Copolyamide resin, and composition, molded article, film, and monofilm containing same

Abstract

Provided are: a copolyamide resin which has a low enthalpy change [Delta] H accompanying melting, has a low degree of crystallinity, and thus has excellent transparency, and which uses a biomass-derived raw material; a composition containing the copolyamide resin; and a molded article such as a film or a monofilament. According to the method, the realization of the target 12 of the SDGs (sustainable development targets, the Sustatable Device Goals) and the like can be facilitated, and the method can be used for realizing the target 12 of the SDGs and the like. The copolyamide resin comprises a structural unit A and a structural unit B, the mass ratio of the structural unit A to the structural unit B is 85 / 15-15 / 85, the structural unit A is derived from reactants of pentamethylenediamine and adipic acid in equal molar weight, and the structural unit B is derived from reactants of pentamethylenediamine and sebacic acid in equal molar weight.

Description

TECHNICAL FIELD

[0001] The present application relates to a copolyamide resin, and particularly to a copolyamide resin using a raw material derived from biomass. BACKGROUND

[0002] Polyamides are polymers comprising a collection of structural units of amide bonds. The structural units of polyamides are generally derived from amino carboxylic acids or lactams, or diamines and dicarboxylic acids. In particular, aliphatic polyamide resins derived from aliphatic chemical species among these compounds have properties such as chemical resistance, toughness, heat resistance, oil resistance, and the like, which are useful as resins in a wide variety of applications. Therefore, aliphatic polyamide resins are useful as raw materials for molded articles for various uses, for example, used as a base material for a single-layer film or a laminated film, particularly in the field of food packaging, which requires properties such as pinhole resistance and gas barrier properties, and further used as a constituent material for a multilayer film obtained by co-extrusion with other resins.

[0003] As one of the advantages of resins, it can be cited that various controls of the properties of the resins can be performed by selection of monomers, use of a plurality of monomers. By combining two or more structural units, copolyamide resins that provide molded articles having properties suitable for the use are manufactured (Patent Literature 1).

[0004] Polyamide resins provide molded articles that are excellent in various properties, and therefore, homopolymers based on various structural units or copolymers based on combinations of structural units are manufactured, and monomers that are raw materials of polyamide resins are mostly industrial fossil raw materials. For example, ε-caprolactam, which is known as a raw material of Nylon (registered trademark), is synthesized from benzene derived from naphtha. With the increase in environmental awareness of suppressing carbon dioxide emissions in recent years, raw materials of polyamide resins are also pursuing a shift from fossil raw materials to raw materials derived from biomass. As a compound derived from biomass and possibly a raw material of polyamide, 1,5-pentanediamine, which can be obtained from starch, sugar cane, by enzyme reaction, yeast reaction, fermentation reaction, and the like, is known. In Patent Literature 2, an attempt was made to manufacture a polyamide resin derived from a biomass raw material with less impurities, using 1,5-pentanediamine as a raw material. In Patent Literature 3 and Patent Literature 4, an attempt was made to manufacture a polyamide resin for large molded articles with improved heat retention stability and the like, using 1,5-pentanediamine as a raw material.

[0005] PRIOR ART DOCUMENTS

[0006] PATENT LITERATURE

[0007] Patent Literature 1: International Publication No. 2022 / 071013

[0008] Patent Literature 2: International Publication No. 2015 / 076233

[0009] Patent Literature 3: Japanese Patent Application Laid-Open (JP-A) No. 2006-348057

[0010] Patent Literature 4: Japanese Patent Application Laid-Open (JP-A) No. 2007-332353 SUMMARY

[0011] PROBLEMS TO BE SOLVED BY THE INVENTION

[0012] Replacement of existing products with resins derived from biomass raw materials is one of global initiatives for building a sustainable society, and Japan is also promoting legal improvement such as setting a certain benchmark for bio-based polymer content, building a recycling process, and demonstration experiments for CO2 emission reduction. On the other hand, replacement of resin raw materials often imposes changes on the molecular structure of the resin, and therefore changes in physical properties are inevitable. Both the quality and the price of the resin are highly concerned by consumers, and there is a general demand for resins that have equal or higher quality than the replaced resins.

[0013] Molded articles using the polyamide resins described in Patent Literatures 1 to 4 exhibit certain mechanical properties (tensile modulus, tensile elongation, etc.), but have problems of high enthalpy change ΔH accompanying resin melting and poor transparency.

[0014] Therefore, an object of the present application is to provide a copolyamide resin and a composition, and a film, a monofilament, and the like, which contain the copolyamide resin, the copolyamide resin having low enthalpy change ΔH accompanying melting, low crystallinity, and therefore excellent transparency, and using a raw material derived from biomass.

[0015] SOLUTION TO THE PROBLEM

[0016] The present application relates to the following [1] to [7].

[0017] [1] A copolyamide resin comprising a structural unit A and a structural unit B, the mass ratio of the structural unit A / the structural unit B being 85 / 15 to 15 / 85,

[0018] The structural unit A is derived from equimolar amounts of reactants of penta methylene diamine represented by the following formula (A) and adipic acid,

[0019] [Chemical Formula 1]

[0020]

[0021] The structural unit B is derived from equimolar amounts of reactants of penta methylene diamine represented by the following formula (B) and sebacic acid,

[0022] [Chemical Formula 2]

[0023] .

[0024] [2] The copolyamide resin according to [1], wherein the melting point of the copolyamide resin is 170 to 240°C as measured by DSC.

[0025] [3] The copolyamide resin according to [1] or [2], wherein the crystallization temperature of the copolyamide resin is 115 to 195°C as measured by DSC.

[0026] [4] A polyamide resin composition comprising the copolyamide resin according to any one of [1] to [3].

[0027] [5] A molded article comprising the copolyamide resin according to any one of [1] to [3].

[0028] [6] A film comprising the copolyamide resin according to any one of [1] to [3].

[0029] [7] A monofilament comprising the copolyamide resin according to any one of [1] to [3].

[0030] Effects of Invention

[0031] According to the present application, it is possible to provide a copolyamide resin and a composition, and a film, a monofilament, and the like, which are excellent in transparency because the copolyamide resin has a low enthalpy change ΔH accompanying melting and a low crystallinity, and which use a raw material derived from biomass. DETAILED DESCRIPTION

[0032] In the present application, the polyamide resin refers to a resin obtained by polymerization or copolymerization using a lactam, an aminocarboxylic acid, or a nylon salt containing a diamine and a dicarboxylic acid as a raw material, by a publicly known method such as melt polymerization, solution polymerization, or solid phase polymerization, and having an amide bond (-CONH-) in the main chain. As long as the effects of the present application are not impaired, other components can be compounded in the polyamide resin to produce a polyamide resin composition.

[0033] The copolyamide resin of the present application contains a structural unit A and a structural unit B, and the mass ratio of the structural unit A / the structural unit B is 85 / 15 to 15 / 85,

[0034] The structural unit A is derived from an equimolar amount of reactants of pentamethylene diamine represented by the following formula (A) and adipic acid,

[0035] [Chemical Formula 3]

[0036]

[0037] The structural unit B is derived from an equimolar amount of reactants of pentamethylene diamine represented by the following formula (B) and sebacic acid,

[0038] [Chemical Formula 4]

[0039]

[0040] The copolyamide resin can improve the biological ratio and reduce the enthalpy change ΔH accompanying melting by containing the structural unit A and the structural unit B in the above proportions, can reduce the crystallinity, and improve the transparency.

[0041] [Structural Unit A]

[0042] The structural unit A is a unit derived from an equimolar amount of reactants of penta methylene diamine 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 penta methylene diamine and adipic acid. Note that the penta methylene diamine and adipic acid constituting the unit can be condensed directly, or can be condensed via other units or diamines or dicarboxylic acids constituting other units. By the copolyamide resin containing the structural unit A, the time to solidification at the time of heat molding can be shortened, the operability and work efficiency can be improved, and the biological ratio can be improved.

[0043] As the penta methylene diamine, for example, 1,5-pentamethylene diamine, 1,4-pentamethylene diamine, 1,3-pentamethylene diamine, and the like can be exemplified, and from the viewpoint of ease of obtaining and strength of the obtained polyamide resin, 1,5-pentamethylene diamine is preferred. The penta methylene diamine can be used alone or two or more kinds can be used in combination.

[0044] The penta methylene diamine can be derived from a fossil raw material, or can be a raw material derived from biomass, and from the viewpoint of improving the biological ratio of the copolyamide resin, it is preferred to be a raw material derived from biomass.

[0045] As the penta methylene diamine derived from biomass, for example, the penta methylene diamine obtained by the production method disclosed in International Publication No. 2015 / 076233, Japanese Patent Application Publication No. 2006-348057, Japanese Patent Application Publication No. 2007-332353, Japanese Patent Application Publication No. 2002-223771, Japanese Patent Application Publication No. 2004-000114, Japanese Patent Application Publication No. 2004-208646, Japanese Patent Application Publication No. 2004-290091, Japanese Patent Application Publication No. 2004-298034, Japanese Patent Application Publication No. 2002-223770, Japanese Patent Application Publication No. 2004-222569, Japanese Patent Application Publication No. 2005-6650, Japanese Patent Application Publication No. 2019-154313, Japanese Patent Application Publication No. 2019-205423, and the like can be used.

[0046] Specifically, it is known that lysine is decarboxylated by an enzyme reaction, whereby 1,5-pentamethylenediamine can be produced, and, for example, 1,5-pentamethylenediamine can be produced from lysine using a lysine decarboxylase, a cell producing a lysine decarboxylase, a processed product of the cell, a lysine decarboxylase-expressing microorganism, or the like. Furthermore, the enzymatic decarboxylation reaction of lysine can also be performed while adding an acid such as adipic acid to a lysine solution to maintain a pH suitable for the enzymatic decarboxylation reaction.

[0047] The adipic acid can be derived from a fossil raw material or a raw material derived from biomass. From the viewpoint of easiness of obtaining, the adipic acid is preferably derived from a fossil raw material.

[0048] [Structural Unit B]

[0049] The structural unit B is a unit derived from equimolar amounts of reactants of pentamethylenediamine represented by the above formula (B) and sebacic acid. The structural unit B is formed by polymerizing an equimolar salt or an equimolar mixture of pentamethylenediamine and sebacic acid. Note that the pentamethylenediamine and the sebacic acid constituting the unit can be condensed directly or via other units or diamines or dicarboxylic acids constituting other units. By including the structural unit B in the copolyamide resin, the water absorption of the molded article can be reduced, and the biobased ratio can be increased.

[0050] As the pentamethylenediamine, the same pentamethylenediamine as exemplified in the structural unit A can be exemplified, and the preferable aspects are also the same.

[0051] The sebacic acid can be derived from a fossil raw material or a raw material derived from biomass, and from the viewpoint of increasing the biobased ratio of the copolyamide resin, the raw material derived from biomass is preferable.

[0052] The sebacic acid derived from biomass can be synthesized, for example, from castor oil acid triglyceride, which is a main component of castor oil obtained from castor seeds.

[0053] [Mass ratio of structural unit A and structural unit B]

[0054] The mass ratio of the structural unit A / the structural unit B in the copolyamide resin is 85 / 15 to 15 / 85, preferably 80 / 20 to 20 / 80, more preferably 70 / 30 to 25 / 75, further preferably 60 / 40 to 30 / 70, and particularly preferably 55 / 45 to 35 / 65. By setting the mass ratio of the structural unit A / the structural unit B to 15 / 85 or more, the time until curing at the time of heat molding is shortened, the operability and work efficiency are improved, and the transparency of the molded article is also improved, and by setting the mass ratio to 85 / 15 or less, the water absorption of the molded article is reduced, and the transparency is improved.

[0055] The total amount of the structural unit A and the structural unit B is preferably 80 to 100 mass%, more preferably 90 to 100 mass%, and further preferably 95 to 100 mass%, relative to 100 mass% of the copolyamide resin. In one embodiment, the total amount of the structural unit A and the structural unit B is 100 mass%, relative to 100 mass% of the copolyamide resin.

[0056] [Other structural units]

[0057] The copolyamide resin can contain a structural unit other than the structural unit A and the structural unit B, as long as the characteristics thereof are not impaired. As such a structural unit, there can be mentioned a structural unit derived from equimolar amounts of reactants of penta methylene diamine and a dicarboxylic acid other than adipic acid and sebacic acid; a structural unit derived from equimolar amounts of reactants of a diamine other than penta methylene diamine and adipic acid or sebacic acid; a structural unit derived from equimolar amounts of reactants of a diamine other than penta methylene diamine and 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.

[0058] As the diamine other than penta methylene diamine, there can be mentioned, for example, aliphatic diamines such as ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecane diamine, tetradecane diamine, pentadecane diamine, hexadecane diamine, heptadecane diamine, octadecane diamine, nonadecane diamine, eicosane diamine, 2-methyl-l,8-octane diamine, 2,2,4 / 2,4,4-trimethylhexamethylene diamine, and the like; alicyclic diamines such as 1,3- / 1,4-cyclohexyl diamine, 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-l-cyclopentanemethylamine, 5-amino-l,3,3-trimethylcyclohexanemethylamine, bis(aminopropyl)piperazine, bis(aminoethyl)piperazine, norbornane dimethylene diamine, and the like.

[0059] As the dicarboxylic acid other than adipic acid and sebacic acid, there can be mentioned, 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, eicosanedioic acid, and the like; alicyclic dicarboxylic acids such as 1,3- / 1,4-cyclohexane dicarboxylic acid, dicyclohexanemethane-4,4'-dicarboxylic acid, norbornane dicarboxylic acid, and the like; and the like.

[0060] As the aminocarboxylic acid, 6-aminohexanoic acid, 7-aminohexanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like can be exemplified. As the lactam, ε-caprolactam, enantholactam, caprylolactam, undecanolactam, laurolactam, α-pyrrolidinone, α-piperidinone, and the like can be exemplified.

[0061] Note that the amount of each structural unit of the copolyamide resin corresponds to the amount of each component input at the time of producing the copolyamide resin, and can also be calculated by measuring the obtained copolyamide resin as it is or after hydrolysis by high performance liquid chromatography, gas chromatography, gas chromatography / atomic emission detector (GC / AED), gel permeation chromatography, or the like. The amount of each structural unit of the copolyamide resin described in the present specification and claims is calculated based on the input ratio (mass ratio) of the raw materials of the copolyamide resin, assuming that all of the raw materials have reacted.

[0062] Note that in the examples, the amount of each structural unit was calculated taking into account the removal of condensation water due to polymerization, as the contribution amount in the molecular weight of 1,5-pentamethylenediamine, 102.18 g / mol = 100.18 (= 102.18 - 2.00) g / mol, the contribution amount in the molecular weight of adipic acid, 146.14 g / mol = 112.14 (= 146.14 - 34.00) g / mol, and the contribution amount in the molecular weight of sebacic acid, 202.25 g / mol = 168.25 (= 202.25 - 34.00) g / mol.

[0063] [Physical properties of copolyamide resin]

[0064] From the viewpoint of moldability, the melting point of the copolyamide resin obtained by differential scanning calorimetry (DSC measurement) 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 copolyamide resin obtained by DSC measurement can increase or decrease depending on the ratio of the structural units, the molecular weight of the copolyamide resin, and the like.

[0065] Further, from the viewpoint of the transparency of the molded article, the heat of fusion (enthalpy change accompanying fusion) ΔH corresponding to the melting point is preferably 40 J / g or less, more preferably 1 to 40 J / g, further preferably 5 to 40 J / g, more further preferably 5 to 30 J / g, and particularly preferably 5 to 20 J / g.

[0066] In the present specification, the melting point determined by DSC is the peak top temperature of the endothermic peak in the DSC curve of the second temperature rise process in the case where the copolyamide resin is heated to 300°C at a rate of 10°C / min, held at the temperature for 1 minute, then cooled to 30°C at a rate of 10°C / min, and then heated to 300°C again at a rate of 10°C / min. Further, the heat of fusion corresponding to the melting point is calculated from the endothermic peak in the DSC curve of the second temperature rise process.

[0067] From the viewpoint of moldability, the crystallization temperature of the copolyamide resin determined by differential scanning calorimetry measurement (DSC measurement) 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 copolyamide resin determined by DSC measurement can increase or decrease depending on the ratio of the structural units, the molecular weight of the copolyamide resin, and the like.

[0068] In the present specification, the crystallization temperature determined by DSC is the peak top temperature of the exothermic peak in the DSC curve of the temperature decrease process in the case where the copolyamide resin is heated to 300°C at a rate of 10°C / min, held at the temperature for 1 minute, and then cooled to 30°C at a rate of 10°C / min under a nitrogen atmosphere.

[0069] From the viewpoint of obtaining a preferable melting point and crystallization temperature, the copolyamide resin is preferably a random copolymer.

[0070] The random copolymer refers to a copolymer in which the structural unit A and the structural unit B are arranged in disorder. The copolyamide resin obtained by mixing and polymerizing the units in the monomer state is generally a random copolymer. On the other hand, for example, a copolyamide resin obtained by mixing and further polymerizing a polyamide resin A obtained by polymerizing a monomer that is a raw material of the structural unit A and a polyamide resin B obtained by polymerizing a monomer that is a raw material of the structural unit B is generally not a random copolymer but a block copolymer. The block copolymer refers to a copolymer in which a block in which the structural unit A or the structural unit B is continuously arranged in a certain amount is present.

[0071] The confirmation of the random copolymer can also be performed by using a nuclear magnetic resonance device to confirm the bonding probability of each structural unit from 13 The C-NMR spectrum analysis each structural unit's bonding probability.

[0072] The biomass degree of the copolyamide resin determined according to ASTM D6866 is preferably 40% or more, and more preferably 50% or more. The biomass degree can be measured by measuring the radioactivity carbon (14C) contained in the copolyamide resin. 14C) is calculated. Specifically, when all of the carbon in the copolyamide resin is derived from fossil raw materials, the biomass degree is 0%, and when all of the carbon is derived from biomass, the biomass degree is 100%.

[0073] The proportion of biomass raw materials in the copolyamide resin (on a mass basis) is preferably 40% or more, and more preferably 50% or more. The proportion of biomass raw materials is the proportion of the amount (mass) of raw materials derived from biomass in the total amount of raw materials (100 mass%) when it is assumed that all of the raw materials of the copolyamide resin have reacted. The upper limit of the proportion of biomass raw materials is 100%, and can be set to 90% or less, for example.

[0074] When the biomass raw materials are only 1,5-pentamethylenediamine and sebacic acid, the proportion of biomass raw materials is the proportion of the amount of the 1,5-pentamethylenediamine and sebacic acid in the total amount of raw materials (100 mass%). Note that in the examples, the proportion of biomass raw materials was calculated based on the contribution amount of the molecular weight of 1,5-pentamethylenediamine (102.18 g / mol) = 100.18 (= 102.18 - 2.00) g / mol, the contribution amount of the molecular weight of adipic acid (146.14 g / mol) = 112.14 (= 146.14 - 34.00) g / mol, and the contribution amount of the molecular weight of sebacic acid (202.25 g / mol) = 168.25 (= 202.25 - 34.00) g / mol.

[0075] [Method for producing copolyamide resin]

[0076] The production of the copolyamide resin can use known polymerization methods such as melt polymerization, solution polymerization, interfacial polymerization, solid phase polymerization, and combinations thereof. In general, it is preferable to use melt polymerization that is performed at a temperature higher than the melting point of the resulting copolyamide resin. Furthermore, in the production of the copolyamide resin, known polymerization devices can be used, and the production can be performed by using batch or continuous processes, and operating at normal pressure, reduced pressure, or pressurized conditions, as appropriate, in combination as needed. 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.

[0077] Furthermore, although not particularly limited, since the copolyamide resin is high in viscosity, depending on the case, from the viewpoint of avoiding difficulties in extraction during polymerization and the like, for example, a copolyamide resin that is low in viscosity can be synthesized by melt polymerization, and then a copolyamide resin that is high in viscosity can be obtained by solid phase polymerization.

[0078] [Use of copolyamide resin]

[0079] The copolyamide resin can improve the biotic ratio, and thus can contribute to achievement of the SDGs (Sustainable Development Goals) Goal 12 and the like, and has excellent transparency when formed into a molded article. The copolyamide resin can be used for a polyamide resin composition and a molded article such as a film and a monofilament.

[0080] <Polyamide resin composition>

[0081] One aspect of the present application is a polyamide resin composition containing a copolyamide resin. The polyamide resin composition can contain other components than the copolyamide resin within a range not impairing the effects of the present application.

[0082] As the other components, there can be mentioned: a polyamide resin other than the copolyamide resin; any resin other than the polyamide resin, such as a modified or unmodified polyolefin resin; a plasticizer, a heat resistance agent, a blowing agent, an antioxidant, an ultraviolet absorber, a weathering agent, a crystallization nucleating agent, a crystallization promoter, a mold releasing agent, a lubricant, an antistatic agent, an antifog agent, a flame retardant, a flame retardant aid, a pigment, a dye, and the like functional imparting agent. The polyamide resin composition containing these other components can be formed into a molded article such as a pellet, a film, and a monofilament.

[0083] The method for producing the polyamide resin composition is not particularly limited, and for example, the copolyamide resin and the other components can be mixed by using a publicly known melt kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll.

[0084] <Molded article>

[0085] One aspect of the present application is a molded article containing a copolyamide resin or a polyamide resin composition. As the method for producing the molded article, there can be mentioned, for example, injection molding, press molding, blow molding, extrusion molding, rotational molding, and the like.

[0086] <Use of the molded article>

[0087] The molded article containing the copolyamide resin or the polyamide resin composition exhibits excellent properties thereof, and is used for various uses such as electronic parts, electric parts, household goods, office supplies, automobile / vehicle-related parts, building materials, sports goods, and the like, in addition to films and monofilaments.

[0088] As electronic component applications, for example, they are preferably used for connectors, coils, sensors, LED lamps, sockets, resistors, relay housings, small switches, coil holders, capacitors, variable capacitor housings, optical pick-up chassis, oscillators, various terminal boards, transformers, plugs, printed boards, tuners, speakers, microphones, earphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD (Floppy Disk Drive) trays, FDD chassis, motor brush holders, transformer components, parabolic antennas, computer-related components, and the like.

[0089] As electrical component applications, for example, they are preferably used for generators, motors, transformers, converters, voltage regulators, rectifiers, inverters, relays, power contacts, openers, circuit breakers, draw-out switches, multipole rods, electrical components, motor housings, notebook personal computer housings and internal components, CRT (Cathode Ray Tube) display housings and internal components, printer housings and internal components; portable telephone, mobile personal computer, hand-held mobile terminal, and the like portable terminal housings and internal components; various gears, various housings, cabinets, and the like.

[0090] As household and office applications, for example, they are preferably used for VTR (videotape recorder) components, television components, irons, hair dryers, electric rice cookers components, microwave oven components; audio components, audio equipment, laser discs (registered trademark), optical discs, DVDs, and the like sound / image equipment components; lighting components, refrigerator components, air conditioner components, typewriter components, word processor components, personal computers, notebook personal computers, and the like electronic equipment housings, office computer-related components, telephone-related components, facsimile-related components, copier-related components, cleaning jigs, motor components, lighters, typewriters, microscopes, binoculars, cameras, watches, and the like.

[0091] As automobile / vehicle-related parts, for example, they are preferably used for various valves such as an alternator terminal, an alternator connector, an IC regulator, a potentiometer base for a dimmer, a waste gate valve, and the like, fuel-related / cooling system / brake system / wiper system / exhaust system / intake system various pipes / hoses / pipes, an intake nozzle breather pipe, an intake manifold, a fuel pump, an engine cooling water joint, a carburetor main body, a carburetor spacer, an exhaust gas sensor, a cooling water sensor, an oil temperature sensor, a brake pad wear sensor, a throttle position sensor, a crank position sensor, an air flow meter, a brake pad wear sensor, a battery peripheral part, an air conditioner thermostat base, a heating and ventilation flow control valve, a radiator motor brush holder, a water pump impeller, a turbine blade, a wiper motor-related part, a distributor, a starter switch, a starter relay, a wire harness for a transmission, an oil pan for a transmission, a window washer nozzle, an air conditioning panel switch substrate, a coil for a fuel-related solenoid; a wire harness connector, an SMJ connector, a PCB connector, a door grommet connector, a fuse connector, and various connectors; a horn terminal, an electrical component insulating plate, a stepper motor rotor, a lamp socket, a lamp reflector, a lamp cover, a brake piston, a solenoid holder, an engine oil pan, an engine oil filter, an ignition device housing, a torque control lever, a seat belt part, a register blade, a washer lever, a window regulator handle, a window regulator handle knob, a passing light lever, a sun visor bracket, an instrument panel, an airbag peripheral part, a door pad, a pillar, a console box, various motor housings, a roof rack, a fender, a garnish, a roof panel, a hood panel, a trunk lid, a door mirror bracket, a spoiler, a hood louver, a wheel cover, a wheel cover, a grille apron cover frame, a lamp frame, a door handle, a door trim, a quarter panel, a wiper, and the like.

[0092] As building material applications, for example, they are preferably used for wall, roof, ceiling material-related parts of civil engineering structures; window material-related parts, thermal insulation material-related parts, floor material-related parts, seismic / damping member-related parts, life line-related parts, and the like.

[0093] As sports equipment applications, for example, they are preferably used for golf clubs, shafts, and the like, golf-related equipment; face guards, helmets, chest protectors, elbow protectors, knee protectors, and the like, sports body protection equipment; shoe-related equipment such as the bottom material of sports shoes; fishing rod, fishing line, and the like, fishing gear-related equipment; summer sports-related equipment such as surfing; winter sports-related equipment such as skiing / snowboarding; other indoor and outdoor sports-related equipment, and the like.

[0094] <Membrane>

[0095] Another aspect of the present application is a film containing the copolyamide resin or the polyamide resin composition. The film can be a single layer film containing only a layer of the copolyamide resin, or a laminated film of two or more layers containing a layer of the copolyamide resin and other layers. As the other layers, there can be cited, for example, layers containing a resin other than the copolyamide resin, such as a thermoplastic resin, a thermosetting resin, etc., layers containing a metal such as aluminum, etc.

[0096] As the resin other than the copolyamide resin, there can be cited, for example, low-density polyethylene, linear low-density polyethylene, ionomer, ethylene-vinyl alcohol copolymer (EVOH), ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ethylene-methacrylate copolymer, etc., ethylene-based resins; polypropylene, etc., polyolefin, modified polyolefin, polyester, polyvinyl alcohol, polyamide other than the copolyamide resin, polyamide elastomer; bioplastic such as polylactic acid (PLA), polyhydroxyalkanoate (PHA), etc.

[0097] The thickness of the film can be appropriately selected depending on the use. For example, in the case of a single layer film, the thickness is preferably 5 to 200 μm, more preferably 10 to 50 μm. In the case of a laminated film, the total thickness is preferably 10 to 1000 μm, more preferably 20 to 500 μm; and the thickness of the layer containing the copolyamide resin or the polyamide resin composition is preferably 5 to 100 μm, more preferably 10 to 50 μm.

[0098] The film can be an unstretched film, or a stretched film obtained by stretching the unstretched film. The stretching method is not particularly limited, and there can be cited, for example, a uniaxial stretching method using a heated roll, a simultaneous biaxial stretching method using a tubular method, a sequential biaxial stretching method using a heated roll or a tenter, etc.

[0099] (Method for producing film)

[0100] The method for producing the film is not particularly limited, and for example, a publicly known production method can be applied. For example, the copolyamide resin or the polyamide resin composition can be melt-kneaded using an extruder, and a single layer film can be produced by a T-die molding method, an air-cooling inflation molding method or a water-cooling inflation molding method, a Triple Bubble molding method, etc.

[0101] The laminated film can be directly laminated by co-extrusion, lamination, etc., or can be laminated via an adhesive or an adhesive resin layer. Co-extrusion is preferred because of the excellent productivity.

[0102] In the case of manufacturing a laminated film by a co-extrusion method, a substantially non-oriented unstretched film is manufactured, for example, by a co-extrusion T-die molding method, a co-extrusion air-cooling inflation molding method, or a co-extrusion water-cooling inflation molding method.

[0103] Among them, the air-cooling inflation molding method and the water-cooling inflation molding method (also simply referred to as "inflation method" or "inflation molding") are not only simple in equipment, but also can easily change the width of the film only by adjusting the blow-up ratio, and thus are excellent in workability and can manufacture the film at a high productivity. The copolyamide resin can suppress curling of the film in the case of being used for the air-cooling or water-cooling inflation molding or the co-extrusion air-cooling or water-cooling inflation molding method. In particular, in the case of manufacturing a multilayer film including a layer containing the copolyamide resin and a low-melting-point thermoplastic resin layer by the co-extrusion air-cooling or water-cooling inflation molding method, the heat deterioration and curling of the film can be suppressed, and thus is preferable.

[0104] As the conditions for molding the inflation molded film, there is no particular limitation, and the resin temperature is preferably equal to or higher than the melting point of the raw material resin used and less than 300°C. In the present application, the resin temperature can be set to, for example, 160°C to 250°C, and is preferably set to 160°C to 220°C. The blow-up ratio (also referred to as blow ratio) is the ratio of the maximum diameter of the bubble to the diameter of the die. The blow-up ratio is preferably 1.1 to 3.0, and more preferably 1.2 to 2.5. The draw speed is determined depending on the thickness and width of the film and the extrusion amount, and can be adjusted within a range in which the stability of film production can be maintained, and is typically preferably 1 to 150 m / minute, and more preferably 5 to 100 m / minute.

[0105] Further, in order to improve the printability, laminatability, or adhesive impartability, the film can be subjected to surface treatment such as corona discharge treatment, plasma treatment, flame treatment, acid treatment, and the like. In addition, after such treatment, secondary processing steps such as printing, lamination, adhesive application, heat sealing, and the like can be performed as needed, and the film can be used for respective target uses.

[0106] (Uses of the film)

[0107] The film is excellent in the handleability and work efficiency at the time of heat molding, and is excellent in transparency, and thus can be used for a food packaging film. In addition, the film is suitable for a blown film use. Further, the film can be used for various uses exemplified as the molded product uses, such as electronic components, electrical components, household goods, office supplies, automobile / vehicle-related components, building materials, sports goods, and the like.

[0108] <filament>

[0109] Another aspect of the present application is a filament comprising the copolyamide resin or the polyamide resin composition. The diameter of the filament is not particularly limited, and is preferably 0.5 to 20 mm, more preferably 1 to 5 mm. The filament can be a continuous fiber, or can also be a short fiber.

[0110] (Method for producing a filament)

[0111] The filament is obtained by a publicly known production method using the copolyamide resin or the polyamide resin composition. As the production method of the filament, for example, the following method can be cited: pellets of the polyamide resin are melted by an extruder or the like and extruded from a spinning nozzle, and cooling is performed in a refrigerant bath of water, trichloroethylene or the like, whereby an unstretched yarn is produced. In this case, the distance from the filament outlet of the spinning nozzle to the refrigerant liquid surface is preferably maintained at about 10 to 300 mm.

[0112] The unstretched yarn can be further subjected to stretching and heat setting. Here, the stretching is preferably two-stage stretching performed in two stages.

[0113] The first-stage stretching of the two-stage stretching is preferably performed to stretch the unstretched yarn to 2 to 5 times, more preferably to 3 to 4 times, in steam or hot water. If the stretching ratio is in this range, the nodule strength tends to further increase.

[0114] In the case where the stretching is performed in steam, the temperature is preferably in the range of 95 to 120°C, more preferably in the range of 100 to 110°C. In the case where the temperature of the steam is in this temperature range, the nodule strength and the transparency of the obtained filament tend to further increase.

[0115] In the case where the stretching is performed in hot water, the temperature of the hot water is preferably in the range of 50 to 95°C, more preferably in the range of 60 to 90°C. In the case where the temperature of the hot water is in this range, the nodule strength and the transparency of the obtained filament tend to further increase.

[0116] The second-stage stretching is preferably performed to stretch to 1.1 to 2.5 times, more preferably to 1.2 to 2.5 times, in a gaseous environment. As the gas, there are no particular limitations, and inert gases such as helium, nitrogen, argon, air and the like can be cited. The temperature of the gaseous environment in the second-stage stretching is preferably in the range of 120 to 300°C, more preferably in the range of 180 to 250°C. In the case where the temperature and the stretching ratio in the second-stage stretching are in the above-mentioned ranges, the nodule strength and the transparency of the obtained filament tend to further increase.

[0117] The two-stretch monofilament is preferably heat-set. For the two-stretch monofilament, relaxation treatment of 0 to 10% can be performed while heat-setting in a gas environment of preferably 160 to 350°C, more preferably 160 to 320°C. In this temperature range, the nub strength tends to further increase.

[0118] In the above two-stretch and heat-setting, the total stretch ratio is preferably in the range of 4.0 to 7.0, more preferably 4.5 to 6.5, and further preferably 5.5 to 6.0.

[0119] (Use of monofilament)

[0120] The monofilament has low water absorption and excellent wear resistance, and thus can be used as a filament, a multifilament, and a structure such as a net for fishing, industrial, clothing, medical, and the like. Also, the monofilament can be used for various uses exemplified as molded products, such as electronic parts, electrical parts, household goods, office supplies, automobile / vehicle-related parts, building materials, sports goods, and the like.

[0121] Examples

[0122] Hereinafter, the present application will be described in more detail by examples and comparative examples, but the present application is not limited to these examples.

[0123] [Measurement of physical properties]

[0124] (1) Melting point (Tm) and heat of fusion (ΔH)

[0125] Using DSC7020 manufactured by Hitachi High-Tech Science, Inc., the polyamide resins of the examples and comparative examples were heated to 300°C at a rate of 10°C / min under a nitrogen atmosphere, held at this temperature for 1 minute, and then cooled to 30°C at a rate of 10°C / min. Subsequently, the second heating process was performed at a rate of 10°C / min, and the peak top temperature of the endothermic peak in the DSC curve in this case was set as the melting point (Tm), and the corresponding heat of fusion was set as ΔH (unit: J / g). If ΔH was 40 J / g or less, it was determined that the molded product had low crystallinity and excellent transparency.

[0126] (2) Crystallization temperature (Tc)

[0127] Using DSC7020 manufactured by Hitachi High-Tech Science, Inc., the polyamide resins of the examples and comparative examples were heated to 300°C at a rate of 10°C / min under a nitrogen atmosphere, held at this temperature for 1 minute, and then cooled to 30°C at a rate of 10°C / min. Subsequently, the second heating process was performed at a rate of 10°C / min, and the peak top temperature of the endothermic peak in the DSC curve in this case was set as the melting point (Tm), and the corresponding heat of fusion was set as ΔH (unit: J / g). If ΔH was 40 J / g or less, it was determined that the molded product had low crystallinity and excellent transparency.

[0128] (3) Calculation of the ratio of each structural unit and biomass raw material

[0129] The ratio of each structural unit and biomass raw material in the polyamide resin of the examples and comparative examples was calculated based on the raw material input amount, assuming that the raw material of the polyamide resin was completely reacted. The ratio of biomass raw material is the ratio of the input amount (mass) of the raw material derived from biomass in the total input amount of 100 mass% of the raw material, assuming that the raw material of the polyamide resin was completely reacted.

[0130] Specifically, regarding the ratio of each structural unit and biomass raw material, the amount of contribution to the molecular weight of 1,5-pentamethylenediamine, 102.18 g / mol, was calculated as 100.18 (= 102.18 - 2.00) g / mol, the amount of contribution to the molecular weight of adipic acid, 146.14 g / mol, was calculated as 112.14 (= 146.14 - 34.00) g / mol, and the amount of contribution to the molecular weight of sebacic acid, 202.25 g / mol, was calculated as 168.25 (= 202.25 - 34.00) g / mol, taking into account the removal of condensation water due to polymerization. The ratio of biomass raw material was set to the proportion of the structural unit derived from 1,5-pentamethylenediamine and sebacic acid in the total structural unit of 100 mass% in the polymer.

[0131] (4) Equilibrium water absorption

[0132] A non-stretched polyamide sheet of 20 mm x 80 mm x 2 mm was produced using the particles of the polyamide resin of the examples and comparative examples, using a hot press manufactured by Shintoh Metal Industry Co., Ltd., after preheating at a temperature of the melting point + 30°C for 3 minutes, hot pressing at 5 MPa for 1 minute, and then cold pressing at 30°C, 5 MPa for 3 minutes. The resulting sheet was vacuum dried at 80°C for 48 hours, and the mass was measured. Then, the sheet was immersed in water at 23°C for 800 hours, and after the sheet was taken out, the surface moisture was absorbed with a cloth, and then the mass of the sheet was measured. The equilibrium water absorption was calculated from the mass of the sheet before and after the sheet was immersed in water, using the following formula.

[0133] Equilibrium water absorption = [ (mass of the sheet after immersion in water - mass of the sheet before immersion in water)

[0134] / mass of the sheet before immersion in water] x 100

[0135] When the equilibrium water absorption was 14.5% or less, it was determined to be low water absorption.

[0136] (5) Abrasion amount

[0137] Pellets of the polyamide resins of Examples and Comparative Examples were hot-pressed using a hot press manufactured by Shintogo Metal Industry Co., Ltd. at a temperature of the melting point + 30°C for 3 minutes, then at 5 MPa for 1 minute, and then at 30°C, 5 MPa for 3 minutes, to produce two unstretched polyamide sheets of 45 mm x 45 mm x 1 mm, and the resulting sheets 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 the measurement of the water absorption amount for the correction of the water absorption amount of the sample (dried sheet) in the abrasion test.

[0138] First, the aluminum bag was opened, and the mass of the two samples was measured. The abrasion test of the sample for the abrasion test was performed on the abrasion wheel of a reciprocating plane abrasion tester manufactured by Suga Test Instruments Co., Ltd. with abrasive paper No. G (Garnet) 50 cut to a length of 157 mm and a width of 12 mm attached thereto, under conditions of a load of 3000 g, a stroke of 30 mm, and 120 reciprocations. After the test, the mass of the sample for the abrasion test was measured after the resin powder on the sample due to abrasion was shaken off. Almost at the same time, the mass of the sample for the measurement of the water absorption amount was measured. The mass obtained by adding the mass difference of the sample for the abrasion test before and after the abrasion test to the mass increment of the sample for the measurement of the water absorption amount (apparent water absorption amount) was used as the abrasion amount.

[0139] When the abrasion amount was less than 11.6 mg, it was judged that the abrasion resistance was excellent.

[0140] [Raw materials used]

[0141] (1) Diamine

[0142] 1,5-pentamethylenediamine: manufactured by CJ Research Co., Ltd. (derived from biomass, purity: 99.90 mass%)

[0143] (2) Carboxylic acid

[0144] Adipic acid: manufactured by Asahi Kasei Corporation (derived from fossil raw material, purity: 99.8 mass%).

[0145] Sebacic acid: manufactured by Casda Biomaterials Co., Ltd. (derived from biomass, purity: 99.5 mass%).

[0146] (3) Organic solvent

[0147] 2-propanol: manufactured by FUJIFILM Wako Pure Chemical Corporation (purity: 99.7 mass%).

[0148] Synthesis of Nylon 56 salt

[0149] To a 700 L reaction vessel was added adipic acid 32.42 kg and 2-propanol 273 kg, heated to 40°C to dissolve the adipic acid, then 1,5-pentanediamine 22.67 kg was slowly added over 71 minutes. Neutralization heat and crystallization heat were generated, and the addition was adjusted so that the solution temperature was in the range of 40°C to 50°C during the addition. After the addition of the 1,5-pentanediamine was completed, the solution was stirred for 30 minutes while maintaining the temperature at 35°C to 40°C, 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 filtrate, then dried at 60°C under reduced pressure for 48 hours to obtain nylon 56 salt 54.8 kg.

[0150] Synthesis of nylon 510 salt

[0151] To a 700 L reaction vessel was added sebacic acid 24.27 kg and 2-propanol 184 kg, heated to 40°C to dissolve the sebacic acid, then 1,5-pentanediamine 12.27 kg was slowly added over 65 minutes. Neutralization heat and crystallization heat were generated, and the addition was adjusted so that the solution temperature was in the range of 40°C to 50°C during the addition. After the addition of the 1,5-pentanediamine was completed, the solution was stirred for 30 minutes while maintaining the temperature at 35°C to 40°C, 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 filtrate, then dried at 60°C under reduced pressure for 48 hours to obtain nylon 510 salt 36.3 kg.

[0152] Example 1

[0153] Into a 1 L polymerization tank was put nylon 56 salt 200.0 g, nylon 510 salt 50.0 g, and deaerated ion exchange water 50.0 g, after nitrogen substitution was performed in the polymerization tank, the polymerization tank was closed and warmed to 200°C, then, while stirring, the pressure in the polymerization tank was adjusted to 1.3 MPa, and polymerization was performed for 3 hours. While the temperature in the polymerization tank was warmed to 280°C, the pressure was released to atmospheric pressure over 40 minutes. After the pressure was released, polymerization was performed for 2 hours under a nitrogen stream of 200 mL / minute, then the stirrer was stopped, nitrogen was introduced, and the pressure was adjusted to 1.0 MPa. After the pressure was adjusted, the polymer was drawn out in the form of a strand, and pelletized. The polyamide pellets were dried at 90°C under reduced pressure for 48 hours to obtain the copolyamide resin of Example 1.

[0154] By 13 The copolyamide resin of Example 1 was confirmed to be a random copolymer by C-NMR spectroscopy.

[0155] Example 2

[0156] Into a 1 L polymerization tank, nylon 56 salt 175.0 g, nylon 510 salt 75.0 g and deaerated ion exchange water 50.0 g were charged, the polymerization tank was replaced with nitrogen, and then, after being closed, the temperature was raised to 200°C. Subsequently, while stirring, the pressure in the polymerization tank was regulated to 1.3 MPa, and polymerization was performed for 3 hours. While raising the temperature in the polymerization tank to 250°C, the pressure was released to the atmosphere over 40 minutes. After the release of the pressure, polymerization was performed under a nitrogen stream of 200 mL / min for 2 hours, and then the stirrer was stopped, nitrogen was introduced, and the pressure was regulated to 1.0 MPa. After the pressure regulation, pelletization was performed in the form of a strand. The polyamide pellets were dried at 90°C under reduced pressure for 48 hours, and a copolyamide resin of Example 2 was obtained.

[0157] By 13 The random nature of the copolyamide resin of Example 2 was confirmed by C-NMR spectroscopy, and the result was a random copolymer.

[0158] Example 3

[0159] Into a 1 L polymerization tank, nylon 56 salt 150.0 g, nylon 510 salt 100.0 g and deaerated ion exchange water 50.0 g were charged, and polymerization was performed by the same method as in Example 2, and pelletization was performed, and a copolyamide resin of Example 3 was obtained.

[0160] Example 4

[0161] Into a 1 L polymerization tank, nylon 56 salt 125.0 g, nylon 510 salt 125.0 g and deaerated ion exchange water 50.0 g were charged, and polymerization was performed by the same method as in Example 2, and pelletization was performed, and a copolyamide resin of Example 4 was obtained.

[0162] Example 5

[0163] Into a 1 L polymerization tank, nylon 56 salt 100.0 g, nylon 510 salt 150.0 g and deaerated ion exchange water 50.0 g were charged, and polymerization was performed by the same method as in Example 2, and pelletization was performed, and a copolyamide resin of Example 5 was obtained.

[0164] Example 6

[0165] Into a 1 L polymerization tank, nylon 56 salt 75.0 g, nylon 510 salt 175.0 g and deaerated ion exchange water 50.0 g were charged, and polymerization was performed by the same method as in Example 2, and pelletization was performed, and a copolyamide resin of Example 6 was obtained.

[0166] Example 7

[0167] Into a 1 L polymerization tank, nylon 56 salt 50.0 g, nylon 510 salt 200.0 g, and ion exchanged water 50.0 g which was degassed were put, and polymerization was carried out by the same method as Example 2, and granulation was carried out, to obtain a copolyamide resin of Example 7.

[0168] Comparative Example 1

[0169] Into a 1 L polymerization tank, nylon 56 salt 225.0 g, nylon 510 salt 25.0 g, and ion exchanged water 50.0 g which was degassed were put, and polymerization was carried out by the same method as Example 1, and granulation was carried out, to obtain a copolyamide resin of Comparative Example 1.

[0170] Comparative Example 2

[0171] Into a 1 L polymerization tank, nylon 56 salt 25.0 g, nylon 510 salt 225.0 g, and ion exchanged water 50.0 g which was degassed were put, and polymerization was carried out by the same method as Example 2, and granulation was carried out, to obtain a copolyamide resin of Comparative Example 2.

[0172] The mass ratio of each structural unit, the ratio of structural units derived from each monomer component, and the proportion of biomass raw material, and the DSC measurement data calculated from the raw material input amount according to Examples 1 to 7 and Comparative Examples 1 and 2 are shown in Table 1.

[0173] [Table 1]

[0174]

[0175] For the copolyamide resins of Example 2 and Comparative Examples 1 and 2, the data of equilibrium water absorption and abrasion amount are shown in Table 2.

[0176] [Table 2]

[0177]

[0178] As shown in Table 1, in Examples 1 to 7, the copolyamides contain structural unit A and structural unit B, the mass ratio of structural unit A / structural unit B is in the range of 85 / 15 to 15 / 85, wherein the structural unit A is derived from equimolar reactants of pentamethylene diamine and adipic acid, and the structural unit B is derived from equimolar reactants of pentamethylene diamine and sebacic acid, and the Examples 1 to 7 have smaller heat of fusion, i.e., enthalpy change ΔH accompanying fusion, and lower crystallinity, and excellent transparency, as compared with Comparative Examples 1 and 2. Among them, Examples 4 having a mass ratio of structural unit A / structural unit B of 49 / 51 and Example 5 having a mass ratio of structural unit A / structural unit B of 39 / 61 have smaller ΔH, and particularly excellent transparency.

[0179] Industrial applicability

[0180] The copolyamide resin of the present application can be suitably used for applications such as molded articles obtained by various molding methods, films for food packaging, and the like. The copolyamide resin can contribute to achievement of Goal 12 and the like of SDGs (Sustainable Development Goals).

Claims

1. A copolyamide resin comprising structural unit A and structural unit B, wherein the mass ratio of structural unit A to structural unit B is 85 / 15 to 15 / 85. The structural unit A is derived from the equimolar amounts of the reactants of pentamethylenediamine and adipic acid, as represented by the following formula (A). [Chemical Formula 1] The structural unit B is derived from an equimolar amount of reactants of pentamethylenediamine and sebacic acid, as represented by the following formula (B). [Chemical Formula 2] 。 2. The copolyamide resin according to claim 1, wherein, The melting point of the copolyamide resin, as determined by DSC, is 170–240 °C.

3. The copolyamide resin according to claim 1, wherein, The crystallization temperature of the copolyamide resin, as determined by DSC, is 115–195 °C.

4. A polyamide resin composition comprising any one of the copolyamide resins according to claims 1 to 3.

5. A molded article comprising the copolyamide resin according to any one of claims 1 to 3.

6. A membrane comprising the copolyamide resin according to any one of claims 1 to 3.

7. A monofilament comprising the copolyamide resin according to any one of claims 1 to 3.

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