Β-methyl-δ-valerolactone copolymer and resin composition

Abstract

A β-methyl-δ-valerolactone copolymer is represented by general formulas (I) or (II).

Description

β-methyl-δ-valerolactone copolymer and resin composition

[0001] The present invention relates to a β-methyl-δ-valerolactone copolymer and a resin composition containing the β-methyl-δ-valerolactone copolymer.

[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 cured coating is flexible, has a low glass transition point, and does not crystallize even at temperatures below 0°C. Patent Document 1 also describes that a resin composition containing the (meth)acrylic acid ester is suitable for coating optical glass fibers for optical transmission. Patent Document 2 also discloses an alkyl-δ-valerolactone polymer obtained by reacting a hydroxyl-containing alkyl-δ-valerolactone polymer with a cyclic ether. Patent Document 2 describes that the alkyl-δ-valerolactone polymer is a liquid derivative with high thermal stability and can be used as a plasticizer. Furthermore, Reference Example 1 of Patent Document 2 discloses a liquid β-methyl-δ-valerolactone polymer obtained by modifying both ends of poly(β-methyl-δ-valerolactone)diol with acetic anhydride.

[0004] JP-A-1-258644 JP-A-3-181516

[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. Furthermore, polymers obtained by modifying the terminal hydroxyl groups of poly(β-methyl-δ-valerolactone)diol, as described in Patent Document 2, have room for improvement as plasticizers for thermoplastic resins. Therefore, an object of the present invention is to provide a β-methyl-δ-valerolactone copolymer that can impart good plasticity to resin compositions, as well as a resin composition having good plasticity and a production method thereof.

[0006] As a result of extensive research, the present inventors have found that the β-methyl-δ-valerolactone copolymer and resin composition of the present disclosure can solve the above problems.

[0007] [1] 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. 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). 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, R １ and R ３ When a plurality of R are present, they may be the same or different from each other. １ is 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. [3] The β-methyl-δ-valerolactone copolymer according to [1] above. ２is 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 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 the group represented by the formula (Y), or a linear or branched alkyl group having 1 to 16 carbon atoms in which one hydrogen atom bonded to at least one carbon atom is substituted with the group represented by the formula (Z). [4] The β-methyl-δ-valerolactone copolymer according to the above [1] or [2], ３ is a linear alkylene group having 2 to 16 carbon atoms or a branched alkylene group having 3 to 16 carbon atoms. [5] The β-methyl-δ-valerolactone copolymer according to any one of [1] to [3] above, having a number average molecular weight of 500 to 200,000. [6] The β-methyl-δ-valerolactone copolymer according to any one of [1] to [5] above, having a block (E) represented by the following formula in general formula (I) at a content of 5 to 95 mass%: [7] A resin composition comprising the β-methyl-δ-valerolactone copolymer according to any one of [1] to [6] above and a thermoplastic resin. [8] The resin composition according to [7] above, comprising 0.1 to 100 parts by mass of the β-methyl-δ-valerolactone copolymer per 100 parts by mass of the thermoplastic resin. [9] The resin composition according to [7] or [8] above, wherein the thermoplastic resin comprises a polyester.

[10] The resin composition according to [7] or [8] above, wherein the thermoplastic resin comprises a biodegradable resin.

[11] The resin composition according to any one of [7] to

[10] above, wherein the number average molecular weight of the resin composition is 1,000 to 1,000,000.

[12] A molded product made of the resin composition according to any one of [7] to

[11] above.

[13] A method for producing a β-methyl-δ-valerolactone copolymer represented by the following general formula (I) or (II), comprising: a step (1) of reacting β-methyl-δ-valerolactone with an initiator and a polymerization catalyst to ring-opening polymerize the β-methyl-δ-valerolactone to obtain a reaction solution; and a step (2) of adding a terminal modifier to the reaction solution and performing a terminal modification reaction to obtain the β-methyl-δ-valerolactone copolymer. [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. 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). 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.]

[14] The method for producing a β-methyl-δ-valerolactone copolymer according to

[13] above, wherein the polymerization catalyst is a base catalyst.

[15] The method for producing a β-methyl-δ-valerolactone copolymer according to

[13] or

[14] above, wherein the polymerization catalyst is butyllithium.

[16] The method for producing a β-methyl-δ-valerolactone copolymer according to any one of

[13] to

[15] above, wherein the terminal modifier is an acid anhydride or an acid halide.

[17] The method for producing a β-methyl-δ-valerolactone copolymer according to any one of

[13] to

[16] above, wherein the terminal modifier is an acid anhydride.

[18] The method for producing a β-methyl-δ-valerolactone copolymer according to any one of

[13] to

[17] above, wherein in step (2), the terminal modifier is added in an amount of 1 to 20 molar equivalents relative to the hydroxyl groups of the initiator.

[19] The method for producing a β-methyl-δ-valerolactone copolymer according to any one of

[13] to

[18] above, wherein the copolymer has a number average molecular weight (Mn) of 500 to 200,000.

[20] The method for producing a β-methyl-δ-valerolactone copolymer according to any one of

[13] to

[19] above, wherein the initiator is a polyether having at least one hydroxyl group.

[21] The method for producing a β-methyl-δ-valerolactone copolymer according to any one of

[13] to

[20] above, wherein in step (2), the terminal-modifying agent is added to the reaction solution without removing at least one selected from the β-methyl-δ-valerolactone, the initiator, and the polymerization catalyst contained in the reaction solution.

[0008] According to the present invention, it is possible to provide a β-methyl-δ-valerolactone copolymer capable of imparting good plasticity to a resin composition, a resin composition having good plasticity, and a method for producing the same.

[0009] The following describes an example of an embodiment of the present invention (hereinafter, sometimes referred to as "this embodiment"). 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] <β-Methyl-δ-valerolactone Copolymer> The β-methyl-δ-valerolactone copolymer of this embodiment is represented by the following general formula (I) or (II).

[0011]

[0012] [R １ 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.

[0013] 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.

[0014] 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.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] 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.

[0019] [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).

[0020]

[0021] 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

[0022] (Formula (X)) In formula (X), the bond indicated by *1 is bonded to an oxygen atom. Note that 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.

[0023] (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 a terminal carbon atom of a linear alkyl group having 1 to 20 carbon atoms or a 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).

[0024] 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.

[0025] R 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 represented 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 represented 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 or the branched alkylene group having 3 to 20 carbon atoms include an ethylene group (-(CH ２ ) ２ -), n-propylene group (-(CH ２ ) ３ -), isopropylene group (-CH ２ -CH(CH ３ )-), n-butylene group (-(CH ２ ) ４ -), 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 )-), n-pentylene group (-(CH ２ ) ５ -), 2-methylbutylene group (-CH ２ -CH ２ -CH(CH ３ )-CH ２ -) etc.

[0032] 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.

[0033] [A] 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.

[0034] [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.

[0035] 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 oxygen atom of the ether 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 above "β-methyl-δ-valerolactone unit" refers to a structural unit derived from a β-methyl-δ-valerolactone unit, and refers to a unit repeated with an average repeat number of n.

[0036] 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.

[0037] [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.

[0038] [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).

[0039]

[0040] [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.

[0041]

[0042] [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):

[0043]

[0044] [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):

[0045]

[0046] [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):

[0047]

[0048] [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).

[0049]

[0050] [Block (E) Content] In general formula (I), the content (% by mass) 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, from the viewpoints of achieving both compatibility with thermoplastic resins and a plasticizing effect, and improving the crystallization rate of the resin composition. In another aspect 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, from the viewpoints of achieving both compatibility with the thermoplastic resin and the plasticizing effect, and of improving the crystallization rate of the resin composition.

[0051]

[0052] The content ratio of the block (E) is the 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. １In 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.

[0053] <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 above 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 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 found in the examples.

[0054] [Block (F) Content] In general formula (II), the content (mass %) 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.

[0055]

[0056] 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).

[0057] [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.

[0058] [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 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] [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 calculated from the number average molecular weight and weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC). The detailed methods for measuring the number average molecular weight and weight average molecular weight can be as described in the Examples.

[0060] [Viscosity] The preferred viscosity range varies depending on the application of the β-methyl-δ-valerolactone copolymer, but from the viewpoints of, for example, ease of handling, substrate retention, strength, adhesiveness, and other functions, as well as the viewpoint of exhibiting a more excellent modifying effect on thermoplastic resins, it 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 is preferably 5,000 to 600,000 mPa·s, more preferably 50,000 to 600,000 mPa·s, even more preferably 100,000 to 400,000 mPa·s, still more preferably 150,000 to 250,000 mPa·s, and even more preferably 170,000 to 220,000 mPa·s at a measurement temperature of 60°C. The "viscosity" described in this specification is the viscosity measured for a β-methyl-δ-valerolactone copolymer using an E-type viscometer. Detailed measurement methods can be performed according to the methods described in the Examples.

[0061] <Method for Producing β-methyl-δ-valerolactone Copolymer> The method for producing a β-methyl-δ-valerolactone copolymer of this embodiment is a method for producing a β-methyl-δ-valerolactone copolymer represented by the following general formula (I) or (II), and includes a step (1) of reacting β-methyl-δ-valerolactone with an initiator and a polymerization catalyst to ring-opening polymerize the β-methyl-δ-valerolactone to obtain a reaction solution, and a step (2) of adding a terminal-modifying agent to the reaction solution and carrying out a terminal modification reaction to obtain the copolymer.

[0062]

[0063] 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.

[0064]

[0065] 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 are present, they may be the same or different from each other.

[0066] By including the steps (1) and (2), a β-methyl-δ-valerolactone copolymer that can be imparted with good plasticity can be easily produced.

[0067] [Step (1)] Step (1) is a step of reacting β-methyl-δ-valerolactone with an initiator and a polymerization catalyst to ring-opening polymerize the β-methyl-δ-valerolactone to obtain a reaction solution. The reaction solution obtained in step (1) contains a ring-opened polymer of β-methyl-δ-valerolactone, unreacted β-methyl-δ-valerolactone (which has not undergone ring-opening polymerization), unreacted initiator, polymerization catalyst, etc. Step (1) is preferably carried out under basic conditions.

[0068] (β-Methyl-δ-valerolactone) β-Methyl-δ-valerolactone produced by a known method can be used. For example, it can be produced by a known method using 2-hydroxy-4-methyltetrahydropyran or the like as a raw material (Japanese Patent Publication No. 6-53691, etc.). In addition, 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. In step (1), β-methyl-δ-valerolactone is added in an amount of preferably 5 to 1,500 molar equivalents, more preferably 5 to 1,200 molar equivalents, and even more preferably 10 to 600 molar equivalents, relative to the hydroxyl groups of the initiator.

[0069] (Initiator) The initiator used in this embodiment is preferably an alcohol, and more preferably a polyether having at least one hydroxyl group. From the viewpoint of obtaining a β-methyl-δ-valerolactone-based copolymer that can impart good plasticity, it is preferable to use a hydroxyl-containing polyether in which the carbon number in the structure constituting the repeating unit in the β-methyl-δ-valerolactone-based copolymer is preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 5 carbon atoms. The hydroxyl-containing polyether may be linear or branched, but from the viewpoint of obtaining a β-methyl-δ-valerolactone-based copolymer that can impart good plasticity, linear polyethers are preferred. Examples of hydroxyl-containing polyethers include polyether monools and polyether polyols. Examples of polyether monools include polyoxyalkylene monools. Examples of polyether polyols include polymers obtained by ring-opening polymerization of cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, and epichlorohydrin, either alone or in combination, using a compound having an active hydrogen atom as a catalyst. Specific examples include polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene ether glycol (PTMG), and polyhexamethylene ether glycol (PGL). Among these, polyethylene glycol is preferred from the viewpoint of obtaining a β-methyl-δ-valerolactone-based copolymer that can impart good plasticity. In addition to the above, examples of initiators include polyethers having at least one amino group and polyethers having at least one thiol group. Examples of polyethers having at least one amino group include triethylene glycolamine, diethylene glycol bis(3-aminopropyl)ether, and poly(ethylene glycol)diamine. Examples of polyethers having at least one thiol group include poly(ethylene glycol)dithiol.

[0070] (Polymerization Catalyst) Step (1) is preferably carried out under basic conditions, and the polymerization catalyst that can be used in this embodiment is preferably one that has catalytic activity under basic conditions. Examples of polymerization catalysts that have 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, and among these, organic lithium compounds such as butyllithium are preferred. Examples of organic base compounds include amine compounds having an amidine skeleton or a guanidine skeleton. In addition, metal catalysts such as organomagnesium compounds and organozinc compounds can also be used as the base catalyst. One type of polymerization catalyst may be used alone, or two or more types may be used in combination. When a base catalyst is used as the polymerization catalyst, the base catalyst is added in an amount of preferably 0.005 to 1.5 molar equivalents, more preferably 0.007 to 1.2 molar equivalents, even more preferably 0.007 to 1.0 molar equivalents, still more preferably 0.007 to 0.8 molar equivalents, and still more preferably 0.007 to 0.6 molar equivalents, relative to the hydroxyl groups of the initiator.

[0071] (Solvent) Step (1) can be carried out in the presence of a solvent inert to the ring-opening polymerization reaction. 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. Among these, toluene is preferred from the viewpoints of solubility and stability (low risk of reaction with the polymerization catalyst).

[0072] (Reaction Conditions) In step (1), the method for mixing β-methyl-δ-valerolactone, the initiator, and the polymerization catalyst is not particularly limited. However, from the viewpoint of operability, it is preferable to mix β-methyl-δ-valerolactone and the initiator, raise the temperature to the reaction temperature for reacting β-methyl-δ-valerolactone, the initiator, and the polymerization catalyst described below, and then add a solution containing a solvent inert to the ring-opening polymerization reaction and the polymerization catalyst dissolved in the solvent. By mixing in this manner, the reaction state is stabilized, a rapid reaction upon addition of the polymerization catalyst is suppressed, and a β-methyl-δ-valerolactone-based copolymer with stable performance is easily obtained. From the viewpoint of productivity, the reaction temperature for reacting β-methyl-δ-valerolactone, the initiator, and the polymerization catalyst is preferably 20 to 100°C, more preferably 30 to 90°C, even more preferably 30 to 80°C, and even more preferably 40 to 80°C. Within the above range, an appropriate reaction rate is achieved, depolymerization can be suppressed, and production efficiency is improved without a decrease in raw material conversion. The reaction time is preferably 1 minute to 24 hours, more preferably 15 minutes to 12 hours, and even more preferably 30 minutes to 6 hours, from the viewpoint of balancing the consumption of β-methyl-δ-valerolactone and the production efficiency of the β-methyl-δ-valerolactone copolymer. The reaction between β-methyl-δ-valerolactone, the initiator, and the polymerization catalyst is preferably carried out under an inert gas to prevent deactivation of the polymerization catalyst. Carrying out the reaction under an inert gas can prevent moisture contamination and prevent deactivation of the polymerization catalyst. Examples of inert gases include nitrogen gas, helium gas, neon gas, argon gas, krypton gas, and carbon dioxide gas. Nitrogen gas is preferred from the viewpoints of availability and versatility.

[0073] [Step (2)] Step (2) is a step of adding a terminal modifier to the reaction solution and carrying out a terminal modification reaction to obtain a β-methyl-δ-valerolactone copolymer. In step (2), it is preferable to add the terminal modifier to the reaction solution without removing at least one selected from the β-methyl-δ-valerolactone, the initiator, and the polymerization catalyst contained in the reaction solution obtained in step (1). That is, after ring-opening polymerization of β-methyl-δ-valerolactone, it is preferable to add the terminal modifier to the reactor in which the ring-opening polymerization was carried out, without removing at least one selected from the β-methyl-δ-valerolactone, the initiator, and the polymerization catalyst, or to remove only the ring-opened polymer of β-methyl-δ-valerolactone and place it in a separate reaction vessel, without adding the terminal modifier to that reaction vessel. In this case, the ring-opening polymerization reaction and the terminal modification reaction can be carried out in one pot, allowing for a simplified production process.

[0074] (Terminal Modifier) ​​Examples of terminal modifiers that can be used in this embodiment include acid anhydrides and acid halides. Among these, acid anhydrides are preferred from the viewpoint of reducing the environmental load. As the acid anhydride and acid halide, for example, an acid anhydride and acid halide having at least one group selected from the group consisting of a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an arylalkyl group having 7 to 14 carbon atoms can be used.

[0075] Specific examples of acid anhydrides include acetic anhydride, oxalic anhydride, propionic anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, glutaric anhydride, methacrylic anhydride, butyric anhydride, isobutyric anhydride, 1,8-naphthalic anhydride, trifluoroacetic anhydride, and cyclohexanecarboxylic anhydride. Of these, acetic anhydride is preferred from the viewpoint of availability. Specific examples of acid halides include acetyl chloride, propionyl chloride, butyroyl chloride, trifluoroacetyl chloride, benzoyl chloride, 2-furoyl chloride, hexanoyl chloride, phenylacetyl chloride, acetyl bromide, propionyl bromide, and benzoyl bromide. Of these, acetyl chloride is preferred from the viewpoint of availability. In step (2), from the viewpoint of achieving both reaction efficiency and suppression of production costs, the terminal modifier is added in an amount of preferably 1 to 20 molar equivalents, more preferably 1 to 10 molar equivalents, and even more preferably 1 to 8 molar equivalents, relative to the hydroxyl groups of the initiator.

[0076] (Co-catalyst) In step (2), a co-catalyst may be added as necessary. Examples of the co-catalyst that can be used include amine compounds such as triethylamine, tributylamine, trioctylamine, imidazole, pyridine, aminopyridine, and 4-dimethylaminopyridine. Among these, 4-dimethylaminopyridine is preferred from the viewpoint of achieving high catalytic activity even in small amounts. In step (2), the co-catalyst is preferably added in an amount of 0.001 to 10 molar equivalents, more preferably 1 to 10 molar equivalents, and even more preferably 1 to 8 molar equivalents, relative to the hydroxyl groups of the initiator.

[0077] [Step (3)] The β-methyl-δ-valerolactone copolymer represented by the general formulas (I) and (II) can be produced through the steps (1) and (2) above. If necessary, step (3), which is a step for isolating the produced β-methyl-δ-valerolactone copolymer, may be performed. A suitable method can be adopted from known methods for step (3). For example, the reaction mixture containing the β-methyl-δ-valerolactone copolymer obtained in step (2) can be washed with a solvent or water, concentrated, and purified by a method typically used for separating and purifying organic compounds, such as distillation. The solvent can be any of those described as (solvent) in [Step (1)] above.

[0078] In the method for producing a β-methyl-δ-valerolactone copolymer of this embodiment, R in the general formulas (I) and (II) １ ~R ３ , n, m, and p, and R in the formula (X), the formula (Y), and the formula (Z). １ , R ３ The details of A, *1 to *3, n, and m, and preferred examples thereof are the same as those in the above-mentioned "β-methyl-δ-valerolactone copolymer."

[0079] <Resin Composition> The resin composition of the present embodiment contains the above-described β-methyl-δ-valerolactone copolymer and a thermoplastic resin.

[0080] [Thermoplastic Resin] Examples of the thermoplastic resin in this embodiment include polyester, biodegradable resins other than polyester, and general-purpose thermoplastic resins.

[0081] (Polyester) The thermoplastic resin may include polyester, which includes non-biodegradable polyester and biodegradable 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 from cyclohexanedimethanol and sebacic acid (TP CH10), copolyester made from hexanediol, isophthalic acid, and terephthalic acid (TP 6I / 6T), copolyester made from bisphenol A, isophthalic acid, and terephthalic acid (TP BAI / BAT), copolyester made from ethylene glycol, cyclohexanedimethanol, and terephthalic acid (or an ester thereof) (TP 2T / CHT), and copolyester made from 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), and a copolyester of neopentyl glycol and terephthalic acid with 1,6-hexanediol and isophthalic acid (TP NGT / 6I).Examples of polyesters that are biodegradable resins include polylactic acid (PLA), 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, the polyester is preferably a biodegradable resin such as polylactic acid (PLA), polycaprolactone (PCL), polybutylene succinate (PBS), polybutylene succinate adipate (PBSA), polybutylene adipate terephthalate (PBAT), polyglycolic acid (PGA), polyethylene furanoate (PEF), polyhydroxyalkanoate (PHA), etc. In other words, the thermoplastic resin preferably contains a biodegradable resin, and more preferably contains a polyester, which is a biodegradable resin.

[0082] From the viewpoint of the required flexibility, the thermoplastic resin is preferably a biodegradable resin, and the biodegradable resin is preferably a polylactic acid polymer.

[0083] (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. Commercially available polylactic acid polymers may also be used. Examples of commercially available polylactic acid polymers include "INGEO series" manufactured by NatureWorks, Inc., "Luminy series" manufactured by TOTALENERGIES CORBION, and Zhejiang Hisun Biomaterials Co., Ltd. "Revode" series manufactured by Supra Chemical Industries, Ltd., and "SUPLA" product name manufactured by Supra Material Technology Co., Ltd.

[0084] From the viewpoint of moldability and compatibility with β-methyl-δ-valerolactone copolymers, the weight-average molecular weight of the polylactic acid polymer (polylactic acid resin) is preferably 50,000 to 600,000, more preferably 100,000 to 400,000, and even more preferably 150,000 to 300,000. A weight-average molecular weight of the polylactic acid resin within the above range is preferred because it provides good moldability and compatibility with β-methyl-δ-valerolactone copolymers. The weight-average molecular weight of the polylactic acid polymer (polylactic acid resin) can be determined in terms of standard polystyrene by gel permeation chromatography (GPC). When using commercially available products, catalog values ​​may be used.

[0085] [Other Thermoplastic Resins] The thermoplastic resin may contain other thermoplastic resins other than the above polyesters. Examples of other thermoplastic resins include biodegradable resins other than the above polyester biodegradable resins and general-purpose thermoplastic resins.

[0086] Examples of biodegradable resins other than the above-mentioned polyester biodegradable resins include cellulose acetate (CA).

[0087] Examples of the general-purpose thermoplastic resin include thermoplastic resins and thermoplastic elastomers having a suitable processing temperature of 200°C or less. Examples of the thermoplastic resin 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 elastomer 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).

[0088] Furthermore, 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 highly heat-resistant resin is preferably a thermoplastic resin having a melting point exceeding 200°C. Examples of the highly heat-resistant resin include polyamide (PA), polyacetal (POM), fluororesins (e.g., polytetrafluoroethylene (PTFE), perfluoroalkoxy fluororesin (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), etc.), polymethylpentene (PMP), etc.

[0089] The thermoplastic resin may be used alone or in combination of two or more. The thermoplastic resin contained in the resin composition of this embodiment is not limited to the above polyester, biodegradable resins other than the above polyester biodegradable resins, and general-purpose thermoplastic resins.

[0090] [Content ratio] In one aspect of the present invention, from the viewpoint of plasticizing effect and suppressing bleed-out, the resin composition preferably contains 0.1 to 100 parts by mass, more preferably 1 to 30 parts by mass, even more preferably 1 to 15 parts by mass, and even more preferably 1 to 10 parts by mass of the β-methyl-δ-valerolactone copolymer per 100 parts by mass of the thermoplastic resin. In another aspect of the present invention, from the viewpoint of plasticizing effect and suppressing bleed-out, the resin composition preferably contains 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, even more preferably 4 to 16 parts by mass, and even more preferably 7 to 13 parts by mass of the β-methyl-δ-valerolactone copolymer per 100 parts by mass of the thermoplastic resin.

[0091] The total content of the β-methyl-δ-valerolactone copolymer and the thermoplastic resin in the resin composition 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. The total content of the β-methyl-δ-valerolactone copolymer and the thermoplastic resin in the resin composition may be 100% by mass or less. The above content ratios allow the effects of the present invention to be more pronounced.

[0092] 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

[0093] [Additives] The resin composition of this embodiment may contain additives in addition to the β-methyl-δ-valerolactone copolymer and thermoplastic resin described above. Examples of additives include inorganic fillers, softeners, heat aging inhibitors, antioxidants, hydrolysis inhibitors, light stabilizers, antistatic agents, release agents, flame retardants, foaming agents, pigments, dyes, brighteners, UV absorbers, and lubricants. 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.

[0094] [Number Average Molecular Weight (Mn)] In one aspect of the present invention, from the viewpoint of achieving both tensile strength and moldability, the number average molecular weight of the resin composition is preferably 1,000 to 1,000,000, more preferably 10,000 to 600,000, even more preferably 30,000 to 500,000, even more preferably 50,000 to 350,000, even more preferably 60,000 to 250,000, and even more preferably 80,000 to 150,000. In another aspect of the present invention, from the same viewpoint, the number average molecular weight of the resin composition is preferably 500 to 300,000, more preferably 700 to 200,000, and even more preferably 1,000 to 180,000. The number average molecular weight of the resin composition can be determined in terms of standard polystyrene by gel permeation chromatography (GPC) measurement, and in detail is a value measured by the method described in the examples.

[0095] [Weight average molecular weight (Mw)] From the viewpoint of achieving both tensile strength and moldability, the weight average molecular weight of the resin composition is preferably 500 to 500,000, more preferably 700 to 300,000, and even more preferably 1,000 to 250,000. The weight average molecular weight of the resin composition is a number average molecular weight calculated in terms of standard polystyrene obtained by gel permeation chromatography (GPC). Detailed measurement methods can be performed according to the methods described in the examples.

[0096] [Glass Transition Temperature (Tg)] The β-methyl-δ-valerolactone copolymer of the present invention can lower the glass transition temperature of a thermoplastic resin. The glass transition temperature of a resin composition containing the β-methyl-δ-valerolactone copolymer of the present invention and a thermoplastic resin can be adjusted by the addition ratio of the β-methyl-δ-valerolactone copolymer. When the resin composition contains 1 to 100 parts by mass of the β-methyl-δ-valerolactone copolymer per 100 parts by mass of thermoplastic resin, the glass transition temperature of the resin composition is preferably lower by 2°C or more, preferably 70°C or less, more preferably 65°C or less, and even more preferably 60°C or less, relative to the glass transition temperature of the thermoplastic resin. That is, the glass transition temperature is preferably lower by 2 to 70°C, more preferably 2 to 65°C, and even more preferably 2 to 60°C. The glass transition temperature of a resin composition containing the β-methyl-δ-valerolactone copolymer of the present invention and a thermoplastic resin is lower than the glass transition temperature of the thermoplastic resin, thereby improving the plasticity and elongation of the resin composition.

[0097] <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, thermoplastic resin, and, if necessary, additives. Examples of mixing methods include melt-kneading using a single-screw extruder, multi-screw extruder, Banbury mixer, heated roll, 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, high-speed mixer, V-blender, ribbon blender, tumbler blender, or 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 thermoplastic resin.

[0098] <Molded Article> The molded article of this embodiment is a molded article made from the resin composition described above. 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, fibrous bodies, rod-shaped bodies, fine particles, particulate bodies, and foams. The method for producing this molded article is not particularly limited, and it can be molded by various known methods such as injection molding, blow molding, press molding, extrusion molding, calendar molding, and molding using a 3D printer.

[0099] <Applications> By mixing the above-mentioned β-methyl-δ-valerolactone copolymer with a thermoplastic resin to form a resin composition, the resin composition can have good plasticity. Therefore, the above-mentioned β-methyl-δ-valerolactone copolymer can be used as a modifier for thermoplastic resins.

[0100] 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.

[0101] The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to these.

[0102] <Measurement and Evaluation Methods> Various physical properties were measured or evaluated by the following methods.

[0103] [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: (Measurement conditions) 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.

[0104] (Examples 1 to 9, 11, and 12, and Comparative 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. １ For 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

[0105] (1)

[0106] (Example 10 and Comparative 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. For the 1H-NMR spectrum obtained from the above measurement, the peak intensity (4.0-4.2 ppm) derived from the proton at the u position in formula (2) multiplied by the molecular weight per structural unit derived from β-methyl-δ-valerolactone (114.12) plus 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) was multiplied by the molecular weight 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 (114.12) derived from β-methyl-δ-valerolactone to the sum of the values ​​multiplied by the molecular weight per structural unit (72.11). 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

[0107] (2)

[0108] [m, n] (Examples 1 to 9, 11, and 12, and Comparative 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

[0109] (Example 10 and Comparative Example 6) m and n were calculated from the H-NMR spectrum measured when calculating the content of block (E). m was calculated by dividing the number of protons at the w-position in formula (2) (3.3-3.5 ppm) by the number of protons at the v-position in formula (2) (3.5-3.6 ppm), and then adding 1 to the result. n was calculated by subtracting the resulting content of 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). 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

[0110] (Comparative 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. Note that "s-position" and "t-position" in the following formula mean "s-position" and "t-position" in formula (3) below. n = ((number of protons at the t-position) / (number of protons at the s-position)) + 1

[0111] [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 examples and comparative 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) using standard polystyrene equivalent molecular weights. The specific measurement methods are as follows.

[0112] (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, K-803 (manufactured by Resonac Inc.), K-802.5 (manufactured by Resonac Inc.), and K-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.

[0113] (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 solution was used as the eluent. 1.0 mg of the sample, calculated as resin, was weighed and dissolved in 1 mL of the above 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 Super HZM-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.

[0114] [Number-average molecular weight of resin composition, and weight-average molecular weight of resin composition and polylactic acid polymer] The resin compositions obtained in the examples and comparative examples were used as samples, and the number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the resin compositions were determined by gel permeation chromatography (GPC) in terms of standard polystyrene. Furthermore, polylactic acid polymer 1 was used as a sample, and the weight-average molecular weight (Mw) of polylactic acid polymer 1 was determined by gel permeation chromatography (GPC) in terms of standard polystyrene. The measurement conditions were as follows. (Measurement conditions) GPC apparatus: High-performance liquid chromatograph LC-20A (manufactured by Shimadzu Corporation) Column: Three columns were connected in series: one K-G 4A (manufactured by Resonac Corporation) and two K-806M (manufactured by Resonac Corporation). Eluent: chloroform Flow rate: 1.0 mL / min Sample injection volume: 100 μL Column temperature: 40°C Standard polystyrene: Polystyrene standard (molecular weight: 2,880 to 6,570,000) manufactured by Agilent Technologies, Inc. Approximation was performed using a quintic equation. Detector: RI detector

[0115] [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 β-methyl-δ-valerolactone copolymer was measured using an E-type viscometer (product name: TVE-25 viscometer, manufactured by Toki Sangyo Co., Ltd.) at the measurement temperatures shown in Table 2.

[0116] [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.

[0117] [Crystallization time (crystallization rate)] The resin compositions obtained in the examples and comparative examples were measured using a differential scanning calorimeter (TA Instruments "DSC25"), 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, cooled to 95°C at a rate of 100°C / min, and then 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.

[0118] [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. After preheating at 200°C for 5 minutes, the resin compositions were pressed at 8 MPa for 3 minutes. The resulting press plate was then pressed at 8 MPa for 3 minutes using a cooling press equipped with water flow cooling to produce a 0.5 mm thick press plate. A 10 cm square test piece was punched out from the resulting press plate. The resulting test piece was stored at 80°C for 16 hours or more, and the surface condition 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 selected from the group consisting of slight bleed-out and stickiness was observed, but this was at a level acceptable for practical use. NG: At least one selected from the group consisting of significant bleed-out and significant stickiness was observed, making the sample unsuitable for practical use.

[0119] <Materials> The materials used in the examples and comparative examples are as follows.

[0120] [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)) 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))

[0121] [Thermoplastic resin] 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.).

[0122] [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 350 rpm. The mixture was heated using 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.

[0123] [Example 1] (1) Production of β-methyl-δ-valerolactone copolymer A 500 mL four-necked glass flask was purged with nitrogen, and 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 as a polymerization catalyst, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution. Next, 19.6 g (192 mmol) of acetic anhydride as a terminal modifier and 1.0 g (8.0 mmol) of 4-dimethylaminopyridine dissolved in 9.1 g of β-methyl-δ-valerolactone were added to the reaction solution in the 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 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 were measured as described above. The results are shown in Table 2. The obtained β-methyl-δ-valerolactone copolymer 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.

[0124] (2) Production of Resin Composition 100 parts by mass of polylactic acid polymer 1 and 10 parts by mass of the above-mentioned β-methyl-δ-valerolactone copolymer were placed in a twin-screw kneader (Technovel Co., Ltd., "ULT nano 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.

[0125] [Example 2] (1) Production of β-methyl-δ-valerolactone copolymer A 500 mL four-necked glass flask was purged with nitrogen, and CH ３37.7 g of PEG-PEG200 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 as a polymerization catalyst, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution. Next, 22.1 g (217 mmol) of acetic anhydride as a terminal modifier and 1.11 g (9.1 mmol) of 4-dimethylaminopyridine dissolved in 10.3 g of β-methyl-δ-valerolactone were added to the reaction solution in the glass four-neck 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 removed by distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 185 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-valerolactone copolymer were measured as described above. The results are shown in Table 2. The obtained β-methyl-δ-valerolactone copolymer was also a copolymer represented by the general formula (I) above, １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0126] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone copolymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0127] [Example 3] (1) Production of β-methyl-δ-valerolactone copolymer A 500 mL four-necked glass flask was purged with nitrogen, and CH ３74.5 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 as a polymerization catalyst, and the mixture was stirred at 30°C for 60 minutes to obtain a reaction solution. Next, 9.2 g (90 mmol) of acetic anhydride as a terminal modifier and 0.46 g (3.8 mmol) of 4-dimethylaminopyridine dissolved in 4.3 g of β-methyl-δ-valerolactone were added to the reaction solution in the four-necked glass flask, and the mixture was 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 removed by distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), yielding 165 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-valerolactone copolymer were measured as described above. The results are shown in Table 2. The obtained β-methyl-δ-valerolactone copolymer 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.

[0128] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone copolymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0129] Example 4 (1) Production of β-methyl-δ-valerolactone-based copolymer 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 as initiators and heated to 60°C. 2.0 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution. 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 as terminal modifiers to the reaction solution in the four-neck glass flask, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone-based 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.), to obtain 212 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-valerolactone copolymer were measured as described above. The results are shown in Table 2. The obtained β-methyl-δ-valerolactone copolymer was also a copolymer represented by the general formula (I) above, １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0130] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone copolymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0131] Example 5 (1) Production of β-methyl-δ-valerolactone-based copolymer 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 as initiators and heated to 60°C. 1.3 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution. Next, 25.1 g (246 mmol) of acetic anhydride as a terminal modifier and 1.25 g (10.3 mmol) of 4-dimethylaminopyridine dissolved in 12.5 g of β-methyl-δ-valerolactone were added to the reaction solution in the four-neck glass flask, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone-based 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.), to obtain 199 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-valerolactone copolymer were measured as described above. The results are shown in Table 2. The obtained β-methyl-δ-valerolactone copolymer was also a copolymer represented by the general formula (I) above, １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0132] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone copolymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0133] [Example 6] (1) Production of β-methyl-δ-valerolactone copolymer A 500 mL four-necked glass flask was purged with nitrogen, and 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 as a polymerization catalyst, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution. Next, 2.5 g (24.1 mmol) of acetic anhydride as a terminal modifier and 0.25 g (2.0 mmol) of 4-dimethylaminopyridine dissolved in 2.5 g of β-methyl-δ-valerolactone were added to the reaction solution in the glass four-neck 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 removed by distillation 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 were measured as described above. The results are shown in Table 2. The obtained β-methyl-δ-valerolactone copolymer was also a copolymer of the formula (I) and R １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0134] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone copolymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0135] [Example 7] (1) Production of β-methyl-δ-valerolactone copolymer A 500 mL four-necked glass flask was purged with nitrogen and charged with CH as an initiator. 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 temperature was raised to 30 ° C. 2.1 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 30 ° C. for 60 minutes to obtain a reaction solution. Next, 1.5 g (14.5 mmol) of acetic anhydride as a terminal modifier and 0.04 g (0.35 mmol) of 4-dimethylaminopyridine dissolved in 0.43 g of β-methyl-δ-valerolactone were added to the reaction solution in the glass four-neck flask, and the mixture was 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 removed by distillation using a vacuum dryer (EYELA Tokyo Rikakikai Co., Ltd., "VACUUM OVEN VOS-450SD") to obtain 166 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-valerolactone copolymer were measured as described above. The results are shown in Table 2. The obtained β-methyl-δ-valerolactone copolymer was also a copolymer of the formula (I) and R １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0136] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone copolymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0137] [Example 8] (1) Production of β-methyl-δ-valerolactone copolymer A 1,000 mL four-neck glass flask was purged with nitrogen, and 63.4 g of PEG 20,000 as an initiator, 150 g (1.316 mol) of β-methyl-δ-valerolactone, and 61.9 g (672 mmol) of toluene were added, and the temperature was raised to 30° C. 1.6 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 30° C. for 120 minutes to obtain a reaction liquid. Next, 1.29 g (12.7 mmol) of acetic anhydride as a terminal modifier and 0.04 g (0.32 mmol) of 4-dimethylaminopyridine dissolved in 0.36 g of β-methyl-δ-valerolactone were added to the reaction solution in the four-necked glass flask, and the mixture was 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 (EYELA Tokyo Rikakikai Co., Ltd., "VACUUM OVEN VOS-450SD") to obtain 191 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-valerolactone copolymer were measured as described above. The results are shown in Table 2. The obtained β-methyl-δ-valerolactone copolymer 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.

[0138] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone copolymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0139] Example 9 (1) Production of β-methyl-δ-valerolactone-based copolymer A 500 mL four-necked 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 as initiators and heated to 30°C. 1.8 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 30°C for 60 minutes to obtain a reaction solution. Next, 23.9 g (234 mmol) of acetic anhydride as a terminal modifier and 1.16 g (9.5 mmol) of 4-dimethylaminopyridine dissolved in 11.6 g of β-methyl-δ-valerolactone were added to the reaction solution in the 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-based 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.), to obtain 210 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-valerolactone copolymer were measured as described above. The results are shown in Table 2. The obtained β-methyl-δ-valerolactone copolymer was also a copolymer represented by the general formula (I) above, １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0140] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone copolymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0141] [Example 10] (1) Production of β-methyl-δ-valerolactone-based copolymer A 500 mL four-necked glass flask was purged with nitrogen, and 91.0 g of PTMG1,000 as an initiator 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 as a polymerization catalyst, and the mixture was stirred at 30 ° C. for 60 minutes to obtain a reaction solution. Next, 22.0 g (215 mmol) of acetic anhydride as a terminal modifier and 1.10 g (8.98 mmol) of 4-dimethylaminopyridine dissolved in 10.7 g of β-methyl-δ-valerolactone were added to the reaction solution in the glass four-necked flask, and the mixture was stirred at 30 ° C. for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone-based 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.), to obtain 178 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-valerolactone copolymer were measured as described above. The results are shown in Table 2. The obtained β-methyl-δ-valerolactone copolymer 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.

[0142] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone copolymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0143] Example 11 (1) Production of β-methyl-δ-valerolactone copolymer A 500 mL four-necked glass flask was purged with nitrogen and charged with CH as an initiator. 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 as a polymerization catalyst, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution. Next, 30.4 g (192 mmol) of butyric anhydride as a terminal modifier and 9.1 g of 4-dimethylaminopyridine dissolved in β-methyl-δ-valerolactone were added to the reaction solution in the 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 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 were measured as described above. The results are shown in Table 2. The obtained β-methyl-δ-valerolactone copolymer 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.

[0144] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone copolymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0145] [Example 12] (1) Production of β-methyl-δ-valerolactone copolymer A 500 mL four-necked glass flask was purged with nitrogen, and 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 as a polymerization catalyst, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution. Next, 43.4 g (192 mmol) of benzoic anhydride as a terminal modifier and 9.1 g of 4-dimethylaminopyridine dissolved in β-methyl-δ-valerolactone were added to the reaction solution in the 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 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 were measured as described above. The results are shown in Table 2. The obtained β-methyl-δ-valerolactone copolymer 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.

[0146] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone copolymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0147] Comparative Example 1 (1) Production of β-methyl-δ-valerolactone Polymer A 500 mL four-neck glass flask was purged with nitrogen, and 5.6 g (90 mmol) of ethylene glycol as an initiator 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 as a polymerization catalyst, and the mixture was stirred at 60°C for 60 minutes to carry out a ring-opening polymerization reaction, yielding a reaction solution. The resulting reaction solution containing the β-methyl-δ-valerolactone polymer 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 190 g of β-methyl-δ-valerolactone polymer. The physical properties of the resulting β-methyl-δ-valerolactone copolymer were measured as described above. The results are shown in Table 2. The resulting β-methyl-δ-valerolactone copolymer is represented by the following structural formula (A), where n is as shown in Table 1.

[0148] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone polymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0149]

[0150] Comparative Example 2 (1) Production of β-methyl-δ-valerolactone copolymer A 500 mL four-necked glass flask was purged with nitrogen and charged with CH as an initiator. 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 as a polymerization catalyst, and the mixture was stirred at 60 ° C. for 60 minutes to obtain a reaction solution. Next, 24.1 g (192 mmol) of acrylic anhydride as a terminal modifier and 0.98 g (8.0 mmol) of 4-dimethylaminopyridine dissolved in 9.1 g of β-methyl-δ-valerolactone were added to the reaction solution in the glass four-neck 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 removed by distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 304 g (0.19 mmol) of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-valerolactone copolymer were measured as described above. The results are shown in Table 2. The obtained β-methyl-δ-valerolactone copolymer was also a copolymer of the formula (I) and R １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0151] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone copolymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0152] Comparative Example 3 (1) Production of β-methyl-δ-valerolactone Polymer A 500 mL four-neck glass flask was purged with nitrogen, and 1.1 g (17.7 mmol) of ethylene glycol as an initiator 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 as a polymerization catalyst, and the mixture was stirred at 60°C for 60 minutes to carry out a ring-opening polymerization reaction, yielding a reaction solution. The resulting reaction solution containing the β-methyl-δ-valerolactone polymer 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 159 g of β-methyl-δ-valerolactone polymer. The physical properties of the resulting β-methyl-δ-valerolactone copolymer were measured as described above. The results are shown in Table 2. The resulting β-methyl-δ-valerolactone copolymer is represented by the above-mentioned structural formula (A), and n is as shown in Table 1.

[0153] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone polymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0154] Comparative Example 4 (1) Production of β-methyl-δ-valerolactone Polymer A 1,000 mL four-neck glass flask was purged with nitrogen, and 1.2 g (19.3 mmol) of ethylene glycol as an initiator, 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 as a polymerization catalyst, and the mixture was stirred at 30°C for 60 minutes to carry out a ring-opening polymerization reaction, yielding a reaction solution. The reaction solution containing the resulting polymer 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 532 g of β-methyl-δ-valerolactone polymer. The physical properties of the resulting β-methyl-δ-valerolactone copolymer were measured as described above. The results are shown in Table 2. The resulting β-methyl-δ-valerolactone copolymer is represented by the above-mentioned structural formula (A), and n is as shown in Table 1.

[0155] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone polymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0156] Comparative Example 5 (1) Production of β-methyl-δ-valerolactone-based polymer 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 as initiators and heated to 60°C. 0.79 mL of n-butyllithium (1.6 M hexane solution) was added as a polymerization catalyst, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution. Next, 22.1 g (216 mmol) of acetic anhydride and 1.1 g (9.0 mmol) of 4-dimethylaminopyridine were added as terminal modifiers to the reaction solution in the four-neck glass flask, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone-based 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.), to obtain 158 g of a β-methyl-δ-valerolactone polymer. The physical properties of the obtained β-methyl-δ-valerolactone copolymer were measured as described above. The results are shown in Table 2. The obtained β-methyl-δ-valerolactone copolymer was also a copolymer of the formula (I) and R １ , R ２ , R ３ , m, n, and A are as shown in Table 1.

[0157] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone polymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0158] Comparative Example 6 (1) Production of β-methyl-δ-valerolactone Copolymer A 500 mL four-neck glass flask was purged with nitrogen, and 91.0 g of PTMG1,000 as an initiator 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 as a polymerization catalyst, and the mixture was stirred at 30°C for 60 minutes to obtain a reaction solution. The reaction solution containing the obtained polymer 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 170 g of β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-valerolactone copolymer were measured as described above. The results are shown in Table 2. The resulting β-methyl-δ-valerolactone copolymer is represented by the following structural formula (B), where m and n are as shown in Table 1.

[0159] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone polymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0160] Comparative Example 7 (1) Production of β-methyl-δ-valerolactone copolymer A 500 mL four-necked glass flask was purged with nitrogen and charged with CH 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 as a polymerization catalyst, and the mixture was stirred at 60°C for 60 minutes to obtain a reaction solution. The reaction solution containing the obtained polymer was extracted with toluene and water, and the volatile components were distilled off using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), yielding 300 g of a β-methyl-δ-valerolactone copolymer. The physical properties of the obtained β-methyl-δ-valerolactone copolymer were measured as described above. The results are shown in Table 2. The obtained β-methyl-δ-valerolactone copolymer is represented by the following structural formula (C), where m and n are as shown in Table 1.

[0161] (2) Production of Resin Composition A resin composition was obtained in the same manner as in Example 1, except that the obtained β-methyl-δ-valerolactone polymer was used. The obtained resin composition was evaluated as described above. The results are shown in Table 2.

[0162] Reference Example 1 For reference, the glass transition temperature and crystallization time of the polylactic acid polymer 1 are shown in Table 2.

[0163]

[0164]

[0165] The notations in Table 1 are as follows: ２ In the column, "(X)" indicates the above formula (X).

[0166] A comparison of Examples 1 to 12 with the Reference Example reveals that the β-methyl-δ-valerolactone copolymer represented by the above-described general formula (I) or (II) significantly lowers the glass transition temperature of the thermoplastic resin, thereby imparting good plasticity to the thermoplastic resin. Furthermore, a comparison of Examples 1, 3 to 5, 9, and 10 with Comparative Examples 1 and 2 reveals that, despite the polymers having similar weight-average molecular weights, the β-methyl-δ-valerolactone copolymer of the present embodiment significantly lowers the glass transition temperature of the thermoplastic resin, thereby imparting good plasticity to the thermoplastic resin. Similarly, a comparison of Example 6 with Comparative Example 3 and Example 7 with Comparative Example 4 reveals that, despite the polymers having similar weight-average molecular weights, the β-methyl-δ-valerolactone copolymer of the present embodiment significantly lowers the glass transition temperature of the thermoplastic resin, thereby imparting good plasticity to the thermoplastic resin.

Claims

1. 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, R １ and R ３ When a plurality of are present, they may be the same or different.

2. The above R １ is 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.

3. The above R ２ is a linear alkyl group having 1 to 8 prime numbers, 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 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 the group represented by the formula (Y), or a linear or branched alkyl group having 1 to 16 carbon atoms in which one hydrogen atom bonded to at least one carbon atom is substituted with the group represented by the formula (Z). The β-methyl-δ-valerolactone copolymer according to claim 1 or 2.

4. The above R ３ The β-methyl-δ-valerolactone copolymer according to any one of claims 1 to 3, wherein is a linear alkyl group having 2 to 16 carbon atoms or a branched alkylene group having 3 to 16 carbon atoms.

5. The β-methyl-δ-valerolactone copolymer according to any one of claims 1 to 4, which has a number average molecular weight of 500 to 200,000.

6. The β-methyl-δ-valerolactone copolymer according to any one of claims 1 to 5, wherein the content of the block (E) represented by the following formula in the general formula (I) is 5 to 95 mass %:

7. A resin composition comprising the β-methyl-δ-valerolactone copolymer according to any one of claims 1 to 6 and a thermoplastic resin.

8. The resin composition according to claim 7, which contains 0.1 to 100 parts by mass of said β-methyl-δ-valerolactone copolymer per 100 parts by mass of said thermoplastic resin.

9. The resin composition according to claim 7 or 8, wherein the thermoplastic resin comprises a polyester.

10. The resin composition according to claim 7 or 8, wherein the thermoplastic resin comprises a biodegradable resin.

11. The resin composition according to any one of claims 7 to 10, wherein the number average molecular weight of the resin composition is 1,000 to 1,000,000.

12. A molded article made of the resin composition according to any one of claims 7 to 11.

13. A method for producing a β-methyl-δ-valerolactone-based copolymer represented by the following general formula (I) or (II), comprising: a step (1) of reacting β-methyl-δ-valerolactone with an initiator and a polymerization catalyst to ring-opening polymerize the β-methyl-δ-valerolactone to obtain a reaction liquid; and a step (2) of adding a terminal modifier to the reaction liquid and carrying out a terminal modification reaction to obtain the β-methyl-δ-valerolactone-based copolymer. [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.

14. The method for producing a β-methyl-δ-valerolactone copolymer according to claim 13, wherein the polymerization catalyst is a base catalyst.

15. The method for producing a β-methyl-δ-valerolactone copolymer according to claim 13 or 14, wherein the polymerization catalyst is butyllithium.

16. The method for producing a β-methyl-δ-valerolactone copolymer according to any one of claims 13 to 15, wherein the terminal modifying agent is an acid anhydride or an acid halide.

17. The method for producing a β-methyl-δ-valerolactone copolymer according to any one of claims 13 to 16, wherein the terminal modifying agent is an acid anhydride.

18. A method for producing a β-methyl-δ-valerolactone copolymer according to any one of claims 13 to 17, wherein in step (2), the terminal modifier is added in an amount of 1 to 20 molar equivalents relative to the hydroxyl groups of the initiator.

19. A method for producing a β-methyl-δ-valerolactone copolymer according to any one of claims 13 to 18, wherein the copolymer has a number average molecular weight (Mn) of 500 to 200,000.

20. A method for producing a β-methyl-δ-valerolactone copolymer according to any one of claims 13 to 19, wherein the initiator is a polyether having at least one hydroxyl group.

21. A method for producing a β-methyl-δ-valerolactone copolymer described in any one of claims 13 to 20, wherein in step (2), the terminal modifying agent is added to the reaction liquid without removing at least one selected from the β-methyl-δ-valerolactone, the initiator, and the polymerization catalyst contained in the reaction liquid.

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