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
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic 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.
• Patent Documents 1 to 4 exhibit certain mechanical properties (tensile modulus, tensile elongation, etc.), but have problems with the high enthalpy change ⁇ H that accompanies melting of the resin and poor transparency.
• the present invention aims to provide a copolymer polyamide resin that exhibits a low enthalpy change ⁇ H upon melting, has excellent transparency due to its low degree of crystallinity, 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.
• the present invention relates to the following [1] to [7].
• a polyamide resin composition comprising the copolymer polyamide resin according to any one of [1] to [3].
• a molded article comprising the copolymer polyamide resin according to any one of [1] to [3].
• a film comprising the copolymer polyamide resin according to any one of [1] to [3].
• a monofilament comprising the copolyamide resin according to any one of [1] to [3].
• the present invention can provide a copolymer polyamide resin that exhibits a low enthalpy change ⁇ H upon melting, has a low degree of crystallinity, and is therefore excellent in transparency, and is made using raw materials derived from biomass, as well as compositions containing the same and molded articles 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 A derived from a reaction product of equimolar amounts of pentamethylenediamine and adipic acid, represented by the following formula (A): and a structural unit B derived from a reaction product of equimolar amounts of pentamethylenediamine and sebacic acid represented by the following formula (B): and the mass ratio of structural unit A/structural unit B is 85/15 to 15/85.
• the copolymerized polyamide resin can increase the bio ratio while decreasing the enthalpy change ⁇ H associated with melting, thereby decreasing the degree of crystallinity and improving transparency.
• the structural unit A is a unit derived from an equimolar reaction product of pentamethylenediamine and adipic acid represented by the above formula (A).
• the structural unit A 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 shorten the time until solidification during heat molding, improve the handling and working efficiency, and increase the bio ratio.
• 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 B is a unit derived from an equimolar reaction product of pentamethylenediamine and sebacic acid, as shown in the above formula (B).
• the structural unit B 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.
• Pentamethylenediamines include those exemplified for structural unit A, and preferred embodiments are also the same.
• Sebacic acid 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 sebacic acid can be synthesized, for example, from ricinoleic acid triglyceride, the main component of castor oil obtained from castor bean seeds.
• the mass ratio of structural unit A/structural unit B in the copolymerized polyamide resin is 85/15 to 15/85, preferably 80/20 to 20/80, more preferably 70/30 to 25/75, even more preferably 60/40 to 30/70, and particularly preferably 55/45 to 35/65.
• 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 a lactam; 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 include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc.
• Lactams include, for example, ⁇ -caprolactam, enantholactam, decalactam, undecalactam, dodecalactam, ⁇ -pyrrolidone, ⁇ -piperidone, etc.
• 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 170 to 240° C., more preferably 175 to 230° C., further preferably 180 to 220° C., and particularly preferably 180 to 210° C.
• the melting point of the copolymer polyamide resin measured by DSC measurement can be increased or decreased depending on the ratio of the constituent units, the molecular weight of the copolymer polyamide resin, etc.
• the heat of fusion (enthalpy change accompanying melting) ⁇ H corresponding to the melting point is preferably 40 J/g or less, more preferably 1 to 40 J/g, even more preferably 5 to 40 J/g, even more preferably 5 to 30 J/g, and particularly preferably 5 to 20 J/g.
• the melting point measured by DSC is the top temperature of the endothermic peak in the DSC curve in the second heating process when the 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 in the second heating process.
• the crystallization temperature of the copolymer polyamide resin measured by differential scanning calorimetry is preferably 115 to 195° C., more preferably 115 to 170° C., further preferably 115 to 160° C., and particularly preferably 115 to 150° C.
• the crystallization temperature of the copolymer polyamide resin measured by DSC measurement can be increased or decreased depending on the ratio of the constituent 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 40% or more, more preferably 50% 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 ratio of the biomass raw material in the copolyamide resin is preferably 40% or more, more preferably 50% or more.
• the ratio of the biomass raw material is the ratio of the amount (mass) of the raw material derived from the biomass in the total amount of raw materials charged, 100 mass%, on the assumption that all the raw materials of the copolyamide resin have reacted.
• the upper limit of the ratio of the biomass raw material is 100%, and can be, for example, 90% 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 can increase the bio-ratio, and therefore can contribute to the achievement of Goal 12 of the Sustainable Development Goals (SDGs), and have excellent transparency when molded.
• Copolymer polyamide resins can be used for polyamide resin compositions and molded articles such as films and monofilaments.
• the method for producing the polyamide resin composition is not particularly limited, and the composition can be produced, for example, 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 goods, 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-related parts, flooring-related parts, seismic isolation/vibration control-related 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 used 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 rate, 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 excellent handling properties and work efficiency during thermoforming, and is also excellent in transparency, so it can be used as a food packaging film.
• the film is also suitable for use as an inflation film.
• the film can be used in a variety of 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 stretching 1.1 to 2.5 times, and more preferably by stretching 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 120 to 300°C, and more preferably 180 to 250°C.
• the two-stage drawn monofilament is preferably heat-set.
• the two-stage drawn monofilament can be heat-set in a gas atmosphere of preferably 160 to 350°C, more preferably 160 to 320°C, while being subjected to a 0 to 10% relaxation treatment. 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.
• the ratio of biomass raw material was the ratio of the constituent units derived from biomass-derived 1,5-pentamethylenediamine and sebacic acid to 100 mass % of all constituent units in the polymer.
• 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 11.6 mg, it was determined that the wear resistance was excellent.
• Diamine 1,5-pentamethylenediamine manufactured by CJ Research (derived from biomass, purity: 99.90% by mass)
• 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)
• Organic solvent 2-propanol manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. (purity: 99.7% by mass)
• 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.
• 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.
• Example 1 A 1L polymerization tank was charged with 200.0 g of nylon 56 salt, 50.0 g of nylon 510 salt, 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 carried out for 2 hours under a nitrogen stream of 200 mL / min, and then the stirrer was stopped and nitrogen was introduced to pressurize to 1.0 MPa.
• Example 1 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 the copolymerized polyamide resin of Example 1. The randomness of the copolyamide resin of Example 1 was confirmed by 13 C-NMR spectrum, and it was found to be a random copolymer.
• Example 2 A 1L polymerization tank was charged with 175.0 g of nylon 56 salt, 75.0 g of nylon 510 salt, 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 2 hours under a nitrogen stream of 200 mL / min, and then the stirrer was stopped and nitrogen was introduced to pressurize to 1.0 MPa.
• Example 2 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 2. The randomness of the copolyamide resin of Example 2 was confirmed by 13 C-NMR spectrum, and it was found to be a random copolymer.
• Example 3 A 1-L polymerization vessel was charged with 150.0 g of nylon 56 salt, 100.0 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 2. The mixture was pelletized to obtain a copolymer polyamide resin of Example 3.
• Example 4 A 1-L polymerization vessel was charged with 125.0 g of nylon 56 salt, 125.0 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 2. The mixture was pelletized to obtain a copolymer polyamide resin of Example 4.
• Example 5 A 1-L polymerization vessel was charged with 100.0 g of nylon 56 salt, 150.0 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 2. The mixture was pelletized to obtain a copolymer polyamide resin of Example 5.
• Example 6 A 1-L polymerization vessel was charged with 75.0 g of nylon 56 salt, 175.0 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 2. The mixture was pelletized to obtain a copolymer polyamide resin of Example 6.
• Example 7 A 1-L polymerization vessel was charged with 50.0 g of nylon 56 salt, 200.0 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 2. The mixture was pelletized to obtain a copolymer polyamide resin of Example 7.
• Comparative Example 1 A 1-L polymerization vessel was charged with 225.0 g of nylon 56 salt, 25.0 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 1. The mixture was pelletized to obtain a copolymer polyamide resin of Comparative Example 1.
• Comparative Example 2 A 1-L polymerization vessel was charged with 25.0 g of nylon 56 salt, 225.0 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 2. The mixture was pelletized to obtain a copolymer polyamide resin of Comparative Example 2.
• Table 1 shows the mass ratio of each constituent unit calculated from the amount of raw material charged for Examples 1 to 7 and Comparative Examples 1 and 2, the ratio of constituent units derived from each monomer component, and the proportion of biomass raw material, as well as the DSC measurement data.
• Table 2 shows the equilibrium water absorption and wear data for the copolymer polyamide resins of Example 2 and Comparative Examples 1 and 2.
• Examples 1 to 7 which contain structural unit A derived from an equimolar reactant of pentamethylenediamine and adipic acid and structural unit B derived from an equimolar reactant of pentamethylenediamine and sebacic acid, and in which the mass ratio of structural unit A/structural unit B is in the range of 85/15 to 15/85, have a smaller heat of fusion, i.e., a smaller enthalpy change ⁇ H associated with melting, a lower degree of crystallinity, and excellent transparency, compared to Comparative Examples 1 and 2.
• Example 4 in which the mass ratio of structural unit A/structural unit B is 49/51
• Example 5 in which the mass ratio of structural unit A/structural unit B is 39/61, have an even smaller ⁇ H and are particularly excellent in transparency.
• 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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