Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
  • C08G63/08—Lactones or lactides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones

Definitions

• the present invention relates to a resin composition containing a polyhydroxyalkanoate polymer and a ⁇ -methyl- ⁇ -valerolactone polymer.
• Patent Document 1 describes a resin composition containing a predetermined amount of polyhydroxybutyrate and an ethylene-vinyl acetate copolymer.
• Patent Document 1 describes the use of polyhydroxybutyrate. However, Patent Document 1 does not describe a resin composition containing a polyhydroxyalkanoate polymer such as polyhydroxybutyrate and an alkyl- ⁇ -valerolactone polyester. Furthermore, Patent Document 1 does not mention the modifying effect of alkyl- ⁇ -valerolactone polyester on polyhydroxyalkanoate polymers that contain structural units derived from 3-hydroxybutanoic acid.
• the present invention provides a resin composition containing a polyhydroxyalkanoate polymer that has improved tensile elongation at break and impact resistance over a wide temperature range, and suppresses bleeding out of the constituent components.
• a resin composition comprising a polyhydroxyalkanoate polymer containing more than 99.0 mol % of a monomer unit represented by the following general formula (M) and a ⁇ -methyl- ⁇ -valerolactone polymer: [2] The resin composition according to [1], wherein the ⁇ -methyl- ⁇ -valerolactone-based 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 arylal
• R2 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms.
• n is 2 to 1,000 and m is 2 to 1,000.
• R 1 represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by formula (X) below, or an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to at
• R2 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms.
• n is 2 to 1,000 and m is 2 to 1,000.
• the present invention provides a resin composition containing a polyhydroxyalkanoate polymer that has improved tensile elongation at break and impact resistance over a wide temperature range, and suppresses bleeding out of the constituent components.
• the polyhydroxyalkanoate polymer used in this embodiment is a polymer containing more than 99.0 mol % of monomer units represented by the following general formula (M).
• the polyhydroxyalkanoate polymer used in this embodiment contains the monomer units derived from 3-hydroxybutanoic acid, and therefore is also referred to as a "3-hydroxybutanoic acid polymer" hereinafter.
• the above 3-hydroxybutanoic acid polymer is highly compatible with the ⁇ -methyl- ⁇ -valerolactone polymer described below. This makes it easy for the resin composition to exhibit the excellent physical properties of the ⁇ -methyl- ⁇ -valerolactone polymer while still being biodegradable.
• the 3-hydroxybutanoic acid polymer contains preferably 99.5 mol% or more, more preferably 99.8 mol%, of the monomer unit represented by the above general formula (M), from the viewpoint of making it easier to increase compatibility with ⁇ -methyl- ⁇ -valerolactone.
• M monomer unit represented by the above general formula (M)
• the 3-hydroxybutanoic acid polymer contains preferably more than 99.0 mol% and 100 mol% or less, more preferably more than 99.0 mol% and less than 100 mol%, of the monomer unit represented by the above general formula (M).
• the weight average molecular weight (Mw) of the 3-hydroxybutanoic acid polymer used in the resin composition of the present embodiment is preferably 100,000 to 1,000,000, and more preferably 150,000 to 700,000, from the viewpoints of fluidity and crystallization rate during injection molding.
• the weight average molecular weight of the 3-hydroxybutanoic acid 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 value listed in the catalog may be used.
• the ⁇ -methyl- ⁇ -valerolactone polymer used in this embodiment is preferably a polymer represented by the following general formula (I).
• the following polymer has a structure represented by the general formula (I) and therefore serves as an excellent modifier for 3-hydroxybutanoic acid polymers.
• the following polymer is a polymer obtained by ring-opening polymerization of ⁇ -methyl- ⁇ -valerolactone, and since at least one hydroxyl group at the molecular end is modified with another functional group, the polymer is inhibited from decreasing in thermal decomposition property, and is capable of inhibiting a decrease in the glass transition temperature of the resin composition.
• the following polymer is expected to be capable of improving the tensile elongation at break of the resin composition due to the structure and number of the molecular ends, and to exhibit a well-balanced property of improving the crystallization rate, improving the impact resistance, improving the hydrolysis resistance, and other functions and ease of handling. Furthermore, since the raw material of the polymer represented by the following general formula (I) is ⁇ -methyl- ⁇ -valerolactone, it is believed that the resin composition of this embodiment has good biodegradability.
• R 1 represents a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen 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.
• linear alkyl groups having 1 to 20 carbon atoms include at least one selected from the group consisting of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icosyl.
• the linear alkyl group having 1 to 20 carbon atoms is preferably a linear alkyl group having 1 to 16 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms, and even more preferably a linear alkyl group having 1 to 5 carbon atoms.
• at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group is preferred.
• Examples of branched alkyl groups having 3 to 20 carbon atoms include isopropyl, 1-methylpropyl, 2-methylpropyl, t-butyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1-ethylpropyl, 2-ethylpropyl, 1,1-diethylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,3,3-trimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, and 3,3-dimethylbutyl.
• a 1-propylbutyl group a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 4,4-dimethylpentyl group, a 1-ethylpentyl group, a 2-ethylpentyl group, a 3-ethylpentyl group, a 4-ethylpentyl group, a 1-propylpentyl group, a 2-propylpentyl group, a 1-butylpentyl group, a 1-methylhexyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 4-methylhexyl group, a 5-methylhexyl group, a 5,5-dimethylhexyl group, a 1-ethylhexyl group, a 2-ethylhexyl group, a 3-ethylhexyl group
• the branched alkyl group having 3 to 20 carbon atoms is preferably a branched alkyl group having 3 to 16 carbon atoms, more preferably a branched alkyl group having 3 to 10 carbon atoms, and even more preferably a branched alkyl group having 3 to 5 carbon atoms.
• at least one selected from the group consisting of an isopropyl group, a 1-methylbutyl group, a 3-methylbutyl group, and a 2,2-dimethylpropyl group is preferred.
• Straight-chain alkenyl groups having 2 to 20 carbon atoms include, for example, ethenyl, n-propenyl, n-butenyl (e.g., 2-butenyl and 3-butenyl), n-pentenyl (e.g., 3-pentenyl and 4-pentenyl), n-hexenyl (e.g., 1-hexenyl and 5-hexenyl), n-heptenyl (e.g., 1-heptenyl and 1,3-heptadienyl), n-octenyl (e.g., 7-octenyl and 2,7-octadienyl), n-nonenyl (e.g., 3-nonenyl and 3,6-nonadienyl), n-decenyl (e.g., 1,3-decadienyl and 1,3,5-decatrienyl), n-unenyl,
• the linear alkenyl group having 2 to 20 carbon atoms is preferably a linear alkenyl group having 2 to 15 carbon atoms, more preferably a linear alkenyl group having 3 to 10 carbon atoms, and even more preferably a linear alkenyl group having 3 to 6 carbon atoms.
• Examples of branched alkenyl groups having 3 to 20 carbon atoms include isopropenyl, 1-methylpropenyl, 2-methylpropenyl, t-butenyl, 1,1-dimethylpropenyl, 2,2-dimethylpropenyl, 1,2-dimethylpropenyl, 1-ethylpropenyl, 2-ethylpropenyl, 1,1-diethylpropenyl, 1-methylbutenyl, 2-methylbutenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethylbutenyl, 2,2-dimethylbutenyl, 3,3-dimethylbutenyl, 1,3,3-trimethylbutenyl, 1-ethylbutenyl, 2-ethylbutenyl, 3,3-dimethylbutenyl group, 1-propylbutenyl group, 1-methylpentenyl group, 2-methylpentenyl group, 3-methylpentenyl group, 4-methyl
• the branched alkenyl group having 3 to 20 carbon atoms is preferably a branched alkenyl group having 3 to 15 carbon atoms, more preferably a branched alkenyl group having 3 to 10 carbon atoms, and even more preferably a branched alkenyl group having 3 to 6 carbon atoms.
• Examples of the aryl group having 6 to 12 carbon atoms include 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.
• a phenyl group is preferable.
• Examples of the arylalkyl group 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.
• a phenylmethyl group is preferred.
• n represents the average number of repetitions.
• 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.
• n is 2 or more, a more excellent modification effect can be obtained.
• n is 1,000 or less, good moldability and productivity can be obtained.
• R2 in the above formula (X) has the same meaning as R2 described below.
• Examples of the linear alkyl group having 1 to 20 carbon atoms bonded to the above formula (X) include the same groups exemplified as the above-mentioned "linear alkyl group having 1 to 20 carbon atoms".
• the linear alkyl group having 1 to 20 carbon atoms bonded to the above formula (X) is preferably a linear alkyl group having 1 to 15 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms, even more preferably a linear alkyl group having 2 to 10 carbon atoms, and even more preferably a linear alkyl group having 2 to 5 carbon atoms.
• Examples of the branched alkyl group having 3 to 20 carbon atoms bonded to the above formula (X) include the same groups exemplified above as the "branched alkyl group having 3 to 20 carbon atoms".
• the branched alkyl group having 3 to 20 carbon atoms bonded to the above formula (X) is preferably a branched alkyl group having 3 to 15 carbon atoms, more preferably a branched alkyl group having 3 to 10 carbon atoms, 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.
• it may be an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to all of the terminal carbon atoms of a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the above formula (X), or it may be an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the above formula (X).
• m represents the average number of repetitions.
• m is 2 to 1,000, preferably 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.
• m is 2 or more, a more excellent modification effect is obtained.
• m is 1,000 or less, good moldability and productivity are obtained.
• Each average number of repetitions (n and m) can be calculated from the overall degree of polymerization of the ⁇ -methyl- ⁇ -valerolactone polymer determined by 1 H-NMR measurement, more specifically, by the method described in the Examples.
• the overall degree of polymerization of a ⁇ -methyl- ⁇ -valerolactone polymer is the sum of the average number of repetitions contained in the polymer.
• the overall degree of polymerization in the ⁇ -methyl- ⁇ -valerolactone polymer is preferably 2 to 10,000, more preferably 4 to 6,000, even more preferably 6 to 3,000, even more preferably 8 to 2,000, and even more preferably 10 to 1,600.
• R1 When a plurality of groups represented by the above formula (X) are present in R1 , they may be the same or different from each other.
• R2 and m may be present in plural. That is, in the above formula (I), two or more groups represented by formula (X) may be present.
• R2s When there are multiple R2s , they may be the same or different from each other.
• m's that is, when there are two or more repeating units represented by the average repeat number m, they may be the same or different from each other.
• R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by the above formula (X)
• specific examples of the above general formula (I) include the following structures.
• Example 1 When R1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the terminal carbon atom of a linear alkyl group having carbon number Q is substituted with a group represented by formula (X) above, the above general formula (I) is represented by the following general formula (I-a), where Q is 1 to 20.
• Example 2 When R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the terminal carbon atom of an ethyl group is substituted with a group represented by the above formula (X), the above general formula (I) is represented by the following general formula (I-b).
• R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the above formula (X)
• specific examples of the above general formula (I) include the following structures.
• Example 3 When R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to all of the terminal carbon atoms of a 2-methylpropyl group is substituted with a group represented by formula (X), the general formula (I) is represented by the following general formula (I-c):
• Example 4 When R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the carbon atom at each of the two terminal carbon atoms of a 2,2-dimethylpropyl group is substituted with a group represented by formula (X), the general formula (I) is represented by the following general formula (I-d):
• Example 5 When R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to the carbon atom at each of the two terminal carbon atoms of a 2,2-dimethylbutyl group is substituted with a group represented by formula (X), the general formula (I) is represented by the following general formula (I-e):
• Example 6 When R 1 represents an oxygen atom-containing hydrocarbon group in which one hydrogen atom bonded to all of the terminal carbon atoms of a 2,2-dimethylpropyl group is substituted with a group represented by formula (X), the general formula (I) is represented by the following general formula (If):
• R 1 is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to a terminal carbon atom in a linear alkyl group having 1 to 20 carbon atoms is substituted with a group represented by the above formula (X), or an oxygen-atom-containing hydrocarbon group in which one hydrogen atom bonded to at least one terminal carbon atom of a branched alkyl group having 3 to 20 carbon atoms is substituted with a group represented by the above formula (X).
• R2 represents a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 12 carbon atoms.
• Examples of the linear alkyl group having 1 to 20 carbon atoms represented by R2 include the same groups exemplified as the "linear alkyl group having 1 to 20 carbon atoms" described above.
• the linear alkyl group having 1 to 20 carbon atoms represented by R2 is preferably a linear alkyl group having 1 to 15 carbon atoms, more preferably a linear alkyl group having 1 to 10 carbon atoms, and even more preferably a linear alkyl group having 1 to 5 carbon atoms.
• at least one selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group is preferable.
• Examples of the branched alkyl group having 3 to 20 carbon atoms represented by R2 include the same groups exemplified as the above-mentioned "branched alkyl group having 3 to 20 carbon atoms".
• the branched alkyl group having 3 to 20 carbon atoms represented by R2 is preferably a branched alkyl group having 3 to 15 carbon atoms, more preferably a branched alkyl group having 3 to 10 carbon atoms, and even more preferably a branched alkyl group having 3 to 5 carbon atoms.
• at least one selected from the group consisting of an isopropyl group, a 1-methylbutyl group, and a 2,2-dimethylpropyl group is preferable.
• Examples of the linear alkenyl group having 2 to 20 carbon atoms represented by R2 include the same groups exemplified as the "linear alkenyl group having 2 to 20 carbon atoms" described above. From the viewpoint of handleability, the linear alkenyl group having 2 to 20 carbon atoms represented by R2 is preferably a linear alkenyl group having 2 to 15 carbon atoms, more preferably a linear alkenyl group having 3 to 10 carbon atoms, and even more preferably a linear alkenyl group having 3 to 6 carbon atoms. Examples of the branched alkenyl group having 3 to 20 carbon atoms represented by R2 include the same groups exemplified above as the "branched alkenyl group having 3 to 20 carbon atoms".
• the branched alkenyl group having 3 to 20 carbon atoms represented by R2 is preferably a branched alkenyl group having 3 to 15 carbon atoms, more preferably a branched alkenyl group having 3 to 10 carbon atoms, and even more preferably a branched alkenyl group having 3 to 6 carbon atoms.
• Examples of the aryl group having 6 to 12 carbon atoms represented by R2 include the same groups exemplified as the "aryl group having 6 to 12 carbon atoms" described above.
• the aryl group having 6 to 12 carbon atoms represented by R2 is preferably a phenyl group.
• Examples of the arylalkyl group having 7 to 12 carbon atoms represented by R2 include the same groups exemplified as the "arylalkyl group having 7 to 12 carbon atoms" described above.
• the arylalkyl group having 7 to 12 carbon atoms represented by R2 is preferably a phenylmethyl group. From the viewpoint of easily obtaining a modifying effect, R2 is preferably a linear alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms.
• the number average molecular weight of the ⁇ -methyl- ⁇ -valerolactone polymer is preferably 500 or more, more preferably 1,000 or more, even more preferably 1,500 or more, and even more preferably 2,000 or more, from the viewpoint of obtaining a more excellent modification effect.
• 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 ⁇ -methyl- ⁇ -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.
• the number average molecular weight of the ⁇ -methyl- ⁇ -valerolactone polymer is a number average molecular weight calculated as a standard polystyrene by gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• the weight average molecular weight of the ⁇ -methyl- ⁇ -valerolactone polymer is preferably 1,500 or more and 200,000 or less. If the weight average molecular weight is 1,500 or more, a more excellent modifying effect is likely to be exhibited. If the weight average molecular weight is 200,000 or less, the handleability and productivity during molding are likely to be excellent.
• the weight average molecular weight is more preferably 2,200 or more, and even more preferably 3,000 or more.
• the weight average molecular weight of the ⁇ -methyl- ⁇ -valerolactone polymer is more preferably 160,000 or less, even more preferably 125,000 or less, and even more preferably 100,000 or less.
• the weight average molecular weight of the ⁇ -methyl- ⁇ -valerolactone polymer is preferably 1,500 to 200,000, more preferably 2,200 to 160,000, even more preferably 3,000 to 125,000, and still more preferably 3,000 to 100,000.
• the weight average molecular weight of the ⁇ -methyl- ⁇ -valerolactone polymer is a weight average molecular weight calculated in terms of standard polystyrene by gel permeation chromatography (GPC). The detailed measurement method can be according to the method described in the Examples.
• the molecular weight distribution (Mw/Mn) of the ⁇ -methyl- ⁇ -valerolactone polymer is preferably 1.0 to 3.0, more preferably 1.0 to 2.6, and even more preferably 1.1 to 2. .5, even more preferably 1.1 to 2.0, and even more preferably 1.2 to 1.8.
• the "molecular weight distribution of the ⁇ -methyl- ⁇ -valerolactone polymer" described in this specification is a value calculated from the number average molecular weight and weight average molecular weight calculated in terms of standard polystyrene by gel permeation chromatography (GPC). The number average molecular weight and the weight average molecular weight can be measured in detail according to the method described in the Examples.
• the viscosity refers to the viscosity of a polymer measured by an E-type viscometer.
• the measurement temperature can be optimized depending on the molecular weight, etc. From the viewpoint of achieving a more excellent modifying effect, the viscosity of the ⁇ -methyl- ⁇ -valerolactone polymer is preferably 10 mPa ⁇ s or more at a measurement temperature of 80° C., and more preferably 50 mPa ⁇ s or more at a measurement temperature of 80° C.
• the viscosity is preferably 200,000 mPa ⁇ s or less at a measurement temperature of 80° C., and more preferably 150,000 mPa ⁇ s or less at a measurement temperature of 80° C. That is, the viscosity of the ⁇ -methyl- ⁇ -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.
• the measurement temperature can be set according to the molecular weight, etc.
• the ⁇ -methyl- ⁇ -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., which is also a preferred embodiment.
• the ⁇ -methyl- ⁇ -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., which is also a preferred embodiment.
• Method for producing ⁇ -methyl- ⁇ -valerolactone polymer As a method for producing the above-mentioned ⁇ -methyl- ⁇ -valerolactone polymer, from the viewpoint of productivity and simplicity, or when producing a high molecular weight polymer, it is preferable to adopt a production method including a step of adding a terminal modifying agent to a reaction solution obtained by reacting ⁇ -methyl- ⁇ -valerolactone, an alcohol compound or water, and a base catalyst to carry out a terminal modification reaction (hereinafter also referred to as a "reaction step").
• the above production method is characterized in that a terminal modifier is added directly to a reaction solution obtained by reacting ⁇ -methyl- ⁇ -valerolactone with an alcohol compound or water and a base catalyst. That is, after ring-opening polymerization of ⁇ -methyl- ⁇ -valerolactone, the terminals of the ring-opened polymer can be modified by adding a terminal modifier to the reactor in which the ring-opening polymerization was carried out, without taking out the ring-opened polymer once. Since the reaction process involves ring-opening polymerization reaction and terminal modification reaction in one pot, the above production method can be said to be a simplified process.
• the ⁇ -methyl- ⁇ -valerolactone polymer is not limited to the above-mentioned production method.
• the alcohol compound that can be used in this embodiment is not particularly limited as long as the effects of the present invention can be obtained.
• the alcohol compound may be 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 alkyl aromatic hydrocarbon alcohols having 7 to 12 carbon atoms. These alcohol compounds may have a saturated or unsaturated hydrocarbon group. In the case of the above-mentioned "branched aliphatic hydrocarbon alcohol", the number of carbon atoms is 3 to 20.
• the alcohol compound may be 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 alkyl aromatic hydrocarbon alcohols having 7 to 12 carbon atoms. These alcohol compounds may have a saturated or unsaturated hydrocarbon group.
• the alcohol compound may be a monohydric alcohol or a polyhydric alcohol such as a dihydric alcohol or a trihydric alcohol.
• the water that can be used in this embodiment is not particularly limited as long as the effects of the present invention can be obtained.
• As the water at least one selected from the group consisting of tap water, distilled water, ion-exchanged water, industrial water, and deionized water can be used.
• the base catalyst that can be used in this embodiment includes at least one selected from the group consisting of metal catalysts such as alkali metals and alkali metal compounds, and organic base compounds.
• the base catalyst may be used alone or in combination of two or more.
• the alkali metal compound may be at least one selected from the group consisting of organic alkali metal compounds, alkali metal hydroxide compounds, and alkali metal hydride compounds, and among these, organic lithium compounds such as butyllithium are preferred.
• Examples of the organic base compound include amine compounds having an amidine skeleton or a guanidine skeleton.
• As the base catalyst at least one metal catalyst selected from the group consisting of organomagnesium compounds and organozinc compounds can also be used.
• the reaction step it is preferable to add 0.005 to 1.5 molar equivalents of the base catalyst relative to the hydroxyl group of the alcohol compound.
• ⁇ -methyl- ⁇ -valerolactone The ⁇ -methyl- ⁇ -valerolactone that can be used in this embodiment can be produced by a known method, for example, by using 2-hydroxy-4-methyltetrahydropyran as a raw material (JP-B-6-53691, etc.).
• ⁇ -methyl- ⁇ -valerolactone a commercially available product can be used, and any product derived from petroleum or biomass can be used.
• water it is preferable to add 5 to 1,500 molar equivalents of ⁇ -methyl- ⁇ -valerolactone to the water.
• the terminal modifying agent that can be used in this embodiment includes at least one selected from the group consisting of acid anhydrides and acid halides (acid halides are also called "halogenated esters").
• the acid anhydrides and acid halides (halogenated esters) are not particularly limited as long as the effects of the present invention can be obtained.
• acid anhydrides and acid halides (halogenated esters) having at least one group selected from the group consisting of 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.
• acid anhydrides and acid halides having at least one group selected from the group consisting of a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a branched alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an arylalkyl group having 7 to 12 carbon atoms can be used.
• the acid anhydride 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.
• the acid halide 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.
• the reaction step it is preferable to add 1 to 20 molar equivalents of the terminal modifier to the hydroxyl group of the alcohol compound.
• water it is preferable to add 1 to 20 molar equivalents of the terminal modifier to the water.
• a promoter may be added, if necessary.
• the co-catalyst 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.
• the promoter can be added in an amount of 0.001 to 10 molar equivalents relative to the hydroxyl groups of the alcohol compound. When water is used, the promoter can be added in an amount of 0.001 to 10 molar equivalents relative to the water.
• the reaction step can be carried out in the presence of a solvent inert to the ring-opening polymerization reaction, such as 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.
• a solvent inert such as at least one selected from the group consisting of aliphatic hydrocarbons, such as cyclohexane, methylcyclohexane, n-hexane, and n-pentane
• aromatic hydrocarbons such as benzene, toluene, and xylene.
• the reaction temperature when reacting ⁇ -methyl- ⁇ -valerolactone with an alcohol compound or water and a base catalyst may usually be 20 to 100° C., and the reaction time is usually 1 minute to 24 hours.
• the reaction temperature for carrying out the terminal modification reaction may usually be 20 to 80° C., and the reaction time is usually 1 minute to 24 hours.
• the polymer represented by the general formula (I) can be produced through the above reaction steps. If necessary, a post-treatment step may be carried out to isolate the produced polymer.
• a suitable method can be adopted from among known methods. For example, the reaction mixture after the reaction step can be washed with a reaction solvent or water, concentrated, and purified by a method typically used for separating and purifying organic compounds, such as distillation.
• the resin composition of this embodiment contains ⁇ -methyl- ⁇ -valerolactone polymer in an amount of preferably 0.1 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, per 100 parts by mass of the 3-hydroxybutanoic acid polymer.
• the above content ratio can provide a resin composition that is even more excellent in improving the tensile elongation at break.
• the resin composition of this embodiment can also contain ⁇ -methyl- ⁇ -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 3-hydroxybutanoic acid polymer.
• the total content of the 3-hydroxybutanoic acid polymer and the ⁇ -methyl- ⁇ -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 3-hydroxybutanoic acid polymer and the ⁇ -methyl- ⁇ -valerolactone polymer in the resin composition of this embodiment may be 100% by mass or less.
• the total content of the 3-hydroxybutanoic acid polymer and the ⁇ -methyl- ⁇ -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 will more significantly exhibit the effects of the present invention.
• the content of the 3-hydroxybutanoic acid polymer in the resin composition of this embodiment is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, and is preferably 99% by mass or less, more preferably 98% by mass or less, and even more preferably 97% by mass or less.
• the content of the 3-hydroxybutanoic acid 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.
• the content of the ⁇ -methyl- ⁇ -valerolactone polymer in the resin composition of this embodiment is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.
• the content of the ⁇ -methyl- ⁇ -valerolactone polymer in the resin composition of this embodiment is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, 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 pronounced.
• the resin composition of this embodiment may contain at least one resin component selected from the group consisting of biomass resins and biodegradable resins, other than the 3-hydroxybutanoic acid polymer and the ⁇ -methyl- ⁇ -valerolactone polymer.
• 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), polyhydroxyalkanoate (PHA) [e.g., at least one selected from the group consisting of polyhydroxybutyrate valerate (PHBV) and 3-hydroxybutyric acid-3-hydroxyhexanoic acid copolymer polyester], and at least one selected from the group consisting of cellulose acetate (CA) and starch polyester (Mater-Bi (registered trademark)).
• PLA polylactic acid
• the resin composition of this embodiment may contain additives other than the 3-hydroxybutanoic acid polymer and the ⁇ -methyl- ⁇ -valerolactone polymer.
• the 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, ultraviolet absorbers, and lubricants. These may be used alone or in combination of two or more. When the above additives are used, the content of the additives in the resin composition may be appropriately determined depending on the desired physical properties of the resin composition.
• Method of producing resin composition There is no particular limitation on the method for producing the resin composition of this embodiment, and it is sufficient to uniformly mix the 3-hydroxybutanoic acid polymer, the ⁇ -methyl- ⁇ -valerolactone polymer, and, if necessary, additives.
• the mixing method include a method of melt-kneading using a single-screw extruder, a multi-screw extruder, a Banbury mixer, a heating roll, a Brabender, or various kneaders, or a method of supplying each component from a separate inlet and melt-kneading the components. Alternatively, the components may be preblended before melt-kneading.
• Examples of the preblending method include a method using a mixer such as a Henschel mixer, a high-speed mixer, a V blender, a ribbon blender, a tumbler blender, or a conical blender.
• the temperature during melt-kneading can be arbitrarily selected, preferably within the range of 140 to 220° C., taking into consideration the melting point and decomposition temperature of the 3-hydroxybutanoic acid polymer.
• the present invention also provides a molded article made of the above resin composition.
• the shape of the molded body may be any molded body that can be produced using the resin composition of this embodiment.
• Examples of the molded body include molded bodies of various shapes selected from the group consisting of pellets, films, sheets, plates, pipes, tubes, bottles, fibrous bodies, rod-shaped bodies, fine particles, particulate bodies, and foams.
• the method for producing this molded body is not particularly limited, and the molded body can be obtained by various known molding methods selected from the group consisting of injection molding, blow molding, press molding, extrusion molding, calendar molding, and molding by a 3D printer.
• the 3-hydroxybutanoic acid polymer can be mixed with the ⁇ -methyl- ⁇ -valerolactone polymer represented by the above general formula (I) to form a resin composition having improved tensile elongation at break and impact resistance.
• the present invention provides a modifier for 3-hydroxybutanoic acid polymers, which comprises the ⁇ -methyl- ⁇ -valerolactone polymer represented by the above general formula (I).
• the use of the ⁇ -methyl- ⁇ -valerolactone polymer represented by the above general formula (I) as a modifier for a 3-hydroxybutanoic acid polymer is also a suitable embodiment.
• the resin composition of this embodiment can be used for various purposes.
• Specific examples of uses of the resin composition include: Food utensils such as food bags, food caps, food trays, straws, cutlery, food containers, etc.; Closures, cap liners for containers for storing food, beverages, medicines, etc.; Single-layer or multi-layer films and sheets for electronic component packaging materials, pharmaceutical packaging materials, food packaging materials, agricultural materials, civil engineering and construction materials, industrial materials, etc.; Fibers such as woven fabrics and nonwoven fabrics; Solvent-type, hot melt-type, heat-stretching-type and other pressure-sensitive adhesives and adhesives; Coating agents such as aqueous, solution, emulsion, and dispersion types; Filament for 3D printers; developing toner; Support material for hydraulic fracturing and water leakage prevention agent for drilling; Anti-vibration rubber, mats, sheets, cushions, dampers, pads, mount rubber, and other various vibration-proofing and vibration-damping materials; Components for household appliances such as
• the overall degree of polymerization of the obtained ⁇ -methyl- ⁇ -valerolactone polymer was determined by 1 H-NMR measurement.
• the overall degree of polymerization was calculated from the ratio of the proton signals of the repeating units in the polymer to the proton signal of the raw alcohol as a reference.
• the average repeat numbers n and m are the total degree of polymerization calculated here divided by the number of hydroxyl groups in the raw alcohol.
• the specific measurement method is as follows.
• THF tetrahydrofuran
• Mn and Mw were determined according to the following measurement.
• a tetrahydrofuran (THF) solution was used as the eluent.
• 1.0 mg of a sample was weighed out in terms of resin and dissolved in 1 mL of the eluent.
• the solution was passed through a 0.2 ⁇ m membrane filter to prepare a measurement sample.
• the measurement conditions were as follows: (Measurement conditions) Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation) Column: Two TSKgel (registered trademark) SuperMultipore HZ-M columns (manufactured by Tosoh Corporation) were connected in series.
• test specimen was stored for 10 hours or more in a low-temperature thermostatic chamber ("HIFLEX FL714C" manufactured by ETAC Co., Ltd.) adjusted to the test temperature (-15°C, 0°C, or 23°C) shown in Table 2, and the humidity was conditioned.
• the test specimen after the humidity conditioning was measured using a DuPont impact resistance tester (manufactured by Taiyu Kizai Co., Ltd.) according to the following procedures (a) to (e) to evaluate the impact resistance.
• the test piece is removed from the thermostatic chamber to an environment of 23° C.
• test piece is placed between the support base and the hammer.
• the pressure bar is pulled out and the weight is dropped toward the hammer.
• the time from removing the test piece in (b) to dropping the weight in (c) must be 5 seconds or less.
• the test piece is checked to see if it “breaks” or “does not break.”
• the operations (a) to (d) were performed on 20 test pieces, and the number of test pieces that did not break was 10 or more, which was judged to be pass (“G"), and the number of test pieces that did not break was less than 10, which was judged to be fail (“NG”).
• test pieces were stored at 23°C and 49% humidity for 24 hours or more, and evaluated at 23°C, 49% humidity, and a tensile speed of 20 mm/min using a universal material testing machine (Instron Corporation, "INSTRON5900R-5666") to measure breaking elongation (breaking strain) (%).
• the measured value was the average value of 5 measurements.
• the reaction solution containing the obtained ⁇ -methyl- ⁇ -valerolactone polymer was purified by extraction with toluene and water and distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.) to obtain 155 g of a ⁇ -methyl- ⁇ -valerolactone polymer.
• the physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone polymer (hereinafter sometimes referred to as "PMVL-1") were measured as described above. The results are shown in Table 1.
• the resulting PMVL-1 is represented by the above general formula (I), and R 1 , R 2 , n and the overall degree of polymerization are as shown in Table 1.
• the reaction solution containing the obtained ⁇ -methyl- ⁇ -valerolactone polymer was purified by extraction with toluene and water and distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.) to obtain 150 g of a ⁇ -methyl- ⁇ -valerolactone polymer.
• the physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone polymer (hereinafter sometimes referred to as "PMVL-2”) were measured as described above. The results are shown in Table 1.
• the resulting PMVL-2 is represented by the above general formula (I), and R 1 , R 2 , n, m and the overall degree of polymerization are as shown in Table 1.
• the reaction solution containing the obtained ⁇ -methyl- ⁇ -valerolactone polymer was purified by extraction with toluene and water and distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.), to obtain 162 g of a ⁇ -methyl- ⁇ -valerolactone polymer.
• the physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone polymer (hereinafter sometimes referred to as "PMVL-3") were measured as described above. The results are shown in Table 1.
• the resulting PMVL-3 is represented by the above general formula (I), and R 1 , R 2 , n and the overall degree of polymerization are as shown in Table 1.
• the reaction solution containing the obtained ⁇ -methyl- ⁇ -valerolactone polymer was purified by extraction with toluene and water and distillation using a thin-film evaporator ("Molecular Distillation Apparatus MS-300" manufactured by Shibata Scientific Co., Ltd.) to obtain 450 g of a ⁇ -methyl- ⁇ -valerolactone polymer.
• the physical properties of the obtained ⁇ -methyl- ⁇ -valerolactone polymer (hereinafter sometimes referred to as "PMVL-4") were measured as described above. The results are shown in Table 1.
• the resulting PMVL-4 is represented by the above general formula (I), and R 1 , R 2 , n and the overall degree of polymerization are as shown in Table 1.
• 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 3-hydroxybutanoic acid-based polymers, and suppresses bleed-out of the constituent components, making it useful in applications where these physical properties are required.
• 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, filaments for 3D printers, toners for development, support materials for hydraulic fracturing, agents to prevent water loss during excavation, vibration-proofing materials, vibration-damping materials, interior and exterior parts for automobiles, or various grips.

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