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
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/44—Polyester-amides
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/12—Polyester-amides
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
  • Y02W30/00—Technologies for solid waste management
  • Y02W30/50—Reuse, recycling or recovery technologies
  • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

• the present invention relates to a biodegradable resin decomposition accelerator, a biodegradable resin composition, a molded body, and a method for decomposing a biodegradable resin.
• PVC polyvinyl chloride resin
• Biodegradable resins are resins that can be broken down into carbon dioxide and water by microorganisms present in soil, water, oceans, etc., and are generally known to be biodegraded over a period of several months to several years.
• biodegradable resins can be accelerated by placing them in a hot and humid environment, but various proposals have been made to further enhance the biodegradability of biodegradable resins (e.g., Patent Documents 1-5).
• a biodegradable resin decomposition accelerator which is a polyester having reactants consisting of one or more amine compounds selected from the group consisting of aliphatic diamines, aliphatic aminocarboxylic acids, aromatic aminocarboxylic acids, and aliphatic amino alcohols, one or more carbonyl compounds selected from the group consisting of aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and hydroxycarboxylic acids, and an aliphatic diol,
• the number average molecular weight of the polyester is in the range of 300 to 5,000.
• R N1 is an alkylene group having 1 to 12 carbon atoms or a heteroalkylene group having 1 to 12 carbon atoms
• R N2 is an alkylene group having 1 to 12 carbon atoms, a heteroalkylene group having 1 to 12 carbon atoms, an aryl group having 5 to 15 carbon atoms, or a heteroaryl group having 5 to 15 carbon atoms
• R N3 is an alkylene group having 1 to 12 carbon atoms or a heteroalkylene group having 1 to 12 carbon atoms.
• R A is a single bond, an alkylene group having 1 to 12 carbon atoms, a heteroalkylene group having 1 to 12 carbon atoms, an aryl group having 5 to 15 carbon atoms, or a heteroaryl group having 5 to 15 carbon atoms
• R L is an alkylene group having 1 to 18 carbon atoms or a heteroalkylene group having 1 to 18 carbon atoms. 4.
• a biodegradable resin composition comprising a biodegradable resin and the biodegradable resin decomposition accelerator according to any one of 1 to 5. 7.
• biodegradable resin composition according to 6 wherein the biodegradable resin is at least one selected from the group consisting of polylactic acid, polybutylene succinate, polybutylene adipate terephthalate, polyhydroxyalkanoic acid, polybutylene succinate adipate, and polyethylene terephthalate succinate.
• a molded article of the biodegradable resin composition according to any one of 6 to 8. 10.
• a method for decomposing a biodegradable resin comprising adding a biodegradable resin decomposition accelerator according to any one of 1 to 5 to a biodegradable resin.
• a biodegradation promoter that improves the biodegradability of a biodegradable resin can be provided.
• a biodegradable resin composition having improved biodegradability and a molded article thereof can be provided.
• the present invention provides a method for decomposing a biodegradable resin, which can decompose the biodegradable resin in a shorter time.
• the present invention is not limited to the following embodiment, and can be implemented by making appropriate modifications within the scope that does not impair the effects of the present invention.
• the compounds in the present specification may be derived from fossil resources or biological resources.
• the biodegradable resin decomposition accelerator of the present invention is a polyester having, as reaction components, one or more amine compounds (N) selected from the group consisting of aliphatic diamines, aliphatic aminocarboxylic acids, aromatic aminocarboxylic acids, and aliphatic amino alcohols, one or more carbonyl compounds (C) selected from the group consisting of aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and hydroxycarboxylic acids, and an aliphatic diol (G), and the number average molecular weight of the polyester is in the range of 300 to 5,000.
• N amine compounds
• C carbonyl compounds
• G an aliphatic diol
• the term “reactive components” refers to components that constitute the polyester, which is the biodegradable resin decomposition accelerator of the present invention, and does not include solvents or catalysts that do not constitute the polyester.
• the biodegradable resin decomposition accelerator of the present invention is a polymer that may contain not only ester bonds but also amide bonds, but for the sake of convenience, the polymer is referred to as "polyester" in the present application.
• the polyester that is the biodegradable resin decomposition promoter of the present invention (hereinafter may be referred to as "the polyester of the present invention") not only promotes the decomposition of biodegradable resins by the polyester itself functioning as an acid catalyst, but also contains nitrogen atoms that are known as a nutrient source for microorganisms, and are therefore presumed to attract and grow microorganisms, thereby promoting the decomposition of biodegradable resins.
• the biodegradable resin decomposition accelerator of the present invention is an oligomer having a number-average molecular weight in the range of 300 to 5,000, it is easily taken up as a nutrient by microorganisms and the decomposition accelerator itself has excellent decomposition properties.
• the amine compound (N) is at least one selected from the group consisting of an aliphatic diamine, an aliphatic aminocarboxylic acid, an aromatic aminocarboxylic acid, and an aliphatic amino alcohol, and is preferably at least one selected from the group consisting of a compound represented by the following general formula (N-1), a compound represented by the following general formula (N-2), and a compound represented by the following general formula (N-3).
• R N1 is an alkylene group having 1 to 12 carbon atoms or a heteroalkylene group having 1 to 12 carbon atoms
• R N2 is an alkylene group having 1 to 12 carbon atoms, a heteroalkylene group having 1 to 12 carbon atoms, an aryl group having 5 to 15 carbon atoms, or a heteroaryl group having 5 to 15 carbon atoms
• R N3 is an alkylene group having 1 to 12 carbon atoms or a heteroalkylene group having 1 to 12 carbon atoms.
• the alkylene group having 1 to 12 carbon atoms for R N1 , R N2 and R N3 may be linear or branched, and may contain an alicyclic structure.
• the alkylene group having 1 to 12 carbon atoms for R N1 , R N2 and R N3 is preferably an alkylene group having 1 to 6 carbon atoms.
• alkylene group having 1 to 12 carbon atoms for R N1 , R N2 , and R N3 include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, a hexylene group, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.
• the heteroalkylene group having 1 to 12 carbon atoms for R N1 , R N2 and R N3 is, for example, a group in which the alkylene group having 1 to 12 carbon atoms further contains one or more bonds selected from an ether bond (-O-), a sulfide bond (-S-) and an amino bond (-NH-).
• the heteroalkylene group having 1 to 12 carbon atoms for R N1 , R N2 and R N3 is preferably a heteroalkylene group having 2 to 10 carbon atoms, and more preferably a heteroalkylene group having 4 to 8 carbon atoms.
• examples of the aryl group having 5 to 15 carbon atoms for R N2 include a phenylene group and a naphthalenylene group.
• the heteroaryl group having 5 to 15 carbon atoms for R N2 is, for example, a group in which one or more carbon atoms in the aromatic ring of the above-mentioned aryl group having 5 to 15 carbon atoms are replaced with a heteroatom (oxygen atom, nitrogen atom, sulfur atom), and examples of the heteroaryl group include a furan ring, an imidazole ring, and an oxazole ring.
• the alkylene group having 1 to 12 carbon atoms and the heteroalkylene group having 1 to 12 carbon atoms of R N2 may be substituted with, for example, an aryl group having 5 to 15 carbon atoms or a heteroaryl group having 5 to 15 carbon atoms.
• the aryl group having 5 to 15 carbon atoms and the heteroaryl group having 5 to 15 carbon atoms for R N2 may be substituted, for example, with an alkyl group having 1 to 6 carbon atoms on the aromatic ring or hetero ring.
• the compound represented by the general formula (N-2) may be a compound having at least one amino group and at least one carboxyl group, and may be a compound having two or more amino groups and/or two or more carboxyl groups.
• aspartic acid is a compound represented by the general formula (N-2) in which two carboxyl groups and one amino group are substituted on an alkylene group.
• lysine is a compound represented by the general formula (N-2) in which one carboxyl group and two amino groups are substituted on an alkylene group.
• aliphatic diamines include propanediamine, hexanediamine, isophoronediamine, bis(3-aminopropyl)ether, 3,3'-iminobis(propylamine), N,N-bis(3-aminopropyl)methylamine, 1,2-bis(3-aminopropoxy)ethane, and 1,4-bis(3-aminopropyl)piperazine.
• propanediamine hexanediamine
• isophoronediamine bis(3-aminopropyl)ether
• 3,3'-iminobis(propylamine) 3,3'-iminobis(propylamine)
• N,N-bis(3-aminopropyl)methylamine 1,2-bis(3-aminopropoxy)ethane
• 1,4-bis(3-aminopropyl)piperazine 1,4-bis(3-aminopropyl)piperazine.
• the aliphatic diamines used may be one
• aliphatic aminocarboxylic acids and aromatic aminocarboxylic acids include 4-aminobutyric acid, glycine, methionine, phenylalanine, aspartic acid, glutamic acid, lysine, histidine, and 12-aminolauric acid.
• the aliphatic aminocarboxylic acid may be used alone or in combination of two or more kinds.
• the aromatic aminocarboxylic acid may be used alone or in combination of two or more kinds.
• aliphatic amino alcohols include ethanolamine, 3-amino-1-propanol, 2-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 1-amino-2-butanol, 2-amino-1-butanol, 3-amino-1-butanol, 2-(3-aminopropylamino)ethanol, 2-(2-aminoethylamino)ethanol, 1-[(2-aminoethyl)amino]-2-propanol, and 2-(2-aminoethoxy)ethanol.
• the aliphatic amino alcohols used may be one type alone or two or more types may be used in combination.
• the carbonyl compound (C) is one or more compounds selected from the group consisting of aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and hydroxycarboxylic acids, and is preferably one or more compounds selected from the group consisting of compounds represented by the following general formula (A) and compounds represented by the following general formula (L):
• R A is a single bond, an alkylene group having 1 to 12 carbon atoms, a heteroalkylene group having 1 to 12 carbon atoms, an aryl group having 5 to 15 carbon atoms, or a heteroaryl group having 5 to 15 carbon atoms
• R L is an alkylene group having 1 to 18 carbon atoms or a heteroalkylene group having 1 to 18 carbon atoms.
• the alkylene group having 1 to 12 carbon atoms, the heteroalkylene group having 1 to 12 carbon atoms, the aryl group having 5 to 15 carbon atoms, and the heteroaryl group having 5 to 15 carbon atoms in the general formulas (A) and (L) are the same as the alkylene group having 1 to 12 carbon atoms, the heteroalkylene group having 1 to 12 carbon atoms, the aryl group having 5 to 15 carbon atoms, and the heteroaryl group having 5 to 15 carbon atoms in the general formulas (N-1), (N-2), and (N-3), respectively.
• the alkylene group having 1 to 12 carbon atoms for R A is preferably an alkylene group having 2 to 12 carbon atoms.
• the alkylene group having 1 to 18 carbon atoms for R L is preferably an alkylene group having 4 to 18 carbon atoms.
• alkylene group having 1 to 12 carbon atoms for R A include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, a hexylene group, a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.
• alkylene group having 1 to 18 carbon atoms for R L include, in addition to the specific examples of the alkylene group having 1 to 12 carbon atoms, a hexadecanyl group, a heptadecanyl group, etc.
• aliphatic dicarboxylic acids include oxalic acid, succinic acid, adipic acid, maleic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, cyclohexanedicarboxylic acid, dodecanedicarboxylic acid, and hexahydrophthalic acid, and preferred are succinic acid, sebacic acid, maleic acid, and adipic acid.
• the aliphatic dicarboxylic acids used may be one type alone or two or more types may be used in combination.
• aromatic dicarboxylic acids include phthalic acid and furandicarboxylic acid.
• the aromatic dicarboxylic acid may be used alone or in combination of two or more kinds.
• hydroxycarboxylic acids include hydroxycarboxylic acids in which one hydroxyl group is substituted on the fatty chain of an aliphatic carboxylic acid, such as propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, caprylic acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, and stearic acid, and preferred examples include lactic acid, 9-hydroxystearic acid, 12-hydroxystearic acid, and 6-hydroxycaproic acid.
• the hydroxycarboxylic acids used may be one type alone or two or more types in combination.
• the aliphatic diol (G) is preferably an aliphatic diol having 2 to 12 carbon atoms.
• Specific examples of aliphatic diols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylol pentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylol heptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol
• the aliphatic diol having 2 to 12 carbon atoms may contain an alicyclic structure and/or an ether bond (-O-).
• Examples of the aliphatic diol having 2 to 12 carbon atoms and containing an alicyclic structure include 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol.
• Examples of the aliphatic diol having 2 to 12 carbon atoms and containing an ether bond include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol.
• the aliphatic diol having 2 to 12 carbon atoms is preferably an aliphatic diol having 2 to 8 carbon atoms, and more preferably ethylene glycol, diethylene glycol, 1,3-propylene glycol, 1,6-hexanediol or 1,4-butanediol.
• G linear aliphatic diol
• compatibility with biodegradable resins can be improved.
• the aliphatic diols used may be one type alone or two or more types in combination.
• reaction components used include derivatives such as the above esters, acid chlorides, and acid anhydrides.
• hydroxycarboxylic acids include compounds with lactone structures such as ⁇ -caprolactone.
• the reactive components of the polyester of the present invention are sufficient as long as they contain the carbonyl compound (C), the aliphatic diol (G) and the amine compound (N), and may contain other components.
• the reactive components of the polyester of the present invention are preferably 90 mass% or more of the carbonyl compound (C), the aliphatic diol (G) and the amine compound (N) based on the total amount of the reactive components, more preferably 95 mass% or more of the carbonyl compound (C), the aliphatic diol (G) and the amine compound (N), and further preferably consist of only the carbonyl compound (C), the aliphatic diol (G) and the amine compound (N).
• the reaction of the amine compound (N), the carbonyl compound (C), and the aliphatic diol (G) can be carried out by a known method.
• the amine compound (N), the carbonyl compound (C), and the aliphatic diol (G) may be reacted at once, or the carbonyl compound (C) and the aliphatic diol (G) may be reacted to form a polyester, and the amine compound (N) may be reacted with the polyester.
• the polyester of the present invention is preferably a terminal amine-modified polyester obtained by reacting a polyester having a carbonyl compound (C) and an aliphatic diol (G) as reaction components with an amine compound (N), and more preferably a terminal amine-modified polyester obtained by reacting a polyester having an aliphatic dicarboxylic acid and an aliphatic diol as reaction components with an amine compound (N).
• the polyester having the terminals modified with the amine compound (N) is expected to have a high microbial attracting effect and a high microbial proliferation effect.
• the contents of the carbonyl compound (C) and the aliphatic diol (G) in the reaction components may be set so that, for example, the equivalent of the carboxyl group contained in the reaction components is equal to or less than the equivalent of the hydroxyl group.
• the content of the amine compound (N) in the reaction components is, for example, in the range of 1 to 50 mass% of the total amount of the reaction components, preferably in the range of 5 to 40 mass% of the total amount of the reaction components, more preferably in the range of 10 to 35 mass% of the total amount of the reaction components, and even more preferably in the range of 15 to 30 mass% of the total amount of the reaction components.
• the reaction of the reaction components may be carried out, if necessary, in the presence of an esterification catalyst, at a temperature within the range of, for example, 180 to 250° C. for a period of 10 to 25 hours.
• the conditions of the esterification reaction, such as temperature and time, are not particularly limited and may be set appropriately.
• esterification catalyst examples include titanium-based catalysts such as tetraisopropyl titanate and tetrabutyl titanate; zinc-based catalysts such as zinc acetate; tin-based catalysts such as dibutyltin oxide; and organic sulfonic acid catalysts such as p-toluenesulfonic acid.
• the amount of the esterification catalyst used may be set as appropriate, but is usually used in the range of 0.001 to 0.1 parts by mass per 100 parts by mass of the total amount of reaction components.
• the number average molecular weight (Mn) of the polyester of the present invention is, for example, in the range of 100 to 6,000, preferably in the range of 300 to 5,000, more preferably in the range of 500 to 4,000, even more preferably in the range of 500 to 3,000, and particularly preferably in the range of 500 to 2,000.
• the number average molecular weight (Mn) is a value calculated in terms of polystyrene based on gel permeation chromatography (GPC) measurement, and is measured by the method described in the Examples.
• the acid value of the polyester of the present invention is, for example, 25 mgKOH/g or more, and is preferably 27 mgKOH/g or more, 30 mgKOH/g or more, 40 mgKOH/g or more, 50 mgKOH/g or more, and more than 50 mgKOH/g, in that order.
• the upper limit of the acid value of the polyester of the present invention is not particularly limited, but is, for example, 400 mgKOH/g or less, and is preferably 250 mgKOH/g or less, 200 mgKOH/g or less, 150 mgKOH/g or less, 120 mgKOH/g or less, 100 mgKOH/g or less, and 95 mgKOH/g or less, in that order.
• the acid value of the polyester is confirmed by the method described in the examples.
• the hydroxyl value of the polyester of the present invention may be, for example, 0 or more, and is preferably in the range of 10 to 200 mgKOH/g, more preferably in the range of 20 to 150 mgKOH/g, and further preferably in the range of 30 to 120 mgKOH/g.
• the hydroxyl value of the polyester is confirmed by the method described in the examples.
• the properties of the polyester of the present invention vary depending on the number average molecular weight, composition, etc., but are usually liquid, solid, paste-like, etc. at room temperature (25°C), preferably solid or liquid at room temperature (25°C), and more preferably solid at room temperature (25°C).
• the biodegradable resin composition of the present invention contains the biodegradable resin decomposition accelerator of the present invention and a biodegradable resin. By doing so, the decomposition of the biodegradable resin can be further promoted.
• the biodegradable resin decomposition accelerator of the present invention can also function as a plasticizer for biodegradable resins, and the present invention can be used without using conventional plasticizers such as benzoic acid esters, phthalic acid esters, and pyromellitic acid esters.
• the biodegradable resin composition of the invention can be used to produce molded articles.
• the content of the biodegradable resin decomposition accelerator of the present invention is not particularly limited, but is, for example, in the range of 1 to 250 parts by mass of the biodegradable resin decomposition accelerator per 100 parts by mass of biodegradable resin, preferably in the range of 1 to 50 parts by mass, and more preferably in the range of 1 to 30 parts by mass.
• the biodegradable resin contained in the biodegradable resin composition of the present invention includes polylactic acid (PLA), polyethylene succinate (PES), polyethylene terephthalate-succinate (PETS), polybutylene succinate (PBS), polybutylene adipate-terephthalate (PBAT), polyethylene adipate-terephthalate (PEAT), polybutylene succinate-terephthalate (PBST), polyethylene succinate-terephthalate (PEST), polybutylene succinate-terephthalate (PBAT), polybutylene succinate-terephthalate (PEST), polybutylene succinate-terephthalate (PBAT), polybutylene succinate-terephthalate (PEST), polybutylene succinate-terephthalate (PET ...
• PLA polylactic acid
• PES polyethylene succinate
• PETS polyethylene terephthalate-succinate
• PBS polybutylene succinate
• PBAT polyethylene adipate-terephthalate
• polyisocyanate examples include poly(butylene succinate)-adipate (PBSA), polybutylene succinate-carbonate (PEC), polybutylene succinate-adipate-terephthalate (PBSAT), polyethylene succinate-adipate-terephthalate (PESAT), polytetramethylene adipate-terephthalate (PTMAT), polyhydroxyalkanoic acid, polycaprolactone (PCL), polycaprolactone-butylene succinate (PCLBS), and cellulose acetate.
• PBSA poly(butylene succinate)-adipate
• PEC polybutylene succinate-carbonate
• PBSAT polybutylene succinate-adipate-terephthalate
• PESAT polyethylene succinate-adipate-terephthalate
• PTMAT polytetramethylene adipate-terephthalate
• PCL polycaprolactone-butylene succinate
• PCLBS polycaprolactone-butylene succinate
• polyhydroxyalkanoic acids include polyhydroxybutyric acid (PHB), polyhydroxybutyric acid-hydroxyhexanoic acid (PHBH), etc.
• the biodegradable resin is preferably one or more selected from the group consisting of polylactic acid, polybutylene succinate, polybutylene adipate terephthalate, polyhydroxyalkanoic acid, polybutylene succinate adipate, and polyethylene terephthalate succinate.
• the biodegradable resin composition of the present invention may contain an inorganic filler.
• the inorganic filler contained in the biodegradable resin composition of the present invention is not particularly limited, and examples thereof include calcium carbonate, talc, silica, alumina, clay, antimony oxide, aluminum hydroxide, magnesium hydroxide, hydrotalcite, calcium silicate, magnesium oxide, potassium titanate, barium titanate, titanium oxide, calcium oxide, magnesium oxide, manganese dioxide, boron nitride, and aluminum nitride.
• the inorganic fillers may be used alone or in combination of two or more kinds.
• the inorganic filler is preferably one or more selected from the group consisting of calcium carbonate, silica, alumina, aluminum hydroxide, barium titanate, talc, boron nitride, and aluminum nitride, and more preferably one or more selected from the group consisting of calcium carbonate, alumina, aluminum hydroxide, and talc.
• the particle size, fiber length, fiber diameter, and other shapes of the inorganic filler are not particularly limited, and may be adjusted appropriately depending on the intended use.
• the surface treatment state of the inorganic filler is not particularly limited, and the surface may be modified with, for example, saturated fatty acid, depending on the intended use.
• the content of the inorganic filler is, for example, in the range of 1 to 200 parts by mass relative to 100 parts by mass of the biodegradable resin, and may be in the range of 1 to 100 parts by mass, 5 to 70 parts by mass, 10 to 60 parts by mass, or 15 to 55 parts by mass.
• the biodegradable resin decomposition accelerator of the present invention can also function as a plasticizer, but the biodegradable resin composition of the present invention may further contain a plasticizer other than the biodegradable resin decomposition accelerator of the present invention.
• the plasticizer include benzoic acid esters such as diethylene glycol dibenzoate; phthalic acid esters such as dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), and ditridecyl phthalate (DTDP); terephthalic acid esters such as bis(2-ethylhexyl) terephthalate (DOTP); isophthalic acid esters such as bis(2-ethylhexyl) isophthalate (DOIP); pyromellitic acid esters such as tetra-2
• fatty acid esters examples include aliphatic dibasic acid esters such as diisononyl phosphate (DINS); phosphate esters such as tri-2-ethylhexyl phosphate (TOP) and tricresyl phosphate (TCP); alkyl esters of polyhydric alcohols such as pentaerythritol; polyesters having a molecular weight of 800 to 4,000 synthesized by polyesterification of a dibasic acid such as adipic acid with a glycol; epoxidized esters such as epoxidized soybean oil and epoxidized linseed oil; alicyclic dibasic acids such as diisononyl hexahydrophthalate; fatty acid glycol esters such as 1,4-butanediol dicaprate; acetyl tributyl citrate (ATBC); chlorinated paraffin obtained by chlorinating paraffin wax or n-paraffin; chlorinated fatty acid
• the amount of the plasticizer is not particularly limited, but is preferably in the range of 10 to 300 parts by mass, and more preferably in the range of 20 to 200 parts by mass, per 100 parts by mass of the biodegradable resin.
• the additives contained in the biodegradable resin composition of the present invention are not limited to the biodegradable resin decomposition accelerator and the plasticizer, and may contain other additives other than these.
• the other additives include viscosity reducers, flame retardants, stabilizers, stabilization aids, colorants, processing aids, fillers, antioxidants (antiaging agents), UV absorbers, light stabilizers, lubricants, antistatic agents, crosslinking aids, and the like.
• the biodegradable resin composition of the present invention may contain a non-biodegradable resin within a range that does not impair the effects of the present invention.
• the non-biodegradable resin is not particularly limited, and examples thereof include polyolefin, polyester, polysulfide, polyvinyl chloride, modified polysulfide, silicone resin, modified silicone resin, acrylic urethane resin, epoxy resin, polyurethane, acrylic resin, polyester, and unsaturated polyester.
• the method for producing the biodegradable resin composition of the present invention is not particularly limited.
• the composition can be obtained by melt-kneading a biodegradable resin, an inorganic filler, and a flowability modifier, as well as a plasticizer and other additives as necessary, using a melt-kneading machine such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a Brabender, or various kneaders.
• the biodegradable resin composition of the present invention can be molded by various molding methods applicable to general-purpose plastics.
• the molding method include compression molding (compression molding, lamination molding, stampable molding), injection molding, extrusion molding and co-extrusion molding (film molding by inflation method or T-die method, laminate molding, pipe molding, electric wire/cable molding, molding of profiled materials), heat press molding, hollow molding (various blow moldings), calendar molding, solid molding (uniaxial stretch molding, biaxial stretch molding, roll rolling molding, stretch-oriented nonwoven fabric molding, thermoforming (vacuum molding, compressed air molding), plastic processing, powder molding (rotational molding), various nonwoven fabric moldings (dry method, adhesion method, entanglement method, spunbond method, etc.), and the like.
• the molding method is preferably injection molding, extrusion molding, compression molding, or heat press molding. As a specific shape, the molding method is preferably applied to a sheet, a film, or a container.
• the molded article obtained above may be subjected to secondary processing.
• secondary processing include embossing, painting, bonding, printing, metallizing (plating, etc.), machining, and surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.).
• the decomposition of the molded article obtained from the biodegradable resin composition of the present invention can be accelerated by the biodegradable resin decomposition promoter of the present invention, and the molded article can be suitably used as a product with a relatively short product life, such as a disposable container.
• the molded articles obtained from the biodegradable resin composition of the present invention are suitably used in a wide range of applications, such as packaging materials for packaging liquids, powders, and solids, agricultural materials, and construction materials.
• Specific applications include injection molded products (e.g., fresh food trays, fast food containers, coffee capsule containers, cutlery, outdoor leisure products, etc.), extrusion molded products (e.g., films, sheets, fishing lines, fishing nets, vegetation nets, secondary processing sheets, water-retaining sheets, etc.), hollow molded products (bottles, etc.), etc.
• Applications are not limited to the above, but can also be used for agricultural films, coating materials, fertilizer coating materials, seedling pots, laminated films, plates, stretched sheets, monofilaments, nonwoven fabrics, flat yarns, staples, crimped fibers, striped tapes, split yarns, composite fibers, blown bottles, shopping bags, garbage bags, compost bags, cosmetic containers, detergent containers, bleach containers, ropes, binding materials, sanitary cover stock materials, cooler boxes, cushioning films, multifilaments, synthetic paper, and for medical purposes, surgical threads, sutures, artificial bones, artificial skin, microcapsules, wound dressings, etc.
• microbial carriers for example, microbial carriers, zooplankton breeding equipment, water treatment carriers, foams, drainage materials, downhole tool components, frac plugs, firework shells, battery materials, capacitors, sensors, shape memory materials and stents.
• the microbial carrier of one embodiment is used for water purification, and can improve, for example, denitrification efficiency.
• the shape of the microbial carrier is not particularly limited, and examples thereof include a film, a pellet, and a hollow cylinder.
• the carrier may be porous.
• the porosity of the microbial carrier containing a biodegradable resin can be kept low, and the carrier can be a rod-shaped carrier having a cross-sectional shape with a recess on the outer periphery.
• the microbial carrier according to the present embodiment can be used to support various microorganisms, and the type of microorganism is not particularly limited.
• denitrifying bacteria particularly heterotrophic denitrifying bacteria
• the oxygen concentration in the vicinity of the biofilm in which the supported microorganisms are assembled in a film form can be reduced, so that it can be preferably used to support anaerobic microorganisms, for example, denitrifying bacteria that perform denitrification under anaerobic conditions.
• the microbial carrier according to the present embodiment is used to support heterotrophic microorganisms, such as denitrifying bacteria, it is preferable to support biodegradable resin-decomposing bacteria having the ability to decompose biodegradable resin together with the denitrifying bacteria.
• the biodegradable resin-decomposing bacteria decompose the biodegradable resin in the microbial carrier, the carbon required for denitrifying nitrite nitrogen and/or nitrate nitrogen in the water to be treated is sufficiently supplied to the denitrifying bacteria. As a result, the growth, growth, activity, etc. of the denitrifying bacteria are promoted, and the denitrification rate and denitrification amount can be improved.
• the denitrifying bacteria, biodegradable resin-decomposing bacteria, etc. can be appropriately selected from known bacteria and used.
• the biodegradable resin a highly degradable biodegradable polyester is preferred.
• a biodegradable polyester having a highly degradable dicarboxylic acid-derived structural unit is particularly preferred, and a biodegradable polyester having a dicarboxylic acid-derived structural unit and a diol-derived structural unit is more preferred.
• the microbial carrier has, for example, a rod-like shape, a cross section perpendicular to the longitudinal direction has a recess on the outer periphery, and a periphery ratio is 0.5 mm-1 or more and 4.5 mm-1 or less.
• the recess on the outer periphery of the cross section of the microbial carrier is derived from a groove formed continuously in the longitudinal direction of the microbial carrier.
• the zooplankton breeding facility includes a culture tank that contains culture water for zooplankton, and a molded article of a biodegradable resin composition. Since the molded article of the biodegradable resin composition is contained in the culture tank, the culture water during culture contains the biodegradable resin together with the zooplankton, thereby promoting the proliferation of the zooplankton.
• the zooplankton breeding equipment of one embodiment includes a culture tank, an aeration pipe, a blower, a liquid drainage pipe, a liquid drainage valve, a zooplankton food tank, and a zooplankton food supply pump.
• the aeration pipe is installed in the culture tank, and the blower installed outside the culture tank and the aeration pipe are connected by piping.
• a liquid drainage pipe is connected to the culture tank, and a liquid drainage valve is provided on the liquid drainage pipe.
• the culture tank and the food tank are connected by piping provided with a food supply pump.
• the water treatment device of one embodiment comprises a water reservoir in which the water to be treated is stored, a denitrification tank containing a denitrification carrier carrying denitrifying bacteria, and a microorganism reduction treatment unit that reduces the number of aerobic heterotrophic bacteria in the water to be treated.
• the microorganism reduction treatment unit is disposed midway along the transport path of the water to be treated from the water reservoir to the denitrification tank.
• the foam is obtained by foam molding a molded body of the biodegradable resin composition.
• the biodegradable resin composition has favorable melt tension and high gas retention, and therefore has good foam moldability and shaping properties, suppresses the occurrence of swirl marks, and has a good appearance.
• the shape of the foam and examples of the foam include various shapes such as containers, plates, cylinders, columns, sheets, boards, and blocks. It can be used as insulation and cushioning materials for daily necessities, toys, industrial materials, industrial materials, and cooler boxes.
• the drain material in one embodiment is used in the plastic board drain method, and is composed of, for example, a plate-shaped core material with grooves formed on at least one side thereof that extend over the entire length of the longitudinal direction, and a sheet-shaped water-permeable material that covers at least the surface of the core material on which the grooves are formed, and the plate-shaped core material is composed of a molded body of a biodegradable resin composition.
• the shell of a firework shell uses a biodegradable resin composition as a matrix that is completely or partially decomposed by microorganisms in soil or water (including seawater), and is mixed with an incompatible biodegradable resin or natural organic materials such as insoluble wood flour or rice husks before molding.
• a biodegradable resin composition as a matrix that is completely or partially decomposed by microorganisms in soil or water (including seawater), and is mixed with an incompatible biodegradable resin or natural organic materials such as insoluble wood flour or rice husks before molding.
• the downhole tool member of one embodiment can be used as a member of a frac plug.
• the downhole tool member By forming the downhole tool member as a molded body of a biodegradable resin composition, it is possible to mold it into a secondary molded product of a desired shape by machining such as cutting, drilling, and shearing, in particular a downhole tool member to be provided in a sealing plug.
• the biodegradable stent of one embodiment includes a stent body made of a cylindrical braid of multiple filament threads made of a molded body of a biodegradable resin composition, and an elastic thread is arranged on the outside of the stent body in the longitudinal direction.
• the elastic thread is arranged in at least a portion of the longitudinal direction, including the vicinity of each end of the stent body.
• One end of the elastic thread is fixed near the end of the stent body, and the other end is fixed to any part of the stent body. When the stent body is contracted, tension is applied to the elastic thread.
• the molded article of the present invention is biocompatible and biodegradable, and can therefore be used in medical sensors and shape-memory materials, as well as battery materials, capacitors, and other applications where these properties are required.
• biodegradable resin decomposition accelerator of the present invention By adding the biodegradable resin decomposition accelerator of the present invention to a biodegradable resin, the decomposition of the biodegradable resin can be accelerated.
• the type of biodegradable resin, the amount of the biodegradable resin decomposition accelerator added, etc. are the same as those explained in the biodegradable resin composition of the present invention.
• the decomposition-promoting effect can be obtained not only in the state of a composition containing a biodegradable resin decomposition promoter and a biodegradable resin, but also in the state of a molded product of a biodegradable resin composition containing a biodegradable resin and a biodegradable resin decomposition promoter.
• the biodegradable resin decomposition accelerator is mixed with the biodegradable resin, the decomposition acceleration effect can be achieved, and it can be carried out regardless of the environment. Therefore, decomposition can be carried out both indoors and outdoors (including in the soil and underwater).
• the decomposition conditions may be appropriately set according to the desired decomposition rate.
• the decomposition of biodegradable resins is accelerated under high temperature and humidity conditions. Therefore, when it is desired to further accelerate the decomposition of biodegradable resins, it is advisable to carry out the decomposition method of the present invention under a high temperature and humidity environment.
• the acid value, hydroxyl value and viscosity values were evaluated by the following methods.
• ⁇ Method of measuring acid value> The measurement was performed according to a method in accordance with JIS K0070-1992.
• ⁇ Method for measuring hydroxyl value> The measurement was performed according to a method in accordance with JIS K0070-1992.
• the number average molecular weight of the polyester is a value calculated in terms of polystyrene based on GPC measurement, and the measurement conditions are as follows.
• Measurement equipment Tosoh Corporation's high-speed GPC equipment "HLC-8320GPC”
• Data processing Tosoh Corporation's "EcoSEC Data Analysis Version 1.07"
• Developing solvent tetrahydrofuran Flow rate: 0.35 mL/min
• Measurement sample 7.5 mg of a sample was 7.5 mg of a sample was
• decomposition accelerator A The presence or absence of residual amino groups in decomposition accelerator A was confirmed by the ninhydrin reaction. Specifically, 100 mg of decomposition accelerator, 10 mg of ninhydrin, and 10 mL of benzyl alcohol were charged into a flask and stirred at 120°C for 10 minutes, after which the appearance of the solution was confirmed. If the solution was not colored, the ninhydrin reaction was negative, indicating that there were no residual amino groups. If the solution turned red to purple, the ninhydrin reaction was positive, indicating that there were residual amino groups.
• Example 1 Biodegradability Test of Decomposition Accelerator
• 200 g of seawater collected from the coast of Chiba Minato and 30 mg of the decomposition accelerator shown in Table 1 were added to a glass container with a stirrer.
• 10 mL of 0.2 M sodium hydroxide solution was further added to the glass container as a CO2 absorbent, and the glass container was sealed and stirred continuously for 4 weeks in a thermostatic chamber at 30 ° C. After stirring was completed, the unreacted sodium hydroxide was titrated with 0.1 M hydrochloric acid solution to calculate the amount of CO2 generated in the container (the amount of NaOH before the test started - the amount of HCl dripped).
• the biodecomposition rate of the decomposition accelerator was evaluated as (amount of CO2 generated in the container / amount of CO2 generated if the decomposition accelerator is completely biodegraded (calculated value)) x 100. The results are shown in Table 1.
• PHB in Reference Example 1 is polyhydroxybutyric acid, a biodegradable resin. It can be seen that the decomposition accelerator in the example has the same degree of biodegradability as known biodegradable resins.
• a biodegradable resin composition was prepared by kneading the components shown in Table 2 for 5 minutes at 130° C. using a mixer. The obtained biodegradable resin composition was hot pressed to a thickness of 1 mm and then powdered using a freeze grinder (Japan Analytical Industry Co., Ltd., “JFC-300”). 30 g of soil (water content 30 wt%) collected from a field in Ichihara City, Chiba Prefecture was mixed with 30 mg of a powdered biodegradable resin composition, and the resulting mixture was filled into a glass container.
• a freeze grinder Japan Analytical Industry Co., Ltd., “JFC-300”.
• the polybutylene succinate used in Table 2 is "BioPBS FZ71PM” manufactured by PTT MCC Biochem.
• 4-aminobutyric acid in Comparative Example 1 is the amino acid used in Synthesis Example 1. It is presumed that in Comparative Example 1, 4-aminobutyric acid attracts and proliferates microorganisms, enhancing biodegradability compared to the blank Comparative Example 2. However, because 4-aminobutyric acid is not very compatible with PBS, the decomposition promoting effect is not as good as that of the decomposition promoters in Examples 9-14.
• a biodegradable resin composition was prepared by kneading the components shown in Table 3 in a mixer for 5 minutes at 170° C.
• the obtained biodegradable resin composition was hot-pressed to a thickness of 1 mm, and the obtained film was cut into a size of 2 cm ⁇ 2 cm to prepare a test piece.
• a glass bottle was filled with soil (water content 30 wt%) collected from a field in Ichihara City, Chiba Prefecture, and the above test piece was buried in the soil. The bottle was closed and left to stand in a thermostatic chamber at 45° C. for two weeks.
• the change in the number average molecular weight of the polylactic acid in the test piece before and after standing was measured, and the number average molecular weight retention rate (number average molecular weight of polylactic acid after standing/number average molecular weight of polylactic acid before standing ⁇ 100) was calculated.
• the measurement sample was dissolved in chloroform, and data processing was performed using "EcoSEC Data Analysis Version 1.15" manufactured by Tosoh Corporation.
• the polylactic acid used in Table 3 is "Luminy LX-175" manufactured by Total Corbion PLA.

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