WO2024029492A1 - ３－ヒドロキシ酪酸からなるコポリエステル及びその製造方法 - Google Patents

３－ヒドロキシ酪酸からなるコポリエステル及びその製造方法 Download PDF

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WO2024029492A1
WO2024029492A1 PCT/JP2023/027959 JP2023027959W WO2024029492A1 WO 2024029492 A1 WO2024029492 A1 WO 2024029492A1 JP 2023027959 W JP2023027959 W JP 2023027959W WO 2024029492 A1 WO2024029492 A1 WO 2024029492A1
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Prior art keywords
acid
copolyester
derived
hydroxybutyric acid
diol
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English (en)
French (fr)
Japanese (ja)
Inventor
翔 稲垣
啓 高野
英知 甲斐
敦好 中山
典起 川崎
尚子 山野
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DIC Corp
National Institute of Advanced Industrial Science and Technology AIST
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DIC Corp
National Institute of Advanced Industrial Science and Technology AIST
Dainippon Ink and Chemicals Co Ltd
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Priority to CN202380054470.3A priority Critical patent/CN119585341A/zh
Priority to EP23850046.6A priority patent/EP4567056A1/en
Priority to JP2023567920A priority patent/JP7537716B2/ja
Publication of WO2024029492A1 publication Critical patent/WO2024029492A1/ja
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    • 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
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • 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
    • C08G63/78—Preparation processes
    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • 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
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable

Definitions

  • the present invention relates to a copolyester consisting of 3-hydroxybutyric acid and a method for producing the same.
  • Patent Document 1 describes a copolyester obtained by the reaction of 3-hydroxybutyric acid, an aliphatic dicarboxylic acid, and an aliphatic diol, wherein the copolyester contains 3-hydroxybutyric acid units relative to all constituent units.
  • Non-Patent Document 1 describes a copolyester consisting of 3-hydroxybutyric acid, 1,4-butanediol, succinic acid, or adipic acid, which has a content of 3-hydroxybutyric acid units of 8.8 to the total structural units. -49% and the average chain length of 3-hydroxybutyric acid is 1.2-19.
  • Patent Document 1 and Non-Patent Document 1 contain information on the content of 3-hydroxybutyric acid units relative to all constituent units (hereinafter also referred to as “3HB content”) and the average chain length of 3-hydroxybutyric acid (hereinafter referred to as “3HB content”). (also referred to as ⁇ 3HB chain length'') on biodegradability is not clear, and because it has a high acid value derived from the decomposition product of 3-hydroxybutyric acid, it has an unpleasant odor and is difficult to hydrolyze. The problem is that it's easy.
  • the present invention was made to solve the above problems, and aims to control the acid value derived from decomposed products to below a certain value while exhibiting high biodegradability with a specific 3HB ratio and 3HB chain length.
  • the present invention aims to provide a copolyester made of 3-hydroxybutyric acid (hereinafter also referred to as "3HB copolyester”) that is hydrolyzable and can suppress odor, and a method for producing the same.
  • 3HB copolyester 3-hydroxybutyric acid
  • a copolyester of 3-hydroxybutyric acid (3HB), dicarboxylic acid (DA), and diol (DO) comprises a structural unit (3HB-U) derived from the 3-hydroxybutyric acid (3HB), a structural unit (DA-U) derived from the dicarboxylic acid (DA), and a structural unit derived from the diol (DO).
  • the dicarboxylic acid (DA) includes an aliphatic dicarboxylic acid
  • the diol (DO) includes an aliphatic diol
  • the content of the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) is 1 to 65 mol% with respect to 100 mol of the total structural units of the copolyester
  • the average chain length of the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) in the copolyester is 2 to 80
  • a compound made of 3-hydroxybutyric acid that exhibits high biodegradability and can suppress hydrolyzability and odor by controlling the acid value derived from the decomposed product to a certain value or less.
  • the purpose of the present invention is to provide polyester and a method for producing the same.
  • 1 is a 1 H-NMR spectrum of the copolyester of Example 1 of the present invention.
  • 1 is a 13 C-NMR spectrum of the copolyester of Example 1 of the present invention.
  • ⁇ means a value greater than or equal to the value before the description " ⁇ ” and less than or equal to the value after the description " ⁇ ".
  • copolyester The copolyester of one embodiment of the present invention (copolyester of the present embodiment) is a copolyester of 3-hydroxybutyric acid (3HB), dicarboxylic acid (DA), and diol (DO) (HB-DA-DO copolyester). (sometimes called polyester).
  • the copolyester of the present embodiment comprises a structural unit (3HB-U) derived from the 3-hydroxybutyric acid (3HB), a structural unit (DA-U) derived from the dicarboxylic acid (DA), and a structural unit derived from the diol (DO). It has a structural unit (DO-U).
  • the dicarboxylic acid (DA) includes an aliphatic dicarboxylic acid
  • the diol (DO) includes an aliphatic diol.
  • the content of the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) is 1 to 65 mol% with respect to 100 mol of all structural units of the copolyester.
  • the average chain length of the structural unit derived from 3-hydroxybutyric acid (3HB-U) in the copolyester of this embodiment is 2 to 80.
  • the acid value of the copolyester of this embodiment is 5 or less.
  • the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) means one residue of 3-hydroxybutyric acid in the copolymer, and specifically, the structural unit derived from the hydrogen atom in the hydroxyl group of 3-hydroxybutyric acid and It means a structure excluding the hydroxyl residue in the carboxyl group.
  • the structural unit derived from dicarboxylic acid (DA) (DA-U) means one residue of dicarboxylic acid (DA) in the copolymer, and specifically, a hydroxyl residue in the carboxyl group of dicarboxylic acid (DA). means the structure excluding.
  • a structural unit derived from diol (DO) (DO-U) means one residue of diol (DO) in a copolymer, and specifically, a structure obtained by removing the hydrogen atom in the hydroxyl group of diol (DO). means.
  • the total number of constituent units of the copolyester means the total number of moles of constituent units derived from all monomers constituting the copolyester.
  • the copolyester of the present embodiment includes a structural unit (3HB-U) derived from the 3-hydroxybutyric acid (3HB), a structural unit (DA-U) derived from the dicarboxylic acid (DA), and the diol (DO ) derived from the above-mentioned 3-hydroxybutyric acid (3HB), and contains no other structural units, all the structural units of the copolyester include the above-mentioned 3-hydroxybutyric acid (3HB)-derived structural units (DO-U) -U), the structural unit (DA-U) derived from the dicarboxylic acid (DA), and the structural unit (DO-U) derived from the diol (DO).
  • the content (mol%) of structural units derived from 3-hydroxybutyric acid (3HB) (3HB-U) is the content (mol%) of structural units derived from 3-hydroxybutyric acid (3HB) relative to the total number of moles of structural units derived from all monomers constituting the copolyester. It is the percentage of the number of moles of the structural unit (3HB-U) derived from 3HB).
  • the evaluation method will be explained in Examples below.
  • the chain structure of the structural unit derived from 3-hydroxybutyric acid (3HB-U) means a structure in which one residue of 3-hydroxybutyric acid is linked with an ester bond, specifically, the hydroxy group of 3-hydroxybutyric acid It means a structure in which the hydrogen atom inside and the structure excluding the hydroxyl residue in the carboxyl group are continuously ester-bonded.
  • the average chain length of the structural units derived from 3-hydroxybutyric acid (3HB-U) is the average value of the number of consecutive structural units derived from 3-hydroxybutyric acid in a sequence of one polyester molecule.
  • the evaluation method will be explained in Examples below.
  • the acid number of a copolyester is the number of milligrams of potassium hydroxide required to neutralize the free acid present in one gram of the copolyester. The evaluation method will be explained in Examples below.
  • the copolyester of the present embodiment is preferably a reaction product of the poly(3-hydroxybutyric acid) (PHB) and a polyester (PAO) of the dicarboxylic acid (DA) and the diol (DO).
  • Poly(3-hydroxybutyric acid) (PHB) which is a polyester of 3-hydroxybutyric acid (3HB)
  • 3HB 3-hydroxybutyric acid
  • the structure of butyric acid excluding the hydrogen atom in the hydroxyl group and the hydroxyl residue in the carboxyl group is a polyester with continuous ester bonds.
  • a polyester (PAO) of dicarboxylic acid (DA) and the diol (DO) is a polyester (PAO) in which a constitutional unit derived from dicarboxylic acid (DA) and a constitutional unit (DO-U) derived from diol (DO) are continuously formed into an ester. It is a bonded polyester.
  • copolyester of this embodiment include the following formulas (1) to (3).
  • the content of the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) according to the present embodiment is 1 to 65 mol%, with respect to 100 mol of all structural units of the copolyester of the present embodiment, and It is preferably from 60 mol% to 60 mol%, more preferably from 3 to 50 mol%, even more preferably from 5 to 30 mol%. If the content of the structural unit (3HB-U) is less than 1 mol%, the biodegradability of the copolyester decreases. When the content of the structural unit (3HB-U) exceeds 65 mol %, acidic decomposition products of 3-hydroxybutyric acid are likely to be generated, causing problems such as generation of an unpleasant odor and easy hydrolysis.
  • the average chain length of the structural unit derived from 3-hydroxybutyric acid (3HB-U) in the copolyester of this embodiment is 2 to 80, preferably 3 to 70, and more preferably 4 to 50. , more preferably 6 to 30.
  • the average chain length of the structural unit (3HB-U) is less than 2, not only the biodegradability of the copolyester but also the mechanical properties and melting point are reduced.
  • the average chain length of the structural unit (3HB-U) exceeds 80, the biodegradability of the copolyester decreases.
  • the content of the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) according to the present embodiment is 5 to 30 mol% with respect to 100 moles of all structural units of the copolyester of the present embodiment, and
  • the average chain length of the structural unit (3HB-U) derived from 3-hydroxybutyric acid in the copolyester of the present embodiment is 6 to 30, the development of high biodegradability, mechanical properties, and melting point, and 3-hydroxybutyric acid It is particularly preferable because it can also suppress the decomposition of .
  • the content of the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) according to the present embodiment can be measured by the 1 H-NMR spectrum of the copolyester of the present embodiment, and in detail, the content of the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) can be measured by the 1 H-NMR spectrum of the copolyester of the present embodiment. It can be measured by the method described in .
  • the content of the structural unit (3HB-U) is determined by the amount of 3-hydroxybutyric acid (3HB) in the raw material for producing the copolyester (or the raw material for the intermediate product) in the copolyester production method of the present embodiment described below. It can be prepared with
  • the average chain length of the 3-hydroxybutyric acid-derived structural unit (3HB-U) in the copolyester of this embodiment can be measured by 1 H-NMR and 13 C-NMR spectra of the copolyester of this embodiment, and can be determined in detail. can be measured by the method described in the Examples below.
  • the average chain length of the structural unit (3HB-U) can be determined by, for example, an esterification reaction between 3-hydroxybutyric acids, an esterification reaction between 3-hydroxybutyric acid and a diol, It can be adjusted by controlling the esterification reaction between dicarboxylic acid (DA) and diol (for example, block polymerization, etc.).
  • Examples include a method of controlling the order in which each raw material is added, a method of adjusting the speed of each reaction, and the like. For example, a method in which an oligomer or polyester (PHB) of 3-hydroxybutyric acid (3HB) is first obtained and then a dicarboxylic acid (DA) and a diol (DO) are reacted; Alternatively, there is a method in which a polyester (PHB) is obtained, a polyester (PAO) of dicarboxylic acid (DA) and a diol (DO) is obtained, and then the obtained polyester (PHB) and polyester (PAO) are reacted. It will be done.
  • the 3-hydroxybutyric acid of the present invention can be used in any of racemic form, (R) form, and (S) form. It is particularly preferable to use the (R) isomer because it can exhibit high biodegradability, mechanical properties, and melting point.
  • the dicarboxylic acid (DA) includes an aliphatic dicarboxylic acid.
  • the content of structures derived from aliphatic dicarboxylic acid is 20 mol% or more. It is preferably 40 mol% or more, more preferably 70 mol% or more.
  • the content of the structure derived from aliphatic dicarboxylic acid is 70 mol % or more, it is possible to achieve both heat resistance, mechanical properties, optical properties, and biodegradability.
  • the dicarboxylic acid (DA) according to this embodiment is an aliphatic dicarboxylic acid. That is, it is preferable that the structural unit (DA-U) derived from dicarboxylic acid (DA) according to the present embodiment is a structural unit derived from aliphatic dicarboxylic acid.
  • the dicarboxylic acid (DA) according to the present embodiment may include, for example, an alicyclic dicarboxylic acid, an aromatic dicarboxylic acid, etc. in addition to the aliphatic dicarboxylic acid.
  • the dicarboxylic acid-derived structural unit (DA-U) according to the present embodiment may include, for example, an alicyclic dicarboxylic acid-derived structural unit, an aromatic dicarboxylic acid-derived structural unit, etc. in addition to the aliphatic dicarboxylic acid. .
  • the dicarboxylic acids (DA) according to this embodiment can be used alone or in combination of two or more.
  • aliphatic dicarboxylic acids examples include alkanedicarboxylic acids (for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, decanedicarboxylic acid) C 1-16 alkene dicarboxylic acids such as C 1-16 alkene dicarboxylic acids, etc.), unsaturated aliphatic dicarboxylic acids (for example, C 2-10 alkene dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, etc.), and the like.
  • alkanedicarboxylic acids for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, decanedicarbox
  • alicyclic dicarboxylic acids examples include cycloalkanedicarboxylic acids (for example, C5-10 cycloalkanedicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid), di- or tricycloalkanedicarboxylic acids (for example, decalinedicarboxylic acids, etc.) acids, norbornane dicarboxylic acid, adamantane dicarboxylic acid, tricyclodecane dicarboxylic acid, etc.), cycloalkenedicarboxylic acids (e.g., C 5-10 cycloalkene-dicarboxylic acids such as cyclohexene dicarboxylic acid), tricycloalkenedicarboxylic acids (e.g., norbornene dicarboxylic acid), dicarboxylic acids, etc.), unsaturated alicyclic dicarboxylic acids (for example, tetrahydrophthalic acid, t
  • Aromatic dicarboxylic acids include, for example, monocyclic aromatic dicarboxylic acids [e.g., phthalic acid, terephthalic acid, isophthalic acid, alkyl isophthalic acids (e.g., C 1-4 alkyl isophthalic acids such as 4-methylisophthalic acid, etc.) C 6-10 arene-dicarboxylic acids such as], polycyclic aromatic dicarboxylic acids [e.g. fused polycyclic aromatic dicarboxylic acids [e.g.
  • Naphthalene dicarboxylic acid having two carboxyl groups in different rings such as 6-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid; 1,2-naphthalene dicarboxylic acid fused polycyclic C 10-24 arene-dicarboxylic acids, preferably is a fused polycyclic C 10-16 arene-dicarboxylic acid, more preferably a fused polycyclic C 10-14 arene-dicarboxylic acid, etc.], an arylarene dicarboxylic acid [e.g., biphenyl dicarboxylic acid (e.g., 2,2'- C 6-10 aryl-C 6-10 arene-dicarboxylic acids such as biphenyldicarboxylic acid, 4,4′-biphenyldicarboxylic acid, etc.], diaryl
  • diarylketone dicarboxylic acids such as diphenylketone dicarboxylic acids (such as 4,4'-diphenylketone dicarboxylic acids) diC 6-10 aryl ketone-dicarboxylic acids such as ), dicarboxylic acids having a fluorene skeleton, etc.
  • dicarboxylic acids having a fluorene skeleton include, for example, dicarboxyfluorene (for example, 2,7-dicarboxyfluorene, etc.); 9,9-bis(carboxyalkyl)fluorene [for example, 9,9-bis(2 -carboxyethyl)fluorene, 9,9-bis(2-carboxypropyl)fluorene, etc.]; 9-(carboxy-carboxyalkyl)fluorene [e.g.
  • 9-(carboxy-carboxyC2-6 alkyl)fluorene such as (1-carboxy-2-carboxyethyl)fluorene, 9-(2-carboxy-3-carboxypropyl)fluorene, etc.]; 9,9-bis(carboxyaryl); ) Fluorene [e.g.
  • DA dicarboxylic acids
  • aliphatic dicarboxylic acids are preferred, succinic acid, adipic acid, and sebacic acid are more preferred, and succinic acid and adipic acid are particularly preferred.
  • the DA-derived structural unit (DA-U) according to the present embodiment includes, in addition to dicarboxylic acid (DA), DA acid anhydride, DA halide, DA esterified product (methyl ester, ethyl ester, monoethylene glycol esters, etc.) can also be used.
  • the diol (DO) includes an aliphatic diol.
  • the content of the structure derived from the aliphatic diol is preferably 20 mol% or more, It is more preferably 40 mol% or more, and even more preferably 70 mol% or more.
  • the content of the structure derived from aliphatic diol is 70 mol % or more, it is possible to achieve both heat resistance, mechanical properties, optical properties, and biodegradability.
  • the diol (DO) according to this embodiment is an aliphatic diol. That is, it is preferable that the diol (DO)-derived structure (DO-U) according to this embodiment is a structural unit derived from an aliphatic diol.
  • the diol (DO) according to the present embodiment may include, for example, an alicyclic diol, an aromatic diol, etc. in addition to the aliphatic diol.
  • the structural unit (DA-U) derived from the diol (DO) according to the present embodiment may include, for example, a structural unit derived from an alicyclic diol acid, a structural unit derived from an aromatic diol acid, etc. in addition to the aliphatic diol. good.
  • the diols (DO) according to this embodiment can be used alone or in combination of two or more.
  • aliphatic diols examples include alkanediols (e.g., ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol) , 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1, C2-10 alkanediols such as 6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol), polyalkanediols (e.g. diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glyco
  • alicyclic diols examples include cycloalkanediols (for example, C 5-8 cycloalkanediols such as cyclohexanediol), di(hydroxyalkyl)cycloalkanes (for example, 1,3-bis(2-hydroxypropyl)cyclo Pentane, 1,3-bis(2-hydroxybutyl)cyclopentane, 1,4-bis(hydroxymethyl)cyclohexane, 1,4-bis(2-hydroxypropyl)cyclohexane, 1,4-bis(2-hydroxybutyl) ) di(hydroxyC 1-4 alkyl) C 5-8 cycloalkanes such as cyclohexane), isosorbide, and the like.
  • cycloalkanediols for example, C 5-8 cycloalkanediols such as cyclohexanediol
  • di(hydroxyalkyl)cycloalkanes for example, 1,3-
  • aromatic diols examples include dihydroxyarenes (e.g., hydroquinone, resorcinol, etc.), di(hydroxyalkyl)arenes (e.g., 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,4-benzenedimethanol) bisphenols (e.g., biphenol , bis(hydroxyphenyl)C 1-10 alkanes such as bisphenol A) , alkylene oxide adducts of bisphenols , diols having a fluorene skeleton, 1,4-bis(2-hydroxyethoxy)benzene, and the like.
  • dihydroxyarenes e.g., hydroquinone, resorcinol, etc.
  • di(hydroxyalkyl)arenes e.g., 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,4-benzenedimethanol
  • bisphenols e.g., biphenol , bis(hydroxyphenyl)C 1-10 alkanes such as bisphenol
  • diols from the viewpoint of biodegradability, aliphatic diols are preferred, and ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol are more preferred. Particularly preferred is 1,4-butanediol.
  • 3HB-U 3HB-derived structural unit
  • DA-U DA-derived structural unit
  • DO-U DO-derived structural unit
  • other structural units include , a unit derived from a hydroxycarboxylic acid (HA) other than 3-hydroxybutyric acid (HA-U) may be included.
  • HA hydroxycarboxylic acid
  • HA-U 3-hydroxybutyric acid
  • the molar content of other structural units is preferably 60 mol% or less, more preferably 40 mol% or less, and 20 mol% of the total structural units of the copolyester of this embodiment. % or less is more preferable. Moreover, the molar content of other structural units may be 1 mol % or more with respect to 100 mol of all structural units of the copolyester of this embodiment.
  • hydroxycarboxylic acid units examples include units such as hydroxyalkanoic acid, hydroxycycloalkanecarboxylic acid (such as hydroxycyclohexanecarboxylic acid), and hydroxybenzoic acid (such as hydroxyarenecarboxylic acid). These hydroxycarboxylic acid units can be used alone or in combination of two or more. Among these hydroxycarboxylic acid units, hydroxyalkanoic acid units are preferred because of their excellent biodegradability.
  • hydroxyalkanoic acid unit examples include glycolic acid, 2-hydroxypropanoic acid (lactic acid), 3-hydroxypropanoic acid, 2-hydroxybutanoic acid (2-hydroxybutyric acid), 4-hydroxybutanoic acid, 3-hydroxy-3 -Methyl-butanoic acid, 2-hydroxypentanoic acid (2-hydroxyvaleric acid), 3-hydroxypentanoic acid, 5-hydroxypentanoic acid, 2-hydroxy-2-methyl-pentanoic acid, 3-hydroxyhexanoic acid, 6- Hydroxyhexanoic acid, 6-hydroxyheptanoic acid, 3-hydroxyheptanoic acid, 7-hydroxyheptanoic acid, 3-hydroxyoctanoic acid, 8-hydroxyoctanoic acid, 3-hydroxynonanoic acid, 9-hydroxynonanoic acid, 3-hydroxydecane
  • units such as acid, hydroxy C 2-15 alkanoic acid which may have a C 1-6 alkyl group such as 10-hydroxydecanoic acid, 12-hydroxystea
  • the hydroxyalkanoic acid unit may be a corresponding lactone unit.
  • the lactone unit has a diC 1-12 alkyl group, such as ⁇ -propiolactone, ⁇ -dimethylpropiolactone, ⁇ -butyrolactone, ⁇ -dimethylbutyrolactone, ⁇ -valerolactone, and ⁇ -caprolactone.
  • Examples include units such as C 3-15 lactone, which may be a C 3-15 lactone.
  • hydroxyalkanoic acid units and lactone units can be used alone or in combination of two or more.
  • hydroxyalkanoic acid units from the viewpoint of biodegradability, 3-hydroxypropanoic acid, 4-hydroxybutanoic acid, 3-hydroxyvaleric acid, 3-hydroxyhexanoic acid, 3-hydroxyheptanoic acid, 3-hydroxyoctane Hydroxy C 3-10 alkanoic acid units such as 3-hydroxynonanoic acid, 3-hydroxydecanoic acid, 6-hydroxyhexanoic acid, 10-hydroxydecanoic acid (hydroxy C 3-10 alkanoic acid units other than 3-hydroxybutyric acid) ) or the corresponding lactone units are preferred.
  • hydroxycarboxylic acid units include a method of reacting in advance with a polyester (PHB) of 3-hydroxybutyric acid (3HB), a method of reacting in advance with a polyester (PAO) of dicarboxylic acid (DA) and the diol (DO), etc.
  • PHB polyester of 3-hydroxybutyric acid
  • PAO dicarboxylic acid
  • DO diol
  • examples include a method of reacting with a polyester of 3-hydroxybutyric acid (3HB) (PHB), a method of adding it at the time of reaction with a polyester (PAO) of dicarboxylic acid (DA), and the diol (DO).
  • the forms of the hydroxycarboxylic acid include monomers of hydroxycarboxylic acid, lactones of hydroxycarboxylic acid, polymers in which hydroxycarboxylic acid is ester-bonded, esterified products of hydroxycarboxylic acid (methyl ester, ethyl ester, monoethylene glycol ester, etc.), hydroxycarboxylic acid Examples include acid halides of carboxylic acids and acid anhydrides of hydroxycarboxylic acids.
  • the copolyester of the present embodiment is a copolyester of 3-hydroxybutyric acid (3HB), dicarboxylic acid (DA), and diol (DO), in which the poly(3-hydroxybutyric acid) (PHB) and the It is preferably a reaction product of dicarboxylic acid (DA) and the diol (DO) with polyester (PAO).
  • the content of the structural unit (HB-U) derived from 3-hydroxybutyric acid (3HB) is 2 to 60 mol% with respect to 100 mol of the total structural units of the copolyester.
  • the average chain length of the 3-hydroxybutyric acid units in the copolyester is 2 to 80, and the acid value of the copolyester is 5 or less.
  • the content of the structural unit (HB-U) derived from 3-hydroxybutyric acid (3HB) is 3 to 50 mol% with respect to 100 mol of the total structural units of the copolyester, and the It is more preferable that the average chain length of 3-hydroxybutyric acid units is 3 to 70, and the acid value of the copolyester is 3 or less.
  • the content of the structural unit (HB-U) derived from 3-hydroxybutyric acid (3HB) is 5 to 30 mol% with respect to 100 mol of the total structural units of the copolyester, and the It is more preferable that the average chain length of 3-hydroxybutyric acid units is 6 to 30, and that the acid value of the copolyester is 2 or less.
  • the acid value (unit: mgKOH/g) of the copolyester of this embodiment is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less.
  • the acid value of the copolyester of this embodiment may be 0.1 or more. When the acid value of the copolyester of this embodiment is 2 or less, hydrolysis and odor can be suppressed.
  • a method for evaluating the acid value of a copolyester will be explained in detail in Examples below.
  • the lower limit of the number average molecular weight (Mn) of the copolyester of the present embodiment may be 5,000 or more, 6,000 or more, or 7,000 or more in terms of polystyrene when measured by gel permeation chromatography (GPC).
  • the upper limit may be 8,000 or more, 10,000 or more, the upper limit may be 1,000,000 or less, 500,000 or less, 100,000 or less, 50,000 or less, 30 ,000 or less. Any combination of these upper and lower limits may be used.
  • the number average molecular weight (Mn) of the copolyester is 1,000,000 or less, molding becomes easy. Further, when the number average molecular weight (Mn) of the copolyester is 5,000 or more, sufficient mechanical properties are exhibited.
  • the copolyester of this embodiment can improve biodegradability, so it can achieve both biodegradability and mechanical properties to a high degree.
  • the above-mentioned preferable structural range of the copolyester of this embodiment can be selected as appropriate depending on the use and the like.
  • the degree of biodegradation can be easily adjusted by adjusting the content of structural units derived from 3-hydroxybutyric acid.
  • the poly(3-hydroxybutyric acid) (PHB) according to the present embodiment is preferably poly(3-hydroxybutyric acid) obtained by subjecting 3-hydroxybutyric acids (3HB) to an esterification reaction.
  • Poly(3-hydroxybutyric acid) (PHB) according to the present embodiment includes a poly(3-hydroxybutyric acid) structure obtained by subjecting 3-hydroxybutyric acids (3HB) to an esterification reaction.
  • the method for producing poly(3-hydroxybutyric acid) is not particularly limited, and includes, for example, a method similar to the method for producing polylactic acid described in the following non-patent literature.
  • Non-patent document A Shinji Yamada, Aknori Takasu, Sadatsugu Takayama, Kazuhiko Kawamura, Microwave-assisted solution polycondensation of L-lactic acid using a Dean-Stark apparatus for a non-thermal microwave polymerization effect induced by the electric fi eld, Polym. Chem. , 5 (2014) 5283-5288.
  • an acid catalyst such as p-toluenesulfonic acid is added to 3-hydroxybutyric acid, and a dehydration esterification reaction is performed in a solvent such as toluene at a temperature of 80 to 150°C.
  • a solvent such as toluene at a temperature of 80 to 150°C.
  • An example of this method is to distill off the solvent, add a solvent such as dichlorobenzene, and then add an alcohol solvent such as methanol to precipitate a solid.
  • the reaction may be carried out without a catalyst or in the presence of a catalyst.
  • the catalyst used in the reaction include metal catalysts, base catalysts, phosphine catalysts, and acid catalysts.
  • the metal catalyst include alkali metals (sodium, etc.), alkaline earth metals (magnesium, calcium, barium, etc.), transition metals (manganese, zinc, cadmium, lead, cobalt, titanium, etc.), Group 13 of the periodic table.
  • Examples include metal compounds containing metals (such as aluminum), metals from group 14 of the periodic table (germanium, tin, etc.), metals from group 15 of the periodic table (antimony, etc.), and the like.
  • the base catalyst examples include tertiary amines (trialkylamines such as trimethylamine and triethylamine), quaternary ammonium salts (tetraalkylammonium halides such as tetraethylammonium chloride and tetraethylammonium bromide, and benzyltrimethylammonium chloride). benzyltrialkylammonium halide, etc.).
  • phosphine catalyst examples include trialkylphosphines (trimethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, etc.), triarylphosphines (triphenylphosphine, tri(o- (tolyl) phosphine, etc.).
  • the acid catalyst examples include inorganic acids (for example, sulfuric acid, hydrogen chloride (or hydrochloric acid), nitric acid, phosphoric acid, etc.), organic acids (for example, sulfonic acids (methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, etc.) alkanesulfonic acids, arenesulfonic acids such as p-toluenesulfonic acid), etc.).
  • the metal compounds include organic acid salts (acetate, propionate, etc.), inorganic acid salts (borate, carbonate, etc.), metal oxides (germanium oxide, etc.), metal chlorides (tin chloride, etc.).
  • metal alkoxides titanium tetraalkoxide, titanium tetra t-butoxide, aluminum isopropoxide, zinc t-butoxide, potassium t-butoxide, etc.
  • alkyl metals titanium, etc.
  • an acid catalyst in that it can increase the activity of the esterification reaction, and arenesulfonic acids such as p-toluenesulfonic acid are preferable in terms of stability in handling and activity as a catalyst.
  • the amount of catalyst used is usually in the range of 0.001 to 5.0% by weight based on the weight of 3-hydroxybutyric acid (3HB).
  • the reaction may be carried out in the presence or absence of a solvent.
  • solvents include hydrocarbons (aliphatic hydrocarbons such as hexane, octane, and cyclohexane, and aromatic hydrocarbons such as toluene, xylene mesitylene, tetralin, chlorobenzene, o-dichlorobenzene, and 1,2,4-trichlorobenzene).
  • Hydrogens halogenated hydrocarbons (dichloromethane, chloroform, carbon tetrachloride, dichloroethane, etc.), ethers (dioxane, tetrahydrofuran, diphenyl ether, etc.), ketones (acetone, methyl ethyl ketone, etc.), esters (methyl acetate, ethyl acetate, etc.) , butyl acetate, etc.), amides (dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, etc.), sulfoxides (dimethylsulfoxide, etc.), cellosolve acetates (C 1-4 alkyl, such as ethyl cellosolve acetate) cellosolve acetate, etc.). These solvents can be used alone or in combination.
  • the reaction atmosphere may be air or an inert gas (nitrogen, helium, etc.) atmosphere, and the reaction pressure may be normal pressure or reduced pressure.
  • the reaction can proceed more easily by distilling water generated in the esterification reaction out of the reaction system.
  • the lower limit of the number average molecular weight (Mn) of poly(3-hydroxybutyric acid) (PHB) may be 1,000 or more, 2,000 or more, 4,000 or more, 8,000 or more, 10, 000 or more, and the upper limit may be 1,000,000 or less, 500,000 or less, 100,000 or less, 50,000 or less, or 10,000 or less. Any combination of these upper and lower limits may be used.
  • the number average molecular weight (Mn) of the copolyester is 1,000,000 or more, it becomes extremely difficult to react the dicarboxylic acid (DA) and the diol (DO) with the polyester (PAO).
  • the polyester (PAO) according to the present embodiment is a reaction product obtained by subjecting a reaction raw material containing the dicarboxylic acid (DA) and the diol (DO) to an esterification reaction.
  • the amount of the diol (DO) present relative to 100 moles of the dicarboxylic acid (DA) is preferably 100 to 110 moles, and preferably 100.1 to 105 moles. is more preferable, and even more preferably 100.2 to 101 mol.
  • the amount of the diol (DO) is 110 moles or more, the molecular weight of the polyester (PAO) decreases, and heat resistance, mechanical properties, optical properties, etc. are no longer exhibited.
  • the amount of the diol (DO) present is less than 100 moles, the acid value tends to increase when used as a raw material for the copolyester of this embodiment due to carboxyl groups existing in excess with respect to hydroxy groups. It's for a reason.
  • the method for producing the polyester (PAO) of the dicarboxylic acid (DA) and the diol (DO) is not particularly limited, and examples include methods described in the following non-patent literature.
  • Non-patent Document B Shuangbao Peng, Zhiyang Bu, Linbo Wu, Bo-Geng Li, Philippe Dubois, High molecular weight poly(butylene succinate-co -furandicarboxylate) with 10 mol% of BF unit: Synthesis, crystallization-melting behavior and mechanical properties, European Polymer Journal 96 (2017) 248-255.
  • polyester is produced by reacting a mixture containing 1,4-butanediol and succinic acid at a temperature of 100 to 250°C, adding a catalyst such as titanium tetraisopropoxide, and further reacting at 100 to 250°C.
  • a catalyst such as titanium tetraisopropoxide
  • the reaction may be carried out without a catalyst or in the presence of a catalyst.
  • the catalyst used in the reaction include acid catalysts.
  • acid catalysts include tin-based catalysts such as monobutyl tin oxide and dibutyl tin oxide, titanium-based catalysts such as titanium tetraisopropoxide and titanyl acetylacetonate, and zirconia-based catalysts such as tetra-butyl-zirconate.
  • titanium-based catalysts examples include titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra n-propoxide, titanium tetra n-butoxide, tetrakis(2-ethylhexyloxy)titanium, tetrastearyloxytitanium, etc.
  • titanium tetraisopropoxide is preferred from the viewpoint of stability in handling and activity as a catalyst.
  • the amount of catalyst used is usually in the range of 0.001 to 5.0% by weight based on the total weight of dicarboxylic acid (DA) and diol (DO).
  • the reaction atmosphere may be air or an inert gas (nitrogen, helium, etc.) atmosphere, and the reaction pressure may be normal pressure or reduced pressure. Furthermore, the reaction can proceed more easily by distilling water, diol (DO), etc. produced in the esterification reaction out of the reaction system.
  • inert gas nitrogen, helium, etc.
  • the reaction time is usually 1 to 48 hours, but the reaction is preferably carried out until no dicarboxylic acid (DA) and diol (DO) remain in the reaction system.
  • the progress of the reaction can be monitored, for example, by monitoring the decrease in dicarboxylic acid (DA) by measuring the acid value.
  • the acid value (unit: mgKOH/g) of the polyester (PAO) of dicarboxylic acid (DA) and the diol (DO) according to the present embodiment is preferably 5 or less, more preferably 3 or less.
  • the number is preferably 2 or less, and more preferably 2 or less. This is because when the acid value of the polyester (PAO) exceeds 5, the acid value of the copolyester of this embodiment tends to become high. Further, when the acid value of the polyester (PAO) is 5 or less, the acid value of the copolyester of this embodiment can be lowered, and hydrolyzability and odor can be suppressed.
  • the method for producing a copolyester of this embodiment (sometimes simply referred to as the production method of this embodiment) is a method for producing the copolyester of this embodiment described above.
  • the manufacturing method of this embodiment includes a step of reacting poly(3-hydroxybutyric acid) (PHB) with a polyester (PAO) of the dicarboxylic acid (DA) and the diol (DO).
  • PHB poly(3-hydroxybutyric acid)
  • PAO polyester
  • the manufacturing method of this embodiment preferably includes the following first to third steps.
  • First step a step of reacting the 3-hydroxybutyric acids with each other to obtain the poly(3-hydroxybutyric acid) (PHB);
  • 2nd step a step of obtaining a polyester (PAO) of the dicarboxylic acid (DA) and the diol (DO) by reacting the dicarboxylic acid (DA) and the diol (DO);
  • Third step A step of reacting the poly(3-hydroxybutyric acid) (PHB) obtained in step 1 with the polyester (PAO) obtained in step 2.
  • ester A method for obtaining the copolyester of this embodiment by carrying out an exchange reaction can be mentioned.
  • the transesterification reaction include the method described in Non-Patent Document 1.
  • the method for producing a copolyester of the present embodiment For example, for a mixture containing poly(3-hydroxybutyric acid) (PHB) and a polyester (PAO) of an aliphatic dicarboxylic acid such as succinic acid and an aliphatic diol such as 1,4-butanediol.
  • PBO poly(3-hydroxybutyric acid)
  • PAO polyester
  • a method for obtaining the copolyester of this embodiment by carrying out a transesterification reaction for a mixture containing poly(3-hydroxybutyric acid) (PHB) and a polyester (PAO) of an aliphatic dicarboxylic acid such as succinic acid and an aliphatic diol such as 1,4-butanediol.
  • the polyester (PHB) When the production method of the present embodiment uses a transesterification reaction between poly(3-hydroxybutyric acid) (PHB) and a polyester (PAO) of the dicarboxylic acid (DA) and the diol (DO), the polyester (PHB)
  • the charging molar ratio of 3-hydroxybutyric acid (3HB) and the polyester (PAO) is the content of the 3-hydroxybutyric acid (3HB) structural unit (3HB-U) in the produced copolyester of this embodiment, the 3-hydroxybutyric acid (3HB) structural unit
  • the average chain length of the copolyester of this embodiment and the acid value of the copolyester of this embodiment are not particularly limited as long as they fall within the above ranges.
  • the molar ratio of polyester (PHB) to polyester (PAO) is usually 1 to 65 mol%, preferably 2 to 60 mol%, and more preferably 3 to 50 mol%. , more preferably 5 to 30 mol%.
  • the molar ratio of poly(3-hydroxybutyric acid) (PHB) and polyester (PAO) exceeds 65 mol%, decomposition of poly(3-hydroxybutyric acid) (PHB) tends to occur, and the copolyester of this embodiment The acid value of will increase.
  • the molar ratio of polyester (PHB) to polyester (PAO) is less than 1 mol%, the average chain length of the constituent units of 3-hydroxybutyric acid (3HB) becomes extremely short.
  • titanium-based catalysts include titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetra n-propoxide, titanium tetra n-butoxide, tetrakis(2-ethylhexyloxy)titanium, tetrastearyloxytitanium, etc.
  • titanium tetraisopropoxide is preferred from the viewpoint of stability in handling and activity as a catalyst.
  • the amount of catalyst used is usually 0.001 to 5.0 mass based on the total mass of poly(3-hydroxybutyric acid) (PHB) and the polyester (PAO) of the dicarboxylic acid (DA) and the diol (DO). % range.
  • the reaction atmosphere may be air or an inert gas (nitrogen, helium, etc.) atmosphere, and the reaction pressure may be normal pressure or reduced pressure.
  • the reaction is carried out until the average chain length of the structural unit (3HB-U) derived from 3-hydroxybutyric acid (3HB) is 2 to 80.
  • the reaction temperature is usually 80 to 250°C, preferably 100 to 200°C, more preferably 110 to 160°C, even more preferably 125 to 150°C.
  • the reaction time is usually 1 minute to 48 hours, preferably 5 minutes to 24 hours, more preferably 10 minutes to 12 hours, and even more preferably 15 minutes to 8 hours.
  • transesterification and esterification can be performed simultaneously.
  • the terminal carboxyl group of poly(3-hydroxybutyric acid) (PHB) or the terminal carboxyl group of polyester (PAO) and the terminal carboxyl group of poly(3-hydroxybutyric acid) (PHB) An esterification reaction with the hydroxy group or the terminal hydroxy group of the polyester (PAO) proceeds, and both terminal groups in the structural formula of the copolyester of this embodiment can be made into hydroxy groups. Since the number of carboxyl groups is reduced, the acid value of the copolyester of this embodiment can be reduced.
  • polyurethane As an application example of the copolyester of this embodiment, for example, a polyurethane derived from the copolyester of this embodiment (sometimes referred to as "polyurethane according to this embodiment") obtained using the copolyester of this embodiment is Can be mentioned.
  • the polyurethane according to this embodiment is obtained, for example, by reacting the copolyester of this embodiment with a polyisocyanate.
  • a polyol other than the copolyester of this embodiment, a chain extender, a chain terminator, and a crosslinking agent may be used in combination.
  • the copolyester of this embodiment for obtaining the polyurethane is preferably a polyester polyol.
  • the polyurethane according to this embodiment is obtained by reacting a polyol and a polyisocyanate, and at least the copolyester of this embodiment is used as the polyol. Therefore, polyurethane is a reaction product obtained by the reaction of polyol and polyisocyanate, and polyurethane has a structural unit derived from a polyol and a structural unit derived from a polyisocyanate, and at least a structural unit derived from the copolyester of this embodiment. has.
  • the copolyester of this embodiment is preferably a polyester polyol.
  • chain extender examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, sucrose, and methylene glycol.
  • aliphatic polyol compounds such as glycerin, sorbitol, and neopentyl glycol
  • aromatic polyol compounds such as bisphenol A, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, and hydroquinone
  • water Ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl- Amine compounds such as 4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, and triethylenetetramine can be used.
  • chain extenders may be used alone or in combination of two or
  • the content of the copolyester of this embodiment in 100% by mass of the total polyol used in the polyurethane synthesis is preferably 10 to 100% by mass, more preferably 50 to 100% by mass.
  • polyisocyanate examples include 1,3- and 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-2,5-phenylene Diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3- Dimethyl-2,4-phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1-methyl-3,5- Diethylbenzene diisocyanate, 3-methyl-1,5-diethylbenzene-2,
  • 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate, and toluene diisocyanate are more preferred.
  • chain terminator having one active hydrogen group may be used if necessary.
  • chain terminators include aliphatic monohydroxy compounds having a hydroxyl group such as methanol, ethanol, propanol, butanol and hexanol, and aliphatic monoamines having an amino group such as morpholine, diethylamine, dibutylamine, monoethanolamine and diethanolamine. is exemplified. These may be used alone or in combination of two or more.
  • a crosslinking agent having three or more active hydrogen groups or isocyanate groups can be used as necessary.
  • the polyurethane according to this embodiment can be obtained by a known polyurethane manufacturing method. Specifically, for example, a method of manufacturing by preparing a polyol, a polyisocyanate, and the chain extender and reacting them can be mentioned. These reactions are preferably carried out, for example, at a temperature of 50 to 100°C for 3 to 10 hours. Moreover, the reaction may be carried out in an organic solvent.
  • organic solvents examples include ketone solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, methyl-n-propyl ketone, acetone, and methyl isobutyl ketone; methyl formate; , ethyl formate, propyl formate, methyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, isobutyl acetate, sec-butyl acetate, and other ester solvents; and the like can be used. These organic solvents may be used alone or in combination of two or more.
  • ketone solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, methyl-n-propyl ketone, acetone, and
  • the content of the structural unit derived from the copolyester of this embodiment in 100% by mass of the polyurethane of this embodiment is preferably 10 to 98% by mass, more preferably 20 to 98% by mass. Thereby, there is a tendency for more favorable effects to be obtained.
  • the content of each structural unit in polyurethane is measured by NMR.
  • the lower limit of the number average molecular weight (Mn) of the polyurethane according to this embodiment may be 5,000 or more, 6,000 or more, 7,000 or more, 8,000 or more, or 10,000 or more.
  • the upper limit may be 1,000,000 or less, 500,000 or less, 100,000 or less, 500,000 or less, or 15,000 or less. Any combination of these upper and lower limits may be used.
  • the number average molecular weight (Mn) of the polyurethane may be 5,000 to 1,000,000, 6,000 to 500,000, 7,000 to 100,000, or 8,000 to 500,000. It may be between 10,000 and 15,000. Within the above range, there is a tendency for more favorable effects to be obtained.
  • the number average molecular weight (Mn) of polyurethane is a value measured by GPC.
  • resin composition examples include the copolyester of this embodiment described above, a thermoplastic resin composition containing polyurethane, or a thermosetting resin composition.
  • thermoplastic resin composition When the resin composition of this embodiment is a thermoplastic resin composition, for example, other resins, crystallization nucleating agents, heat stabilizers, hydrolysis inhibitors, other additives, etc. may be added as necessary. may also be included.
  • the crystallization nucleating agent used in the thermoplastic resin composition according to the present embodiment may be any crystallization nucleating agent used for thermoplastic resins derived from biomass resources such as polylactic acid and polybutylene succinate. But that's fine.
  • a talc-based nucleating agent, a nucleating agent made of a metal salt-based material having a phenyl group, a nucleating agent made of a benzoyl compound, etc. are preferably used.
  • Other known crystallization nucleating agents such as lactate, benzoate, silica, and phosphate ester salts may also be used.
  • the thermoplastic polyester composition of the present embodiment contains a phenolic antioxidant and a phosphite antioxidant as a heat stabilizer of the resin composition, and a carbodiimide compound-based hydrolysis inhibitor as a hydrolysis inhibitor, for example, It is preferable that the resin contains polycarbodiimide resin (trade name: Carbodilite, manufactured by Nisshinbo Chemical Co., Ltd.).
  • the heat stabilizer and hydrolysis inhibitor to be added may be one selected from the above three types of additives, but the above two types of heat stabilizer and hydrolysis inhibitor have different functions. , and those in which each additive is added together are preferred.
  • the amount of the heat stabilizer and hydrolysis inhibitor to be added varies depending on the type, but is generally preferably about 0.1 parts by mass to 5 parts by mass, respectively, per 100 parts by mass of the thermoplastic polyester composition.
  • thermoplastic resin composition of this embodiment may further contain a silicone flame retardant, an organic metal salt flame retardant, an organic phosphorus flame retardant, a metal oxide flame retardant, a metal hydroxide flame retardant, etc. is preferred. This improves flame retardancy and suppresses the spread of fire, and also improves the fluidity of the biodegradable resin composition, making it possible to ensure better moldability.
  • a filler can be added to the thermoplastic resin composition of this embodiment.
  • fillers include talc, mica, montmorillonite, kaolin, and the like. When these fillers serve as crystal nuclei, crystallization of the copolyester is promoted, and the impact strength and heat resistance of the molded article are improved. Moreover, the rigidity of the molded body can also be increased.
  • thermoplastic resin composition of this embodiment includes an antioxidant, an anti-blocking agent, a coloring agent, a flame retardant, a mold release agent, an antifogging agent, a surface wetting improver, an incineration aid, a lubricant, a dispersion aid, and various other additives.
  • Various additives such as surfactants, plasticizers, compatibilizers, weatherability improvers, ultraviolet absorbers, processing aids, antistatic agents, colorants, lubricants, and mold release agents can also be blended as appropriate.
  • any known plasticizer that is generally used as a polymer plasticizer can be used without particular limitation, such as polyester plasticizers, glycerin plasticizers, polyhydric carboxylic acid ester plasticizers, and polyalkylene glycol plasticizers. and epoxy plasticizers.
  • the compatibilizer is not particularly limited as long as it functions as a compatibilizer for copolymer A and copolymer B.
  • the compatibilizing agent include inorganic fillers, glycidyl compounds, polymer compounds grafted or copolymerized with acid anhydrides, and organometallic compounds, and one or more of these may be used. By kneading these materials, heat resistance, bending strength, impact strength, flame retardance, etc. are also improved, which further promotes their application to molded products such as casings for electronic devices such as notebook computers and mobile phones. Ru.
  • fillers can also be blended as fillers.
  • functional additives chemical fertilizers, soil conditioners, plant activators, etc. can also be added.
  • the fillers are broadly classified into inorganic fillers and organic fillers. These can also be used singly or as a mixture of two or more.
  • Inorganic fillers include anhydrous silica, mica, talc, titanium oxide, calcium carbonate, diatomaceous earth, allophane, bentonite, potassium titanate, zeolite, sepiolite, smectite, kaolin, kaolinite, glass, limestone, carbon, and wollastenite.
  • silicates such as calcined perlite, calcium silicate, and sodium silicate, hydroxides such as aluminum oxide, magnesium carbonate, and calcium hydroxide, salts such as ferric carbonate, zinc oxide, iron oxide, aluminum phosphate, and barium sulfate, etc. can be mentioned.
  • the content of the inorganic filler is generally 1 to 80% by weight, preferably 3 to 70% by weight, and more preferably 5 to 60% by weight in the entire composition.
  • organic fillers include raw starch, processed starch, pulp, chitin/chitosan, coconut shell powder, wood powder, bamboo powder, bark powder, and powders such as kenaf and straw. These can also be used singly or as a mixture of two or more.
  • the amount of organic filler added is usually 0.01 to 70% by weight based on the total composition.
  • a horizontal cylindrical mixer a horizontal cylindrical mixer, a V-shaped mixer, a double cone mixer, a ribbon blender, a blender such as a super mixer, and various continuous mixers can be used.
  • a batch kneading machine such as a roll or internal mixer, a one-stage or two-stage continuous kneading machine, a twin-screw extruder, a single-screw extruder, or the like can be used.
  • the kneading method include a method in which various additives, fillers, and thermoplastic resins are added and blended after heating and melting the mixture. Further, blending oil or the like can also be used for the purpose of uniformly dispersing the various additives mentioned above.
  • thermosetting resin composition When the resin composition of this embodiment is a thermosetting resin composition, it may contain, for example, another resin, a copolyester of this embodiment having a reactive group such as a hydroxyl group or a carboxyl group, as a thermosetting resin main ingredient. , further includes a curing agent such as an isocyanate curing agent or a polyamine curing agent that can thermally react with the reactive group.
  • a curing agent such as an isocyanate curing agent or a polyamine curing agent that can thermally react with the reactive group.
  • Examples of the curing agent according to this embodiment include tolylene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate, etc., which have an aromatic structure in their molecular structure.
  • Polyisocyanates compounds in which some of the isocyanate groups of these polyisocyanates are modified with carbodiimide; allophanate compounds derived from these polyisocyanates; isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,3-(isocyanate)
  • Polyfunctional isocyanates such as polyisocyanates, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, octaethylenenonamine, nonaethylenedecamine, piperazine, or Examples include polyethylene polyamines such as N-aminoalkylpiperazine having an alkyl chain having 2 to 6 carbon atoms, and amine compounds such as 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine or IPDA). It will be done.
  • IPDA 3-aminomethyl-3,5,5-trimethylcyclohexylamine
  • the cured product of the resin composition of this embodiment is a cured product of the resin composition as the above-mentioned thermoplastic resin composition or the cured product of the polyester composition as the above-mentioned thermosetting resin composition.
  • the copolyester of this embodiment can be used for various purposes. Specifically, it can be used in a wide range of applications, including artificial leather, synthetic leather, shoes, thermoplastic resins, foamed resins, thermosetting resins, paints, laminating adhesives, elastic fibers, urethane raw materials, automobile parts, and sporting goods. . Since the copolyester of this embodiment, which has excellent biodegradability, is used, the product for the above application has excellent biodegradability.
  • the polyurethane of this embodiment can be used for various purposes. Specifically, artificial leather, synthetic leather, shoes, thermoplastic resin, foamed resin, thermosetting resin, paint, laminating adhesive, vibration isolating material, damping material, automobile parts, sporting goods, fiber treatment agent, binder. It can be used for a wide range of purposes. Since the copolyester of this embodiment, which has excellent biodegradability, is used, the product for the above application has excellent biodegradability.
  • the resin composition of this embodiment can be used for various purposes. Specifically, artificial leather, synthetic leather, shoes, thermoplastic resin, foamed resin, thermosetting resin, paint, laminating adhesive, vibration isolating material, damping material, automobile parts, sporting goods, fiber treatment agent, binder. It can be used for a wide range of purposes. Since the copolyester of this embodiment, which has excellent biodegradability, is used, the product for the above application has excellent biodegradability.
  • the coating agent contains the copolyester of this embodiment, and further contains other components such as other resins, water, and organic solvents, if necessary.
  • Coatings can be applied onto a variety of substrates.
  • the coating agent is used, for example, to coat the surface of a base material of a food packaging container.
  • the base material include plastic films such as styrene resin films, polyolefin resin films, polyester resin films, and nylon resin films, or laminates thereof.
  • the base material include paper, metallized film, aluminum foil, and the like.
  • the coating agent is preferably used for biodegradable substrates. Examples of biodegradable substrates include paper, polyester films, polyolefin films, starch films, and the like.
  • the coating agent can be used as an ink, an adhesive, or the like.
  • the ink contains the copolyester of this embodiment and a colorant, and further contains other components such as a pigment dispersant, water, and an organic solvent, if necessary.
  • the ink is, for example, a printing ink.
  • the ink may be, for example, a water-based ink or an ink that does not contain water (solvent-based ink).
  • the adhesive contains the copolyester of this embodiment, and further contains other components such as other resins, curing agents, and organic solvents, if necessary.
  • the adhesive can also be used as a laminating adhesive composition used when laminating onto the various base materials mentioned above to produce composite films used primarily as packaging materials for foods, medicines, detergents, and the like.
  • Such adhesives include, for example, a two-component curing adhesive containing the copolyester of the present embodiment, a polyester polyol, and a polyisocyanate, or an acrylic resin, a urethane resin, or an ethylene-vinyl acetate copolymer.
  • One-component adhesive can be used. These adhesives may be solvent-based, non-solvent-based, water-based, or alcohol-based adhesives, as required.
  • the sheet is made using the resin composition of this embodiment described above.
  • the resin composition may contain other resins and various additives in addition to the copolyester of this embodiment.
  • various additives include plasticizers, antistatic agents, antioxidants, ultraviolet absorbers, lubricants, antiblocking agents, heat stabilizers, and the like.
  • the sheet include a non-stretched sheet, a biaxially stretched sheet, and a foamed sheet.
  • the sheet can be used in a wide variety of applications, including, but not limited to, food packaging containers, construction materials, home appliances, and miscellaneous goods.
  • the film is made using the resin composition of this embodiment described above.
  • the resin composition may contain other resins and various additives in addition to the copolyester of this embodiment.
  • various additives include plasticizers, antistatic agents, antioxidants, ultraviolet absorbers, lubricants, antiblocking agents, heat stabilizers, and the like.
  • the film include unstretched film, biaxially stretched film, uniaxially stretched film, etc., and can be produced by, for example, melting pellets of film raw material in an extruder and then forming into a film using a T-die or inflation method. .
  • T-die method a biaxially stretched film is obtained by performing longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter.
  • the laminate includes at least one member selected from the sheets and films of this embodiment, and further includes other components such as a printed layer and a resin film as necessary.
  • the laminate is obtained, for example, by laminating a film or sheet on one or both sides of at least one selected from the sheets and films of the present embodiment in order to improve mechanical strength and chemical resistance. Specifically, it can be obtained by thermally laminating a polystyrene-based blown film on at least one of the front side and back side of a sheet or film, or by bonding an olefin-based film (CPP) using an adhesive.
  • the adhesive used is not particularly limited, and may be, for example, the adhesive of this embodiment or a known adhesive.
  • the molded product is obtained by molding at least one member selected from the sheet, film, and laminate of this embodiment.
  • the molded body is obtained, for example, by thermoforming the sheet, film, and laminate of this embodiment.
  • the thermoforming method include a hot plate contact thermoforming method, a vacuum forming method, a vacuum pressure forming method, a plug assist molding method, etc.
  • indirect heat forming using an infrared heater as a heat source can be preferably used. .
  • the molecular weight of the resin is a value measured using gel permeation chromatography (GPC) under the following conditions.
  • FIG. 1 is a 1 H-NMR spectrum of the copolyester of Example 1.
  • the 3HB content was calculated for the peak on the 1 H-NMR spectrum based on the formula shown below.
  • 3HB content (integral value of 5.2 ppm) / ⁇ (integral value of 4.1 ppm - integral value of 3.6 ppm) / 4 + integral value of 5.2 ppm + integral value of 2.6 ppm / 4 ⁇
  • FIG. 2 is a 13 C-NMR spectrum of the copolyester of Example 1.
  • S, B, H, L BS , L 3HB , I XYZ and ⁇ each represent the following.
  • S Structural unit derived from succinic acid
  • B Structural unit derived from 1,4-butanediol
  • H Structural unit derived from 3-hydroxybutyric acid
  • I X-Y-Z Peak derived from the triad of structural units X, Y, and Z Integral value (X, Y, and Z are either S, B, or H)
  • L BS Average chain length of a dyad (combination of two monomer chains) of a structural unit derived from 1,4-butanediol and a structural unit derived from succinic acid
  • L 3HB Average chain length of a structural unit derived from 3-hydroxybutyric acid ⁇ : It is an index representing the randomness of copolyester and takes a value of 0 to 2.
  • Non-patent Document C Atsuyoshi Nakayama*, Naoko Yamano, Norioki Kawasaki, Biodegradation in seawater of aliphati c polyesters, Polymer Degradation and Stability 166 (2019) 290-299.
  • Biodegradation measurement method A soda lime (carbon dioxide absorbent) and a pressure sensor (manufactured by WTW, OxiTop-IDS (registered trademark)) were attached to the test bottle, and BOD (biochemical oxygen demand) was measured under the following conditions. was measured and the degree of biodegradation was calculated. Culture temperature: 27°C, dark Culture period: 28 days
  • Biodegradability (%) (BOD 0 - BOD B )/ThOD ⁇ 100
  • BOD 0 Biochemical oxygen demand of test material (measured value: mg)
  • BOD B Average biochemical oxygen demand of blank test (measured value: mg)
  • ThOD Theoretical oxygen demand required if the test material is completely oxidized (calculated value: mg)
  • the average molecular weight was measured using the method for measuring average molecular weight described above.
  • the number average molecular weight Mn was 10,200, and the weight average molecular weight Mw was 38,000.
  • the acid value was measured using the acid value measurement method described above. As a result, the acid value was 0.44 mg-KOH/g.
  • Example 1 In a test tube equipped with a stirrer and a nitrogen gas introduction tube, 0.41 g (4.8 mmol) of poly(3-hydroxybutyric acid) obtained in Synthesis Example 1, 5.70 g (66.2 mmol) of PBS obtained in Synthesis Example 3, 0.01% by mass of titanium tetraisopropoxide was charged, and the transesterification reaction was allowed to proceed at a temperature of 140° C. for 15 minutes while removing water produced by the esterification reaction under reduced pressure.
  • the copolyester of this embodiment a copolyester of 3-hydroxybutyric acid-succinic acid-1,4-butanediol was obtained.
  • the mass ratio of PHB to PBS was 6.7/93.3.
  • the average molecular weight was measured using the method for measuring average molecular weight described above.
  • the number average molecular weight Mn was 7,100, and the weight average molecular weight Mw was 17,400.
  • the content of the structure derived from 3-hydroxybutyric acid was measured by the method described in ⁇ Calculation of 3-hydroxybutyric acid content> above. The results are shown in Table 1.
  • the average chain length of the structure derived from 3-hydroxybutyric acid was measured by the method described in ⁇ Evaluation of Average Chain Length> above. The results are shown in Table 1.
  • Biodegradability was evaluated by the method described in ⁇ Biodegradability Evaluation> above.
  • the results are shown in Table 1.
  • the acid value was evaluated according to the above ⁇ Measurement of acid value>. The results are shown in Table 1.
  • Example 2 Same as Example 1 except that the charged mass ratio of poly(3-hydroxybutyric acid) obtained in Synthesis Example 1 and PBS obtained in Synthesis Example 3 was as shown in Table 1 at a temperature of 130 ° C. for 15 minutes.
  • a copolyester of 3-hydroxybutyric acid-succinic acid-1,4-butanediol was obtained as the copolyester of the present embodiment by a similar method.
  • the average molecular weight was measured using the method for measuring average molecular weight described above.
  • the number average molecular weight Mn was 7,600, and the weight average molecular weight Mw was 20,100.
  • the content of 3-hydroxybutyric acid, average chain length, acid value, and biodegradability were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 Same as Example 1 except that the charged mass ratio of poly(3-hydroxybutyric acid) obtained in Synthesis Example 1 and PBS obtained in Synthesis Example 3 was as shown in Table 1 at a temperature of 150 ° C. for 2 hours.
  • a copolyester of 3-hydroxybutyric acid-succinic acid-1,4-butanediol was obtained as the copolyester of the present embodiment by a similar method.
  • the average molecular weight was measured using the method for measuring average molecular weight described above.
  • the number average molecular weight Mn was 10,400, and the weight average molecular weight Mw was 17,800.
  • the content of 3-hydroxybutyric acid, average chain length, acid value, and biodegradability were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 4 Same as Example 1 except that the charged mass ratio of poly(3-hydroxybutyric acid) obtained in Synthesis Example 1 and PBS obtained in Synthesis Example 3 was as shown in Table 1 at a temperature of 150 ° C. for 15 minutes.
  • a copolyester of 3-hydroxybutyric acid-succinic acid-1,4-butanediol was obtained as the copolyester of the present embodiment by a similar method.
  • the average molecular weight was measured using the method for measuring average molecular weight described above.
  • the number average molecular weight Mn was 7,600, and the weight average molecular weight Mw was 16,100.
  • the content of 3-hydroxybutyric acid, average chain length, acid value, and biodegradability were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 5 Same as Example 1 except that the charged mass ratio of poly(3-hydroxybutyric acid) obtained in Synthesis Example 1 and PBS obtained in Synthesis Example 2 was as shown in Table 1 at a temperature of 150 ° C. for 2 hours.
  • a copolyester of 3-hydroxybutyric acid-succinic acid-1,4-butanediol was obtained as the copolyester of the present embodiment by a similar method.
  • the average molecular weight was measured using the method for measuring average molecular weight described above.
  • the number average molecular weight Mn was 7,500, and the weight average molecular weight Mw was 19,200.
  • the content of 3-hydroxybutyric acid, average chain length, acid value, and biodegradability were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 1 The same method as in Example 1 was carried out at a temperature of 175° C. for 2 hours, except that the charged mass ratio of poly(3-hydroxybutyric acid) obtained in Synthesis Example 1 and PBS obtained in Synthesis Example 3 was as shown in Table 1. Thus, a copolyester of 3-hydroxybutyric acid-succinic acid-1,4-butanediol was obtained.
  • the average molecular weight was measured using the method for measuring average molecular weight described above.
  • the number average molecular weight Mn was 13,000, and the weight average molecular weight Mw was 25,600.
  • the content of 3-hydroxybutyric acid, average chain length, acid value, and biodegradability were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 2 The same method as in Example 1 was carried out at a temperature of 175° C. for 2 hours, except that the charged mass ratio of poly(3-hydroxybutyric acid) obtained in Synthesis Example 1 and PBS obtained in Synthesis Example 3 was as shown in Table 1. Thus, a copolyester of 3-hydroxybutyric acid-succinic acid-1,4-butanediol was obtained.
  • the average molecular weight was measured using the method for measuring average molecular weight described above.
  • the number average molecular weight Mn was 8,200, and the weight average molecular weight Mw was 15,200.
  • the content of 3-hydroxybutyric acid, average chain length, acid value, and biodegradability were evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • the copolyester of this embodiment has a structure derived from 3-hydroxybutyric acid, and while exhibiting biodegradability, the acid value derived from the decomposition product is controlled to a certain value or less, thereby reducing hydrolyzability and odor. Therefore, the resin composition containing the copolyester of this embodiment is expected to be used in various applications such as sustainable product groups (packaging materials, films).

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