization rate and crystallization speed, 65 or more is preferable, 70 to 2 20 is more preferable, and 80 to 190 is still more preferable.
  • the compound having a hydroxyl group and an amide group in the molecule include hydroxy fatty acid monoamides such as 1-hydroxystearic acid monoethanol amide, methyl bis 1 2-hydroxystearic acid, ethylene bis 1 Examples thereof include hydroxy fatty acid bisamides such as 2-hydroxystearic acid amide and hexamethylene bis 1 2-hydroxystearic acid amide.
  • hydroxy fatty acid monoamides such as 1-hydroxystearic acid monoethanol amide, methyl bis 1 2-hydroxystearic acid, ethylene bis 1
  • examples thereof include hydroxy fatty acid bisamides such as 2-hydroxystearic acid amide and hexamethylene bis 1 2-hydroxystearic acid amide.
  • An alkylene bishydroxystearic acid amide such as hydroxystearic acid amide is preferred, and ethylene bis 12-hydroxystearic acid amide is more preferred.
  • the organic nucleating agent used in the present invention includes a crystal nucleating agent (1) and a phenylphosphonic acid metal from the viewpoint of moldability, heat resistance, impact resistance, and bloom resistance of the organic nucleating agent.
  • crystal nucleating agent (2) used in the present invention include phenylphosphonic acid metal salts such as phenylphosphonic acid phosphite; sodium 1,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate, Metal salts of phosphate esters such as aluminum bis (2,2'-methylenbis-1,4,6-di-tert-butylphenyl phosphate); 5-dimethylsulfoisophthalate, 2-sulfoisophthalate Metal salts of aromatic sulfonic acid dialkyl esters such as dimethyl dicalcium phosphate; Metal salts of rosin acids such as methyl dehydroabietic acid power; Trimesic acid tris (t-butylamide), m-xylylene bis 1 2-hydroxystearin Acid amide, 1, 3, 5 — Aromatic carboxylic acid amide such as benzenetrisulphonic acid tricyclohexylamide; p — Rosin acid acid
  • a metal salt of phenylphosphonic acid is preferable from the viewpoint of crystallization speed.
  • the phenylphosphonic acid metal salt used in the present invention is a phenylphosphonic acid metal salt having a phenyl group and a phosphonic group (one PO (OH) 2 ) which may have a substituent. And an alkyl group having 1 to 10 carbon atoms and an alkoxycarbonyl group having 1 to 10 carbon atoms in the alkoxy group.
  • phenylphosphonic acid examples include unsubstituted phenylphosphonic acid, methylphenylphosphonic acid, ethylphenylphosphonic acid, propylphenylphosphonic acid, butylphenylphosphonic acid, dimethoxycarbonylphenylphosphonic acid, diethoxycarbo Examples thereof include unsubstituted phenyl phosphonic acid, and unsubstituted phenyl phosphonic acid is preferable.
  • metal salts of phenylphosphonic acid examples include salts of lithium, sodium, magnesium, aluminum, potassium, calcium, barium, copper, zinc, iron, cobalt, nickel, and the like, and zinc salts are preferable.
  • an organic nucleating agent when used in combination with a crystal nucleating agent (1) and a crystal nucleating agent (2), preferably a phenylphosphonic acid metal salt, these proportions are expressed from the viewpoint of expressing the effects of the present invention.
  • Crystal nucleating agent (1) / Crystal nucleating agent (2) (weight ratio) 20 80 ⁇ 80 20 is preferable, 30/70 to 70/30 is more preferable, and 40Z60 to 60/40 is still more preferable.
  • the polylactic acid resin composition of the present invention has a special effect that the crystallization rate is good and the heat resistance is excellent.
  • the reason why the exceptional effect of the present invention can be expressed is not clear, but in the presence of a polylactic acid resin having an optical purity of 99% or more and a specific plasticizer, it is considered that the crystallization speed is significantly improved by their synergistic effect. It is done.
  • the crystal nucleating agent (1) is dissolved during the melt-kneading of the polylactic acid resin composition, and a large number of crystal nuclei can be generated in the cooling process during molding, and the crystal nucleating agent (2) is a metal ion in the compound.
  • the interaction (adsorbability) with the polylactic acid resin is excellent, so that the crystallization speed of the present invention is synergistically excellent and the heat resistance is excellent. It is thought that the fruit is expressed.
  • the polylactic acid resin composition of the present invention contains a polylactic acid resin having an optical purity of 99% or more and the above-mentioned specific plasticizer, and preferably further contains an organic nucleating agent.
  • the polylactic acid resin composition of the present invention preferably has a half crystallization time at 70 of 1 minute or less from the viewpoint of exhibiting excellent moldability at a mold temperature of 70 or less at the following mold temperature. More preferably, it is more preferably 0.6 minutes or less.
  • the half crystallization time at 70 ° C. is a value determined by the method shown in the examples.
  • the content of the polylactic acid resin in the polylactic acid resin composition of the present invention is preferably 50% by weight or more, more preferably 70% by weight or more from the viewpoint of achieving the object of the present invention.
  • the content of the plasticizer in the polylactic acid resin composition of the present invention is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the polylactic acid resin from the viewpoint of obtaining a sufficient crystallization speed and impact resistance. More preferred is ⁇ 30 parts by weight, and more preferred is 8 to 30 parts by weight.
  • the content of the organic nucleating agent in the polylactic acid resin composition of the present invention is preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the polylactic acid resin from the viewpoint of obtaining a sufficient crystallization rate. 0.1 to 3 parts by weight is more preferable, and 0.2 to 2 parts by weight is particularly preferable.
  • the composition of the present invention preferably further contains an inorganic filler from the viewpoint of improving physical properties such as rigidity.
  • inorganic filler used in the present invention fibers, plates, granules, and powders that are usually used for strengthening thermoplastic resins can be used.
  • the aspect ratio of the fibrous inorganic filler is preferably 5 or more, more preferably 10 or more, and further preferably 20 or more.
  • the inorganic filler 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.
  • a coupling agent such as amino silane or epoxy silane. It may be processed by.
  • the average particle size of the inorganic filler is preferably from 0.1 to 20 / m, more preferably from 0.1 to 10 m, from the viewpoint of obtaining good dispersibility.
  • the average particle diameter of the inorganic filler can be obtained by measuring a volume-based median system by a diffraction / scattering method.
  • a diffraction / scattering method for example, as a commercially available apparatus, there is a laser diffraction / light scattering particle size measuring apparatus L S 2 30 manufactured by Cole Yuichi.
  • the content of the inorganic filler in the polylactic acid resin composition of the present invention is 1 in terms of 100 parts by weight of the polylactic acid resin from the viewpoint of obtaining sufficient crystallization speed, moldability, heat resistance and impact resistance. ⁇ 20 parts by weight is preferable, 3 to 50 parts by weight is more preferable, and 5 to 40 parts by weight is particularly preferable.
  • the polylactic acid resin composition of the present invention can further contain a hydrolysis inhibitor.
  • the hydrolysis inhibitor include calpositiodide compounds such as polycarpoimide compounds and monocarpoimide compounds.
  • the polycalcoimide compound is preferable, the heat resistance of the polylactic acid resin molded body, From the viewpoint of formability, fluidity, impact resistance, and bloom resistance of the organic nucleating agent, monocarbohydrate compounds are more preferable.
  • monocalcoid compounds include N, N'-di-2,6-disopropyl.
  • Examples include phenyl carboimide.
  • the above-mentioned calpositimide compounds may be used alone or in combination of two or more.
  • Poly (4,4'-dicyclohexylmethane carbopositimide) is calpolite LA-1 (manufactured by Nisshinbo Co., Ltd.), poly (1,3,5-trisopropylbenzene) polycarbohydrate and poly (1,3,5_triisopropylbenzene and 1,5-diisopropylbenzene)
  • Polycarboximide is Subuvazol P and Subuvazol P-1 100 (Rhein Chemie)
  • N, N, Oji-2, 6-Diisopropylphenylcarbodiimide is
  • the content of the hydrolysis inhibitor in the polylactic acid resin composition of the present invention is 0.05 to 3 parts by weight with respect to 100 parts by weight of the polylactic acid resin from the viewpoint of moldability of the polylactic acid resin molded article. Is preferably 0.1 to 2 parts by weight.
  • the polylactic acid resin composition of the present invention can further contain a flame retardant.
  • flame retardants include halogen compounds containing bromine or chlorine, antimony compounds such as antimony trioxide, inorganic hydrates (metal hydroxides such as aluminum hydroxide and magnesium hydroxide) and Examples thereof include phosphorus compounds. From the viewpoint of safety, inorganic hydrates are preferred.
  • the polylactic acid resin composition of the present invention may contain other resins from the viewpoint of improving physical properties such as rigidity, flexibility, heat resistance, and durability.
  • resins include polyethylene, polypropylene, polystyrene, ABS resin, AS resin, acrylic resin, polyamide, polyphenylene sulfide, polyether ether ketone, polyester, polyacetal, polysulfone, polyphenylene oxide, poly Reimide, polyether imide, etc., or ethylene Z glycidyl methacrylate copolymer, polyester elastomer, polyamide elastomer, ethylene / Thermoplastic resins such as soft thermoplastic resins such as propylene yunichi polymer, ethylene nobten 1 copolymer, phenolic resin, melamine resin, unsaturated polyester resin, silicone resin, epoxy resin, etc.
  • resins having bonds containing carbonyl groups such as amide bonds, ester bonds,
  • the polylactic acid resin composition of the present invention further contains other components such as a hindered phenol or a phosphoric acid-based antioxidant, or a lubricant that is a hydrocarbon-based wax or an anionic surfactant. can do.
  • the content of each of the antioxidant and the lubricant is preferably from 0.05 to 3 parts by weight, more preferably from 0.1 to 2 parts by weight, based on 100 parts by weight of the polylactic acid resin.
  • the polylactic acid resin composition of the present invention comprises an antistatic agent, an antifogging agent, a light stabilizer, an ultraviolet absorber, a pigment, an antifungal agent, an antibacterial agent, a foaming agent and the like as components other than the above. It can contain in the range which does not prevent achievement of the objective.
  • the polylactic acid resin composition of the present invention has good processability and can be processed at a low temperature of 200 or less, for example, it has an advantage that the plasticizer is hardly decomposed. Can be used for various purposes.
  • the polylactic acid resin composition described in detail above can be used in the method for producing the molded body of the polylactic acid resin of the present invention. That is, the polylactic acid resin composition contains a polylactic acid resin having an optical purity of 99% or more and a plasticizer from the viewpoint of obtaining a sufficient crystallization rate even at low temperatures, and further contains an organic nucleating agent. It is preferable to contain.
  • the polylactic acid resin molded article of the present invention can be obtained by molding the polylactic acid resin composition of the present invention. Specifically, for example, polylactic acid resin is melted using an extruder or the like. Then, a plasticizer and, if necessary, an organic nucleating agent and an inorganic filler are mixed, and the obtained melt is filled into a mold with an injection molding machine or the like and molded.
  • the mold temperature is not particularly limited, but is preferably 8 Ot: or less, more preferably 70 or less, and even more preferably 10 to 50.
  • a preferred method for producing the polylactic acid resin molded article of the present invention is a step of melt-kneading a polylactic acid resin composition containing a polylactic acid resin having an optical purity of 99% or more and a plasticizer (hereinafter referred to as step (1)), This is a method comprising the step of filling the resulting melt into the following mold at 70 (hereinafter referred to as step (2)).
  • the method for producing a polylactic acid resin molded article of the present invention comprises a step of melt-kneading a polylactic acid resin composition containing a polylactic acid resin and a plasticizer having an optical purity of 99% or more (hereinafter referred to as step (1)), and obtained. It consists of a process (hereinafter referred to as step (2)) in which the molten material is filled into the following mold at 70.
  • the step (2) is performed after the step (1).
  • the method of performing the step (2) is preferably performed after cooling through the step (1). From the viewpoint of the effect of improving the crystallization speed of the present invention, the step of cooling is performed after the step (1). A method in which step (2) is immediately performed is more preferable.
  • a specific example of the step (1) can be performed by an ordinary method, for example, a method of mixing a plasticizer, an organic nucleating agent, etc. while melting a polylactic acid resin using an extruder or the like. Can be mentioned.
  • the temperature of step (1) is not less than the melting point (Tm) of the polylactic acid resin from the viewpoint of dispersibility of plasticizers, organic nucleating agents, etc., preferably in the range of Tm to Tm + 10 O:
  • the range is preferably Tm to Tm + 50.
  • it is preferably 170 to 240, more preferably 170 to 220.
  • the step (2) in the method for producing a molded article of the present invention examples thereof include a method in which the polylactic acid resin composition is filled in the following mold at 70 with a molding machine or the like and molded.
  • the mold temperature in the step (2) is preferably from 10 to 70, more preferably from 10 to 50, and even more preferably from the viewpoint of improving the crystallization speed and improving workability. ⁇ 50.
  • the melting point (Tm) of the polylactic acid resin is a value obtained from the crystal melting endothermic peak temperature by the temperature rising method of differential scanning calorimetry (DSC) based on JIS—K7 1 2 1.
  • the holding time in the mold is preferably 60 to 60 seconds, from the viewpoint of achieving a relative crystallinity of 60% or more and improving productivity. Is more preferable, and 10 to 45 seconds is more preferable.
  • a molded body crystallized to a relative crystallinity of 60% or more, preferably 80% or more, more preferably 90% or more, and further preferably 95% or more can be obtained. it can.
  • the relative crystallinity is a value obtained by the method described in Examples.
  • the reason for prescribing the degree of crystallinity after molding as described above is that the effect of the present invention is exhibited when the base resin is crystallized, and heat resistance, temperature sensitivity, blocking resistance, This is because improvement in solvent resistance and the like is also an effect of crystallization.
  • the improvement of the flexibility by the plasticizer decrease in elastic modulus and improvement in elongation at break
  • the improvement in impact resistance can be sufficiently exerted by crystallization.
  • the products of the present invention shown in Table 1-11 (11-A to I-H) and the comparative product (1-a to I-h) were made into Niichi Daichi (Moriyama Seisakusho Co., Ltd.).
  • DS3-20MWB-E melted and kneaded at 1 80 for 10 minutes, and then immediately stretched to a thickness of about 5 mm with 80 8-inch rolls (manufactured by Nippon Roll Manufacturing Co., Ltd.). After cutting into a size of about 8 cm ⁇ 8 cm, it was pulverized with a pulverizer (S-20 manufactured by Daiko Seiki Co., Ltd.) at 40 or less to obtain a pulverized product of the polylactic acid resin composition.
  • S-20 manufactured by Daiko Seiki Co., Ltd. a pulverizer
  • the obtained pulverized product was dried for 1 day under a reduced pressure of 70 to reduce the water content to 50 Oppm or less.
  • the pulverized product thus obtained was injection molded using an injection molding machine (Japan Steel Works J75E-D) with a cylinder temperature of 200 ° C.
  • Table 1-2 and Table 1 Separation of test pieces [flat plate (70 mm x 40 mm x 3 mm), prismatic specimen (1 2 5 mm x 12 mm x 6 mm) and prismatic specimen (63 mm x 12 mm x 5 mm)] at the mold temperature shown in Fig. 3
  • the mold holding time required for the mold was evaluated according to the following criteria. These results are shown in Table 1-12 and Table 1-13.
  • the time required until each test piece piece was not deformed and could be easily taken out was defined as the mold holding time required for mold release.
  • the mold holding time was required for more than 150 seconds, it was evaluated that the mold could not be released. Note that the faster the melt crystallization speed of the test piece in the mold and part of the runner, the shorter the mold holding time required for mold release.
  • the polylactic acid resin composition of the present invention (1 A to 1 H) containing polylactic acid having an optical purity of 99% or more and a specific plasticizer is 30 Molding was possible with a short mold holding time at a mold temperature of ⁇ 80.
  • a comparative polylactic acid resin composition (1a, 1c, 1-e) using polylactic acid with an optical purity of less than 99% and polylactic acid with an optical purity of 99% or more can be used.
  • Polylactic acid resin compositions that do not contain a specific plasticizer (1-b, 1-d, 1-f to l-h) cannot be molded at a mold temperature of 60-80 with a short mold holding time. It was possible.
  • the products of the present invention shown in Table 11-11 11 A to lH
  • the comparative product 11 a to l h
  • a pulverized product of the polylactic acid resin composition was obtained.
  • the half crystallization time was measured by the following method. The results are shown in Table 1-14 and Table 1-15.
  • the half-crystallization time of 0 minutes indicates that the crystallization cannot be measured after quenching at a rate of 1 minute from 200 to the holding temperature at a rate of 1 500 and Z, and the crystallization speed is extremely high.
  • Table 1-4 the half-crystallization time of 0 minutes indicates that the crystallization cannot be measured after quenching at a rate of 1 minute from 200 to the holding temperature at a rate of 1 500 and Z, and the crystallization speed is extremely high.
  • the product of the present invention (1 1 A to 1 H) and the comparative product (l_a to lh) shown in Table 1 1 to 1 were used in the same manner as in Example 1 11.
  • a powdered product of a polylactic acid resin composition was obtained.
  • the obtained powdered product was injection molded using an injection molding machine (J75E-D, manufactured by Nippon Steel Works) at the mold temperature and mold holding time shown in Table 1-16.
  • the mold releasability was evaluated according to the following criteria.
  • prismatic specimens (1 25 mm x 12 mm x 6 mm) have thermal deformation temperature and impact resistance
  • flat plates (70 mm x 40 mm x 3 mm) have crystallinity and bleed resistance as shown below. The method was evaluated. These results are shown in Table 1-6.
  • Crush test piece of flat plate after injection molding (70 0 X 40 0 X 3), weigh accurately 7 ⁇ mg, enclose it in aluminum pan, and then use DSC device (Diamond DSC manufactured by Perkin Elma Co., Ltd.)
  • I st RUN the temperature is increased from 20 to 20 00 at a temperature increase rate of 20 minutes, held at 20 00 for 5 minutes, and then the temperature decrease rate is 20 and 20 minutes in Z minutes.
  • the temperature was decreased from 20 to 20 and held at 20 for 1 minute, and then 2nd RUN was performed, and the temperature was increased from 2 to 200 at a temperature increase rate of 20 ° CZ.
  • the absolute value of the cold crystallization process rupee of polylactic acid resin observed at 1 st RUN ⁇ ⁇ cc, the crystal melting enthalpy AHm observed at 2 nd RU N were obtained, and the relative crystal was calculated from the obtained values using the following formula. The degree of conversion (%) was obtained.
  • Relative crystallinity (%) ⁇ ((AHm-AHc c) / AHmX 1 0 0) ⁇
  • the injection-molded flat plate (7 Ommx 4 OmmX 3mm) was left to stand for 1 month at a high temperature and high humidity of 5 O 80% Rh, and the presence or absence of plasticizer bleed on the surface was observed with the naked eye.
  • Table IV6 The injection-molded flat plate (7 Ommx 4 OmmX 3mm) was left to stand for 1 month at a high temperature and high humidity of 5 O 80% Rh, and the presence or absence of plasticizer bleed on the surface was observed with the naked eye.
  • the polylactic acid resin composition (i—A to 1—H) of the present invention containing a polylactic acid resin having an optical purity of 99% or more and a specific plasticizer is 30 to 80. Molding with a short mold holding time was possible even at a mold temperature of 950, and the molded product showed a heat resistance of 95 or more, an impact strength of 50 J Zm or more, and excellent bleed resistance. .
  • Polylactic acid resin composition (1 1 b, 1 d, 1 1 f to l 1 h) without specific plasticizer is good.
  • a mold temperature of 80 or 1 1 to obtain a good molded product If a long mold holding time was required and the mold temperature was set to 70, crystallization was incomplete even with a long mold time, and demoldability was reduced. Further, the obtained molded product could not exhibit excellent heat resistance or impact resistance. Furthermore, when the comparative product was molded with a 30 mold, crystallization did not proceed and the demolding time was increased, and physical properties were inferior in heat resistance and impact resistance.
  • the polylactic acid resin composition of the present invention containing a polylactic acid resin having an optical purity of 99% or more and a specific plasticizer exhibits excellent moldability at a low mold temperature, and the molded product is excellent. It can be seen that it exhibits high heat resistance and impact resistance.
  • Example 1_2 1 and Example 1 1 24 when the injection pressure was measured for Example 1_2 1 and Example 1 1 24, they were 89 kgfXcm 2 and 7 S kg / cm 2 , respectively. From this, it can be seen that the resin composition using the monocalcoid is superior in fluidity than the resin composition using the polycalcoid in the hydrolysis inhibitor.
  • the present invention products (2- A to 2 _ F) and comparative products (2- a to 2 — b) shown in Table 2-1 were replaced with Nidaichi (Moriyama Seisakusho DS3- 20MWB-E) melted and kneaded at 1800 for 10 minutes, and then immediately 8
  • a powder mill D-20, manufactured by Daiko Seiki Co., Ltd.
  • the obtained powdered product was dried at 70 ° C under reduced pressure for 1 day, and the water content was adjusted to 50 Oppm or less.
  • polylactic acid resin in Table 2-1 * 1 * 2 * 3 and the plasticizer * 4 * 5 * 6 are the same as in Table 1-1.
  • * 7, * 8, and * 9, which are organic nucleating agents, are * 10, * 1 1, and * in Table 1_1, respectively.
  • the inorganic fillers * 10 and * 11 are the same as * 13 and * 14 in Table 1-1, respectively.
  • the crystallization time of the pulverized product of the polylactic acid resin composition was measured by the above method. The results are shown in Table 2-2. However, the temperature was lowered to the holding temperature (70) at a speed of 500 ° CZ.
  • the pulverized product of this polylactic acid resin composition was injection-molded using an injection molding machine (Nippon Steel Works J75E-D) with a cylinder temperature of 200, and the mold shown in Table 2-3 Separation of test pieces (flat plate (70 mm x 40 mm x 3 mm), prismatic specimen (1 2 ⁇ mm 12 mm x 6 mm) and prismatic specimen (6 3 mm x 12 mm x ⁇ mm))
  • the mold holding time required for the mold was evaluated according to the following criteria. These results are shown in Table 2-3.
  • the product of the present invention (2-A to 2-F) shown in Table 2-1 and And comparative products (2-a to 2-b) were used in the same manner as in Example 2-1 to obtain a powdered product of a polylactic acid resin composition.
  • test pieces were obtained in the same manner as described above at the mold temperatures and mold holding times shown in Table 2-4, and the mold releasability was evaluated.
  • the thermal deformation temperature and impact resistance of the prismatic specimen were evaluated, and the crystallinity and bleed resistance of the flat plate were evaluated.
  • the polylactic acid resin composition (2-A to 2-F) of the present invention containing a polylactic acid resin and a plasticizer having an optical purity of 99% or more is a mold of 70 ° C or less. Molding was possible even at a short mold holding time, and the molded product exhibited heat resistance of 100 ° C or higher, impact resistance of 50 JZm or higher, and excellent bleed resistance.
  • a comparative polylactic acid resin composition (2-b) using polylactic acid having an optical purity of less than 99%, and a polylactic acid resin containing no plasticizer even if polylactic acid having an optical purity of 99% or more is used
  • the composition (2-a) required a long mold holding time at a mold temperature of 80 ° C or 110 to obtain a good molded product. Furthermore, when a 30 ° C mold is used as a comparative product, crystallization does not proceed and the time required for demolding is increased, as well as heat resistance and impact resistance. The physical properties were inferior.
  • the polylactic acid resin composition of the present invention containing a polylactic acid resin having an optical purity of 99% or more and a plasticizer exhibits excellent moldability at a mold temperature of 7 Ot or less. It can be seen that the product exhibits excellent heat resistance and impact resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

L'invention a trait à une composition de résine à base d'acide polylactique contenant une résine à base d'acide polylactique et un plastifiant, la résine à base d'acide polylactique ayant une pureté optique d'au moins 99 %, et le plastifiant ayant deux groupes ester ou plus dans une molécule et au moins l'un des composants alcooliques constituant les esters étant un composé, 0,5 à 5 moles d'oxyde d'éthylène ayant 2 à 3 atomes de carbone étant ajoutées en moyenne par groupe hydroxy. L'invention décrit également un corps moulé en résine à base d'acide polylactique obtenu en moulant une composition de résine à base d'acide polylactique. L'invention décrit en outre un procédé permettant de produire un corps moulé en résine à base d'acide polylactique ayant une cristallinité relative d'au moins 60 %, une composition de résine à base d'acide polylactique contenant une résine à base d'acide polylactique ayant une pureté optique d'au moins 99 % et un plastifiant étant fondu et malaxé puis la matière fondue ainsi obtenue étant versée dans un moule métallique à 70 °C et moulée à l'intérieur de celui-ci.
PCT/JP2007/074767 2006-12-19 2007-12-18 Composition de résine à base d'acide polylactique et procédé de production d'un corps moulé en résine à base d'acide polylactique WO2008075775A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006-340704 2006-12-19
JP2006340704 2006-12-19
JP2006-340703 2006-12-19
JP2006340703 2006-12-19

Publications (1)

Publication Number Publication Date
WO2008075775A1 true WO2008075775A1 (fr) 2008-06-26

Family

ID=39536395

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/074767 WO2008075775A1 (fr) 2006-12-19 2007-12-18 Composition de résine à base d'acide polylactique et procédé de production d'un corps moulé en résine à base d'acide polylactique

Country Status (1)

Country Link
WO (1) WO2008075775A1 (fr)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009004769A1 (fr) * 2007-06-29 2009-01-08 Unitika Ltd. Composition de résine d'acide polylactique cristallin et corps moulé fait en cette résine
JP2010037439A (ja) * 2008-08-05 2010-02-18 Kao Corp ポリ乳酸樹脂組成物
WO2010053167A1 (fr) * 2008-11-05 2010-05-14 帝人化成株式会社 Compositions d'acide polylactique et articles moulés à partir de celles-ci
JP2010126580A (ja) * 2008-11-26 2010-06-10 Kao Corp ポリ乳酸樹脂組成物
JP2010150394A (ja) * 2008-12-25 2010-07-08 Teijin Chem Ltd ポリ乳酸組成物およびその成形品
JP2010150392A (ja) * 2008-12-25 2010-07-08 Teijin Chem Ltd ポリ乳酸組成物およびその成形品
JP2010150393A (ja) * 2008-12-25 2010-07-08 Teijin Chem Ltd ポリ乳酸組成物およびその成形品
JP2010270290A (ja) * 2008-08-08 2010-12-02 Kao Corp 生分解性樹脂組成物
JP2010270289A (ja) * 2008-07-22 2010-12-02 Kao Corp 生分解性樹脂組成物
CN102190813A (zh) * 2011-03-28 2011-09-21 中国科学院宁波材料技术与工程研究所 一种成核剂及其制备方法和应用
WO2012015491A1 (fr) * 2010-07-28 2012-02-02 Hallstar Innovations Corp. Compositions de biopolymeres ayant une resistance amelioree aux chocs
JP2012167219A (ja) * 2011-02-16 2012-09-06 Takemoto Oil & Fat Co Ltd ポリ乳酸樹脂用可塑剤、ポリ乳酸樹脂組成物及びポリ乳酸樹脂成形体
EP2604649A1 (fr) * 2011-12-12 2013-06-19 Dai-Ichi Kogyo Seiyaku Co., Ltd. Composition de résine d'acide polylactique et article moulé en résine à partir de celle-ci
WO2013179801A1 (fr) * 2012-05-29 2013-12-05 三洋テグス株式会社 Monofilament pour fauchage
US9376546B2 (en) 2011-12-12 2016-06-28 Dai-Ichi Kogyo Seiyaku Co., Ltd. Polylactic acid resin composition and resin molded article thereof
US9518169B2 (en) 2011-12-12 2016-12-13 Dai-Ichi Kogyo Seiyaku Co., Ltd. Polylactic acid resin composition and resin molded article thereof
US9593229B2 (en) 2012-12-14 2017-03-14 Dai-Ichi Kogyo Seiyaku Co., Ltd. Polylactic acid resin composition and resin molded article thereof
CN112920572A (zh) * 2021-01-29 2021-06-08 大连盈诺环保科技有限公司 一种耐高温聚乳酸树脂及其改性生产工艺

Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1135808A (ja) * 1997-07-17 1999-02-09 Shimadzu Corp 乳酸系ポリマー組成物及びその成型品
JPH11181262A (ja) * 1997-12-25 1999-07-06 Shimadzu Corp 乳酸系ポリマー組成物及びその成型品
JP2000086877A (ja) * 1998-09-08 2000-03-28 Shimadzu Corp 可塑化ポリ乳酸組成物
JP2002146170A (ja) * 2000-11-17 2002-05-22 Unitika Ltd 結晶性ポリ乳酸樹脂組成物、これを用いたフィルムおよびシート
WO2003042302A1 (fr) * 2001-11-15 2003-05-22 New Japan Chemical Co., Ltd. Composition a base de polymere d'acide lactique et objet moule associe
WO2003087031A1 (fr) * 2002-04-02 2003-10-23 Daihachi Chemical Industry Co., Ltd. Compose esterique, plastifiant pour resine polyester aliphatique biodegradable, et composition de resine biodegradable
JP2004238448A (ja) * 2003-02-05 2004-08-26 Sakamoto Yakuhin Kogyo Co Ltd ポリエステル樹脂組成物
JP2005023091A (ja) * 2002-05-14 2005-01-27 Daihachi Chemical Industry Co Ltd 生分解性樹脂組成物
JP2005206813A (ja) * 2003-12-26 2005-08-04 Toray Ind Inc 発泡体およびその製造方法
JP2005298687A (ja) * 2004-04-13 2005-10-27 Kao Corp ポリエステル樹脂用可塑剤
JP2006152102A (ja) * 2004-11-29 2006-06-15 Arakawa Chem Ind Co Ltd 乳酸系樹脂組成物、当該組成物を用いて得られる成形品及びフィルム
JP2006176747A (ja) * 2004-05-11 2006-07-06 Kao Corp 生分解性樹脂組成物
JP2006176748A (ja) * 2004-11-25 2006-07-06 Kao Corp 生分解性樹脂用可塑剤
JP2006206868A (ja) * 2004-12-27 2006-08-10 Toyota Central Res & Dev Lab Inc 脂肪族ポリエステル組成物及びその成形体
JP2006241378A (ja) * 2005-03-04 2006-09-14 Taoka Chem Co Ltd 樹脂用可塑剤および樹脂組成物
JP2006241445A (ja) * 2005-02-04 2006-09-14 Mitsui Chemicals Inc 熱可塑性樹脂組成物とその成形体
JP2006307036A (ja) * 2005-04-28 2006-11-09 Sony Corp 樹脂組成物、及びこれより作製された成形物
JP2007130895A (ja) * 2005-11-10 2007-05-31 Kao Corp 生分解性樹脂成形品の製造法。
JP2007131690A (ja) * 2005-11-09 2007-05-31 Kao Corp 生分解性樹脂組成物
JP2007262422A (ja) * 2004-05-11 2007-10-11 Kao Corp 生分解性樹脂組成物
JP2007308650A (ja) * 2006-05-22 2007-11-29 Kao Corp 生分解性樹脂組成物

Patent Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1135808A (ja) * 1997-07-17 1999-02-09 Shimadzu Corp 乳酸系ポリマー組成物及びその成型品
JPH11181262A (ja) * 1997-12-25 1999-07-06 Shimadzu Corp 乳酸系ポリマー組成物及びその成型品
JP2000086877A (ja) * 1998-09-08 2000-03-28 Shimadzu Corp 可塑化ポリ乳酸組成物
JP2002146170A (ja) * 2000-11-17 2002-05-22 Unitika Ltd 結晶性ポリ乳酸樹脂組成物、これを用いたフィルムおよびシート
WO2003042302A1 (fr) * 2001-11-15 2003-05-22 New Japan Chemical Co., Ltd. Composition a base de polymere d'acide lactique et objet moule associe
WO2003087031A1 (fr) * 2002-04-02 2003-10-23 Daihachi Chemical Industry Co., Ltd. Compose esterique, plastifiant pour resine polyester aliphatique biodegradable, et composition de resine biodegradable
JP2005023091A (ja) * 2002-05-14 2005-01-27 Daihachi Chemical Industry Co Ltd 生分解性樹脂組成物
JP2004238448A (ja) * 2003-02-05 2004-08-26 Sakamoto Yakuhin Kogyo Co Ltd ポリエステル樹脂組成物
JP2005206813A (ja) * 2003-12-26 2005-08-04 Toray Ind Inc 発泡体およびその製造方法
JP2005298687A (ja) * 2004-04-13 2005-10-27 Kao Corp ポリエステル樹脂用可塑剤
JP2007262422A (ja) * 2004-05-11 2007-10-11 Kao Corp 生分解性樹脂組成物
JP2006176747A (ja) * 2004-05-11 2006-07-06 Kao Corp 生分解性樹脂組成物
JP2006176748A (ja) * 2004-11-25 2006-07-06 Kao Corp 生分解性樹脂用可塑剤
JP2006152102A (ja) * 2004-11-29 2006-06-15 Arakawa Chem Ind Co Ltd 乳酸系樹脂組成物、当該組成物を用いて得られる成形品及びフィルム
JP2006206868A (ja) * 2004-12-27 2006-08-10 Toyota Central Res & Dev Lab Inc 脂肪族ポリエステル組成物及びその成形体
JP2006241445A (ja) * 2005-02-04 2006-09-14 Mitsui Chemicals Inc 熱可塑性樹脂組成物とその成形体
JP2006241378A (ja) * 2005-03-04 2006-09-14 Taoka Chem Co Ltd 樹脂用可塑剤および樹脂組成物
JP2006307036A (ja) * 2005-04-28 2006-11-09 Sony Corp 樹脂組成物、及びこれより作製された成形物
JP2007131690A (ja) * 2005-11-09 2007-05-31 Kao Corp 生分解性樹脂組成物
JP2007130895A (ja) * 2005-11-10 2007-05-31 Kao Corp 生分解性樹脂成形品の製造法。
JP2007308650A (ja) * 2006-05-22 2007-11-29 Kao Corp 生分解性樹脂組成物

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009004769A1 (fr) * 2007-06-29 2009-01-08 Unitika Ltd. Composition de résine d'acide polylactique cristallin et corps moulé fait en cette résine
US8268918B2 (en) 2007-06-29 2012-09-18 Unitika Ltd. Crystalline polylactic acid resin composition and product molded/formed therefrom
US8722774B2 (en) 2008-07-22 2014-05-13 Kao Corporation Biodegradable resin composition
JP2011006712A (ja) * 2008-07-22 2011-01-13 Kao Corp 生分解性樹脂組成物
JP2010270289A (ja) * 2008-07-22 2010-12-02 Kao Corp 生分解性樹脂組成物
JP2010037439A (ja) * 2008-08-05 2010-02-18 Kao Corp ポリ乳酸樹脂組成物
JP2010270290A (ja) * 2008-08-08 2010-12-02 Kao Corp 生分解性樹脂組成物
US8716373B2 (en) 2008-08-08 2014-05-06 Kao Corporation Biodegradable resin composition
JP2011046954A (ja) * 2008-08-08 2011-03-10 Kao Corp 生分解性樹脂組成物
JP5560198B2 (ja) * 2008-11-05 2014-07-23 帝人株式会社 ポリ乳酸組成物の製造方法
WO2010053167A1 (fr) * 2008-11-05 2010-05-14 帝人化成株式会社 Compositions d'acide polylactique et articles moulés à partir de celles-ci
CN102203184B (zh) * 2008-11-05 2013-03-27 帝人化成株式会社 聚乳酸组合物及其成形品
JP2010126580A (ja) * 2008-11-26 2010-06-10 Kao Corp ポリ乳酸樹脂組成物
JP2010150392A (ja) * 2008-12-25 2010-07-08 Teijin Chem Ltd ポリ乳酸組成物およびその成形品
JP2010150394A (ja) * 2008-12-25 2010-07-08 Teijin Chem Ltd ポリ乳酸組成物およびその成形品
JP2010150393A (ja) * 2008-12-25 2010-07-08 Teijin Chem Ltd ポリ乳酸組成物およびその成形品
WO2012015491A1 (fr) * 2010-07-28 2012-02-02 Hallstar Innovations Corp. Compositions de biopolymeres ayant une resistance amelioree aux chocs
JP2012167219A (ja) * 2011-02-16 2012-09-06 Takemoto Oil & Fat Co Ltd ポリ乳酸樹脂用可塑剤、ポリ乳酸樹脂組成物及びポリ乳酸樹脂成形体
CN102190813A (zh) * 2011-03-28 2011-09-21 中国科学院宁波材料技术与工程研究所 一种成核剂及其制备方法和应用
KR101378710B1 (ko) 2011-12-12 2014-03-27 다이이치 고교 세이야쿠 가부시키가이샤 폴리유산 수지 조성물 및 그 수지 성형체
JP2013144772A (ja) * 2011-12-12 2013-07-25 Dai Ichi Kogyo Seiyaku Co Ltd ポリ乳酸樹脂組成物およびその樹脂成形体
EP2604649A1 (fr) * 2011-12-12 2013-06-19 Dai-Ichi Kogyo Seiyaku Co., Ltd. Composition de résine d'acide polylactique et article moulé en résine à partir de celle-ci
US9376546B2 (en) 2011-12-12 2016-06-28 Dai-Ichi Kogyo Seiyaku Co., Ltd. Polylactic acid resin composition and resin molded article thereof
US9518168B2 (en) 2011-12-12 2016-12-13 Dai-Ichi Kogyo Seiyaku Co., Ltd. Polylactic acid resin composition and resin molded article thereof
US9518169B2 (en) 2011-12-12 2016-12-13 Dai-Ichi Kogyo Seiyaku Co., Ltd. Polylactic acid resin composition and resin molded article thereof
JP5363684B1 (ja) * 2012-05-29 2013-12-11 三洋テグス株式会社 草刈用モノフィラメント
WO2013179801A1 (fr) * 2012-05-29 2013-12-05 三洋テグス株式会社 Monofilament pour fauchage
US9534321B2 (en) 2012-05-29 2017-01-03 Toray Industries, Inc. Monofilament for mowing
US9593229B2 (en) 2012-12-14 2017-03-14 Dai-Ichi Kogyo Seiyaku Co., Ltd. Polylactic acid resin composition and resin molded article thereof
CN112920572A (zh) * 2021-01-29 2021-06-08 大连盈诺环保科技有限公司 一种耐高温聚乳酸树脂及其改性生产工艺

Similar Documents

Publication Publication Date Title
WO2008075775A1 (fr) Composition de résine à base d'acide polylactique et procédé de production d'un corps moulé en résine à base d'acide polylactique
JP2008174735A (ja) ポリ乳酸樹脂組成物
KR101346751B1 (ko) 생분해성 수지조성물
JP5794731B2 (ja) 樹脂組成物
JP4130695B2 (ja) 生分解性樹脂組成物
JP5107873B2 (ja) ポリ乳酸樹脂組成物
JP4130696B2 (ja) 生分解性樹脂組成物
KR101889135B1 (ko) 폴리에스테르 수지 조성물로 이루어진 성형체
JP5833463B2 (ja) ポリ乳酸樹脂組成物
US8455579B2 (en) Method for promoting crystallization of biodegradable resin composition
JP4297510B2 (ja) ポリ乳酸樹脂成形体の製造方法
TWI614303B (zh) 聚乳酸樹脂組合物
US9428607B2 (en) Polylactic acid-polyalkylene glycol copolymer with fast crystallization rate and composition comprising the same
JP5107793B2 (ja) ポリ乳酸樹脂射出成形体の製造方法
JP5184695B2 (ja) ポリ乳酸樹脂組成物
JP5107792B2 (ja) ポリ乳酸樹脂射出成形体の製造方法
JP5273847B2 (ja) ポリ乳酸樹脂組成物
JP2010001413A (ja) ポリ乳酸樹脂組成物及びそれを成形してなる成形体
JP5525830B2 (ja) ポリ乳酸樹脂組成物
JP2017036434A (ja) ポリ乳酸樹脂組成物
JP2013047335A (ja) ポリ乳酸系樹脂用改質剤及び該改質剤を含むポリ乳酸系樹脂組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07859996

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07859996

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载