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
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
• • 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 ⁇ -methyl- ⁇ -valerolactone copolymer and a polylactic acid polymer, a molded article made of the resin composition, a modifier for polylactic acid polymers made of the ⁇ -methyl- ⁇ -valerolactone copolymer, and use of the modifier.
• Patent Document 1 a technology has been disclosed relating to a (meth)acrylic acid ester obtained by reacting (meth)acrylic acid with a reaction product of ⁇ -methyl- ⁇ -valerolactone and a compound having one hydroxyl group in the molecule.
• Patent Document 1 describes that the (meth)acrylic acid ester has a fast curing rate, the coating obtained by curing is flexible, has a low glass transition point, and does not crystallize even at temperatures below 0°C.
• Patent Document 1 also describes that a resin composition containing the (meth)acrylic acid ester is suitable for coating optical glass fibers for optical transmission.
• Patent Document 1 describes that the coating film obtained by using the above (meth)acrylic acid ester is flexible and has a low glass transition point.
• the above (meth)acrylic acid ester is mixed with a thermoplastic resin to form a resin composition
• the obtained resin composition has low plasticity and is not fully satisfactory in elongation. Therefore, an object of the present invention is to provide a resin composition having good plasticity and improved elongation, and a molded article made of the resin composition.
• Another object of the present invention is to provide a modifier for polylactic acid polymers capable of imparting good plasticity and elongation, and use of said modifier.
• 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 ⁇ -methyl- ⁇ -valerolactone copolymer represented by the following general formula (I) or (II) and a polylactic acid polymer:
• R 1 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 14 carbon atoms.
• R 2 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 14 carbon atoms, a group represented by the following formula (X), a 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 following formula (Y), a group in which one hydrogen atom bonded to at least one terminal carbon atom in a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the following formula (Y), or a group in which one hydrogen atom bonded to at least one carbon atom in a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the following formula (Z).
• X a
• the bond indicated by *1 is bonded to an oxygen atom.
• the bond indicated by *2 is bonded to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms.
• the bond indicated by *3 is bonded to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms.
• R3 represents a linear alkylene group having 2 to 20 carbon atoms or a branched alkylene group having 3 to 20 carbon atoms.
• A represents an oxygen atom, a sulfur atom, or an imino group.
• n 2 to 1,000
• m 2 to 1,000
• p 2 to 1,000
• n, m, A, p, R 1 , R 2 and R 3 may be the same or different from each other.
• a modifier for polylactic acid-based polymers comprising a ⁇ -methyl- ⁇ -valerolactone-based copolymer represented by the following general formula (I) or (II):
• R 1 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 14 carbon atoms.
• R 2 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 14 carbon atoms, a group represented by the following formula (X), a 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 following formula (Y), a group in which one hydrogen atom bonded to at least one terminal carbon atom in a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the following formula (Y), or a group in which one hydrogen atom bonded to at least one carbon atom in a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the following formula (Z).
• X a
• the bond indicated by *1 is bonded to an oxygen atom.
• the bond indicated by *2 is bonded to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms.
• the bond indicated by *3 is bonded to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms.
• R3 represents a linear alkylene group having 2 to 20 carbon atoms or a branched alkylene group having 3 to 20 carbon atoms.
• A represents an oxygen atom, a sulfur atom, or an imino group.
• R 2 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 14 carbon atoms, a group represented by the following formula (X), a 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 following formula (Y), a group in which one hydrogen atom bonded to at least one terminal carbon atom in a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the following formula (Y), or a group in which one hydrogen atom bonded to at least one carbon atom in a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the following formula (Z).
• X a
• the bond indicated by *1 is bonded to an oxygen atom.
• the bond indicated by *2 is bonded to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms.
• the bond indicated by *3 is bonded to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms.
• R3 represents a linear alkylene group having 2 to 20 carbon atoms or a branched alkylene group having 3 to 20 carbon atoms.
• A represents an oxygen atom, a sulfur atom, or an imino group.
• n is 2 to 1,000
• m is 2 to 1,000
• p is 2 to 1,000.
• the present invention it is possible to provide a resin composition having good plasticity and improved elongation, and a molded article made of the resin composition. Furthermore, according to the present invention, it is possible to provide a modifier for polylactic acid polymers capable of imparting good plasticity and elongation, and the use of said modifier.
• the resin composition of the present embodiment contains a ⁇ -methyl- ⁇ -valerolactone copolymer represented by general formula (I) or (II) and a polylactic acid polymer.
• a ⁇ -methyl- ⁇ -valerolactone copolymer represented by general formula (I) or (II) and the polylactic acid polymer, the resin composition has good plasticity and improved elongation.
• ⁇ -Methyl- ⁇ -valerolactone copolymer The ⁇ -methyl- ⁇ -valerolactone copolymer of the present embodiment is represented by the following general formula (I) or (II).
• R 1 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 14 carbon atoms.
• 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 8 carbon atoms.
• methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, etc. are 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
• aryl group having 6 to 14 carbon atoms examples include a phenyl group, a 2-methylphenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group, a 2-naphthyl group, etc.
• the aryl group having 6 to 14 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group.
• arylalkyl group having 7 to 14 carbon atoms examples include a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, a naphthylmethyl group, a naphthylethyl group, etc.
• the arylalkyl group having 7 to 14 carbon atoms is preferably an arylalkyl group having 7 to 12 carbon atoms, and more preferably a phenylmethyl group.
• R 2 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms, an arylalkyl group having 7 to 14 carbon atoms, a group represented by the following formula (X), a 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 following formula (Y), a group in which one hydrogen atom bonded to at least one terminal carbon atom in a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the following formula (Y), or a group in which one hydrogen atom bonded to at least one carbon atom in a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the following formula (Y), or a group in which
• the linear alkyl group having 1 to 20 carbon atoms bonded to the bond indicated by *2 is a linear alkyl group having 1 to 20 carbon atoms in a "group in which one hydrogen atom bonded to a terminal carbon atom of a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by formula (Y)".
• the branched alkyl group having 3 to 20 carbon atoms bonded to the bond indicated by *2 is a branched alkyl group having 3 to 20 carbon atoms in a "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 (Y)".
• R 1 in the group represented by formula (Y) has the same meaning as the above-mentioned R 1. Furthermore, n and A in the group represented by formula (Y) have the same meaning as n and A described below.
• the linear alkyl group having 1 to 20 carbon atoms can be exemplified similarly to the groups exemplified as the "linear alkyl group having 1 to 20 carbon atoms" represented by R 1 described above.
• 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.
• the branched alkyl group having 3 to 20 carbon atoms can be exemplified similarly to the groups exemplified as the "branched alkyl group having 3 to 20 carbon atoms" represented by R 1 described above.
• 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.
• Formula (Z) in formula (Z), the bond indicated by *3 is bonded to a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms. Specifically, it is bonded to the terminal carbon atom of the linear alkyl group having 1 to 20 carbon atoms and the terminal carbon atom of the branched alkyl group having 3 to 20 carbon atoms.
• the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms bonded to the bond indicated by *3 is the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms in the "group in which one hydrogen atom bonded to at least one carbon atom in the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by formula (Z)".
• R 1 in the group represented by formula (Z) has the same meaning as R 1 described above.
• R 3 , n, m and A in the group represented by formula (Z) have the same meaning as R 3 , n, m and A described below.
• the linear alkyl group having 1 to 20 carbon atoms can be exemplified similarly to the groups exemplified as the "linear alkyl group having 1 to 20 carbon atoms" represented by R 1 described above.
• 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.
• 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.
• R2 is preferably a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, a group represented by the above formula (X), a linear alkyl group having 1 to 16 carbon atoms in which one hydrogen atom bonded to a terminal carbon atom is substituted with a group represented by the above formula (Y), and a linear alkyl group having 1 to 16 carbon atoms or a branched alkyl group having 3 to 16 carbon atoms in which one hydrogen atom bonded to at least one carbon atom is substituted with a group represented by the above formula (Z), and more preferably a carbon atom.
• R2 is preferably a group represented by the above formula (X).
• R 3 represents a linear alkylene group having 2 to 20 carbon atoms or a branched alkylene group having 3 to 20 carbon atoms.
• linear alkylene groups having 2 to 20 carbon atoms include an ethylene group (-(CH 2 ) 2 -), an n-propylene group (-(CH 2 ) 3 -), an n-butylene group (-(CH 2 ) 4 -), and an n-pentylene group (-(CH 2 ) 5 -).
• Examples of branched alkylene groups having 3 to 20 carbon atoms include an isopropylene group (-CH 2 -CH(CH 3 )-), a 1-methylpropylene group (-CH 2 -CH 2 -CH(CH 3 )-), a 2-methylpropylene group (-CH 2 -CH(CH 3 )-CH 2 -), a dimethylethylene group (-CH 2 -C(CH 3 ) 2 -), an ethylethylene group (-CH 2 -CH(CH 2 CH 3 )-), a 2-methylbutylene group (-CH 2 -CH 2 -CH(CH 3 )-CH 2 -), and the like.
• R 3 is preferably a linear alkylene group having 2 to 16 carbon atoms or a branched alkylene group having 3 to 16 carbon atoms, more preferably a linear alkylene group having 2 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms, even more preferably a linear alkylene group having 2 to 5 carbon atoms or a branched alkylene group having 3 to 5 carbon atoms, and still more preferably a linear alkylene group having 2 to 5 carbon atoms.
• A represents an oxygen atom, a sulfur atom, or an imino group (—NH—), and from the viewpoint of excellent biodegradability, A is preferably an oxygen atom.
• n, m, and p each represent the average number of repetitions.
• n is 2 to 1,000.
• n is preferably 2 to 800, more preferably 4 to 500, and even more preferably 4 to 200.
• n is preferably 3 to 1,450, more preferably 3 to 250, even more preferably 3 to 100, and even more preferably 3 to 40.
• m is 2 to 1,000.
• m is preferably 2 to 400, more preferably 4 to 200, and even more preferably 4 to 50.
• m is preferably 3 to 1,450, more preferably 3 to 100, even more preferably 3 to 50, and even more preferably 3 to 40.
• p is 2 to 1,000. In one embodiment of the present invention, p is preferably 2 to 200, more preferably 4 to 100. In another embodiment of the present invention, p is preferably 3 to 1,450, more preferably 3 to 200, and even more preferably 3 to 50.
• m and n can be calculated from the 1 H-NMR spectrum of the ⁇ -methyl- ⁇ -valerolactone copolymer. Specifically, when A is an oxygen atom, in the spectrum obtained by 1 H-NMR measurement of the ⁇ -methyl- ⁇ -valerolactone copolymer, m and n can be calculated from the peak intensity of the hydrogen atom bonded to the carbon atom next to the oxygen atom in the block (E) described below and the peak intensity of the hydrogen atom bonded to the carbon atom next to the ether oxygen atom bonded to the ⁇ -methyl- ⁇ -valerolactone unit.
• a detailed calculation method of m and n can follow the method described in the Examples.
• the above " ⁇ -methyl- ⁇ -valerolactone unit” means a structural unit derived from ⁇ -methyl- ⁇ -valerolactone, and means a unit repeated with an average repeat number n.
• Example 1 In general formula (I), when R 2 represents a group represented by the above formula (X), it is represented by the following general formula (Ia).
• Example 2 In the general formula (I), when R2 represents a linear alkyl group having 1 to 20 carbon atoms in which one hydrogen atom bonded to the terminal carbon atom is substituted with a group represented by the above formula (Y), the group is represented by the following general formula (I-b), where R in the general formula (I-b) represents a linear alkylene group having 1 to 20 carbon atoms.
• Example 3 In general formula (I), when R 2 represents a 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 the group represented by the above formula (Y) and one hydrogen atom bonded to all terminal carbon atoms of a 2-methylpropyl group is substituted with the group represented by the above formula (Y), the compound is represented by the following general formula (I-c):
• Example 4 In general formula (I), when R 2 represents a group in which one hydrogen atom bonded to at least one carbon atom in the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms is a group represented by the above formula (Z), and one hydrogen atom bonded to at least one carbon atom in the n-propyl group is substituted with a group represented by the above formula (Z), the compound is represented by the following general formula (I-d).
• Example 5 In general formula (I), when R 2 represents a group in which one hydrogen atom bonded to at least one carbon atom in the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms is a group represented by the above formula (Z), and one hydrogen atom bonded to at least one carbon atom in the 2-methylpropyl group is substituted with a group represented by the above formula (Z), the compound is represented by the following general formula (I-e).
• the content of block (E) represented by the following formula is preferably 5 to 95 mass%.
• the ⁇ -methyl- ⁇ -valerolactone copolymer can more reliably achieve both compatibility with thermoplastic resins and a plasticizing effect, and the crystallization rate of the resin composition is further improved, which is preferable.
• the ⁇ -methyl- ⁇ -valerolactone copolymer tends to have higher compatibility with thermoplastic resins, making it easier to suppress bleed-out.
• the content ratio of block (E) is determined from the content ratio of the molecular weight of block (E) relative to the molecular weight of the ⁇ -methyl- ⁇ -valerolactone copolymer.
• the content ratio of block (E) can be calculated from the molecular weight calculated by 1 H-NMR measurement of the ⁇ -methyl- ⁇ -valerolactone copolymer.
• the content ratio of block (E) can be calculated from the peak intensity of the hydrogen atom bonded to the carbon atom next to the oxygen atom in block (E), the peak intensity of the hydrogen atom bonded to the carbon atom next to the oxygen atom of the ether bonded to the ⁇ -methyl- ⁇ -valerolactone unit, and the peak intensity of the hydrogen atom bonded to the carbon atom at the ester ⁇ -position of the ⁇ -methyl- ⁇ -valerolactone unit.
• the detailed method for measuring the content of the block (E) can be according to the method described in the Examples.
• Weight average molecular weight of block (E) in ⁇ -methyl- ⁇ -valerolactone copolymer represented by general formula (I) Weight average molecular weight Mw of ⁇ -methyl- ⁇ -valerolactone copolymer ⁇ Content (mass%) of block (E) in general formula (I)/100
• the weight average molecular weight Mw of the ⁇ -methyl- ⁇ -valerolactone copolymer is a weight average molecular weight calculated in terms of standard polystyrene by gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• the content of block (F) represented by the following formula is preferably 5 to 95 mass%.
• the ⁇ -methyl- ⁇ -valerolactone copolymer can more reliably achieve both compatibility with thermoplastic resins and a plasticizing effect, and the crystallization rate of the resin composition is further improved, which is preferable.
• the ⁇ -methyl- ⁇ -valerolactone copolymer has block (F) at a content within the above numerical range, it tends to have higher compatibility with thermoplastic resins, and bleed-out can be easily suppressed.
• the content (mass%) of block (F) is the molecular weight of block (F) relative to the molecular weight of the ⁇ -methyl- ⁇ -valerolactone copolymer.
• the content of block (F) can be measured in the same manner as for block (E) above.
• the molecular weight distribution (Mw/Mn) of the ⁇ -methyl- ⁇ -valerolactone copolymer is preferably 1.0 to 3.0, more preferably 1.1 to 2.0, and even more preferably 1.2. ⁇ 1.8.
• the molecular weight distribution of the ⁇ -methyl- ⁇ -valerolactone copolymer is a value calculated from the number average molecular weight and weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• the viscosity is preferably 500 to 600,000 mPa ⁇ s, more preferably 700 to 500,000 mPa ⁇ s, and even more preferably 900 to 150,000 mPa ⁇ s at a measurement temperature of 30° C.
• the viscosity is preferably 600 to 550,000 mPa ⁇ s, more preferably 600 to 10,000 mPa ⁇ s, and even more preferably 600 to 2,200 mPa ⁇ s at a measurement temperature of 30° C. From the same viewpoint, in yet another embodiment of the present invention, the viscosity is preferably 500 to 500,000 mPa ⁇ s, more preferably 700 to 300,000 mPa ⁇ s, even more preferably 900 to 200,000, and even more preferably 900 to 150,000 mPa ⁇ s at a measurement temperature of 60° C.
• the viscosity is preferably 50,000 to 600,000 mPa ⁇ s, more preferably 100,000 to 400,000 mPa ⁇ s, even more preferably 150,000 to 250,000 mPa ⁇ s, and even more preferably 170,000 to 220,000 mPa ⁇ s at a measurement temperature of 60° C.
• the "viscosity" described in this specification is the viscosity of the ⁇ -methyl- ⁇ -valerolactone copolymer measured by an E-type viscometer. The detailed measurement method can be according to the method described in the Examples.
• 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 copolymer is not limited to the above-mentioned method.
• examples of the initiator include polyethers having at least one hydroxyl group.
• the polyethers may be linear or branched.
• examples of polyethers having at least one hydroxyl group include polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene ether glycol (PTMG), polyglycerin (PGL), and the like.
• examples of the initiator include polyethers having at least one amino group, such as triethylene glycol amine, diethylene glycol bis(3-aminopropyl) ether, and poly(ethylene glycol) diamine.
• examples of the initiator include polyethers having at least one thiol group.
• examples of polyethers having at least one thiol group include poly(ethylene glycol) dithiol.
• ⁇ -Methyl- ⁇ -valerolactone can be produced by a known method, for example, from 2-hydroxy-4-methyltetrahydropyran or the like as a raw material (JP-B-6-53691, etc.).
• ⁇ -methyl- ⁇ -valerolactone a commercially available product can be used, and any product derived from petroleum or biomass can be used.
• the amount of ⁇ -methyl- ⁇ -valerolactone used is not particularly limited as long as the effects of the present invention can be obtained, but it is usually 5 to 1,500 molar equivalents relative to the initiator, for example.
• Polymerization Catalyst As a method for producing the above-mentioned ⁇ -methyl- ⁇ -valerolactone-based copolymer, a production method in which ⁇ -methyl- ⁇ -valerolactone, the above-mentioned initiator, and a polymerization catalyst are reacted under basic conditions is preferable, and the polymerization catalyst is preferably one having catalytic action under basic conditions.
• polymerization catalysts that have catalytic activity under basic conditions include base catalysts.
• Known base catalysts can be used as the base catalyst.
• the base catalyst include metal catalysts such as alkali metals and alkali metal compounds, and organic base compounds.
• 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.
• 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 polymerization catalyst may be used alone or in combination of two or more kinds. The amount of the polymerization catalyst used is not particularly limited as long as the effects of the present invention can be obtained, but it is usually 0.005 to 1.5 molar equivalents relative to the initiator, for example.
• terminal modifiers include acid anhydrides and acid halides.
• the acid anhydrides and acid halides are not particularly limited as long as the effects of the present invention can be obtained.
• acid anhydrides and acid halides having at least one group selected from the group consisting of linear alkyl groups having 1 to 20 carbon atoms, branched alkyl groups having 3 to 20 carbon atoms, aryl groups having 6 to 14 carbon atoms, and arylalkyl groups having 7 to 14 carbon atoms can be used.
• the number of carbon atoms is 3 to 20.
• the amount of the terminal modifying agent used is not particularly limited as long as the effects of the present invention can be obtained, but is usually 1 to 20 molar equivalents relative to the initiator, for example.
• Co-catalyst and solvent in the method for producing the ⁇ -methyl- ⁇ -valerolactone copolymer of the present embodiment, a co-catalyst and a solvent may be used as necessary.
• the co-catalyst include amine compounds such as triethylamine, tributylamine, trioctylamine, imidazole, pyridine, aminopyridine, and 4-dimethylaminopyridine.
• the amount of the co-catalyst used is not particularly limited as long as the effects of the present invention can be obtained, but it is usually 0.001 to 10 molar equivalents relative to the initiator, for example.
• Solvents include, for example, aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, and n-pentane; and aromatic hydrocarbons such as benzene, toluene, and xylene.
• reaction temperature is usually about 20 to 100° C.
• reaction time is usually about 1 minute to 24 hours.
• a post-treatment step may be carried out as necessary.
• the post-treatment step a suitable method can be adopted from among known methods.
• the ⁇ -methyl- ⁇ -valerolactone copolymer obtained by the above-mentioned terminal modification can be washed with a reaction solvent or water, concentrated, and purified by a method commonly used for separating and purifying organic compounds, such as distillation or removal of low-boiling compounds.
• the polylactic acid polymer is a polymer having at least a structural unit derived from lactic acid.
• the polylactic acid polymer used in this embodiment 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, and a polymer of lactide, which is a cyclic dimer of lactic acid.
• the polylactic acid polymer may be a copolymer of lactic acid and at least one selected from the group consisting of an aliphatic hydroxycarboxylic acid other than lactic acid, an aliphatic dicarboxylic acid, an aliphatic diol, and an aromatic dicarboxylic acid.
• the copolymer preferably contains 70 mol % or more, more preferably 90 mol % or more, of structural units derived from lactic acid.
• a homopolymer of L-lactic acid, a homopolymer of D-lactic acid, or a copolymer of L-lactic acid and D-lactic acid is preferable, and a homopolymer of L-lactic acid is more preferable.
• the structural units derived from L-lactic acid in the polylactic acid polymer are preferably 0.1 to 99.9% by mass, more preferably 1 to 99% by mass, and even more preferably 2 to 98% by mass, and the structural units derived from D-lactic acid in the polylactic acid polymer are preferably 0.1 to 99.9% by mass, more preferably 1 to 99% by mass, and even more preferably 2 to 98% by mass.
• the polylactic acid polymers may be used alone or in combination of two or more kinds.
• polylactic acid polymers may be used.
• examples of commercially available products include the "Ingeo series” manufactured by Natureworks Co., Ltd., the "Luminy series” manufactured by TOTALENERGIES CORBION Co., Ltd., the "Revode” series manufactured by Zhejiang Hisun Biomaterials Co., Ltd., and the "SUPLA” series manufactured by SUPLA Material Technology Co., Ltd.
• the weight average molecular weight of the polylactic acid polymer is preferably 50,000 or more, more preferably 100,000 or more, and even more preferably 150,000 or more, from the viewpoint of tensile elongation at break. From the viewpoint of moldability and compatibility with the ⁇ -methyl- ⁇ -valerolactone copolymer, it is preferably 600,000 or less, more preferably 400,000 or less, and even more preferably 300,000 or less. That is, the weight average molecular weight of the polylactic acid polymer is preferably 50,000 to 600,000, more preferably 100,000 to 400,000, and even more preferably 150,000 to 300,000.
• the weight average molecular weight of the polylactic acid polymer can be determined by gel permeation chromatography (GPC) measurement in terms of standard polystyrene. When a commercially available product is used, the value given in the catalog may be used.
• the resin composition of this embodiment contains ⁇ -methyl- ⁇ -valerolactone copolymer in an amount of preferably 0.1 parts by mass or more and 100 parts by mass or less, more preferably 0.1 parts by mass or more and 50 parts by mass or less, even more preferably 0.5 parts by mass or more and 30 parts by mass or less, and even more preferably 1 part by mass or more and 15 parts by mass or less, relative to 100 parts by mass of polylactic acid polymer.
• the above content ratio can provide a resin composition having better elongation.
• the resin composition of this embodiment can also contain ⁇ -methyl- ⁇ -valerolactone copolymer in an amount of 2 parts by mass or more and 15 parts by mass or less relative to 100 parts by mass of polylactic acid polymer.
• a more preferred embodiment is a resin composition containing 2 to 100 parts by mass of ⁇ -methyl- ⁇ -valerolactone copolymer (more preferably 2 to 50 parts by mass, even more preferably 2 to 30 parts by mass, and even more preferably 2 to 15 parts by mass) per 100 parts by mass of polylactic acid polymer, and the number average molecular weight of the ⁇ -methyl- ⁇ -valerolactone copolymer is 500 to 200,000 (more preferably 2,000 to 70,000).
• the above resin composition exhibits more pronounced elongation.
• the total content of the ⁇ -methyl- ⁇ -valerolactone copolymer and polylactic acid 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, and even more preferably 98% by mass or more. With the above content ratios, the effects of the present invention are more pronounced.
• the content of block (E) in the ⁇ -methyl- ⁇ -valerolactone copolymer represented by the general formula (I) in the resin composition of this embodiment is preferably 0.3 to 10.0% by mass, more preferably 0.3 to 8.0% by mass, and even more preferably 0.5 to 7.0% by mass.
• the resin composition of this embodiment may contain a thermoplastic resin other than the ⁇ -methyl- ⁇ -valerolactone copolymer and the polylactic acid polymer.
• the thermoplastic resin means a thermoplastic resin other than the ⁇ -methyl- ⁇ -valerolactone copolymer and the polylactic acid polymer.
• the thermoplastic resin include polyester, biodegradable resins other than polyester, general-purpose thermoplastic resins, etc.
• the polyester includes polyester, which is a biodegradable resin.
• polyesters examples include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), polycyclohexylene dimethylene terephthalate (PCT), polytrimethylene terephthalate (PTT), polyethylene adipate (TP26), polybutylene isophthalate (TP41), polyethylene terephthalate succinate (PETS), polyester made of cyclohexane dimethanol and sebacic acid (TP CH10), copolyester made of hexanediol, isophthalic acid and terephthalic acid (TP 6I/6T), copolyester made of bisphenol A, isophthalic acid and terephthalic acid (TP BAI/BAT), copolyester made of ethylene glycol, cyclohexane dimethanol and terephthalic acid (or its ester) (TP 2T/CHT), copolyester made of ethylene glycol,
• biodegradable polyesters are preferred, specifically biodegradable resins such as polycaprolactone (PCL), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polyglycolic acid (PGA), polyethylene furanoate (PEF), and polyhydroxyalkanoate (PHA).
• PCL polycaprolactone
• PBS polybutylene succinate
• PBSA polybutylene succinate adipate
• PBAT polybutylene adipate terephthalate
• PGA polyglycolic acid
• PEF polyethylene furanoate
• PHA polyhydroxyalkanoate
• a biodegradable resin other than the above polyesters is cellulose acetate (CA).
• thermoplastic resins include thermoplastic resins and thermoplastic elastomers with a suitable processing temperature of 200°C or less.
• thermoplastic resins include polymethyl methacrylate (PMMA), polyvinyl alcohol (PVA), ethylene vinyl acetate copolymer (EVA), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS), and polycarbonate (PC).
• PMMA polymethyl methacrylate
• PVA polyvinyl alcohol
• EVA ethylene vinyl acetate copolymer
• PE polyethylene
• PP polypropylene
• PVC polyvinyl chloride
• PS polystyrene
• ABS acrylonitrile-butadiene-styrene copolymer
• PC polycarbonate
• the general-purpose thermoplastic resin may be a thermoplastic resin having high heat resistance at temperatures exceeding 200° C. (also referred to as a "high heat resistant resin").
• the high heat resistant resin is preferably a thermoplastic resin having a melting point exceeding 200° C.
• the high heat resistant resin include polyamide (PA), polyacetal (POM), fluororesin (e.g., polytetrafluoroethylene (PTFE), perfluoroalkoxy fluororesin (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), etc.), polymethylpentene (PMP), etc.
• the thermoplastic resins may be used alone or in combination of two or more kinds.
• the content of the thermoplastic resin in the resin composition is preferably 1 to 20% by mass, more preferably 1 to 15% by mass, and further preferably 1 to 10% by mass.
• the resin composition of this embodiment may contain additives other than the ⁇ -methyl- ⁇ -valerolactone copolymer and the polylactic acid 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, impact resistance improvers, etc. These may be used alone or in combination of two or more. When the above additives are used, the content of the additives in the resin composition may be appropriately determined depending on the desired physical properties of the resin composition.
• Method of producing resin composition There is no particular limitation on the method for producing the resin composition of this embodiment, and it is sufficient to uniformly mix the ⁇ -methyl- ⁇ -valerolactone copolymer, the polylactic acid 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 polylactic acid polymer.
• the present invention also provides a molded article made of the resin composition.
• the shape of the molded body may be any molded body that can be produced using the resin composition of this embodiment.
• Examples of the molded body include molded bodies of various shapes such as pellets, films, sheets, plates, pipes, tubes, bottles, fibrous bodies, rod-shaped bodies, fine particles, particulate bodies, and foams.
• the method for producing the molded body is not particularly limited, and it can be molded by various molding methods, such as injection molding, blow molding, press molding, extrusion molding, calendar molding, and molding using a 3D printer.
• the present invention provides a modifier for polylactic acid polymers, which comprises the ⁇ -methyl- ⁇ -valerolactone copolymer represented by the above general formula (I) or (II).
• a modifier for polylactic acid polymers which comprises the ⁇ -methyl- ⁇ -valerolactone copolymer represented by the above general formula (I) or (II).
• the use of the ⁇ -methyl- ⁇ -valerolactone copolymer represented by the above general formula (I) or (II) as a modifier for polylactic acid polymers is also a preferred embodiment.
• the resin composition of this embodiment can be used for various purposes.
• the resin composition can be used for the following purposes: Food utensils such as food bags, food caps, food trays, straws, cutlery, food containers, etc.; Closures, cap liners for containers for storing food, beverages, medicines, etc.; Single-layer or multi-layer films and sheets for electronic component packaging materials, pharmaceutical packaging materials, food packaging materials, agricultural materials, civil engineering and construction materials, industrial materials, etc.; Fibers such as woven fabrics and nonwoven fabrics; Solvent-type, hot melt-type, heat-stretching-type and other pressure-sensitive adhesives and adhesives; Coating agents such as aqueous, solution, emulsion, and dispersion types; Filament for 3D printers; developing toner; Support material for hydraulic fracturing and water leakage prevention agent for drilling; Anti-vibration rubber, mats, sheets, cushions, dampers, pads, mount rubber, and other various vibration-proofing and vibration-damping materials; Components for household appliances such
• the obtained ⁇ -methyl- ⁇ -valerolactone copolymer is a compound containing a structure represented by the following formula (1) in which R 3 in the above general formula (I) is an ethylene group (-(CH 2 ) 2 -).
• R 3 in the above general formula (I) is an ethylene group (-(CH 2 ) 2 -).
• * represents a bond.
• the content of block (E) in the ⁇ -methyl- ⁇ -valerolactone copolymer was calculated from the ratio of the sum of the peak intensity (3.6-3.8 ppm) derived from the proton at the y position in formula (1) and the peak intensity (3.6-3.7 ppm) derived from the proton at the z position in formula (1) multiplied by the molecular weight per structural unit derived from ⁇ -methyl
• Content (mass %) of block (E) ((((peak intensity at proton at position y+peak intensity at proton at position z)/4) ⁇ molecular weight per structural unit derived from ethylene glycol 44.03)/((((peak intensity at proton at position y+peak intensity at proton at position z)/4) ⁇ molecular weight per structural unit derived from ethylene glycol 44.03)+((peak intensity at proton at position x/2) ⁇ molecular weight per structural unit derived from ⁇ -methyl- ⁇ -valerolactone 114.12))) ⁇ 100
• the ⁇ -methyl- ⁇ -valerolactone copolymer obtained in Production Example 10 is a compound containing a structure represented by the following formula (2) in which R 3 in the general formula (I) is an n-butylene group (-(CH 2 ) 4 -).
• the ⁇ -methyl- ⁇ -valerolactone copolymer obtained in Comparative Production Example 6 is also a compound containing a structure represented by the following formula (2).
• * represents a bond.
• Content (mass %) of block (E) ((((peak intensity at proton at position v+peak intensity at proton at position w)/4) ⁇ molecular weight per structural unit derived from butylene glycol 72.11)/((((peak intensity at proton at position v+peak intensity at proton at position w)/4) ⁇ molecular weight per structural unit derived from butylene glycol 72.11)+((peak intensity at proton at position u/2) ⁇ molecular weight per structural unit derived from ⁇ -methyl- ⁇ -valerolactone 114.12))) ⁇ 100
• m and n were calculated from the 1 H-NMR spectrum measured when calculating the content ratio of the block (E).
• m was calculated by dividing the number of protons at the z position in formula (1) (3.6-3.7 ppm) by the number of protons at the y position in formula (1) (3.7-3.8 ppm), and then adding 1 to the result.
• n was calculated by multiplying the value obtained by subtracting the content ratio of the block (E) obtained from 100 by m and the molecular weight of the block (E), and dividing the result by the molecular weight per structural unit derived from ⁇ -methyl- ⁇ -valerolactone.
• y position and “z position” mean “y position” and "z position” in the formula (1).
• m ((number of protons at z position/4)/(number of protons at y position/2)) + 1
• n (m x molecular weight per structural unit derived from ethylene glycol 44.03 x (100 - content ratio of block (E)) / 100) / molecular weight per structural unit derived from ⁇ -methyl- ⁇ -valerolactone 114.12
• m and n were calculated from the 1 H-NMR spectrum measured when calculating the content ratio of the block (E).
• m was calculated by dividing the number of protons at the w position in formula (2) (3.3-3.5 ppm) by the number of protons at the v position in formula (2) (3.5-3.6 ppm) and adding 1 to the result.
• n was calculated by multiplying the value obtained by subtracting the content ratio of the block (E) obtained from 100 by m and the molecular weight of the block (E), and dividing the result by the molecular weight per structural unit derived from ⁇ -methyl- ⁇ -valerolactone. Specifically, it was calculated by the following formula.
• n ((number of protons at t position)/(number of protons at s position)) + 1
• Mn and Mw were determined according to the following measurement.
• a tetrahydrofuran (THF) solution was used as the eluent. 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.
• THF tetrahydrofuran
• the measurement conditions were as follows: (Measurement conditions) GPC device: 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. Eluent: tetrahydrofuran Flow rate: 0.9 mL/min Sample injection volume: 30 ⁇ L Column temperature: 40°C Standard polystyrene: PSt Oligomer Kit (molecular weight 589 to 98,900) manufactured by Tosoh Corporation was used and approximated by a third order equation. Detector: RI detector Mw/Mn was calculated from the obtained Mn and Mw.
• 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)
• the viscosity of the polymers obtained in the Production Examples and Comparative Production Examples was measured in accordance with JIS K 7117-2: 1999. Specifically, the viscosity (unit: mPa s) of the polymers obtained in the Production Examples and Comparative Production Examples was measured at the measurement temperatures shown in Table 2 using an E-type viscometer ("TVE-25 type viscometer” manufactured by Toki Sangyo Co., Ltd.).
• the surface condition of the obtained test piece when stored at 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 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.
• CH 3 -PEG200 Tetraethylene monomethyl ether, manufactured by Tokyo Chemical Industry Co., Ltd., product name "Tetraethylene monomethyl ether” (weight average molecular weight: 208.25)
• CH 3 -PEG550 polyethylene glycol monomethyl ether, manufactured by Tokyo Chemical Industry Co., Ltd., product name "Polyethylene Glycol Monomethyl Ether 550” (weight average molecular weight (median value of catalog value): 550, weight average molecular weight (catalog value): 525 to 575))
• CH 3 -PEG1,000 polyethylene glycol monomethyl ether, manufactured by Tokyo Chemical Industry Co., Ltd., product name "Polyethylene Glycol Monomethyl Ether 1,000” (weight average molecular weight (catalog value median): 1,000, weight average molecular weight (catalog value) 950 to 1,050)
• CH 3 -PEG 2,000 polyethylene glycol monomethyl ether, manufactured by Tokyo Chemical Industry Co., Ltd., product name "Polyethylene
• Polylactic acid polymer 1 Natureworks, trade name "INGEO 2500HP” (weight average molecular weight: 200,000, melting point: 177°C, copolymer of L-lactic acid and D-lactic acid, content of structural units derived from L-lactic acid: 99% by mass)
• n-Butyllithium FUJIFILM Wako Pure Chemical Industries, Ltd., product name "1.6 mol/L n-butyllithium hexane solution”
• Acetic anhydride Fujifilm Wako Pure Chemical Industries, Ltd. 4-Dimethylaminopyridine: Tokyo Chemical Industry Co., Ltd. Acrylic anhydride: Tokyo Chemical Industry Co., Ltd.
• Ethylene glycol Tokyo Chemical Industry Co., Ltd.
• Toluene Kishida Chemical Co., Ltd. (special grade)
• Water Ion-exchanged water (water obtained by ion-exchanging tap water using the "Autostill WA500 pure water production device" (manufactured by Yamato Scientific Co., Ltd.).
• the reaction solution was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 304 g of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone copolymer (hereinafter sometimes referred to as "PMVL-1") were measured as described above. The results are shown in Table 1.
• the obtained PMVL-1 is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• PMVL-2 The physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone copolymer (hereinafter sometimes referred to as "PMVL-2") were measured as described above. The results are shown in Table 1.
• the obtained PMVL-2 is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• PMVL-3 The physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone copolymer (hereinafter sometimes referred to as "PMVL-3") were measured as described above. The results are shown in Table 1.
• the obtained PMVL-3 is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• PMVL-4 ⁇ -methyl- ⁇ -valerolactone copolymer
• Table 1 The physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone copolymer (hereinafter sometimes referred to as "PMVL-4") were measured as described above. The results are shown in Table 1.
• the obtained PMVL-4 is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• PMVL-5 ⁇ -methyl- ⁇ -valerolactone copolymer
• Table 1 The physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone copolymer (hereinafter sometimes referred to as "PMVL-5") were measured as described above. The results are shown in Table 1.
• the obtained PMVL-5 is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• the reaction solution was extracted with toluene and water, and the volatile components were distilled off using a vacuum dryer (EYELA Tokyo Rikakikai Co., Ltd., "VACUUM OVEN VOS-450SD”) to obtain 202 g of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone copolymer (hereinafter sometimes referred to as "PMVL-6") were measured as described above. The results are shown in Table 1.
• the obtained PMVL-6 is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• PMVL-7 ⁇ -methyl- ⁇ -valerolactone copolymer
• PMVL-8 The physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone copolymer (hereinafter sometimes referred to as "PMVL-8") were measured as described above. The results are shown in Table 1.
• the obtained PMVL-8 is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• the reaction solution was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator in the same manner as in Production Example 1, to obtain 210 g (0.09 mmol) of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone copolymer (hereinafter sometimes referred to as "PMVL-9”) were measured as described above. The results are shown in Table 1.
• the obtained PMVL-9 is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• the reaction solution was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator in the same manner as in Production Example 1, to obtain 178 g (0.07 mmol) of a ⁇ -methyl- ⁇ -valerolactone copolymer.
• the physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone copolymer (hereinafter sometimes referred to as "PMVL-10") were measured as described above. The results are shown in Table 1.
• the obtained PMVL-10 is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• PMVL-11 The physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone copolymer (hereinafter sometimes referred to as "PMVL-11") were measured as described above. The results are shown in Table 1.
• the obtained PMVL-11 is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• PMVL-12 ⁇ -methyl- ⁇ -valerolactone copolymer
• Table 1 The physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone copolymer (hereinafter sometimes referred to as "PMVL-12") were measured as described above. The results are shown in Table 1.
• the obtained PMVL-12 is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• the reaction solution containing the obtained ⁇ -methyl- ⁇ -valerolactone-based copolymer was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator in the same manner as in Production Example 1, thereby obtaining 190 g of a ⁇ -methyl- ⁇ -valerolactone-based copolymer.
• the physical properties of the resulting ⁇ -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 following structural formula (A), where n is as shown in Table 1.
• PMVL'-2 The physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer (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-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• the reaction solution containing the obtained ⁇ -methyl- ⁇ -valerolactone polymer was extracted with toluene and water, and the volatile components were distilled off using a thin film evaporator in the same manner as in Production Example 1, to obtain 159 g of a ⁇ -methyl- ⁇ -valerolactone polymer.
• the physical properties of the resulting ⁇ -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-mentioned structural formula (A), and n is as shown in Table 1.
• the reaction solution containing the obtained polymer was extracted with toluene and water, and the volatile components were distilled off using a thin film evaporator in the same manner as in Production Example 1, to obtain 532 g of a ⁇ -methyl- ⁇ -valerolactone polymer.
• the physical properties of the resulting ⁇ -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-mentioned structural formula (A), and n is as shown in Table 1.
• the reaction solution was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator in the same manner as in Production Example 1, to obtain 158 g of a ⁇ -methyl- ⁇ -valerolactone polymer.
• the physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone polymer (hereinafter sometimes referred to as "PMVL'-5") were measured as described above. The results are shown in Table 1.
• the resulting PMVL'-5 is represented by the above-mentioned general formula (I), and R 1 , R 2 , R 3 , m, n and A are as shown in Table 1.
• PMVL'-6 The physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer (hereinafter sometimes referred to as "PMVL'-6") were measured as described above. The results are shown in Table 1.
• the resulting PMVL'-6 is represented by the following structural formula (B), where n and m are as shown in Table 1.
• PMVL'-7 The physical properties of the resulting ⁇ -methyl- ⁇ -valerolactone copolymer (hereinafter sometimes referred to as "PMVL'-7") were measured as described above. The results are shown in Table 1.
• the resulting PMVL'-7 is represented by the following structural formula (C), where n and m are as shown in Table 1.
• Example 1 100 parts by mass of polylactic acid polymer 1 and the above ⁇ -methyl- ⁇ -valerolactone copolymer (PMVL-1) in the blending amounts shown in Table 2 were charged into a twin-screw kneader (Technovel's "ULT nano 50") and extruded into a strand shape at a cylinder temperature of 200°C, a screw rotation speed of 50 rpm, and a residence time of 1 to 10 minutes. The resulting strand was cut into pellets to obtain a resin composition. The obtained resin composition was evaluated as described above. The results are shown in Table 2.
• Example 3 and Comparative Example 2 when the resin composition obtained in the Example and the resin composition obtained in the Comparative Example, which have the same weight average molecular weight, are compared (for example, Example 3 and Comparative Example 2), it is found that the resin composition having the ⁇ -methyl- ⁇ -valerolactone copolymer represented by the general formula (I) or (II) of this embodiment has good plasticity and improved elongation. Furthermore, a comparison of Examples 1 to 15 and Comparative Examples 1 to 10 shows that the resin composition containing the ⁇ -methyl- ⁇ -valerolactone copolymer represented by the general formula (I) or (II) of this embodiment has an improved crystallization rate and suppresses bleed-out.

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