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
  • C08G63/60—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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
• • 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 copolyester and a method for producing the same.
• This application claims priority based on Japanese Patent Application No. 2022-110293 filed in Japan on July 8, 2022, the contents of which are incorporated herein.
• PHA has attracted attention as a resin that is friendly to the natural environment, and is widely used, and is expected to expand its application areas in the future.
• PHA has a melting temperature close to a thermal decomposition temperature, and thermal decomposition progresses during processing, so it has poor thermoformability compared to general-purpose resins.
• the upper limit of the polymerization temperature is low, making it difficult to synthesize a polymer. Therefore, there is a need for biodegradable resins that can be synthesized at relatively high temperatures similar to general-purpose resins and that can be thermoformed.
• Non-Patent Document 1 describes a copolyester containing a biodegradable block (X) derived from a poly(caprolactone) structure and a non-biodegradable block (Y) derived from a polybutylene terephthalate structure.
• Copolyesters are disclosed in which the molar ratio (X/Y) in the copolyesters is 38/62, 41/59, 55/45. It is also disclosed that this copolyester has a melting point of 200° C. or higher and is biodegradable by activated sludge.
• Non-Patent Document 1 is limited to applications that are disposed of in an activated sludge environment. Furthermore, in order to exhibit biodegradability in an activated sludge environment, the proportion of the biodegradable block (X) derived from the poly(caprolactone) structure in the copolyester is high. As a result, it is difficult to design a resin structure that achieves both decomposability and thermophysical properties such as melting point. Copolyesters are expected to have a high degree of freedom in design and are biodegradable in all environments, including seawater.
• the present invention has been made to solve the above problems, and in addition to the proportion of biodegradable blocks (X) in the copolyester, the average chain length of the degradable blocks (X) in the copolyester is observed, By controlling a specific average chain length, the melting point is 180°C or less, which reduces thermal energy during molding, and is biodegradable in multiple environments (seawater, freshwater, soil, and compost).
• the purpose of the present invention is to provide a copolyester that has both good thermal properties such as melting point, and a method for producing the same.
• a copolyester comprising a biodegradable block (X) and a non-biodegradable block (Y),
• the biodegradable block (X) is a block containing one or more structural units of biodegradable poly(caprolactone)
• the non-biodegradable block (Y) is a block containing one or more constitutional units of the non-biodegradable polymer (y)
• the molar ratio (X/Y) of the biodegradable block (X) and the non-biodegradable block (Y) is 1/99 to 50/50
• a copolyester in which the biodegradable block (X) has an average chain length of more than 1.2.
• DA dicarboxylic acid
• DO diol
• Tm melting point
• a resin composition comprising the copolyester according to any one of [1] to [5].
• the melting point is 180°C or less, which can suppress thermal energy during molding, is biodegradable in multiple environments (seawater, freshwater, soil, compost), and has thermophysical properties such as biodegradability and melting point.
• the purpose of the present invention is to provide a copolyester and a method for producing the same that are compatible with the above.
• ⁇ means a value greater than or equal to the value before the description " ⁇ ” and less than or equal to the value after the description " ⁇ ".
• the copolyester of one embodiment of the present invention is a copolyester containing a biodegradable block (X) and a non-biodegradable block (Y),
• the biodegradable block (X) is a block containing one or more structural units of biodegradable poly(caprolactone).
• the non-biodegradable block (Y) is a block containing one or more non-biodegradable polyester structural units.
• the molar ratio (X/Y) of the biodegradable block (X) and the non-biodegradable block (Y) is 1/99-50/50.
• the biodegradable block (X) has an average chain length of more than 1.2.
• the structural unit of poly(caprolactone) is a structural unit (6HH-U) derived from 6-hydroxyhexanoic acid (6HH), and means one residue of 6-hydroxyhexanoic acid (6HH) in the copolyester.
• the structural unit of poly(caprolactone) refers to a structure obtained by removing the hydrogen atom in the hydroxyl group and the hydroxyl residue in the carboxyl group of 6-hydroxyhexanoic acid (6HH).
• a substance is "biodegradable" it means, for example, that when discharged into the natural environment, the substance is decomposed into carbon dioxide and water by the action of microorganisms and the like.
• Examples of the "environment" in which it is decomposed include a seawater environment, a freshwater environment, a soil environment, and compost.
• the present invention particularly focuses on biodegradability in a seawater environment.
• “showing biodegradability” means showing a seawater decomposition rate of 15% or more.
• “showing non-biodegradability” means showing a seawater decomposition rate of less than 15%.
• the present invention specifies degradability in a "seawater environment,” environments other than seawater environments are not excluded from the scope. It is more preferable that the material not only exhibits biodegradability in a seawater environment, but also exhibits a decomposition rate of 15% or more in environments other than seawater, such as a freshwater environment, a soil environment, or a compost environment.
• the molar ratio (X/Y) between the biodegradable block (X) and the non-biodegradable block (Y) means the ratio of the number of moles of the structural units contained in each block.
• a copolyester is described which is the reaction product of poly(caprolactone) and a polyester of dicarboxylic acid (DA) and diol (DO).
• the molar ratio (X/Y) of the biodegradable block (X) and the non-biodegradable block (Y) is the mole of the constituent unit of poly(caprolactone) contained in this copolyester.
• 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 chain structure of the biodegradable block (X) means a structure in which one residue of 6-hydroxyhexanoic acid (6HH) is continuously ester bonded.
• the chain structure of the biodegradable block (X) is a structure in which the hydrogen atom in the hydroxyl group of 6-hydroxyhexanoic acid and the hydroxyl residue in the carboxyl group are continuously ester bonded.
• the average chain length of the biodegradable block (X) is the average number of consecutive constituent units of 6-hydroxyhexanoic acid (6HH) in a sequence of one polyester molecule.
• the non-biodegradable polyester is preferably a polyester (PAO) of dicarboxylic acid (DA) and diol (DO). More preferably, the non-biodegradable polyester is polybutylene succinate or polybutylene adipate terephthalate.
• the copolyester of this embodiment is more preferably a reaction product of poly(caprolactone) and a polyester (PAO) of dicarboxylic acid (DA) and diol (DO).
• the copolyester of the present embodiment contains a structural unit (6HH-U) derived from 6-hydroxyhexanoic acid (6HH), a structural unit (DA-U) derived from dicarboxylic acid (DA), and a structural unit derived from diol (DO). It is preferable to include a structural unit (DO-U).
• copolyester of this embodiment include copolyesters shown in the following formulas (1) and (2).
• the biodegradable block (X) contained in the copolyester of this embodiment is composed of a poly(caprolactone) structural unit.
• Poly(caprolactone) is a polyester represented by the following formula (3).
• Poly(caprolactone) is a ring-opening reaction product of ⁇ -caprolactone.
• the structural unit of poly(caprolactone) is a structural unit (6HH-U) derived from 6-hydroxyhexanoic acid (6HH).
• the biodegradability of poly(caprolactone) will be explained in Synthesis Example 1 below.
• the structural units contained in the polymer (y) may be used alone or in combination of two or more.
• the non-biodegradable structural unit is not particularly limited as long as it is non-biodegradable and can form a copolymer with the biodegradable structural unit.
• the structural unit having non-biodegradability is not particularly limited, but it is a structure in which a structural unit derived from dicarboxylic acid (DA) (DA-U) and a structural unit derived from diol (DO) (DO-U) are bonded. It is preferable that there be. More preferably, the polymer (y) is a polyester of dicarboxylic acid (DA) and diol (DO). Examples of the polyester of dicarboxylic acid (DA) and diol (DO) include structural units derived from polybutylene succinate, polybutylene adipate terephthalate, and the like. Among these, polybutylene succinate-derived structural units represented by the following formula (4) and polybutylene adipate terephthalate represented by the following formula (5) are preferred.
• 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)
• 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
• C1-16 alkanedicarboxylic acids such as C1-16 alkene dicarboxylic acids such as C1-16 alkene dicarboxylic acids such as C2-10 alkene dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and the like.
• 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, decalindicarboxylic acid), , norbornane dicarboxylic acid, adamantane dicarboxylic acid, tricyclodecane dicarboxylic acid, etc.), cycloalkenedicarboxylic acids (e.g., C5-10 cycloalkene-dicarboxylic acids such as cyclohexene dicarboxylic acid), tricycloalkenedicarboxylic acids (e.g., norbornene dicarboxylic acid) etc.), unsaturated alicyclic dicarboxylic acids (eg, tetrahydrophthalic acid, tetrahydromethylphthalic anhydride),
• aromatic dicarboxylic acids examples include monocyclic aromatic dicarboxylic acids [e.g., phthalic acid, terephthalic acid, isophthalic acid, alkyl isophthalic acids (e.g., C1-4 alkyl isophthalic acids such as 4-methylisophthalic acid), etc. C6-10 arene-dicarboxylic acids], 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 naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid; 1,2-naphthalene dicarboxylic acid; (naphthalene dicarboxylic acid having two carboxyl groups on the same ring such as 1,4-naphthalene dicarboxylic acid), fused polycyclic C10-24 arene-dicarboxylic acids such as anthracene dicarboxylic acid, phenanthrene dicarboxylic acid, preferably fused polycyclic C10-24 arene-dicarboxylic acids, such as cyclic C10-16 arene-dicarboxylic acids, more preferably fused polycyclic C10-14 arene-dicarboxylic acids], aryl arene dicarboxylic acids [e.
• 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 diol (DO) according to the present embodiment includes, in addition to aliphatic dicarboxylic acid, a structural unit derived from alicyclic dicarboxylic acid, a structural unit derived from aromatic dicarboxylic acid, etc. But that's fine.
• 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-dimethyl-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, tetra
• 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 diol acids are preferred, and ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol are more preferred. , 1,4-butanediol are particularly preferred.
• ⁇ Other hydroxycarboxylic acid units preferably the structural unit derived from 6-hydroxyhexanoic acid (6HH) (6HH-U), the structural unit derived from dicarboxylic acid (DA) (DA-U), and the structural unit derived from DO
• a unit derived from hydroxycarboxylic acid (HA) (HA-U) may be included as another structural unit.
• the copolyester of this embodiment has a structural unit derived from 6-hydroxyhexanoic acid (6HH) (6HH-U), a structural unit derived from DA (DA-U), and a structural unit derived from DO (DO-U).
• the molar content of the other structural units is preferably 60 mol% or less, and 40 mol% or less with respect to 100 mol of all structural units of the copolyester of this embodiment. It is more preferable that the amount is 20 mol % or less. 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.
• other hydroxycarboxylic acid units 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- Hydroxyheptanoic acid, 3-hydroxyheptanoic acid, 7-hydroxyheptanoic acid, 3-hydroxyoctanoic acid, 8-hydroxyoctanoic acid, 3-hydroxynonanoic acid, 9-hydroxynonanoic acid, 3-hydroxydecanoic acid, 10-hydroxydecane Examples include units such as hydroxy C 2-15 alkanoic acid, 12-hydroxystearic acid, and ricinoleic acid, which may have a C 1-6 alkyl
• the hydroxyalkanoic acid unit may be a corresponding lactone unit.
• the lactone unit include those having a diC 1-12 alkyl group other than ⁇ -caprolactone, such as ⁇ -propiolactone, ⁇ -dimethylpropiolactone, ⁇ -butyrolactone, ⁇ -dimethylbutyrolactone, and ⁇ -valerolactone.
• Examples include units such as C 3-15 lactone, which may be oxidized.
• 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 (4-hydroxybutyric acid), 3-hydroxyvaleric acid, 3-hydroxyhexanoic acid, and 3-hydroxyheptane Hydroxy C 3-10 alkanoic acid units such as 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid, 3-hydroxydecanoic acid, 10-hydroxydecanoic acid (hydroxy C 3-10 alkanoic acid units other than 3-hydroxybutyric acid) ) or the corresponding lactone units are preferred.
• Examples of other methods for introducing hydroxycarboxylic acid units include the following three methods.
• (I) A method of reacting with poly(caprolactone) (PCL) in advance.
• (II) A method in which dicarboxylic acid (DA) is reacted with a polyester (PAO) of the diol (DO) in advance.
• (III) A method of adding during the reaction of poly(caprolactone) and polyester (PAO) of (PCL), dicarboxylic acid (DA), and 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 biodegradable block (X) is a block containing one or more biodegradable poly(caprolactone) constitutional units.
• the non-biodegradable block (Y) is a block containing one or more constitutional units of the non-biodegradable polymer (y).
• the non-biodegradable polymer (y) is preferably a polyester (PAO) of dicarboxylic acid (DA) and diol (DO).
• the non-biodegradable polymer (y) is poly(1,4-butanediol/succinic acid) (P(BG/SA), which is a polyester of 1,4-butanediol (BG) and succinic acid (SA). )) is more preferable.
• P(BG/SA) poly(1,4-butanediol/succinic acid)
• SA succinic acid
• the melting point of the obtained copolyester of this embodiment can be set to 180° C. or lower.
• the melting point of the copolyester is preferably 150°C or lower, more preferably 120°C or lower. Moreover, it is preferable that it is 100 degreeC or more.
• the molar ratio (X/Y) of the biodegradable block (X) and the non-biodegradable block (Y) is 1/99 to 50/50, and preferably 1/99 to 45/55. It is preferably from 1/99 to 40/60, even more preferably from 1/99 to 35/65. Within these ranges, thermophysical properties suitable for moldability can be obtained.
• the average chain length of the biodegradable block (X) exceeds 1.2, preferably 1.3 or more, more preferably 1.5 or more, and even more preferably 1.8 or more. . Moreover, it is preferable that the average chain length of the biodegradable block (X) is 55.0 or less. Within these ranges, biodegradability can be achieved in multiple environments (seawater, freshwater, soil, compost).
• 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.
• the number average molecular weight (Mn) of the copolyester is 5000 or more, sufficient mechanical properties etc. are exhibited.
• the copolyester of this embodiment can improve biodegradability, and therefore can achieve both biodegradability and moldability to a high degree. Moreover, 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 of the copolyester of this embodiment in a seawater environment is preferably 15% or more, more preferably 24% or more, even more preferably 40% or more, and particularly preferably 50% or more.
• the degree of biodegradation of a copolyester in a seawater environment is a value calculated by the following method.
• Inoculum source The inoculum source is seawater collected from the coast of Akane Bay (near Akanehama, Narashino City, Chiba Prefecture).
• 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. Measure and calculate the degree of biodegradation. Culture temperature: 27°C, dark Culture period: 28 days Calculation of biodegradation degree: The biodegradability of the sample is calculated based on the following formula.
• Biodegradability (%) (BOD0-BODB)/ThOD ⁇ 100
• BOD0 Biochemical oxygen demand of sample (measured value: mg)
• BODB Average biochemical oxygen demand of blank test (measured value: mg)
• ThOD Theoretical oxygen demand required when the sample is completely oxidized (calculated value: mg)
• the degree of biodegradation of the copolyester of this embodiment in a freshwater environment is preferably 15% or more, more preferably 24% or more, even more preferably 40% or more, and particularly preferably 50% or more.
• the biodegradability of the copolyester in a freshwater environment is determined by the same method as the seawater biodegradability described above, except that the inoculum source is river water collected from the Inagawa River (near Momozono, Ikeda City, Hyogo Prefecture). This is the value calculated from the biodegradation level.
• the degree of biodegradation of the copolyester of this embodiment in a soil environment is preferably 15% or more, more preferably 24% or more, even more preferably 40% or more, and particularly preferably 50% or more.
• the biodegradability of the copolyester in the soil environment is the seawater biodegradability described above, except that the inoculum source is soil collected at Oshinozuka citizens' Farm (near Oshinozuka, Sakura City, Chiba Prefecture). This is the value calculated by the biodegradation level using the same method.
• the compost decomposition rate of the copolyester of this embodiment under compost conditions is preferably 15% or more, more preferably 24% or more, even more preferably 40% or more, and particularly preferably 50% or more.
• the compost decomposition rate of copolyester under compost conditions is a value determined by a method based on JIS K6953-1:2011. Culture temperature: 58°C Culture period: 28 days
• PCL Poly(caprolactone) according to the present embodiment
• ⁇ CL ⁇ -caprolactone
• Poly(caprolactone) (PCL) according to the present embodiment includes a polyester structure obtained by subjecting 6-hydroxyhexanoic acids to an esterification reaction.
• the method for producing poly(caprolactone) is not particularly limited, and includes, for example, a method similar to the production method described in Non-Patent Document A below.
• Non-patent Document A Nicolas Superregui, Damien Delcroix, Blanca Martin-Vaca, Didier Bourissou, and Laurent Maron; Ring-Opening Polymeri zation of ⁇ -Caprolactone Catalyzed by Sulfonic Acids: Computational Evidence for Bifunctional Activation, Journal of Organi c Chemistry; 2010, 75, 19, 6581-6587.
• an acid catalyst such as methanesulfonic acid is added to ⁇ -caprolactone, and the ring-opening polymerization reaction is allowed to proceed for 2 to 10 hours while maintaining the temperature of the reaction solution at 80 to 150°C.
• an acid catalyst such as methanesulfonic acid is added to ⁇ -caprolactone, and the ring-opening polymerization reaction is allowed to proceed for 2 to 10 hours while maintaining the temperature of the reaction solution at 80 to 150°C.
• One example is how to do it.
• 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 ring-opening polymerization 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 ⁇ -caprolactone ( ⁇ CL).
• 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 (C1-4 alkyl cellosolves such as ethyl cellosolve acetate, 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 lower limit of the number average molecular weight (Mn) of poly(caprolactone) (PCL) may be 1,000 or more, 2,000 or more, 4,000 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, 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.
• 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.
• the method for producing these polyesters is as follows: For example, the following methods may be mentioned. A mixture containing 1,4-butanediol and succinic acid is reacted at a temperature of 100 to 250°C, a catalyst such as titanium tetraisopropoxide is added, and the mixture is further reacted at 100 to 250°C to produce polyester.
• 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.
• a specific example of a polyester (PAO) of dicarboxylic acid (DA) and the diol (DO) is represented by the following formula (6) (poly(1,4-butanediol/succinic acid) (P(BG/SA )), poly(butanediol/adipic acid/terephthalic acid) (P(BG/AA/tPA) represented by formula (7).
• P(BG/SA) is a combination of 1,4-butanediol and succinic acid.
• P(BG/AA/tPA) is a polyester of tandiol, adipic acid, and terephthalic acid.
• 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 method of reacting poly(caprolactone) (PCL) with the polymer (y). Particularly when the polymer (y) is a polyester, the above reaction is a transesterification reaction. In the transesterification reaction, the structural units of poly(caprolactone) (PCL) and the structural units of polymer (y) are exchanged to form a biodegradable block (X) containing the structural units of poly(caprolactone) (PCL) and the polymer (y).
• the copolyester of this embodiment having a non-biodegradable block (Y) containing the structural unit of y) can be produced.
• the polymer (y) is a polyester (PAO) of the dicarboxylic acid (DA) and the diol (DO), the method for producing the copolyester of this embodiment will be described in more detail.
• PAO polyester of the dicarboxylic acid
• DO diol
• the manufacturing method of the present embodiment preferably includes a step of reacting poly(caprolactone) (PCL) with a polyester (PAO) of the dicarboxylic acid (DA) and the diol (DO).
• PCL poly(caprolactone)
• PAO polyester
• DA dicarboxylic acid
• DO diol
• a transesterification reaction is performed on a mixed liquid containing poly(caprolactone) (PCL) and a polyester (PAO) of the dicarboxylic acid (DA) and the diol (DO).
• PCL poly(caprolactone)
• PAO polyester
• DA dicarboxylic acid
• DO diol
• Examples of the transesterification reaction include the method described in Non-Patent Document C.
• Non-patent Document C Thibaud Debuissy, Eric Pollet, Luc Averous, Ohkita, “Titanium-catalyzed transsterification as” a route to the synthesis of fully biobased poly(3-hydroxybutyrate-co-butylene dicarboxylate) copolyesters, from their homopolyesters”, European Polymer Journal, 90 (2017) 92-104.
• the method for producing a copolyester of the present embodiment For example, when the dicarboxylic acid (DA) is an aliphatic dicarboxylic acid such as succinic acid and the diol (DO) is an aliphatic diol such as 1,4-butanediol, the method for producing a copolyester of the present embodiment For example, the following method may be mentioned. A transesterification reaction is carried out on a mixture containing poly(caprolactone) (PCL) and a polyester (PAO) of an aliphatic dicarboxylic acid such as succinic acid and an aliphatic diol such as 1,4-butanediol, A copolyester of this embodiment is obtained.
• PCL poly(caprolactone)
• PAO polyester
• the temperature of the transesterification reaction is, for example, preferably 150 to 250°C, more preferably 200 to 230°C.
• the time for the transesterification reaction depends on the temperature of the reaction, but is preferably 1 to 24 hours, more preferably 3 to 12 hours, and even more preferably 4 to 6 hours.
• the reaction temperature is constant, the average chain length of the biodegradable block (X) can be adjusted by adjusting the reaction time.
• the molar ratio of the charged poly(caprolactone) (PCL) and polyester (PAO) is particularly Not limited.
• the molar ratio (X/Y) of the biodegradable block (X) and the non-biodegradable block (Y) in the produced copolyester of this embodiment, and the average chain length of the biodegradable block (X) are: It should be within the range mentioned above.
• the polyester (PAO) is a polyester of the dicarboxylic acid (DA) and the diol (DO).
• the molecular weight (Mn) of poly(caprolactone) (PCL) used is preferably 10,000 to 100,000, more preferably 15,000 to 70,000, More preferably, it is 20,000 to 50,000.
• the molecular weight (Mn) of the polymer (y) used is preferably 10,000 to 100,000, more preferably 15,000 to 70,000, and preferably 20,000 to 60,000. More preferred.
• the production method of this embodiment uses a transesterification reaction, the molecular weight of the final product, the copolyester of this embodiment, and the average chain length of the biodegradable block (X) can be adjusted independently. Therefore, it is possible to easily achieve both melting point and biodegradability, which are the design goals of copolyester.
• 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 the catalyst used is usually in the range of 0.001 to 5.0% by mass based on the total mass of poly(caprolactone) (PCL) and the polyester (PAO) of the dicarboxylic acid (DA) and the diol (DO). It is.
• 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 preferably carried out until the average chain length of the biodegradable block (X) is 1.2 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(caprolactone) (PCL) or the terminal carboxyl group of polyester (PAO) and the terminal hydroxy group of poly(caprolactone) (PCL) or the terminal carboxyl group of polyester (PAO) proceeds, and both terminal groups in the structural formula of the copolyester of this embodiment can be made into hydroxy groups.
• 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. , glycerin, sorbitol, neopentyl glycol, and other aliphatic polyol compounds; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone, etc.
• Aromatic polyol compounds water; ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine , 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethylethanolamine, hydrazine, diethylenetriamine, triethylenetetramine, and other amine compounds may be used. Can be done. These chain extenders may be used alone or in combination of two or more. Among them, aliphatic polyol compounds are preferred, and neopentyl glycol is more preferred.
• 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,
• 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 crystallizing 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 this embodiment preferably contains a phenolic antioxidant, a phosphite antioxidant, etc. as a heat stabilizer for the resin composition. Furthermore, the thermoplastic polyester composition of the present embodiment may contain a carbodiimide compound-based hydrolysis inhibitor, such as a polycarbodiimide resin (trade name: Carbodilite, manufactured by Nisshinbo Chemical Co., Ltd.), as a hydrolysis inhibitor. preferable.
• 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 part 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.
• Sheets, films, laminates, and molded bodies made of the resin composition of this embodiment include bottles, films or sheets, hollow tubes, laminates, vacuum (pressure) molded containers, (mono, multi) filaments, nonwoven fabrics, and foamed bodies.
• the body is further processed and used for packaging and container materials, materials for agriculture, civil engineering, fisheries, etc.
• packaging container materials include shopping bags, shrink films, packaging bands, adhesive tapes, tapes, food packaging containers, food packaging lids, food packaging films, food wrap films, cosmetic containers, diapers, etc.
• Various packaging containers and lids for food, cosmetics, medical care, drugs, electronics, etc. including sanitary napkin packaging film, pharmaceutical packaging film, pharmaceutical film, surgical adhesive wrap film, disc product packaging film for recording materials, etc. Examples include materials and films.
• Examples of materials for agriculture, civil engineering, and fisheries include agricultural and horticultural films, greenhouse films, tarpaulins, fertilizer bags, seedling pots, sandbags, construction films, weed prevention sheets, tapes, and yarns.
• Examples include materials used in the agriculture, civil engineering, and fisheries fields, such as vegetation nets.
• Other examples include garbage bags and compost bags, which can be suitably used as materials in a wide range of applications.
• 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 acid value of the resin was calculated using the following procedure. Approximately 1 g of the sample was weighed into a stoppered Erlenmeyer flask, 20 mL of acetone was added to dissolve it, phenolphthalein test solution was added as an indicator, and the sample was held for 30 seconds. Thereafter, titration was performed with a 0.1N alcoholic potassium hydroxide solution until the solution turned pale pink, and the acid value was determined using the following formula.
• Acid value (mgKOH/g) (5.611 x a x F)/S S: Amount of sample collected (g) a: Consumption amount (mL) of 0.1N alcoholic potassium hydroxide solution F: Factor of 0.1N alcoholic potassium hydroxide solution
• Measuring device Mettler DSC822 Measurement conditions: under nitrogen flow, temperature rise/fall rate 5°C/min, measurement temperature range -60°C to 180°C
• biodegradability was calculated by the following procedure, and the biodegradability was evaluated from the biodegradability value.
• Inoculum source Seawater collected from the coast of Akane Bay (near Akanehama, Narashino City, Chiba Prefecture) was used as the inoculum source.
• 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 Calculation of biodegradation degree: The biodegradability of the resin samples of Examples and Comparative Examples was calculated based on the following formula.
• Biodegradability (%) (BOD 0 - BOD B )/ThOD ⁇ 100
• BOD 0 Biochemical oxygen demand of sample (measured value: mg)
• BOD B Average biochemical oxygen demand of blank test (measured value: mg)
• ThOD Theoretical oxygen demand required when the sample is completely oxidized (calculated value: mg)
• C Good
• Biodegradability Biodegradability is 24% or more and less than 40%
• D Acceptable
• Biodegradable degree is 15% or more and less than 24% (practical lower limit)
• compost decomposition rate was measured by a method based on JIS K6953-1:2011. Culture temperature: 58°C Culture period: 28 days Evaluation criteria: A (best): Compost decomposition rate is 50% or more B (excellent): Compost decomposition rate is 40% or more and less than 50% C (good): Compost decomposition rate is 24% or more and less than 40% D (fair): Compost decomposition rate is 15% or more and less than 24% (practical lower limit) E (impossible): Compost decomposition rate is less than 15% (not suitable for practical use)
• the average molecular weight was measured using the method for measuring average molecular weight described above.
• the number average molecular weight Mn was 14,630, and the weight average molecular weight Mw was 23,882.
• a 1 H-NMR spectrum was measured using the 1 H-NMR measurement method described above. The results are as follows.
• the average molecular weight was measured using the method for measuring average molecular weight described above.
• the number average molecular weight Mn was 12,254, and the weight average molecular weight Mw was 28,416.
• a 1 H-NMR spectrum was measured using the 1 H-NMR measurement method described above. The results are as follows.
• Example 1 In a glass container equipped with a stirrer and a nitrogen gas introduction tube, 5.4 parts by mass of Capa 6400 (Ingevity, product PCL), 400 parts by mass of BioPBS (Mitsubishi Chemical, product P (BG/SA)), and titanium tetraisopropoxide (TIPT) were added.
• Capa 6400 Ingevity, product PCL
• BioPBS Mitsubishi Chemical, product P (BG/SA)
• TIPT titanium tetraisopropoxide
• the average chain length of the structural unit (6HH-U) derived from 6-hydroxyhexanoic acid (6HH) constituting PCL was calculated as the average chain length of the biodegradable block (X).
• biodegradability was evaluated and average molecular weight was measured. The results are shown in Table 1.
• Example 2 In a glass container equipped with a stirrer and a nitrogen gas introduction tube, 11 parts by mass of PCL obtained in Synthesis Example 1, 400 parts by mass of P(BG/SA) obtained in Synthesis Example 2, and 0.08 parts by mass of titanium tetraisopropoxide (TIPT). Parts by mass were charged and maintained at a container temperature of 200° C. for 3 hours under a nitrogen stream to obtain a copolyester containing PCL and BG/SA as constituent units. The structure of the obtained copolyester is shown in formula (11).
• Examples 3, 5, 6, 8-10 A copolyester was obtained in the same manner as in Example 2, except that the blending amounts of PCL and P(BG/SA) and the reaction time (reaction time) were changed to the values listed in Table 1. The same evaluation as in Example 1 was performed. The results are shown in Table 1.
• Example 4 A copolyester was obtained in the same manner as in Example 1, except that the blending amounts of PCL and P (BG/SA) and the reaction time (reaction time) were changed to the values listed in Table 1. The same evaluation as in Example 1 was performed. The results are shown in Table 1.
• Example 12 In a glass container equipped with a stirrer and a nitrogen gas introduction tube, 197 parts by mass of Capa 6400 (Ingevity, product PCL), 300 parts by mass of BioPBS (Mitsubishi Chemical, product P (BG/SA)), and 0.5 parts of titanium tetraisopropoxide (TIPT) were added. 09 parts by mass was charged and maintained at a container temperature of 200° C. for 5 hours under a nitrogen stream to obtain a copolyester containing PCL and BG/SA as constituent units. The structure of the obtained copolyester is shown in formula (12).
• Example 13 As raw materials, 52 parts by mass of Capa6400 (Ingevity, product PCL), 351 parts by mass of Ecoflex (BASF, product P (BG/AA/tPA)), and 0.08 parts by mass of titanium tetraisopropoxide (TIPT) were used. A copolyester was obtained in the same manner as in 1. The structure of the obtained copolyester is shown in formula (13).
• biodegradable blocks derived from the highly biodegradable poly(caprolactone) structure are arranged in a specific proportion and with a specific average chain length, the biodegradable block sites are cleaved by enzymes secreted by microorganisms in the environment. do. This turns the copolyester into an oligomer that can be metabolized by microorganisms, and the entire copolyester biodegrades. At the same time, the intermolecular forces of the polymer chains decrease, thereby lowering the melting point.
• the copolyester of this embodiment has a melting point of 180°C or less, can suppress thermal energy during molding, is biodegradable in multiple environments (seawater, freshwater, soil, compost), and has a combination of biodegradability and melting point. Since it has both thermophysical properties, 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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• 2023
  • 2023-06-30 JP JP2024521316A patent/JPWO2024009906A1/ja active Pending
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