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
  • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
  • C08G63/08—Lactones or lactides
• • 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 containing a polybutylene succinate-based polymer and a ⁇ -methyl- ⁇ -valerolactone-based polymer, a molded article made of the resin composition, and a modifier for polybutylene succinate-based polymers made of the ⁇ -methyl- ⁇ -valerolactone-based polymer.
• plastic materials that use polybutylene succinate-based polymers, which are a type of "biodegradable plastic.” Molded bodies made from polybutylene succinate-based polymers tend to have better viscosity, flexibility, impact resistance, and heat resistance than molded bodies made from general biodegradable plastics such as polylactic acid, but these are not fully satisfactory and further improvements are desired.
• Patent Document 1 describes the use of an ester (mixed ester) of an aliphatic polybasic acid and two or more types of alcohol or ether alcohol as a plasticizer in an aliphatic polyester resin in order to improve the water resistance and bleed-out resistance of a resin composition containing a biodegradable aliphatic polyester resin.
• Patent Document 2 describes the use of either an adipic acid ester or an ester-based elastomer as a soft plasticizer in order to improve the impact resistance of a resin composition containing polybutylene succinate.
• Patent Document 3 describes the mixing of polyethylene to improve the brittleness of polybutylene succinate, and the blending of an ethylene-stat-glycidyl methacrylate copolymer having an epoxy group as a reactive group in a specific ratio in order to further improve the heat sealability and impact resistance.
• Patent Document 4 describes a flexibility imparting agent that can impart flexibility to biodegradable plastics such as polybutylene succinate and can improve the impact resistance and processing moldability.
• an object of the present invention is to provide a resin composition having good impact resistance, flexibility and bleed-out 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.
• a resin composition comprising a polybutylene succinate-based polymer and a ⁇ -methyl- ⁇ -valerolactone-based polymer.
• R 1 represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by formula (X) below, or an
• R2 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms.
• n is 2 to 1,000 and m is 2 to 1,000.
• a modifier for polybutylene succinate-based polymers comprising a ⁇ -methyl- ⁇ -valerolactone-based polymer represented by the following general formula (I):
• R 1 represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by formula (X) below, or an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group
• R2 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms.
• n is 2 to 1,000 and m is 2 to 1,000.
• the present invention provides a resin composition that has good impact resistance, flexibility, and bleed-out resistance.
• the resin composition of the present embodiment contains a polybutylene succinate-based polymer and a ⁇ -methyl- ⁇ -valerolactone-based polymer.
• the resin composition has good impact resistance, flexibility, and bleed-out resistance.
• additives that tend to bleed out such as plasticizers, have had to be added.
• a resin composition containing a polybutylene succinate polymer and a ⁇ -methyl- ⁇ -valerolactone polymer improves impact resistance without adding additives that tend to bleed out, such as plasticizers.
• the resin composition of the present embodiment also has good bleed-out resistance.
• the polybutylene succinate polymer used in this embodiment is a polymer containing polyester units (a) which contain units derived from a diol (a1) and a dicarboxylic acid (a2).
• the diol (a1) contains 1,4-butanediol as an essential component.
• the diol (a1) may contain a diol other than 1,4-butanediol.
• diols other than 1,4-butanediol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,
• the content of 1,4-butanediol in the diol (a1) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and may be 100% by mass, i.e., preferably 50 to 100% by mass, more preferably 60 to 100% by mass, even more preferably 70 to 100% by mass.
• the content of diols other than 1,4-butanediol in the diol (a1) is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, and may not be contained at all.
• the dicarboxylic acid (a2) contains an aliphatic dicarboxylic acid as an essential component.
• aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, dimethylmalonic acid, 2,2-diethylsuccinic acid, 2,2-dimethylglutaric acid, 2-methyladipic acid, and trimethyladipic acid.
• At least one selected from the group consisting of succinic acid, adipic acid, azelaic acid, sebacic acid, and undecanedicarboxylic acid is preferred, and succinic acid is more preferred.
• the dicarboxylic acid (a2) may include an aromatic dicarboxylic acid.
• aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, diphenic acid, furandicarboxylic acid, 4,4'-biphenyldicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 1,6-naphthalenedicarboxylic acid.
• the dicarboxylic acid (a2) may include dicarboxylic acids other than aliphatic dicarboxylic acids and aromatic dicarboxylic acids.
• dicarboxylic acids other than aliphatic dicarboxylic acids and aromatic dicarboxylic acids include alicyclic dicarboxylic acids.
• alicyclic dicarboxylic acids examples 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 content of the aliphatic dicarboxylic acid in the dicarboxylic acid (a2) is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 70% by mass or more, and may be 100% by mass.
• the content of aromatic dicarboxylic acid in dicarboxylic acid (a2) is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 30% by mass or less, and may not be contained.
• the content of dicarboxylic acids other than aliphatic dicarboxylic acids and aromatic dicarboxylic acids in the dicarboxylic acid (a2) is preferably 10% by mass or less, more preferably 5% by mass or less, and may not be present.
• the polybutylene succinate-based polymer may contain units other than the polyester unit (a).
• the polybutylene succinate polymer preferably contains polyester units (a) in an amount of 70 mol % or more, more preferably 90 mol % or more, and may contain 100 mol %.
• the polybutylene succinate-based polymer preferably contains polyester units (a) containing units derived from 1,4-butanediol as the diol (a1) and units derived from succinic acid as the dicarboxylic acid (a2), more preferably polybutylene succinate (PBS) and polybutylene succinate adipate (PBSA), and even more preferably polybutylene succinate (PBS).
• the polybutylene succinate polymers may be used alone or in combination of two or more kinds.
• the number average molecular weight of the polybutylene succinate polymer is preferably 10,000 or more, more preferably 30,000 or more, and even more preferably 50,000 or more. From the viewpoint of moldability and compatibility with the ⁇ -methyl- ⁇ -valerolactone polymer, it is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 300,000 or less. That is, the number average molecular weight of the polybutylene succinate polymer is preferably 10,000 to 1,000,000, more preferably 30,000 to 500,000, and even more preferably 50,000 to 300,000.
• the number average molecular weight of the polybutylene succinate polymer 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.
• GPC gel permeation chromatography
• the ⁇ -methyl- ⁇ -valerolactone polymer used in this embodiment is preferably a polymer represented by the following general formula (I).
• the following polymer has a structure represented by general formula (I) and therefore serves as an excellent modifier for polybutylene succinate-based polymers.
• the following polymer is a polymer obtained by ring-opening polymerization of ⁇ -methyl- ⁇ -valerolactone, and since at least one hydroxyl group at the molecular end is modified with another functional group, the polymer is prevented from decreasing in thermal decomposition property, and can prevent a decrease in the glass transition temperature of the resin composition.
• the following polymer can improve the impact resistance of the resin composition depending on the structure and number of the molecular ends. Furthermore, since the raw material of the polymer represented by the following general formula (I) is ⁇ -methyl- ⁇ -valerolactone, it is believed that the resin composition of this embodiment has good biodegradability.
• R 1 represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by formula (X) described below, or an oxygen-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by formula (X) described below.
• linear alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl.
• the linear alkyl group having 1 to 20 carbon atoms is preferably a linear alkyl group having 1 to 16 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms, and even more preferably a linear alkyl group having 1 to 5 carbon atoms.
• at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group is preferred.
• Examples of branched alkyl groups having 3 to 20 carbon atoms include isopropyl, 1-methylpropyl, 2-methylpropyl, t-butyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1-ethylpropyl, 2-ethylpropyl, 1,1-diethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,3,3-trimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 3,3-dimethylbutyl, butylbutyl group, 1-propylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 4,4-dimethylpentyl group, 1-ethylpenty
• the branched alkyl group having 3 to 20 carbon atoms is preferably a branched alkyl group having 3 to 16 carbon atoms, more preferably a branched alkyl group having 3 to 10 carbon atoms, and even more preferably a branched alkyl group having 3 to 5 carbon atoms.
• at least one selected from the group consisting of an isopropyl group, a 1-methylbutyl group, a 3-methylbutyl group, and a 2,2-dimethylpropyl group is preferred.
• Straight-chain alkenyl groups having 2 to 20 carbon atoms include, for example, ethenyl, n-propenyl, n-butenyl (e.g., 2-butenyl and 3-butenyl), n-pentenyl (e.g., 3-pentenyl and 4-pentenyl), n-hexenyl (e.g., 1-hexenyl and 5-hexenyl), n-heptenyl (e.g., 1-heptenyl and 1,3-heptadienyl), n-octenyl (e.g., 7-octenyl and 2,7-octadienyl), n-nonenyl (e.g., 3-nonenyl and 3,6-nonadienyl), n-decenyl (e.g., 1,3-decadienyl and 1,3,5-decatrienyl), nyl group), n
• the linear alkenyl group having 2 to 20 carbon atoms is preferably a linear alkenyl group having 2 to 15 carbon atoms, more preferably a linear alkenyl group having 3 to 10 carbon atoms, and even more preferably a linear alkenyl group having 3 to 6 carbon atoms.
• Examples of branched alkenyl groups having 3 to 20 carbon atoms include isopropenyl, 1-methylpropenyl, 2-methylpropenyl, t-butenyl, 1,1-dimethylpropenyl, 2,2-dimethylpropenyl, 1,2-dimethylpropenyl, 1-ethylpropenyl, 2-ethylpropenyl, 1,1-diethylpropenyl, 1-methylbutenyl, 2-methylbutenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethylbutenyl, 2,2-dimethylbutenyl, 3,3-dimethylbutenyl, 1,3,3-trimethylbutenyl, 1-ethylbutenyl, 2-ethylbutenyl, butenyl group, 3,3-dimethylbutenyl group, 1-propylbutenyl group, 1-methylpentenyl group, 2-methylpentenyl group, 3-methylpenten
• the branched alkenyl group having 3 to 20 carbon atoms is preferably a branched alkenyl group having 3 to 15 carbon atoms, more preferably a branched alkenyl group having 3 to 10 carbon atoms, and even more preferably a branched alkenyl group having 3 to 6 carbon atoms.
• Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a 2-methylphenyl group, a 2,4-dimethylphenyl group, and a 2-naphthyl group, with a phenyl group being preferred.
• Examples of the arylalkyl group having 7 to 12 carbon atoms include a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a naphthylmethyl group, and a naphthylethyl group, with a phenylmethyl group being preferred.
• n represents the average number of repetitions. n is 2 to 1,000, preferably 2 to 800, more preferably 4 to 500, and even more preferably 8 to 300. When n is 2 or more, a more excellent modification effect can be obtained. Also, when n is 1,000 or less, good moldability and productivity can be obtained.
• R2 in the above formula (X) has the same meaning as R2 described below.
• Examples of the linear alkyl group having 1 to 20 carbon atoms bonded to the above formula (X) include the same groups exemplified as the above-mentioned "linear alkyl group having 1 to 20 carbon atoms".
• the linear alkyl group having 1 to 20 carbon atoms bonded to the above formula (X) is preferably a linear alkyl group having 1 to 15 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms, even more preferably a linear alkyl group having 2 to 10 carbon atoms, and even more preferably a linear alkyl group having 2 to 5 carbon atoms.
• Examples of the branched alkyl group having 3 to 20 carbon atoms bonded to the above formula (X) include the same groups exemplified above as the "branched alkyl group having 3 to 20 carbon atoms".
• the branched alkyl group having 3 to 20 carbon atoms bonded to the above formula (X) is preferably a branched alkyl group having 3 to 15 carbon atoms, more preferably a branched alkyl group having 3 to 10 carbon atoms, and even more preferably a branched alkyl group having 3 to 5 carbon atoms.
• it may be an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to all of the terminal carbon atoms of a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the above formula (X), or it may be an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the above formula (X).
• m represents the average number of repetitions.
• m is 2 to 1,000, preferably 2 to 800, more preferably 4 to 500, further preferably 5 to 300, and may be 8 to 300.
• m is 2 or more, the viscosity of the polymer does not become too low. Also, when m is 1,000 or less, the handleability and productivity of the polymer become good.
• Each average number of repetitions (n and m) can be calculated from the overall degree of polymerization of the ⁇ -methyl- ⁇ -valerolactone polymer determined by 1 H-NMR measurement, more specifically, by the method described in the Examples.
• the overall degree of polymerization of a ⁇ -methyl- ⁇ -valerolactone polymer is the sum of the average number of repetitions contained in the polymer.
• the overall degree of polymerization in the ⁇ -methyl- ⁇ -valerolactone polymer is preferably 2 to 10,000, more preferably 4 to 6,000, even more preferably 6 to 3,000, even more preferably 8 to 2,000, and even more preferably 10 to 1,600.
• R1 When a plurality of groups represented by the above formula (X) are present in R1 , they may be the same or different from each other.
• R2 and m may be present in plural. That is, in the above formula (I), two or more groups represented by formula (X) may be present.
• R2s When there are multiple R2s , they may be the same or different from each other.
• ms that is, when there are two or more repeating units represented by the average repeat number m, they may be the same or different from each other.
• R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by the above formula (X)
• specific examples of the above general formula (I) include the following structures.
• Example 1 When R1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the terminal carbon atom of a linear alkyl group having carbon number Q is substituted with a group represented by formula (X) above, the above general formula (I) is represented by the following general formula (I-a), where Q is 1 to 20.
• Example 2 When R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the terminal carbon atom of an ethyl group is substituted with a group represented by the above formula (X), the above general formula (I) is represented by the following general formula (I-b).
• R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the above formula (X)
• specific examples of the above general formula (I) include the following structures.
• Example 3 When R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to all of the terminal carbon atoms of a 2-methylpropyl group is substituted with a group represented by formula (X), the general formula (I) is represented by the following general formula (I-c):
• Example 4 When R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the carbon atom at each of the two terminal carbon atoms of a 2,2-dimethylpropyl group is substituted with a group represented by formula (X), the general formula (I) is represented by the following general formula (I-d):
• Example 5 When R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the carbon atom at each of the two terminal carbon atoms of a 2,2-dimethylbutyl group is substituted with a group represented by formula (X), the general formula (I) is represented by the following general formula (I-e):
• Example 6 When R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to all of the terminal carbon atoms of a 2,2-dimethylpropyl group is substituted with a group represented by formula (X), the general formula (I) is represented by the following general formula (If):
• R 1 is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by the above formula (X), or an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the above formula (X).
• R2 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms.
• Examples of the linear alkyl group having 1 to 20 carbon atoms represented by R2 include the same groups exemplified as the "linear alkyl group having 1 to 20 carbon atoms" described above.
• the linear alkyl group having 1 to 20 carbon atoms represented by R2 is preferably a linear alkyl group having 1 to 15 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms, and even more preferably a linear alkyl group having 1 to 5 carbon atoms.
• at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group is preferable.
• Examples of the branched alkyl group having 3 to 20 carbon atoms represented by R2 include the same groups exemplified as the above-mentioned "branched alkyl group having 3 to 20 carbon atoms".
• the branched alkyl group having 3 to 20 carbon atoms represented by R2 is preferably a branched alkyl group having 3 to 15 carbon atoms, more preferably a branched alkyl group having 3 to 10 carbon atoms, and even more preferably a branched alkyl group having 3 to 5 carbon atoms.
• at least one selected from the group consisting of an isopropyl group, a 1-methylbutyl group, and a 2,2-dimethylpropyl group is preferable.
• Examples of the linear alkenyl group having 2 to 20 carbon atoms represented by R2 include the same groups exemplified as the "linear alkenyl group having 2 to 20 carbon atoms" described above. From the viewpoint of handleability, the linear alkenyl group having 2 to 20 carbon atoms represented by R2 is preferably a linear alkenyl group having 2 to 15 carbon atoms, more preferably a linear alkenyl group having 3 to 10 carbon atoms, and even more preferably a linear alkenyl group having 3 to 6 carbon atoms. Examples of the branched alkenyl group having 3 to 20 carbon atoms represented by R2 include the same groups exemplified above as the "branched alkenyl group having 3 to 20 carbon atoms".
• the branched alkenyl group having 3 to 20 carbon atoms represented by R2 is preferably a branched alkenyl group having 3 to 15 carbon atoms, more preferably a branched alkenyl group having 3 to 10 carbon atoms, and even more preferably a branched alkenyl group having 3 to 6 carbon atoms.
• Examples of the aryl group having 6 to 12 carbon atoms represented by R2 include the same groups exemplified as the "aryl group having 6 to 12 carbon atoms" described above.
• the aryl group having 6 to 12 carbon atoms represented by R2 is preferably a phenyl group.
• Examples of the arylalkyl group having 7 to 12 carbon atoms represented by R2 include the same groups exemplified as the "arylalkyl group having 7 to 12 carbon atoms" described above.
• the arylalkyl group having 7 to 12 carbon atoms represented by R2 is preferably a phenylmethyl group. From the viewpoint of easily obtaining a modifying effect, R2 is preferably a linear alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms.
• the number average molecular weight of the ⁇ -methyl- ⁇ -valerolactone polymer is preferably 500 or more, more preferably 1,000 or more, and even more preferably 1,500 or more.
• the number average molecular weight of the ⁇ -methyl- ⁇ -valerolactone polymer is preferably 100,000 or less, more preferably 80,000 or less, and even more preferably 50,000 or less. That is, the number average molecular weight of the ⁇ -methyl- ⁇ -valerolactone polymer is preferably 500 to 100,000, more preferably 1,000 to 80,000, and even more preferably 1,500 to 50,000.
• the "number average molecular weight" of the ⁇ -methyl- ⁇ -valerolactone polymer described in this specification is a number average molecular weight calculated as standard polystyrene by gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• the weight average molecular weight of the ⁇ -methyl- ⁇ -valerolactone polymer is preferably 1,500 or more and 200,000 or less. If the weight average molecular weight is 1,500 or more, a more excellent modification effect is likely to be exhibited. Furthermore, if the weight average molecular weight is 200,000 or less, the handling property and productivity during molding are likely to be excellent.
• the weight average molecular weight of the ⁇ -methyl- ⁇ -valerolactone polymer is more preferably 2,200 or more, and even more preferably 3,000 or more.
• the weight average molecular weight of the ⁇ -methyl- ⁇ -valerolactone polymer is more preferably 160,000 or less, even more preferably 125,000 or less, and even more preferably 100,000 or less. That is, the weight average molecular weight of the ⁇ -methyl- ⁇ -valerolactone polymer is preferably 1,500 to 200,000, more preferably 2,200 to 160,000, even more preferably 3,000 to 125,000, and still more preferably 3,000 to 100,000.
• the "weight average molecular weight" of the ⁇ -methyl- ⁇ -valerolactone polymer described in this specification is a weight average molecular weight calculated in terms of standard polystyrene by gel permeation chromatography (GPC). The detailed measurement method can be the method described in the examples.
• the molecular weight distribution (Mw/Mn) of the ⁇ -methyl- ⁇ -valerolactone polymer is preferably 1.0 to 3.0, more preferably 1.0 to 2.6, and even more preferably 1.1 to 2.5, even more preferably 1.1 to 2.0, and even more preferably 1.2 to 1.8.
• the "molecular weight distribution" of the ⁇ -methyl- ⁇ -valerolactone polymer described in this specification is a value calculated from the number average molecular weight and weight average molecular weight calculated in terms of standard polystyrene by gel permeation chromatography (GPC). The number average molecular weight and the weight average molecular weight can be measured in detail according to the method described in the Examples.
• the viscosity refers to the viscosity of a polymer measured by an E-type viscometer.
• the measurement temperature can be optimized depending on the molecular weight, etc. From the viewpoint of achieving a more excellent modifying effect, the viscosity of the ⁇ -methyl- ⁇ -valerolactone polymer is preferably 10 mPa ⁇ s or more at a measurement temperature of 80° C., and more preferably 50 mPa ⁇ s or more at a measurement temperature of 80° C.
• the viscosity is preferably 200,000 mPa ⁇ s or less at a measurement temperature of 80° C., and more preferably 150,000 mPa ⁇ s or less at a measurement temperature of 80° C. That is, the viscosity of the polymer is preferably 10 to 200,000 mPa ⁇ s, and more preferably 50 to 150,000 mPa ⁇ s at a measurement temperature of 80° C.
• the measurement temperature can be set according to the molecular weight, etc.
• the ⁇ -methyl- ⁇ -valerolactone polymer is also preferably in an embodiment having a viscosity of 100 to 150,000 mPa ⁇ s, more preferably 400 to 150,000 mPa ⁇ s, and even more preferably 600 to 100,000 mPa ⁇ s at a measurement temperature of 30° C.
• the ⁇ -methyl- ⁇ -valerolactone polymer is also preferably in an embodiment having a viscosity of 50 to 150,000 mPa ⁇ s, more preferably 200 to 150,000 mPa ⁇ s, and even more preferably 600 to 120,000 mPa ⁇ s at a measurement temperature of 30° C.
• Method for producing ⁇ -methyl- ⁇ -valerolactone polymer As a method for producing the above-mentioned ⁇ -methyl- ⁇ -valerolactone polymer, from the viewpoints of productivity and simplicity, when producing a high molecular weight polymer, it is preferable to adopt a production method including a step of adding a terminal modifying agent to a reaction solution obtained by reacting ⁇ -methyl- ⁇ -valerolactone, an alcohol compound or water, and a base catalyst to carry out a terminal modification reaction (hereinafter also referred to as a "reaction step").
• the above production method is characterized in that a terminal modifier is added directly to a reaction solution obtained by reacting ⁇ -methyl- ⁇ -valerolactone with an alcohol compound or water and a base catalyst. That is, after ring-opening polymerization of ⁇ -methyl- ⁇ -valerolactone, the terminals of the ring-opened polymer can be modified by adding a terminal modifier to the reactor in which the ring-opening polymerization was carried out, without taking out the ring-opened polymer once. Since the reaction process involves ring-opening polymerization reaction and terminal modification reaction in one pot, the above production method can be said to be a simplified process.
• the method for producing the ⁇ -methyl- ⁇ -valerolactone polymer is not limited to the above-mentioned method.
• the alcohol compound that can be used in this embodiment is not particularly limited as long as the effects of the present invention can be obtained.
• the alcohol compound include linear or branched aliphatic hydrocarbon alcohols having 1 to 20 carbon atoms, aromatic hydrocarbon alcohols having 6 to 12 carbon atoms, and alkyl aromatic hydrocarbon alcohols having 7 to 12 carbon atoms. These alcohol compounds may have a saturated or unsaturated hydrocarbon group. In the case of the above-mentioned "branched aliphatic hydrocarbon alcohols", the number of carbon atoms is 3 to 20.
• examples of the alcohol compound include linear aliphatic hydrocarbon alcohols having 1 to 20 carbon atoms, branched aliphatic hydrocarbon alcohols having 3 to 20 carbon atoms, aromatic hydrocarbon alcohols having 6 to 12 carbon atoms, and alkyl aromatic hydrocarbon alcohols having 7 to 12 carbon atoms. These alcohol compounds may have a saturated or unsaturated hydrocarbon group.
• the alcohol compound may be a monohydric alcohol or a polyhydric alcohol such as a dihydric alcohol or a trihydric alcohol.
• the water that can be used in this embodiment is not particularly limited as long as the effects of the present invention can be obtained. For example, tap water, distilled water, ion-exchanged water, industrial water, deionized water, etc. can be used.
• the base catalyst examples include metal catalysts such as alkali metals and alkali metal compounds, and organic base compounds.
• the base catalyst may be used alone or in combination of two or more kinds.
• the alkali metal compound examples include organic alkali metal compounds, alkali metal hydroxide compounds, and alkali metal hydride compounds, and among these, organic lithium compounds such as butyllithium are preferred.
• the organic base compound examples include amine compounds having an amidine skeleton or a guanidine skeleton.
• metal catalysts such as organomagnesium compounds and organozinc compounds can also be used.
• the reaction step it is preferable to add 0.005 to 1.5 molar equivalents of the base catalyst relative to the hydroxyl group of the alcohol compound.
• ⁇ -methyl- ⁇ -valerolactone The ⁇ -methyl- ⁇ -valerolactone that can be used in this embodiment can be produced by a known method, for example, by using 2-hydroxy-4-methyltetrahydropyran or the like as a raw material (JP-B-6-53691, etc.).
• a commercially available product can be used, and any product derived from petroleum or biomass can be used.
• water it is preferable to add 5 to 1,500 molar equivalents of ⁇ -methyl- ⁇ -valerolactone to the water.
• Examples of the terminal modifying agent that can be used in this embodiment include acid anhydrides and acid halides (acid halides are also called “halogenated esters").
• the acid anhydrides and acid halides (halogenated esters) are not particularly limited as long as the effects of the present invention can be obtained.
• acid anhydrides and acid halides (halogenated esters) having at least one group selected from the group consisting of a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an arylalkyl group having 7 to 12 carbon atoms can be used.
• acid anhydrides and acid halides having at least one group selected from the group consisting of a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an arylalkyl group having 7 to 12 carbon atoms can be used.
• acid anhydrides include acetic anhydride, oxalic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, glutaric anhydride, methacrylic anhydride, butyric anhydride, isobutyric anhydride, 1,8-naphthalic anhydride, trifluoroacetic anhydride, and cyclohexanecarboxylic anhydride.
• acid halides include acetyl chloride, propionyl chloride, butyroyl chloride, trifluoroacetyl chloride, benzoyl chloride, 2-furoyl chloride, hexanoyl chloride, phenylacetyl chloride, acetyl bromide, propionyl bromide, and benzoyl bromide.
• the reaction step it is preferable to add 1 to 20 molar equivalents of the terminal modifier to the hydroxyl group of the alcohol compound.
• water it is preferable to add 1 to 20 molar equivalents of the terminal modifier to the water.
• a promoter may be added, if necessary.
• an amine compound such as triethylamine, tributylamine, trioctylamine, imidazole, pyridine, aminopyridine, or 4-dimethylaminopyridine can be used.
• the promoter can be added in an amount of 0.001 to 10 molar equivalents relative to the hydroxyl groups of the alcohol compound.
• water the promoter can be added in an amount of 0.001 to 10 molar equivalents relative to the water.
• the reaction step can be carried out in the presence of a solvent inert to the ring-opening polymerization reaction, such as aliphatic hydrocarbons, such as cyclohexane, methylcyclohexane, n-hexane, and n-pentane, and aromatic hydrocarbons, such as benzene, toluene, and xylene.
• a solvent inert to the ring-opening polymerization reaction such as aliphatic hydrocarbons, such as cyclohexane, methylcyclohexane, n-hexane, and n-pentane
• aromatic hydrocarbons such as benzene, toluene, and xylene.
• the reaction temperature when reacting ⁇ -methyl- ⁇ -valerolactone with an alcohol compound or water and a base catalyst may usually be 20 to 100° C., and the reaction time is usually 1 minute to 24 hours.
• the reaction temperature for carrying out the terminal modification reaction may usually be 20 to 80° C., and the reaction time is usually 1 minute to 24 hours.
• the polymer represented by the general formula (I) can be produced through the above reaction steps. If necessary, a post-treatment step may be carried out to isolate the produced polymer.
• a suitable method can be adopted from among known methods. For example, the reaction mixture after the reaction step can be washed with a reaction solvent or water, concentrated, and purified by a method typically used for separating and purifying organic compounds, such as distillation.
• the resin composition of this embodiment contains ⁇ -methyl- ⁇ -valerolactone polymer in an amount of preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, even more preferably 3 to 40 parts by mass, and even more preferably 10 to 30 parts by mass, per 100 parts by mass of polybutylene succinate polymer.
• the above content ratios make it possible to obtain a resin composition having even more excellent impact resistance.
• the total content of the polybutylene succinate polymer and the ⁇ -methyl- ⁇ -valerolactone polymer 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.
• the effects of the present invention are more pronounced at the above content ratios.
• the content of the polybutylene succinate polymer in the resin composition of this embodiment is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 97% by mass or less.
• the content of the polybutylene succinate polymer in the resin composition of this embodiment is preferably 60 to 99% by mass, more preferably 70 to 98% by mass, and even more preferably 80 to 97% by mass.
• the content of the ⁇ -methyl- ⁇ -valerolactone polymer in the resin composition of this embodiment is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.
• the content of the ⁇ -methyl- ⁇ -valerolactone polymer in the resin composition of this embodiment is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, and even more preferably 3 to 20% by mass. With the above content ratios, the effects of the present invention are more pronounced.
• 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 ⁇ -methyl- ⁇ -valerolactone polymer and the polybutylene succinate polymer.
• biomass resins or biodegradable resins include polylactic acid (PLA), polycaprolactone (PCL), 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.
• the resin composition of this embodiment may contain additives other than the polybutylene succinate polymer and the ⁇ -methyl- ⁇ -valerolactone polymer.
• 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, 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 it is sufficient to uniformly mix the polybutylene succinate polymer, the ⁇ -methyl- ⁇ -valerolactone polymer, and, if necessary, additives.
• 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 220° C., taking into consideration the melting point and decomposition temperature of the polybutylene succinate polymer.
• the present invention also provides a molded article made of the resin composition.
• the shape of the molded article may be any molded article that can be produced using the resin composition of this embodiment.
• Examples of the molded article include films, sheets, foams, plates, fibers, containers, etc. More specifically, examples of the molded article include laminated films, monofilaments, multifilaments, nonwoven fabrics, flat yarns, staples, crimped fibers, split yarns, composite fibers, etc.
• the method for producing the molded article is not particularly limited, and it can be molded by various known methods such as injection molding, blow molding, press molding, extrusion molding, calendar molding, and molding using a 3D printer.
• ⁇ Applications> By mixing a polybutylene succinate polymer with a ⁇ -methyl- ⁇ -valerolactone polymer represented by the above general formula (I) to form a resin composition, the ⁇ -methyl- ⁇ -valerolactone polymer does not bleed out and the impact resistance can be improved.
• the present invention provides a modifier for polybutylene succinate polymers, which comprises the ⁇ -methyl- ⁇ -valerolactone polymer represented by the above general formula (I).
• the use of the ⁇ -methyl- ⁇ -valerolactone polymer represented by the above general formula (I) as a modifier for polybutylene succinate polymers is also a preferred embodiment.
• the resin composition of this embodiment can be used for various purposes. Applications of the above resin composition include food films, fresh food trays and fast food containers, outdoor leisure products, fishing lines, fishing nets, vegetation nets, water-retaining sheets, coating materials, agricultural mulch films, fertilizer coating materials, striped tapes, split yarns, composite fibers, shopping bags, garbage bags, compost bags, cosmetic containers, detergent containers, bleach containers, ropes, binding materials, surgical thread, sanitary cover stock materials, cooler boxes, cushioning materials, synthetic papers, and the like.
• the overall degree of polymerization of the obtained ⁇ -methyl- ⁇ -valerolactone polymer was determined by 1 H-NMR measurement.
• the overall degree of polymerization was calculated from the ratio of the proton signals of the repeating units in the polymer to the proton signal of the raw alcohol as a reference.
• the average repeat numbers n and m are the total degree of polymerization calculated here divided by the number of hydroxyl groups in the raw alcohol.
• the specific measurement method is as follows.
• 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. (Measurement conditions) Apparatus: HLC-EcoSEC8320GPC (manufactured by Tosoh Corporation) Columns: Three columns, KF-803 (manufactured by Resonac Corporation), KF-802.5 (manufactured by Resonac Corporation), and KF-802 (manufactured by Resonac Corporation), were connected in series.
• Mn and Mw were determined according to the following measurement.
• a tetrahydrofuran (THF) solution was used as the eluent.
• 1.0 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 measurement conditions were as follows: (Measurement conditions) Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation) Column: Two TSKgel (registered trademark) SuperMultipore HZ-M columns (manufactured by Tosoh Corporation) were connected in series.
• test specimen was stored for 10 hours or more in a low-temperature thermostatic chamber ("HIFLEX FL714C" manufactured by ETAC Co., Ltd.) adjusted to the test temperature (-15°C or -30°C) shown in Table 2, and humidity was controlled.
• the test specimen after humidity control was measured using a DuPont impact tester (manufactured by Taiyu Kizai Co., Ltd.) according to the following procedures (a) to (e) to evaluate impact resistance.
• a) Using a support bar, set a 1 kg weight 0.5 m from the support base.
• the test piece is removed from the thermostatic chamber to an environment of 23° C. and 49% humidity, and the test piece is placed between the support and the hammer.
• Biodegradability test (1) Preparation of test specimens The press plate prepared for the impact resistance test was cut into a size of 10 ⁇ 10 mm to prepare a test specimen. Using this test specimen, biodegradability was evaluated according to the following procedure in accordance with JIS K 6953-1:2011. (2) Measurement of total organic carbon amount and total amount of theoretical carbon dioxide generation The total organic carbon amount of the test piece and the control material (cellulose microcrystals (manufactured by MERCK)) was measured using an organic trace element analyzer ("Microcorder JM10" manufactured by J Science Lab Co., Ltd.), and the theoretical carbon dioxide generation amount was calculated based on the results.
• Biodegradability ⁇ (CO 2 ) T ⁇ (CO 2 ) B ⁇ /ThCO 2 ⁇ 100 ( CO2 ) T : Total accumulated amount of carbon dioxide released from the compost container during the culture period ( CO2 ) B : Average accumulated amount of carbon dioxide released by the blank test ThCO2 : Total theoretical amount of carbon dioxide of the test piece in the test container (compost container) A biodegradability of 60% or more after 180 days was rated as pass (“G”), and a biodegradability of less than 60% was rated as fail (“NG”).
• test piece was stored for 24 hours or more under conditions of 23°C and 49% humidity, and the breaking elongation (%) was measured at 23°C, 49% humidity, and a tensile speed of 500 mm/min using a universal material testing machine (Instron Corporation, "INSTRON5900R-5666"). The measured value was the average value of 5 times.
• the surface condition of the obtained test piece when stored in an environment of 80 ° C. for 16 hours or more was evaluated visually and by touch according to the following evaluation criteria.
• VG No obvious bleeding out or stickiness was observed.
• G At least one phenomenon selected from the group consisting of slight bleeding out and slight stickiness is observed, but is at a level that does not cause any practical problems.
• NG At least one phenomenon selected from the group consisting of significant bleeding out and significant stickiness is observed, and the composition is not suitable for practical use.
• the reaction solution containing the obtained ⁇ -methyl- ⁇ -valerolactone polymer was extracted with toluene and water and purified by a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 155 g of ⁇ -methyl- ⁇ -valerolactone polymer.
• the physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone polymer (hereinafter sometimes referred to as "PMVL-1") were measured as described above. The results are shown in Table 1.
• the resulting PMVL-1 is represented by the above general formula (I), and R 1 , R 2 , n and the overall degree of polymerization are as shown in Table 1.
• the reaction solution containing the obtained ⁇ -methyl- ⁇ -valerolactone polymer was extracted with toluene and water and purified by a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 150 g of ⁇ -methyl- ⁇ -valerolactone polymer.
• the physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone polymer (hereinafter sometimes referred to as "PMVL-2”) were measured as described above. The results are shown in Table 1.
• the resulting PMVL-2 is represented by the above general formula (I), and R 1 , R 2 , n, m and the overall degree of polymerization are as shown in Table 1.
• the reaction solution containing the obtained ⁇ -methyl- ⁇ -valerolactone polymer was extracted with toluene and water and purified by a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 162 g of ⁇ -methyl- ⁇ -valerolactone polymer.
• the physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone polymer (hereinafter sometimes referred to as "PMVL-3") were measured as described above. The results are shown in Table 1.
• the resulting PMVL-3 is represented by the above general formula (I), and R 1 , R 2 , n and the overall degree of polymerization are as shown in Table 1.
• the reaction solution containing the obtained ⁇ -methyl- ⁇ -valerolactone polymer was extracted with toluene and water and purified by a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.) to obtain 450 g of ⁇ -methyl- ⁇ -valerolactone polymer.
• the physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone polymer (hereinafter sometimes referred to as "PMVL-4") were measured as described above. The results are shown in Table 1.
• the resulting PMVL-4 is represented by the above general formula (I), and R 1 , R 2 , n and the overall degree of polymerization are as shown in Table 1.
• PMVL-5 ⁇ -methyl- ⁇ -valerolactone polymer
• PMVL-6 ⁇ -methyl- ⁇ -valerolactone polymer
• the physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone polymer (hereinafter sometimes referred to as "PMVL-7") were measured as described above. The results are shown in Table 1.
• the obtained PMVL-7 is represented by the above-mentioned general formula (I), specifically, by the above-mentioned general formula (I-e).
• R 1 , R 2 , n, m, and the overall degree of polymerization are as shown in Table 1.
• the starting alcohol has three hydroxyl groups, and m is two.
• PMVL-8 ⁇ -methyl- ⁇ -valerolactone polymer
• PMVL-9 ⁇ -methyl- ⁇ -valerolactone polymer
• Table 1 The physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone polymer (hereinafter sometimes referred to as "PMVL-9") were measured as described above. The results are shown in Table 1.
• the resulting PMVL-9 is represented by the above general formula (I), and R 1 , R 2 , n, m and the overall degree of polymerization are as shown in Table 1.
• Example 1 A resin composition was obtained in the same manner as in Example 1, except that the ⁇ -methyl- ⁇ -valerolactone polymer was not used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.
• Comparative Example 2 A resin composition was obtained in the same manner as in Example 1, except that the impact modifier 1 was used instead of the ⁇ -methyl- ⁇ -valerolactone polymer. The obtained resin composition was evaluated as described above. The results are shown in Table 2.
• Comparing Examples 1 to 29 with Comparative Examples 1 to 3 it can be seen that the resin compositions obtained in the Examples have improved impact resistance at the above temperatures and are resin compositions with good bleed-out resistance. It can also be seen that the ⁇ -methyl- ⁇ -valerolactone polymers obtained in Production Examples 1 to 9 are useful as modifiers for polybutylene succinate.

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