Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
  • C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
• • 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
  • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy 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
• • 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
  • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic 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

Definitions

• the present invention relates to a resin composition that suppresses the deterioration of tensile properties and transparency, improves the crystallinity and melting point, and has excellent heat resistance properties. It also relates to a resin composition that has an excellent balance of biodegradability, heat resistance, and transparency.
• polylactic acid a bioplastic
• Polylactic acid is made from renewable resources derived from plants such as corn, which are produced by photosynthesis, and is expected to be used in a wide range of fields.
• polylactic acid is known to be brittle, inferior in viscosity, flexibility, impact resistance, and heat resistance, and more easily hydrolyzed, compared to petroleum-based plastics. Therefore, the use of polylactic acid as a resin material may be limited.
• a technique using a specific plasticizer or crystal nucleating agent has been considered (for example, Patent Document 1).
• Patent Document 2 a technique of copolymerizing a polyester using a monomer having a specific carbon number with polylactic acid has been considered (for example, Patent Document 2). Also, a technique using a specific plasticizer or crystal nucleating agent has been considered (for example, Patent Document 3). Also, a technique using a composition of a block copolymer obtained by copolymerizing a specific polyester with polylactic acid and polylactic acid has been considered (for example, Patent Document 4).
• JP 2015-044984 A Japanese Patent Application Publication No. 8-157577 JP 2018-62573 A JP 2001-335623 A
• Patent Documents 1 to 4 improve the shortcomings of polylactic acid to some extent, they are not fully satisfactory.
• final products made of bioplastic materials are desired to have excellent heat resistance while being biodegradable under a wide range of conditions, or to have excellent impact resistance, heat resistance, and transparency while being biodegradable.
• the crystallization degree of polylactic acid is increased in order to improve heat resistance, the tensile properties and transparency tend to decrease.
• the present invention aims to provide a resin composition that has biodegradable properties over a wide range of conditions and has an excellent balance of crystallinity, tensile properties, transparency, and heat resistance. It also aims to provide a resin composition that has an excellent balance of biodegradability, heat resistance, and transparency.
• 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 block copolymer (I) contains a block structural unit (A) mainly composed of a polylactic acid unit (a) and a block structural unit (B) mainly composed of a polyester unit (b) containing a unit derived from an aliphatic diol (b1) and an aliphatic dicarboxylic acid (b
• the present invention it is possible to provide a resin composition which has biodegradable properties over a wide range of conditions and has an excellent balance of crystallinity, tensile properties, transparency, and heat resistance. Moreover, according to the present invention, it is possible to provide a resin composition that has an excellent balance of biodegradability, heat resistance, and transparency.
• 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 term “L-lactic acid unit” refers to a structural unit derived from L-lactic acid in the block structural unit (A).
• the block structural unit (A) contains a structural unit derived from lactide and the structural unit derived from lactide contains a structural unit derived from L-lactic acid
• the portion corresponding to the L-lactic acid is also included in the L-lactic acid unit.
• the term "D-lactic acid unit” refers to a structural unit derived from D-lactic acid in the block structural unit (A).
• the block structural unit (A) contains a structural unit derived from lactide and the structural unit derived from lactide contains a structural unit derived from D-lactic acid
• the portion corresponding to the D-lactic acid is also included in the D-lactic acid unit.
• poly DL-lactic acid refers to polylactic acid containing L-lactic acid units and D-lactic acid units.
• examples of poly DL-lactic acid include block copolymers containing poly L-lactic acid blocks and poly D-lactic acid blocks, and random copolymers containing L-lactic acid units and D-lactic acid units randomly.
• DL-lactic acid refers to a mixture of D-lactic acid and L-lactic acid.
• DL-lactide refers to a mixture of D-lactide and L-lactide.
• meo-lactide refers to lactide formed from one unit each of D-lactic acid and L-lactic acid.
• melting point means a melting peak temperature, and when there are multiple melting peaks, it means the melting peak temperature of the melting point peak that is present on the highest temperature side.
• the melting point can be determined by a differential scanning calorimeter, and specifically, can be measured by the method described in the Examples.
• a resin composition according to a first embodiment of the present invention is a resin composition containing a block copolymer (I) and a cyclic ester compound (II), wherein the block copolymer (I) contains a block structural unit (A) mainly composed of a polylactic acid unit (a) and a block structural unit (B) mainly composed of a polyester unit (b) derived from an aliphatic diol (b1) and an aliphatic dicarboxylic acid (b2).
• the resin composition contains 0.01 to 15% by mass of the cyclic ester compound (II) relative to 100% by mass of the total of the block copolymer (I) and the cyclic ester compound (II).
• the resin composition according to the first embodiment of the present invention has an excellent balance of crystallinity, tensile properties, transparency, and heat resistance is not clear and may be due to a combination of various factors, but is presumed to be as follows. Since the cyclic ester compound (II) contains an ester structure, it is highly compatible with the block copolymer (I) that also contains an ester structure. As a result, even when the crystallinity of the resin composition is improved, the decrease in tensile properties and the decrease in transparency are suppressed.
• the cyclic ester compound (II) is cyclic, it has a low degree of molecular freedom and contributes to the effect of a crystal nucleating agent, that is, the improvement of crystallinity and the improvement of melting point (improvement of heat resistance).
• the resin composition according to the first embodiment has an excellent balance of crystallinity, tensile properties, transparency, and heat resistance.
• a resin composition according to a second embodiment of the present invention is the resin composition according to the first embodiment, which further contains an aliphatic polyester-based resin (III), and the content of the cyclic ester compound (II) is 0.005 to 10 mass% relative to 100 mass% in total of the preblock copolymer (I), the cyclic ester compound (II), and the aliphatic polyester-based resin (III).
• the present inventors have found that a resin composition according to a second embodiment, which contains a specific block copolymer (I), a specific amount of a cyclic ester compound (II), and an aliphatic polyester resin (III), has an excellent balance of biodegradability, heat resistance, and transparency.
• the resin composition according to the second embodiment of the present invention has an excellent balance of biodegradability, heat resistance, and transparency is not clear and may be due to a combination of various factors, but is presumed to be as follows. Since the cyclic ester compound (II) contains an ester structure, it is highly compatible with the block copolymer (I) and the aliphatic polyester resin (III) that also contain an ester structure. As a result, even when the crystallization degree of the resin composition is improved, the decrease in transparency is suppressed.
• the resin composition according to the second embodiment has an excellent balance of biodegradability, heat resistance, and transparency.
• the block copolymer (I) contains a block structural unit (A) mainly composed of a polylactic acid unit (a), and a block structural unit (B) mainly composed of a polyester unit (b) containing units derived from an aliphatic diol (b1) and an aliphatic dicarboxylic acid (b2).
• the block structural unit (A) is mainly composed of a polylactic acid unit (a).
• the above-mentioned "main component” means the unit that is contained at the highest content ratio among the units constituting the block structural unit (A).
• the content of the polylactic acid unit (a) in the block structural unit (A) is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, and even more preferably 90% by mass or more, and may be 100% by mass.
• There is no upper limit to the content of the polylactic acid unit (a) in the block structural unit (A) is, for example, 100% by mass or less.
• the polylactic acid constituting the polylactic acid unit (a) may be prepared by a direct condensation method of lactic acid or by a ring-opening polymerization method of lactide.
• lactic acid for example, at least one selected from the group consisting of L-lactic acid, D-lactic acid, and DL-lactic acid can be used.
• lactide for example, at least one selected from the group consisting of L-lactide, D-lactide, DL-lactide, and meso-lactide can be used.
• the polylactic acid may be poly-L-lactic acid, poly-D-lactic acid, poly-DL-lactic acid, an intramolecular stereocomplex obtained by mixing poly-L-lactic acid and poly-D-lactic acid, or an intermolecular stereocomplex polylactic acid.
• the polylactic acid is preferably poly-L-lactic acid, poly-D-lactic acid, or poly-DL-lactic acid, and more preferably poly-L-lactic acid or poly-D-lactic acid.
• the polylactic acid is not an intramolecular stereocomplex or intermolecular stereocomplex polylactic acid.
• the block structural unit (A) preferably contains a structural unit derived from poly-L-lactic acid or a structural unit derived from poly-D-lactic acid.
• the block structural unit (A) preferably contains 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more of structural units derived from poly-L-lactic acid or poly-D-lactic acid.
• one preferred embodiment is one in which the block structural unit (A) is composed of structural units derived from poly-L-lactic acid or structural units derived from poly-D-lactic acid, that is, the structural units derived from poly-L-lactic acid or structural units derived from poly-D-lactic acid account for 100% by mass.
• the block structural unit (A) may or may not contain a unit (a') other than the polylactic acid unit (a).
• the monomer constituting the unit (a') is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include intermolecular cyclic esters and lactones.
• Examples of ⁇ -hydroxycarboxylic acids that form intermolecular cyclic esters include glycolic 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 include ⁇ -propiolactone, ⁇ -butyrolactone, pivalolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, ⁇ -caprolactone, and the like.
• the content of units (a') in the block structural unit (A) is preferably 30 mass % or less, more preferably 20 mass % or less, even more preferably 15 mass % or less, and further more preferably 10 mass % or less.
• the number average molecular weight of the block structural unit (A) is not limited as long as it does not impair the effects of the present invention.
• the number average molecular weight of the block structural unit (A) is preferably 500 or more, more preferably 1,000 or more, even more preferably 1,500 or more, still more preferably 3,000 or more, still more preferably 5,000 or more, still more preferably 10,000 or more, and is preferably 200,000 or less, more preferably 150,000 or less, still more preferably 100,000 or less, still more preferably 50,000 or less, still more preferably 30,000 or less, and still more preferably 20,000 or less.
• the number average molecular weight of the block structural unit (A) is preferably 500 to 200,000, more preferably 1,000 to 150,000, even more preferably 1,500 to 100,000, even more preferably 3,000 to 50,000, even more preferably 5,000 to 30,000, even more preferably 5,000 to 20,000, and even more preferably 10,000 to 20,000. Within the above numerical range, the productivity in synthesizing the block copolymer (I) is good. Note that, when the block copolymer (I) has a plurality of block structural units (A), the number average molecular weight of the block structural unit (A) means the total of all blocks. The number average molecular weight of the block structural unit (A) can be determined from the number average molecular weight of the block copolymer (I) described below and the mass content of the block structural unit (A).
• the block structural unit (B) is mainly composed of a polyester unit (b).
• the above-mentioned "main component” means the unit that is contained in the largest proportion among the units that constitute the block structural unit (B).
• the content of the polyester units (b) in the block structural unit (B) is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, still more preferably 85% by mass or more, particularly preferably 90% by mass or more, and may be 100% by mass.
• the polyester unit (b) contains units derived from an aliphatic diol (b1) and an aliphatic dicarboxylic acid (b2). Specifically, the polyester unit (b) contains units derived from a polyester obtained by reacting an aliphatic diol (b1) with an aliphatic dicarboxylic acid (b2).
• the polyester unit (b) may or may not contain units derived from monomers other than the aliphatic diol (b1) and the aliphatic dicarboxylic acid (b2).
• the monomer other than the aliphatic diol (b1) and the aliphatic dicarboxylic acid (b2) is not particularly limited as long as the effects of the present invention are not impaired.
• the total amount of the aliphatic diol (b1) and the aliphatic dicarboxylic acid (b2) in the polyester unit (b) 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 %.
• the carbon number of the aliphatic diol acid (b1) is not limited as long as it does not impair the effects of the present invention.
• the "carbon number” is the total carbon number of the aliphatic diol (b1) including the carbon number of the alkyl group.
• the carbon number of the aliphatic diol (b1) is preferably 4 to 12, more preferably 5 to 10, even more preferably 6 to 9, and even more preferably 6.
• the carbon number of the aliphatic diol (b1) is preferably 4 to 30, more preferably 5 to 18, and even more preferably 6 to 9.
• the aliphatic diol (b1) When the aliphatic diol (b1) has an alkyl group as a branched chain, the block structural unit (B) becomes flexible, and the block copolymer (I) exhibits excellent tensile properties, biodegradability, and impact resistance, and has improved hydrolysis resistance. Therefore, the aliphatic diol (b1) preferably has an alkyl group as a branched chain, and more preferably is an aliphatic diol having 4 or more carbon atoms and an alkyl group as a branched chain.
• the "branched chain” in the aliphatic diol (b1) refers to a partial structure branching off from the "main chain” in the aliphatic diol (b1), and no hydroxyl group is bonded to the end thereof.
• the block structural unit (B) tends to become an amorphous polymer, so that when the block structural unit (B) biodegrades, microorganisms are more likely to enter the polymer structure, and it is thought that it is easier to have biodegradability under a wide range of conditions.
• the block structural unit (B) is not an amorphous polymer, it is thought that microorganisms are less likely to enter the polymer structure during biodegradation.
• being an amorphous polymer is only one factor that affects biodegradability.
• the number of branched chains is preferably 1 or 2, more preferably 1.
• 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 (b1) has hydroxyl groups at both ends of the main chain.
• Examples of the aliphatic diol (b1) include 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, 2-methyl-
• Examples of the aliphatic diol (b1) include 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,5-pentanediol, 2,4-dimethyl
• the aliphatic diol (b1) 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 (b1) may be used alone or in combination of two or more kinds.
• the number of carbon atoms of the aliphatic dicarboxylic acid (b2) is not limited as long as it does not impair the effects of the present invention.
• the number of carbon atoms of the aliphatic dicarboxylic acid (b2) is preferably 4 to 12, more preferably 5 to 10, and even more preferably 6 to 8.
• the number of carbon atoms of the aliphatic dicarboxylic acid (b2) is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more, and from the viewpoint of exerting even more excellent biodegradability, it is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. That is, in the second embodiment of the present invention, the number of carbon atoms of the aliphatic dicarboxylic acid (b2) is preferably 4 to 12, more preferably 5 to 10, and even more preferably 6 to 8.
• Examples of the aliphatic dicarboxylic acid (b2) include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, decanedicarboxylic acid, etc. Preferred are succinic acid, adipic acid, and sebacic acid, and more preferred is adipic acid.
• the aliphatic dicarboxylic acid (b2) may be used alone or in combination of two or more kinds.
• the content of the aromatic carboxylic acid unit in the polyester unit (b) is preferably 20% by mass or less. When the content is 20% by mass or less, biodegradability is improved.
• the aromatic carboxylic acid unit also includes a heteroaromatic carboxylic acid unit containing a heteroatom.
• the aromatic carboxylic acid unit may contain one or both of a heteroaromatic carboxylic acid unit containing a heteroatom and a heteroaromatic carboxylic acid unit not containing a heteroatom, or may contain only a heteroaromatic carboxylic acid unit not containing a heteroatom.
• 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, and a combination of 2,4-diethyl-1,5-pentanediol and adipic acid are examples of more preferred embodiments, and a combination of 3-methyl-1,5-pentanediol and adipic acid is an example of a further preferred embodiment.
• the number average molecular weight of the block structural unit (B) is preferably 1,000 or more and less than 200,000, more preferably 4,000 or more and less than 100,000, even more preferably 8,000 or more and less than 80,000, and even more preferably 10,000 or more and less than 50,000.
• the number average molecular weight of the block structural unit (B) is preferably less than 300,000, more preferably less than 100,000, even more preferably less than 80,000, and even more preferably less than 50,000 from the viewpoint of productivity, and the number average molecular weight of the block structural unit (B) is preferably 1,000 or more, more preferably 4,000 or more, even more preferably 8,000 or more, even more preferably 10,000 or more, and even more preferably 20,000 or more from the viewpoint of glass transition temperature, crystal melting enthalpy, etc.
• the number average molecular weight of the block structural unit (B) is preferably 1,000 or more and less than 300,000, more preferably 4,000 or more and less than 100,000, even more preferably 8,000 or more and less than 80,000, even more preferably 10,000 or more and less than 50,000, and even more preferably 20,000 or more and less than 50,000.
• the number average molecular weight of the block structural unit (B) can be determined by gel permeation chromatography (GPC) from the number average molecular weight of the block copolymer (I) described below and the mass content of the block structural unit (B). Specifically, it can be measured by the method described in the Examples.
• the content of the block structural unit (A) is preferably 5% by mass or more and 95% by mass or less relative to 100% by mass of the total of the block structural unit (A) and the block structural unit (B).
• the proportion of the block structural unit (A) is 5% by mass or more, the heat resistance of the resin composition tends to be more excellent, and when the proportion of the block structural unit (A) is 95% by mass or less, the tensile properties and biodegradability of the resin composition tend to be more excellent, and the tensile properties are even more excellent.
• the proportion of the block structural unit (A) is more preferably 10% by mass or more, and even more preferably 15% by mass or more. From the viewpoints of biodegradability and tensile properties, the proportion of the block structural unit (A) is more preferably 80% by mass or less, even more preferably 75% by mass or less, still more preferably 70% by mass or less, and even more preferably 60% by mass or less.
• the proportion of the block structural unit (A) can be determined by 1 H-NMR, specifically, by the method described in the Examples.
• the total content of the block structural unit (A) and the block structural unit (B) in the block copolymer (I) is preferably 90% by mass or more, more preferably 95% by mass or more, and may be 100% by mass. There is no upper limit to the total content of the block structural unit (A) and the block structural unit (B) in the block copolymer (I), and it may be, for example, 100% by mass or less.
• the block copolymer (I) may or may not contain units other than the block structural unit (A) and the block structural unit (B).
• the units other than the block structural unit (A) and the block structural unit (B) are not particularly limited as long as they do not impair the effects of the present invention.
• the content of units other than the block structural unit (A) and the block structural unit (B) is preferably 10% by mass or less, more preferably 5% by mass or less.
• the number average molecular weight of the block copolymer (I) is preferably 2,000 or more, more preferably 5,000 or more, even more preferably 10,000 or more, and still more preferably 20,000 or more.
• the number average molecular weight of the block copolymer (I) is preferably 450,000 or less, more preferably 350,000 or less, even more preferably 250,000 or less, still more preferably 200,000 or less, still more preferably 150,000 or less, and may be 100,000 or less.
• the number average molecular weight of the block copolymer (I) is preferably 2,000 to 450,000, more preferably 2,000 to 400,000, even more preferably 2,000 to 350,000, still more preferably 2,000 to 250,000, still more preferably 2,000 to 200,000, still more preferably 5,000 to 150,000, still more preferably 10,000 to 100,000, and still more preferably 20,000 to 100,000.
• the number average molecular weight of the block copolymer (I) is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 15,000 or more, and still more preferably 20,000 or more.
• the number average molecular weight of the block copolymer (I) is preferably 400,000 or less, more preferably 200,000 or less, and even more preferably 100,000 or less. That is, in the second embodiment of the present invention, the number average molecular weight of the block copolymer (I) is preferably 5,000 to 400,000, more preferably 10,000 to 200,000, and further preferably 15,000 to 100,000.
• the number average molecular weight of the block copolymer (I) can be determined by gel permeation chromatography (GPC), specifically, by the method described in the examples.
• the bonding form of the block copolymer (I) is preferably a triblock type or a diblock type, and more preferably a triblock type.
• the block copolymer (I) may be a mixture of a triblock type and a diblock type.
• the bonding form is preferably [block structural unit (A)]-[block structural unit (B)]-[block structural unit (A)].
• the melting point of the block copolymer (I) is preferably 110°C or higher and lower than 180°C.
• the melting point of the block copolymer (I) is 110°C or higher, the block copolymer (I) is not easily softened even at a temperature equal to or higher than the glass transition temperature thereof, and the resin composition has excellent heat resistance.
• the melting point of the block copolymer (I) is less than 180°C, the melting point is not too high, and the processability is excellent, for example, melt processing is easy.
• the melting point of the block copolymer (I) is preferably 115°C or higher, more preferably 120°C or higher, even more preferably 125°C or higher, and preferably 175°C or lower, more preferably 170°C or lower, even more preferably 160°C or lower, and even more preferably 155°C or lower. That is, the melting point of the block copolymer (I) is preferably 115°C or higher and 175°C or lower, more preferably 115°C or higher and 170°C or lower, even more preferably 120°C or higher and 160°C or lower, and even more preferably 125°C or higher and 155°C or lower.
• the melting point of the block copolymer (I) can be determined by a differential scanning calorimeter, specifically, by the method described in the examples.
• the glass transition temperature of the block copolymer (I) is preferably ⁇ 80° C. or more and 15° C. or less, more preferably ⁇ 80° C. or more and ⁇ 10° C. or less, and even more preferably ⁇ 80° C. or more and ⁇ 15° C. or less. Within the above numerical range, the resin composition tends to be excellent in flexibility and impact resistance. From the viewpoint of impact resistance at low temperatures, the glass transition temperature of the block copolymer (I) is preferably ⁇ 20° C. or lower, more preferably ⁇ 25° C. or lower, and further preferably ⁇ 30° C. or lower, and may be ⁇ 35° C.
• the glass transition temperature of the block copolymer (I) is preferably ⁇ 80° C. or higher, and the lower limit is preferably lower.
• the glass transition temperature may be ⁇ 70° C. or higher, ⁇ 60° C. or higher, or ⁇ 50° C. or higher.
• the glass transition temperature of the block copolymer (I) is preferably ⁇ 80° C. or more and ⁇ 20° C. or less, more preferably ⁇ 80° C. or more and ⁇ 25° C. or less, even more preferably ⁇ 80° C. or more and ⁇ 30° C. or less, still more preferably ⁇ 80° C. or more and ⁇ 35° C.
• the glass transition temperature of the block copolymer (I) is preferably -70°C or more and -20°C or less, more preferably -70°C or more and -30°C or less.
• the temperature may be -60°C or higher and -10°C or lower, -60°C or higher and -20°C or lower, -60°C or higher and -30°C or lower, -50°C or higher and -30°C or lower, -50°C or higher and -35°C or lower, or -50°C or higher and -45°C or lower.
• the glass transition temperature of the block copolymer (I) can be determined by differential scanning calorimetry.
• the block copolymer (I) can be produced by a known production method.
• a known method for producing the block copolymer (I) may be, for example, a method in which a polyester constituting the polyester unit (b) is synthesized and the polyester is polymerized with lactide.
• the polyester can be synthesized by a known method.
• the polyester can be synthesized by reacting an aliphatic diol (b1) with an aliphatic dicarboxylic acid (b2) using an esterification catalyst (e.g., tin octylate, tin chloride, or tin oxide).
• a ring-opening polymerization catalyst e.g., tin octoate, tin chloride, tin oxide.
• the polymerization reaction may be performed by solution polymerization, melt polymerization, interfacial polycondensation, or the like, and any of the polymerization reaction conditions may be set as known in the art.
• a known method for producing the block copolymer (I) may be, for example, a method in which a polylactic acid constituting the polylactic acid unit (a) and a polyester constituting the polyester unit (b) are separately synthesized and the polylactic acid and the polyester are reacted with each other.
• Polylactic acid can be synthesized by a known method.
• polylactic acid may be synthesized by reacting lactic acid by a direct condensation method, or polylactic acid may be synthesized by reacting lactide by a ring-opening polymerization method.
• an esterification catalyst e.g., tin octoate, tin chloride, tin oxide.
• the polymerization reaction may be solution polymerization, melt polymerization, interfacial polycondensation, or the like, and any of these may be carried out under known polymerization reaction conditions.
• the cyclic ester compound (II) 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.
• a hydroxycarboxylic acid such as an intermolecular cyclic ester of an ⁇ -hydroxycarboxylic acid, a ⁇ -hydroxycarboxylic acid, or a 3-hydroxycarboxylic acid
• a condensation cyclization product of an alcohol such as a lactone
• 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 (II) preferably contains a structure derived from an aliphatic diol (c1) and an aliphatic dicarboxylic acid (c2), that is, it is preferably 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, and examples thereof include the same ones as the above-mentioned aliphatic diol (b1).
• the aliphatic dicarboxylic acid (c2) is not particularly limited, but examples thereof include the same as the above-mentioned aliphatic dicarboxylic acid (b2).
• Specific examples of the cyclic ester compound (II) containing a structure derived from an aliphatic diol (c1) and an aliphatic dicarboxylic acid (c2) include the cyclic ester compound obtained by reacting the above-mentioned aliphatic diol (b1) with an aliphatic dicarboxylic acid (b2).
• a preferred combination of the aliphatic diol (c1) and the aliphatic dicarboxylic acid (c2) is the same as the preferred combination of the aliphatic diol (b1) and the aliphatic dicarboxylic acid (b2) described above.
• the cyclic ester compound (II) containing a structure derived from an aliphatic diol (c1) and an aliphatic dicarboxylic acid (c2) is preferably a cyclic ester compound obtained by reacting 3-methyl-1,5-pentanediol with adipic acid, from the viewpoint of obtaining a resin composition having an excellent balance of crystallinity, tensile properties, transparency, and heat resistance.
• the aliphatic diol (c1) and the aliphatic diol (b1) are the same, and the aliphatic dicarboxylic acid (c2) and the aliphatic dicarboxylic acid (b2) are the same.
• the method for producing the cyclic ester compound (II) is not particularly limited, but it can be produced by a known condensation reaction using hydroxycarboxylic acid or alcohol and carboxylic acid as raw materials.
• the aliphatic polyester resin (III) is preferably at least one selected from the group consisting of biomass resins and biodegradable resins from the viewpoint of environmental protection.
• the aliphatic polyester resin (III) include polylactic acid (PLA), polycaprolactone (PCL), poly(caprolactone/butylene succinate) (PCLBS), polybutylene succinate (PBS), poly(butylene succinate/adipate) (PBSA), poly(butylene succinate/carbonate) (PEC), poly(ethylene terephthalate/succinate) (PETS), poly(butylene adipate/terephthalate) (PBAT), poly(tetramethylene adipate/terephthalate) (PTMT), polyethylene succinate (PES), polyglycolic acid (PGA), polyethylene furanoate (PEF), polyhydroxyalkanoate (PHA) [e.g., polyhydroxybutyrate (PHB), poly
• the aliphatic polyester resin (III) is preferably PLA, PBS, PBSA, or PBAT, and more preferably PLA or its copolymer, i.e., polylactic acid resin.
• the melting point of the aliphatic polyester resin (III) is preferably 100°C or higher, more preferably 110°C or higher, even more preferably 130°C or higher, even more preferably 140°C or higher, even more preferably 155°C or higher, and even more preferably 170°C or higher. Also, from the viewpoint of moldability, the melting point of the aliphatic polyester resin (III) is preferably 300°C or lower, more preferably 270°C or lower, even more preferably 240°C or lower, even more preferably 220°C or lower, and even more preferably 200°C or lower.
• examples of the polylactic acid resin include 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 resin 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 80 mol % or more, and even more preferably 90 mol % or more of structural units derived from lactic acid.
• the polylactic acid-based resin a homopolymer of L-lactic acid, a homopolymer of D-lactic acid, or a copolymer of L-lactic acid and D-lactic acid is preferable, and a homopolymer of L-lactic acid is more preferable.
• the polylactic acid resin may be used alone or in combination of two or more kinds.
• the polylactic acid resin may be a commercially available product.
• 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 resin is preferably 50,000 or more, more preferably 100,000 or more, and even more preferably 150,000 or more from the viewpoint of heat resistance, and is preferably 600,000 or less, more preferably 550,000 or less, and even more preferably 500,000 or less from the viewpoint of moldability and compatibility with the block copolymer (I). That is, the weight average molecular weight of the polylactic acid resin is preferably 50,000 to 600,000, more preferably 100,000 to 550,000, and even more preferably 150,000 to 500,000.
• the weight average molecular weight of the polylactic acid resin can be determined by gel permeation chromatography (GPC) measurement in terms of standard polystyrene. When a commercially available product is used, the value listed in the catalog may be used.
• the resin composition according to the first embodiment of the present invention contains the block copolymer (I) in an amount of preferably 85% by mass or more and less than 100% by mass, more preferably 90% by mass or more and less than 100% by mass, even more preferably 92% by mass or more and less than 100% by mass, even more preferably 96% by mass or more and less than 100% by mass, even more preferably 98% by mass or more and less than 100% by mass, and even more preferably 98% by mass or more and less than 100% by mass, relative to the total amount of the block copolymer (I) and the cyclic ester compound (II) being 100% by mass.
• the above content ratio can provide a resin composition having better heat resistance, tensile properties, and transparency.
• the resin composition according to the first embodiment of the present invention contains 0.01 to 15% by mass of the cyclic ester compound (II) relative to 100% by mass of the block copolymer (I) and the cyclic ester compound (II).
• the content of the cyclic ester compound (II) relative to 100% by mass of the block copolymer (I) and the cyclic ester compound (II) in the resin composition according to the first embodiment is preferably 0.02% by mass or more, more preferably 0.04% by mass or more, even more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, and preferably 12% by mass or less, more preferably 8% by mass or less, even more preferably 4% by mass or less, even more preferably 3% by mass or less, and even more preferably 1% by mass or less.
• the content of the cyclic ester compound (II) can be determined by gas chromatography, and specifically, can be measured by the method described in the examples. That is, the content of the cyclic ester compound (II) in the resin composition according to the first embodiment relative to the total of 100% by mass of the block copolymer (I) and the cyclic ester compound (II) is preferably 0.02% by mass or more and 12% by mass or less, more preferably 0.04% by mass or more and 8% by mass or less, even more preferably 0.1% by mass or more and 4% by mass or less, even more preferably 0.2% by mass or more and 3% by mass or less, and even more preferably 0.3% by mass or more and 1% by mass or less.
• the resin composition according to the first embodiment of the present invention contains block structural units (A) in an amount of preferably 4 to 95% by mass, more preferably 8 to 80% by mass, even more preferably 12 to 70% by mass, and even more preferably 17 to 60% by mass, relative to a total of 100% by mass of the block copolymer (I) and the cyclic ester compound (II).
• the above content ratios make it possible to obtain a resin composition with even better heat resistance and tensile properties.
• the resin composition according to the first embodiment of the present invention contains block structural units (B) in an amount of preferably 4 to 95% by mass, more preferably 8 to 80% by mass, even more preferably 12 to 70% by mass, and even more preferably 17 to 60% by mass, relative to a total of 100% by mass of the block copolymer (I) and the cyclic ester compound (II).
• the above content ratios make it possible to obtain a resin composition with even better heat resistance and tensile properties.
• the total content of the block copolymer (I) and the cyclic ester compound (II) in the resin composition according to the first embodiment of the present invention is preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more.
• the total content of the block copolymer (I) and the cyclic ester compound (II) in the resin composition according to the first embodiment may be 100% by mass or less. With the above content ratio, the effect of the present invention is more significantly exhibited.
• the resin composition according to the second embodiment of the present invention contains the block copolymer (I) in an amount of preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, even more preferably 1.5 to 30% by mass, and even more preferably 2 to 20% by mass, based on 100% by mass of the total of the block copolymer (I), the cyclic ester compound (II), and the aliphatic polyester resin (III).
• the above content ratios make it possible to obtain a resin composition having even more excellent biodegradability, heat resistance, and transparency.
• the resin composition according to the second embodiment of the present invention contains block copolymer (I) in an amount of preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, even more preferably 1.5 to 30% by mass, and even more preferably 2 to 20% by mass, relative to 100% by mass of the total of block copolymer (I) and aliphatic polyester resin (III).
• block copolymer (I) in an amount of preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, even more preferably 1.5 to 30% by mass, and even more preferably 2 to 20% by mass, relative to 100% by mass of the total of block copolymer (I) and aliphatic polyester resin (III).
• the above content ratios make it possible to obtain a resin composition with even more excellent biodegradability, heat resistance, and transparency.
• the resin composition according to the second embodiment of the present invention contains the cyclic ester compound (II) in an amount of preferably 0.005 to 10 mass%, more preferably 0.01 to 10 mass%, even more preferably 0.015 to 5 mass%, still more preferably 0.025 to 3 mass%, and even more preferably 0.03 to 2 mass%, relative to 100 mass% in total of the block copolymer (I), the cyclic ester compound (II), and the aliphatic polyester-based resin (III).
• the content of the cyclic ester compound (II) can be determined by gas chromatography, specifically, by the method described in the examples.
• the resin composition according to the second embodiment of the present invention contains the aliphatic polyester resin (III) in an amount of preferably 50 to 99.5% by mass, more preferably 60 to 99% by mass, even more preferably 70 to 98.5% by mass, and even more preferably 80 to 98% by mass, relative to a total of 100% by mass of the block copolymer (I), the cyclic ester compound (II), and the aliphatic polyester resin (III).
• the above content ratios make it possible to obtain a resin composition with even more excellent biodegradability, heat resistance, and transparency.
• the resin composition according to the second embodiment of the present invention contains the aliphatic polyester resin (III) in an amount of preferably 50 to 99.5% by mass, more preferably 60 to 99% by mass, even more preferably 70 to 98.5% by mass, and even more preferably 80 to 98% by mass, relative to a total of 100% by mass of the block copolymer (I) and the aliphatic polyester resin (III).
• the above content ratios make it possible to obtain a resin composition with even more excellent biodegradability, heat resistance, and transparency.
• the resin composition according to the second embodiment of the present invention contains block structural units (A) in an amount of preferably 0.1 to 40% by mass, more preferably 0.3 to 30% by mass, even more preferably 0.5 to 25% by mass, and even more preferably 1 to 15% by mass, relative to a total of 100% by mass of the block copolymer (I), the cyclic ester compound (II), and the aliphatic polyester resin (III).
• block structural units (A) in an amount of preferably 0.1 to 40% by mass, more preferably 0.3 to 30% by mass, even more preferably 0.5 to 25% by mass, and even more preferably 1 to 15% by mass, relative to a total of 100% by mass of the block copolymer (I), the cyclic ester compound (II), and the aliphatic polyester resin (III).
• the above content ratios make it possible to obtain a resin composition with even more excellent heat resistance and transparency.
• the resin composition according to the second embodiment of the present invention contains block structural units (B) in an amount of preferably 0.2 to 40% by mass, more preferably 0.5 to 30% by mass, even more preferably 1 to 20% by mass, and even more preferably 1.5 to 15% by mass, relative to a total of 100% by mass of the block copolymer (I), the cyclic ester compound (II), and the aliphatic polyester resin (III).
• the above content ratios make it possible to obtain a resin composition with even better biodegradability and heat resistance.
• the total content of the block copolymer (I), the cyclic ester compound (II), and the aliphatic polyester resin (III) 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, and even more preferably 98% by mass or more.
• the total content of the block copolymer (I), the cyclic ester compound (II), and the aliphatic polyester resin (III) may be 100% by mass or less. With the above content ratio, the effect of the present invention is more significantly exhibited.
• the resin composition according to the first embodiment of the present invention may contain, in addition to the block copolymer (I) and the cyclic ester compound (II), a plasticizer, a resin other than the block copolymer (I) and the aliphatic polyester resin (III), an additive, etc.
• the resin composition according to the second embodiment of the present invention may contain, in addition to the block copolymer (I), the cyclic ester compound (II), and the aliphatic polyester resin (III), a plasticizer, a resin other than the block copolymer (I) and the aliphatic polyester resin (III), an additive, etc.
• a plasticizer may be added to adjust the viscosity of the resin composition to a level suitable for molding, to obtain a molded product having a desired hardness, etc.
• the plasticizer is not particularly limited, but is preferably a plasticizer that is biodegradable in any of the following environments: industrial compost, household compost, soil, and marine. Suitable examples include vegetable esters such as rapeseed oil and castor oil, synthetic esters such as triacetin, diethyl phthalate, and triethyl citrate, polyols such as ethylene glycol and trimethylolpropane, and derivatives thereof, and sugars such as sorbitol. These may be used alone or in combination of two or more. When the above plasticizer is used, the content of the plasticizer in the resin composition may be appropriately determined depending on the desired physical properties of the resin composition.
• additives examples include inorganic fillers, softeners, heat aging inhibitors, antioxidants, hydrolysis inhibitors, light stabilizers, antistatic agents, release agents, flame retardants, foaming agents, pigments, dyes, brightening agents, ultraviolet absorbers, lubricants, 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.
• the crystalline melting enthalpy of the resin composition according to the first embodiment of the present invention is preferably higher than the crystalline melting enthalpy of the block copolymer (I).
• the rate of increase (( ⁇ Hm2/ ⁇ Hm1) ⁇ 100 ⁇ 100(%)) of the crystalline melting enthalpy ( ⁇ Hm2) of the resin composition according to the first embodiment of the present invention relative to the crystalline melting enthalpy ( ⁇ Hm1) of the block copolymer (I) is preferably 0.5% or more, more preferably 1.0% or more, even more preferably 2.0% or more, even more preferably 5.0% or more, and even more preferably 10.0% or more.
• the rate of increase (( ⁇ Hm2/ ⁇ Hm1) ⁇ 100 ⁇ 100(%)) of the crystalline melting enthalpy ( ⁇ Hm2) of the resin composition according to the second embodiment of the present invention relative to the crystalline melting enthalpy ( ⁇ Hm1) of the mixture is preferably 0.2% or more, more preferably 0.5% or more, even more preferably 1.0% or more, even more preferably 3.0% or more, and even more preferably 5.0% or more.
• the upper limit of the rate of increase is not particularly limited, and may be 300% or less, 200% or less, 100% or less, 50% or less, 20% or less, or 10% or less.
• the crystalline fusion enthalpy of the resin composition can be determined by a differential scanning calorimeter, specifically, by the method described in the examples.
• the melting point of the resin composition according to the first embodiment of the present invention is preferably higher by 0.1° C. or more, more preferably 0.3° C. or more, even more preferably 0.5° C. or more, still more preferably 0.8° C. or more, still more preferably 1.0° C. or more, still more preferably 1.5° C. or more, and still more preferably 2.0° C. or more than the melting point of the block copolymer (I).
• the upper limit of the difference between the melting point of the resin composition according to the first embodiment of the present invention and the melting point of the block copolymer (I) is not particularly limited, and may be 70° C. or less, 50° C. or less, 30° C. or less, 10° C. or less, or 5° C. or less.
• the melting point of the resin composition can be determined by a differential scanning calorimeter, specifically, by the method described in the examples.
• the upper limit of the difference between the glass transition temperature of the resin composition according to the second embodiment of the present invention and the glass transition temperature of the block copolymer (I) is not particularly limited, and may be 50° C. or less, 30° C. or less, 10° C. or less, 5° C. or less, or 3° C. or less.
• the glass transition temperature of the resin composition can be determined by a differential scanning calorimeter, specifically, by the method described in the examples.
• the breaking elongation retention rate of the resin composition according to the first embodiment of the present invention is, from the viewpoint of moldability, preferably 90% or more, more preferably 95% or more, even more preferably 97% or more, still more preferably 99% or more, and still more preferably 100% or more, and there is no particular upper limit, and it may be 3000% or less, 2000% or less, 1000% or less, 500% or less, 300% or less, 200% or less, 150% or less, or 120% or less.
• breaking elongation refers to a value obtained by preparing a press sheet having a thickness of 100 ⁇ m using the resin composition or the block copolymer (I) at 140° C., 40 kN, and 1 min, annealing the press sheet at 110° C. for 3 hours, punching out a dumbbell-shaped No. 3 test piece, and then measuring the elongation at break at a tensile speed of 5 mm/min using the test piece in accordance with JIS K7161-1:2014, and the measurement can be performed by the method described in the examples.
• the rate of change (%) of the haze (absolute value) of the resin composition according to the first embodiment of the present invention relative to the haze (absolute value) of the block copolymer (I) is, from the viewpoint of visibility, preferably 99% or less, more preferably 97% or less, even more preferably 95% or less, still more preferably 90% or less, and even more preferably 85% or less.
• the rate of change (%) of the haze (absolute value) of the resin composition according to the first embodiment of the present invention relative to the haze (absolute value) of the block copolymer (I) is measured and calculated by the following methods (i) to (iii).
• a press sheet having a thickness of 125 ⁇ m is prepared by using the resin composition according to the first embodiment at 140° C., 40 kN, and 1 min to obtain a measurement sheet (s2).
• a measurement sheet (s1) is obtained by the same method for the block copolymer (I).
• the haze of the obtained measurement sheets (s1) and (s2) is measured using a haze meter "HZ-1" (manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K7136:2000.
• the rate of change (%) of the haze (absolute value) of the resin composition according to the first embodiment of the present invention (measurement sheet (S2)) relative to the haze (absolute value) of the block copolymer (I) (measurement sheet (S1)) is calculated from the following formula (2).
• the lower limit is not particularly limited, and may be 0.1% or more, 1% or more, 10% or more, 50% or more, or 80% or more.
• the rate of change (%) of the haze (absolute value) of the resin composition according to the second embodiment of the present invention relative to the haze (absolute value) of the mixture of the block copolymer (I) and the aliphatic polyester (III) is measured and calculated by the following methods (iv) to (vi).
• the resin composition according to the second embodiment is decompressed to 0.1 MPaG using a pressure reducing hot press machine (Imoto Machinery Co., Ltd. "IMC-183B") using an oil rotary pump, preheated at 200 ° C.
• a measurement sheet (s1') is also obtained by the same method for a mixture of block copolymer (I) and aliphatic polyester (III) (a mixture of block copolymer (I) and aliphatic polyester (III) in the same ratio as the block copolymer (I) and aliphatic polyester (III) contained in the resin composition according to the second embodiment of the present invention, which is a comparison target).
• the haze of the obtained measurement sheets (s1') and (s2') is measured using a Spectral Haze Meter SH7000 (light source D65) manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS-K7136:2000.
• the cyclic ester compound (II) may be synthesized simultaneously during the synthesis of the block copolymer (I) and mixed with the block copolymer (I).
• 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, they may be preblended before melt-kneading.
• the compounds used in the examples and comparative examples are as follows. 3-Methyl-1,5-pentanediol (Kuraray Co., Ltd.) Adipic acid (Tokyo Chemical Industry Co., Ltd.) Stannous octoate (Tokyo Chemical Industry Co., Ltd.) Toluene (Kishida Chemical Co., Ltd.) L-Lactide (Tokyo Chemical Industry Co., Ltd.) Methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 2,4-Diethyl-1,5-pentanediol (Tokyo Chemical Industry Co., Ltd.) 2-Methyl-1,3-propanediol (Tokyo Chemical Industry Co., Ltd.) Succinic acid (Tokyo Chemical Industry Co., Ltd.) 1,4-Butanediol (Tokyo Chemical Industry Co., Ltd.) Propylene glycol (Tokyo Chemical Industry Co., Ltd.) Di-n-alkyl Adip
• Biodegradability (composting) Biodegradability in compost was measured according to ISO 14855-2:2018.
• Examples 1 to 10 and Comparative Examples 1 to 10 if the decomposition rate after 15 days was 20% by mass or more, it was evaluated as A, if it was 10% by mass or more and less than 20% by mass, it was evaluated as B, and if it was 5% by mass or more and less than 10% by mass, it was evaluated as C.
• Examples 11 to 24 and Comparative Examples 11 to 15 if the decomposition rate after 15 days was 10% by mass or more, it was rated as A, and if it was less than 10% by mass, it was rated as B.
• Biodegradability in activated sludge was measured in accordance with ISO 14851: 2019. If the decomposition rate after 90 days was 5% by mass or more, it was rated as A, and if it was less than 5% by mass, it was rated as B.
• the midpoint glass transition temperature in JIS K7121:2012 is defined as the glass transition temperature
• the heat of fusion in the melting curve during the 2nd run is defined as the crystalline melting enthalpy.
• Apparatus: Mettler Toledo differential scanning calorimeter "DSC822" A measurement sample (block copolymer, polymer, or resin composition) at 25 ° C. was heated to 200 ° C. at a heating rate of 10 ° C. / min ( 1st run), held at 200 ° C. for 5 minutes, then cooled from 200 ° C. to 75 ° C.
• the obtained resin composition was decompressed to 0.1 MPaG using a pressure reducing hot press machine (Imoto Manufacturing Co., Ltd. "IMC-183B") using an oil rotary pump, preheated at 200 ° C. for 5 minutes, and pressed at 40 kN for 1 minute. Then, it was pressed at 20 kgf / cm 2 for 1 minute using a cooling press machine equipped with water flow cooling to prepare a press plate with a thickness of 0.125 mm. A square piece of 50 ⁇ 50 mm was cut out from the obtained press plate and crystallized in a 110 ° C. thermostatic bath for 3 hours to obtain a measurement sheet (s2').
• a pressure reducing hot press machine Imoto Manufacturing Co., Ltd. "IMC-183B”
• a measurement sheet (s1') was obtained by the same method for the mixture A of block copolymer and aliphatic polyester (a mixture of block copolymer and aliphatic polyester in the same ratio as the block copolymer and aliphatic polyester contained in the resin composition to be compared).
• the haze of the obtained measuring sheets (s1') and (s2') was measured using a Spectral Haze Meter SH7000 (light source D65) manufactured by Nippon Denshoku Industries Co., Ltd., in accordance with JIS-K7136:2000.
• Detector FID Analysis conditions: Injection temperature: 200°C, Detection temperature: 250°C Temperature rise conditions: 50 to 110°C; 10°C/min, 110 to 180°C; 40°C/min, 180 to 280°C; 10°C/min
• the pressure was reduced to 2,000 Pa and the reaction was continued for 3 hours, and then the pressure was reduced to 80 Pa and the reaction was continued while appropriately checking until the number average molecular weight reached 9,500, thereby synthesizing a polymer consisting of structural units (B') mainly composed of polyester units.
• B' structural units mainly composed of polyester units.
• the pressure was returned to normal and the temperature was cooled to 80° C., and then toluene was added to dilute the mixture so that the solid content was 40% by mass.
• the toluene solution was then poured into methanol in an amount twice the total amount of the solution. The supernatant was discarded, and the same amount of methanol as the amount of the toluene solution poured in was added again for washing.
• the toluene solution of the polymer consisting of the structural unit (B') was cooled to 80°C, and the polymer consisting of the structural unit (B') and L-lactide were added so that the ratio of the polymer consisting of the structural unit (B')/L-lactide was 50/50, and the amount of toluene distilled off as described above was further added to adjust the solid content of the toluene solution of the polymer consisting of the structural unit (B') and L-lactide to 50 mass%.
• tin octylate was added in an amount of 0.1 mass% relative to the polymer consisting of the structural unit (B'), and the reaction was allowed to proceed for 4 hours to synthesize a block copolymer (I) consisting of a block structural unit (A) mainly composed of a polylactic acid unit (a) and a block structural unit (B) mainly composed of a polyester unit (b), and a toluene solution of the block copolymer (I) was obtained.
• Toluene was further added to this solution to dilute it to a solid content of 40% by mass, and then the above-mentioned toluene solution with a solid content of 40% by mass was added to methanol in an amount twice the total amount of the solution to precipitate a solid. The supernatant methanol was discarded, and the same amount of methanol as the amount of the toluene solution added was added again for washing.
• a block copolymer (I-1) consisting of a block structural unit (A) mainly composed of a polylactic acid unit (a) and a block structural unit (B) mainly composed of a polyester unit (b).
• the number average molecular weight (Mn) of the resulting block copolymer (I) was 19,000.
• Example 2 to 5 A resin composition containing a block copolymer (I) composed of a block structural unit (A) mainly composed of a polylactic acid unit (a) and a block structural unit (B) mainly composed of a polyester unit (b), and a cyclic ester compound (II), was obtained in the same manner as in Example 1, except that the amount of the cyclic ester compound (II) composed of 3-methyl-1,5-pentanediol and adipic acid (4-methyl-1,7-dioxacyclotridecane-8,13-dione) was changed to the amount shown in Table 1. The resin composition thus obtained was subjected to the above-mentioned measurements and evaluations. The results are shown in Table 1.
• Example 6 A resin composition containing a block copolymer (I) composed of a block structural unit (A) mainly composed of a polylactic acid unit (a) and a block structural unit (B) mainly composed of a polyester unit (b) and a cyclic ester compound (II) was obtained in the same manner as in Example 5, except that a polymer composed of a structural unit (B') having a number average molecular weight of 23,800 was synthesized and used. The resin composition thus obtained was subjected to the above-mentioned measurements and evaluations. The results are shown in Table 1.
• Example 7 A resin composition containing a block copolymer (I) composed of a block structural unit (A) mainly composed of a polylactic acid unit (a) and a block structural unit (B) mainly composed of a polyester unit (b) and a cyclic ester compound (II) was obtained in the same manner as in Example 5, except that a cyclic ester compound (II) (3-methyl-1,5-dioxacyclodecane-6,11-dione) was used. The resin composition thus obtained was subjected to the above-mentioned measurements and evaluations. The results are shown in Table 2.
• Example 8 A resin composition containing a block copolymer (I) composed of a block structural unit (A) mainly composed of a polylactic acid unit (a) and a block structural unit (B) mainly composed of a polyester unit (b), and a cyclic ester compound (II) was obtained in the same manner as in Example 3, except that a polymer composed of a structural unit (B') shown in Table 2 was synthesized and used using 2-methyl-1,3-propanediol instead of 3-methyl-1,5-pentanediol, and a cyclic ester compound (II) (3-methyl-1,5-dioxacyclodecane-6,11-dione) was used. The resin composition thus obtained was subjected to the above-mentioned measurements and evaluations. The results are shown in Table 2.
• Example 9 A resin composition containing a block copolymer (I) composed of a block structural unit (A) mainly composed of a polylactic acid unit (a) and a block structural unit (B) mainly composed of a polyester unit (b), and a cyclic ester compound (II) was obtained in the same manner as in Example 5, except that 2-methyl-1,3-propanediol was used instead of 3-methyl-1,5-pentanediol, the reaction time was adjusted to synthesize and use a polymer composed of a structural unit (B') shown in Table 2, and a cyclic ester compound (II) was used (3-methyl-1,5-dioxacyclodecane-6,11-dione). The resin composition thus obtained was subjected to the above-mentioned measurements and evaluations. The results are shown in Table 2.
• Example 10 A resin composition containing a block copolymer (I) composed of a block structural unit (A) mainly composed of a polylactic acid unit (a) and a block structural unit (B) mainly composed of a polyester unit (b), and a cyclic ester compound (II) was obtained in the same manner as in Example 5, except that 2,4-diethyl-1,5-pentanediol was used instead of 3-methyl-1,5-pentanediol and the reaction time was adjusted to synthesize and use a polymer composed of a structural unit (B') shown in Table 2. The resin composition thus obtained was subjected to the above-mentioned measurements and evaluations. The results are shown in Table 2.
• Example 11 A resin composition containing a block copolymer (I) composed of a block structural unit (A) mainly composed of a polylactic acid unit (a) and a block structural unit (B) mainly composed of a polyester unit (b), and a cyclic ester compound (II) was obtained in the same manner as in Example 3, except that succinic acid was used instead of adipic acid and the reaction time was adjusted to synthesize and use a polymer composed of the structural unit (B') shown in Table 2. The resin composition thus obtained was subjected to the above-mentioned measurements and evaluations. The results are shown in Table 2.
• Example 12 A resin composition containing a block copolymer (I) composed of a block structural unit (A) mainly composed of a polylactic acid unit (a) and a block structural unit (B) mainly composed of a polyester unit (b), and a cyclic ester compound (II) was obtained in the same manner as in Example 5, except that succinic acid was used instead of adipic acid and the reaction time was adjusted to synthesize and use a polymer composed of the structural unit (B') shown in Table 2. The resin composition thus obtained was subjected to the above-mentioned measurements and evaluations. 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 cyclic ester compound (II) composed of 3-methyl-1,5-pentanediol and adipic acid was not used. The above-mentioned measurements and evaluations were carried out on the obtained resin composition. The results are shown in Table 3. The obtained resin composition had a lower melting point than the resin compositions obtained in the examples. This is believed to be because the resin composition does not contain the cyclic ester compound (II).
• Example 3 A resin composition was obtained in the same manner as in Example 8, except that the cyclic ester compound (II) composed of 3-methyl-1,5-pentanediol and adipic acid was not used. The above-mentioned measurements and evaluations were carried out on the obtained resin composition. The results are shown in Table 3. The obtained resin composition had a higher haze value and a lower melting point value than the resin compositions obtained in the examples. This is believed to be because the resin composition does not contain the cyclic ester compound (II).
• Example 4 A resin composition was obtained in the same manner as in Example 10, except that the cyclic ester compound (II) composed of 2,4-diethyl-1,5-pentanediol and adipic acid was not used. The above-mentioned measurements and evaluations were carried out on the obtained resin composition. The results are shown in Table 3. The obtained resin composition had a higher haze value and a lower melting point value than the resin compositions obtained in the examples. This is believed to be because the resin composition does not contain the cyclic ester compound (II).
• Example 5 A resin composition was obtained in the same manner as in Example 11, except that the cyclic ester compound (II) composed of 3-methyl-1,5-pentanediol and succinic acid was not used. The above-mentioned measurements and evaluations were carried out on the obtained resin composition. The results are shown in Table 3. The obtained resin composition had a higher haze value and a lower melting point value than the resin compositions obtained in the examples. This is believed to be because the resin composition does not contain the cyclic ester compound (II).
• a resin composition containing a block copolymer composed of block structural units (A) mainly composed of polylactic acid units (a) and block structural units (B) mainly composed of polyester units (b) and a Di-n-alkyl adipate was obtained in the same manner as in Example 1, except that a Di-n-alkyl adipate (plasticizer), which is an ester compound not having a cyclic structure, was used in an amount of 5 parts by mass per 100 parts by mass of the total of the block copolymer (I) and the Di-n-alkyl adipate, instead of the cyclic ester compound (II).
• a Di-n-alkyl adipate plasticizer
• the above-mentioned measurements and evaluations were carried out on the obtained resin composition.
• the results are shown in Table 4.
• the obtained resin composition had a lower breaking elongation than the resin compositions obtained in the examples. This is thought to be because the ester compound without a cyclic structure has a high degree of molecular freedom, and the resin composition became too flexible.
• a resin composition containing a block copolymer consisting of block structural units (A) mainly composed of polylactic acid units (a) and block structural units (B) mainly composed of polyester units (b) and a crystal nucleating agent was obtained in the same manner as in Example 1, except that the crystal nucleating agent N,N'-ethylenebisoctadecaneamide was used in an amount of 5 parts by mass per 100 parts by mass of the total of the block copolymer (I) and the crystal nucleating agent instead of the cyclic ester compound (II).
• the resin composition thus obtained was subjected to the above-mentioned measurements and evaluations. The results are shown in Table 4.
• the resin composition thus obtained had a lower breaking elongation and a higher haze than the resin compositions obtained in the examples. This is believed to be due to poor compatibility between the crystal nucleating agent and the block copolymer.
• Example 8 A resin composition was obtained in the same manner as in Example 1, except that the cyclic ester compound (II) composed of 3-methyl-1,5-pentanediol and adipic acid was not used. The above-mentioned measurements and evaluations were carried out on the obtained resin composition. The results are shown in Table 4. The obtained resin composition had a higher haze value and a lower melting point value than the resin compositions obtained in the examples. This is believed to be because the resin composition does not contain the cyclic ester compound (II).
• a resin composition containing a polymer consisting of a structural unit (B') mainly composed of polyester units (b) and a cyclic ester compound (II) (4-methyl-1,7-dioxacyclotridecane-8,13-dione) consisting of 3-methyl-1,5-pentanediol and adipic acid was obtained in the same manner as in Example 1, except that a polymer consisting of a structural unit (B') mainly composed of polyester units (b) was used instead of the block copolymer (I), and 5.0 parts by mass of a cyclic ester compound (II) (4-methyl-1,7-dioxacyclotridecane-8,13-dione) consisting of 3-methyl-1,5-pentanediol and adipic acid was used per 100 parts by mass of the total of the polymer consisting of a structural unit (B') mainly composed of polyester units (b) and the cyclic ester compound (II)
• a resin composition containing polylactic acid and a cyclic ester compound (II) was obtained in the same manner as in Example 1, except that the obtained polylactic acid was used instead of the block copolymer (I), and 5.0 parts by mass of a cyclic ester compound (II) (4-methyl-1,7-dioxacyclotridecane-8,13-dione) consisting of 3-methyl-1,5-pentanediol and adipic acid was used per 100 parts by mass of the total of polylactic acid and the cyclic ester compound (II).
• the resin composition thus obtained was subjected to the above-mentioned measurements and evaluations. The results are shown in Table 4.
• the resin composition thus obtained had poor biodegradability, low elongation at break, and high haze. This is believed to be because the resin composition does not contain a block copolymer (I) containing a structural unit (B') mainly composed of a flexible polyester unit (b).
• PLLA Poly-L-lactic acid
• MPD 3-methyl-1,5-pentanediol
• MPDiol 2-methyl-1,3-propanediol
• DEPD 2,4-diethyl-1,5-pentanediol
• Adipic acid SA Succinic acid
• the resin composition according to the first embodiment of the present invention which contains a block copolymer (I) including a block structural unit (A) mainly composed of a specific polylactic acid unit (a) and a block structural unit (B) mainly composed of a polyester unit (b), and a cyclic ester compound (II), has biodegradable properties under a wide range of conditions and has an excellent balance of crystallinity, tensile properties, transparency, and heat resistance. Therefore, the industrial usefulness of the resin composition according to the first embodiment of the present invention is extremely high.
• 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, which is the cyclic ester compound (II).
• the pressure was returned to normal and the temperature was cooled to 80° C., and then toluene was added to dilute the mixture so that the solid content was 40% by mass.
• the toluene solution was then poured into methanol in an amount twice the total amount of the solution.
• the toluene solution of the polymer consisting of the structural unit (B') was cooled to 80°C, and the polymer consisting of the structural unit (B') and L-lactide were added so that the ratio of the polymer consisting of the structural unit (B')/L-lactide was 50/50, and the amount of toluene distilled off as described above was further added to adjust the solid content of the toluene solution of the polymer consisting of the structural unit (B') and L-lactide to 50 mass%.
• tin octylate was added in an amount of 0.1 mass% relative to the polymer consisting of the structural unit (B'), and the reaction was allowed to proceed for 4 hours to synthesize a block copolymer (I-1) consisting of a block structural unit (A) mainly composed of a polylactic acid unit (a) and a block structural unit (B) mainly composed of a polyester unit (b), and a toluene solution of the block copolymer (I-1) was obtained.
• a block copolymer (I-1) consisting of a block structural unit (A) mainly composed of a polylactic acid unit (a) and a block structural unit (B) mainly composed of a polyester unit (b).
• the obtained block copolymer was subjected to the above-mentioned measurements and evaluations. The results are shown in Table 5.
• the obtained block copolymer (I-1), 4-methyl-1,7-dioxacyclotridecane-8,13-dione as the cyclic ester compound (II), and the polylactic acid polymer "INGEO 2500HP" (manufactured by Nature Works) as the aliphatic polyester resin (III) were charged into a kneader Laboplastomill (manufactured by Toyo Seiki Seisakusho Co., Ltd., product name "3S150", roller mixer model "R60") in the mass ratio shown in Table 5, and melt-kneaded for 5 minutes at a cylinder temperature of 210°C and a screw rotation speed of 50 rpm to obtain a resin composition.
• the resin composition thus obtained was subjected to the above-mentioned measurements and evaluations. The results are shown in Table 5.
• Example 14 to 17 A resin composition was obtained by melt kneading in the same manner as in Example 13, except that the mass ratio of 4-methyl-1,7-dioxacyclotridecane-8,13-dione, which is the cyclic ester compound (II), was changed to the amount shown in Table 5. The resin composition thus obtained was subjected to the above-mentioned measurements and evaluations. The results are shown in Table 5.
• Example 18 A block copolymer (I-2) was obtained in the same manner as in Example 10, except that the number average molecular weight was adjusted by adjusting the reaction time during synthesis of the polymer consisting of the structural unit (B') having the polyester unit (b) as the main unit, the mass ratio of the L-lactide used was changed, and the dilution concentration during synthesis was appropriately changed to a concentration that was easy to handle.
• Example 19 As the cyclic ester compound (II), 3-methyl-1,5-dioxacyclooundecane-6,11-dione, which is a condensed cyclization product of 2-methyl-1,3-propanediol and adipic acid, was used instead of 4-methyl-1,7-dioxacyclotridecane-8,13-dione.
• a resin composition was obtained by melt kneading in the same manner as in Example 18, except that the cyclic ester compound (II) was 3-methyl-1,5-dioxacyclooundecane-6,11-dione. The resin composition thus obtained was subjected to the above-mentioned measurements and evaluations. The results are shown in Table 6.
• Example 20 A block copolymer (I-3) was obtained in the same manner as in Example 15, except that 2-methyl-1,3-propanediol was used instead of 3-methyl-1,5-pentanediol, that the number average molecular weight was adjusted by adjusting the reaction time during synthesis of the polymer composed of structural units (B') having polyester units as main units, and that the dilution concentration during synthesis was appropriately changed to a concentration that was easy to handle.
• Example 21 The block copolymer (I-3) obtained in Example 20, 3-methyl-1,5-dioxacyclodecane-6,11-dione as the cyclic ester compound (II), and the polylactic acid polymer "INGEO 2500HP" as the aliphatic polyester resin (III) were melt-kneaded in the same manner as in Example 20 so as to have the mass ratio shown in Table 5, to obtain a resin composition.
• the resin composition thus obtained was subjected to the above-mentioned measurements and evaluations. The results are shown in Table 6.
• Example 22 A block copolymer (I-4) was obtained in the same manner as in Example 18, except that 2,4-diethyl-1,5-pentanediol was used instead of 3-methyl-1,5-pentanediol, that the number average molecular weight was adjusted by adjusting the reaction time during synthesis of the polymer composed of structural units (B') having polyester units as main units, and that the dilution concentration during synthesis was appropriately changed to a concentration that was easy to handle.
• Example 23 A block copolymer (I-5) was obtained in the same manner as in Example 18, except that propylene glycol was used instead of 3-methyl-1,5-pentanediol, succinic acid was used instead of adipic acid, the number average molecular weight was adjusted by adjusting the reaction time during the synthesis of the polymer composed of structural units (B') having polyester units as main units, and the dilution concentration during the synthesis was appropriately changed to a concentration that was easy to handle.
• Example 24 A block copolymer (I-6) was obtained in the same manner as in Example 18, except that 1,4-butanediol was used instead of 3-methyl-1,5-pentanediol, succinic acid was used instead of adipic acid, the number average molecular weight was adjusted by adjusting the reaction time during the synthesis of the polymer composed of structural units (B') having polyester units as main units, and the dilution concentration during the synthesis was appropriately changed to a concentration that was easy to handle.
• PLLA Poly-L-lactic acid
• MPD 3-methyl-1,5-pentanediol
• DEPD 2,4-diethyl-1,5-pentanediol
• MPDiol 2-methyl-1,3-propanediol
• 1,4-BD 1,4-butanediol
• PG Propylene glycol
• Adipic acid SA Succinic acid
• the resin composition according to the second embodiment of the present invention which contains the block copolymer (I) having a specific structure, the aliphatic polyester resin (III), and the cyclic ester compound (II), has an excellent balance of biodegradability, heat resistance, and transparency.
• the resin compositions obtained in Comparative Examples 11 and 12 were inferior in heat resistance since they did not contain the cyclic ester compound (II).
• the resin composition obtained in Comparative Example 13 was inferior in heat resistance since it contained an ester compound having no cyclic structure instead of the cyclic ester compound (II).
• the resin composition obtained in Comparative Example 14 was inferior in transparency since it contained a crystal nucleating agent instead of the cyclic ester compound (II). Moreover, the resin composition obtained in Comparative Example 15 had a very low glass transition temperature and poor transparency due to the large content of the cyclic ester compound (II).
• the resin composition according to the second embodiment of the present invention has an excellent balance of biodegradability, heat resistance, and transparency. Therefore, the resin composition according to the second embodiment of the present invention is highly useful industrially.

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