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
• • 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
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy 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
  • 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 resin and a method for producing the same.
• PHA polyhydroxyalkanoate
• the melting temperature and thermal decomposition temperature of PHA are close to each other, and thermal decomposition progresses during processing, resulting in 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 polymerized at relatively high temperatures similar to general-purpose resins and that can be thermoformed.
• Non-Patent Documents 1 and 2 report copolyester resins having seawater degradability and thermophysical properties.
• Non-Patent Documents 1 and 2 are triblock copolymers
• the seawater biodegradability of the copolyester resins depends on the molecular weight of the polylactic acid moiety, which is a non-seawater degradable moiety. Dependent. For this reason, there are restrictions on molecular weight when designing copolyester resins. Furthermore, further improvements in thermoformability and biodegradability are required.
• an object of the present invention is to provide a copolyester resin with excellent thermoformability and biodegradability, and a method for producing the same.
• the copolyester resin is The triad unit (unit (A) )and, It is derived from a structure expressed by "second glycol/dibasic acid/second glycol" in which a dibasic acid and a second glycol of a different type from the first glycol are combined, and is biodegradable.
• the copolyester resin according to [1], wherein the structural unit exhibiting biodegradability in the polymer (x) is represented by the following formula (3A) or the following formula (3B).
• Formula (3A) Formula (3B) (In formula (3A) and formula (3B), R 3 represents a hydrogen atom or a methyl group, l and m are each independently an integer of 0 to 4, and l+m is 1 or more, and n is , represents an integer from 4 to 8.) [3] The copolyester resin according to [1], wherein the dibasic acid (I-a) is at least one selected from the group consisting of adipic acid, azelaic acid, and sebacic acid.
• the glycol (I-b) is ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1 , 4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, and 1,9-nonanediol, The copolyester resin described in [1].
• the structural unit exhibiting biodegradability in the polymer (x) is A structural unit derived from a structure in which ethylene glycol and adipic acid are bonded, a structural unit derived from a structure in which diethylene glycol and adipic acid are bonded, and a structural unit derived from a structure in which 1,2-propylene glycol and adipic acid are bonded.
• a structural unit derived from a structure in which 1,9-nonanediol and adipic acid are bonded A structural unit derived from a structure in which ethylene glycol and sebacic acid are combined, a structural unit derived from a structure in which diethylene glycol and sebacic acid are combined, a structural unit derived from a structure in which 1,2-propylene glycol and sebacic acid are combined.
• a structural unit derived from a structure in which 1,9-nonanediol and sebacic acid are combined A structural unit derived from a structure in which 1,9-nonanediol and sebacic acid are combined, A structural unit derived from a structure in which ethylene glycol, 1,6-hexanediol, and adipic acid are bonded, and a structure in which ethylene glycol, 1,6-hexanediol, 2-methyl-1,3-propanediol, and adipic acid are bonded.
• the structural unit derived from the structure A structural unit derived from a structure in which ethylene glycol, diethylene glycol, and adipic acid are combined, a structural unit derived from a structure in which ethylene glycol, diethylene glycol, 2-methyl-1,3-propanediol, and adipic acid are combined, A structural unit derived from a structure in which ethylene glycol and sebacic acid are combined, and a structural unit derived from a structure in which ethylene glycol, 2-methyl-1,3-propanediol, adipic acid, and sebacic acid are combined,
• the copolyester resin according to [1] which is at least one selected from the group of.
• the non-biodegradable structural unit in the polymer (y) is Either a structural unit derived from a structure in which 1,4 butanediol and succinic acid are combined, or a structural unit derived from a structure in which 1,4 butanediol, adipic acid, and terephthalic acid are combined, [ 1].
• the unit (A) is a triad unit derived from "a structure in which 2-methyl-1,3-propanediol, adipic acid, and 2-methyl-1,3-propanediol are combined," and the unit (B) is , is a triad unit derived from "a structure in which 1,4 butanediol, adipic acid, and 1,4 butanediol are bonded",
• the unit (A) is a triad unit derived from "a structure in which 2-methyl-1,3-propanediol, sebacic acid, and 2-methyl-1,3-propanediol are combined," and the unit (B) is , is a triad unit derived from "a structure in which 1,4 butanediol, sebacic acid, and 1,4 butanediol are bonded", or (iii) The unit (A) is a triad unit derived from "a structure in which 2-methyl-1,3-
• a manufacturing method of manufacturing a copolyester resin by any one of the following methods manufacturing a copolyester resin containing the block (X) and the block (Y). [9] A resin composition containing the copolyester resin according to any one of [1] to [7]. [10] A sheet or film made of the resin composition according to [9].
• copolyester resin of the present invention will be described in detail, but the explanation of the constituent elements described below is an example as one embodiment of the present invention, and the content is not limited to these.
• the copolyester resin of the present invention is derived from a structure in which a dibasic acid (I-a) and a glycol (I-b) are bonded, and a block ( X) and A copolyester resin containing a block (Y) derived from a polymer (y) that is derived from a structure in which a dibasic acid and a glycol are bonded and has a non-biodegradable structural unit, Copolyester resin is The triad unit (unit (A) )and, It is derived from a structure expressed by "second glycol/dibasic acid/second glycol" in which a dibasic acid and a second glycol of a different type from the first glycol are combined, and is biodegradable.
• a substance When 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.
• 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 copolyester resin of the present invention has excellent biodegradability and can be polymerized and thermoformed at relatively high temperatures comparable to those of general-purpose resins. That is, the copolyester resin of the present invention has excellent thermoformability and biodegradability. Then, sheets, films, etc. can be obtained using the resin composition containing the copolyester resin.
• the copolyester resin of the present invention includes a block derived from a polymer (x) that is derived from a structure in which a dibasic acid (I-a) and a glycol (I-b) are bonded and has a biodegradable structural unit. (X) is included. Cleavage of this block (X) site proceeds by enzymes in the environment. This turns the copolyester resin into an oligomer that can be metabolized by microorganisms, and the entire copolyester resin biodegrades.
• the copolyester resin of the present invention contains a block (Y) derived from a polymer (y) having a structural unit exhibiting excellent thermoformability and non-biodegradability.
• the entire copolyester resin has excellent thermoformability.
• the copolyester resin of the present invention further has the following characteristics.
• the triad unit (unit (A) ) derived from a structure represented by "second glycol/dibasic acid/second glycol" in which a dibasic acid and a second glycol of a different type from the first glycol are combined, and A triad unit (unit (B)) exhibiting biodegradability is contained in a specific proportion.
• the constituent components of the copolyester resin will be explained below.
• the copolyester resin includes a block (X) derived from a polymer (x) and a block (Y) derived from a polymer (y).
• Polymer (x) is derived from a structure in which dibasic acid (Ia) and glycol (Ib) are bonded, and has a biodegradable structural unit.
• the polymer (y) is derived from a structure in which a dibasic acid and a glycol are bonded, and has a non-biodegradable structural unit.
• ⁇ Polymer (x) having a structural unit exhibiting biodegradability examples include those shown below.
• the seawater decomposition rate of the resulting structure differs depending on the combination of dibasic acids and glycols. Therefore, in order to form a biodegradable polymer (x), the following examples are required: It is preferable to appropriately select a preferable type from among dibasic acids and glycols so that the structure when bonded exhibits a seawater decomposition rate of 15% or more.
• the dibasic acid is not particularly limited, and examples thereof include non-aromatic dicarboxylic acids, aromatic dicarboxylic acids, dicarboxylic acids, their anhydrides, their halides, and their esters.
• Non-aromatic dicarboxylic acids include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and unsaturated bond-containing non-aromatic dicarboxylic acids.
• the number of carbon atoms in the non-aromatic dicarboxylic acid is not particularly limited, but is, for example, 3 to 15 carbon atoms.
• Examples of aliphatic dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid.
• Examples of the alicyclic dicarboxylic acids include alicyclic dicarboxylic acids having 8 to 15 carbon atoms.
• Examples of the alicyclic dicarboxylic acid include 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid.
• Examples of the unsaturated bond-containing nonaromatic dicarboxylic acid include maleic acid and fumaric acid.
• aromatic dicarboxylic acids include aromatic dicarboxylic acids having 6 to 20 carbon atoms.
• Aromatic dicarboxylic acids are more specifically, for example, orthophthalic acid, terephthalic acid, isophthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, naphthalic acid, biphenyl
• dibasic acids from the viewpoint of biodegradability, non-aromatic dicarboxylic acids are preferred, aliphatic dicarboxylic acids are more preferred, and adipic acid, pimelic acid, suberic acid represented by the following formula (1), Azelaic acid and sebacic acid are more preferred, adipic acid, azelaic acid, and sebacic acid are even more preferred, and adipic acid and sebacic acid are particularly preferred. Two or more dibasic acids may be used in combination.
• n an integer from 4 to 8.
• Glycols include non-aromatic glycols and aromatic glycols.
• Non-aromatic glycols include aliphatic glycols and alicyclic glycols.
• the number of carbon atoms in the non-aromatic glycol includes, for example, 1 to 15 carbon atoms.
• Aliphatic glycols include, for example, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, neo Pentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-methylpentane-2,4-diol, 3,3-dimethyl-1 , 2-butanediol, 2,3-dimethyl-2,3-butanediol, butylethylpropanediol, 1,9-nonanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, etc. Can be mentioned.
• alicyclic glycol examples include alicyclic diols having 6 to 15 carbon atoms.
• Alicyclic diols include, for example, 1,3-bis(2-hydroxypropyl)cyclopentane, 1,3-bis(2-hydroxybutyl)cyclopentane, 1,4-bis(hydroxymethyl)cyclohexane, 1,4 -bis(2-hydroxypropyl)cyclohexane, 1,4-bis(2-hydroxybutyl)cyclohexane, and the like.
• aromatic glycols include aromatic glycols having 6 to 20 carbon atoms.
• aromatic glycols having 6 to 20 carbon atoms include 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,4-benzenedimethanol, and 1,4-bis(2-hydroxyethoxy)benzene. Can be mentioned.
• glycols from the viewpoint of biodegradability, non-aromatic glycols are preferred, aliphatic glycols are more preferred, and glycols represented by the following formula (2) are particularly preferred. Two or more types of glycols may be used in combination.
• Formula (2) (In formula (2), A represents a carbon atom or an oxygen atom, R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyl group, and R 2 represents a hydrogen atom or a hydroxyl group. and m are each independently an integer of 0 to 4, and l+m represents 1 or more. However, when A is an oxygen atom, H bonded to R 1 and A does not exist. Moreover, either R 1 or R 2 is a hydroxyl group, and neither R 1 nor R 2 is a hydroxyl group. )
• alkyl group having 1 to 4 carbon atoms examples include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t -butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, etc.
• methyl group is preferred from the viewpoint of excellent reactivity.
• 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 3-methyl-1, 5-pentanediol, 2-(2-hydroxyethoxy)ethanol, and 3-(3-hydroxypropoxy)propan-1-ol are preferred, and from the viewpoint of excellent biodegradability, 2-methyl-1,3propanediol and 3-propanediol are preferred.
• -Methyl-1,5-pentanediol is more preferred.
• the structural unit having biodegradability is derived from a structure, and the structure can be obtained by arbitrarily selecting the above-mentioned dibasic acid and the above-mentioned glycol and subjecting them to an esterification reaction using a known method.
• a preferable example of a biodegradable structural unit includes a structural unit represented by the following formula (3A) or the following formula (3B).
• R 3 represents a hydrogen atom or a methyl group
• l and m are each independently an integer of 0 to 4, and l+m is 1 or more
• n is , represents an integer from 4 to 8.
• R 3 is a methyl group
• l and m are each independently an integer of 1 or 2
• n is an integer of 4 to 8.
• the dibasic acid (Ia) forming the biodegradable polymer (x) is preferably at least one selected from the group consisting of adipic acid, azelaic acid, and sebacic acid.
• glycol (Ib) described below among the glycols exemplified above.
• the glycol (I-b) forming the biodegradable polymer (x) is ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 2-methyl-1,3-propanediol, From the group consisting of 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, and 1,9-nonanediol It is preferable that at least one kind is selected.
• the structural units exhibiting biodegradability in polymer (x) include: A structural unit derived from a structure in which ethylene glycol and adipic acid are bonded, a structural unit derived from a structure in which diethylene glycol and adipic acid are bonded, and a structural unit derived from a structure in which 1,2-propylene glycol and adipic acid are bonded.
• a structural unit derived from a structure in which 1,9-nonanediol and adipic acid are bonded A structural unit derived from a structure in which ethylene glycol and sebacic acid are combined, a structural unit derived from a structure in which diethylene glycol and sebacic acid are combined, a structural unit derived from a structure in which 1,2-propylene glycol and sebacic acid are combined.
• the structural unit derived from the structure A structural unit derived from a structure in which ethylene glycol, diethylene glycol, and adipic acid are combined, a structural unit derived from a structure in which ethylene glycol, diethylene glycol, 2-methyl-1,3-propanediol, and adipic acid are combined, A structural unit derived from a structure in which ethylene glycol and sebacic acid are combined, and a structural unit derived from a structure in which ethylene glycol, 2-methyl-1,3-propanediol, adipic acid, and se
• a structural unit derived from a structure in which 2-methyl-1,3 propanediol and adipic acid are bonded a structural unit derived from a structure in which 2-methyl-1,3 propanediol and sebacic acid are bonded, and 3 More preferably, it is any structural unit derived from a structure in which -methyl-1,5-pentanediol and adipic acid are bonded.
• examples include structural units represented by the following formulas (3-1) to (3-3).
• the dibasic acids and glycols used to form the polymer (y) are as exemplified by the dibasic acids and glycols described in the section ⁇ Polymer (x) having biodegradable structural unit> above.
• the seawater decomposition rate of the resulting structure differs depending on the combination of dibasic acids and glycols, so in order to form a non-biodegradable polymer (y), the above example Among the dibasic acids and glycols, a preferable type may be selected as appropriate so that the structure when bonded exhibits a seawater decomposition rate of less than 15%.
• the non-biodegradable structural unit is not particularly limited, but may be other than the dibasic acid represented by the above formula (1) described in the column ⁇ Polymer (x) having a biodegradable structural unit> above.
• it contains a structural unit derived from a structure in which a dibasic acid and a glycol are bonded.
• the structural unit having non-biodegradability is not particularly limited, and examples thereof include structural units derived from butylene succinate, butylene adipate terephthalate, lactic acid, and the like.
• the non-biodegradable structural unit in the polymer (y) is a butylene succinate-derived structural unit represented by the following formula (4-1) (1,4 butanediol and succinic acid bonded).
• the copolyester resin of the present invention may contain any polymer having structural units other than those mentioned above, as necessary, within a range that does not impede the effects of the present invention.
• the copolyester resin of the present invention is a copolymer containing a block (X) and a block (Y), and includes a polymer (x) having the above biodegradable structural unit and the above non-biodegradable structure. It is obtained by copolymerizing a polymer (y) having the unit.
• preferred examples of the copolyester resin of the present invention include the following formulas (5) to (8).
• the content ratio of block (X) constituting the copolyester resin is preferably 5% by mass or more, more preferably 10% by mass or more, based on the copolyester resin (100% by mass) from the viewpoint of obtaining sufficient biodegradability. preferable.
• the content ratio is preferably 50% by mass or less, more preferably 45% by mass or less, from the viewpoint of obtaining sufficient thermoformability. Any combination of these upper and lower limits may be used.
• the content ratio is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 45% by mass or less.
• the content ratio of the block (Y) constituting the copolyester resin is preferably 50% by mass or more, more preferably 55% by mass or more, based on the copolyester resin (100% by mass) from the viewpoint of obtaining sufficient thermoformability. preferable. On the other hand, from the viewpoint of obtaining sufficient biodegradability, the content ratio is preferably 95% by mass or less, more preferably 90% by mass or less. Any combination of these upper and lower limits may be used. The content ratio is preferably 50% by mass or more and 95% by mass or less, more preferably 55% by mass or more and 90% by mass or less.
• the molar ratio (X/Y) between block (X) and block (Y) is more than 5/95, preferably 10/90 or more, and 15/85 or more. More preferred.
• the molar ratio (X/Y) is 95/5 or less, preferably 80/20 or less, and more preferably 70/30 or less. Any combination of these upper and lower limits may be used.
• the molar ratio (X/Y) is more than 5/95 and less than 95/5, preferably 10/90 or more and 80/20 or less, and more preferably 15/85 or more and 70/30 or less.
• the polystyrene equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the copolyester resin is preferably 5,000 or more, more preferably 7,000 or more, from the viewpoint of processability and handleability. More preferably 8,000 or more.
• the same number average molecular weight (Mn) is preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 50,000 or less, from the viewpoint of obtaining sufficient biodegradability. Any combination of these upper and lower limits may be used.
• the same number average molecular weight (Mn) is preferably 5,000 or more and 100,000 or less, more preferably 7,000 or more and 70,000 or less, and even more preferably 8,000 or more and 50,000 or less.
• the weight average molecular weight (Mw) of the copolyester resin measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 10,000 or more, more preferably 15,000 or more, and 20,000 or more from the viewpoint of processability and handleability. ,000 or more is more preferable.
• the weight average molecular weight (Mw) is preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less. Any combination of these upper and lower limits may be used.
• the weight average molecular weight (Mw) is preferably 10,000 or more and 200,000 or less, more preferably 15,000 or more and 150,000 or less, and even more preferably 20,000 or more and 100,000 or less.
• the molecular weight distribution (Mw/Mn) obtained by dividing the weight average molecular weight (Mw) in terms of polystyrene measured by GPC by the number average molecular weight (Mn) has a low degree of dispersion and is not desirable. From the viewpoint of obtaining a resin exhibiting the following characteristics, it is preferably 4.5 or less, more preferably 4.0 or less, and even more preferably 3.7 or less.
• the melting point (Tm) of the copolyester resin is preferably 40°C or higher, more preferably 70°C or higher, and even more preferably 100°C or higher.
• the upper limit of the thermal decomposition temperature of the copolyester resin is not particularly limited, but is usually 250° C. or lower. When the melting point is within the above range, thermal processability during molding is excellent.
• the biodegradation rate of copolyester resin in a seawater environment is 15% or more because it is necessary for the copolyester resin to exhibit "biodegradability" as defined in the present invention, but the seawater decomposition rate is 24% or more. More preferably, it is 40% or more, even more preferably 50% or more.
• the biodegradation rate of a copolyester resin 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 (biological oxygen demand) was measured under the following conditions. Measure and calculate the degree of biodegradation. Culture temperature: 27°C, dark place Culture period: 28 days Calculation of biodegradation rate: The biodegradation rate of the sample is calculated based on the following formula.
• Biodegradation rate (%) (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)
• the biodegradation rate of the copolyester resin 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 biodegradation rate of the copolyester resin in a freshwater environment is determined by the same method as the seawater degradability 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 rate.
• the biodegradation rate of the copolyester resin 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 resin in the soil environment is the same as the seawater decomposition rate 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 rate using the same method.
• the compost decomposition rate of the copolyester resin 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 the copolyester resin under compost conditions is a value determined by a method based on JIS K6953-1:2011. Culture temperature: 58°C Culture period: 28 days
• the copolyester resin of the present invention has two types of biodegradable triad units (units (A) and units (B)) in a desired ratio.
• one unit (unit (A)) is a "first triad unit” in which a first glycol and a dibasic acid are bonded. It is a unit derived from a structure represented by "glycol/dibasic acid/first glycol".
• the other unit (unit (B)) is a "second glycol/dibasic acid/second glycol" in which a dibasic acid is bonded to a second glycol of a different type from the first glycol. It is a unit derived from the represented structure.
• Units (A) and units (B) are each contained in a triad mole fraction of 0.01 or more in the copolyester resin of the present invention, and furthermore, the triad mole fraction of units (A) and units (B) is The total must be 0.05 or more.
• the triad mole fraction can be calculated, for example, by the method below.
• -Identification of chemical structure of resin The chemical structure of the copolyester resin is identified using nuclear magnetic resonance ( 13 C-NMR) under the following conditions.
• Measuring device “JNM-ECM400S” manufactured by JEOL RESONANCE Magnetic field strength: 100MHz Number of integrations: 1000 times
• Solvent Deuterated chloroform Paramagnetic relaxation reagent: Chromium (III) acetylacetate Sample concentration: 200 mg/1.0 mL
• M x-y-z I x-y-z /(I x-y-z +I x-y-x +I z-y-z +I z-y-x +I x-w-z +I x-w- x +I z-w-z +I z-w-x )
• the unit (A) is a triad unit derived from "a structure in which 2-methyl-1,3-propanediol, adipic acid, and 2-methyl-1,3-propanediol are bonded"
• the unit (B) is " Is it a triad unit derived from a structure in which 1,4-butanediol, adipic acid, and 1,4-butanediol are combined?
• the unit (A) is a triad unit derived from "a structure in which 2-methyl-1,3-propanediol, sebacic acid, and 2-methyl-1,3-propanediol are combined," and the unit (B) is " or (iii)
• the unit (A) is a triad unit derived from "a structure in which 3-methyl-1,5-pentanediol, adipic acid, and 3-methyl-1,5-pentanediol are combined," and the unit (B) is , or a triad unit derived from "a structure in which 1,4 butanediol, adipic acid, and 1,4 butanediol are bonded".
• copolyester resin of the present invention shows polymer (x) obtained by reacting 2-methyl-1,3-propanediol (2MPD) and adipic acid (AA), and polymer (x) obtained by reacting 2-methyl-1,3-propanediol (2MPD) with adipic acid (AA), and 1,4-butanediol (BG) with succinic acid (SA).
• the copolyester resin obtained by transesterifying the polymer (y) obtained by reacting with the polymer (y) will be described.
• the method for producing the copolyester resin will be described in detail in the section below (method for producing the copolyester resin).
• Formula (9) (In formula (9), a represents a positive integer)
• the structural unit represented by the following formula (3-1) is a structural unit derived from a structure in which 2MPD and AA are bonded, and is biodegradable. This is the structural unit shown.
• Formula (10) (In formula (10), b represents a positive integer)
• the structural unit represented by the following formula (4-1) is a structural unit derived from a structure in which BG and SA are bonded, and is non-biodegradable. It is a structural unit that indicates.
• the copolyester resin represented by formula (5) contains a block (X) represented by the above formula (3-1) derived from the polymer (x) and the above formula (4-1) derived from the polymer (y).
• the block (Y) represented by is included.
• the copolyester resin represented by the above formula (5) obtained by transesterifying the above polymer (x) and the above polymer (y) includes: - A triad unit (A) which is a triad unit derived from a structure represented by "2MPD/AA/2MPD" and exhibits biodegradability; ⁇ It is a triad unit derived from a structure represented by "BG/AA/BG” and may contain a triad unit (B) that exhibits biodegradability.
• the unit (A) and the unit (B) are each contained in a triad mole fraction of 0.01 or more.
• the present invention stipulates that the sum of the triad mole fractions of units (A) and (B) is 0.05 or more.
• the unit (A) derived from the structure represented by "2MPD/AA/2MPD” is represented by the following formula (A-1).
• Formula (A-1) The triad mole fraction of the unit (A) represented by the above formula (A-1) is calculated as follows.
• M x-y-x I x-y-x /(I x-y-x +I x-y-z +I z-y-z +I z-y-x +I x-w-z +I x-w- x +I z-w-z +I z-w-x )
• M Triad mole fraction
• I Triad peak integral value x: 2MPD y:AA z:BG w:SA
• the copolyester resin of the present invention can be produced using a common method for producing copolyester resins, but the copolyester resin of the present invention can be produced using two types of triad units (units (A) and units (B) that exhibit biodegradability as defined in the present invention. ))
• the polyesterification reaction it is preferable to use the polyesterification reaction by polyesterification or polycondensation reaction described below.
• the method for producing a copolyester resin of the present invention includes a step of polycondensing a dibasic acid and a glycol to synthesize a polymer (x) having a biodegradable structural unit; Polycondensing dibasic acid and glycol to synthesize a polymer (y) having a non-biodegradable structural unit; It is preferable to include a step of transesterifying polymer (x) and polymer (y) to produce a copolyester resin containing block (X) and block (Y).
• the method for synthesizing the polymer (x) and the polymer (y) is not particularly limited, and can be performed using a general method for synthesizing polyester resins.
• the polymer (y) is a polyester resin containing a structural unit derived from a structure in which a dibasic acid other than the dibasic acid represented by the above formula (1) and glycol are bonded will be described.
• the dibasic acids and glycols that are raw materials in the synthesis of polymer (x) or polymer (y) are the examples of the dibasic acids and glycols listed in the section of ⁇ Polymer (x) having a biodegradable structural unit> above. The one explained in can be used.
• the raw materials in the synthesis of polymer (x) or polymer (y) may optionally contain other raw materials other than dibasic acid and glycol.
• Other raw materials include, but are not particularly limited to, polyhydric alcohols having a valence of 3 or more, polyhydric carboxylic acids having a valence of 3 or more, and the like.
• the blending ratio of dibasic acid and glycol is not particularly limited, but the mass ratio (dibasic acid: glycol) is preferably 90:10 to 50:50, more preferably 80:20 to 50:50.
• 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.
• the acid catalyst 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. It is preferable to use a titanium-based catalyst because it can increase the activity of the transesterification reaction and the esterification reaction.
• 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 dibasic acid and glycol.
• the reaction for synthesizing polymer (x) or polymer (y) produces water, lower alcohol, etc. as by-products. By removing them from the reaction system during the reaction process, the condensation reaction can proceed more easily.
• the reaction temperature is not particularly limited, but is usually 50 to 300°C.
• the reaction atmosphere may be air or an inert gas atmosphere such as nitrogen gas or argon gas.
• the reaction time is usually 1 to 48 hours, but the reaction is preferably carried out until no dibasic acid or glycol remains in the reaction system. The progress of the reaction can be monitored, for example, by monitoring the decrease in dibasic acid by measuring the acid value.
• the method for synthesizing a polymer by transesterification is not particularly limited, and it can be performed using a general method for synthesizing a polymer by transesterification.
• titanium-based catalyst As the catalyst used for the transesterification reaction, it is preferable to use a titanium-based catalyst.
• 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 in the range of 0.001 to 5.0% by weight based on the total weight of polymer (x) and polymer (y).
• the reaction temperature is not particularly limited, but is usually 50 to 300°C.
• the reaction atmosphere may be air or an inert gas atmosphere such as nitrogen gas or argon gas.
• the reaction time is usually 1 to 48 hours.
• the reaction temperature is set at 150°C.
• the reaction time is preferably 10 hours or more, more preferably 15 hours or more, even more preferably 20 hours or more, and particularly preferably 24 hours or more.
• the method for producing a copolyester resin of the present invention comprises a dibasic acid and a glycol used to synthesize a polymer (x) having a biodegradable structural unit, and a polymer (x) having a non-biodegradable structural unit.
• a step of preparing at least a dibasic acid and a glycol to be used for synthesizing y) It is preferable to include a step of producing a copolyester resin containing block (X) and block (Y) by polycondensing these and subjecting them to an esterification reaction.
• the dibasic acids and glycols that are raw materials in the synthesis of polymer (x) or polymer (y) are the examples of the dibasic acids and glycols listed in the section of ⁇ Polymer (x) having a biodegradable structural unit> above. The one explained in can be used.
• the raw materials in the synthesis of polymer (x) or polymer (y) may optionally contain other raw materials other than dibasic acid and glycol.
• Other raw materials include, but are not particularly limited to, polyhydric alcohols having a valence of 3 or more, polyhydric carboxylic acids having a valence of 3 or more, and the like.
• the blending ratio of dibasic acid and glycol is not particularly limited, but the mass ratio (dibasic acid: glycol) is preferably 90:10 to 50:50, more preferably 80:20 to 50:50.
• the reaction may be carried out without a catalyst or in the presence of a catalyst.
• the catalyst used in the reaction are those described in the above section ⁇ Production method of copolyester resin using polyester exchange method>.
• the reaction temperature is not particularly limited, but is usually 50 to 300°C.
• the reaction atmosphere may be air or an inert gas atmosphere such as nitrogen gas or argon gas.
• the reaction time is usually 1 to 48 hours, but the reaction is preferably carried out until no dibasic acid or glycol remains in the reaction system. The progress of the reaction can be monitored, for example, by monitoring the decrease in dibasic acid by measuring the acid value.
• the reaction time is 10 hours or more.
• the heating time is preferably 18 hours or more, more preferably 24 hours or more, and even more preferably 24 hours or more.
• polyurethane One embodiment of the copolyester resin obtained as described above is polyurethane.
• Polyurethane is obtained by reacting the copolyester of the invention with a polyisocyanate. If necessary, a polyol other than the copolyester, a chain extender, a chain terminator, and a crosslinking agent may be used in combination. Specifically, polyurethane is obtained by reacting a polyol and a polyisocyanate, and at least the copolyester of the present invention is used as the polyol.
• 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 the present invention.
• the copolyester of the present invention is a polyester polyol.
• polyester polyols include condensed polyester polyols.
• Condensed polyester polyols include, for example, low-molecular polyhydric alcohols (ethylene glycol (EG), diethylene glycol, propylene glycol (PG), dipropylene glycol, (1,3- or 1,4-)butanediol, pentanediol, neo low molecular weight polyols such as pentyl glycol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane (TMP), 1,2,5-hexanetriol, pentaerythritol, sugars such as sorbitol, etc.), Polybasic carboxylic acids (glutaric acid, adipic acid, azelaic acid, fumaric acid, maleic acid, pimelic acid, suberic acid
• chain extenders include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, sucrose, methylene Aliphatic polyol compounds such as glycol, glycerin, sorbitol, neopentyl glycol; bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, hydroquinone Aromatic polyol compounds such as water; ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethane Using amine compounds such as diamine, 3,3'-d
• the content of the copolyester of the present invention in 100% by mass of the polyol 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.
• Polyurethane can be obtained by a known method for producing polyurethane. 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 structural units derived from the copolyester of the present invention in 100% by mass of polyurethane 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 polyurethane may be 5,000 or more, 6,000 or more, 7,000 or more, 8,000 or more, 10,000 or more, and the upper limit is 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 resin 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 amounts of the heat stabilizer and hydrolysis inhibitor to be added vary depending on the type, but are generally preferably about 0.1 parts by mass to 5 parts by mass, respectively, per 100 parts by mass of the thermoplastic resin 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 the present embodiment is a cured product of the resin composition as the thermoplastic resin composition described above or the resin composition as the thermosetting resin composition described above.
• the polymers herein can be used in a variety of applications. Specifically, artificial leather, synthetic leather, shoes, thermoplastic resins, foamed resins, thermosetting resins, paints, laminating adhesives, elastic fibers, urethane raw materials, automobile parts, sporting goods, vibration isolation materials, and damping materials. It can be used in a wide range of applications, including as a fiber treatment agent and binder.
• Copolyester can be used for a variety of 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. .
• Polyurethane can be used for a variety of 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.
• the coating agent contains the copolyester resin of the present invention, 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 resin of the present invention 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 resin of the present invention, 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 the above-mentioned various base materials to produce a composite film mainly used for packaging materials for foods, medicines, detergents, and the like.
• Such adhesives include, for example, two-component curable adhesives containing the copolyester resin of the present invention, polyester polyol, and polyisocyanate, and acrylic resins, urethane resins, and ethylene-vinyl acetate copolymers.
• 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 a resin composition containing the copolyester resin of the present invention.
• the resin composition may contain other resins and various additives in addition to the copolyester resin of the present invention.
• 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 a resin composition containing the copolyester resin of the present invention.
• the resin composition may contain other resins and various additives in addition to the copolyester resin of the present invention.
• 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. .
• 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. .
• M x-y-x I x-y-x /(I x-y-x +I x-y-z +I z-y-z +I z-y-x +I x-w-z +I x-w- x +I z-w-z +I z-w-x )
• the molecular weight of the resin is a value measured using gel permeation chromatography (GPC) under the following conditions.
• Measuring device System controller Waters 600 Controller Liquid pump Waters Model Code 60F RI (differential refractometer) detector Waters 2414 Autosampler Waters 717plus Autosampler Data processing: Waters Empower3 Measurement conditions Measurement conditions: Column temperature 40°C Eluent Chloroform ( CHCl3 ) Flow rate 1.0 mL/min Standard: Polystyrene Column: 1 Shodex GPC LF-G 4 Shodex GPC LF-804 Sample: 0.4% by mass chloroform solution in terms of resin solid content filtered through a microfilter (100 ⁇ L)
• 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 (biological 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)
• the biodegradability was 63% in seawater, 65% in fresh water, and 78% in soil, and the compost decomposition rate was 83%.
• the number average molecular weight Mn was 10,071
• the weight average molecular weight Mw was 31,524.
• the biodegradability was 3% in seawater, 3% in fresh water, and 10% in soil, and the compost decomposition rate was 13%.
• the number average molecular weight Mn was 12,254, and the weight average molecular weight Mw was 28,416.
• the biodegradability was 65% in seawater, 65% in freshwater, and 74% in soil, and the compost decomposition rate was 83%.
• the number average molecular weight Mn was 19,587, and the weight average molecular weight Mw was 63,356.
• the biodegradability was 63% in seawater, 64% in fresh water, and 78% in soil, and the compost decomposition rate was 85%.
• the number average molecular weight Mn was 13,880, and the weight average molecular weight Mw was 42,954.
• the biodegradability was 3% in seawater, 3% in fresh water, and 8% in soil, and the compost decomposition rate was 10%.
• the number average molecular weight Mn was 26,445
• the weight average molecular weight Mw was 81,430.
• the biodegradability was 50% in seawater, 52% in fresh water, and 55% in soil, and the compost decomposition rate was 65%.
• the number average molecular weight Mn was 5568 and the weight average molecular weight Mw was 14619.
• the biodegradability was 63% in seawater, 65% in fresh water, and 70% in soil, and the compost decomposition rate was 78%.
• the number average molecular weight Mn was 14,200, and the weight average molecular weight Mw was 102,600.
• the biodegradability was 71% in seawater, 67% in fresh water, and 75% in soil, and the compost decomposition rate was 81%.
• the number average molecular weight Mn was 6,870
• the weight average molecular weight Mw was 14,070.
• the biodegradability was 60% in seawater, 59% in fresh water, and 63% in soil, and the compost decomposition rate was 78%.
• the number average molecular weight Mn was 14,700, and the weight average molecular weight Mw was 92,000.
• the biodegradability was 47% in seawater, 49% in fresh water, and 55% in soil, and the compost decomposition rate was 68%.
• the number average molecular weight Mn was 5,540, and the weight average molecular weight Mw was 24,500.
• the biodegradability was 61% in seawater, 62% in fresh water, and 68% in soil, and the compost decomposition rate was 78%.
• the number average molecular weight Mn was 27,200, and the weight average molecular weight Mw was 132,000.
• the biodegradability was 63% in seawater, 65% in fresh water, and 67% in soil, and the compost decomposition rate was 76%.
• the number average molecular weight Mn was 6,210, and the weight average molecular weight Mw was 26,900.
• the biodegradability was 55% in seawater, 54% in fresh water, and 62% in soil, and the compost decomposition rate was 68%.
• the number average molecular weight was Mn9634, and the weight average molecular weight Mw was 30394.
• the biodegradability was 58% in seawater, 57% in fresh water, and 65% in soil, and the compost decomposition rate was 75%.
• the number average molecular weight Mn was 4410, and the weight average molecular weight Mw was 28900.
• Example 1 In a glass container equipped with a stirrer and a nitrogen gas introduction tube, 57 parts by mass of P(2MPD/AA) obtained in Synthesis Example 1, 443 parts by mass of P(BG/SA) obtained in Synthesis Example 2, and titanium tetraisopropoxide. (TIPT) 0.05 parts by mass was charged and maintained at a container temperature of 200° C. for 24 hours under a nitrogen stream to obtain a copolyester resin containing 2MPD/AA and BG/SA as constituent units. The structure of the obtained copolyester resin is shown in formula (5).
• the triad mole fractions of block X were 0.04 for 2MPD/AA/2MPD, 0.01 for BG/AA/BG, and the sum of these was 0.05.
• the biodegradability was 16% in seawater, 18% in fresh water, and 43% in soil, and the compost decomposition rate was 62%.
• Table 1A and Table 1B will be collectively referred to as Table 1.
• Example 2 Into a polyester reaction vessel equipped with a stirrer, nitrogen gas introduction tube, rectification tube, water separator, etc., 22 parts by mass of 2-methyl-1,3 propanediol (2MPD), 34 parts by mass of adipic acid (AA), 1 , 198 parts by mass of 4-butanediol (BG), 246 parts by mass of succinic acid (SA), and 0.1 part by mass of titanium tetraisopropoxide (TIPT) were added, and the temperature of the reaction solution was 200°C under a nitrogen stream, and steam was added.
• 2MPD 2-methyl-1,3 propanediol
• AA adipic acid
• BG 4-butanediol
• SA succinic acid
• TIPT titanium tetraisopropoxide
• the esterification reaction was allowed to proceed while maintaining the temperature at 98°C, and the reaction was terminated when the acid value of the reaction solution became 2 mgKOH/g or less, and the copolyester resin containing 2MPD/AA/BG/SA as a constituent unit was Obtained.
• the structure of the obtained copolyester resin is shown in formula (30).
• Formula (30) (In formula (30), o, p, and q each independently represent a positive integer)
• the triad mole fractions of block X were 0.02 for 2MPD/AA/2MPD and 0.09 for BG/AA/BG, and the sum of these was 0.11.
• the results of biodegradability evaluation are shown in Table 1 below.
• Examples 3-4 A copolyester resin was obtained in the same manner as in Example 1, except that the blending amounts of P (2MPD/AA) and P (BG/SA) and the reaction time (reaction time) were changed to the values listed in Table 1. Ta.
• Example 5 As raw materials, the blending amounts of 2-methyl-1,3-propanediol (2MPD), adipic acid (AA), 1,4-butanediol (BG), and succinic acid (SA) were changed to the values listed in Table 1.
• a copolyester resin was obtained in the same manner as in Example 2 except for this.
• Example 7 As raw materials, 195 parts by mass of P(2MPD/SebA) obtained in Synthesis Example 3, 305 parts by mass of P(BG/SA) obtained in Synthesis Example 2, and 0.05 parts by mass of titanium tetraisopropoxide (TIPT) were charged. A copolyester resin was obtained in the same manner as in Example 1, except that the holding time, which is the reaction time, was changed to the value shown in Table 1. The structure of the obtained copolyester resin is shown in formula (6).
• Example 8 As raw materials, 181 parts by mass of P(3MPD/AA) obtained in Synthesis Example 4, 319 parts by mass of P(BG/SA) obtained in Synthesis Example 2, and 0.05 parts by mass of titanium tetraisopropoxide (TIPT) were charged. A copolyester resin was obtained in the same manner as in Example 1, except that the holding time, which is the reaction time, was changed to the value shown in Table 1. The structure of the obtained copolyester resin is shown in formula (7).
• Example 9 As raw materials, 104 parts by mass of P (2MPD/AA) obtained in Synthesis Example 1, 390 parts by mass of P (BG/AA/tPA) obtained in Synthesis Example 5, and 0.05 parts by mass of titanium tetraisopropoxide (TIPT). A copolyester resin was obtained in the same manner as in Example 1, except that the holding time, which is the reaction time, was changed to the value shown in Table 1. The structure of the obtained copolyester resin is shown in formula (8).
• Example 10 Put 500 parts by mass of P (2MPD/AA/BG/SA) obtained in Example 6 into a four-necked flask equipped with a thermometer, stirrer, nitrogen gas inlet, and reflux condenser, and add 300 parts by mass of ethyl acetate. By dissolving the polyester polyol, an ethyl acetate solution was obtained. 0.1 parts by mass of dibutyltin dilaurate (DBTDL) and 13 parts by mass of isophorone diisocyanate (IPDI) were added to the solution, and the reaction was carried out while maintaining the temperature at 70 to 80°C under a nitrogen stream. The reaction was terminated when the isocyanate weight percentage became less than 0.05% by mass, and a polyester urethane polyol solution was obtained.
• DBTDL dibutyltin dilaurate
• IPDI isophorone diisocyanate
• Example 11 A polyester urethane polyol solution was obtained in the same manner as in Example 10, except that the raw material was changed to 10 parts by mass of hexamethylene diisocyanate (HDI).
• HDI hexamethylene diisocyanate
• Example 12 A polyester urethane polyol solution was obtained in the same manner as in Example 10, except that 15 parts by mass of diphenylmethane diisocyanate (MDI) was used as the raw material.
• MDI diphenylmethane diisocyanate
• the copolyester resin of the present invention has excellent thermoformability and biodegradability.
• the resin of the comparative example did not have as high biodegradability as the example.

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