Resin composition

Abstract

A resin composition containing: a polyhydroxyalkanoate polymer having a first monomer unit represented by general formula (M1) and a second monomer unit represented by general formula (M2); and a β-methyl-δ-valerolactone polymer.

Description

resin composition

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

[0002] From the perspective of global environmental conservation, there is a need to reduce the environmental impact of plastic materials used in products in a wide range of fields. To reduce the environmental impact, active development has been conducted on plastic materials using polylactic acid, a type of "biodegradable plastic." However, molded products made from polylactic acid tend to be more brittle than petroleum-based plastics and have inferior viscosity, flexibility, and heat resistance. Furthermore, they are prone to hydrolysis, which may limit their use as resin materials.

[0003] As a biodegradable plastic other than polylactic acid, a resin composition containing polyhydroxyalkanoate (PHA) is also known. For example, Patent Document 1 describes a polyester composition containing at least one PHA and at least one plasticizer for the PHA.

[0004] Special Publication No. 9-504808

[0005] Patent Document 1 describes that a PHA containing hydroxybutyrate units and hydroxyvalerate units can be used as the PHA. However, Patent Document 1 does not describe a resin composition containing a PHA and an alkyl-δ-valerolactone polyester. Furthermore, Patent Document 1 does not mention the modifying effect of an alkyl-δ-valerolactone polyester on a polyhydroxyalkanoate polymer containing structural units derived from hydroxyvalerate.

[0006] The present invention provides a resin composition containing a polyhydroxyalkanoate polymer, which has improved tensile elongation at break and impact resistance over a wide temperature range, and in which bleeding out of the constituent components is suppressed.

[0007] As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have arrived at the following invention and found that the above-mentioned problems can be solved. That is, the present invention is as follows: [1] A resin composition containing a polyhydroxyalkanoate-based polymer containing a first monomer unit represented by the following general formula (M1) and a second monomer unit represented by the following general formula (M2), and a β-methyl-δ-valerolactone-based polymer: [2] The resin composition according to [1], wherein the β-methyl-δ-valerolactone polymer is represented by the following general formula (I): [In general formula (I), R １ represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms has been substituted with a group represented by the following formula (X), or an oxygen-atom-containing hydrocarbon 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 has been substituted with a group represented by the following formula (X). In the following formula (X), the bond represented by * bonds to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms. R ２ represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms. n is 2 to 1,000, and m is 2 to 1,000. R ２When a plurality of and m are present, they may be the same or different from each other.] [3] The resin composition according to [1] or [2] above, containing 0.1 parts by mass or more and 100 parts by mass or less of the β-methyl-δ-valerolactone polymer per 100 parts by mass of the polyhydroxyalkanoate polymer. [4] The resin composition according to any one of [1] to [3] above, wherein the number average molecular weight of the β-methyl-δ-valerolactone polymer is 500 or more and 100,000 or less. [5] The resin composition according to any one of [1] to [4] above, wherein in the polyhydroxyalkanoate polymer, the bonding form of the first monomer unit and the second monomer unit is at least one selected from the group consisting of random, block, and combinations thereof. [6] A molded product made of the resin composition according to any one of [1] to [5] above. [7] A modifier for a polyhydroxyalkanoate polymer contained in the resin composition according to any one of [1] to [5] above, which comprises a β-methyl-δ-valerolactone polymer represented by the general formula (I): [In general formula (I), R １ represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms has been substituted with a group represented by the following formula (X), or an oxygen-atom-containing hydrocarbon 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 has been substituted with a group represented by the following formula (X). In the following formula (X), the bond represented by * bonds to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms. R ２represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms. n is 2 to 1,000, and m is 2 to 1,000. R ２ When a plurality of m's are present, they may be the same or different from each other.

[0008] According to the present invention, there is provided a resin composition containing a polyhydroxyalkanoate polymer, which has improved tensile elongation at break and impact resistance over a wide temperature range, and in which bleeding out of the constituent components is suppressed.

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

[0010] <Resin Composition> [Polyhydroxyalkanoate Polymer (Polyhydroxyvalerate Polymer)] The polyhydroxyalkanoate polymer used in the present embodiment is a polymer containing a first monomer unit represented by the following general formula (M1) and a second monomer unit represented by the following general formula (M2). The polyhydroxyalkanoate polymer used in this embodiment contains the second monomer unit derived from hydroxyvalerate, and therefore is hereinafter also referred to as a "polyhydroxyvalerate polymer."

[0011] The polyhydroxyvalerate polymer is highly compatible with the β-methyl-δ-valerolactone polymer described below, and therefore the resin composition can easily exhibit the excellent physical properties of the β-methyl-δ-valerolactone polymer while retaining biodegradability.

[0012] The first and second monomer units are preferably of the (R)-3-hydroxy type.

[0013] In the polyhydroxyvalerate polymer, the bonding form between the first monomer unit and the second monomer unit is not particularly limited, and may be random, tapered, completely alternating, partially block, block, or a combination of two or more thereof. From the viewpoint of ease of production, the bonding form between the first monomer unit and the second monomer unit in the polyhydroxyvalerate polymer is preferably at least one selected from the group consisting of random, block, and combinations thereof.

[0014] In the polyhydroxyvalerate polymer, the second monomer unit is preferably contained in an amount of 1 to 40 mol %, more preferably 2 to 30 mol %, and even more preferably 4 to 20 mol %, from the viewpoint of processability.

[0015] In the polyhydroxyvalerate polymer, the first monomer unit is preferably contained in an amount of 60 to 99 mol %, more preferably 70 to 98 mol %, and even more preferably 80 to 96 mol %, from the viewpoint of mechanical properties.

[0016] In the polyhydroxyvalerate polymer, the total amount of the first monomer unit and the second monomer unit is preferably 80 to 100 mol %, more preferably 90 to 100 mol %, even more preferably 95 to 100 mol %, and still more preferably 99 to 100 mol %, from the viewpoint of mechanical properties.

[0017] The ratio of each monomer in the polyhydroxyvalerate polymer can be measured by gas chromatography as follows. 2 ml of a sulfuric acid / methanol mixture (15 / 85 (weight ratio)) and 2 ml of chloroform are added to approximately 20 mg of dried polyhydroxyvalerate polymer, the mixture is sealed, and heated at 100°C for 140 minutes to obtain a methyl ester of a polyhydroxyvalerate polymer decomposition product. After cooling, 1.5 g of sodium bicarbonate is added little by little to neutralize the mixture, and the mixture is allowed to stand until the evolution of carbon dioxide gas stops. 4 ml of diisopropyl ether is added and mixed well, and the monomer unit composition of the polyhydroxyvalerate polymer decomposition product in the supernatant is analyzed by capillary gas chromatography to determine the ratio of each monomer in the polyhydroxyvalerate polymer.

[0018] The gas chromatograph used was a "GC-17A" manufactured by Shimadzu Corporation, and the capillary column used was a "NEUTRA BOND-1" manufactured by GL Sciences (column length: 25 m, column inner diameter: 0.25 mm, liquid film thickness: 0.4 μm). He was used as the carrier gas, the column inlet pressure was 100 kPa, and 1 μl of sample was injected. The temperature conditions were as follows: the initial temperature was raised from 100°C to 200°C at a rate of 8°C / min, and then the temperature was further raised from 200 to 290°C at a rate of 30°C / min.

[0019] Specific examples of the polyhydroxyvalerate polymer are as follows: (a) a polyhydroxyvalerate polymer containing 2 to 5 mol % of the second monomer unit, with the remainder being the first monomer unit; and (b) a polyhydroxyvalerate polymer containing 5 to 30 mol % of the second monomer unit, with the remainder being the first monomer unit. In this case, in the first and second monomer units, the structural portion between "-O-" and "-CO-" including the side chain is represented by "-C ｊ H ｋ -" and the entire monomer units are assumed to be represented by the following formula (Y): "-O-C ｊ H ｋ-CO-" ... (Y) In this case, the proportions in such blends are preferably such as to give an average j=4 content, for example in the range of 4 to 20 mole %. In each such polyhydroxyvalerate-based polymer having j=3 structural units and j=4 structural units, there may be a very small, typically insignificant, proportion of units having higher j values. The polyhydroxyvalerate-based polymer may contain up to 20 mole % of other units, whether consciously introduced or not, and preferably up to 10 mole %, more preferably up to 5 mole %, and even more preferably up to 1 mole % of other units. The PHA is preferably the product of fermentation, especially of a microbiological process, in which a microorganism produces the PHA during its normal growth or is induced to produce the PHA by cultivation in the absence of one or more nutrients necessary for cell growth. The microorganism may be wild-type or mutant, or may have the necessary genetic material introduced into it. Alternatively, the necessary genetic material can be harbored by eukaryotes to carry out the microbiological process. Examples of suitable microbiological processes include: EP-A-69497 (Alcaligenes eutrophus) for substances of formula (Y) where j=3, or j=some 3, some 4; US Pat. No. 4,101,533 (A. eutrophus H-16), EP-A-144,017 (A. latus) for substances of formula I where j=3; EP-A-0,392,687 (various Pseudomonas) for substances of formula (Y) where j=7-13. PHAs can be extracted from fermentation cells using organic solvents, or the cellular protein material can be degraded to leave microscopic granules of polymer. For specific end uses, the cellular proteins can be partially or completely left to contain the PHA, but preferably are lysed. The resin composition of this embodiment contains more than 50 wt. %, particularly more than 80 wt. % of the microbiologically produced PHA.Alternatively, the polyhydroxyvalerate polymers can be the product of synthetic chemistry (Blömbergen and Holden, Macromolecules 1989, 22, 1656-1663; Bloembergen, Holden, Bluhn, Hamer and Marchessault, Macromolecules 1989, 22, 1663-1669).

[0020] The polyhydroxyvalerate polymers may be used alone or in combination of two or more.

[0021] The weight average molecular weight of the polyhydroxyvalerate polymer is preferably greater than 50,000, particularly greater than 100,000, e.g., 2×10 ６ In this specification, the weight average molecular weight of the polyhydroxyvalerate polymer is a weight average molecular weight calculated in terms of standard polystyrene by gel permeation chromatography (GPC) using chloroform as an eluent. When a commercially available product is used, the catalog value may be used.

[0022] [β-Methyl-δ-valerolactone Polymer] The β-methyl-δ-valerolactone polymer used in this embodiment is preferably a polymer represented by the following general formula (I). Due to the structure represented by general formula (I), the following polymer serves as a superior modifier for polyhydroxyvalerate polymers. The following polymer is a polymer obtained by ring-opening polymerization of β-methyl-δ-valerolactone, in which at least one hydroxyl group at the molecular end is modified with another functional group, resulting in a polymer with reduced thermal decomposition properties and capable of suppressing a decrease in the glass transition temperature of the resin composition. Furthermore, the following polymer can improve the tensile elongation at break of the resin composition depending on the structure and number of molecular ends. In addition, it is expected to exhibit properties with a good balance of improved crystallization rate, improved impact resistance, improved hydrolysis resistance, other functions, and ease of handling. Furthermore, since the raw material for the polymer represented by the following general formula (I) is β-methyl-δ-valerolactone, the resin composition of this embodiment is considered to have good biodegradability.

[0023]

[0024] In general formula (I), R １ represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by formula (X) described below, or an oxygen atom-containing hydrocarbon 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 formula (X) described below.

[0025] Examples of the linear alkyl group having 1 to 20 carbon atoms include at least one selected from the group consisting of 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.

[0026] 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. Specifically, at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group is preferred.

[0027] 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 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-propylheptyl group butyl group, 1-methyloctyl group, 2-methyloctyl group, 3-methyloctyl group, 4-methyloctyl 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, and 3,5,5-trimethylhexyl group.

[0028] 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. Specifically, at least one selected from the group consisting of an isopropyl group, a 1-methylbutyl group, a 3-methylbutyl group, and a 2,2-dimethylpropyl group is preferred.

[0029] Examples of the linear alkenyl group having 2 to 20 carbon atoms include ethenyl, n-propenyl, n-butenyl (e.g., 2-butenyl and 3-butenyl), n-pentenyl (e.g., 3-pentenyl and 4-pentenyl), n-hexenyl (e.g., 1-hexenyl and 5-hexenyl), n-heptenyl (e.g., 1-heptenyl and 1,3-heptadienyl), n-octenyl (e.g., 7-octenyl and 2,7-octadienyl), n-nonenyl (e.g., 3-nonenyl and 3,6-nonadienyl), n-decenyl (e.g., 1,3-decadienyl and 1,3,5-decatrienyl), and n-undecenyl. and n-octadecenyl groups (e.g., 2-octadecenyl groups), n-hexadecenyl groups (e.g., 2-hexadecenyl groups), n-heptadecenyl groups (e.g., 2-heptadecenyl groups), n-octadecenyl groups (e.g., 2-octadecenyl groups), n-nonadecenyl groups (e.g., 2-nonadecenyl groups), and n-icosenyl groups (e.g., 2-icosenyl groups).

[0030] From the viewpoint of handleability, the linear alkenyl group having 2 to 20 carbon atoms is preferably a linear alkenyl group having 2 to 15 carbon atoms, more preferably a linear alkenyl group having 3 to 10 carbon atoms, and even more preferably a linear alkenyl group having 3 to 6 carbon atoms.

[0031] Examples of branched alkenyl groups having 3 to 20 carbon atoms include an isopropenyl group, a 1-methylpropenyl group, a 2-methylpropenyl group, a t-butenyl group, a 1,1-dimethylpropenyl group, a 2,2-dimethylpropenyl group, a 1,2-dimethylpropenyl group, a 1-ethylpropenyl group, a 2-ethylpropenyl group, a 1,1-diethylpropenyl group, a 1-methylbutenyl group, a 2-methylbutenyl group, a 3-methyl-2-butenyl group, a 3-methyl-3-butenyl group, a 1,1-dimethylbutenyl group, a 2,2-dimethylbutenyl group, 3,3-dimethylbutenyl group, 1,3,3-trimethylbutenyl group, 1-ethylbutenyl group, 2-ethylbutenyl group, 3,3-dimethylbutenyl group, 1-propylbutenyl group, 1-methylpentenyl group, 2-methylpentenyl group, 3-methylpentenyl group, 4-methylpentenyl group, 4,4-dimethylpentenyl group, 1-ethylpentenyl group, 2-ethylpentenyl group, 3-ethylpentenyl group, 4-ethylpentenyl group, 1-propylpentenyl group, 2-propylpentenyl group, 1-butylpentenyl group, 1-methylhexenyl group, 2-methylhexenyl group, 3-methylhexenyl group, 4-methylhexenyl group, 5-methylhexenyl group, 5,5-dimethylhexenyl group, 1-ethylhexenyl group, 2-ethylhexenyl group, 3-ethylhexenyl group, 4-ethylhexenyl group, 1-propylhexenyl group, 2-propylhexenyl group, 3-propylhexenyl group, 1-butylhexenyl group, 2-butylhexenyl group, 1-methylheptenyl group, 2-methylheptenyl group, 3-methylheptenyl group, 4-methylheptenyl group a 1-methyloctenyl group, a 5-methylheptenyl group, a 6-methylheptenyl group, a 6,6-dimethylheptenyl group, a 1-ethylheptenyl group, a 2-ethylheptenyl group, a 3-ethylheptenyl group, a 4-ethylheptenyl group, a 5-ethylheptenyl group, a 1-propylheptenyl group, a 2-propylheptenyl group, a 3-propylheptenyl group, a 1-methyloctenyl group, a 2-methyloctenyl group, a 3-methyloctenyl group, a 4-methyloctenyl group, a 5-methyloctenyl group, a 6-methyloctenyl group, a 7-methyloctenyl group, a 7,At least one selected from the group consisting of a 7-dimethyloctenyl group, a 1-ethyloctenyl group, a 2-ethyloctenyl group, a 3-ethyloctenyl group, a 4-ethyloctenyl group, a 5-ethyloctenyl group, a 6-ethyloctenyl group, a 1-methylnonenyl group, a 2-methylnonenyl group, a 3-methylnonenyl group, a 4-methylnonenyl group, a 5-methylnonenyl group, a 6-methylnonenyl group, a 7-methylnonenyl group, an 8-methylnonenyl group, and a 3,5,5-trimethylhexenyl group can be mentioned.

[0032] From the viewpoint of handleability, the branched alkenyl group having 3 to 20 carbon atoms is preferably a branched alkenyl group having 3 to 15 carbon atoms, more preferably a branched alkenyl group having 3 to 10 carbon atoms, and even more preferably a branched alkenyl group having 3 to 6 carbon atoms.

[0033] Examples of aryl groups having 6 to 12 carbon atoms include at least one selected from the group consisting of a phenyl group, a 2-methylphenyl group, a 4-methylphenyl group, a 2,4-dimethylphenyl group, and a 2-naphthyl group. Phenyl groups are preferred. Examples of arylalkyl groups having 7 to 12 carbon atoms include at least one selected from the group consisting of 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. Phenylmethyl groups are preferred.

[0034] In formula (I), n represents the average number of repeating units. n is 2 to 1,000, preferably 4 to 800, more preferably 6 to 600, even more preferably 8 to 500, and even more preferably 10 to 300. When n is 2 or more, a more excellent modifying effect can be obtained. Furthermore, when n is 1,000 or less, good moldability and productivity can be obtained.

[0035] In an oxygen atom-containing hydrocarbon 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 the following formula (X), and in an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the following formula (X), the bond represented by * in the following formula (X) is bonded to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms:

[0036]

[0037] R in the above formula (X) ２ is R ２ The linear alkyl group having 1 to 20 carbon atoms bonded to the above formula (X) can be exemplified by the same groups exemplified above as the "linear alkyl group having 1 to 20 carbon atoms". The linear alkyl group having 1 to 20 carbon atoms bonded to the above formula (X) is preferably a linear alkyl group having 1 to 15 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms, even more preferably a linear alkyl group having 2 to 10 carbon atoms, and still more preferably a linear alkyl group having 2 to 5 carbon atoms.

[0038] Examples of the branched alkyl group having 3 to 20 carbon atoms bonded to formula (X) above include the same groups exemplified above as the "branched alkyl group having 3 to 20 carbon atoms." The branched alkyl group having 3 to 20 carbon atoms bonded to formula (X) above is preferably a branched alkyl group having 3 to 15 carbon atoms, more preferably a branched alkyl group having 3 to 10 carbon atoms, and even more preferably a branched alkyl group having 3 to 6 carbon atoms, and may be a branched alkyl group having 3 to 5 carbon atoms. Alternatively, it may be an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to all terminal carbon atoms of a branched alkyl group having 3 to 20 carbon atoms has been substituted with a group represented by formula (X) above, or an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group having 3 to 20 carbon atoms has been substituted with a group represented by formula (X) above.

[0039] In formula (X), m represents the average number of repeating units. m is 2 to 1,000, preferably 4 to 800, more preferably 6 to 500, and even more preferably 8 to 300, and may be 10 to 100, 10 to 80, or 10 to 60. When m is 2 or more, a more excellent modifying effect is obtained. Furthermore, when m is 1,000 or less, good moldability and productivity are obtained.

[0040] The average number of repetitions (n ​​and m) is １ It can be calculated from the overall degree of polymerization of the β-methyl-δ-valerolactone polymer determined by H-NMR measurement. More specifically, it can be calculated by the method described in the Examples. The overall degree of polymerization of the β-methyl-δ-valerolactone polymer is the sum of the average number of repeating units contained in the polymer.

[0041] The overall degree of polymerization in the β-methyl-δ-valerolactone polymer is preferably 2 to 10,000, more preferably 4 to 6,000, even more preferably 6 to 3,000, still more preferably 8 to 2,000, and even more preferably 10 to 1,600.

[0042] R １ In the above general formula (I), when a plurality of groups represented by the above formula (X) are present, they may be the same or different from each other. ２ There may be a plurality of m and m. That is, there may be two or more groups represented by formula (X) in the above formula (I). ２ When a plurality of m's are present, they may be the same or different from each other. When a plurality of m's are present, that is, when two or more repeating units represented by the average repeat number m are present, they may be the same or different from each other.

[0043] R １ represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the terminal carbon atom of a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by the above formula (X), the following structure can be specifically exemplified as the above general formula (I): Example 1: R １However, when the linear alkyl group having carbon number Q represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the terminal carbon atom is substituted with a group represented by formula (X), the general formula (I) is represented by the following general formula (I-a), where Q is 1 to 20.

[0044]

[0045] <Example 2> R １ However, when the ethyl group represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the terminal carbon atom in the ethyl group is substituted with a group represented by the above formula (X), the above general formula (I) is represented by the following general formula (I-b):

[0046]

[0047] R １ represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the formula (X), the following structure can be specifically exemplified as the general formula (I): Example 3: R １ However, when all of the terminal carbon atoms of the 2-methylpropyl group represent an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the carbon atom is substituted with a group represented by formula (X), the general formula (I) is represented by the following general formula (I-c):

[0048]

[0049] <Example 4> R １ represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the carbon atom at each of the two terminal carbon atoms of a 2,2-dimethylpropyl group is substituted with a group represented by formula (X), then general formula (I) is represented by the following general formula (I-d):

[0050]

[0051] <Example 5> R １ represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the carbon atom at each of the two terminal carbon atoms of a 2,2-dimethylbutyl group is substituted with a group represented by formula (X), then general formula (I) is represented by the following general formula (I-e):

[0052]

[0053] <Example 6> R １ represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the carbon atom at each terminal carbon atom of a 2,2-dimethylpropyl group is substituted with a group represented by formula (X), the general formula (I) is represented by the following general formula (If):

[0054]

[0055] R １ From the viewpoint of easily obtaining a modifying effect, is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms has been substituted with a group represented by formula (X) above, or an oxygen atom-containing hydrocarbon 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 has been substituted with a group represented by formula (X) above.

[0056] In the general formula (I) and the general formulas (I-a) to (1-f), R ２ represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms. ２ The linear alkyl group having 1 to 20 carbon atoms represented by R can be exemplified by the same groups exemplified above as the "linear alkyl group having 1 to 20 carbon atoms". ２From the viewpoint of ease of handling, the linear alkyl group having 1 to 20 carbon atoms represented by R is preferably a linear alkyl group having 1 to 15 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms, and even more preferably a linear alkyl group having 1 to 5 carbon atoms. Specifically, at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group is preferred. ２ The branched alkyl group having 3 to 20 carbon atoms represented by R can be exemplified by the same groups exemplified above as the "branched alkyl group having 3 to 20 carbon atoms". ２ 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 15 carbon atoms, more preferably a branched alkyl group having 3 to 10 carbon atoms, and even more preferably a branched alkyl group having 3 to 5 carbon atoms. Specifically, at least one selected from the group consisting of an isopropyl group, a 1-methylbutyl group, and a 2,2-dimethylpropyl group is preferred.

[0057] R ２ The linear alkenyl group having 2 to 20 carbon atoms represented by R can be exemplified by the same groups exemplified above as the "linear alkenyl group having 2 to 20 carbon atoms". ２ From the viewpoint of ease of handling, the linear alkenyl group having 2 to 20 carbon atoms represented by R is preferably a linear alkenyl group having 2 to 15 carbon atoms, more preferably a linear alkenyl group having 3 to 10 carbon atoms, and even more preferably a linear alkenyl group having 3 to 6 carbon atoms. ２ Examples of the branched alkenyl group having 3 to 20 carbon atoms represented by R include the same groups exemplified above as the "branched alkenyl group having 3 to 20 carbon atoms". ２ From the viewpoint of ease of handling, the branched alkenyl group having 3 to 20 carbon atoms represented by R is preferably a branched alkenyl group having 3 to 15 carbon atoms, more preferably a branched alkenyl group having 3 to 10 carbon atoms, and even more preferably a branched alkenyl group having 3 to 6 carbon atoms. ２ The aryl group having 6 to 12 carbon atoms represented by R can be exemplified by the same groups exemplified above as the "aryl group having 6 to 12 carbon atoms". ２The aryl group having 6 to 12 carbon atoms represented by R is preferably a phenyl group. ２ The arylalkyl group having 7 to 12 carbon atoms represented by R can be exemplified by the same groups exemplified above as the "arylalkyl group having 7 to 12 carbon atoms". ２ The arylalkyl group having 7 to 12 carbon atoms represented by R is preferably a phenylmethyl group. ２ is preferably a linear alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, from the viewpoint of easily obtaining a modifying effect.

[0058] (Number Average Molecular Weight) From the viewpoint of easily obtaining a more excellent modifying effect, the number average molecular weight of the β-methyl-δ-valerolactone polymer is preferably 500 or more, more preferably 1,000 or more, even more preferably 1,500 or more, and even more preferably 2,000 or more. Furthermore, from the viewpoint of moldability and productivity, the number average molecular weight is preferably 100,000 or less, more preferably 80,000 or less, and even more preferably 50,000 or less. That is, the number average molecular weight of the β-methyl-δ-valerolactone polymer is preferably 500 to 100,000, more preferably 1,000 to 80,000, even more preferably 1,500 to 80,000, and even more preferably 2,000 to 50,000. In this specification, the number average molecular weight of the β-methyl-δ-valerolactone polymer is the number average molecular weight calculated in terms of standard polystyrene as determined by gel permeation chromatography (GPC). Detailed measurement methods can be performed according to the methods described in the Examples.

[0059] (Weight-average molecular weight) The weight-average molecular weight of the β-methyl-δ-valerolactone polymer is preferably 1,500 or more and 200,000 or less. If the weight-average molecular weight is 1,500 or more, an even more excellent modifying effect is likely to be exhibited. If the weight-average molecular weight is 200,000 or less, excellent handleability and productivity during molding are likely to be achieved. The weight-average molecular weight is more preferably 2,200 or more, and even more preferably 3,000 or more. Furthermore, the weight-average molecular weight of the β-methyl-δ-valerolactone polymer is more preferably 160,000 or less, even more preferably 125,000 or less, and even more preferably 100,000 or less. That is, the weight average molecular weight of the β-methyl-δ-valerolactone polymer is preferably 1,500 to 200,000, more preferably 2,200 to 160,000, even more preferably 3,000 to 125,000, and still more preferably 3,000 to 100,000. In this specification, the weight average molecular weight of the β-methyl-δ-valerolactone polymer is a weight average molecular weight calculated in terms of standard polystyrene as determined by gel permeation chromatography (GPC). Details of the measurement method can be found in the methods described in the Examples.

[0060] (Molecular Weight Distribution (Mw / Mn)) The molecular weight distribution (Mw / Mn) of the β-methyl-δ-valerolactone polymer is preferably 1.0 to 3.0, more preferably 1.0 to 2.6, even more preferably 1.1 to 2.5, still 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 polymer" described in this specification is a value determined from the number average molecular weight and weight average molecular weight in terms of standard polystyrene determined by gel permeation chromatography (GPC) measurement. The detailed methods for measuring the number average molecular weight and weight average molecular weight can be those described in the Examples.

[0061] (Viscosity) In the present invention, "viscosity" refers to the viscosity of a polymer measured with an E-type viscometer. The measurement temperature can be optimized depending on the molecular weight, etc. The viscosity of the β-methyl-δ-valerolactone polymer is preferably 10 mPa·s or more at a measurement temperature of 80°C, and more preferably 50 mPa·s or more at a measurement temperature of 80°C, from the viewpoint of achieving a more excellent modifying effect. Furthermore, from the viewpoint of moldability and productivity, the viscosity is preferably 200,000 mPa·s or less at a measurement temperature of 80°C, and more preferably 150,000 mPa·s or less at a measurement temperature of 80°C. That is, the viscosity of the β-methyl-δ-valerolactone polymer is preferably 10 to 200,000 mPa·s, and more preferably 50 to 150,000 mPa·s at a measurement temperature of 80°C. Furthermore, when the β-methyl-δ-valerolactone polymer is measured with an E-type viscometer, the measurement temperature can be set according to the molecular weight, etc. The β-methyl-δ-valerolactone polymer preferably has a viscosity of 100 to 150,000 mPa·s, more preferably a viscosity of 400 to 150,000 mPa·s, and even more preferably a viscosity of 600 to 100,000 mPa·s, at a measurement temperature of 30°C. The β-methyl-δ-valerolactone polymer preferably has a viscosity of 50 to 150,000 mPa·s, more preferably a viscosity of 200 to 150,000 mPa·s, and even more preferably a viscosity of 600 to 120,000 mPa·s, at a measurement temperature of 60°C.

[0062] (Method for Producing β-methyl-δ-valerolactone Polymer) From the viewpoint of productivity and simplicity, or when producing a high-molecular-weight polymer, it is preferable to employ a method for producing the β-methyl-δ-valerolactone polymer, which includes a step (hereinafter also referred to as the "reaction step") of adding a terminal modifier to a reaction solution obtained by reacting β-methyl-δ-valerolactone, an alcohol compound or water, and a base catalyst to carry out a terminal modification reaction. The production method is characterized in that the terminal modifier is added directly to a reaction solution obtained by reacting β-methyl-δ-valerolactone, an alcohol compound or water, and a base catalyst. That is, after ring-opening polymerization of β-methyl-δ-valerolactone, the terminal modifier can be added to the reactor in which the ring-opening polymerization was carried out, without first removing the ring-opened polymer, thereby carrying out terminal modification of the ring-opened polymer. Because the reaction step involves carrying out the ring-opening polymerization reaction and the terminal modification reaction in one pot, the production method can be considered a simplified process. The β-methyl-δ-valerolactone polymer is not limited to being produced by the above production method.

[0063] <Alcohol Compound or Water> The alcohol compound that can be used in this embodiment is not particularly limited as long as the effects of the present invention can be obtained. Examples of alcohol compounds include at least one selected from the group consisting of linear or branched aliphatic hydrocarbon alcohols having 1 to 20 carbon atoms, aromatic hydrocarbon alcohols having 6 to 12 carbon atoms, and alkylaromatic hydrocarbon alcohols having 7 to 12 carbon atoms. These alcohol compounds may have a saturated or unsaturated hydrocarbon group. Note that the "branched aliphatic hydrocarbon alcohol" has 3 to 20 carbon atoms. That is, examples of alcohol compounds include at least one selected from the group consisting of linear aliphatic hydrocarbon alcohols having 1 to 20 carbon atoms, branched aliphatic hydrocarbon alcohols having 3 to 20 carbon atoms, aromatic hydrocarbon alcohols having 6 to 12 carbon atoms, and alkylaromatic hydrocarbon alcohols having 7 to 12 carbon atoms. These alcohol compounds may have a saturated or unsaturated hydrocarbon group. Furthermore, the alcohol compound may be a monohydric alcohol or a polyhydric alcohol such as a dihydric alcohol or a trihydric alcohol. The water that can be used in this embodiment is not particularly limited as long as the effects of the present invention can be obtained. For example, at least one type of water selected from the group consisting of tap water, distilled water, ion-exchanged water, industrial water, and deionized water can be used.

[0064] <Base Catalyst> Examples of base catalysts that can be used in this embodiment include at least one selected from the group consisting of metal catalysts such as alkali metals and alkali metal compounds, and organic base compounds. A single base catalyst may be used alone, or two or more may be used in combination. Examples of alkali metal compounds include at least one selected from the group consisting of organic alkali metal compounds, alkali metal hydroxide compounds, and alkali metal hydrides, with organic lithium compounds such as butyllithium being preferred. Examples of organic base compounds include amine compounds having an amidine skeleton or a guanidine skeleton. Additionally, at least one metal catalyst selected from the group consisting of organomagnesium compounds and organozinc compounds may also be used as the base catalyst. In the reaction step, it is preferable to add 0.005 to 1.5 molar equivalents of the base catalyst relative to the hydroxyl groups of the alcohol compound. Furthermore, when water is used, it is preferable to add 0.005 to 3 molar equivalents of the base catalyst relative to the water.

[0065] <β-Methyl-δ-valerolactone> The β-methyl-δ-valerolactone that can be used in this embodiment can be produced by a known method. For example, it can be produced by a known method using 2-hydroxy-4-methyltetrahydropyran as a raw material (see, for example, Japanese Patent Publication No. 6-53691). Furthermore, commercially available β-methyl-δ-valerolactone can be used, and it can be derived from either petrochemicals or biomass. In the reaction step, it is preferable to add 5 to 1,500 molar equivalents of β-methyl-δ-valerolactone relative to the hydroxyl groups of the alcohol compound. Furthermore, when water is used, it is preferable to add 5 to 1,500 molar equivalents of β-methyl-δ-valerolactone relative to the water.

[0066] <Terminal Modifier> Examples of terminal modifiers that can be used in this embodiment include at least one selected from the group consisting of acid anhydrides and acid halides (acid halides are also referred to as "halogenated esters"). The acid anhydrides and acid halides (halogenated esters) are not particularly limited as long as the effects of the present invention can be obtained. For example, acid anhydrides and acid halides (halogenated esters) having at least one group selected from the group consisting of linear or branched alkyl groups having 1 to 20 carbon atoms, linear or branched alkenyl groups having 2 to 20 carbon atoms, aryl groups having 6 to 12 carbon atoms, and arylalkyl groups having 7 to 12 carbon atoms can be used. Note that in the case of the "branched alkyl group," the number of carbon atoms is 3 to 20, and in the case of the "branched alkenyl group," the number of carbon atoms is 3 to 20. That is, acid anhydrides and acid halides (halogenated esters) having at least one group selected from the group consisting of a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an arylalkyl group having 7 to 12 carbon atoms can be used.

[0067] Specific examples of acid anhydrides include at least one selected from the group consisting of 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. Specific examples of acid halides (halogenated esters) include at least one selected from the group consisting of acetyl chloride, propionyl chloride, butyroyl chloride, trifluoroacetyl chloride, benzoyl chloride, 2-furoyl chloride, hexanoyl chloride, phenylacetyl chloride, acetyl bromide, propionyl bromide, and benzoyl bromide. In the reaction step, it is preferable to add 1 to 20 molar equivalents of a terminal modifier relative to the hydroxyl groups of the alcohol compound. Furthermore, when water is used, it is preferable to add 1 to 20 molar equivalents of a terminal modifier relative to the water.

[0068] <Co-catalyst> In the reaction step, a co-catalyst may be added as needed. For example, at least one amine compound selected from the group consisting of triethylamine, tributylamine, trioctylamine, imidazole, pyridine, aminopyridine, and 4-dimethylaminopyridine can be used as the co-catalyst. In the reaction step, the co-catalyst can be added in an amount of 0.001 to 10 molar equivalents relative to the hydroxyl groups of the alcohol compound. Furthermore, when water is used, the co-catalyst can be added in an amount of 0.001 to 10 molar equivalents relative to the water.

[0069] The reaction step can be carried out in the presence of a solvent inert to the ring-opening polymerization reaction. Examples of the solvent include at least one selected from the group consisting of aliphatic hydrocarbons such as cyclohexane, methylcyclohexane, n-hexane, and n-pentane; and aromatic hydrocarbons such as benzene, toluene, and xylene.

[0070] <Reaction Conditions> In the reaction step, the reaction temperature when reacting β-methyl-δ-valerolactone with an alcohol compound or water and a base catalyst is usually 20 to 100°C, and the reaction time is usually 1 minute to 24 hours. In addition, in the reaction step, the reaction temperature when carrying out the terminal modification reaction after adding a terminal modifying agent to the reaction solution is usually 20 to 80°C, and the reaction time is usually 1 minute to 24 hours.

[0071] <Post-treatment step> The polymer represented by the general formula (I) can be produced through the above reaction step. If necessary, a post-treatment step may be carried out to isolate the produced polymer. As the post-treatment step, a suitable method can be adopted from known methods. For example, the reaction mixture after the reaction step can be washed with a reaction solvent or water, concentrated, and purified by a method typically used for separating and purifying organic compounds, such as distillation.

[0072] [Content Ratio] The resin composition of this embodiment preferably contains 0.1 parts by mass or more and 100 parts by mass or less, more preferably 0.5 parts by mass or more and 50 parts by mass or less, and even more preferably 1 part by mass or more and 30 parts by mass or less, of the β-methyl-δ-valerolactone polymer per 100 parts by mass of the polyhydroxyvalerate polymer. The above content ratios can result in a resin composition that is even more excellent in improving the tensile elongation at break. Furthermore, from the viewpoint of significantly improving the tensile elongation at break, the resin composition of this embodiment can also contain the β-methyl-δ-valerolactone polymer in an amount of 2 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the polyhydroxyvalerate polymer.

[0073] Furthermore, the total content of the polyhydroxyvalerate polymer and the β-methyl-δ-valerolactone polymer in the resin composition of this embodiment is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 98% by mass or more. The total content of the polyhydroxyvalerate polymer and the β-methyl-δ-valerolactone polymer in the resin composition of this embodiment may be 100% by mass or less. That is, the total content of the polyhydroxyvalerate polymer and the β-methyl-δ-valerolactone polymer in the resin composition of this embodiment is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, even more preferably 95 to 100% by mass, and even more preferably 98 to 100% by mass. The above content ratios more significantly enhance the effects of the present invention.

[0074] The content of the polyhydroxyvalerate polymer in the resin composition of this embodiment is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 97% by mass or less. That is, the content of the polyhydroxyvalerate polymer in the resin composition of this embodiment is preferably 60 to 99% by mass, more preferably 70 to 99% by mass, even more preferably 70 to 98% by mass, and even more preferably 80 to 97% by mass. With the above content ratios, the effects of the present invention are more significantly exhibited.

[0075] The content of the β-methyl-δ-valerolactone polymer in the resin composition of this embodiment is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. That is, the content of the β-methyl-δ-valerolactone polymer in the resin composition of this embodiment is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, even more preferably 3 to 30% by mass, and even more preferably 3 to 20% by mass. With the above content ratios, the effects of the present invention are more significantly exhibited.

[0076] The resin composition of this embodiment may contain at least one resin component selected from the group consisting of biomass resins and biodegradable resins other than the polyhydroxyvalerate polymer and the β-methyl-δ-valerolactone polymer. Examples of such biomass resins or 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., at least one selected from the group consisting of polyhydroxybutyrate (PHB) and 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolymer polyesters], cellulose acetate (CA), and starch polyester (Mater-Bi (registered trademark)).

[0077] [Additives] The resin composition of this embodiment may contain additives other than the polyhydroxyvalerate polymer and the β-methyl-δ-valerolactone polymer. Examples of additives include at least one selected from the group consisting of 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.

[0078] [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 polyhydroxyvalerate polymer, β-methyl-δ-valerolactone polymer, and, if necessary, additives. Examples of mixing methods include melt-kneading using a single-screw extruder, multi-screw extruder, Banbury mixer, heated roll, Brabender, or various kneaders, or melt-kneading by feeding each component through separate inlets. 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 200°C, taking into account the melting point and decomposition temperature of the polyhydroxyvalerate polymer.

[0079] <Molded Article> The present invention also provides a molded article made from the resin composition. The shape of the molded article may be any molded article that can be produced using the resin composition of this embodiment. Examples of molded articles include pellets, films, sheets, plates, pipes, tubes, bottles, fibrous bodies, rods, fine particles, particulate bodies, and foamed bodies. The method for producing this molded article is not particularly limited, and the molded article can be obtained by any of the known forming methods selected from the group consisting of injection molding, blow molding, press molding, extrusion molding, calendar molding, and molding using a 3D printer.

[0080] <Applications> Polyhydroxyvalerate polymers can be mixed with β-methyl-δ-valerolactone polymers represented by the above general formula (I) to form resin compositions that can improve tensile elongation at break and impact resistance. Therefore, the present invention provides a modifier for polyhydroxyvalerate polymers, which comprises the β-methyl-δ-valerolactone polymer represented by the above general formula (I). A preferred embodiment of the present invention is the use of the β-methyl-δ-valerolactone polymer represented by the above general formula (I) as a modifier for polyhydroxyvalerate polymers.

[0081] The resin composition of this embodiment can be used in various applications. Specific examples of 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 materials, pharmaceutical packaging materials, food packaging materials, 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; Automotive interior and exterior parts such as bumper parts, body panels, weather strips, grommets, instrument panel coverings, and airbag covers; and various grips such as scissors, screwdrivers, toothbrushes, and ski poles.

[0082] The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to these.

[0083] <Measurement and Evaluation Methods> Various physical properties of the β-methyl-δ-valerolactone polymer and resin composition were measured or evaluated by the following methods.

[0084] [Total Degree of Polymerization of β-methyl-δ-valerolactone Polymer] In the Production Examples, the total degree of polymerization of the obtained β-methyl-δ-valerolactone polymer was １ The degree of polymerization was determined by H-NMR measurement. The proton signal of the raw material alcohol was used as a reference and the overall degree of polymerization was calculated from the ratio of the proton signals of the repeating units in the polymer. The average repeat numbers n and m are the values ​​obtained by dividing the overall degree of polymerization calculated here by the number of hydroxyl groups in the raw material alcohol. The specific measurement method is as follows. (Measurement conditions) Apparatus: 400YH (manufactured by JEOL Ltd.) Solvent: deuterated chloroform (CDCl３ ) Measurement temperature: 23°C Number of times of accumulation: 32 (Method of calculating the overall degree of polymerization) For example, in the case of Production Example 1, the terminal CH ３ (0.90-0.92 ppm, d) Proton number X and the repeating structural unit methyl branch CH of β-methyl-δ-valerolactone ３ Using the number of protons Y of (0.98-1.00 ppm, d), the overall degree of polymerization was calculated using the following formula (1). The average repeat number n is the overall degree of polymerization calculated here divided by 1, which is the number of hydroxyl groups in the raw material isoamyl alcohol. Overall degree of polymerization = 2 x Y / X (1)

[0085] [Number-Average Molecular Weight, Weight-Average Molecular Weight, and Molecular Weight Distribution of β-Methyl-δ-Valerolactone Polymers] Each of the β-methyl-δ-valerolactone polymers obtained in the Production Examples was used as a sample, and the number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC) using standard polystyrene equivalent molecular weights according to the following procedure. <For Mn Less than 15,000> Samples with Mn 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 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) Apparatus: HLC-EcoSEC8320GPC (manufactured by Tosoh Corporation) Column: Three columns, KF-803 (manufactured by Resonac Corporation), KF-802.5 (manufactured by Resonac Corporation), and KF-802 (manufactured by Resonac Corporation), were connected in series. Eluent: tetrahydrofuran Flow rate: 0.9 mL / min Sample injection amount: 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.

[0086] <For Mn of 15,000 or More> Samples with an Mn of 15,000 or more were measured as follows to determine Mn and Mw. A tetrahydrofuran (THF) solution was used as the eluent. 1.0 mg of the sample, calculated as resin, was weighed 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) Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation) Column: Two TSKgel (registered trademark) SuperMultipore HZ-M (manufactured by Tosoh Corporation) columns were 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.

[0087] [Viscosity] In accordance with JIS K 7117-2:1999, the viscosity (unit: mPa s) of the polymers obtained in the Production Examples was measured at the measurement temperatures shown in Table 1 using an E-type viscometer ("TVE-25 type viscometer" manufactured by Toki Sangyo Co., Ltd.).

[0088] [Impact Resistance] (1) Preparation of Test Pieces for Impact Resistance Test The resin compositions obtained in the Examples and Comparative Examples were each subjected to a pressure reduction hot press ("IMC-183B" manufactured by Imoto Machinery Co., Ltd.) using an oil rotary pump to reduce the pressure to -0.1 MPaG, preheated at 150°C for 5 minutes, and pressed at 50 kN for 3 minutes. Thereafter, the resin compositions were subjected to a pressure reduction of 70 kgf / cm using a cooling press equipped with water flow cooling. ２The specimen was pressed at 100°C for 3 minutes to produce a 1.0 mm thick press plate. A 50 x 50 mm square piece was cut out from the obtained press plate and used as a test specimen. (2) Impact Resistance Test Impact resistance was evaluated with reference to JIS K 7211-1:2006. Specifically, the test specimen was stored for 10 hours or more in a low-temperature constant temperature bath (ETAC Corporation's "HIFLEX FL714C") adjusted to the test temperature (-15°C, 0°C, or 23°C) shown in Table 2. After humidity conditioning, the test specimen was measured using a DuPont impact resistance tester (manufactured by Taiyu Kizai Co., Ltd.) according to the following steps (a) to (e) to evaluate impact resistance. (a) Using a support bar, a 1 kg weight was set 0.5 m from the support stand. (b) The test specimen is removed from the thermostatic chamber and placed in an environment of 23°C and 49% humidity, and the test specimen is placed between the support base and the hammer. (c) The pressure rod is pulled out, and the weight is dropped toward the hammer. Here, the time from removing the test specimen in (b) to dropping the weight in (c) must be completed in 5 seconds or less. (d) After the weight is dropped, the test specimen is checked for "breaking" or "not breaking." (e) The operations (a) to (d) are performed on 20 test specimens, and 10 or more test specimens that did not break were considered to have passed ("G"), and less than 10 were considered to have failed ("NG").

[0089] [Tensile Test] (1) Preparation of Test Pieces for Tensile Test The resin compositions obtained in the Examples and Comparative Examples were injection molded using an injection molding machine ("SE18DU" manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 150°C to prepare JIS No. 3 (dumbbell-shaped No. 3) dumbbell test pieces in accordance with JIS K 6251:2017. (2) Tensile Test The prepared dumbbell-shaped test pieces were measured for breaking elongation in accordance with JIS K 7127:1999. Specifically, the test pieces were stored at 23°C and 49% humidity for 24 hours or more, and then evaluated using a universal testing machine ("INSTRON 5900R-5666" manufactured by Instron) at 23°C, 49% humidity, and a tensile speed of 200 mm / min. The breaking elongation (breaking strain) (%) was measured. The measured value was the average of five measurements.

[0090] [Bleeding test] The dumbbell test specimens prepared by the above-mentioned method for preparing test specimens for tensile tests were stored at 80°C for 16 hours or more, and the surface condition was evaluated visually and by touch. VG: No clear bleed-out or stickiness was observed. G: At least one selected from the group consisting of slight bleed-out and slight stickiness was observed, but it was at a level that was acceptable for practical use. NG: At least one selected from the group consisting of significant bleed-out and significant stickiness was observed, and it was not suitable for practical use.

[0091] <Resin Composition> The following polyhydroxyvalerate polymers and β-methyl-δ-valerolactone polymers, as well as other components, were used in the Examples and Comparative Examples. (Polyhydroxyvalerate Polymer) - Aldrich, trade name "PHBV" (weight average molecular weight: 650,000, containing a monomer unit represented by general formula (M1) and a monomer unit represented by general formula (M2), with the molar amount M1 of the former and the molar amount M2 of the latter being in a ratio of M1 / M2 = 92 / 8). (Polymer) - β-methyl-δ-valerolactone polymers produced in Production Examples 1 to 4. (Plasticizer) - Plasticizer 1: DAIFATTY-101, manufactured by Daihachi Chemical Industry Co., Ltd.

[0092] [Production Example 1] A 500 mL four-neck glass flask was purged with nitrogen, and 7.9 g (90 mmol) of isoamyl alcohol and 231 g (2.0 mol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.84 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 11.0 g (108 mmol) of acetic anhydride and 0.55 g (4.5 mmol) of 4-dimethylaminopyridine dissolved in 5.5 g of β-methyl-δ-valerolactone were added to the four-neck glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone polymer. The reaction solution containing the obtained β-methyl-δ-valerolactone polymer was extracted with toluene and water and purified by distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), yielding 155 g of a β-methyl-δ-valerolactone polymer. The physical properties of the obtained β-methyl-δ-valerolactone polymer (hereinafter sometimes referred to as "PMVL-1") were measured as described above. The results are shown in Table 1. The obtained PMVL-1 is a β-methyl-δ-valerolactone polymer represented by the above-mentioned general formula (I), １ , R ２ , n, and the overall degree of polymerization are as shown in Table 1.

[0093] [Production Example 2] A 500 mL four-neck glass flask was purged with nitrogen, and 11.3 g (183 mmol) of ethylene glycol and 184 g (1.6 mol) of β-methyl-δ-valerolactone were added and heated to 60°C. 1.18 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 44.2 g (433 mmol) of acetic anhydride and 2.23 g (18.3 mmol) of 4-dimethylaminopyridine dissolved in 20.8 g of β-methyl-δ-valerolactone were added to the four-neck glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone polymer. The reaction solution containing the obtained β-methyl-δ-valerolactone polymer was extracted with toluene and water and purified by distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), yielding 150 g of a β-methyl-δ-valerolactone polymer. The physical properties of the obtained β-methyl-δ-valerolactone polymer (hereinafter sometimes referred to as "PMVL-2") were measured as described above. The results are shown in Table 1. The obtained PMVL-2 is a β-methyl-δ-valerolactone polymer represented by the above-mentioned general formula (I), １ , R ２ , n, m, and the overall degree of polymerization are as shown in Table 1.

[0094] [Production Example 3] A 500 mL four-neck glass flask was purged with nitrogen, and 1.6 g (18.2 mmol) of isoamyl alcohol and 231 g (2.0 mol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.83 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 2.3 g (22.5 mmol) of acetic anhydride and 0.11 g (0.9 mmol) of 4-dimethylaminopyridine dissolved in 1.1 g of β-methyl-δ-valerolactone were added to the four-neck glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone polymer. The reaction solution containing the obtained β-methyl-δ-valerolactone polymer was extracted with toluene and water and purified by distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), yielding 162 g of a β-methyl-δ-valerolactone polymer. The physical properties of the obtained β-methyl-δ-valerolactone polymer (hereinafter sometimes referred to as "PMVL-3") were measured as described above. The results are shown in Table 1. The obtained PMVL-3 is a β-methyl-δ-valerolactone polymer represented by the above-mentioned general formula (I), １ , R ２ , n, and the overall degree of polymerization are as shown in Table 1.

[0095] [Production Example 4] A 1,000 mL four-necked glass flask was purged with nitrogen, and 1.6 g (18.2 mmol) of isoamyl alcohol and 623 g (5.5 mol) of β-methyl-δ-valerolactone were added and heated to 60°C. 2.21 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 2.2 g (21.8 mmol) of acetic anhydride and 0.11 g (0.9 mmol) of 4-dimethylaminopyridine dissolved in 1.1 g of β-methyl-δ-valerolactone were added to the four-necked glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone polymer. The reaction solution containing the obtained β-methyl-δ-valerolactone polymer was extracted with toluene and water and purified by distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), yielding 450 g of a β-methyl-δ-valerolactone polymer. The physical properties of the obtained β-methyl-δ-valerolactone polymer (hereinafter sometimes referred to as "PMVL-4") were measured as described above. The results are shown in Table 1. The obtained PMVL-4 is a β-methyl-δ-valerolactone polymer represented by the above-mentioned general formula (I), １ , R ２ , n, and the overall degree of polymerization are as shown in Table 1.

[0096] [Production Example 5] A 2,000 mL four-neck glass flask was purged with nitrogen, and 1.8 g (29 mmol) of ethylene glycol, 202 g (1.8 mol) of β-methyl-δ-valerolactone, and 86.8 g of toluene were added and heated to 30°C. 1.5 mL of n-butyllithium (1.6 M hexane solution) was added thereto, and the mixture was stirred at 30°C for 210 minutes. Next, 7.1 g (69 mmol) of acetic anhydride and 0.4 g (2.9 mmol) of 4-dimethylaminopyridine dissolved in 3.5 g of β-methyl-δ-valerolactone were added to the four-neck glass flask, and the mixture was stirred at 30°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone polymer. The reaction solution containing the obtained β-methyl-δ-valerolactone polymer was extracted with toluene and water and purified by distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), yielding 139 g of a β-methyl-δ-valerolactone polymer. The physical properties of the obtained β-methyl-δ-valerolactone polymer (hereinafter sometimes referred to as "PMVL-5") were measured as described above. The results are shown in Table 1. The obtained PMVL-5 is a β-methyl-δ-valerolactone polymer represented by the above-mentioned general formula (I), １ , R ２ , n, m, and the overall degree of polymerization are as shown in Table 1.

[0097] [Production Example 6] A 5,000 mL four-neck glass flask was purged with nitrogen, and 7.6 g (122 mmol) of ethylene glycol and 1,457 g (12.8 mol) of β-methyl-δ-valerolactone were added and heated to 60°C. 1.18 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 11 hours. Next, 29.98 g (294 mmol) of acetic anhydride and 1.50 g (12.0 mmol) of 4-dimethylaminopyridine dissolved in 13.5 g of β-methyl-δ-valerolactone were added to the four-neck glass flask and stirred at 60°C for 30 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone polymer. The reaction solution containing the obtained β-methyl-δ-valerolactone polymer was extracted with toluene and water and purified by distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), yielding 955 g of a β-methyl-δ-valerolactone polymer. The physical properties of the obtained β-methyl-δ-valerolactone polymer (hereinafter sometimes referred to as "PMVL-6") were measured as described above. The results are shown in Table 1. The obtained PMVL-6 is a β-methyl-δ-valerolactone polymer represented by the above-mentioned general formula (I), １ , R ２ , n, m, and the overall degree of polymerization are as shown in Table 1.

[0098] [Production Example 7] A 500 mL four-neck glass flask was purged with nitrogen, and 7.9 g (58.6 mmol) of trimethylolpropane and 130 g (1.1 mol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.76 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 33.45 g (328 mmol) of acetic anhydride and 1.65 g (13.5 mmol) of 4-dimethylaminopyridine dissolved in 14.9 g of β-methyl-δ-valerolactone were added to the four-neck glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone polymer. The reaction solution containing the obtained β-methyl-δ-valerolactone polymer was extracted with toluene and water and purified by distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), yielding 77 g of β-methyl-δ-valerolactone polymer. The physical properties of the obtained β-methyl-δ-valerolactone polymer (hereinafter sometimes referred to as "PMVL-7") were measured as described above. The results are shown in Table 1. The obtained PMVL-7 is represented by the above-mentioned general formula (I), specifically, the above-mentioned general formula (I-e). R １ , R ２ , n, m, and the overall degree of polymerization are as shown in Table 1. In Production Example 7, the starting alcohol has three hydroxyl groups and two m's.

[0099] [Production Example 8] 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 mmol) of β-methyl-δ-valerolactone were added, followed by heating to 60°C. 0.79 mL of n-butyllithium (1.6 M hexane solution) was added, followed by stirring at 60°C for 60 minutes. Next, 34.2 g (216 mmol) of butyric anhydride and 1.1 g (9.0 mmol) of 4-dimethylaminopyridine dissolved in 11 g of β-methyl-δ-valerolactone were added to the four-neck glass flask, followed by stirring at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone polymer. The reaction solution containing the obtained β-methyl-δ-valerolactone polymer was extracted with toluene and water and purified by distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), yielding 158 g of a β-methyl-δ-valerolactone polymer. The physical properties of the obtained β-methyl-δ-valerolactone polymer (hereinafter sometimes referred to as "PMVL-8") were measured as described above. The results are shown in Table 1. The obtained PMVL-8 is a β-methyl-δ-valerolactone polymer represented by the above-mentioned general formula (I), １ , R ２ , n, m, and the overall degree of polymerization are as shown in Table 1.

[0100] [Production Example 9] 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 mmol) of β-methyl-δ-valerolactone were added and heated to 60°C. 0.84 mL of n-butyllithium (1.6 M hexane solution) was added thereto and stirred at 60°C for 60 minutes. Next, 48.9 g (216 mmol) of benzoic anhydride and 1.1 g (9.0 mmol) of 4-dimethylaminopyridine dissolved in 11 g of β-methyl-δ-valerolactone were added to the four-neck glass flask and stirred at 60°C for 60 minutes to obtain a reaction solution containing a β-methyl-δ-valerolactone polymer. The reaction solution containing the obtained β-methyl-δ-valerolactone polymer was extracted with toluene and water and purified by distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), yielding 153 g of a β-methyl-δ-valerolactone polymer. The physical properties of the obtained β-methyl-δ-valerolactone polymer (hereinafter sometimes referred to as "PMVL-9") were measured as described above. The results are shown in Table 1. The obtained PMVL-9 is a β-methyl-δ-valerolactone polymer represented by the above-mentioned general formula (I), １ , R ２ , n, m, and the overall degree of polymerization are as shown in Table 1.

[0101]

[0102] R in Table 1 １ In the column, "X" represents the above formula (X).

[0103] [Examples 1 to 12 and Comparative Examples 1 and 2] A polyhydroxyvalerate polymer, a polymer obtained in a production example, and a plasticizer were charged into a twin-screw kneader (manufactured by Technovel Co., Ltd., product name "ULTnano 50") in the formulations shown in Table 2, and extruded into strands at a cylinder temperature of 150°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 resin compositions. The resulting resin compositions were evaluated as described above. The results are shown in Table 2. In Table 2, "PHBV" means polyhydroxyvalerate polymer.

[0104]

[0105] [Examples 13 to 27] A polyhydroxyvalerate polymer, a polymer obtained in a Production Example, and a plasticizer were charged into a twin-screw kneader (manufactured by Technovel Co., Ltd., product name "ULTnano 50") in the formulations shown in Table 3, and extruded into strands at a cylinder temperature of 150°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 resin compositions. The resulting resin compositions were evaluated as described above. The results are shown in Table 3. In Table 3, "PHBV" means polyhydroxyvalerate polymer.

[0106]

[0107] A comparison of Examples 1 to 27 with Comparative Examples 1 and 2 reveals that the resin compositions of the Examples containing a polyhydroxyvalerate polymer and a β-methyl-δ-valerolactone polymer have significantly improved tensile elongation at break, improved impact resistance in the low temperature range, and suppressed bleed-out caused by the use of a plasticizer, as occurred in Comparative Example 2.

[0108] The resin composition of this embodiment is a resin composition that has improved tensile elongation at break and impact resistance over a wide temperature range compared to polyhydroxyvalerate, and has suppressed bleed-out of the constituent components, making it useful in applications requiring these physical properties. The resin composition of this embodiment can be used, for example, in food utensils, stoppers, cap liners, films and sheets, fibers, tackifiers, adhesives, coating agents, 3D printer filaments, developing toners, support materials for hydraulic fracturing, agents to prevent water loss during excavation, vibration-isolating materials, vibration-damping materials, automotive interior and exterior parts, or various grips.

Claims

1. A resin composition comprising a polyhydroxyalkanoate polymer containing a first monomer unit represented by the following general formula (M1) and a second monomer unit represented by the following general formula (M2), and a β-methyl-δ-valerolactone polymer: 【Chemistry 1】 【Chemistry 2】

2. 2. The resin composition according to claim 1, wherein the β-methyl-δ-valerolactone polymer is represented by the following general formula (I): 【Transformation 3】 [In general formula (I), R １ represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms has been substituted with a group represented by the following formula (X), or an oxygen-atom-containing hydrocarbon 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 has been substituted with a group represented by the following formula (X). In the following formula (X), the bond represented by * bonds to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms. 【Chemistry 4】 R ２ represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms. n is 2 to 1,000, and m is 2 to 1,000. R ２ When a plurality of m's are present, they may be the same or different from each other.

3. 2. The resin composition according to claim 1, wherein the β-methyl-δ-valerolactone polymer is contained in an amount of 0.1 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the polyhydroxyalkanoate polymer.

4. 2. The resin composition according to claim 1, wherein the number average molecular weight of the β-methyl-δ-valerolactone polymer is 500 or more and 100,000 or less.

5. 2. The resin composition according to claim 1, wherein in the polyhydroxyalkanoate-based polymer, the bonding form of the first monomer unit and the second monomer unit is at least one selected from the group consisting of random, block, and combinations thereof.

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

7. A modifier for a polyhydroxyalkanoate polymer contained in the resin composition according to any one of claims 1 to 5, comprising a β-methyl-δ-valerolactone polymer represented by the following general formula (I): 【Transformation 5】 [In general formula (I), R １ represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms has been substituted with a group represented by the following formula (X), or an oxygen-atom-containing hydrocarbon 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 has been substituted with a group represented by the following formula (X). In the following formula (X), the bond represented by * bonds to the linear alkyl group having 1 to 20 carbon atoms or the branched alkyl group having 3 to 20 carbon atoms. 【Transformation 6】 R ２ represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms. n is 2 to 1,000, and m is 2 to 1,000. R ２ When a plurality of m's are present, they may be the same or different from each other.

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