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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/20—Carboxylic acid 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
• • 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
• • 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 biodegradable resin decomposition accelerator, a biodegradable resin composition, a molded article, and a method for decomposing a biodegradable resin.
• PVC polyvinyl chloride
• Biodegradable resins are resins that can be decomposed into carbon dioxide and water by the action of microorganisms present in soil, water, oceans, etc., and are generally known to biodegrade over a long period of time, from 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 and 2).
• a method for decomposing a biodegradable resin comprising adding the biodegradable resin decomposition accelerator according to any one of 1 to 5 to the biodegradable resin.
• R N 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 represented by R 1 N may be linear or branched, and may contain an alicyclic structure.
• the alkylene group having 1 to 12 carbon atoms for R 1 N is preferably an alkylene group having 1 to 6 carbon atoms.
• the heteroalkylene group having 1 to 12 carbon atoms for R N 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 1 N is preferably a heteroalkylene group having 2 to 10 carbon atoms, and more preferably a heteroalkylene group having 4 to 8 carbon atoms.
• amino alcohol (N) examples 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 amino alcohol (N) may be used alone or in combination of two or more kinds.
• the dicarboxylic acid (A) is a compound having two carboxyl groups, and is preferably a compound represented by the following general formula (A).
• 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.
• the alkylene group having 1 to 12 carbon atoms and the heteroalkylene group having 1 to 12 carbon atoms in the general formula (A) are the same as the alkylene group having 1 to 12 carbon atoms and the heteroalkylene group having 1 to 12 carbon atoms in the general formula (N), respectively.
• the alkylene group having 1 to 12 carbon atoms for R A is preferably an alkylene group having 2 to 12 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.
• Examples of the aryl group having 5 to 15 carbon atoms represented by R A include a phenylene group and a naphthalenylene group.
• the heteroaryl group having 5 to 15 carbon atoms for R A 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 substituted with a heteroatom (oxygen atom, nitrogen atom, sulfur atom), and examples thereof include a furan ring, an imidazole ring, and an oxazole ring.
• the aryl group having 5 to 15 carbon atoms and the heteroaryl group having 5 to 15 carbon atoms for R 1 A may be substituted on the aromatic ring or hetero ring with, for example, an alkyl group having 1 to 6 carbon atoms.
• the reaction components for the amide ester of the present invention may include an amino alcohol (N) and a dicarboxylic acid (A), and may also include other components.
• the reaction components of the amide ester of the present invention preferably comprise 90 mass % or more of the amino alcohol (N) and the dicarboxylic acid (A) based on the total amount of the reaction components, more preferably 95 mass % or more of the amino alcohol (N) and the dicarboxylic acid (A), and even more preferably comprise only the amino alcohol (N) and the dicarboxylic acid (A).
• the amide esters of the present invention preferably do not include glycols as reactants.
• the reaction of the amino alcohol (N) with the dicarboxylic acid (A) is not particularly limited and may be carried out by a known method, for example, by carrying out an amide esterification reaction in the presence of a catalyst as needed at a temperature range of 180 to 250°C for 10 to 25 hours.
• the conditions for the amide esterification reaction, such as temperature and time, are not particularly limited and may be set appropriately.
• Such catalysts 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 amide ester of the present invention preferably does not contain an amino group.
• the amide ester does not contain an amino group
• the amide ester is mixed with a biodegradable resin, dispersibility in the biodegradable resin can be ensured.
• the fact that the amide ester does not contain an amino group is confirmed by the method described in the Examples. Since amides are structurally more stable than esters and are preferentially formed during the reaction, an amide ester containing no amino group can be obtained, for example, by setting the equivalent of the carboxyl group derived from the dicarboxylic acid (A) contained in the reaction components to be greater than the equivalent of the amino group derived from the amino alcohol (N).
• the acid value of the amide ester 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 amide ester 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 amide ester is confirmed by the method described in the Examples.
• the hydroxyl value of the amide ester 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 even more preferably in the range of 30 to 120 mgKOH/g.
• the hydroxyl value of the amide ester is confirmed by the method described in the examples.
• 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 (PEST), polybutylene succinate terephthalate (PET ...
• PLA polylactic acid
• PES polyethylene succinate
• PETS polyethylene terephthalate succinate
• PBS polybutylene succinate
• PBAT polybutylene adipate terephthalate
• PEAT polyethylene adipate terephthalate
• PEST polybutylene succinate terephthalate
• PET polybutylene succinate terephthalate
• polyisoprene examples include polyisoprene 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 polyisoprene 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.
• 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 also not particularly limited, and the surface may be modified with, for example, saturated fatty acids, depending on the intended use.
• the content of the inorganic filler is, for example, in the range of 1 to 200 parts by mass per 100 parts by mass of biodegradable resin, and may also 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 composition of the present invention may further contain a plasticizer.
• the plasticizer include benzoate esters such as diethylene glycol dibenzoate; phthalate esters such as dibutyl phthalate (DBP), di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), and ditridecyl phthalate (DTDP); terephthalate esters such as bis(2-ethylhexyl) terephthalate (DOTP); isophthalate esters such as bis(2-ethylhexyl) isophthalate (DOIP); pyromellitic acid esters such as tetra-2-ethylhexyl pyromellitic acid (TOPM); di-2-ethylhexyl adipate (DOA), diisononyl a
• phosphates 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 paraffins obtained by chlorinating paraffin wax or n-paraffin; chlorinated fatty acid esters such as chlorinated stearic acid ester; and higher fatty acid esters such as butyl oleate.
• the amount of plasticizer contained is not particularly limited, but is preferably in the range of 10 to 300 parts by mass, and more preferably 20 to 200 parts by mass, per 100 parts by mass of 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 in addition to these.
• the other additives include viscosity reducers, flame retardants, stabilizers, stabilization aids, colorants, processing aids, fillers, antioxidants (antiaging agents), ultraviolet absorbers, light stabilizers, lubricants, antistatic agents, and crosslinking aids.
• 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, a flowability modifier, and, if necessary, a plasticizer and the other additives described above, using a melt-kneader 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, laminate 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, blow molding (various types of blow molding), calendar molding, solid molding (uniaxial stretch molding, biaxial stretch molding, roll rolling molding, stretch-oriented nonwoven fabric molding, thermoforming (vacuum forming, pressure forming), plastic processing, powder molding (rotational molding), various nonwoven fabric moldings (dry method, adhesive method, entanglement method, spunbond method, etc.), and the like.
• Injection molding, extrusion molding, compression molding, or heat press molding is preferably applied, and specifically, the shape is preferably a sheet, film, or 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 molded articles obtained from the biodegradable resin composition of the present invention can be accelerated by the biodegradable resin decomposition accelerator of the present invention, making them suitable for use in products with a relatively short product lifespan, such as disposable containers.
• Molded articles obtained from the biodegradable resin composition of the present invention are suitable for a wide range of uses, such as packaging materials for packaging liquids, powders, and solids, agricultural materials, and construction materials. Specific applications include injection molded products (for example, trays for fresh food, fast food containers, coffee capsule containers, cutlery, outdoor leisure products, etc.), extrusion molded products (for example, films, sheets, fishing lines, fishing nets, vegetation nets, sheets for secondary processing, water-retaining sheets, etc.), and hollow molded products (bottles, etc.).
• microbial carriers for example, microbial carriers, zooplankton breeding facilities, water treatment carriers, foams, drainage materials, downhole tool components, flak 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 denitrification efficiency, for example.
• the shape of the microbial carrier is not particularly limited, and examples include a film, a pellet, and a hollow cylinder. To increase the surface area of the carrier, it may be porous. Furthermore, the porosity of the microbial carrier containing a biodegradable resin can be kept low, and it can also be a rod-shaped carrier with a cross-sectional shape having a recess on the periphery.
• the microbial carrier according to this embodiment can be used to support various microorganisms, and the type of microorganism is not particularly limited. Examples of suitable microorganisms include denitrifying bacteria, particularly heterotrophic denitrifying bacteria.
• the carrier can reduce the oxygen concentration in the vicinity of a biofilm formed by the supported microorganisms, and is therefore preferably used to support anaerobic microorganisms, such as denitrifying bacteria that perform denitrification under anaerobic conditions.
• anaerobic microorganisms such as denitrifying bacteria that perform denitrification under anaerobic conditions.
• the microbial carrier according to this embodiment is used to support heterotrophic microorganisms, such as denitrifying bacteria, it is preferable to support biodegradable resin-degrading bacteria that have the ability to decompose biodegradable resins together with the denitrifying bacteria.
• the zooplankton rearing facility includes a culture tank that contains culture water for zooplankton and a molded article of a biodegradable resin composition.
• the culture water during culture contains both zooplankton and the biodegradable resin, thereby promoting the proliferation of the zooplankton.
• One embodiment of the zooplankton rearing equipment includes a culture tank, an aeration pipe, a blower, a liquid drain pipe, a liquid drain valve, a zooplankton food tank, and a zooplankton food supply pump.
• One embodiment of the drain material is used in the plastic board drain method, and consists, for example, of a plate-shaped core material with grooves formed on at least one side extending the entire length in the longitudinal direction, and a sheet-shaped permeable material covering at least the surface of the core material on which the grooves are formed, with the plate-shaped core material being made of a molded product of a biodegradable resin composition.
• the downhole tool component can be used as a component of a flak plug. It is particularly preferable to use it as a mandrel, load ring, socket, cone, ball, or ball seat for a flak plug.
• the downhole tool component By forming the downhole tool component from a molded article of a biodegradable resin composition, it can be machined by cutting, drilling, cutting, or other methods to form a secondary molded product of the desired shape, particularly a downhole tool component to be provided in a sealing plug.
• the biodegradable stent comprises a stent body made of a cylindrical braid of multiple filament threads formed from a molded product of a biodegradable resin composition, with elastic threads arranged along the length of the outside of the stent body.
• the elastic threads are arranged along at least a portion of the length of the stent body, including near 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 somewhere on the stent body.
• tension is applied to the elastic threads.
• the contractile force of the elastic threads acts near each end of the stent body to spread the stent body outward, allowing the ends of the stent body to be reliably expanded.
• the molded article of the present invention is biocompatible and biodegradable, and can therefore be used in medical sensors, shape-memory materials, 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 biodegradable resin decomposition accelerator added, etc. are the same as those explained in the biodegradable resin composition of the present invention.
• the decomposition-accelerating effect is obtained not only in the state of a composition containing a biodegradable resin decomposition accelerator and a biodegradable resin, but also in the state of a molded article of a biodegradable resin composition containing a biodegradable resin and a biodegradable resin decomposition accelerator.
• biodegradable resin decomposition accelerator is mixed with the biodegradable resin, the decomposition acceleration effect can be achieved, and it can be used regardless of the environment. Therefore, decomposition can be carried out both indoors and outdoors (including in 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 molecular weight were evaluated by the following methods.
• ⁇ Method for measuring acid value> Measurement was carried out according to the method of JIS K0070-1992.
• Method for measuring hydroxyl value> Measurement was carried out according to the method of JIS K0070-1992.

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• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2025
  • 2025-03-13 JP JP2025567983A patent/JPWO2025204978A1/ja active Pending
  • 2025-03-13 WO PCT/JP2025/009583 patent/WO2025204978A1/ja active Pending

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