JP2012031268A - Polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition having excellent flexibility and contractibility.SOLUTION: The polyamide resin composition includes a copolyamide composed of two or more kinds of raw materials in which the copolyamide (A) is a copolymer composed of raw materials containing two or more kinds of a polyamide 12 raw material (a), a polyamide 6 raw material (b) and/or a nylon salt (c), the polyamide 12 raw material (a) is 12-aminododecanoic acid and/or laurolactam, the polyamide 6 raw material (b) is caprolactam and/or aminocaproic acid and the nylon salt (c) is a nylon salt composed of a 6-32C dicarboxylic acid (c1) and a 6-32C diamine (c2).

Description

  The present invention relates to a polyamide resin composition that can be used for molded articles, monofilaments, fibers and films.

Polyamide has excellent mechanical strength, thermal properties, chemical properties, and molding processability, so it is widely used in various parts in the automotive field, electronic and electrical fields, as well as monofilaments, fibers and films. . In these applications, various copolyamides are used in fields that require characteristics such as flexibility and transparency. Polyamide resins used in the field of monofilaments, fibers and films in these applications also include nylon 6, nylon 66, nylon 6 / nylon 66 copolymer, nylon 6 / nylon 12 copolymer, nylon 6 / nylon 66 / nylon. 12 copolymer and the like.
Monofilaments, fibers, and films obtained from these copolymerized polyamides are widely used in these fields because of their excellent wear resistance and impact resistance as well as mechanical and thermal properties. 1 and Patent Document 2.

JP 61-194215 A JP-A-8-225644

  However, further improvements in flexibility and shrinkage of monofilaments, fibers, and films made from the copolymerized polyamide are further required. Therefore, an object of the present invention is to provide a polyamide resin composition excellent in flexibility and shrinkage.

The above problems are solved by the present invention described below.
A polyamide resin composition comprising a copolyamide made of two or more raw materials, wherein the copolyamide (A) comprises a polyamide 12 raw material (a), a polyamide 6 raw material (b) and / or a nylon salt (c The polyamide 12 raw material (a) is 12-aminododecanoic acid and / or laurolactam, and the polyamide 6 raw material (b) is caprolactam and / or aminocaproic acid. A polyamide resin composition in which the nylon salt (c) is a nylon salt composed of a C6-C32 dicarboxylic acid (c1) and a C6-C32 diamine (c2).

  The polyamide resin composition of the present invention has excellent flexibility and excellent shrinkage after molding.

  The copolymerized polyamide (A) of the present invention is a known method such as melt polymerization, solution polymerization or solid phase polymerization of polyamide 12 raw material (a) and polyamide 6 raw material (b) and / or nylon salt (c). Can be obtained by copolymerization with

  As the raw material of the copolymerized polyamide (A), the polyamide 12 raw material (a) is 12-aminododecanoic acid and / or laurolactam, the polyamide 6 raw material (b) is caprolactam or aminocaproic acid, and a nylon salt ( c) is a nylon salt consisting of a C6-C32 dicarboxylic acid (c1) and a C6-C32 diamine (c2).

  The copolymerized polyamide (A) preferably contains 50% by weight to 99% by weight of the polyamide 12 raw material (a), more preferably 50% by weight to 90% by weight, more preferably 50% by weight to the total raw material. It is more preferable to include 80% by weight, and it is particularly preferable to include 55% to 70% by weight.

  Examples of the C6-C32 dicarboxylic acid (C1) constituting the nylon salt (c) include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, Aliphatic dicarboxylic acids such as tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, eicosanedicarboxylic acid, 1,3- / 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4'-dicarboxylic acid Examples include cycloaliphatic dicarboxylic acids such as acids and norbornane dicarboxylic acids, and aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, and 1,4- / 2-6- / 2,7-naphthalenedicarboxylic acid. Adipic acid is preferred because of its ease. These can use 1 type (s) or 2 or more types.

  On the other hand, as the diamine (C2) having 6 to 32 carbon atoms constituting the nylon salt (c), ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylene Diamine, Decamemethylenediamine, Undecamethylenediamine, Dodecamethylenediamine, Tridecamethylenediamine, Tetradecamethylenediamine, Pentadecamethylenediamine, Hexadecamethylenediamine, Heptadecamethylenediamine, Octadecamethylenediamine, Nonadecamethylenediamine, Eicosamethylenediamine, 2- / 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4- / 2,4,4-trimethylhexene Methylenediamine, aliphatic diamines such as 5-methyl-1,9-nonanediamine, 1,3- / 1,4-cyclohexanediamine, 1,3- / 1,4-cyclohexanedimethylamine, bis (4-aminocyclohexyl) Methane, bis (4-aminocyclohexyl) propane, bis (3-methyl-4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2,2,4-trimethyl-1 -Cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophoronediamine), bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornane dimethylamine, tricyclodecane dimethylamine, etc. Cycloaliphatic diamine, m- / p-xylile Examples include aromatic diamines such as diamines. From the viewpoint of economic efficiency and availability, hexamethylene diamine, nonamethylene diamine, dodecamethylene diamine, 3-trimethylcyclohexanemethylamine (isophorone diamine), m / p-xylylenediamine Is preferred, and hexamethylenediamine is more preferred. These can use 1 type (s) or 2 or more types.

  Nylon salts (c) comprising a C6-C32 dicarboxylic acid (C1) and a C6-C32 diamine (C2) include hexamethylene adipamide, decamethylene decanamide, decamethylene dodecamide and nona, among others. One or more nylon salts selected from the group consisting of methylene sebacamide are preferred.

  The copolymerized polyamide (A) of the present invention may contain at least one kind of enantolactam, undecane lactam, α-pyrrolidone, α-piperidone as a lactam other than laurolactam and caprolactam which are polyamide 12 raw materials (a). it can.

  Specific examples of the copolymerized polyamide (A) include a polyamide 12/66 copolymer (a copolymer of polyamide 12 and polyamide 66, hereinafter the copolymer is described in the same manner), and a polyamide 6/12/69 copolymer. , Polyamide 12/69 copolymer, polyamide 12/610 copolymer, polyamide 6/12/610 copolymer, polyamide 12/611 copolymer, polyamide 6/12/611 copolymer, polyamide 12/612 copolymer Polymer, polyamide 6/12/612 copolymer, polyamide 6/12 copolymer, polyamide 6/66/12 copolymer, polyamide 12/910 copolymer, polyamide 6/12/910 copolymer, polyamide 12/912 copolymer, polyamide 6/12/912 copolymer, polyamide 12 / 6T copolymer, polyamide 6/12 / 6T copolymer , Polyamide 12 / 6I copolymer, polyamide 6/12 / 6I copolymer, polyamide 12 / IPD6 copolymer, polyamide 6/12 / IPD6 copolymer, polyamide 12 / IPDT copolymer, polyamide 6/12 / IPDT copolymer, polyamide 12/66 / 6T copolymer, polyamide 6/12/66 / 6T copolymer, polyamide 12/66 / 6I copolymer, polyamide 6/12/66 / 6I copolymer, Polyamide 12 / 6T / 6I copolymer, Polyamide 6/12 / 6T / 6I copolymer, Polyamide 12/66 / 6T / 6I copolymer, Polyamide 6/12/66 / 6T / 6I copolymer, Polyamide 12 / MXD6 and the like, polyamide 6/12 copolymer, polyamide 6/66/12 copolymer, polyamide 12/610 copolymer, poly 6/12/610 copolymer bromide, 12/611 copolymer polyamide, 6/12/611 copolymer polyamide, 12/612 copolymer polyamide, polyamide 6/12/612 copolymer.

  The melting point of the copolymerized polyamide (A) is preferably 170 ° C. or lower, more preferably 160 ° C. or lower, and further preferably 150 ° C. or lower, from the viewpoints of flexibility and shrinkage.

  The copolymerized polyamide (A) has a relative viscosity of 2.0 or more in accordance with JIS K-6920 measured in 96% by mass sulfuric acid under the conditions of a polyamide concentration of 1% by mass and a temperature of 25 ° C. It is preferably 0 or less, more preferably 2.2 or more and 4.5 or less. If the relative viscosity of the polyamide resin is less than the above value, the resulting polyamide film may have poor mechanical properties. On the other hand, when the above value is exceeded, the viscosity at the time of melting increases, and it may be difficult to form a film.

  In addition, there is no special restriction | limiting in the kind of terminal group of copolyamide (A), its concentration, and molecular weight distribution. In order to adjust the molecular weight or stabilize the melt at the time of molding, one or more of monoamine, diamine, monocarboxylic acid, and dicarboxylic acid can be added as a molecular weight modifier. For example, alicyclic such as aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dicyclohexylamine Aromatic monoamines such as monoamine, aniline, toluidine, diphenylamine, and naphthylamine, aliphatic diamines such as hexamethylenediamine, nonamethylenediamine, decamethylenediamine, and dodecamethylenediamine, cycloaliphatic diamines such as cyclohexanediamine, methylcyclohexanediamine, and isophoronediamine Aromatic diamines such as diamine, m- / p-phenylenediamine, m- / p-xylylenediamine, acetic acid, propionic acid, butyric acid, Acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid and other aliphatic monocarboxylic acids, cyclohexanecarboxylic acid and other alicyclic monocarboxylic acids, benzoic acid Aromatic monocarboxylic acids such as toluic acid, α- / β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid, adipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid , Aliphatic dicarboxylic acids such as dodecane dicarboxylic acid, alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,3- / 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, 1,4- Aromatic dicals such as / 2,6- / 2,7-naphthalenedicarboxylic acid It is phosphate and the like. These can use 1 type (s) or 2 or more types. The amount of these molecular weight regulators used varies depending on the reactivity of the molecular weight regulator and the polymerization conditions, but is appropriately determined so that the relative viscosity of the copolymerized polyamide (A) to be finally obtained falls within the above range.

  Regarding the copolymerized polyamide (A), the amount of water extraction measured according to the method for measuring the content of low molecular weight substances specified in JIS K-6920 is preferably 1.0% by mass or less. More preferably, it is 5 mass% or less. When the amount of water extraction exceeds the above value, the oligomer component is remarkably attached to the vicinity of the die, and appearance defects are liable to occur due to the generation of die lines and fish eyes caused by these attachments. Furthermore, the polyamide resin has a higher hygroscopicity than the olefin resin, and if a hygroscopic material is used, an oligomer is generated when the raw material is melt-extruded, resulting in difficulty in film production. It is preferable that the moisture content is 0.1% by mass or less after drying.

  In the copolymer polyamide (A) of the present invention, various additives and modifiers that are usually blended within a range that does not impair the flexibility and shrinkage characteristics, such as heat stabilizers, ultraviolet absorbers, light Stabilizer, antioxidant, antistatic agent, lubricant, antiblocking agent, filler, tackifier, sealability improver, antifogging agent, crystal nucleating agent, mold release agent, plasticizer, crosslinking agent, foaming agent, A polyamide resin composition can be obtained by adding a colorant (pigment, dye, etc.), a bending fatigue resistance improving material, or the like.

  There is no restriction | limiting in particular in manufacture to the monofilament using the polyamide resin composition of this invention, It can carry out by a normal method. For example, kneaded pellets or dry blended pellets of the resin composition are melted by an extruder or the like, extruded from a spinning nozzle, and cooled in a refrigerant bath such as water or trichlene to produce an undrawn yarn. In this case, the distance from the filament outlet of the spinning nozzle to the coolant level is preferably maintained at about 10 to 3000 mm.

The undrawn yarn obtained as described above is stretched in two stages and heat treated. There are no particular restrictions on the stretching conditions, but from the viewpoint of the transparency of the resulting monofilament, the first-stage stretching is preferably performed in steam or hot water by 3 to 5.0 times. When extending | stretching by, the temperature of 95-120 degreeC is preferable. Moreover, when extending | stretching in hot water from a transparent viewpoint of the monofilament obtained, 50-95 degreeC is preferable. A preferable first stage stretching temperature is 100 to 110 ° C. when steam is used, and 60 to 90 ° C. when hot water is used. The second stage stretching is performed 1.1 to 3.0 times in a gas atmosphere of 180 to 300 ° C. Examples of the gas include air and an inert gas such as nitrogen, but usually air is sufficient. A preferable temperature is about 180 to 300 ° C., and a preferable draw ratio is about 1.2 to 2.5 times.
There is no particular limitation on the heat treatment of the stretched monofilament, but from the viewpoint of transparency, heat treatment is preferably performed in a gas atmosphere of 160 to 350 ° C. with a yield ratio of 1.1 to 0.9 times. More preferably, it is 160-320 degreeC. If the take-up ratio is too small, the slack operation of the monofilament becomes difficult. A preferred scraping ratio is about 0.94 to 0.98. In the above stretching and heat treatment, the total stretching ratio is preferably about 4.0 to 8.0, and preferably about 4.5 to 7.0.

  Moreover, in the polyamide resin composition of this invention, a polyamide film is obtained by applying a well-known film manufacturing method and forming into a film. For example, a casting method in which the polyamide resin composition of the present invention is melt-kneaded with an extruder, extruded into a flat film shape with a T-die or a coat hanger die, cast on a casting roll surface, and cooled to produce a film, a ring shape There is a tubular method for producing a film by air-cooling or water-cooling a tubular material melt-extruded into a cylinder by a die. The produced film can be used as a substantially non-oriented unstretched film, but is preferably a biaxially stretched film from the viewpoint of the strength and gas barrier properties of the obtained film.

  Stretching the obtained unstretched film can be performed by a conventionally known industrial method. For example, a film produced by the casting method can be obtained by a simultaneous biaxial stretching method in which an unstretched sheet is stretched simultaneously in the longitudinal and transverse directions by a tenter-type simultaneous biaxial stretching machine, or an unstretched sheet melt-extruded from a T-die in a longitudinal direction by a roll stretching machine. Examples thereof include a sequential biaxial stretching method in which the film is stretched and then stretched in the transverse direction with a tenter-type stretching machine, and a tubular stretching method in which a tubular sheet formed from an annular die is stretched simultaneously in the longitudinal and transverse directions by a gas pressure. The stretching step may be carried out continuously following the production of the polyamide film, or the polyamide film may be wound once and then stretched as a separate step.

  The polyamide film of the present invention can be subjected to surface treatments such as corona discharge treatment, plasma treatment, flame treatment, and acid treatment in order to enhance printability, lamination, and adhesive application. Moreover, after performing such a process as needed, it can be used for each intended use through secondary processing steps such as printing, laminating, adhesive application, and heat sealing.

  In addition, the polyamide film of the present invention is excellent in transparency, slipperiness, printability, and flexibility, and has a high utility value by itself, but by laminating other thermoplastic resin on this, more properties can be obtained. It is possible to add. Specifically, a thermoplastic resin layer can be laminated on at least one side of the polyamide film of the present invention to be used as a laminated film.

  Examples of the lamination method of the laminated film include a co-extrusion method, an extrusion lamination method, and a dry lamination method. The coextrusion method is a method of coextruding the polyamide resin composition of the present invention and another thermoplastic resin, and examples thereof include coextrusion sheet molding, coextrusion casting film molding, and coextrusion inflation film molding. In the extrusion laminating method, the anchor coating agent is applied to the polyamide film of the present invention and a base material such as a thermoplastic resin, respectively, and after drying, the thermoplastic resin is melt-extruded while being cooled and pressed between rolls. In this method, a laminate film is obtained by pressure bonding. In the dry laminating method, a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, or a polyurethane compound is applied to the polyamide film of the present invention, dried, and then laminated to a base material such as a thermoplastic resin. This is a method for obtaining a film. The film after lamination can be increased in adhesive strength by aging. When laminating, it is preferable to use one or both sides of the polyamide film after corona treatment.

  The thermoplastic resin to be laminated includes high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra high molecular weight polyethylene (UHMWPE), polypropylene ( PP), ethylene / propylene copolymer (EPR), ethylene / butene copolymer (EBR), ethylene / vinyl acetate copolymer (EVA), saponified ethylene / vinyl acetate copolymer (EVOH), ethylene / acrylic Acid copolymer (EAA), ethylene / methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer Polyolefin resin such as coalescence (EEA), acrylic acid, meta Rylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endobicyclo- [2.2.1] -5 Carboxyl groups such as heptene-2,3-dicarboxylic acid and metal salts thereof (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2.2.1] Contains functional groups such as acid anhydride groups such as -5-heptene-2,3-dicarboxylic acid anhydride, epoxy groups such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and glycidyl citraconic acid. The above-mentioned polyolefin resin, polybutylene terephthalate (PBT), polyethylene Polyester resins such as tarate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), polyethylene naphthalate (PEN), liquid crystal polyester (LCP) Polyether resins such as polyacetal (POM) and polyphenylene oxide (PPO), polysulfone resins such as polysulfone (PSF) and polyethersulfone (PES), polyphenylene sulfide (PPS) and polythioethersulfone (PTES) Polyketone resins such as thioether resin, polyether ether ketone (PEEK), polyallyl ether ketone (PAEK), polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene Polynitrile resins such as len copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), methacrylonitrile / styrene / butadiene copolymer (MBS), polymethacryl Polymethacrylate resins such as methyl methacrylate (PMMA) and polyethyl methacrylate (PEMA), polyvinyl ester resins such as polyvinyl acetate (PVAc), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / Polyvinyl resins such as vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer, cellulose resins such as cellulose acetate and cellulose butyrate, polycarbonate resins such as polycarbonate (PC), thermoplastic polyimide (PI), polyamideimide (P I), polyimide resins such as polyetherimide, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), ethylene / tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene / chloro Trifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV) ), Fluororesin such as tetrafluoroethylene / fluoro (alkyl vinyl ether) copolymer (PFA), thermoplastic polyurethane resin, polyurethane elastomer, polyester elastomer, polyamide elastomer, etc. It is. It is also possible to laminate the polyamide resin defined in the present invention. From the viewpoint of balance of film strength and gas barrier properties, polymetaxylylene adipamide (polyamide MXD6) or saponified ethylene / vinyl acetate copolymer ( EVOH) is preferably laminated.

  Moreover, it is desirable to provide a sealant layer in the polyamide film of the present invention from the viewpoint of imparting heat sealability. The material used for the sealant layer may be any resin that can be heat-sealed, and generally includes polyolefin resins, polyester resins, and the like, and it is preferable to use polyolefin resins. Specifically, polypropylene (PP), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene / vinyl acetate copolymer (EVA), ethylene / acrylic acid copolymer (EAA), ethylene / Methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer (EEA), ionomer resin, amorphous Polyester (A-PET) etc. are mentioned as a preferable thing.

  Furthermore, non-stretched, uniaxially or biaxially stretched thermoplastic resin film or sheet, or any base material other than thermoplastic resin, for example, paper, metal-based material, woven fabric, non-woven fabric, metal cotton, wood, etc. may be laminated. Is possible. Examples of the metal-based material include aluminum, iron, copper, nickel, gold, silver, titanium, molybdenum, magnesium, manganese, lead, tin, chromium, beryllium, tungsten, cobalt, and other metals and metal compounds, and two or more of these. Examples include alloy steels such as stainless steel, aluminum alloys, copper alloys such as brass and bronze, and alloys such as nickel alloys. In particular, in order to improve the gas barrier and water vapor barrier properties, it is also possible to deposit a metal and / or a metal compound. Examples of the material to be deposited include metals such as Si, Al, Ti, Zn, Zr, Mg, Sn, Cu, and Fe, and oxides, nitrides, fluorides, and sulfides thereof. Specifically, inorganic compounds such as SiOx (x = 1.0 to 2.0), alumina, magnesia, zinc sulfide, titania, zirconia, cerium oxide, organic compounds such as HMDSO (hexamethyldisiloxane), Examples thereof include silicon oxide obtained by reaction after mixing an inorganic gas such as silane gas with a carrier gas and oxygen for oxidizing. As a method for producing a vapor deposition film, a known method, a vacuum deposition method as a physical deposition method (PVD method), an EB deposition method, a sputtering method, an ion plating method, or a plasma CVD method as a chemical deposition method (CVD) method is used. Or a chemical reaction method can be used.

  The polyamide resin composition of the present invention can be used as a raw material for fibers and various molded products in addition to monofilaments and films. The production of fibers and various molded products is not particularly limited and can be produced by a known molding method. For example, the molded product can be manufactured by a method such as an injection molding method, a blow molding method, or a vacuum molding method, and the fiber can be manufactured by a method such as a melt spinning method. When the melt molding method is used, the molding temperature is usually set to 200 to 300 ° C.

  The present invention will be described below with reference to examples and comparative examples, but is not limited to the following examples.

1) Relative viscosity According to JIS K6810, 96 wt% concentrated sulfuric acid was used as a solvent, and the polyamide concentration was 1% by mass and measured at 25 ° C.
2) Amount of water extraction Measured according to the method for measuring the content of low molecular weight substances specified in JIS K-6920.
3) The moisture content was measured by the Karl Fischer method according to ISO15512.
4) Melting point According to ISO11357-3, it measured using DSC6220 by Seiko Instruments Inc.
3) Characteristic evaluation of monofilament Using a CS-40-26N type extruder manufactured by Uniplus, the temperature of the extruder is 280 ° C, the temperature of the cooling water is 15 ° C, the first stage stretching temperature is 95 ° C, and the first stage stretching. The magnification is 3.8 times, the second stage stretching temperature is melting point + 20 ° C., the second stretching ratio is 1.45 times, the heat setting temperature is melting point + 20 ° C., the hot air heat treatment scraping ratio is 0.95, and the total stretching ratio is 5 A monofilament was prepared by adjusting to .5. The tensile elastic modulus of the produced monofilament was measured according to JIS L1070.
The hot water shrinkage of the prepared monofilament is as follows: the monofilament is cut to about 1 m, its length (l1) is measured, and then immersed in hot water at 100 ° C. for 1 hour, under conditions of 23 ° C. and relative humidity 50% RH. The length (l2) of the monofilament after standing for 24 hours was measured and determined by the following formula (1).
Hot water shrinkage = (l1-l2) / l1 × 100 (1)

Example 1
While stirring 13.5 kg of 12-aminododecanoic acid and 7.5 kg of caprolactam in a uniform state in a pressure-resistant reaction vessel equipped with a stirrer with an internal volume of 70 liters, the temperature was raised to 240 ° C. and polymerized at the same temperature for 10 hours. The reaction product taken out in the form of a strand from the lower nozzle of the reaction vessel was introduced into a water bath, cooled, and cut to obtain a copolymer polyamide (A-1) pellet. Next, the pellet was immersed in hot water to extract and remove unreacted monomers, and then dried under reduced pressure. The relative viscosity, water content, and water extraction amount of the obtained copolymer polyamide (A-1) were 2.6, 0.03% by mass, and 0.5% by mass, respectively. Using a cylindrical mixer, 0.05 part by weight of a fatty acid metal salt was blended with 100 parts by weight of the obtained copolymer polyamide (A-1) to obtain a polyamide resin composition. Using this polyamide resin composition, monofilaments were prepared and evaluated. Table 1 shows the diameter and the draw ratio of the monofilament when the result and the characteristic evaluation were performed.

Example 2
In Example 1, the same procedure was carried out except that the amounts of 12-aminododecanoic acid and caprolactam were changed to 16.4 kg and 3.6 kg, respectively. The relative viscosity, water content, and water extraction amount were 2.6, 0. Copolymer polyamide (A-2) of 0.04% by mass and 0.5% by mass was obtained. Using a cylindrical mixer, 0.05 part by weight of a fatty acid metal was blended with 100 parts by weight of the obtained copolymer polyamide (A-1) to obtain a polyamide resin composition. Using this polyamide resin composition, monofilaments were prepared and evaluated. Table 1 shows the diameter and the draw ratio of the monofilament when the result and the characteristic evaluation were performed.

Comparative Example 1
While stirring 20 kg of caprolactam and 2 kg of water in a pressure-resistant reaction vessel equipped with a stirrer with an internal volume of 70 liters so as to be in a uniform state, the temperature was raised to 260 ° C. and stirred for 1 hour at a pressure of 2.0 MPa. Thereafter, the polymerization reaction was performed at 260 ° C. for 2 hours under normal pressure while releasing the pressure to evaporate water from the reaction vessel, and further for 2 hours under reduced pressure of 260 ° C. and 53 kPa. The reaction product taken out in a strand form from the lower nozzle of the reaction vessel was introduced into a water bath, cooled, and cut to obtain polyamide (A-3) pellets. Next, the pellet was immersed in hot water to extract and remove unreacted monomers, and then dried under reduced pressure. The relative viscosity, water content, and water extraction amount of the obtained copolymer polyamide were 2.8, 0.04% by mass, and 0.3% by mass, respectively. Using a cylindrical mixer, 0.05 part by weight of a fatty acid metal was blended with 100 parts by weight of the obtained polyamide (A-3) to obtain a polyamide resin composition. Using this polyamide resin composition, monofilaments were prepared and evaluated. Table 1 shows the diameter and the draw ratio of the monofilament when the result and the characteristic evaluation were performed.

Comparative Example 2
In Example 1, the same procedure was performed except that the blending amounts of a 50% aqueous solution of hexamethylenediamine and adipic acid nylon salt and caprolactam were changed to 6.0 kg and 17.0 kg, respectively, relative viscosity, saturated water absorption in water, A copolymer polyamide (A-4) having a water extraction amount of 2.8, 0.05% by mass, and 0.5% by mass was obtained. Using a cylindrical mixer, 0.05 part by weight of fatty acid metal was blended with 100 parts by weight of the obtained copolymer polyamide (A-4) to obtain a polyamide resin composition. Using this polyamide resin composition, monofilaments were prepared and evaluated. Table 1 shows the diameter and the draw ratio of the monofilament when the result and the characteristic evaluation were performed.

Claims (5)

A polyamide resin composition comprising a copolyamide (A) made of two or more raw materials, wherein the copolyamide (A) is a polyamide 12 raw material (a) and a polyamide 6 raw material (b) and / or nylon A copolymer made from a raw material containing two or more of the salt (c), the polyamide 12 raw material (a) is 12-aminododecanoic acid and / or laurolactam, and the polyamide 6 raw material (b) is caprolactam and / or A polyamide resin composition, which is aminocaproic acid, wherein the nylon salt (c) is a nylon salt (c) comprising a dicarboxylic acid (c1) having 6 to 32 carbon atoms and a diamine (c2) having 6 to 32 carbon atoms. The nylon salt (c) is at least one nylon salt selected from the group consisting of hexamethylene adipamide, decamethylene decanamide, decamethylene dodecamide and nonamethylene sebacamide. The polyamide resin composition as described. The polyamide resin composition according to claim 1 or 2, wherein the copolymerized polyamide (A) has a melting point of 170 ° C or lower. The copolyamide (A) is a copolyamide (A) made from a raw material containing 50% by weight to 99% by weight of the polyamide 12 raw material (a) with respect to all the raw materials. The polyamide resin composition according to any one of the above. The monofilament, fiber, or film formed by shape | molding the polyamide resin composition of any one of Claims 1-4.