Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
  • C08G63/183—Terephthalic acids
• • 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
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

• the present invention relates to a resin composition.
• polylactic acid-based polymers which are bioplastics, are made from renewable resources derived from plants such as corn, which are produced by photosynthesis, and are expected to be used in a wide range of fields.
• polylactic acid-based polymers are brittle and inferior in flexibility (elongation) and impact resistance, etc., compared with petroleum-based plastics. Therefore, the use of polylactic acid-based polymers as resin materials may be limited.
• a technology using a polyester polyol having a specific hydroxyl value has been considered (for example, Patent Document 1).
• an object of the present invention is to provide a resin composition in which the decrease in glass transition temperature is suppressed and which has good elongation and impact resistance.
• the present inventors have conceived the following invention and found that the problems can be solved. That is, the present invention is as follows.
• the polyvalent carboxylic acid (a2) is an aliphatic dicarboxylic acid (a2-1).
• the present invention provides a resin composition that suppresses the decrease in glass transition temperature and has good elongation and impact resistance.
• a "polylactic acid unit” means a “structural unit derived from polylactic acid”
• a “polyester unit” means a “structural unit derived from polyester”.
• the term “main chain” refers to the longest molecular chain in a molecule
• the term “branched chain” refers to a molecular chain other than the main chain in a molecule.
• the resin composition of the present embodiment contains a polyester polyol (A) and a polylactic acid polymer (B).
• the polyester polyol (A) contains units derived from a polyhydric alcohol (a1) and a polycarboxylic acid (a2), and the polyhydric alcohol (a1) contains an aliphatic diol (a1-1) having 4 or more carbon atoms and having an alkyl group as a branched chain.
• the present inventors have found that a resin composition containing a specific polyester polyol (A) and a polylactic acid polymer (B) suppresses a decrease in glass transition temperature and has good elongation and impact resistance.
• the reason why the resin composition of the present embodiment suppresses a decrease in glass transition temperature and has good elongation and impact resistance is not clear and may be due to a combination of various factors, but is presumed to be as follows. Since the polyester polyol (A) contains an ester structure, it has a suitable compatibility with the polylactic acid polymer (B) which also contains an ester structure, which is presumably why the resin composition of the present embodiment has good elongation and impact resistance.
• the compatibility between the plasticizer and the polylactic acid polymer (B) is very high, and therefore the plasticizer and the polylactic acid polymer (B) are completely compatible with each other, causing a decrease in the glass transition temperature.
• the polyester polyol (A) and the polylactic acid polymer (B) have a moderate compatibility and form a phase-separated structure, which is presumed to suppress the decrease in the glass transition temperature.
• the polyester polyol (A) contains units derived from a polyhydric alcohol (a1) and a polycarboxylic acid (a2), and the polyhydric alcohol (a1) contains an aliphatic diol (a1-1) having 4 or more carbon atoms and having an alkyl group as a branched chain.
• the polyhydric alcohol (a1) contains an aliphatic diol (a1-1) having 4 or more carbon atoms and having an alkyl group as a branched chain.
• the "main chain” in the aliphatic diol (a1-1) is the longest molecular chain in the molecule, and hydroxyl groups are bonded to both ends of the main chain.
• the "branched chain” in the aliphatic diol (a1-1) refers to a partial structure branched from the "main chain” in the aliphatic diol (a1-1), and no hydroxyl groups are bonded to the ends of the main chain.
• the “number of carbon atoms” refers to the total number of carbon atoms in the aliphatic diol (a1-1), including the number of carbon atoms constituting the alkyl group.
• the polyester polyol (A) becomes flexible, and the resin composition exhibits excellent elongation and impact resistance.
• the number of branched chains is preferably one or two, more preferably one.
• the branched chains are preferably methyl groups, ethyl groups, and propyl groups, more preferably methyl groups and ethyl groups, and even more preferably methyl groups.
• the respective branched chains may be the same or different.
• the aliphatic diol (a1-1) has hydroxyl groups at both ends of the main chain.
• the carbon number of the aliphatic diol (a1-1) is preferably 10 or less, more preferably 9 or less. Also, from the viewpoint of elongation and impact resistance, the carbon number of the aliphatic diol (a1-1) is preferably 4 or more, more preferably 6 or more. That is, the carbon number of the aliphatic diol (a1-1) is preferably 4 to 10, more preferably 6 to 9.
• Examples of the aliphatic diol (a1-1) include 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 1,4-pentanediol, Examples of the aliphatic diol (a1-1) include 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-
• the aliphatic diol (a1-1) is preferably 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, and 2,4-diethyl-1,5-pentanediol, and more preferably 3-methyl-1,5-pentanediol.
• the aliphatic diol (a1-1) may be used alone or in combination of two or more kinds.
• the total amount of the aliphatic diol (a1-1) in the polyhydric alcohol (a1) is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more, and may be 100 mol%. In other words, it is preferable that the polyhydric alcohol (a1) is an aliphatic diol (a1-1).
• the polyhydric alcohol (a1) may contain a polyhydric alcohol (a1-2) other than the aliphatic diol (a1-1).
• examples of the polyhydric alcohol (a1-2) other than the aliphatic diol (a1-1) include ethylene glycol, propylene glycol (1,2-propanediol), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, dibutylene glycol, tributylene glycol, tetrabutylene glycol, and trimethylolpropane.
• the polyvalent carboxylic acid (a2) is not limited as long as it does not impair the effects of the present invention.
• Examples of the polyvalent carboxylic acid (a2) include aliphatic dicarboxylic acids (a2-1), aromatic dicarboxylic acids (a2-2), alicyclic dicarboxylic acids (a2-3), etc. Among these, aliphatic dicarboxylic acids (a2-1) are preferred from the viewpoint of biodegradability.
• the number of carbon atoms in the polyvalent carboxylic acid (a2) is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more, and from the viewpoint of exhibiting even better biodegradability, it is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.
• the number of carbon atoms in the polyvalent carboxylic acid (a2) is preferably 4 to 12, more preferably 5 to 10, even more preferably 6 to 10, and even more preferably 6 to 8.
• Examples of the aliphatic dicarboxylic acid (a2-1) include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, decanedicarboxylic acid, dodecylsuccinic acid, dodecenylsuccinic acid, octenylsuccinic acid, etc. From the viewpoint of exhibiting good elongation and impact resistance, the aliphatic dicarboxylic acid (a2-1) is preferably at least one selected from adipic acid and sebacic acid.
• the aliphatic dicarboxylic acid (a2-1) may be used alone or in combination of two or more kinds.
• aromatic dicarboxylic acid (a2-2) examples include phthalic acid, terephthalic acid, isophthalic acid, diphenic acid, 4,4'-biphenyldicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-furandicarboxylic acid, 2,4-furandicarboxylic acid, 1,
• the aromatic dicarboxylic acid (a2-2) is preferably at least one selected from terephthalic acid and isophthalic acid.
• the aromatic dicarboxylic acid (a2-2) may be used alone or in combination of two or more kinds.
• Examples of the alicyclic dicarboxylic acid (a2-3) include 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cycloheptanedicarboxylic acid, cyclooctanedicarboxylic acid, cyclodecanedicarboxylic acid, decahydro-1,4-naphthalenedicarboxylic acid, and 1,3-adamantanedicarboxylic acid.
• the alicyclic dicarboxylic acid (a2-3) may be used alone or in combination of two or more kinds.
• the polyester polyol (A) may or may not contain units (a') other than the units derived from the polyhydric alcohol (a1) and the polyvalent carboxylic acid (a2).
• the monomer constituting the unit (a') is not particularly limited as long as it does not impair the effects of the present invention.
• the content of units (a') in the polyester polyol (A) is preferably 50 mol % or less, more preferably 30 mol % or less, even more preferably 20 mol % or less, still more preferably 15 mol % or less, and particularly preferably 10 mol % or less.
• the number average molecular weight of the polyester polyol (A) is preferably at least 500, more preferably at least 1,000, even more preferably at least 2,000, still more preferably at least 3,000, and even more preferably at least 4,000. From the viewpoints of moldability and compatibility with the polylactic acid polymer (B), the number average molecular weight is preferably at most 100,000, more preferably at most 50,000, and even more preferably at most 20,000.
• the number average molecular weight of the polyester polyol (A) is preferably 500 to 100,000, more preferably 1,000 to 100,000, even more preferably 2,000 to 50,000, and still more preferably 4,000 to 20,000.
• the number average molecular weight of the polyester polyol (A) can be determined by gel permeation chromatography (GPC) measurement in terms of standard polystyrene. When a commercially available product is used, the value given in the catalog may be used.
• the polyvalent carboxylic acid (a2) is an aliphatic dicarboxylic acid (a2-1), the aliphatic dicarboxylic acid (a2-1) contains adipic acid, and the number average molecular weight of the polyester polyol (A) is preferably 2,000 to 100,000, more preferably 4,000 to 100,000.
• the polyvalent carboxylic acid (a2) is an aliphatic dicarboxylic acid (a2-1), the aliphatic dicarboxylic acid (a2-1) contains sebacic acid, and the number average molecular weight of the polyester polyol (A) is 2,000 to 100,000.
• the polylactic acid polymer (B) used in this embodiment may be, for example, at least one selected from the group consisting of a homopolymer of L-lactic acid, a homopolymer of D-lactic acid, a copolymer of L-lactic acid and D-lactic acid, a homopolymer of DL-lactic acid, a copolymer of DL-lactic acid and L-lactic acid, a copolymer of DL-lactic acid and D-lactic acid, and a polymer of lactide, which is a cyclic dimer of lactic acid.
• the polylactic acid polymer (B) may be a copolymer of lactic acid with an aliphatic hydroxycarboxylic acid other than lactic acid, an aliphatic dicarboxylic acid, an aliphatic diol, an aromatic dicarboxylic acid, etc.
• the copolymer preferably contains 70 mol % or more, more preferably 90 mol % or more, of units derived from lactic acid.
• a homopolymer of L-lactic acid, a homopolymer of D-lactic acid, or a copolymer of L-lactic acid and D-lactic acid is preferred, and a homopolymer of L-lactic acid is more preferred.
• the polylactic acid polymer (B) may be used alone or in combination of two or more kinds.
• a commercially available product may be used as the polylactic acid polymer (B).
• Examples of commercially available products include the "Ingeo series” manufactured by NatureWorks, the "Luminy series” manufactured by TOTAL CORBION, the “Revode” series manufactured by Zhejiang Hisun Biomaterials Co., Ltd., and the "SUPLA” series manufactured by SUPLA Material Technology Co., Ltd.
• the weight average molecular weight of the polylactic acid polymer (B) is preferably 50,000 or more, more preferably 100,000 or more, and even more preferably 150,000 or more, from the viewpoints of elongation and impact resistance. From the viewpoints of moldability and compatibility with the polyester polyol (A), it is preferably 600,000 or less, more preferably 400,000 or less, and even more preferably 300,000 or less. That is, the weight average molecular weight of the polylactic acid polymer (B) is preferably 50,000 to 600,000, more preferably 100,000 to 400,000, and even more preferably 150,000 to 300,000.
• the weight average molecular weight of the polylactic acid polymer (B) can be determined by gel permeation chromatography (GPC) in terms of standard polystyrene. When a commercially available product is used, the value given in the catalog may be used.
• the resin composition of this embodiment may further contain a cyclic ester compound (C).
• a cyclic ester compound (C) By containing the cyclic ester compound (C), the decrease in the glass transition temperature of the resin composition can be further suppressed.
• the cyclic ester compound (C) is not particularly limited, and may be a cyclization product of a hydroxycarboxylic acid, such as an intermolecular cyclic ester of an ⁇ -hydroxycarboxylic acid, a ⁇ -hydroxycarboxylic acid, or a 3-hydroxycarboxylic acid, or a condensation cyclization product of an alcohol, such as a lactone, and a carboxylic acid, or may be another cyclic compound having an ester structure.
• Examples of ⁇ -hydroxycarboxylic acids that form intermolecular cyclic esters include glycolic acid, L- and/or D-lactic acid, ⁇ -hydroxybutyric acid, ⁇ -hydroxyisobutyric acid, ⁇ -hydroxyvaleric acid, ⁇ -hydroxycaproic acid, ⁇ -hydroxyisocaproic acid, ⁇ -hydroxyheptanoic acid, ⁇ -hydroxyoctanoic acid, ⁇ -hydroxydecanoic acid, ⁇ -hydroxymyristic acid, ⁇ -hydroxystearic acid, and alkyl-substituted derivatives thereof.
• lactones examples include ⁇ -propiolactone, ⁇ -butyrolactone, pivalolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, and ⁇ -caprolactone.
• Other examples of cyclic compounds having an ester structure include dioxanones such as trimethylene carbonate, etc. When the cyclic ester has an asymmetric carbon, it may be in any of the D-form, L-form, and racemic form. These cyclic esters may be used alone or in combination of two or more.
• the cyclic ester compound (C) preferably contains units derived from an aliphatic diol (c1) and an aliphatic dicarboxylic acid (c2), i.e., it is preferable that the cyclic ester compound (C) is a cyclic ester compound obtained by reacting an aliphatic diol (c1) with an aliphatic dicarboxylic acid (c2).
• the aliphatic diol (c1) is not particularly limited, but examples thereof include the same aliphatic diol (a1-1) as above.
• the aliphatic dicarboxylic acid (c2) is not particularly limited, but examples thereof include the same as the aliphatic dicarboxylic acid (a2-1) described above.
• combinations of aliphatic diols (c1) and aliphatic dicarboxylic acids (c2) from the viewpoint of further suppressing the decrease in the glass transition temperature of the resin composition, for example, a combination of 2-methyl-1,3-propanediol and succinic acid, a combination of 3-methyl-1,5-pentanediol and succinic acid, a combination of 2,4-diethyl-1,5-pentanediol and succinic acid, a combination of 2-methyl-1,3-propanediol and adipic acid, a combination of 3-methyl-1,5-pentanediol and adipic acid, a combination of 3-methyl-1,5-pentanediol and sebacic acid, and a combination of 2,4-diethyl-1,5-pentanediol and adipic acid are available.
• a combination of dipic acid is an example of a preferred embodiment
• a combination of 3-methyl-1,5-pentanediol and succinic acid, a combination of 2,4-diethyl-1,5-pentanediol and succinic acid, a combination of 3-methyl-1,5-pentanediol and adipic acid, a combination of 3-methyl-1,5-pentanediol and sebacic acid, and a combination of 2,4-diethyl-1,5-pentanediol and adipic acid are examples of more preferred embodiments
• a combination of 3-methyl-1,5-pentanediol and adipic acid, and a combination of 3-methyl-1,5-pentanediol and sebacic acid are examples of even more preferred embodiments.
• the cyclic ester compound (C) containing units derived from the aliphatic diol (c1) and the aliphatic dicarboxylic acid (c2) is preferably a cyclic ester compound (4-methyl-1,7-dioxacyclotridecane-8,13-dione) obtained by reacting 3-methyl-1,5-pentanediol and adipic acid, from the viewpoint of further suppressing the decrease in the glass transition temperature of the resin composition.
• the method for producing the cyclic ester compound (C) is not particularly limited, but it can be produced by a known condensation reaction using hydroxycarboxylic acid, alcohol, and carboxylic acid as raw materials.
• the resin composition of this embodiment contains, per 100 parts by mass of the polylactic acid polymer (B), preferably 0.1 to 50 parts by mass, more preferably 1 to 40 parts by mass, even more preferably 3 to 15 parts by mass, and even more preferably 3 to 10 parts by mass of the polyester polyol (A). With the above content ratio, a resin composition having even more excellent elongation and impact resistance can be obtained.
• the total content of the polyester polyol (A) and the polylactic acid polymer (B) in the resin composition of this embodiment is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and may be 100% by mass. With the above content ratio, the effect of the present invention is more significantly exhibited.
• the resin composition of this embodiment further contains a cyclic ester compound (C) in addition to the polyester polyol (A) and the polylactic acid polymer (B), it preferably contains 0.001 to 3.0 parts by mass of the cyclic ester compound (C) per 100 parts by mass of the polylactic acid polymer (B), more preferably 0.005 to 2.5 parts by mass, even more preferably 0.01 to 2.0 parts by mass, and even more preferably 0.01 to 1.5 parts by mass.
• the resin composition of this embodiment may contain at least one resin component selected from the group consisting of biomass resins and biodegradable resins other than the polyester polyol (A), the polylactic acid polymer (B), and the cyclic ester compound (C).
• biomass resins or biodegradable resins include polycaprolactone (PCL), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polyglycolic acid (PGA), polyethylene furanoate (PEF), polyhydroxyalkanoate (PHA) [e.g., polyhydroxybutyrate (PHB), polyhydroxybutyrate valerate (PHBV), 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolymer polyester, etc.], cellulose acetate (CA), starch polyester (Mater-Bi (registered trademark)), etc.
• PCL polycaprolactone
• PBS polybutylene succinate
• PBSA
• the glass transition temperature of the resin composition is preferably from 40° C. to 75° C. Within the above numerical range, the resin composition tends to be excellent in elongation and impact resistance. From the viewpoint of heat resistance, the glass transition temperature of the resin composition is more preferably 45° C. or higher, further preferably 50° C. or higher, and even more preferably 52° C. or higher. From the viewpoint of elongation and impact resistance, the glass transition temperature of the resin composition is more preferably 70° C. or lower, and further preferably 60° C. or lower. That is, the glass transition temperature of the resin composition is more preferably 45° C. or higher and 70° C. or lower, even more preferably 50° C. or higher and 60° C. or lower, and even more preferably 52° C. or higher and 60° C. or lower.
• the glass transition temperature of the resin composition can be determined by differential scanning calorimetry, specifically under the measurement conditions described in the examples below.
• the resin composition of this embodiment may contain additives other than the polyester polyol (A) and the polylactic acid polymer (B).
• the additives include inorganic fillers, softeners, heat aging inhibitors, antioxidants, hydrolysis resistance inhibitors, light stabilizers, antistatic agents, release agents, flame retardants, foaming agents, pigments, dyes, brightening agents, ultraviolet absorbers, lubricants, impact resistance improvers, etc. These may be used alone or in combination of two or more. When the above additives are used, the content of the additives in the resin composition may be appropriately determined depending on the desired physical properties of the resin composition.
• ⁇ Method of producing resin composition> There is no particular limitation on the method for producing the resin composition of this embodiment, and the polyester polyol (A), the polylactic acid polymer (B), and, if necessary, the cyclic ester compound (C) and additives may be mixed uniformly.
• the mixing method include a method of melt-kneading using a single-screw extruder, a multi-screw extruder, a Banbury mixer, a heating roll, a Brabender, various kneaders, etc., or a method of feeding each component through a separate inlet and melt-kneading the components. Alternatively, the components may be preblended before melt-kneading.
• Examples of the preblending method include a method using a mixer such as a Henschel mixer, a high-speed mixer, a V blender, a ribbon blender, a tumbler blender, or a conical blender.
• the temperature during melt-kneading can be arbitrarily selected, preferably within the range of 140 to 250° C., taking into consideration the melting point and decomposition temperature of the polyester polyol (A).
• the present invention also provides a molded article made of the resin composition.
• the shape of the molded body may be any molded body that can be produced using the resin composition of this embodiment.
• Examples of the molded body include molded bodies of various shapes such as pellets, films, sheets, plates, pipes, tubes, bottles, fibrous bodies, rod-shaped bodies, fine particles, particulate bodies, and foams.
• the method for producing the molded body is not particularly limited, and it can be molded by various molding methods, such as injection molding, blow molding, press molding, extrusion molding, calendar molding, and molding using a 3D printer.
• the polylactic acid polymer (B) can be mixed with the polyester polyol (A) to form a resin composition, thereby improving the elongation and impact resistance while suppressing a decrease in the glass transition temperature.
• the present invention provides a modifier for the polylactic acid polymer (B), which is made of the polyester polyol (A).
• the polyester polyol (A) may be used as a modifier for the polylactic acid polymer (B) in a preferred embodiment.
• the resin composition of this embodiment can be used for various purposes.
• the resin composition can be used for the following purposes: Food utensils such as food bags, food caps, food trays, straws, cutlery, food containers, etc.; Closures, cap liners for containers for storing food, beverages, medicines, etc.; Single-layer or multi-layer films and sheets for electronic component packaging materials, pharmaceutical packaging materials, food packaging materials, agricultural materials, civil engineering and construction materials, industrial materials, etc.; Fibers such as woven fabrics and nonwoven fabrics; Solvent-type, hot melt-type, heat-stretching-type and other pressure-sensitive adhesives and adhesives; Coating agents such as aqueous, solution, emulsion, and dispersion types; Filament for 3D printers; developing toner; Support material for hydraulic fracturing and water leakage prevention agent for drilling; Anti-vibration rubber, mats, sheets, cushions, dampers, pads, mount rubber, and other various vibration-proofing and vibration-damping materials; Components for household appliances such
• ⁇ Number average molecular weight> The polyester polyols obtained in the Production Examples and Comparative Production Examples were used as samples, and their number average molecular weights (Mn) were determined by gel permeation chromatography (GPC) in terms of standard polystyrene.
• the specific measurement method was as follows. (1) In the case of Mn less than 15,000, a tetrahydrofuran (THF) solution was used as an eluent, and 10 mg of a sample was weighed out in terms of resin and dissolved in 1 mL of the eluent. The solution was passed through a 0.2 ⁇ m membrane filter to prepare a measurement sample.
• the specific measurement method is as follows.
• RI detector 2 In the case of Mn 15,000 or more, a tetrahydrofuran (THF) solution was used as the eluent. 1.0 mg of a sample was weighed in terms of resin and dissolved in 1 mL of the above eluent. The solution was passed through a 0.2 ⁇ m membrane filter to prepare a measurement sample. The measurement conditions were as follows. (Measurement conditions) Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation) Column: Two TSK-gel SuperMultipore HZ-M columns (manufactured by Tosoh Corporation) were connected in series.
• HLC-8220GPC manufactured by Tosoh Corporation
• Column Two TSK-gel SuperMultipore HZ-M columns (manufactured by Tosoh Corporation) were connected in series.
• ⁇ DuPont impact resistance test> Preparation of test pieces for DuPont impact resistance test
• the resin compositions obtained in the examples and comparative examples were decompressed to -0.1 MPaG using a reduced pressure hot press machine (Imoto Manufacturing Co., Ltd. "IMC-183B") using an oil rotary pump, preheated at 200 ° C for 5 minutes, and pressed at 8 MPa for 3 minutes. Then, pressed at 8 MPa for 3 minutes using a cooling press machine equipped with water flow cooling to prepare a pressed plate with a thickness of 0.4 mm.
• the obtained pressed plate was cut into a size of 50 ⁇ 50 mm and stored in an environment of 23 ° C and humidity of 49% for 24 hours or more to prepare a test piece.
• dumbbell test pieces dumbbell-shaped No. 3 test pieces prepared in the above "Preparation of test pieces for tensile test” were stored at 80°C for 16 hours or more, and the surface condition was evaluated visually and by touch.
• VG No obvious bleeding out or stickiness was observed.
• G Slight bleeding or stickiness is observed, but at a level that does not cause any practical problems.
• NG Significant bleeding out or stickiness is observed, and the composition is not suitable for practical use.
• Polylactic acid polymer (B) Polylactic acid polymer (B-1): Ingeo Biopolymer 2003D (NatureWorks) (weight average molecular weight: 220,000)
• Polylactic acid polymer (B-2) Ingeo Biopolymer 3001D (NatureWorks) (weight average molecular weight: 150,000)
• Plasticizer 1 DAIFATTY-101 (Daihachi Chemical Industry Co., Ltd.)
• polyester polyol (A-1) 150 ⁇ L of tetraisopropyl titanate was added, and the pressure was reduced to 2,000 Pa and the reaction was carried out for 3 hours, and then the pressure was further reduced to 80 Pa and the reaction was continued while appropriately checking until the number average molecular weight reached 3,000, thereby obtaining polyester polyol (A-1).
• a polyester polyol (A-6) was obtained in the same manner as in Production Example 1, except that sebacic acid was used instead of adipic acid, 150 ⁇ L of tetraisopropyl titanate was added, the pressure was reduced to 2,000 Pa and the reaction was allowed to proceed for 3 hours, and then the pressure was further reduced to 80 Pa and the reaction time was adjusted to adjust the number average molecular weight to that shown in Table 1.
• a polyester polyol (A-7) was obtained in the same manner as in Production Example 1, except that terephthalic acid was used instead of adipic acid, 150 ⁇ L of tetraisopropyl titanate was added, the pressure was reduced to 2,000 Pa and the reaction was allowed to proceed for 3 hours, and then the pressure was further reduced to 80 Pa and the reaction time was adjusted to adjust the number average molecular weight to that shown in Table 1.
• a polyester polyol (A-8) was obtained in the same manner as in Production Example 1, except that isophthalic acid was used instead of adipic acid, 150 ⁇ L of tetraisopropyl titanate was added, the pressure was reduced to 2,000 Pa and the reaction was allowed to proceed for 3 hours, and then the pressure was further reduced to 80 Pa and the reaction time was adjusted to adjust the number average molecular weight to that shown in Table 1.
• a polyester polyol (A-11) was obtained in the same manner as in Production Example 1, except that succinic acid was used instead of adipic acid, 150 ⁇ L of tetraisopropyl titanate was added, the pressure was reduced to 2,000 Pa and the reaction was allowed to proceed for 3 hours, and then the pressure was further reduced to 80 Pa and the reaction time was adjusted to adjust the number average molecular weight to that shown in Table 1.
• a polyester polyol (A'-1) was obtained in the same manner as in Production Example 1, except that 1,4-butanediol was used instead of 3-methyl-1,5-pentanediol, 150 ⁇ L of tetraisopropyl titanate was added, the pressure was reduced to 2,000 Pa and the reaction was allowed to proceed for 3 hours, and then the pressure was further reduced to 80 Pa and the reaction time was adjusted to adjust the number average molecular weight to that shown in Table 1.
• polyester polyol (A-1) 150 ⁇ L of tetraisopropyl titanate was added, and the pressure was reduced to 2,000 Pa and the reaction was carried out for 3 hours, and then the pressure was further reduced to 80 Pa and the reaction was continued while appropriately checking until the number average molecular weight reached 3,000, thereby obtaining polyester polyol (A-1).
• the toluene layer was added to an eggplant flask and air-dried overnight at 20°C to volatilize the toluene, and then dried in a vacuum dryer at 20°C and 100 Pa for 1 hour to obtain crystals of 4-methyl-1,7-dioxacyclotridecane-8,13-dione (cyclic ester compound (C-1)), which is a cyclic ester compound.
• cyclic ester compound (C-1) 4-methyl-1,7-dioxacyclotridecane-8,13-dione
• polyester polyols (A-1) to (A-8), polylactic acid polymer (B-1) and cyclic ester compound (C) obtained in the production examples were each charged into a twin-screw kneader (Technovel's "ULT nano 50") in the formulations shown in Table 2, extruded into strands at a cylinder temperature of 200°C, a screw rotation speed of 50 rpm and a residence time of 1 minute, and the resulting strands were cut into pellets to obtain a resin composition.
• the obtained resin composition was evaluated as described above. The results are shown in Table 2.
• Example 1 A resin composition was obtained in the same manner as in Example 1, except that the polyester polyol (A-1) was not used. The obtained resin composition was subjected to the above-mentioned evaluations. The results are shown in Table 2.

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