Resin composition, molded body, modifier, and use as modifier

Abstract

A resin composition contains a β-methyl-δ-valerolactone copolymer represented by general formulas (I) or (II) and a polylactic acid polymer.

Description

Resin composition, molded article, modifier, and use as modifier

[0001] The present invention relates to a resin composition containing a β-methyl-δ-valerolactone copolymer and a polylactic acid polymer, a molded article made from the resin composition, a modifier for polylactic acid polymers made from the β-methyl-δ-valerolactone copolymer, and use of the modifier.

[0002] δ-valerolactone polymers synthesized from δ-valerolactone are known as biodegradable materials. Biodegradable materials are used in a wide range of fields due to increasing environmental awareness. Therefore, improvements to δ-valerolactone polymers have been made to impart properties suited to the applications of biodegradable materials.

[0003] For example, Patent Document 1 discloses a technology relating to a (meth)acrylic acid ester obtained by reacting (meth)acrylic acid with a reaction product of β-methyl-δ-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, and the glass transition point is low, and it 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.

[0004] Japanese Patent Application Publication No. 1-258644

[0005] As mentioned above, Patent Document 1 describes that coatings obtained using the above (meth)acrylic acid esters are flexible and have low glass transition temperatures. However, when the above (meth)acrylic acid esters are mixed with thermoplastic resins to form resin compositions, the resulting resin compositions have low plasticity and insufficient 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 from the resin composition. Another object of the present invention is to provide a modifier for polylactic acid-based polymers that can impart good plasticity and elongation, and its use as the modifier.

[0006] As a result of intensive research to solve the above problems, the present inventors have conceived the following invention and found that the above problems can be solved.

[0007] [1] A resin composition containing a β-methyl-δ-valerolactone copolymer represented by the following general formula (I) or (II) and a polylactic acid polymer: [In general formulas (I) and (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. 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). In the following formula (X), the bond represented by *1 is bonded to an oxygen atom. In the following formula (Y), the bond represented 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. In the following formula (Z), 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. R ３ 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, and p is 2 to 1,000. n, m, A, p, R １ , R ２ and R ３When a plurality of groups are present, they may be the same or different from one another.] [2] The resin composition according to [1] above, containing 0.1 parts by mass or more and 100 parts by mass or less of the β-methyl-δ-valerolactone copolymer per 100 parts by mass of the polylactic acid polymer. [3] The resin composition according to [1] or [2] above, wherein the number average molecular weight of the β-methyl-δ-valerolactone copolymer is 500 or more and 200,000 or less. [4] The resin composition according to any one of [1] to [3] above, wherein the polylactic acid polymer is a homopolymer of L-lactic acid, a homopolymer of D-lactic acid, or a copolymer of L-lactic acid and D-lactic acid. [5] A molded article made from the resin composition according to any one of [1] to [4] above. [6] A modifier for polylactic acid polymers, comprising a β-methyl-δ-valerolactone copolymer represented by the following general formula (I) or (II): [In general formulas (I) and (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. 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). In the following formula (X), the bond represented by *1 is bonded to an oxygen atom. In the following formula (Y), the bond represented 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. In the following formula (Z), 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. R ３represents 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, and p is 2 to 1,000. n, m, A, p, R １ , R ２ and R ３ When a plurality of groups are present, they may be the same or different from each other.] [7] Use of a β-methyl-δ-valerolactone copolymer represented by the following general formula (I) or (II) as a modifier for a polylactic acid polymer: [In general formulas (I) and (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. 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). In the following formula (X), the bond represented by *1 is bonded to an oxygen atom. In the following formula (Y), the bond represented 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. In the following formula (Z), 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. R ３represents 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, and p is 2 to 1,000. n, m, A, p, R １ , R ２ and R ３ When there are a plurality of groups, they may be the same or different from each other.

[0008] According to 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. Also, according to the present invention, it is possible to provide a modifier for polylactic acid polymers that can impart good plasticity and elongation, and use of the modifier as the modifier.

[0009] The following is a description based on one example of an embodiment of the present invention. However, the embodiment shown below is an example for embodying the technical idea of ​​the present invention, and the present invention is not limited to the following description. Furthermore, although preferred embodiments are shown in this specification, a combination of two or more of the individual preferred embodiments is also a preferred embodiment. For matters shown as numerical ranges, when there are several numerical ranges, the lower limit and upper limit can be selectively combined to form a preferred embodiment. Furthermore, in this specification, when a numerical range is described as "XX to YY," it means "XX or more and YY or less."

[0010] <Resin Composition> The resin composition of this embodiment contains a β-methyl-δ-valerolactone copolymer represented by general formula (I) or (II) and a polylactic acid polymer. By containing the β-methyl-δ-valerolactone copolymer represented by general formula (I) or (II) and a polylactic acid polymer, the resin composition has good plasticity and improved elongation.

[0011] [β-Methyl-δ-valerolactone Copolymer] The β-methyl-δ-valerolactone copolymer of this embodiment is represented by the following general formula (I) or (II).

[0012]

[0013] <R１ In general formulas (I) and (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.

[0014] Examples of the linear alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group.

[0015] From the viewpoint of ease of handling, 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. Specifically, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-octyl group, etc. are preferred.

[0016] Examples of the branched alkyl group having 3 to 20 carbon atoms include an isopropyl group, a 1-methylpropyl group, a 2-methylpropyl group, a t-butyl group, a 1,1-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1,2-dimethylpropyl group, a 1-ethylpropyl group, a 2-ethylpropyl group, a 1,1-diethylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1,1-dimethylbutyl group, a 2,2-dimethylbutyl group, a 3,3-dimethylbutyl group, a 1,3,3-trimethylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 3, 3-dimethylbutyl group, 1-propylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 4,4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 4-ethylpentyl group, 1-propylpentyl group, 2-propylpentyl group, 1-butylpentyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 5,5-dimethylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group ethyl group, 3-ethylhexyl group, 4-ethylhexyl group, 1-propylhexyl group, 2-propylhexyl group, 3-propylhexyl group, 1-butylhexyl group, 2-butylhexyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 6-methylheptyl group, 6,6-dimethylheptyl group, 1-ethylheptyl group, 2-ethylheptyl group, 3-ethylheptyl group, 4-ethylheptyl group, 5-ethylheptyl group, 1-propylheptyl group, 2-propylheptyl group, 3-propyl dimethyloctyl group, 1-ethyloctyl group, 2-ethyloctyl group, 3-ethyloctyl group, 4-ethyloctyl group, 5-methyloctyl group, 6-methyloctyl group, 7-methyloctyl group, 7,7-dimethyloctyl group, 1-ethyloctyl group, 2-ethyloctyl group, 3-ethyloctyl group, 4-ethyloctyl group, 5-ethyloctyl group, 6-ethyloctyl group, 1-methylnonyl group, 2-methylnonyl group, 3-methylnonyl group, 4-methylnonyl group, 5-methylnonyl group, 6-methylnonyl group, 7-methylnonyl group, 8-methylnonyl group, 3,5,5-trimethylhexyl group, etc.

[0017] From the viewpoint of ease of handling, 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 8 carbon atoms. Specifically, an isopropyl group, a 1-methylbutyl group, a 3-methylbutyl group, a 2,2-dimethylpropyl group, a 2-ethylhexyl group, etc. are preferred.

[0018] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a 2-methylphenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group, and a 2-naphthyl group. 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. Examples of the arylalkyl group having 7 to 14 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. 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.

[0019] From the viewpoint of ease of handling, R １ is preferably a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, more preferably a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms, and even more preferably a linear alkyl group having 1 to 3 carbon atoms.

[0020] <R ２ In general formulas (I) and (II), R ２represents 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).

[0021]

[0022] R ２ The "linear alkyl group having 1 to 20 carbon atoms", "branched alkyl group having 3 to 20 carbon atoms", "aryl group having 6 to 14 carbon atoms", and "arylalkyl group having 7 to 14 carbon atoms" shown by １ Examples of such groups include the groups exemplified as "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," and "an arylalkyl group having 7 to 14 carbon atoms" shown in

[0023] Formula (X): In formula (X), the bond indicated by *1 is bonded to an oxygen atom. The oxygen atom is the same as R in the general formula (I) above. ２ R in the group represented by formula (X) is an oxygen atom bonded to １ is the above-mentioned R １ In addition, n in the group represented by formula (X) has the same meaning as n described below.

[0024] Formula (Y) In formula (Y), the bond indicated by *2 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 a linear alkyl group having 1 to 20 carbon atoms or the terminal carbon atom of a branched alkyl group having 3 to 20 carbon atoms. 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).

[0025] R in the group represented by formula (Y) １ is the above-mentioned R １ In addition, n and A in the group represented by formula (Y) have the same meanings as n and A described below. ２ In the "group in which one hydrogen atom bonded to the terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by formula (Y)", the linear alkyl group having 1 to 20 carbon atoms is the same as the above-mentioned R １ From the viewpoint of ease of handling, 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. ２ In the "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)", the branched alkyl group having 3 to 20 carbon atoms is the same as the above-mentioned R １From the viewpoint of ease of handling, 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.

[0026] 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)".

[0027] R in the group represented by formula (Z) １ is the above-mentioned R １ In addition, R in the group represented by formula (Z) ３ , n, m and A are R ３ , n, m and A. R ２ In the "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 formula (Z)", the linear alkyl group having 1 to 20 carbon atoms is the same as the above-mentioned R １ From the viewpoint of ease of handling, 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. ２In the "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 formula (Z)", the branched alkyl group having 3 to 20 carbon atoms is １ From the viewpoint of ease of handling, 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.

[0028] In general formula (I), R ２ 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 The alkyl group is preferably a linear alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 3 to 5 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 5 carbon atoms in which one hydrogen atom bonded to a terminal carbon atom is substituted with a group represented by the above formula (Y), or a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 3 to 5 carbon atoms in which one hydrogen atom bonded to at least one carbon atom is represented by the above formula (Z), and more preferably a linear alkyl group having 1 to 3 carbon atoms.

[0029] In general formula (II), R ２ is preferably a group represented by the above formula (X).

[0030] <R ３ In general formulas (I) and (II), R ３represents a linear alkylene group having 2 to 20 carbon atoms or a branched alkylene group having 3 to 20 carbon atoms.

[0031] Examples of the linear alkylene group having 2 to 20 carbon atoms include an ethylene group (-(CH ２ ) ２ -), n-propylene group (-(CH ２ ) ３ -), n-butylene group (-(CH ２ ) ４ -), n-pentylene group (-(CH ２ ) ５ -) etc.

[0032] Examples of the branched alkylene group having 3 to 20 carbon atoms include an isopropylene group (—CH ２ -CH(CH ３ )-), 1-methylpropylene group (—CH ２ -CH ２ -CH(CH ３ )-), 2-methylpropylene group (—CH ２ -CH(CH ３ )-CH ２ -), dimethylethylene group (-CH ２ -C(CH ３ ) ２ -), ethylethylene group (-CH ２ -CH(CH ２ CH ３ )-), 2-methylbutylene group (—CH ２ -CH ２ -CH(CH ３ )-CH ２ -) etc.

[0033] From the viewpoint of ease of handling, 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.

[0034] In the general formulae (I) and (II), A represents an oxygen atom, a sulfur atom, or an imino group (—NH—). From the viewpoint of excellent biodegradability, A is preferably an oxygen atom.

[0035] <n, m, p> In general formulas (I) and (II), n, m, and p represent the average number of repeating units. n is 2 to 1,000. In one embodiment of the present invention, n is preferably 2 to 800, more preferably 4 to 500, and even more preferably 4 to 200. In another embodiment of the present invention, 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. In one embodiment of the present invention, m is preferably 2 to 400, more preferably 4 to 200, and even more preferably 4 to 50. In another embodiment of the present invention, 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, and 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.

[0036] m and n are the β-methyl-δ-valerolactone copolymers １ Specifically, when A is an oxygen atom, the β-methyl-δ-valerolactone copolymer can be calculated from the H-NMR spectrum. １ In a spectrum obtained by H-NMR measurement, m and n can be calculated from the peak intensity of the hydrogen atom bonded to the carbon atom adjacent to the oxygen atom in block (E) described below and the peak intensity of the hydrogen atom bonded to the carbon atom adjacent to the ether oxygen atom bonded to the β-methyl-δ-valerolactone unit. A detailed method for calculating m and n can follow the method described in the Examples. The "β-methyl-δ-valerolactone unit" refers to a structural unit derived from β-methyl-δ-valerolactone, and refers to a unit that is repeated with an average repeat number of n.

[0037] In the general formulas (I) and (II), n, m, A, p, R １ , R ２ , and R ３ When a plurality of are present, they may be the same or different from each other.

[0038] <Examples of general formula (I)> In general formula (I), R ２ However, examples of structures include a group represented by the above 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 the group represented by the above 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 the group represented by the above 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 the group represented by the above formula (Z). Note that general formula (I) is not limited to these examples.

[0039] Example 1 In general formula (I), R ２ represents a group represented by the above formula (X), it is represented by the following general formula (Ia).

[0040]

[0041] Example 2 In general formula (I), R ２ 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 formula (Y) above, the group is represented by the following general formula (I-b): In general formula (I-b), R represents a linear alkylene group having 1 to 20 carbon atoms.

[0042]

[0043] Example 3 In general formula (I), R ２represents 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) above, and a group in which one hydrogen atom bonded to all terminal carbon atoms of a 2-methylpropyl group is substituted with a group represented by formula (Y) above, the group is represented by the following general formula (I-c):

[0044]

[0045] Example 4 In general formula (I), 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 group is represented by the following general formula (I-d):

[0046]

[0047] Example 5 In general formula (I), 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 group is represented by the following general formula (I-e):

[0048]

[0049] <Examples of General Formula (II)> In general formula (II), R ２ The following are examples of structures showing the group represented by the formula (X). Note that the general formula (II) is not limited to these examples. Example 6 In the general formula (II), R ２ represents a group represented by the above formula (X), it is represented by the following general formula (II-a).

[0050]

[0051] <Block (E) Content> In general formula (I), the content of block (E) represented by the following formula is preferably 5 to 95% by mass. When the content of block (E) is within the above range, the β-methyl-δ-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. Furthermore, by having block (E) in a content within the above range, the β-methyl-δ-valerolactone copolymer tends to have improved compatibility with thermoplastic resins, making it easier to suppress bleed-out. In one aspect of the present invention, the content (% by mass) of block (E) represented by the following formula in general formula (I) is more preferably 5 to 50% by mass, and even more preferably 10 to 40% by mass. In another embodiment of the present invention, the content (% by mass) of the block (E) represented by the following formula in general formula (I) is more preferably 5 to 80% by mass, even more preferably 10 to 80% by mass, and still more preferably 10 to 50% by mass:

[0052]

[0053] The content ratio of the block (E) is determined from the content ratio of the molecular weight of the block (E) to the molecular weight of the β-methyl-δ-valerolactone copolymer. １ It can be calculated from the molecular weight calculated by H-NMR measurement. １ In a spectrum obtained by H-NMR measurement, the content of block (E) can be calculated from the peak intensity of the hydrogen atom bonded to the carbon atom adjacent to the oxygen atom in block (E), the peak intensity of the hydrogen atom bonded to the carbon atom adjacent to the oxygen atom of the ether bonded to the β-methyl-δ-valerolactone unit, and the peak intensity of the hydrogen atom bonded to the carbon atom at the α-position of the ester in the β-methyl-δ-valerolactone unit. The detailed method for measuring the content of block (E) can be according to the method described in the Examples.

[0054] <Weight-Average Molecular Weight of Block (E)> In the β-methyl-δ-valerolactone copolymer represented by general formula (I), the weight-average molecular weight of block (E) represented by the following formula is preferably 100 to 40,000, more preferably 100 to 10,000, even more preferably 100 to 5,000, and even more preferably 500 to 5,000, from the viewpoint of shortening the crystallization time. The weight-average molecular weight of block (E) can be calculated using the following formula: Weight-average molecular weight of block (E) in the β-methyl-δ-valerolactone copolymer represented by general formula (I) = Weight-average molecular weight Mw of β-methyl-δ-valerolactone copolymer × Content (% by mass) of block (E) in general formula (I) / 100. The weight-average molecular weight Mw of the β-methyl-δ-valerolactone copolymer is the weight-average molecular weight in terms of standard polystyrene determined by gel permeation chromatography (GPC). Details of the measurement method can be determined according to the method described in the Examples.

[0055] <Block (F) Content> In general formula (II), the content of block (F) represented by the following formula is preferably 5 to 95 mass%. When the content of block (F) is within this range, the β-methyl-δ-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. Furthermore, by having block (F) in a content within this range, the β-methyl-δ-valerolactone copolymer tends to have improved compatibility with thermoplastic resins, making it easier to suppress bleed-out.

[0056]

[0057] The content (% by mass) of block (F) is the molecular weight of block (F) relative to the molecular weight of the β-methyl-δ-valerolactone copolymer. The content of block (F) can be measured in the same manner as for block (E).

[0058] <Number Average Molecular Weight (Mn)> The number average molecular weight of the β-methyl-δ-valerolactone copolymer is preferably 500 to 200,000, more preferably 500 to 110,000, even more preferably 1,000 to 66,000, even more preferably 1,000 to 33,000, even more preferably 1,000 to 10,000, and even more preferably 1,000 to 6,000. When the number average molecular weight is within the above range, the viscosity of the β-methyl-δ-valerolactone copolymer does not become too low, resulting in good handling during molding and improved productivity. The number average molecular weight of the β-methyl-δ-valerolactone copolymer is the number average molecular weight calculated in terms of standard polystyrene as determined by gel permeation chromatography (GPC). Detailed measurement methods can be performed according to the methods described in the Examples.

[0059] <Weight Average Molecular Weight (Mw)> The weight average molecular weight of the β-methyl-δ-valerolactone copolymer is preferably 720 to 400,000, more preferably 720 to 220,000, even more preferably 1,600 to 132,000, even more preferably 1,600 to 66,000, even more preferably 1,600 to 20,000, and even more preferably 1,600 to 12,000. When the weight average molecular weight is within the above range, the viscosity of the β-methyl-δ-valerolactone copolymer does not become too low, resulting in good handling during molding and improved productivity. The weight average molecular weight of the β-methyl-δ-valerolactone copolymer is the weight average molecular weight calculated in terms of standard polystyrene by gel permeation chromatography (GPC). Detailed measurement methods can be performed according to the methods described in the Examples.

[0060] <Molecular Weight Distribution (Mw / Mn)> The molecular weight distribution (Mw / Mn) of the β-methyl-δ-valerolactone copolymer is preferably 1.0 to 3.0, more preferably 1.1 to 2.0, and even more preferably 1.2 to 1.8. The molecular weight distribution of the β-methyl-δ-valerolactone copolymer is a value determined from the number average molecular weight and weight average molecular weight in terms of standard polystyrene determined by gel permeation chromatography (GPC). The detailed methods for measuring the number average molecular weight and weight average molecular weight can be those described in the Examples.

[0061] <Viscosity> The preferred viscosity range varies depending on the application of the β-methyl-δ-valerolactone copolymer, but from the viewpoints of, for example, handleability, substrate retention, strength, adhesiveness, and other functions, and from the viewpoint of exhibiting a more excellent modifying effect on thermoplastic resins, in one embodiment of the present invention, 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, measured at a temperature of 30° C. From the same viewpoint, in another embodiment of the present invention, 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, measured at a temperature of 30° C. From the same viewpoint, in yet another embodiment of the present invention, the viscosity at a measurement temperature of 60°C is preferably 500 to 500,000 mPa·s, more preferably 700 to 300,000 mPa·s, even more preferably 900 to 200,000 mPa·s, and even more preferably 900 to 150,000 mPa·s. From the same viewpoint, in yet another embodiment of the present invention, the viscosity at a measurement temperature of 60°C 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. The "viscosity" described herein refers to the viscosity of a β-methyl-δ-valerolactone copolymer measured using an E-type viscometer. Detailed measurement methods can be performed according to the methods described in the Examples.

[0062] <Production Method> From the viewpoint of productivity and simplicity, or when producing a high-molecular-weight polymer, a preferred method for producing the β-methyl-δ-valerolactone copolymer includes a step of adding a terminal-modifying agent to a reaction solution obtained by reacting β-methyl-δ-valerolactone, an initiator (described below), and a polymerization catalyst under basic conditions to carry out a terminal modification reaction (hereinafter also referred to as the "reaction step"). In this production method, the terminal-modifying agent is added directly to the reaction solution obtained by reacting β-methyl-δ-valerolactone, the initiator, and the polymerization catalyst. That is, after ring-opening polymerization of β-methyl-δ-valerolactone, the terminal-modifying agent can be added to the reactor in which the ring-opening polymerization was carried out without first removing the ring-opened polymer, thereby carrying out terminal modification of the ring-opened polymer. Because the reaction step involves carrying out the ring-opening polymerization reaction and the terminal-modifying reaction in one pot, the production method can be considered a simplified process. It should be noted that the β-methyl-δ-valerolactone copolymer is not limited to the production method described above.

[0063] Initiator An example of the initiator is a polyether having at least one hydroxyl group. The polyether 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. In addition to the above, an example of the initiator is a polyether having at least one amino group. Examples of polyethers having at least one amino group include triethylene glycol amine, diethylene glycol bis(3-aminopropyl) ether, poly(ethylene glycol) diamine, and the like. In addition to the above, an example of the initiator is a polyether having at least one thiol group. Examples of polyethers having at least one thiol group include poly(ethylene glycol) dithiol, and the like.

[0064] β-Methyl-δ-valerolactone can be produced by known methods. For example, it can be produced by known methods using 2-hydroxy-4-methyltetrahydropyran or the like as a raw material (see, for example, Japanese Patent Publication No. 6-53691). Furthermore, commercially available β-methyl-δ-valerolactone can be used, and β-methyl-δ-valerolactone can be used regardless of whether it is derived from petrochemicals or bio-sources. The amount of β-methyl-δ-valerolactone used is not particularly limited as long as the effects of the present invention can be obtained, but is typically 5 to 1,500 molar equivalents relative to the initiator.

[0065] Polymerization Catalyst: A suitable method for producing the β-methyl-δ-valerolactone copolymer involves reacting β-methyl-δ-valerolactone, the initiator, and a polymerization catalyst under basic conditions. The polymerization catalyst preferably exhibits catalytic activity under basic conditions. Examples of polymerization catalysts exhibiting catalytic activity under basic conditions include base catalysts. Known base catalysts can be used as the base catalyst. Examples of the base catalyst include metal catalysts such as alkali metals and alkali metal compounds, as well as organic base compounds. Examples of alkali metal compounds include organic alkali metal compounds, alkali metal hydroxide compounds, and alkali metal hydrides. Of these, organic lithium compounds such as butyllithium are preferred. Examples of organic base compounds include amine compounds having an amidine or guanidine skeleton. Metal catalysts such as organomagnesium compounds and organozinc compounds can also be used as base catalysts. One polymerization catalyst may be used alone, or two or more may be used in combination. 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.

[0066] Terminal Modifier Examples of 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. For example, 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. In the case of the above-mentioned "branched alkyl groups," the number of carbon atoms is 3 to 20. The amount of terminal modifier used is not particularly limited as long as the effects of the present invention can be obtained, but is typically 1 to 20 molar equivalents relative to the initiator.

[0067] Co-catalyst and Solvent In the method for producing a β-methyl-δ-valerolactone copolymer of this embodiment, a co-catalyst and a solvent may be used as needed. Examples of 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 is usually 0.001 to 10 molar equivalents relative to the initiator, for example.

[0068] Examples of the solvent include aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, and n-pentane; and aromatic hydrocarbons such as benzene, toluene, and xylene.

[0069] Reaction Conditions In the ring-opening polymerization reaction and terminal modification reaction, the reaction temperature is usually about 20 to 100° C., and the reaction time is usually about 1 minute to 24 hours. In the method for producing a β-methyl-δ-valerolactone copolymer of this embodiment, a post-treatment step may be carried out as necessary.

[0070] As the post-treatment step, a suitable method can be adopted from known methods. For example, the β-methyl-δ-valerolactone copolymer obtained by the above-mentioned terminal modification 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 or removal of low-boiling compounds.

[0071] [Polylactic Acid Polymer] In this embodiment, a polylactic acid polymer is a polymer having at least structural units derived from lactic acid. Examples of polylactic acid polymers used in this embodiment include at least one selected from the group consisting of homopolymers of L-lactic acid, homopolymers of D-lactic acid, copolymers of L-lactic acid and D-lactic acid, and polymers of lactide, a cyclic dimer of lactic acid. Furthermore, the polylactic acid polymer may be a copolymer of lactic acid and at least one selected from the group consisting of aliphatic hydroxycarboxylic acids other than lactic acid, aliphatic dicarboxylic acids, aliphatic diols, and aromatic dicarboxylic acids. The copolymer preferably contains structural units derived from lactic acid in an amount of 70 mol % or more, more preferably 90 mol % or more. Among these, the polylactic acid polymer is preferably a homopolymer of L-lactic acid, a homopolymer of D-lactic acid, or a copolymer of L-lactic acid and D-lactic acid, with a homopolymer of L-lactic acid being more preferred. When the polylactic acid polymer is a copolymer of L-lactic acid and D-lactic acid, 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. One type of polylactic acid polymer may be used alone, or two or more types may be used in combination.

[0072] Commercially available polylactic acid polymers may be used, such as the "Ingeo series" manufactured by NatureWorks Inc., the "Luminy series" manufactured by TOTALENERGIES CORBION, the "Revode" series manufactured by Zhejiang Hisun Biomaterials Co., Ltd., and the "SUPLA" series manufactured by SUPLA Material Technology Co., Ltd.

[0073] 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 β-methyl-δ-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 in terms of standard polystyrene by gel permeation chromatography (GPC). When using a commercially available product, the catalog value may be used.

[0074] [Content Ratio] The resin composition of this embodiment preferably contains 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, of the β-methyl-δ-valerolactone copolymer per 100 parts by mass of the polylactic acid polymer. The above content ratios can result in a resin composition with better elongation. Furthermore, from the viewpoint of more significantly exhibiting good elongation, the resin composition of this embodiment can also contain 2 parts by mass or more and 15 parts by mass or less of the β-methyl-δ-valerolactone copolymer per 100 parts by mass of the polylactic acid polymer.

[0075] In one more preferred embodiment, the resin composition contains 2 to 100 parts by mass of a β-methyl-δ-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 the polylactic acid polymer, and the number average molecular weight of the β-methyl-δ-valerolactone copolymer is 500 to 200,000 (more preferably 2,000 to 70,000). This resin composition exhibits more pronounced elongation.

[0076] Furthermore, the total content of the β-methyl-δ-valerolactone copolymer and the 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, still more preferably 95% by mass or more, and even more preferably 98% by mass or more. With this content, the effects of the present invention are more significantly exhibited.

[0077] The content of block (E) in the β-methyl-δ-valerolactone copolymer represented by general formula (I) in the resin composition of this embodiment (content of block (E) in the resin composition) is preferably 0.3 to 10.0 mass%, more preferably 0.3 to 8.0 mass%, and even more preferably 0.5 to 7.0 mass%. The content of block (E) in the resin composition can be calculated using the following formula: content (mass%) of block (E) in resin composition = content (mass%) of block (E) in general formula (I) × content (mass%) of β-methyl-δ-valerolactone copolymer in resin composition / 100

[0078] [Thermoplastic Resin] The resin composition of this embodiment may contain a thermoplastic resin in addition to the β-methyl-δ-valerolactone copolymer and the polylactic acid polymer. Note that the thermoplastic resin refers to a thermoplastic resin other than the β-methyl-δ-valerolactone copolymer and the polylactic acid polymer. Examples of the thermoplastic resin include polyester, biodegradable resins other than polyester, and general-purpose thermoplastic resins. The polyester includes polyester, which is a biodegradable resin.

[0079] <Polyester> Examples of polyesters 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 cyclohexanedimethanol 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, cyclohexanedimethanol, and terephthalic acid (or an ester thereof) (TP 2T / CHT), and copolyester made of ethylene glycol, terephthalic acid, and isophthalic acid (or an ester thereof) (TP 2T / 2I), a copolyester of ethylene glycol, 1,6-hexanediol, and neopentyl glycol with terephthalic acid, isophthalic acid, and adipic acid (TP 2 / 6 / NG / / T / I / 6), a copolyester of ethylene glycol and terephthalic acid with ethylene glycol and adipic acid (TP 2T / 26), a copolyester of neopentyl glycol and terephthalic acid with 1,6-hexanediol and isophthalic acid (TP NGT / 6I), and examples of polyesters that are biodegradable resins include polycaprolactone (PCL), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polyglycolic acid (PGA), polyethylene furanoate (PEF), polyhydroxyalkanoates (PHAs) [e.g., polyhydroxybutyrate (PHB), polyhydroxybutyrate hexanoate (PHBH), polyhydroxybutyrate valerate (PHBV), 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolymer polyester, etc.], and starch polyester (Mater-Bi (registered trademark)). Among these, 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) are preferred.

[0080] Examples of biodegradable resins other than the polyesters include cellulose acetate (CA).

[0081] General-purpose thermoplastic resins include thermoplastic resins and thermoplastic elastomers with a suitable processing temperature of 200°C or less. Examples of the 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). Examples of the thermoplastic elastomers include olefin-based, styrene-based, ester-based, urethane-based, acrylic-based, vinyl chloride-based, amide-based, and fluorine-based thermoplastic elastomers. Specific examples include polyester elastomer (TPC) and thermoplastic polyurethane (TPU).

[0082] Further, examples of the general-purpose thermoplastic resin include thermoplastic resins (also referred to as "high heat-resistant resins") that have high heat resistance at temperatures exceeding 200°C. The high heat-resistant resin is preferably a thermoplastic resin having a melting point exceeding 200°C. Examples of the high heat-resistant resin include polyamide (PA), polyacetal (POM), fluororesins (e.g., polytetrafluoroethylene (PTFE), perfluoroalkoxy fluororesin (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), etc.), polymethylpentene (PMP), etc. The thermoplastic resin may be used alone or in combination of two or more. 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 even more preferably 1 to 10% by mass.

[0083] [Additives] The resin composition of this embodiment may contain additives in addition to the β-methyl-δ-valerolactone copolymer and the polylactic acid polymer. Examples of additives include inorganic fillers, softeners, heat aging inhibitors, antioxidants, hydrolysis resistance inhibitors, light stabilizers, antistatic agents, release agents, flame retardants, foaming agents, pigments, dyes, brighteners, UV absorbers, lubricants, and impact modifiers. These may be used alone or in combination of two or more. When using the above additives, the content of the additives in the resin composition may be determined appropriately depending on the desired physical properties of the resin composition.

[0084] [Method for Producing Resin Composition] The method for producing the resin composition of this embodiment is not particularly limited, and it is sufficient to uniformly mix the β-methyl-δ-valerolactone copolymer, the polylactic acid polymer, and, if necessary, additives. Examples of mixing methods include melt-kneading using a single-screw extruder, a multi-screw extruder, a Banbury mixer, a heated roll, a Brabender, various kneaders, etc., or melt-kneading by feeding each component through a separate inlet. Pre-blending may also be performed before melt-kneading. Examples of pre-blending methods include 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 selected arbitrarily, preferably within the range of 140 to 220°C, taking into account the melting point and decomposition temperature of the polylactic acid polymer.

[0085] <Molded Article> The present invention also provides a molded article made from a 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 molded articles include molded articles in various shapes such as pellets, films, sheets, plates, pipes, tubes, bottles, fibers, rods, fine particles, particles, and foams. The method for producing this molded article is not particularly limited, and it can be molded by various known molding methods, such as injection molding, blow molding, press molding, extrusion molding, calendar molding, and molding using a 3D printer.

[0086] <Applications> By mixing a polylactic acid polymer with a β-methyl-δ-valerolactone copolymer represented by the above general formula (I) to form a resin composition, the plasticity and elongation can be improved. Therefore, the present invention provides a modifier for polylactic acid polymers, comprising the β-methyl-δ-valerolactone copolymer represented by the above general formula (I) or (II). In addition, a preferred embodiment is the use of the β-methyl-δ-valerolactone copolymer represented by the above general formula (I) or (II) as a modifier for polylactic acid polymers.

[0087] The resin composition of this embodiment can be used in various applications. Applications of the resin composition include: food utensils such as food bags, food caps, food trays, straws, cutlery, and food containers; stoppers and cap liners for containers storing food, beverages, medicines, and the like; single-layer or multi-layer films and sheets for electronic component packaging, pharmaceutical packaging, food packaging, agricultural materials, civil engineering and construction materials, industrial materials, and the like; fibers such as woven fabrics and nonwoven fabrics; adhesives and bonding agents such as solvent-based, hot-melt-based, and heat-stretched types; coating agents such as aqueous-based, solution-based, emulsion-based, and dispersion-based types; filaments for 3D printers; developing toners; support materials for hydraulic fracturing and agents for preventing water leakage during excavation; various vibration-isolating and vibration-damping materials such as vibration-isolating rubber, mats, sheets, cushions, dampers, pads, and mounting rubber; components for home appliances such as televisions, stereos, vacuum cleaners, refrigerators, and housings for mobile phones; Automobile interior and exterior parts such as bumper parts, body panels, weather strips, grommets, instrument panel coverings, airbag covers, etc.; various grips such as scissors, screwdrivers, toothbrushes, ski poles, etc.; etc.

[0088] The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to these.

[0089] <Measurement and Evaluation Methods> Various physical properties were measured or evaluated by the following methods.

[0090] [Content of Block (E)] The content (mass%) of block (E) in the β-methyl-δ-valerolactone copolymer was measured by using the obtained β-methyl-δ-valerolactone copolymer (after hydroxyl group blocking) as a sample. １ The specific measurement method is as follows: Apparatus: AVANCE III 400N (manufactured by Bruker Japan Co., Ltd.) Solvent: deuterated chloroform Measurement temperature: 23 to 25°C Number of accumulations: 16 Calculation method: The value obtained from the above measurement １ Calculation was performed using the following method for the H-NMR spectrum.

[0091] <Production Examples 1 to 9, 11, and 12, and Comparative Production Examples 2, 5, and 7> The obtained β-methyl-δ-valerolactone copolymers were those represented by the general formula (I) where R ３ is an ethylene group (-(CH ２ ) ２ The compound is a compound having a structure represented by the following formula (1), where * represents a bond. １For the H-NMR spectrum, the peak intensity (4.0-4.2 ppm) derived from the proton at the x position in formula (1) multiplied by the molecular weight (114.12) per structural unit derived from β-methyl-δ-valerolactone, the sum of the peak intensity (3.7-3.8 ppm) derived from the proton at the y position in formula (1) and the peak intensity (3.6-3.8 ppm) derived from the proton at the z position in formula (1), and the sum of the peak intensity (3.6-3.8 ppm) derived from the proton at the z position in formula (1) multiplied by the molecular weight (114.12) per structural unit derived from ethylene glycol The content of block (E) in the β-methyl-δ-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 β-methyl-δ-valerolactone (114.12) to the sum of the values ​​obtained by multiplying the peak intensity (3.6-3.8 ppm) derived from the proton at the z position in formula (1) by the molecular weight (44.03) of the structural unit derived from β-methyl-δ-valerolactone. Specifically, it was calculated using the following formula. Content (mass%) of block (E)=((((peak intensity derived from proton at position y+peak intensity derived from proton at position z) / 4)×molecular weight per structural unit derived from ethylene glycol 44.03) / ((((peak intensity derived from proton at position y+peak intensity derived from proton at position z) / 4)×molecular weight per structural unit derived from ethylene glycol 44.03)+((peak intensity derived from proton at position x / 2)×molecular weight per structural unit derived from β-methyl-δ-valerolactone 114.12)))×100

[0092]

[0093] <Production Example 10 and Comparative Production Example 6> The β-methyl-δ-valerolactone copolymer obtained in Production Example 10 was a copolymer of the formula (I) R ３ is an n-butylene group (-(CH ２ ) ４ The β-methyl-δ-valerolactone copolymer obtained in Comparative Production Example 6 is also a compound containing a structure represented by the following formula (2). In formula (2), * represents a bond. １For the H-NMR spectrum, the peak intensity (4.0-4.2 ppm) derived from the proton at the u position in formula (2) multiplied by the molecular weight (114.12) per structural unit derived from β-methyl-δ-valerolactone, the peak intensity (3.5-3.6 ppm) derived from the proton at the v position in formula (2) and the peak intensity (3.3-3.5 ppm) derived from the proton at the w position in formula (2) multiplied by the molecular weight (114.12) per structural unit derived from butylene glycol The content of (E) in the β-methyl-δ-valerolactone copolymer was calculated from the ratio of the sum of the peak intensity (3.5-3.6 ppm) derived from the proton at position v in formula (2) and the peak intensity (3.3-3.5 ppm) derived from the proton at position w in formula (2) multiplied by the molecular weight per structural unit (72.11) per structural unit derived from β-methyl-δ-valerolactone (114.12). Specifically, it was calculated using the following formula. Content (mass%) of block (E)=((((peak intensity derived from proton at position v+peak intensity derived from proton at position w) / 4)×molecular weight per structural unit derived from butylene glycol 72.11) / ((((peak intensity derived from proton at position v+peak intensity derived from proton at position w) / 4)×molecular weight per structural unit derived from butylene glycol 72.11)+((peak intensity derived from proton at position u / 2)×molecular weight per structural unit derived from β-methyl-δ-valerolactone 114.12)))×100

[0094]

[0095] [m, n] <Production Examples 1 to 9, 11, and 12, and Comparative Production Examples 2, 5, and 7> m and n were measured when calculating the content of the block (E). １It was calculated from the H-NMR spectrum. 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 subtracting the content of the obtained block (E) from 100, multiplying this value by m and the molecular weight of block (E), and dividing the result by the molecular weight per structural unit derived from β-methyl-δ-valerolactone. Specifically, it was calculated using the following formula. Note that "y-position" and "z-position" in the following formula mean "y-position" and "z-position" in formula (1) above. m = ((number of protons at z-position / 4) / (number of protons at y-position / 2)) + 1 n = (m × molecular weight per structural unit derived from ethylene glycol 44.03 × (100 - content ratio of block (E)) / 100) / molecular weight per structural unit derived from β-methyl-δ-valerolactone 114.12

[0096] <Production Example 10 and Comparative Production Example 6> m and n were measured when calculating the content of the block (E). １ It was calculated from the H-NMR spectrum. 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 then adding 1 to the result. n was calculated by subtracting the content of the obtained block (E) from 100, multiplying this value by m and the molecular weight of block (E), and dividing the result by the molecular weight per structural unit derived from β-methyl-δ-valerolactone. Specifically, it was calculated using the following formula. Note that "v-position" and "w-position" in the following formula mean "v-position" and "w-position" in formula (2) above. m = ((number of protons at w-position / 4) / (number of protons at v-position / 2)) + 1 n = (m × molecular weight per structural unit derived from butylene glycol 72.11 × (100 - content ratio of block (E)) / 100) / molecular weight per structural unit derived from β-methyl-δ-valerolactone 114.12

[0097] Comparative Production Examples 1, 3, and 4 n was calculated by adding 1 to the value obtained by dividing the number of protons at the t-position in formula (3) (4.0-4.2 ppm) by the number of protons at the s-position in formula (3) (3.6-3.7 ppm). Specifically, it was calculated using the following formula. In the following formula, "s-position" and "t-position" mean "s-position" and "t-position" in formula (3). n = ((number of protons at the t-position) / (number of protons at the s-position)) + 1

[0098]

[0099] [Number-average molecular weight, weight-average molecular weight, and molecular weight distribution of β-methyl-δ-valerolactone copolymers] The β-methyl-δ-valerolactone copolymers obtained in the Production Examples and Comparative Production Examples were used as samples, and the number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the β-methyl-δ-valerolactone copolymers were determined by gel permeation chromatography (GPC) in terms of molecular weight in terms of standard polystyrene. The specific measurement methods are as follows:

[0100] <When Mn is less than 15,000> Samples with an Mn of less than 15,000 were measured as follows to determine Mn and Mw. A tetrahydrofuran (THF) solution was used as the eluent. 10 mg of the sample, calculated as resin, was weighed out and dissolved in 1 mL of the eluent. The solution was passed through a 0.2 μm membrane filter to prepare a measurement sample. The measurement conditions were as follows. (Measurement conditions) GPC apparatus: HLC-EcoSEC8320GPC (manufactured by Tosoh Corporation) Column: Three columns, KF-803 (manufactured by Resonac Inc.), KF-802.5 (manufactured by Resonac Inc.), and KF-802 (manufactured by Resonac Inc.), were connected in series. Eluent: tetrahydrofuran Flow rate: 0.9 mL / min Sample injection volume: 30 μL Column temperature: 40°C Standard polystyrene: PSt Oligomer Kit (molecular weight 589 to 98,900) manufactured by Tosoh Corporation was used for cubic approximation. Detector: RI detector Mw / Mn was calculated from the obtained Mn and Mw.

[0101] <For Mn of 15,000 or More> Samples with an Mn of 15,000 or more were measured as follows to determine Mn and Mw. A tetrahydrofuran (THF) solution was used as the eluent. 1.0 mg of the sample, calculated as resin, was weighed out and dissolved in 1 mL of the eluent. The solution was passed through a 0.2 μm membrane filter to prepare a measurement sample. The measurement conditions were as follows: (Measurement Conditions) GPC Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation) Column: Two TSK-gel SuperMultipore HZ-M (manufactured by Tosoh Corporation) connected in series. Eluent: tetrahydrofuran Flow rate: 0.35 mL / min Sample injection volume: 10 μL Column temperature: 40°C Standard polystyrene: Polystyrene molecular weight standard (molecular weight 580 to 1,214,000) manufactured by GL Sciences Inc. was used for cubic approximation. Detector: RI detector Mw / Mn was calculated from the obtained Mn and Mw.

[0102] [Weight-average molecular weight of resin composition and polylactic acid polymer] The resin compositions and polylactic acid polymer 1 obtained in the examples and comparative examples were used as samples, and the weight-average molecular weight (Mw) of the resin composition and polylactic acid polymer 1 was determined by gel permeation chromatography (GPC) in terms of standard polystyrene. The measurement conditions were as follows. (Measurement conditions) Apparatus: High-performance liquid chromatograph LC-20A (Shimadzu Corporation) Column: Three columns were connected in series: K-G 4A (one column) (Resonac Corporation) and K-806M (two columns) (Resonac Corporation). Eluent: Chloroform Flow rate: 1.0 mL / min Sample injection amount: 100 μL Column temperature: 40°C Standard polystyrene: Polystyrene standard (molecular weight: 2,880 to 6,570,000) manufactured by Agilent Technologies, Inc., and approximated by a quintic equation. Detector: RI detector

[0103] [Viscosity] The viscosity of the polymers obtained in 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 Production Examples and Comparative Production Examples was measured using an E-type viscometer ("TVE-25 Viscometer" manufactured by Toki Sangyo Co., Ltd.) at the measurement temperatures shown in Table 2.

[0104] [Glass transition temperature (Tg) of resin composition] The resin compositions obtained in the examples and comparative examples were measured using a differential scanning calorimeter (TA Instrument "DSC25") under a nitrogen flow rate (100 mL / min) by raising the temperature from 30°C to 220°C at a rate of 10°C / min, holding at 220°C for 5 minutes, and then lowering the temperature to -70°C at a rate of 10°C / min. The glass transition temperature was evaluated when the temperature was raised to 220°C at 10°C / min after holding at -70°C for 5 minutes.

[0105] [Crystallization time (crystallization rate)] Using a differential scanning calorimeter (TA Instrument "DSC25"), the resin compositions obtained in the examples and comparative examples were heated from 30°C to 220°C at a rate of 10°C / min under a nitrogen flow rate (100 mL / min), held at 220°C for 5 minutes, then cooled to 95°C at a rate of 100°C / min, and held at 95°C for 60 minutes. The peak top time of the crystallization peak was taken as the crystallization time. The smaller this value, the faster the resin composition crystallizes.

[0106] [Tensile Test] (1) Preparation of Test Pieces for Tensile Tests The resin compositions obtained in the Examples and Comparative Examples were each subjected to a reduced pressure hot press ("IMC-183B" manufactured by Imoto Machinery Co., Ltd.) using an oil rotary pump to reduce the pressure to -0.1 MPaG, preheated at 200°C for 5 minutes, and then pressed at 8 MPa for 3 minutes. The resin compositions were then pressed at 8 MPa for 3 minutes using a cooling press equipped with water flow cooling to produce a 0.5 mm thick pressed plate. JIS No. 3 (dumbbell-shaped No. 3) dumbbell test pieces were punched out of the resulting pressed plate in accordance with JIS K 6251:2017, and subjected to crystallization treatment in an 80°C constant temperature bath for 16 hours. (2) Tensile Test The prepared dumbbell test specimens were stored at 23°C and 49% humidity for 24 hours or more, and evaluated using a universal testing machine (Instron Corporation, "INSTRON5900R-5666") or a precision universal testing machine (Shimadzu Corporation, "AG-2000B") at 23°C, 49% humidity, and a tensile speed of 5 mm / min. The initial tensile modulus (MPa), maximum point strength (MPa), and tensile elongation (breaking strain) (%) were measured. The average value of 5 measurements was used.

[0107] [Bleeding Test] The resin compositions obtained in the examples and comparative examples were each subjected to a reduced pressure hot press ("IMC-183B" manufactured by Imoto Machinery Co., Ltd.) using an oil rotary pump to reduce the pressure to -0.1 MPaG, preheated at 200°C for 5 minutes, and then pressed at 8 MPa for 3 minutes. The resin compositions were then pressed at 8 MPa for 3 minutes using a cooling press equipped with water flow cooling ("AYSR-5" manufactured by Shinto Metal Industries Co., Ltd.) to produce a 0.5 mm thick pressed plate. A 10 cm square test piece was punched out from the obtained pressed plate. The surface condition of the obtained test piece after storing it at 80°C for 16 hours or more was evaluated visually and by touch according to the following evaluation criteria. VG: No clear bleed-out or stickiness was observed. G: At least one type selected from the group consisting of slight bleed-out and stickiness was observed, but this was at a level that was acceptable for practical use. 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.

[0108] <Materials> The materials used in the examples and comparative examples are as follows.

[0109] (Initiator) CH ３ -PEG200: Tetraethylene monomethyl ether, manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Tetraethylene monomethyl ether" (weight average molecular weight: 208.25) CH ３ -PEG550: polyethylene glycol monomethyl ether, manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Polyethylene Glycol Monomethyl Ether 550" (weight average molecular weight (median value of catalogue value): 550, weight average molecular weight (catalogue value): 525 to 575)) CH ３ -PEG1,000: polyethylene glycol monomethyl ether, manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Polyethylene Glycol Monomethyl Ether 1,000" (weight average molecular weight (median value of catalog value): 1,000, weight average molecular weight (catalog value) 950 to 1,050)) CH ３PEG 2,000: polyethylene glycol monomethyl ether, manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Polyethylene Glycol Monomethyl Ether 2,000" (weight average molecular weight (median catalog value): 2,000, weight average molecular weight (catalog value): 1,900 to 2,100)) PEG 400: polyethylene glycol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "Polyethylene Glycol 400" (weight average molecular weight (median catalog value): 400, weight average molecular weight (catalog value): 360 to 440)) PEG 1,000: polyethylene glycol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "Polyethylene Glycol 1,000" (weight average molecular weight (median catalog value): 1,000, weight average molecular weight (catalog value): 900 to 1,100)) PEG 1,540: Polyethylene glycol, manufactured by Fujifilm Wako Pure Chemical Corporation, trade name "Polyethylene Glycol 1,540" (weight average molecular weight (median catalog value): 1,540, weight average molecular weight (catalog value): 1,350-1,650)) PEG 2,000: Polyethylene glycol, manufactured by Fujifilm Wako Pure Chemical Corporation, trade name "Polyethylene Glycol 2,000" (weight average molecular weight (median catalog value): 2,000, weight average molecular weight (catalog value): 1,800-2,200)) PEG 20,000: Polyethylene glycol, manufactured by Fujifilm Wako Pure Chemical Corporation, trade name "Polyethylene Glycol 20,000" (weight average molecular weight (median catalog value): 20,000, weight average molecular weight (catalog value): 15,000-25,000)) PTMG1,000: Polytetramethylene ether glycol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "Polytetramethylene Oxide 1,000" (weight average molecular weight: 1,000 (median of catalog value, weight average molecular weight (catalog value): 950 to 1,100))

[0110] (Thermoplastic resins) Polylactic acid polymer 1: manufactured by 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) (Other chemicals) n-Butyllithium: manufactured by Fujifilm Wako Pure Chemical Industries, trade name "1.6 mol / L n-butyllithium hexane solution" Acetic anhydride: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. 4-Dimethylaminopyridine: manufactured by Tokyo Chemical Industry Co., Ltd. Acrylic anhydride: manufactured by Tokyo Chemical Industry Co., Ltd. Ethylene glycol: manufactured by Tokyo Chemical Industry Co., Ltd. Toluene: manufactured by Kishida Chemical Co., Ltd. (special grade) Water: ion-exchanged water (water obtained by ion-exchanging tap water using "Autostill WA500 pure water production system" (manufactured by Yamato Scientific Co., Ltd.)

[0111] [Production of β-methyl-δ-valerolactone] A copper chromium oxide catalyst (CuO—Cr ２ O ３ 5 g of 2-hydroxy-4-methyltetrahydropyran (MHP) and 1 L of liquid paraffin were then added and stirred at a rotation speed of 350 rpm. The mixture was heated with a mantle heater, and after the internal temperature reached 235°C, MHP was added dropwise at a rate of 150 mL / 30 min continuously for 12 hours. The solution distilled from the distillation tube yielded 3.5 kg of β-methyl-δ-valerolactone. The resulting β-methyl-δ-valerolactone was confirmed to have a purity of 99% or higher.

[0112] [Production Example 1] A 500 mL four-necked glass flask was purged with nitrogen and filled with CH ３87.9 g of PEG-PEG550 and 268 g (2.351 mol) of β-methyl-δ-valerolactone were added and the temperature was raised to 60°C. 2.6 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 19.6 g (192 mmol) of acetic anhydride and 1.0 g (8.0 mmol) of 4-dimethylaminopyridine dissolved in 9.1 g of β-methyl-δ-valerolactone were added to the four-necked glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone copolymer. The reaction solution was extracted with toluene and water, and the volatile components were removed by distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), yielding 304 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-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 was a copolymer represented by the general formula (I) above, １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0113] [Production Example 2] A 500 mL four-necked glass flask was purged with nitrogen and filled with CH ３37.7 g of PEG-200 and 185 g (1.623 mol) of β-methyl-δ-valerolactone were added and the temperature was raised to 60°C. 1.2 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 22.1 g (217 mmol) of acetic anhydride and 1.11 g (9.1 mmol) of 4-dimethylaminopyridine dissolved in 10.3 g of β-methyl-δ-valerolactone were added to the four-necked glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone copolymer. 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, yielding 185 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-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 was a copolymer represented by the general formula (I) above, １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0114] [Production Example 3] A 500 mL four-necked glass flask was purged with nitrogen and filled with CH ３ 74.5 g of PEG 1,000 and 113 g (0.993 mol) of β-methyl-δ-valerolactone were added and the temperature was raised to 30°C. 2.1 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 30°C for 60 minutes. Next, 9.2 g (90 mmol) of acetic anhydride and 0.46 g (3.8 mmol) of 4-dimethylaminopyridine dissolved in 4.3 g of β-methyl-δ-valerolactone were added to the four-necked glass flask and stirred at 30°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone copolymer. 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, yielding 165 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-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 was a copolymer represented by the general formula (I) above,１ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0115] [Production Example 4] A 500 mL four-neck glass flask was purged with nitrogen, and 40.2 g of PEG 400 and 210 g (1.843 mol) of β-methyl-δ-valerolactone were added and heated to 60°C. 2.0 mL of n-butyllithium (1.6 M hexane solution) was added and stirred at 60°C for 60 minutes. Next, 24.9 g (244 mmol) of acetic anhydride and 1.23 g (10.1 mmol) of 4-dimethylaminopyridine dissolved in 11.9 g of β-methyl-δ-valerolactone were added to the four-neck glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone copolymer. The reaction solution was extracted with toluene and water, and volatile components were removed by distillation using a thin-film evaporator in the same manner as in Production Example 1, yielding 212 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-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 was a copolymer represented by the general formula (I) above, １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0116] [Production Example 5] A 500 mL four-neck glass flask was purged with nitrogen, and 103 g of PEG 1,000 and 150 g (1.313 mol) of β-methyl-δ-valerolactone were added and heated to 60°C. 1.3 mL of n-butyllithium (1.6 M hexane solution) was added and stirred at 60°C for 60 minutes. Next, 25.1 g (246 mmol) of acetic anhydride and 1.25 g (10.3 mmol) of 4-dimethylaminopyridine dissolved in 12.5 g of β-methyl-δ-valerolactone were added to the four-neck glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone copolymer. The reaction solution was extracted with toluene and water, and the volatile components were removed by distillation using a thin-film evaporator in the same manner as in Production Example 1, yielding 199 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-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 a copolymer represented by the general formula (I) above, １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0117] [Production Example 6] A 500 mL four-necked glass flask was purged with nitrogen and filled with CH ３40.2 g of PEG-2,000 and 208 g (1.818 mol) of β-methyl-δ-valerolactone were added, and the temperature was raised to 60°C. 1.8 mL of n-butyllithium (1.6 M hexane solution) was added, and the mixture was stirred at 60°C for 60 minutes. Next, 2.5 g (24.1 mmol) of acetic anhydride and 0.25 g (2.0 mmol) of 4-dimethylaminopyridine dissolved in 2.5 g of β-methyl-δ-valerolactone were added to the above four-necked glass flask, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone copolymer. 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 β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-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 was a copolymer represented by the above-mentioned general formula (I), １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0118] [Production Example 7] A 500 mL four-necked glass flask was purged with nitrogen and filled with CH ３14.2 g of PEG-2,000, 179 g (1.564 mol) of β-methyl-δ-valerolactone, and 73.3 g (796 mmol) of toluene were added and the mixture was heated to 30°C. 2.1 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 30°C for 60 minutes. Next, 1.5 g (14.5 mmol) of acetic anhydride and 0.043 g (0.35 mmol) of 4-dimethylaminopyridine dissolved in 0.43 g of β-methyl-δ-valerolactone were added to the four-necked glass flask and stirred at 30°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone copolymer. The reaction solution was extracted with toluene and water, and the volatile components were distilled off using a vacuum dryer in the same manner as in Production Example 6, yielding 166 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-valerolactone copolymer (hereinafter, sometimes referred to as "PMVL-7") were measured as described above. The results are shown in Table 1. The obtained PMVL-7 was a copolymer represented by the general formula (I) above, １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0119] [Production Example 8] A 1,000 mL four-neck glass flask was purged with nitrogen, and 63.4 g of PEG 20,000, 150 g (1.316 mol) of β-methyl-δ-valerolactone, and 61.9 g (672 mmol) of toluene were added and heated to 30 ° C. 1.6 mL of n-butyllithium (1.6 M hexane solution) was added and stirred at 30 ° C. for 120 minutes. Next, 1.29 g (12.7 mmol) of acetic anhydride and 0.04 g (0.32 mmol) of 4-dimethylaminopyridine dissolved in 0.36 g of β-methyl-δ-valerolactone were added to the four-neck glass flask and stirred at 30 ° C. for 120 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone copolymer. The reaction solution was extracted with toluene and water, and the volatile components were distilled off using a vacuum dryer in the same manner as in Production Example 6, to obtain 191 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-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 was a copolymer represented by the above-mentioned general formula (I), １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0120] [Production Example 9] A 500 mL four-neck glass flask was purged with nitrogen, and 150 g of PEG 1,540 and 74.4 g (0.652 mol) of β-methyl-δ-valerolactone were added and heated to 30°C. 1.8 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 30°C for 60 minutes. Next, 23.9 g (234 mmol) of acetic anhydride and 1.16 g (9.5 mmol) of 4-dimethylaminopyridine dissolved in 11.6 g of β-methyl-δ-valerolactone were added to the four-neck glass flask and stirred at 30°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone copolymer. 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 β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-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 was a copolymer represented by the above-mentioned general formula (I), １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0121] [Production Example 10] A 500 mL four-neck glass flask was purged with nitrogen, and 91.0 g of PTMG1,000 and 102 g (0.896 mol) of β-methyl-δ-valerolactone were added and heated to 30 ° C. 0.8 mL of n-butyllithium (1.6 M hexane solution) was added and stirred at 30 ° C. for 60 minutes. Next, 22.0 g (215 mmol) of acetic anhydride and 1.10 g (8.98 mmol) of 4-dimethylaminopyridine dissolved in 10.7 g of β-methyl-δ-valerolactone were added to the four-neck glass flask and stirred at 30 ° C. for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone copolymer. 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 β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-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 was a copolymer represented by the above-mentioned general formula (I), １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0122] [Production Example 11] A 500 mL four-necked glass flask was purged with nitrogen and filled with CH ３87.9 g of PEG-PEG550 and 268 g (2.351 mol) of β-methyl-δ-valerolactone were added and the temperature was raised to 60°C. 2.6 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 30.4 g (192 mmol) of butyric anhydride and 1.0 g (8.0 mmol) of 4-dimethylaminopyridine dissolved in 9.1 g of β-methyl-δ-valerolactone were added to the four-necked glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone copolymer. 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, yielding 304 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-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 was a copolymer represented by the general formula (I) above, １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0123] [Production Example 12] A 500 mL four-necked glass flask was purged with nitrogen and filled with CH ３87.9 g of PEG-PEG550 and 268 g (2.351 mol) of β-methyl-δ-valerolactone were added and the temperature was raised to 60°C. 2.6 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 43.4 g (192 mmol) of benzoic anhydride and 1.0 g (8.0 mmol) of 4-dimethylaminopyridine dissolved in 9.1 g of β-methyl-δ-valerolactone were added to the four-necked glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone copolymer. 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, yielding 304 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-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 a copolymer represented by the general formula (I) above, １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0124] Comparative Production Example 1 A 500 mL four-neck glass flask was purged with nitrogen, and 5.6 g (90 mmol) of ethylene glycol and 231 g (2.025 mol) of β-methyl-δ-valerolactone were added and heated to 60°C. 1.5 mL of n-butyllithium (1.6 M hexane solution) was added, and the mixture was stirred at 60°C for 60 minutes to carry out a ring-opening polymerization reaction. The resulting reaction solution containing the β-methyl-δ-valerolactone 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, yielding 190 g of the β-methyl-δ-valerolactone copolymer. The physical properties of the resulting β-methyl-δ-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.

[0125]

[0126] Comparative Production Example 2 A 500 mL four-neck glass flask was purged with nitrogen and ３ 87.9 g of PEG-PEG550 and 268 g (2.351 mol) of β-methyl-δ-valerolactone were added and the temperature was raised to 60°C. 2.6 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 24.1 g (192 mmol) of acrylic anhydride and 0.98 g (8.0 mmol) of 4-dimethylaminopyridine dissolved in 9.1 g of β-methyl-δ-valerolactone were added to the four-necked glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone copolymer. 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, yielding 304 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-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 a copolymer represented by the general formula (I) above, １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0127] Comparative Production Example 3 A 500 mL four-neck glass flask was purged with nitrogen, and 1.1 g (17.7 mmol) of ethylene glycol and 229 g (2.007 mol) of β-methyl-δ-valerolactone were added and heated to 60°C. 1.5 mL of n-butyllithium (1.6 M hexane solution) was added, and the mixture was stirred at 60°C for 60 minutes to carry out a ring-opening polymerization reaction. The resulting reaction solution containing a β-methyl-δ-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, yielding 159 g of a β-methyl-δ-valerolactone polymer. The physical properties of the resulting β-methyl-δ-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.

[0128] Comparative Production Example 4 A 1,000 mL four-neck glass flask was purged with nitrogen, and 1.2 g (19.3 mmol) of ethylene glycol, 625 g (5.476 mol) of β-methyl-δ-valerolactone, and 258 g (2.796 mol) of toluene were added and heated to 30°C. 4.1 mL of n-butyllithium (1.6 M hexane solution) was added, and the mixture was stirred at 30°C for 60 minutes to carry out a ring-opening polymerization reaction. The reaction solution containing the resulting 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, yielding 532 g of a β-methyl-δ-valerolactone polymer. The physical properties of the resulting β-methyl-δ-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.

[0129] Comparative Production Example 5 A 500 mL four-neck glass flask was purged with nitrogen, and 5.6 g (90 mmol) of ethylene glycol and 231 g (2.025 mol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.79 mL of n-butyllithium (1.6 M hexane solution) was added and stirred at 60°C for 60 minutes. Next, 22.1 g (216 mmol) of acetic anhydride and 1.1 g (9.0 mmol) of 4-dimethylaminopyridine were added to the four-neck glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a polymer. The reaction solution was extracted with toluene and water, and volatile components were distilled off using a thin-film evaporator in the same manner as in Production Example 1, yielding 158 g of a β-methyl-δ-valerolactone polymer. The physical properties of the obtained β-methyl-δ-valerolactone polymer (hereinafter, sometimes referred to as "PMVL'-5") were measured as described above. The results are shown in Table 1. The obtained PMVL'-5 is a polymer represented by the general formula (I) above, １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0130] Comparative Production Example 6 A 500 mL four-neck glass flask was purged with nitrogen, and 91.0 g of PTMG1,000 and 102 g (0.896 mol) of β-methyl-δ-valerolactone were added and heated to 30°C. 0.8 mL of n-butyllithium (1.6 M hexane solution) was added, followed by stirring at 30°C for 60 minutes. The reaction solution was extracted with toluene and water, and the volatile components were removed by distillation using a thin-film evaporator in the same manner as in Production Example 1, yielding 170 g of β-methyl-δ-valerolactone copolymer. The physical properties of the resulting β-methyl-δ-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.

[0131]

[0132] Comparative Production Example 7 A 500 mL four-necked glass flask was purged with nitrogen and ３ 87.9 g of PEG-PEG550 and 268 g (2.351 mol) of β-methyl-δ-valerolactone were added and the temperature was raised to 60°C. 2.6 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. 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, yielding 300 g of β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-valerolactone copolymer (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 following structural formula (C), where n and m are as shown in Table 1.

[0133]

[0134]

[0135] Example 1 100 parts by mass of polylactic acid polymer 1 and the above-mentioned β-methyl-δ-valerolactone copolymer (PMVL-1) in the blending amounts shown in Table 2 were charged into a twin-screw kneader (Technovel Co., Ltd., "ULTnano 50") and extruded into strands 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 strands were cut into pellets to obtain a resin composition. The resulting resin composition was evaluated as described above. The results are shown in Table 2.

[0136] [Examples 2 to 15 and Comparative Examples 2 to 5, 7 to 10] Resin compositions were obtained in the same manner as in Example 1, except that the β-methyl-δ-valerolactone copolymers shown in Tables 2 and 3 were used. The obtained resin compositions were evaluated as described above. The results are shown in Table 2.

[0137] Comparative Example 1 A resin composition was obtained in the same manner as in Example 1, except that the β-methyl-δ-valerolactone copolymer was not used. The obtained resin composition was evaluated as described above. The results are shown in Table 3.

[0138] Comparative Example 6 A resin composition was obtained in the same manner as in Example 1, except that PEG 2,000 was used instead of the β-methyl-δ-valerolactone copolymer. The obtained resin composition was evaluated as described above. The results are shown in Table 3.

[0139]

[0140]

[0141] The notations in Table 1 are as follows: ２ In the column, "(X)" indicates the above formula (X).

[0142] Comparing Examples 1 to 15 with Comparative Example 1, which did not use a β-methyl-δ-valerolactone copolymer, it can be seen that the β-methyl-δ-valerolactone copolymer represented by general formula (I) or (II) of this embodiment significantly lowers the glass transition temperature of the thermoplastic resin, thereby imparting good plasticity to the thermoplastic resin. Furthermore, the addition of the β-methyl-δ-valerolactone copolymer represented by general formula (I) or (II) obtained by the production method of this embodiment improves the elongation at break, indicating that the elongation of the resin composition is improved. Furthermore, comparing the resin compositions obtained in the Examples and Comparative Examples, which have similar weight-average molecular weights (e.g., Example 3 and Comparative Example 2), it can be seen that the resin composition containing the β-methyl-δ-valerolactone copolymer represented by general formula (I) or (II) of this embodiment has good plasticity and improved elongation. Furthermore, a comparison of Examples 1 to 15 with Comparative Examples 1 to 10 reveals that the resin composition containing the β-methyl-δ-valerolactone copolymer represented by general formula (I) or (II) of this embodiment has an improved crystallization rate and suppresses bleed-out.

Claims

1. A resin composition comprising a β-methyl-δ-valerolactone copolymer represented by the following general formula (I) or (II) and a polylactic acid polymer: [In general formulas (I) and (II), R １ R 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. 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). In the following formula (X), the bond represented by *1 bonds to an oxygen atom. In the following formula (Y), the bond represented by *2 bonds to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms. In the following formula (Z), 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. R ３ 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, and p is 2 to 1,000. n, m, A, p, R １ , R ２ and R ３ When a plurality of are present, they may be the same or different.

2. The resin composition according to claim 1, comprising 0.1 to 100 parts by mass of said β-methyl-δ-valerolactone copolymer per 100 parts by mass of said polylactic acid polymer.

3. The resin composition according to claim 1 or 2, wherein the number average molecular weight of the β-methyl-δ-valerolactone copolymer is 500 or more and 200,000 or less.

4. A resin composition according to any one of claims 1 to 3, wherein the polylactic acid polymer is a homopolymer of L-lactic acid, a homopolymer of D-lactic acid, or a copolymer of L-lactic acid and D-lactic acid.

5. A molded article made of the resin composition according to any one of claims 1 to 4.

6. A modifier for polylactic acid polymers, comprising a β-methyl-δ-valerolactone copolymer represented by the following general formula (I) or (II): [In general formulas (I) and (II), R １ R 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. 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). In the following formula (X), the bond represented by *1 bonds to an oxygen atom. In the following formula (Y), the bond represented by *2 bonds to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms. In the following formula (Z), 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. R ３ 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, and p is 2 to 1,000. n, m, A, p, R １ , R ２ and R ３ When a plurality of are present, they may be the same or different.

7. Use of a β-methyl-δ-valerolactone copolymer represented by the following general formula (I) or (II) as a modifier for polylactic acid polymers: [In general formulas (I) and (II), R １ R 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. 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). In the following formula (X), the bond represented by *1 bonds to an oxygen atom. In the following formula (Y), the bond represented by *2 bonds to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms. In the following formula (Z), 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. R ３ 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, and p is 2 to 1,000. n, m, A, p, R １ , R ２ and R ３ When a plurality of are present, they may be the same or different.

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