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
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids

Definitions

• the present invention relates to copolymer polyamide resins, in particular copolymer polyamide resins made using raw materials derived from biomass.
• Polyamides are polymers formed by the assembly of structural units containing amide bonds.
• the structural units of polyamides are generally derived from aminocarboxylic acids or lactams, or diamines and dicarboxylic acids.
• aliphatic polyamide resins derived from the aliphatic chemical species of these compounds have versatile and beneficial properties as resins, such as chemical resistance, toughness, heat resistance, and oil resistance. For this reason, aliphatic polyamide resins are useful as raw materials for molded products with various applications, and are used, for example, as the base material for single-layer or laminated films for packaging films that require pinhole resistance and gas barrier properties, especially in the food packaging field, and as a structural material for multilayer films co-extruded with other resins.
• resins are produced that their properties as a resin can be controlled in various ways by selecting the monomer or using multiple types of monomers. By combining two or more types of structural units, copolymer polyamide resins are produced that give molded articles with properties suited to their intended use (Patent Document 1).
• polyamide resins give molded products with excellent properties, homopolymers made from various structural units or copolymers made from combinations of structural units are manufactured, but many of the monomers used as raw materials for polyamide resins are industrially made from fossil raw materials.
• ⁇ -caprolactam which is well known as a raw material for nylon (registered trademark)
• nylon registered trademark
• 1,5-pentanediamine which can be obtained from starch or sugar cane by enzyme reactions, yeast reactions, fermentation reactions, etc.
• a compound derived from biomass that can be used as a raw material for polyamides.
• Patent Document 2 an attempt is made to manufacture polyamide resins with fewer impurities derived from biomass raw materials using 1,5-pentanediamine as a raw material.
• Patent Documents 3 and 4 an attempt is made to manufacture polyamide resins for large molded products using 1,5-pentanediamine as a raw material, with improved heat retention stability, etc.
• the present invention aims to provide a copolymer polyamide resin that has low water absorption and excellent abrasion resistance when made into a molded product, and that uses raw materials derived from biomass, as well as a composition containing the same and molded products such as films and monofilaments.
• a polyamide resin composition comprising the copolymer polyamide resin according to any one of [1] to [8].
• a molded article comprising the copolymer polyamide resin according to any one of [1] to [8].
• a film comprising the copolymer polyamide resin according to any one of [1] to [8].
• a monofilament comprising the copolyamide resin according to any one of [1] to [8].
• the present invention provides a copolymer polyamide resin that has low water absorption and excellent abrasion resistance when molded into a molded product, and is made using raw materials derived from biomass, as well as a composition containing the same and molded products such as films and monofilaments.
• polyamide resin refers to a resin that has an acid amide bond (-CONH-) in the main chain and is obtained by polymerizing or copolymerizing lactam, aminocarboxylic acid, or nylon salt consisting of diamine and dicarboxylic acid as raw materials by a known method such as melt polymerization, solution polymerization, or solid-phase polymerization. As long as the effect of the present invention is not impaired, other components may be blended with the polyamide resin to form a polyamide resin composition.
• the copolymerized polyamide resin of the present invention comprises a structural unit A1 derived from a reaction product of equimolar amounts of pentamethylenediamine and adipic acid, represented by the following formula (A1): and a structural unit A2 derived from a reaction product of equimolar amounts of pentamethylenediamine and sebacic acid, represented by the following formula (A2): and a structural unit B derived from at least one aminocarboxylic acid selected from 10-aminodecanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, and/or at least one lactam selected from decalactam, undecalactam, and dodecalactam.
• A1 derived from a reaction product of equimolar amounts of pentamethylenediamine and adipic acid
• A2 derived from a reaction product of equimolar amounts of pentamethylenediamine and sebacic acid
• A2 derived
• the structural unit A is selected from the group consisting of structural unit A1 derived from an equimolar reaction product of pentamethylenediamine and adipic acid represented by the above formula (A1) and structural unit A2 derived from an equimolar reaction product of pentamethylenediamine and sebacic acid represented by the above formula (A2).
• structural unit A By including structural unit A, the copolymerized polyamide resin can increase the bio ratio while maintaining the low water absorption rate and high abrasion resistance of the obtained molded article.
• the structural unit A only one of structural units A1 and A2 may be used, or both may be used in combination.
• the structural unit A1 is a unit derived from an equimolar reaction product of pentamethylenediamine and adipic acid represented by the above formula (A1).
• the structural unit A1 is formed by polymerizing an equimolar salt or an equimolar mixture of pentamethylenediamine and adipic acid.
• the pentamethylenediamine and adipic acid constituting the unit may be directly condensed, or may be condensed via other units or diamines or dicarboxylic acids constituting other units.
• the copolymerized polyamide resin can increase the bio ratio while maintaining the low water absorption and high abrasion resistance of the obtained molded article.
• pentamethylenediamines examples include 1,5-pentamethylenediamine, 1,4-pentamethylenediamine, and 1,3-pentamethylenediamine, but 1,5-pentamethylenediamine is preferred from the standpoint of availability and the strength of the resulting polyamide resin. Pentamethylenediamines may be used alone or in combination of two or more types.
• Pentamethylenediamine may be derived from a fossil raw material or a biomass-derived raw material, but from the viewpoint of increasing the bio ratio of the copolyamide resin, it is preferable that it is a biomass-derived raw material.
• biomass-derived pentamethylenediamine include those obtained by the production methods disclosed in International Publication No. 2015/076233, JP 2006-348057 A, JP 2007-332353 A, JP 2002-223771 A, JP 2004-000114 A, JP 2004-208646 A, JP 2004-290091 A, JP 2004-298034 A, JP 2002-223770 A, JP 2004-222569 A, JP 2005-6650 A, JP 2019-154313 A, and JP 2019-205423 A.
• 1,5-pentamethylenediamine can be produced by decarboxylating lysine through an enzymatic reaction.
• 1,5-pentamethylenediamine can be produced from lysine using lysine decarboxylase, cells that produce lysine decarboxylase, processed products of the cells, microorganisms that express lysine decarboxylase, etc.
• the enzymatic decarboxylation of lysine can also be carried out while adding an acid such as adipic acid to the lysine solution so that the pH is maintained at a level suitable for the enzymatic decarboxylation.
• Adipic acid may be derived from fossil raw materials or from biomass. From the viewpoint of availability, it is preferable that the adipic acid be derived from fossil raw materials.
• the structural unit A2 is a unit derived from an equimolar reaction product of pentamethylenediamine and sebacic acid, as shown in the above formula (A2).
• the structural unit A2 is formed by polymerizing an equimolar salt or an equimolar mixture of pentamethylenediamine and sebacic acid.
• the pentamethylenediamine and sebacic acid constituting the unit may be directly condensed, or may be condensed via another unit or a diamine or dicarboxylic acid constituting another unit.
• the copolymerized polyamide resin can increase the bio ratio while maintaining the low water absorption and high abrasion resistance of the obtained molded article.
• pentamethylenediamine those exemplified in structural unit A1 can be used.
• the preferred embodiment of pentamethylenediamine and its production method are also as described in structural unit A1.
• Sebacic acid may be derived from a fossil raw material or a biomass-derived raw material, but is preferably derived from biomass from the viewpoint of increasing the bio ratio of the copolyamide resin.
• Biomass-derived sebacic acid can be synthesized, for example, from ricinoleic acid triglyceride, the main component of castor oil obtained from castor bean seeds.
• the structural unit B is a unit derived from at least one aminocarboxylic acid selected from 10-aminodecanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, and/or at least one lactam selected from decalactam, undecalactam, and dodecalactam.
• aminocarboxylic acids and lactams may be derived from fossil raw materials or biomass-derived raw materials, but from the viewpoint of easy availability, they are preferably derived from fossil raw materials.
• structural unit B is a unit derived from 12-aminododecanoic acid and/or dodecalactam.
• the mass ratio of structural unit A/structural unit B in the copolymerized polyamide resin is preferably 97/3 to 7/93, more preferably 95/5 to 9/91, even more preferably 93/7 to 10/90, and particularly preferably 90/10 to 20/80. By setting it in this range, handling during molding is good, and the molded product maintains low water absorption and has high abrasion resistance.
• the mass ratio of structural unit A1/structural unit B in the copolymerized polyamide resin is preferably 95/5 to 9/91, more preferably 93/7 to 10/90, and particularly preferably 90/10 to 20/80. By setting it in this range, handling during molding is good, and the molded product maintains low water absorption and has high abrasion resistance.
• the mass ratio of structural unit A2/structural unit B in the copolymerized polyamide resin is preferably 97/3 to 7/93, more preferably 95/5 to 9/91, even more preferably 93/7 to 10/90, and particularly preferably 90/10 to 20/80.
• the total amount of structural unit A and structural unit B is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass, relative to 100% by mass of the copolymerized polyamide resin. In one embodiment, the total amount of structural unit A and structural unit B is 100% by mass relative to 100% by mass of the copolymerized polyamide resin.
• the copolymerized polyamide resin may contain a structural unit other than the structural unit A and the structural unit B, so long as the properties of the copolymerized polyamide resin are not impaired.
• structural units include a structural unit derived from an equimolar reaction product of pentamethylenediamine with a dicarboxylic acid other than adipic acid and sebacic acid; a structural unit derived from an equimolar reaction product of a diamine other than pentamethylenediamine with adipic acid or sebacic acid; a structural unit derived from an equimolar reaction product of a diamine other than pentamethylenediamine with a dicarboxylic acid other than adipic acid and sebacic acid; a structural unit derived from an aminocarboxylic acid and/or lactam other than the aminocarboxylic acid and lactam constituting the structural unit B; and the like.
• Diamines other than pentamethylenediamine include, for example, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,8-octanediamine, 2,2,4/2,4,4-trimethylhexamethylenediamine, and other fatty acids.
• Aliphatic diamines such as 1,3-/1,4-cyclohexyldiamine, bis(4-aminocyclohexyl)methane, bis(4-aminocyclohexyl)propane, bis(3-methyl-4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)propane, 1,3-/1,4-bisaminomethylcyclohexane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, bis(aminopropyl)piperazine, bis(aminoethyl)piperazine, and norbornanedimethylenediamine; and the like.
• 1,3-/1,4-cyclohexyldiamine bis(4-aminocyclohexyl)methane, bis(4-aminocyclohexy
• Dicarboxylic acids other than adipic acid and sebacic acid include, for example, aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, and eicosanedioic acid; alicyclic dicarboxylic acids such as 1,3-/1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4'-dicarboxylic acid, and norbornanedicarboxylic
• aminocarboxylic acids other than the aminocarboxylic acids that make up structural unit B include 6-aminocaproic acid, 7-aminoheptanoic acid, and 9-aminononanoic acid.
• lactams other than the lactams that make up structural unit B include ⁇ -caprolactam, enantholactam, ⁇ -pyrrolidone, and ⁇ -piperidone.
• the amount of each structural unit of the copolymer polyamide resin corresponds to the amount of each component charged during the production of the copolymer polyamide resin, but the amount can also be determined by measuring the obtained copolymer polyamide resin as is or after hydrolysis using high performance liquid chromatography, gas chromatography, gas chromatograph/atomic emission detector (GC/AED), gel permeation chromatography, etc.
• the amount of each structural unit of the copolymer polyamide resin described in this specification and claims is calculated from the charge ratio (mass ratio) of the raw materials, assuming that all the raw materials for the copolymer polyamide resin have reacted.
• the melting point of the copolymer polyamide resin measured by differential scanning calorimetry is preferably 100 to 250° C., and more preferably 125 to 240° C.
• the melting point of the copolymer polyamide resin measured by DSC can be increased or decreased depending on the ratio of the constituent units, the molecular weight of the copolymer polyamide resin, etc.
• the structural unit A is the structural unit A1
• the melting point of the copolymerized polyamide resin measured by differential scanning calorimetry (DSC measurement) is preferably 130 to 250° C.
• the melting point of the copolymerized polyamide resin can also be 125 to 240° C.
• the melting point of the copolymerized polyamide resin measured by differential scanning calorimetry is preferably from 100 to 250°C, and more preferably from 125 to 240°C.
• the heat of fusion (enthalpy change accompanying melting) ⁇ H corresponding to the melting point is preferably 50 J/g or less, more preferably 2 to 50 J/g, and particularly preferably 5 to 50 J/g.
• the melting point measured by DSC is the top temperature of the endothermic peak in the DSC curve during the second heating process when a copolymer polyamide resin is heated to 300°C at a rate of 10°C/min in a nitrogen gas atmosphere, held at that temperature for 1 minute, cooled to 30°C at a rate of 10°C/min, and then heated again to 300°C at a rate of 10°C/min.
• the heat of fusion corresponding to the melting point is calculated from the endothermic peak in the DSC curve during the second heating process.
• the crystallization temperature of the copolymer polyamide resin measured by differential scanning calorimetry is preferably 110 to 200° C.
• the crystallization temperature of the copolymer polyamide resin measured by DSC measurement can be increased or decreased depending on the ratio of the structural units, the molecular weight of the copolymer polyamide resin, etc.
• the crystallization temperature measured by DSC is the top temperature of the exothermic peak in the DSC curve during the temperature drop process when a copolymer polyamide resin is heated to 300°C at a rate of 10°C/min in a nitrogen gas atmosphere, held at that temperature for 1 minute, and then cooled to 30°C at a rate of 10°C/min.
• the copolyamide resin is preferably a random copolymer from the viewpoint of obtaining a preferable melting point and crystallization temperature.
• a random copolymer is a copolymer in which the structural units A and B are randomly arranged.
• a copolymerized polyamide resin obtained by mixing and polymerizing each unit in the monomer state is usually a random copolymer.
• a copolymerized polyamide resin obtained by mixing polyamide resin A obtained by polymerizing a monomer that is the raw material of structural unit A and polyamide resin B obtained by polymerizing a monomer that is the raw material of structural unit B, and further polymerizing the mixture is usually not a random copolymer but a block copolymer.
• a block copolymer is a copolymer obtained by polymerizing a block in which a certain number of structural units A or structural units B are arranged continuously.
• the random copolymer can also be confirmed by examining the bonding probability of each structural unit from a 13 C-NMR spectrum using a nuclear magnetic resonance apparatus.
• the biomass degree of the copolymer polyamide resin measured in accordance with ASTM D6866 is preferably 3% or more, more preferably 10% or more, and even more preferably 20% or more.
• the biomass degree can be determined by measuring the radioactive carbon ( 14 C) content contained in the copolymer polyamide resin. Specifically, if all the carbon in the copolymer polyamide resin is derived from fossil raw materials, the biomass degree is 0%, and if all the carbon is derived from biomass, the biomass degree is 100%.
• the proportion of biomass raw material in the copolymer polyamide resin is preferably 3% or more, more preferably 10% or more, and even more preferably 20% or more.
• the proportion of the biomass raw material is the proportion of the amount (mass) of raw material derived from biomass in the total amount of raw material charged, 100% by mass, assuming that all raw materials of the copolymer polyamide resin have reacted.
• the upper limit of the proportion of the biomass raw material is 100%.
• the upper limit of the proportion of the biomass raw material can be, for example, 45% or less.
• the upper limit of the proportion of the biomass raw material can be, for example, 95% or less.
• the ratio of the biomass raw material is the ratio of the amount of the 1,5-pentamethylenediamine and sebacic acid charged to the total amount of the raw materials charged (100 mass %).
• the copolymer polyamide resin can be produced by known polymerization methods such as melt polymerization, solution polymerization, interfacial polymerization, solid-phase polymerization, and combinations thereof. Usually, melt polymerization carried out at a temperature higher than the melting point of the copolymer polyamide resin to be obtained is preferably used.
• the copolymer polyamide resin can be produced by known polymerization equipment, and can be produced by appropriately combining operations such as normal pressure, reduced pressure, and increased pressure, as necessary, by a batch or continuous method. For example, the monomer that is the raw material of the structural unit A and the monomer that is the raw material of the structural unit B can be introduced at once.
• copolymer polyamide resins have a high viscosity
• in some cases in order to avoid difficulties in extracting the resin during polymerization, it is possible, for example, to synthesize a copolymer polyamide resin with a low viscosity by melt polymerization, and then to obtain a copolymer polyamide resin with an increased viscosity by solid-phase polymerization.
• Copolymer polyamide resins can increase the bio-ratio, which can contribute to the achievement of Goal 12 of the SDGs (Sustainable Development Goals), and when molded into articles, they have low water absorption and excellent abrasion resistance.
• Copolymer polyamide resins can be used in polyamide resin compositions and molded articles such as films and monofilaments.
• One aspect of the present invention is a polyamide resin composition containing a copolymer polyamide resin.
• the polyamide resin composition may contain components other than the copolymer polyamide resin as long as the effects of the present invention are not impaired.
• other components include polyamide resins other than copolymerized polyamide resins, any resin other than polyamide resins, for example, modified or unmodified polyolefin resins, and functionality-imparting agents such as plasticizers, heat resistance agents, foaming agents, antioxidants, ultraviolet absorbers, weather resistance agents, crystal nucleating agents, crystallization accelerators, release agents, lubricants, antistatic agents, antifogging agents, flame retardants, flame retardant assistants, pigments, dyes, etc.
• Polyamide resin compositions containing these other components can be made into the form of molded products such as pellets, films, monofilaments, etc.
• the method for producing the polyamide resin composition is not particularly limited, and for example, the composition can be produced by mixing the copolymer polyamide resin with other components using a known melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, or a mixing roll.
• a known melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, or a mixing roll.
• One aspect of the present invention is a molded article comprising a copolymerized polyamide resin or a polyamide resin composition.
• the method for producing the molded article is not particularly limited, and examples thereof include injection molding, press molding, blow molding, extrusion molding, and rotational molding.
• Molded articles containing copolymerized polyamide resins or polyamide resin compositions take advantage of their excellent properties and are used in a variety of applications, including films and monofilaments, as well as electronic components, electrical components, household products, office supplies, automobile and vehicle-related parts, building materials, and sporting goods.
• Preferred applications for electronic components include, for example, connectors, coils, sensors, LED lamps, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable capacitor cases, optical pickup chassis, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystal, FDD carriages, FDD chassis, motor brush holders, transformer components, parabolic antennas, and computer-related parts.
• Examples of electrical component applications include generators, electric motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, circuit breakers, knife switches, other-pole rods, electrical components, motor cases, notebook computer housings and internal parts, CRT display housings and internal parts, printer housings and internal parts; mobile terminal housings and internal parts such as mobile phones, mobile personal computers, and handheld mobile devices; various gears, various cases, cabinets, etc.
• Preferred uses for household goods and office goods include, for example, VTR parts, television parts, irons, hair dryers, rice cooker parts, microwave oven parts; audio parts, audio/visual equipment parts such as laser discs (registered trademark), compact discs, and DVDs; lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, electronic device housings for personal computers and notebook computers, office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, lighters, typewriters, microscopes, binoculars, cameras, and clocks.
• VTR parts television parts, irons, hair dryers, rice cooker parts, microwave oven parts
• audio parts audio/visual equipment parts such as laser discs (registered trademark), compact discs, and DVDs
• lighting parts refrigerator parts, air conditioner parts, typewriter parts, word processor parts
• electronic device housings for personal computers and notebook computers
• office computer-related parts telephone-related parts, facsimile-related parts, copier-related parts, cleaning
• Automobile and vehicle-related part applications include, for example, alternator terminals, alternator connectors, IC regulators, potentiometer bases for light dimmers, various valves such as exhaust gas valves, various pipes, hoses and tubes for fuel-related, cooling, brake, wiper, exhaust and intake systems, air intake nozzle snorkels, intake manifolds, fuel pumps, engine coolant joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, coolant sensors, oil temperature sensors, brake pad wear sensors, throttle position sensors, crankshaft position sensors, air flow meters, brake pad wear sensors, battery peripherals, thermostat bases for air conditioners, heating hot air flow control valves, brush holders for radiator motors, water pump impellers, turbine vanes, wiper motor-related parts, distributors, starter switches, starter relays, transmission wire harnesses, transmission oil pans, windshield washer nozzles, air conditioners, etc.
• various valves such as exhaust gas valves, various pipes, hoses and tubes for fuel-related, cooling, brake, wiper, exhaust
• Preferred uses include for engine panel switch boards, coils for fuel-related electromagnetic valves; various connectors such as wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors, and fuse connectors; horn terminals, insulating plates for electrical components, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil pans, engine oil filters, ignition device cases, torque control levers, safety belt parts, register blades, washer levers, window regulator handles, window regulator handle knobs, passing light levers, sun visor brackets, instrument panels, airbag peripheral parts, door pads, pillars, console boxes, various motor housings, roof rails, fenders, garnishes, roof panels, hood panels, trunk lids, door mirror stays, spoilers, hood louvers, wheel covers, wheel caps, grill apron cover frames, lamp bezels, door handles, door moldings, rear finishers, and wipers.
• various connectors such as wire harness connectors, SMJ
• the material is preferably used for wall, roof, and ceiling-related parts of civil engineering buildings; window-related parts, heat-insulating parts, flooring-related parts, seismic isolation and vibration-damping parts, and lifeline-related parts.
• applications for sporting goods include golf-related goods such as golf clubs and shafts; personal protective equipment for sports such as masks, helmets, bibs, elbow pads, and knee pads for American football, baseball, softball, etc.; shoe-related goods such as soles for sports shoes; fishing equipment-related goods such as fishing rods and fishing lines; summer sports-related goods for surfing, etc.; winter sports-related goods such as skiing and snowboarding; and other indoor and outdoor sports-related goods.
• the film may be a single-layer film consisting of only a copolymerized polyamide resin layer, or a laminated film of two or more layers including a copolymerized polyamide resin layer and another layer.
• the other layer include a layer containing a resin other than the copolymerized polyamide resin, such as a thermoplastic resin, a thermosetting resin, or a layer made of a metal such as aluminum.
• resins other than copolymer polyamide resins include ethylene-based resins such as low-density polyethylene, linear low-density polyethylene, ionomers, ethylene-vinyl alcohol copolymers (EVOH), ethylene-acrylic acid copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid ester copolymers, and ethylene-methacrylic acid copolymers; polyolefins such as polypropylene, modified polyolefins, polyesters, polyvinyl alcohols, polyamides other than copolymer polyamide resins, polyamide elastomers; and biomass plastics such as polylactic acid (PLA) and polyhydroxyl alkanoates (PHA).
• PHA polylactic acid
• PHA polyhydroxyl alkanoates
• the thickness of the film can be appropriately selected depending on the application.
• the thickness is preferably 5 to 200 ⁇ m, more preferably 10 to 50 ⁇ m.
• the total thickness is preferably 10 to 1000 ⁇ m, more preferably 20 to 500 ⁇ m; the thickness of the layer containing the copolymerized polyamide resin or polyamide resin composition is preferably 5 to 100 ⁇ m, more preferably 10 to 50 ⁇ m.
• the film may be an unstretched film, or a stretched film obtained by stretching the unstretched film.
• the stretching method is not particularly limited, and examples include uniaxial stretching using a heated roll, simultaneous biaxial stretching using a tubular method, and sequential biaxial stretching using a heated roll or tenter.
• the method for producing the film is not particularly limited, and for example, a known production method can be applied.
• a copolymer polyamide resin or a polyamide resin composition can be melt-kneaded using an extruder, and a monolayer film can be produced by a molding method such as a T-die molding method, an air-cooled inflation molding method, a water-cooled inflation molding method, or a triple bubble molding method.
• the laminated film may be directly laminated by coextrusion, lamination, etc., or may be laminated via an adhesive or adhesive resin layer. Coextrusion is preferred because of its excellent productivity.
• the laminate film is produced by a coextrusion method, for example, a coextrusion T-die molding method in which a copolymerized polyamide resin or a composition thereof, a thermoplastic resin or a composition thereof, etc. are melted in separate extruders and continuously extruded through a T-die and cooled with a casting roll to form a film; a coextrusion air-cooled inflation molding method in which the resins are continuously extruded through a ring die and cooled with air; or a coextrusion water-cooled inflation molding method in which the resins are continuously extruded through a ring die and cooled by contacting with water, etc., are used to produce a substantially unoriented unstretched film.
• a coextrusion T-die molding method in which a copolymerized polyamide resin or a composition thereof, a thermoplastic resin or a composition thereof, etc. are melted in separate extruders and continuously extruded through a T-die and cooled
• air-cooled inflation molding and water-cooled inflation molding require simple equipment and are easy to work with since the film width can be easily changed simply by adjusting the blow-up ratio, allowing film to be produced with good productivity.
• Copolymer polyamide resins can suppress film curling when used in air-cooled or water-cooled inflation molding or co-extrusion air-cooled or water-cooled inflation molding.
• thermal deterioration and curling of the film can be suppressed, which is preferable.
• the conditions for forming the inflation film are not particularly limited, but the resin temperature is preferably from the melting point of the raw resin to less than 300°C. In the present invention, the resin temperature can be, for example, 160°C to 250°C, preferably 160°C to 220°C.
• the blow-up ratio (also called the blow ratio) refers to the ratio of the maximum bubble diameter to the die diameter. The blow-up ratio is preferably 1.1 to 3.0, and more preferably 1.2 to 2.5.
• the take-up speed is determined by the thickness and width of the film and the extrusion amount, and can be adjusted within a range that maintains film formation stability, but is generally preferably 1 to 150 m/min, and more preferably 5 to 100 m/min.
• the film can be subjected to surface treatments such as corona discharge treatment, plasma treatment, flame treatment, acid treatment, etc., to improve printability, lamination, or adhesive application. Furthermore, after such treatments have been performed as necessary, the film can be used for the intended purpose through secondary processing steps such as printing, lamination, adhesive application, and heat sealing.
• surface treatments such as corona discharge treatment, plasma treatment, flame treatment, acid treatment, etc.
• the film has low water absorption and excellent abrasion resistance, so it can be used as a food packaging film.
• the film is also suitable for inflation molding.
• the film can be used for various applications such as electronic parts, electrical parts, household goods, office supplies, automobile and vehicle related parts, building materials, and sporting goods, which are exemplified as applications of molded products.
• a monofilament comprising a copolymerized polyamide resin or a polyamide resin composition.
• the diameter of the monofilament is not particularly limited, but is preferably 0.5 to 20 mm, more preferably 1 to 5 mm.
• the monofilament may be a continuous fiber or a staple fiber.
• the monofilament can be obtained by a known manufacturing method using a copolymerized polyamide resin or a polyamide resin composition.
• a method of manufacturing the monofilament includes melting polyamide resin pellets using an extruder or the like, extruding them from a spinning nozzle, and cooling them in a refrigerant bath such as water or trichloroethylene to produce an undrawn yarn.
• the distance between the filament outlet of the spinning nozzle and the refrigerant liquid level is preferably kept at about 10 to 300 mm.
• the undrawn yarn may be further drawn and heat-set.
• the drawing is preferably performed in two stages, that is, two-stage drawing.
• the undrawn yarn is preferably drawn in steam or hot water 2 to 5 times, more preferably 3 to 4 times. If the draw ratio is within this range, the knot strength tends to be further improved.
• a temperature range of 95 to 120°C is preferred, with a temperature range of 100 to 110°C being more preferred.
• the temperature of the water vapor is within this range, the knot strength and transparency of the resulting monofilament tend to be improved.
• the temperature of the hot water is preferably 50 to 95°C, and more preferably 60 to 90°C.
• the temperature of the hot water is within this range, the knot strength and transparency of the resulting monofilament tend to be improved.
• the second stage drawing is preferably performed in a gas atmosphere by drawing 1.1 to 2.5 times, and more preferably by drawing 1.2 to 2.5 times.
• the gas is not particularly limited, and examples include inert gases such as helium, nitrogen, and argon, and air.
• the temperature of the gas atmosphere in the second stage drawing is preferably 100 to 300°C, more preferably 120 to 300°C, even more preferably 150 to 250°C, and particularly preferably 180 to 250°C. When the temperature range and draw ratio for the second stage drawing are within the above range, the knot strength and transparency of the resulting monofilament tend to be further improved.
• the two-stage drawn monofilament is preferably heat-set.
• the two-stage drawn monofilament can be heat-set in a gas atmosphere of preferably 120 to 350°C, more preferably 160 to 350°C, and even more preferably 160 to 320°C, while being subjected to a 0 to 10% relaxation treatment.
• the temperature of the gas atmosphere during heat setting can also be 150 to 320°C. When the temperature is within this range, the knot strength tends to be further improved.
• the total stretching ratio is preferably in the range of 4.0 to 7.0 times, more preferably 4.5 to 6.5 times, and even more preferably 5.5 to 6.0 times.
• the monofilament Since the monofilament has low water absorption and excellent abrasion resistance, it can be used as filaments, multifilaments, nets, and other structures for applications such as fishing, industrial use, clothing, and medical care, etc. Furthermore, the monofilament can be used for various applications such as electronic parts, electrical parts, household goods, office supplies, automobile and vehicle-related parts, building materials, and sporting goods, which are exemplified as applications of molded products.
• the ratio of each structural unit and biomass raw material in the polyamide resin of the examples and comparative examples was calculated from the raw material charge amount, assuming that all the raw materials of the polyamide resin had reacted.
• the ratio of the biomass raw material is the ratio of the charge amount (mass) of the raw material derived from biomass in the total charge amount of raw materials 100 mass %, assuming that all the raw materials of the polyamide resin had reacted.
• Abrasion volume Using the polyamide resin pieces or pellets of the examples and comparative examples, a heat press machine manufactured by Shinto Metal Industries Co., Ltd. was used to preheat at a temperature of melting point + 30°C for 3 minutes, heat press at 5 MPa for 1 minute, and then cold press at 30°C and 5 MPa for 3 minutes to produce two unstretched polyamide sheets of 45 mm x 45 mm x 1 mm, which were vacuum dried at 80°C for 48 hours and sealed in an aluminum bag. One of the two sheets was used as a sample for the abrasion test, and the other was used as a sample for measuring the amount of water absorption to correct the amount of water absorption of the sample (dried sheet) during the abrasion test.
• the aluminum bag was opened, and the mass of the two samples was measured.
• Abrasive paper G (garnet)-50 cut to a length of 157 mm and a width of 12 mm was attached to the abrasion wheel of a reciprocating motion flat abrasion tester manufactured by Suga Test Instruments Co., Ltd., and the abrasion test of the sample for the abrasion test was carried out under the conditions of a load of 3000 g, a stroke of 30 mm, and 120 reciprocations.
• the resin powder on the sample generated by abrasion was brushed off, and then the mass of the sample was measured. At almost the same time, the mass of the sample for measuring the amount of water absorption was measured.
• the mass difference before and after the abrasion test of the sample for the abrasion test plus the mass increment (apparent amount of water absorption) of the sample for measuring the amount of water absorption was taken as the amount of abrasion.
• the amount of wear was less than 11.5 mg, it was determined that the wear resistance was excellent.
• the tensile modulus of the sample for tensile testing was measured in accordance with ISO 527-1 and 2 under the conditions of an atmosphere of 23 ° C and 50% RH, a chuck distance of 50 mm, and a crosshead speed of 300 mm / min. If the tensile modulus was 500 to 1,000 MPa, it was determined that the balance between strength and flexibility was excellent.
• Nylon salt Equimolar salt of 1,6-hexamethylenediamine and adipic acid (nylon 66 salt): manufactured by Asahi Kasei Corporation (derived from fossil raw materials, 48% by weight aqueous solution)
• Diamine 1,5-pentamethylenediamine manufactured by CJ Research (derived from biomass, purity: 99.90% by mass)
• 1,6-Hexamethylenediamine manufactured by Tokyo Chemical Industry Co., Ltd.
• Dicarboxylic acid adipic acid manufactured by Asahi Kasei Corporation (derived from fossil raw materials, purity: 99.8% by mass)
• Sebacic acid manufactured by Casda Biomaterials (derived from biomass, purity: 99.5% by mass)
• Aminocarboxylic acid 12-aminododecanoic acid manufactured by UBE Corporation (derived from fossil raw materials, purity: 99.7% by mass)
• 6-Aminocaproic acid Fujifilm Wako Pure Chemical Industries, Ltd. (derived from fossil raw materials, purity: 97.0% by mass)
• Organic solvent 2-propanol manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. (purity: 99.7% by mass)
• Ethanol Fujifilm Wako Pure Chemical Industries, Ltd. (purity: 99.5% by mass)
• Example A Synthesis of Nylon 56 Salt 32.42 kg of adipic acid and 273 kg of 2-propanol were placed in a 700 L reaction vessel, and the adipic acid was dissolved by heating to 40°C. Then, 22.67 kg of 1,5-pentamethylenediamine was slowly added over 71 minutes. Heat of neutralization and heat of crystallization were generated, but the solution temperature was adjusted to be within the range of 40°C to 50°C during the addition. After the addition of 1,5-pentamethylenediamine was completed, the solution was stirred for 30 minutes while maintaining the temperature at 35°C to 40°C, and then the solution was cooled and stirred for 2 hours while maintaining the temperature at 0°C to 5°C. The precipitated nylon 56 salt was obtained as a filter cake, and then dried under reduced pressure at 60°C for 48 hours to obtain 54.8 kg of nylon 56 salt.
• Example A1 A 1L polymerization tank was charged with 237.5 g of nylon 56 salt, 12.5 g of 12-aminododecanoic acid, and 50.0 g of degassed ion-exchanged water, and the inside of the polymerization tank was replaced with nitrogen, then sealed and heated to 200 ° C., and then the inside of the polymerization tank was adjusted to 1.3 MPa with stirring and polymerized for 3 hours. The pressure in the polymerization tank was released to atmospheric pressure over 40 minutes while raising the temperature to 280 ° C. After releasing the pressure, polymerization was performed for 2 hours under a nitrogen stream of 200 mL / min, and then nitrogen was introduced to pressurize to 1.0 MPa.
• Example A1 shows the raw material charge amount, composition ratio in the polymer, and physical property value of the copolymerized polyamide resin of Example A1. Furthermore, the randomness of the copolyamide resin of Example A1 was confirmed by 13 C-NMR spectrum, and it was found to be a random copolymer.
• Examples A2 to A4 Copolyamide resins of Examples A2 to A4 were obtained in the same manner as in Example A1, except that the amounts of nylon 56 salt and 12-aminododecanoic acid used as raw materials were changed as shown in Table 1.
• Example A5 A 1L polymerization tank was charged with 150.0 g of nylon 56 salt, 100.0 g of 12-aminododecanoic acid, and 50.0 g of degassed ion-exchanged water, and the inside of the polymerization tank was replaced with nitrogen, then sealed and heated to 200 ° C., and then the inside of the polymerization tank was adjusted to 1.3 MPa with stirring and polymerized for 3 hours. The pressure in the polymerization tank was released to atmospheric pressure over 40 minutes while raising the temperature to 250 ° C. After releasing the pressure, polymerization was performed for 2 hours under a nitrogen stream of 200 mL / min, and then nitrogen was introduced to pressurize to 1.0 MPa.
• Example A5 After pressurization, the mixture was extracted as strands and pelletized. The polyamide pellets were dried under reduced pressure at 90 ° C. for 48 hours to obtain a copolymerized polyamide resin of Example A5.
• Table 1 shows the raw material charge amount, composition ratio in the polymer, and physical property value of the copolymerized polyamide resin of Example A5. Furthermore, when the randomness of the copolyamide resin of Example A5 was confirmed by 13 C-NMR spectrum, it was found to be a random copolymer.
• Examples A6 to A10 Copolyamide resins of Examples A6 to A10 were obtained in the same manner as in Example A5, except that the amounts of nylon 56 salt and 12-aminododecanoic acid used as raw materials were changed as shown in Table 1.
• Comparative Example A1 205.0 g of 6-aminocaproic acid and 93.75 g of a nylon 66 salt aqueous solution (48% by mass aqueous solution) were charged into a 1 L polymerization tank, and polymerization was carried out in the same manner as in Example A5, followed by pelletization to obtain a copolymerized polyamide resin of Comparative Example A1.
• the amounts of raw materials charged, the composition ratios in the polymer, and the physical properties of the copolymerized polyamide resin of Comparative Example A1 are shown in Table 1.
• Comparative Example A2 A 1-L polymerization vessel was charged with 100.0 g of 6-aminocaproic acid, 150.0 g of nylon 56 salt, and 50.0 g of degassed ion-exchanged water, and polymerization was carried out in the same manner as in Example A5, followed by pelletization to obtain a copolymerized polyamide resin of Comparative Example A2.
• the amounts of raw materials charged, the composition ratios in the polymer, and the physical properties of the copolymerized polyamide resin of Comparative Example A2 are shown in Table 1.
• Comparative Example A3 A 1 L polymerization tank was charged with 250.0 g of nylon 56 salt and 50.0 g of degassed ion-exchanged water, and polymerization was carried out in the same manner as in Example A1, followed by pelletization to obtain a homopolyamide resin of Comparative Example A3. The amounts of raw materials charged, the composition ratios in the polymer, and the physical properties of the homopolyamide resin of Comparative Example A3 are shown in Table 1.
• Comparative Example A4 A 1 L polymerization tank was charged with 250.0 g of 12-aminododecanoic acid and 50.0 g of degassed ion-exchanged water, and polymerization was carried out in the same manner as in Example A5, followed by pelletization to obtain a homopolyamide resin of Comparative Example A4. The amounts of raw materials charged, the composition ratio in the polymer, and the physical properties of the homopolyamide resin of Comparative Example A4 are shown in Table 1.
• Comparative Example A5 60 parts by mass of the homopolyamide resin of Comparative Example A3 and 40 parts by mass of the homopolyamide resin of Comparative Example A4 were mixed to obtain a pellet mixture of Comparative Example A5.
• the composition ratio and physical properties of the polymer of Comparative Example A5 are shown in Table 1. Since Comparative Example A5 is a pellet mixture, the column of the amount of raw materials charged in Table 1 is not filled in.
• Table 1 shows the composition ratio of each structural unit in the polymer of Examples A1 to A10 and Comparative Examples A1 to A5 (calculated on a mass basis from the amount of raw material charged), the DSC measurement data of the obtained copolyamide resin, and the proportion of biomass raw material.
• n.d. indicates that no crystallization temperature peak was detected.
• Example A2 which contains the structural unit A1 derived from an equimolar reaction product of pentamethylenediamine and adipic acid and the structural unit B derived from 12-aminododecanoic acid, has a lower equilibrium water absorption rate than Comparative Examples A1 and A3.
• Examples A5 and A8 have a lower equilibrium water absorption rate than Comparative Examples A2 and A5.
• Examples A2, A5 and A8 all have a wear amount of less than 11.5 mg, and are superior in wear resistance to Comparative Examples A1 to A5.
• Example A5 shows that the copolymerized polyamide resin of Example A5 containing structural units A1 and structural unit B has significantly superior equilibrium water absorption and abrasion resistance compared to Comparative Example A5 in which a homopolyamide resin consisting of structural unit A1 and a homopolyamide resin consisting of structural unit B were mixed to have a similar composition.
• Table 4 shows the data on equilibrium water absorption, wear volume and Charpy impact strength for the copolymer polyamide resins of Example A5 and Comparative Example A1.
• Example A5 which contains structural unit A1 derived from the equimolar reaction product of pentamethylenediamine and adipic acid and structural unit B derived from 12-aminododecanoic acid, has a lower water absorption rate, excellent abrasion resistance and impact strength, and a higher bio ratio than Comparative Example A1.
• Example B Synthesis of Nylon 510 Salt 24.27 kg of sebacic acid and 184 kg of 2-propanol were placed in a 700 L reaction vessel and heated to 40°C to dissolve the sebacic acid, and then 12.27 kg of 1,5-pentamethylenediamine was slowly added over 65 minutes. Heat of neutralization and heat of crystallization were generated, but the solution temperature was adjusted to be within the range of 40°C to 50°C during the addition. After the addition of 1,5-pentamethylenediamine was completed, the solution was stirred for 30 minutes while maintaining the temperature at 35°C to 40°C, and then the solution was cooled and stirred for 2 hours while maintaining the temperature at 0°C to 5°C. The precipitated nylon 510 salt was obtained as a filter cake and then dried under reduced pressure at 60°C for 48 hours to obtain 36.3 kg of nylon 510 salt.
• Nylon 66 Salt 250.0 g of adipic acid and 1900 ml of ethanol were placed in a 3 L separable flask and heated to 40°C to dissolve the adipic acid. 198.8 g of 1,6-hexamethylenediamine and 200 ml of ethanol were placed in a 500 mL beaker and stirred to obtain a homogeneous solution. The 1,6-hexamethylenediamine solution in the beaker was slowly added to the adipic acid solution in the separable flask over 90 minutes. Heat of neutralization and heat of crystallization were generated, but the solution temperature was adjusted to be within the range of 40°C to 50°C during the addition.
• nylon 66 salt was obtained as a filter cake, and then dried under reduced pressure at 60°C for 15 hours to obtain 442.3 g of nylon 66 salt.
• Example B1 A 50cc autoclave was charged with 6.65g of nylon 510 salt, 0.35g of 12-aminododecanoic acid, and 1.4g of degassed ion-exchanged water, and the inside of the autoclave was replaced with nitrogen, then sealed and immersed in an oil bath at 200°C, and pressure-polymerized for 200 minutes without stirring at a pressure of 0.5 MPa to obtain a prepolymer. The obtained prepolymer was transferred to a glass test tube, and the glass test tube was immersed in an oil bath at a temperature of 250°C and polymerized for 190 minutes under a nitrogen stream of 50mL/min with stirring to obtain a polyamide resin.
• the obtained resin was chopped into 3-5mm squares and dried under reduced pressure at 90°C for 48 hours to obtain pieces of the copolymerized polyamide resin of Example B1.
• Table 5 shows the raw material charge amount, composition ratio in the polymer, and physical property value of the copolymerized polyamide resin of Example B1. Furthermore, the randomness of the copolyamide resin of Example B1 was confirmed by 13 C-NMR spectrum, and it was found to be a random copolymer.
• Example B2 A 1L polymerization tank was charged with 225.0 g of nylon 510 salt, 25.0 g of 12-aminododecanoic acid, and 50.0 g of degassed ion-exchanged water, and the inside of the polymerization tank was replaced with nitrogen, then sealed and heated to 200 ° C., and then the inside of the polymerization tank was adjusted to 1.3 MPa while stirring, and polymerization was carried out for 3 hours. The pressure in the polymerization tank was released to atmospheric pressure over 40 minutes while raising the temperature to 250 ° C. After releasing the pressure, polymerization was carried out for 100 minutes under a nitrogen stream of 200 mL / min, and then nitrogen was introduced to pressurize to 1.0 MPa.
• Example B2 After pressurization, the mixture was extracted as strands and pelletized. The polyamide pellets were dried under reduced pressure at 90 ° C. for 48 hours to obtain a copolymerized polyamide resin of Example B2.
• Table 5 shows the raw material charge amount, composition ratio in the polymer, and physical property value of the copolymerized polyamide resin of Example B2. Furthermore, the randomness of the copolyamide resin of Example B2 was confirmed by 13 C-NMR spectrum, and it was found to be a random copolymer.
• Examples B3, B4, B6, B7 and B8 Except for changing the amounts of nylon 510 salt and 12-aminododecanoic acid used as raw materials as shown in Table 5, the copolymer polyamide resins of Examples B3, B4, B6, B7 and B8 were obtained in the same manner as in Example B1.
• Examples B5, B9 and B10 Except for changing the amounts of nylon 510 salt and 12-aminododecanoic acid used as raw materials as shown in Table 5, the copolymer polyamide resins of Examples B5, B9 and B10 were obtained in the same manner as in Example B2.
• Comparative Example B1 A 1-L polymerization tank was charged with 150.0 g of nylon 510 salt, 100.0 g of 6-aminocaproic acid, and 50.0 g of degassed ion-exchanged water, and polymerization was carried out in the same manner as in Example B2, followed by pelletization to obtain a copolymerized polyamide resin of Comparative Example B1.
• the amounts of raw materials charged, the composition ratios in the polymer, and the physical properties of the copolymerized polyamide resin of Comparative Example B1 are shown in Table 5.
• Comparative Example B2 A 1L polymerization tank was charged with 225.0 g of nylon 66 salt, 25.0 g of 12-aminododecanoic acid, and 50.0 g of degassed ion-exchanged water, and the inside of the polymerization tank was replaced with nitrogen, then sealed and heated to 200 ° C., and then the inside of the polymerization tank was adjusted to 1.3 MPa while stirring, and polymerization was carried out for 3 hours. The pressure in the polymerization tank was released to atmospheric pressure over 40 minutes while raising the temperature to 280 ° C. After releasing the pressure, polymerization was carried out for 100 minutes under a nitrogen stream of 200 mL / min, and then nitrogen was introduced to pressurize to 1.0 MPa.
• Table 5 shows the raw material charge amount, composition ratio in the polymer, and physical property value of the copolymerized polyamide resin of Comparative Example B2.
• Reference Example B3 A 1 L polymerization tank was charged with 150.0 g of nylon 66 salt, 100.0 g of 12-aminododecanoic acid, and 50.0 g of degassed ion-exchanged water, and polymerization was carried out in the same manner as in Example B2, followed by pelletization to obtain a copolymerized polyamide resin of Reference Example B3.
• the amounts of raw materials charged, the composition ratio in the polymer, and the physical properties of the copolymerized polyamide resin of Reference Example B3 are shown in Table 5.
• Comparative Example B4 205.0 g of 6-aminocaproic acid, 45.0 g of 12-aminododecanoic acid, and 50.0 g of degassed ion-exchanged water were charged into a 1 L polymerization tank, and polymerization was carried out in the same manner as in Example B2, followed by pelletization to obtain a copolymerized polyamide resin of Comparative Example B4.
• the amounts of raw materials charged, the composition ratio in the polymer, and the physical properties of the copolymerized polyamide resin of Comparative Example B4 are shown in Table 5.
• Comparative Example B5 A 1 L polymerization tank was charged with 250.0 g of 12-aminododecanoic acid and 50.0 g of degassed ion-exchanged water, and polymerization was carried out in the same manner as in Example B2, followed by pelletization to obtain a homopolyamide resin of Comparative Example B5. The amounts of raw materials charged, the composition ratio in the polymer, and the physical properties of the homopolyamide resin of Comparative Example B5 are shown in Table 5.
• Comparative Example B6 A 1 L polymerization tank was charged with 250.0 g of nylon 510 salt and 50.0 g of degassed ion-exchanged water, and polymerization was carried out in the same manner as in Example B2, followed by pelletization to obtain a homopolyamide resin of Comparative Example B6.
• the amounts of raw materials charged, the composition ratios in the polymer, and the physical properties of the homopolyamide resin of Comparative Example B6 are shown in Table 5.
• Table 5 shows the composition ratios of each structural unit in the polymer (calculated on a mass basis from the amount of raw materials charged) of Examples B1 to B10, Comparative Examples B1, B2, and B4 to B6, and Reference Example B3, as well as the DSC measurement data of the resulting polyamide resin and the proportion of biomass raw materials.
• n.d. indicates that no peak at the crystallization temperature was detected.
• Table 6 shows data on equilibrium water absorption, wear volume, and tensile modulus for the polyamide resins of Examples B2, B5, B9, and B10, Comparative Examples B1, B2, B4 to B6, and Reference Example B3.
• Tables 5 and 6 show that the copolymer polyamide resins of Examples B2, B5, B9, and B10, which contain structural unit A2 derived from the equimolar reaction product of pentamethylenediamine and sebacic acid and structural unit B derived from 12-aminododecanoic acid, have low equilibrium water absorption, excellent abrasion resistance and tensile modulus, and a high bio ratio.
• Comparative Example B1 which contains the structural unit A2 and a structural unit derived from 6-aminocaproic acid, had a high equilibrium water absorption rate, poor abrasion resistance, and a tensile modulus outside the acceptable range.
• Comparative Example B2 which contains a structural unit derived from a nylon 66 salt different from the structural unit A and a structural unit derived from 12-aminododecanoic acid, had a high equilibrium water absorption rate, poor abrasion resistance, and the tensile modulus was outside the range of the pass criteria.
• Reference Example B3 which is composed of structural units similar to Comparative Example B2 and has a different composition ratio of the structural units, had a high equilibrium water absorption rate compared to Examples B2, B5, B9, and B10, although the abrasion resistance and tensile modulus were within the pass range.
• Comparative Example B4 which contains a structural unit derived from 6-aminocaproic acid and a structural unit derived from 12-aminododecanoic acid, had a high equilibrium water absorption rate and poor abrasion resistance.
• Comparative Examples B2, B4, and B5 and Reference Example B3 did not use biomass raw materials and could not contribute to the construction of a sustainable society.
• Comparative Example B6 which contained only the structural unit A, was poor in abrasion resistance, and the tensile modulus was also outside the acceptable range.
• the copolymer polyamide resin of the present invention can be suitably used for applications such as molded products produced by various molding methods and food packaging films.
• the copolymer polyamide resin can contribute to the achievement of Goal 12 of the SDGs (Sustainable Development Goals).

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